Block polyimide, block polyamide acid imide and use thereof

Abstract

The purpose of the present invention is to provide a block polyamide acid imide having an appropriate solubility in aqueous alkaline solutions, and block polyimides that are obtained using same and have high transparency and a low coefficient of linear thermal expansion (low CTE). This block polyimide comprises blocks configured from repeating structural units represented by formula (1A) and blocks configured from repeating structural units represented by formula (1B).

1 . A block polyimide comprising a block composed of repeating structural units represented by formula (1A), and a block composed of repeating structural units represented by formula (1B): 
       
         
           
           
               
               
           
         
         wherein: 
         m represents the number of the repeating structural units represented by formula (1A), and n represents the number of the repeating structural units represented by formula (1B), 
         an average value of m is defined as a quotient of the total number of the repeating structural units represented by formula (1A) contained in the block polyimide divided by the number of blocks composed of the repeating structural units represented by formula (1A), an average value of n is defined as a quotient of the total number of the repeating structural units represented by formula (1B) contained in the block polyimide divided by the number of the blocks composed of the repeating structural units represented by formula (1B), and ratio between the average values of m and n (average of m:average of n) is (less than 10:more than 0) to (more than 9:less than 1), 
         R and R″ each independently represent a C 4 -C 27  tetravalent group which is a monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group or condensed polycyclic aromatic group, or a non-condensed polycyclic aliphatic group in which cyclic aliphatic groups are mutually linked to each other either directly or via a crosslinking member, or a non-condensed polycyclic aromatic group in which aromatic groups are mutually linked to each other either directly or via a crosslinking member, and 
         R′ is a C 4 -C 51  divalent group which is a monocyclic aliphatic group (but exclusive of a 1,4-cyclohexylene group), condensed polycyclic aliphatic group, or non-condensed polycyclic aliphatic group in which cyclic aliphatic groups are mutually linked to each other either directly or via a crosslinking member. 
       
     
     
         2 . The block polyimide according to  claim 1 , wherein the average values of m and n each independently are 2 to 1,000. 
     
     
         3 . The block polyimide according to  claim 1 , wherein:
 a cyclohexane skeleton in the repeating structural unit represented by formula (1A) is either a trans-isomer represented by formula (1A-1) or a cis-isomer represented by formula (1A-2), and   a molar ratio or mass ratio between the trans-isomer and the cis-isomer (trans-isomer: cis-isomer) is 10:0 to 5:5.   
       
         
           
           
               
               
           
         
       
     
     
         4 . The block polyimide according to  claim 1  having a logarithmic viscosity of 0.1 to 3.0 dl/g, the logarithmic viscosity being measured in a mixed solvent of p-chlorophenol/phenol=9:1 (weight ratio) at a concentration of 0.5 g/dl and at 35° C. 
     
     
         5 . The block polyimide according to  claim 1 , wherein a film of the block polyimide has a glass transition temperature (Tg) of 260° C. or more as measured by TMA method under a tensile mode at a temperature range of 25° C. to 350° C., a temperature-raising rate of 5° C./min., and a load of 14 g/mm 2 . 
     
     
         6 . The block polyimide according to  claim 1 , wherein the film of the block polyimide has a coefficient of linear thermal expansion of 30 ppm/K or less as measured by TMA method under a tensile mode at a temperature range of 25° C. to 350° C., a temperature-raising rate of 5° C./min., and a load of 14 g/mm 2 . 
     
     
         7 . The block polyimide according to  claim 1 , wherein the film of the block polyimide has a total light transmittance of 80% or more as measured in accordance with JIS K 7105. 
     
     
         8 . A block polyamic acid imide comprising a block composed of a repeating structural unit represented by formula (2A) and a block composed of a repeating structural unit represented by formula (2B): 
       
         
           
           
               
               
           
         
         wherein: 
         m represents the number of the repeating structural units represented by formula (2A), and n represents the number of the repeating structural units represented by formula (2B), 
         an average value of m is defined as a quotient of the total number of the repeating structural units represented by formula (2A) contained in the block polyamic acid imide divided by the number of blocks composed of the repeating structural units represented by formula (2A), an average value of n is defined as a quotient of the total number of the repeating structural units represented by formula (2B) contained in the block polyamic acid imide divided by the number of the blocks composed of the repeating structural units represented by formula (2B), and ratio between the average values of m and n (average of m:average of n) is (less than 10: more than 0) to (more than 9:less than 1), 
         R and R″ each independently represent a C 4 -C 27  tetravalent group which is a monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group or condensed polycyclic aromatic group, or a non-condensed polycyclic aliphatic group in which cyclic aliphatic groups are mutually linked to each other either directly or via a crosslinking member, or a non-condensed polycyclic aromatic group in which aromatic groups are mutually linked to each other either directly or via a crosslinking member, and 
         R′ is a C 4 -C 51  divalent group which is a monocyclic aliphatic group (but exclusive of a 1,4-cyclohexylene group), condensed polycyclic aliphatic group, or non-condensed polycyclic aliphatic group in which cyclic aliphatic groups are mutually linked to each other either directly or via a crosslinking member. 
       
     
     
         9 . The block polyamic acid imide according to  claim 8 , wherein the average values of m and n each independently are 2 to 1,000. 
     
     
         10 . The block polyamic acid imide according to  claim 8 , wherein a polyimide composed of the repeating structural units represented by formula (2B) is soluble in an aprotic polar solvent. 
     
     
         11 . The block polyamic acid imide according to  claim 8  having a logarithmic viscosity of 0.1 to 3.0 dl/g, the logarithmic viscosity being measured in N-methyl-2-pyrrolidone solvent or N,N-dimethylacetamide solvent at a concentration of 0.5 g/dl and at 35° C. 
     
     
         12 . The block polyamic acid imide according to  claim 8 , wherein a dry film of the block polyamic acid imide having a residual solvent content of 10% by mass and a thickness of 15 μm exhibits a dissolution rate in the range of from 5 to 60 μm/min. at 20° C., the dissolution rate being measured by immersing the dry film in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. 
     
     
         13 . A method of manufacturing the block polyamic acid imide according to  claim 8 , comprising:
 reacting, in an aprotic polar solvent, a polyamic acid composed of the repeating structural units represented by formula (2A) with a polyimide composed of the repeating structural units represented by formula (2B) which is soluble in an aprotic polar solvent,   wherein:   a cyclohexane skeleton in the repeating structural unit represented by formula (2A) is either a trans-isomer represented by formula (2A-1) or a cis-isomer represented by formula (2A-2), and   a molar ratio or mass ratio between the trans-isomer and the cis-isomer (trans-isomer: cis-isomer) is 10:0 to 5:5.   
       
         
           
           
               
               
           
         
       
     
     
         14 . A method of manufacturing the block polyamic acid imide according to  claim 8 , comprising:
 reacting, in an aprotic polar solvent, an amine-terminated polyamic acid represented by formula (2A′) with an acid anhydride-terminated polyimide represented by formula (2B′)   wherein:   the amine-terminated polyamic acid represented by formula (2A′) is obtained from 1,4-cyclohexanediamine represented by formula (3) and tetracarboxylic dianhydride represented by formula (4); a molar ratio of the diamine represented by formula (3) to the tetracarboxylic dianhydride represented by formula (4) is more than 1 and 2 or less, and   the acid anhydride-terminated polyimide represented by formula (2B′) is obtained from a diamine represented by formula (5) and tetracarboxylic dianhydride represented by formula (6); and a molar ratio of the diamine represented by formula (5) to the tetracarboxylic dianhydride represented by formula (6) is 0.5 or more and less than 1.   
       
         
           
           
               
               
           
         
         wherein: 
         R is a C 4 -C 27  tetravalent group which is a monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group or condensed polycyclic aromatic group, or is a non-condensed polycyclic aliphatic group in which cyclic aliphatic groups are mutually linked to each other either directly or via a crosslinking member, or is a non-condensed polycyclic aromatic group in which aromatic groups are mutually linked to each other either directly or via a crosslinking member, and 
         the 1,4-cyclohexanediamine represented by formula (3) is a trans-isomer represented by formula (3-1) or a cis-isomer represented by formula (3-2); and a molar ratio or mass ratio between the trans-isomer and the cis-isomer (trans-isomer:cis-isomer) is 10:0 to 5:5. 
       
       
         
           
           
               
               
           
         
         wherein: 
         R′ is a C 4 -C 51  divalent group which is a monocyclic aliphatic group (but exclusive of a 1,4-cyclohexylene group), condensed polycyclic aliphatic group, or non-condensed polycyclic aliphatic group in which cyclic aliphatic groups are mutually linked to each other either directly or via a crosslinking member, and 
         R″ is a C 4 -C 27  tetravalent group which is a monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group or condensed polycyclic aromatic group, or is a non-condensed polycyclic aliphatic group in which cyclic aliphatic groups are mutually linked to each other either directly or via a crosslinking member, or is a non-condensed polycyclic aromatic group in which aromatic groups are mutually linked to each other either directly or via a crosslinking member. 
       
     
     
         15 . A method of manufacturing a block polyimide comprising thermally or chemically imidizing the block polyamic acid imide obtained by the method of  claim 13 , wherein the block polyimide comprises a block composed of repeating structural units represented by formula (1A), and a block composed of repeating structural units represented by formula (1B): 
       
         
           
           
               
               
           
         
         wherein: 
         m represents the number of the repeating structural units represented by formula (1A), and n represents the number of the repeating structural units represented by formula (1B), 
         an average value of m is defined as a quotient of the total number of the repeating structural units represented by formula (1A) contained in the block polyimide divided by the number of blocks composed of the repeating structural units represented by formula (1A), an average value of n is defined as a quotient of the total number of the repeating structural units represented by formula (1B) contained in the block polyimide divided by the number of the blocks composed of the repeating structural units represented by formula (1B), and ratio between the average values of m and n (average of m:average of n) is (less than 10:more than 0) to (more than 9:less than 1), 
         R and R″ each independently represent a C 4 -C 27  tetravalent group which is a monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group or condensed polycyclic aromatic group, or a non-condensed polycyclic aliphatic group in which cyclic aliphatic groups are mutually linked to each other either directly or via a crosslinking member, or a non-condensed polycyclic aromatic group in which aromatic groups are mutually linked to each other either directly or via a crosslinking member, and 
         R′ is a C 4 -C 51  divalent group which is a monocyclic aliphatic group (but exclusive of a 1,4-cyclohexylene group), condensed polycyclic aliphatic group, or non-condensed polycyclic aliphatic group in which cyclic aliphatic groups are mutually linked to each other either directly or via a crosslinking member. 
       
     
     
         16 . A method of manufacturing a block polyimide comprising thermally or chemically imidizing the block polyamic acid imide obtained by the method of  claim 14 , wherein the block polyimide comprises a block composed of repeating structural units represented by formula (1A), and a block composed of repeating structural units represented by formula (1B): 
       
         
           
           
               
               
           
         
         wherein: 
         m represents the number of the repeating structural units represented by formula (1A), and n represents the number of the repeating structural units represented by formula (1B), 
         an average value of m is defined as a quotient of the total number of the repeating structural units represented by formula (1A) contained in the block polyimide divided by the number of blocks composed of the repeating structural units represented by formula (1A), an average value of n is defined as a quotient of the total number of the repeating structural units represented by formula (1B) contained in the block polyimide divided by the number of the blocks composed of the repeating structural units represented by formula (1B), and ratio between the average values of m and n (average of m:average of n) is (less than 10:more than 0) to (more than 9:less than 1), 
         R and R″ each independently represent a C 4 -C 27  tetravalent group which is a monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group or condensed polycyclic aromatic group, or a non-condensed polycyclic aliphatic group in which cyclic aliphatic groups are mutually linked to each other either directly or via a crosslinking member, or a non-condensed polycyclic aromatic group in which aromatic groups are mutually linked to each other either directly or via a crosslinking member, and 
         R′ is a C 4 -C 51  divalent group which is a monocyclic aliphatic group (but exclusive of a 1,4-cyclohexylene group), condensed polycyclic aliphatic group, or non-condensed polycyclic aliphatic group in which cyclic aliphatic groups are mutually linked to each other either directly or via a crosslinking member. 
       
     
     
         17 . A dry film comprising the block polyamic acid imide according to  claim 8 . 
     
     
         18 . An interlayer insulation film material comprising the block polyamic acid imide according to  claim 8 . 
     
     
         19 . A block polyamic acid imide varnish comprising the block polyamic acid imide according to  claim 8  and a solvent. 
     
     
         20 . A photosensitive resin composition comprising the block polyamic acid imide according to  claim 8 , a photopolymerizable compound, and a photopolymerization initiator. 
     
     
         21 . A laminate comprising a metal substrate and the dry film according to  claim 17 . 
     
     
         22 . A circuit substrate comprising a substrate, a patterned layer comprising the block polyimide according to  claim 1 , and a patterned conductor layer. 
     
     
         23 . The circuit substrate according to  claim 22 , wherein the circuit substrate is a suspension substrate or a semiconductor package substrate. 
     
     
         24 . A method of manufacturing a circuit substrate, comprising:
 preparing a laminate comprising a substrate and a photosensitive resin composition layer consisting of the photosensitive resin composition according to  claim 20 ;   disposing a patterned photomask on the photosensitive resin composition layer of the laminate;   subjecting the photosensitive resin composition layer to light exposure through the photomask, followed by a developing treatment with an aqueous alkaline solution to pattern the photosensitive resin composition layer; and   heating the patterned photosensitive resin composition layer to imidize the block polyamic acid imide contained in the photosensitive resin composition.   
     
     
         25 . A polyimide film comprising the block polyimide according to  claim 1 . 
     
     
         26 . An optical film comprising the polyimide film according to  claim 25 .