Nir-inert substrates comprising bis-oxodihydroindolylen-benzodifuranones

Abstract

A method for producing infra-red inert substrates, including moulded polymeric articles, films, fibers and coatings and other organic and inorganic materials, by incorporating into the substrate or onto the surface of the substrate an effective amount of a dispersed bis-oxodihydroindolylen-benzodifuranone colourant. The thus obtained, also claimed substrates so produced are reflective and transparent to much of the near infra red radiation not reflected. There are multiple applications for cases of devices comprising electronic components, outdoor construction elements, outdoor furniture, automotive, marine or aerospace parts, laminates, artificial leather or textile materials, as well as in polychrome printing processes and optical fibers. The thus obtained substrates can also be subjected to laser welding. New bis-oxo-dihydroindolylen-benzodifuranone compounds are also claimed.

1 . A method for preparing a near infra red inert organic or inorganic substrate, which method comprises the incorporation into the substrate, or the application onto the surface of the substrate, of a composition containing a bis-oxodihydroindolylen-benzodifuranone colourant of formula 
     
       
         
         
             
             
         
       
       or an isomer or tautomer thereof, 
       wherein the bis-oxodihydroindolylen-benzodifuranone colourant of formula (Ia) or (Ib) or isomer or tautomer thereof is in the form of particles of mean size ≦0.5 μm or of mean size >0.5 μm and thickness ≧0.4 μm which are well dispersed in the composition, in an amount effective to impart to a reflective organic or inorganic substrate an infra red reflectance of ≧20%, to a transparent organic or inorganic substrate an infra red transmittance of ≧30%, or to a semi-transparent organic or inorganic substrate a combined infra red reflectance and transmittance of ≧25%, each at wavelengths from 850 to 1600 nm, in which formulae (Ia) and (Ib) 
       R 1  and R 6  are each independently of the other H, CH 3 , CF 3 , F or Cl; 
       R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9  and R 10  are each independently of all others H, halogen, R 11 , COOH, COOR 11 , COO − , CONH 2 , CONHR 11 , CONR 11 R 12 , CN, OH, OR 11 , OOCR 11 , OOCNH 2 , OOCNHR 11 , OOCNR 11 R 12 , NO 2 , NH 2 , NHR 11 , NR 11 R 12 , NHCOR 12 , NR 11 COR 12 , N═CH 2 , N═CHR 11 , N═CR 11 R 12 , SH, SR 11 , SOR 11 , SO 2 R 11 , SO 3 R 11 , SO 3 H, SO 3 , SO 2 NH 2 , SO 2 NHR 11  or SO 2 NR 11 R 12 ; whereby R 2  and R 3 , R 3  and R 4 , R 4  and R 5 , R 7  and R 5 , R 5  and R 9 , and/or R 9  and R 10  can optionally be linked together by a direct bond or an O, S, NH or NR 11  bridge; 
       R 11  and R 12  are each independently of the other C 1 -C 12 alkyl, C 1 -C 12 cycloalkyl, C 1 -C 12 alkenyl, C 1 -C 12 cycloalkenyl or C 1 -C 12 alkinyl, each of which is uninterrupted or interrupted by O, NH, NR 13  and/or S in two or more fragments each comprising at least 2 C atoms, and each of which is also unsubstituted or substituted one or more times with COOH, COOR 13 , COO − , CONH 2 , CONHR 13 , CONR 13 R 14 , CN, O, OH, OR 13 , OOCR 13 , OOCNH 2 , OOCNHR 13 , OOCNR 13 R 14 , NR 13 , NH 2 , NHR 13 , NR 13 R 14 , NHCOR 14 , NR 13 COR 14 , N═CH 2 , N═CHR 13 , N═CR 13 R 14 , SH, SR 13 , SOR 13 , SO 2 R 13 , SO 3 R 13 , SO 3 H, SO 3   − , SO 2 NH 2 , SO 2 NHR 13 , SO 2 NR 13 R 14  or halogen; 
       or C 7 -C 12 aralkyl, C 1 -C 11 heteroaryl or C 6 -C 12 aryl, each of which is unsubstituted or substituted one or more times with COOH, COOR 13 , COO, CONH 2 , CONHR 13 , CONR 13 R 14 , CN, OH, OR 13 , OOCR 13 , OOCNH 2 , OOCNHR 13 , OOCNR 13 R 14 , NO 2 , NH 2 , NHR 13 , NR 13 R 14 , NHCOR 14 , NR 13 COR 14 , N═CH 2 , N═CHR 13 , N═CR 13 R 14 , SH, SR 13 , SOR 13 , SO 2 R 13 , SO 3 R 13 , SO 3 H, SO 3 , SO 2 NH 2 , SO 2 NHR 13 , SO 2 NR 13 R 14  or halogen; and 
       each R 13  or R 14  is, independently of any other R 13  or R 14 , C 1 -C 6 alkyl, benzyl or phenyl, each of which is unsubstituted or substituted one or more times with COOH, COOR 13 , COO − , CONH 2 , CONHR 13 , CONR 13 R 14 , CN, O, OH, OR 13 , OOCR 13 , OOCNH 2 , OOCNHR 13 , OOCNR 13 R 14 , NR 13 , NH 2 , NHR 13 , NR 13 R 14 , NHCOR 14 , NR 13 COR 14 , N═CH 2 , N═CHR 13 , N═CR 13 R 14 , SH, SR 13 , SOR 13 , SO 2 R 13 , SO 3 R 13 , SO 3 H, SO 3   − , SO 2 NH 2 , SO 2 NHR 13 , SO 2 NR 13 R 14  or halogen with the proviso that the total number of atoms in any substituent of R 13  and R 14  is from 1 to 8; whereby pairs of substituents selected from the group consisting of all R 13  and R 14  can optionally be linked together by a direct bond or an O, S, NH or NR 11  bridge so as to form rings. 
     
   
   
       2 . A method according to  claim 1 , wherein the colourant of formula (Ia) or (Ib) is incorporated into a thermoplastic, elastomeric, crosslinked or inherently crosslinked polymer. 
   
   
       3 . The method according to  claim 1 , wherein the bis-oxodihydroindolylen-benzodifuranone is incorporated into a coating composition which is applied to the surface of the substrate. 
   
   
       4 . A near infra red inert composition or article comprising an organic or inorganic substrate and, in an amount effective to impart to the organic or inorganic substrate an infra red reflectance of ≧20%, an infra red transmittance of ≧30%, or a combined infra red reflectance and transmittance of ≧25%, each at wavelengths from 850 to 1600 nm, a bis-oxodihydroindolylen-benzodifuranone colourant of formula 
     
       
         
         
             
             
         
       
       or an isomer or tautomer thereof, 
       wherein the bis-oxodihydroindolylen-benzodifuranone colourant of formula (Ia) or (Ib) or isomer or tautomer thereof is in the form of particles of mean size ≦0.5 μm or of mean size >0.5 μm and thickness ≧0.4 μm which are well dispersed in the composition, in which formulae (Ia) and (Ib) 
       R 1  and R 6  are each independently of the other H, CH 3 , CF 3 , F or Cl; 
       R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9  and R 10  are each independently of all others H, halogen, R 11 , COOH, COOR 11 , COO, CONH 2 , CONHR 11 , CONR 11 R 12 , CN, OH, OR 11 , OOCR 11 , OOCNH 2 , OOCNHR 11 , OOCNR 11 R 12 , NO 2 , NH 2 , NHR 11 , NR 11 R 12 , NHCOR 12 , NR 11 COR 12 , N═CH 2 , N═CHR 11 , N═CR 11 R 12 , SH, SR 11 , SOR 11 , SO 2 R 11 , SO 3 R 11 , SO 3 H, SO 3 , SO 2 NH 2 , SO 2 NHR 11  or SO 2 NR 11 R 12 ; whereby R 2  and R 3 , R 3  and R 4 , R 4  and R 5 , R 7  and R 8 , R 8  and R 9 , and/or R 9  and R 10  can optionally be linked together by a direct bond or an O, S, NH or NR 11  bridge; 
       R 11  and R 12  are each independently of the other C 1 -C 12 alkyl, C 1 -C 12 cycloalkyl, C 1 -C 12 alkenyl, C 1 -C 12 cycloalkenyl or C 1 -C 12 alkinyl, each of which is uninterrupted or interrupted by O, NH, NR 13  and/or S in two or more fragments each comprising at least 2 C atoms, and each of which is also unsubstituted or substituted one or more times with COOH, COOR 13 , COO − , CONH 2 , CONHR 13 , CONR 13 R 14 , CN, O, OH, OR 13 , OOCR 13 , OOCNH 2 , OOCNHR 13 , OOCNR 13 R 14 , NR 13 , NH 2 , NHR 13 , NR 13 R 14 , NHCOR 14 , NR 13 COR 14 , N═CH 2 , N═CHR 13 , N═CR 13 R 14 , SH, SR 13 , SOR 13 , SO 2 R 13 , SO 3 R 13 , SO 3 H, SO 3 , SO 2 NH 2 , SO 2 NHR 13 , SO 2 NR 13 R 14  or halogen; 
       or C 7 -C 12 aralkyl, C 1 -C 11 heteroaryl or C 6 -C 12 aryl, each of which is unsubstituted or substituted one or more times with COOH, COOR 13 , COO − , CONH 2 , CONHR 13 , CONR 13 R 14 , CN, OH, OR 13 , OOCR 13 , OOCNH 2 , OOCNHR 13 , OOCNR 13 R 14 , NO 2 , NH 2 , NHR 13 , NR 13 R 14 , NHCOR 14 , NR 13 COR 14 , N═CH 2 , N═CHR 13 , N═CR 13 R 14 , SH, SR 13 , SOR 13 , SO 2 R 13 , SO 3 R 13 , SO 3 H, SO 3 , SO 2 NH 2 , SO 2 NHR 13 , SO 2 NR 13 R 14  or halogen; and 
       each R 13  or R 14  is, independently of any other R 13  or R 14 , C 1 -C 6 alkyl, benzyl or phenyl, each of which is unsubstituted or substituted one or more times with COOH, COOR 13 , COO − , CONH 2 , CONHR 13 , CONR 13 R 14 , CN, O, OH, OR 13 , OOCR 13 , OOCNH 2 , OOCNHR 13 , OOCNR 13 R 14 , NR 13 , NH 2 , NHR 13 , NR 13 R 14 , NHCOR 14 , NR 13 COR 14 , N═CH 2 , N═CHR 13 , N═CR 13 R 14 , SH, SR 13 , SOR 13 , SO 2 R 13 , SO 3 R 13 , SO 3 H, SO 3   − , SO 2 NH 2 , SO 2 NHR 13 , SO 2 NR 13 R 14  or halogen with the proviso that the total number of atoms in any substituent of R 13  and R 14  is from 1 to 8; whereby pairs of substituents selected from the group consisting of all R 13  and R 14  can optionally be linked together by a direct bond or an O, S, NH or NR 11  bridge so as to form rings. 
     
   
   
       5 . The infra red inert composition of  claim 4 , wherein the substrate is a thermoplastic, elastomeric, crosslinked or inherently crosslinked polymer. 
   
   
       6 . The composition of  claim 4 , which is a coating composition. 
   
   
       7 . A multilayer coating comprising
 a primer coating composition according to  claim 6  comprising a colourant of formulae (Ia) or (Ib), or an isomer or tautomer thereof and a white pigment in a weight ratio of from 1:99 to 99:1;   a basecoat comprising a black, colour, metallic or interference pigment; and   optionally a clear topcoat.   
   
   
       8 . An article comprising a substrate which is coated with the composition according to  claim 6 . 
   
   
       9 . An item comprising the composition according to  claim 4  on which there is a mark showing a pattern which is different when viewed or recorded under sequential irradiation by two electromagnetic waves of different emission spectra in the range from 400 nm to 2 μm under the same or different dihedral angles to the surface of the item, or viewed or recorded under irradiation by electromagnetic waves of the same emission spectrum in the range from 400 nm to 2 μm under different dihedral angles to the surface of the item, which mark comprises at least two different colourants, each colourant being embedded in a wet, dry or cured ink which may be the same or different for part or all of the colourants, at least two wet, dry or cured inks preferably reflecting differently under irradiation by electromagnetic waves of emission spectrum in the range from 400 nm to 2 μm, characterized in that the mark comprises an effective amount of a colourant of formula (Ia) or (Ib) or an isomer or tautomer thereof, in at least one of the wet, dry or cured inks. 
   
   
       10 . A method for identifying an item, characterized in that said item comprises a mark comprising an effective amount of a colourant of formula (Ia) or (Ib) according to  claim 1 , or an isomer or tautomer thereof wherein said mark is recorded under irradiation by electromagnetic waves of wavelength from 715 to 2000 nm, and the mark's image is used for identifying the item. 
   
   
       11 . A case for a device comprising electronic components, which case comprises or is coated with a composition according to  claim 4  wherein the colourant of formula (Ia) or (Ib) is applied in combination with a white, low- or non-NIR-absorbingblack, colour, metallic or interference pigment, in a weight ratio of from 1:99 to 99:1. 
   
   
       12 . An outdoor construction element, outdoor furniture, automotive, marine or aerospace part, laminate, artificial leather or textile material which comprises or is coated with a composition according to  claim 4  wherein the colourant of formula (Ia) or (Ib) is applied in combination with a white, low- or non-NIR-absorbingblack, colour, metallic or interference pigment, in a weight ratio of from 1:99 to 99:1. 
   
   
       13 . A polychrome printing process, wherein the black ink, or one of the black inks, comprises a bis-oxodihydroindolylen-benzodifuranone colourant of formula (Ia) or (Ib) according to  claim 1 , or an isomer or tautomer thereof. 
   
   
       14 . A method for laser welding an article, wherein a bis-oxodihydroindolylen-benzodifuranone colourant of formula (Ia) or (Ib) according to  claim 1 , or an isomer or tautomer thereof is incorporated into a polymeric composition which is in contact with a surface of a meltable substrate containing a near infra red absorbing material, then near infra red radiation preferably from a laser of wavelength in the range from 700 to 2000 nm is passed through the layer containing the colourant of formula (Ia) or (Ib) to the underlying substrate generating enough heat at the point of irradiation to melt together the two materials. 
   
   
       15 . A compound of formula (Ia) or (Ib) according to  claim 1 , or an isomer or tautomer thereof, with the proviso that the compound is not the compound of formula 
     
       
         
         
             
             
         
       
     
   
   
       16 . A method according to  claim 2 , wherein the colourant of formula (Ia) or (Ib) is incorporated into a polyolefin, polyamide, polyurethane, polyacrylate, polyacrylamide, polyvinyl alcohol, polycarbonate, polystyrene, polyester, polyacetal, a natural or synthetic rubber or a halogenated vinyl polymer. 
   
   
       17 . The method according to  claim 1 , wherein the bis-oxodihydroindolylen-benzodifuranone is incorporated into a coating composition which is applied to the surface a thermoplastic, elastomeric, crosslinked or inherently crosslinked polymer substrate which is in the form of a film or coating applied to the surface of a substrate, or in the form of a fiber, sheet or other moulded or shaped article. 
   
   
       18 . The infra red inert composition according to  claim 5 , wherein the thermoplastic, elastomeric, crosslinked or inherently crosslinked polymer is a polyolefin, polyamide, polyurethane, polyacrylate, polyacrylamide, polyvinyl alcohol, polycarbonate, polystyrene, polyester, polyacetal, a natural or synthetic rubber or a halogenated vinyl polymer.