Polymethine compounds, method of producing same, and use thereof

Abstract

The invention provides near infrared absorbing materials showing high light-to-heat conversion efficiency and high sensitivity to lasers whose emission bands are within the range of 750 nm to 900 nm, original plates for direct printing plate making, and novel compounds which can be applied to such absorbing materials and plates. The compounds are polymethine compounds of the general formula (I) A detailed description of general formula (I) may be found in the specification. wherein R 1 represents an alkoxy group which may be substituted; R 2 represents an alkyl group which may be substituted; R 3 and R 4 each represents a lower alkyl group or R 3 and R 4 taken together represent a ring; X represents a hydrogen atom, a halogen atom or a substituted amino group; Y represents an alkoxy group which may be substituted or an alkyl group which may be substituted; Z represents a charge neutralizing ion.

1. A polymethine compound of the following general formula 
                 
 
       wherein R 1  represents an alkoxy group which may be substituted; R 2  represents an alkyl group which may be substituted; R 3  and R 4  each represents a lower alkyl group or R 3  and R 4  may combinedly form a cyclic structure; X represents a hydrogen atom, a halogen atom or a substituted amino group; Y represents an alkoxy group which may be substituted or an alkyl group which may be substituted; Z represents a charge neutralizing ion. 
     
     
       2. A polymethine compound as claimed in  claim 1  wherein R 1  is an alkoxy group containing 1˜4 carbon atoms, R 2  is an alkyl group containing 1˜8 carbon atoms, an alkoxyalkyl group containing a total of 1˜8 carbon atoms, a sulfoalkyl group containing 1˜8 carbon atoms or a carboxyalkyl group containing a total of 2˜9 carbon atoms, and Y is an alkoxy group containing 1˜4 carbon atoms or an alkyl group containing 1˜4 carbon atoms. 
     
     
       3. A polymethine compound as claimed in  claim 1  wherein Z is Cl − , Br − , I − , ClO 4   − , BF 4   − , CF 3 CO 2   − , PF 6   − , SbF 6   − , CH 3 SO 3   − , p-toluenesulfonate, Na + , K +  or triethylammonium ion. 
     
     
       4. A polymethine compound as claimed in  claim 1  wherein R 3  and R 4  each is methyl or R 3  and R 4  taken together is a cyclopentane ring or a cyclohexane ring. 
     
     
       5. A polymethine compound as claimed in  claim 1  wherein X is H, Cl, Br or diphenylamino. 
     
     
       6. A polymethine compound as claimed in  claim 1  which is a low-melting crystal modification of 2-(2-{2-chloro-3-[(1,3-dihydro-3,3,7-trimethyl-5-methoxy-1-methoxyethyl-2H-indol-2-ylidene)ethylidene]-1-cyclohexen-1-yl}ethenyl)-3,3,7-trimethyl-5-methoxy-1-methoxyethyl-indolium-tetrafluoroborate having the following formula and showing a powder X-ray diffraction pattern with characteristic peaks at the diffraction angles (2θ±0.2°) of 11.6°, 14.6°, 15.6°, 19.6° and 22.9° in Cu—Kα powder X-ray diffractometry 
                 
 
     
     
       7. A polymethine compound as claimed in  claim 1  which is a high-melting crystal modification of 2-(2-{2-chloro-3-[(1,3-dihydro-3,3,7-trimethyl-5-methoxy-1-methoxyethyl-2H-indol-2-ylidene)ethylidene]-1-cyclohexen-1-yl}ethenyl)-3,3,7-trimethyl-5-methoxy-1-methoxyethyl-indolium-tetrafluoroborate having the following formula and showing a powder X-ray diffraction pattern with a characteristic high-intensity peak at the diffraction angle (2θ±0.2°) of 8.4° in Cu—Kα powder X-ray diffractometry 
                 
 
     
     
       8. A polymethine compound as claimed in  claim 1  which is a crystalline methanol adduct of 2-(2-{2-chloro-3-[(1,3-dihydro-3,3,7-trimethyl-5-methoxy-1-methoxyethyl-2H-indol-2-ylidene)ethylidene]-1-cyclohexen-1-yl}ethenyl)-3,3,7-trimethyl-5-methoxy-1-methoxyethyl-indolium-tetrafluoroborate having the following formula and showing a powder X-ray diffraction pattern with characteristic peaks at the diffraction angles (2θ±0.2°) of 13.3°, 17.4°, 19.8°, 21.8° and 26.9° in Cu—Kα powder X-ray diffractometry 
                 
 
     
     
       9. A polymethine compound as claimed in  claim 1  which is an amorphous form of 2-(2-{2-chloro-3-[(1,3-dihydro-3,3,7-trimethyl-5-methoxy-1-methoxyethyl-2H-indol-2-ylidene)ethylidene]-1-cyclohexen-1-yl}ethenyl)-3,3,7-trimethyl-5-methoxy-1-methoxyethylindolium-tetrafluoroborate having the following formula and showing a powder X-ray diffraction pattern having no characteristic peak at the diffraction angles (2θ±0.2°) in Cu—Kα powder X-ray diffractometry 
                 
 
     
     
       10. A process for producing the polymethine compound of  claim 1  which comprises subjecting an indolenium compound of the following general formula (II) and either a diformyl compound of the following formula (III) or a dianil compound of the following formula (IV) to condensation reaction in a dehydrating organic acid in the presence of a fatty acid salt 
                   
       wherein R 1  represents an alkoxy group which may be substituted; R 2  represents an alkyl group which may be substituted; R 3  and R 4  each represents a lower alkyl group or R 3  and R 4  taken together represent a ring; Y represents an alkoxy group which may be substituted or an alkyl group which may be substituted; Z 1  represents a charge neutralizing ion; n represents a number of 0 or 1 
                 
 
       wherein X represents a hydrogen atom, a halogen atom or a substituted amino group 
                 
 
       wherein X represents a hydrogen atom, a halogen atom or a substituted amino group. 
     
     
       11. A process for producing low-melting crystals of the polymethine compound of  claim 1  which comprises treating a crystalline solvent adduct or amorphous form of the polymethine compound of  claim 1  with a solvent. 
     
     
       12. A process for producing high-melting crystals of the polymethine compound of  claim 1  which comprises recrystallizing the polymethine compound of  claim 1  from a ketonic or alcoholic solvent. 
     
     
       13. A near infrared absorbing material comprising the polymethine compound claimed in  claim 1 . 
     
     
       14. An original plate for direct printing plate making which comprises the polymethine compound of  claim 1  in a light-to-heat conversion layer constructed on a substrate. 
     
     
       15. A method of manufacturing a printing plate which comprises irradiating the original plate for direct printing plate making claimed in  claim 14  with light using a semiconductor laser having a light emission band of 750 nm˜900 nm as a light source.