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CN103524735A - Photosensitive polyimide - Google Patents

Photosensitive polyimide Download PDF

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Publication number
CN103524735A
CN103524735A CN201310413998.3A CN201310413998A CN103524735A CN 103524735 A CN103524735 A CN 103524735A CN 201310413998 A CN201310413998 A CN 201310413998A CN 103524735 A CN103524735 A CN 103524735A
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group
photosensitive polyimide
polyimide polymer
photosensitive
integer
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Inventor
周孟彦
李传宗
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Eternal Materials Co Ltd
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Eternal Chemical Co Ltd
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Abstract

The invention relates to isocyanate modified photosensitive polyimide. The photosensitive polyimide has excellent heat resistance, chemical resistance and flexibility and can be used as a liquid state photoresist or dry film photoresist or can be applied to a solder resist, a cover film or a printed circuit board.

Description

Photosensitive polyimide
The present application is a divisional application of an invention patent application having an application date of 25/01/2008, an application number of 200810007025.9 and an invention name of "photosensitive polyimide".
Technical Field
The present invention relates to isocyanate modified photosensitive polyimide. The photosensitive polyimide has excellent heat resistance, chemical resistance and flexibility, and can be used as a liquid photoresist or a dry film photoresist, or used for a solder resist, a cover film or a printed circuit board.
Background
Nowadays, electronic products are becoming thinner and smaller, and the sizes of various electronic components are also being reduced. Due to the advantages of flexible printed wiring boards in terms of flexibility and weight, the demand for flexible printed wiring boards has increased.
Currently, the cover film materials can be classified into three types, the first type is a photosensitive cover film (photosensitive cover film), the second type is a non-photosensitive cover film (non-photosensitive cover film), and the third type is a thermoplastic cover film (thermoplastic cover film). The first type of photosensitive coverlay film is classified into a polyimide-based coverlay film (PI-based coverlay) and a non-polyimide-based coverlay film (non-PI-based coverlay), wherein the application of the polyimide-based coverlay film is limited due to factors such as poor heat resistance and high coefficient of thermal expansion ("CTE"). The second type of non-photosensitive coverlay is not as practical as the photosensitive coverlay because processing is more complicated than that of the photosensitive coverlay. As for the thermoplastic cover film, it requires post-processing for hole formation, and therefore is inferior in convenience to the photosensitive cover film.
U.S. Pat. No. 6,605,353 discloses photosensitive polyimides modified with epoxy. However, since the polymer is obtained by reacting an epoxide with an acid, the reactivity is poor, and the ring-opened OH functional group reacts with an epoxy group (epoxy), and thus, problems such as stability and thermal stability are encountered.
In order to improve the heat resistance and the processing convenience of the cover film, there is still a need in the art for photosensitive polyimides that can solve the above problems.
Disclosure of Invention
The present invention provides an isocyanate-modified photosensitive polyimide which has preferable reactivity, and is excellent in stability, thermal stability, and can be hardened at low temperature. The photosensitive polyimide of the present invention can be used as a liquid photoresist or for a dry film photoresist, and can be used to form a thick film.
The invention also provides a photosensitive composition containing the photosensitive polyimide, which can be used as a protective film material. Therefore, the photosensitive composition of the present invention can be applied to a solder resist as a protective film material, a cover film material and a printed wiring board.
Detailed Description
The photosensitive polyimide polymer of the present invention has the following structure of formula (I):
Figure BDA0000380676580000021
formula (I)
Wherein
A and C may be the same or different and are each independently a tetravalent organic group;
b is at least one selected from
Figure BDA0000380676580000022
A divalent organic group of (a);
wherein R represents an unsaturated group containing a vinyl group or a group selected from:
Figure BDA0000380676580000023
wherein
R1 is a substituted or unsubstituted saturated or unsaturated organic group having C1-C20; and
r2 is an unsaturated group containing a vinyl group.
D is a divalent organic group;
n is an integer greater than 0, and
m is equal to 0 or an integer greater than 0.
Preferably, the above-mentioned unsaturated group containing a vinyl group is selected from the following groups:
Figure BDA0000380676580000031
wherein:
r4 and R5 are each H or a substituted or unsubstituted alkyl group having C1-C5, and
r6 is a covalent bond or a substituted or unsubstituted organic group having C1-C20.
More preferably, the vinyl group-containing unsaturated group is selected from the group consisting of:
Figure BDA0000380676580000032
Figure BDA0000380676580000041
wherein z is an integer of 0 to 6.
Particularly preferably, the vinyl group-containing unsaturated group is selected from the group consisting of:
Figure BDA0000380676580000042
wherein each z represents an integer of 0 to 6.
Preferably, the above-mentioned R1 group may be selected from the following groups:
Figure BDA0000380676580000043
Figure BDA0000380676580000051
wherein
o, p, q and r are each 0 or an integer greater than 0;
r4, R5 and R6 have the definitions described above;
r7 is H or a substituted or unsubstituted organic group having C1-C12; and
r8 is a covalent bond or an organic group selected from:
more preferably, the R1 group is selected from the group consisting of:
Figure BDA0000380676580000061
the tetravalent organic groups a and C contained in the photosensitive polyimide polymer of formula (I) of the present invention are not particularly limited, and are, for example, tetravalent aromatic groups or tetravalent aliphatic groups. Preferably, A and C are each selected from the group consisting of:
Figure BDA0000380676580000062
the photosensitive polyimide polymer of formula (I) of the present invention contains B derived from a diamine having reactive functional groups including OH, COOH, NH2Or SH, preferably OH, NH2. Preferably, B is independently selected from the group consisting of:
Figure BDA0000380676580000071
wherein:
r' is selected from
Figure BDA0000380676580000072
Wherein R has the definition as described above;
r9 is H, methyl or ethyl;
s is an integer of 1 to 4;
t is an integer of 0 to 5;
u is equal to 0 or an integer greater than 0;
v is an integer greater than 0; and is
R11 each represents a covalent bond or a group selected from:
Figure BDA0000380676580000073
Figure BDA0000380676580000081
wherein:
w and x are each an integer greater than 0, and
r12 is a covalent bond or a substituted or unsubstituted organic group having C1-C18.
More preferably, B in the above formula (I) is selected from the group consisting of:
Figure BDA0000380676580000082
wherein R' has the definition as described above.
Most preferably, B in formula (I) above is selected from the group consisting of:
Figure BDA0000380676580000091
wherein R' has the definition as described above.
D contained in the photosensitive polyimide of formula (I) of the present invention is derived from a diamine monomer which may or may not have a reactive functional group. Preferably, D is independently selected from the group consisting of:
Figure BDA0000380676580000092
wherein:
r' is-H, C1-C4 alkyl, C1-C4 perfluoroalkyl, methoxy, ethoxy, halogen, OH, COOH, NH2Or SH;
r9 and R11 have the definitions described above;
c is an integer of 0 to 4;
a is an integer greater than 0; and is
b is an integer greater than 0.
More preferably, D in the above formula (I) is each selected from the group consisting of:
wherein y is an integer of 1 to 12, preferably an integer of 1 to 6.
The photosensitive polyimide polymer of the present invention can be obtained by a polymerization method known to those skilled in the art, and can be prepared, for example, by a method comprising the steps of:
(a) reacting a dianhydride monomer having the following formula (1) with a monomer having the formula
Figure BDA0000380676580000102
Of a diamine monomer of the formula (I) and a compound of the formula (H)2N-P2-NH2To form a compound having the following formula (2):
Figure BDA0000380676580000103
wherein:
g can be a reactive functional group, for example OH, the following steps are performed:
(b) adding to the product of step (a) an isocyanate compound having the formula O ═ C ═ N — R to form a compound of formula (3)
Figure BDA0000380676580000111
Wherein
f+g=i。
In the above-described method for preparing a photosensitive polyimide polymer, dianhydride monomers which can be used in the method of the present invention may be generally aliphatic or aromatic, and preferred examples include, but are not limited to, dianhydrides having the following structures:
Figure BDA0000380676580000112
wherein,
E. f and H each represent a covalent bond or a substituted or unsubstituted saturated or unsaturated, cyclic or acyclic organic group having C1-C20;
r3 is a covalent bond or is selected from the group consisting of:
Figure BDA0000380676580000121
preferably, the dianhydride useful in the present invention is selected from the following compounds:
Figure BDA0000380676580000122
or mixtures thereof.
In the above-mentioned process for producing a photosensitive polyimide polymer, the diamine monomer (I) is usedMust have a reactive functional group (e.g. OH, COOH, NH)2SH, etc.). Diamine monomer (I) useful in the present invention is exemplified by, but not limited to:
Figure BDA0000380676580000131
wherein:
r' is a group containing
Figure BDA0000380676580000132
Wherein R has the definition as described above;
r9 is H, methyl or ethyl;
s is an integer of 1 to 4;
t is an integer of 0 to 5;
u is equal to 0 or an integer greater than 0;
v is an integer greater than 0;
r11 each represents a covalent bond or a group selected from;
Figure BDA0000380676580000133
Figure BDA0000380676580000141
wherein:
w and x are each an integer greater than 0, and
r12 is a covalent bond or a substituted or unsubstituted organic group having C1-C18.
Preferably, the diamine monomer is selected from the group consisting of:
Figure BDA0000380676580000142
wherein R' has the definition as described above.
More preferably, the diamine monomer is selected from the group consisting of:
Figure BDA0000380676580000151
wherein R' has the definition as described above.
In the above-mentioned process for producing a photosensitive polyimide polymer, a diamine monomer is usedBody (II) H2N-P2-NH2And, without particular limitation, it may or may not have a reactive functional group. Diamine monomers (II) having no reactive functional groups useful in the present invention are well known to those skilled in the art, such as, but not limited to:
Figure BDA0000380676580000152
wherein:
r' is-H, C1-C4 alkyl, C1-C4 perfluoroalkyl, methoxy, ethoxy or halogen, OH, COOH, NH2Or SH;
r9 and R11 have the definitions described above;
c is an integer of 0 to 4;
a is an integer greater than 0; and is
b is an integer greater than 0.
Preferably, the above diamine monomer (II) is a diamine selected from the group consisting of:
Figure BDA0000380676580000161
in order to provide photosensitive groups to the polyimide polymer to facilitate the application of a radiation curing mechanism to the polymer, the present invention uses a photosensitive group-containing isocyanate to modify the polyimide polymer so that it has photosensitive groups, for example, C ═ C double bonds, after modification. The isocyanate may be a mono-isocyanate or a di-isocyanate, preferably a mono-isocyanate. The isocyanate used in the present invention may be reacted with hydroxyl (-OH), carboxyl (-COOH), mercapto (-SH), or amino (-NH) groups in the polyimide polymer2) The reactive groups react to modify the polyimide polymer. The isocyanates used in the present invention have the following structures: o = C = N-R, whichWherein R is R or a group having the structure:
Figure BDA0000380676580000171
wherein:
r and R2 each represent an optically active group containing an unsaturated group of a vinyl group; and
r1 is a substituted or unsubstituted saturated or unsaturated organic group having C1-C20.
According to a specific embodiment of the present invention, the above-mentioned unsaturated group containing a vinyl group is a group selected from:
Figure BDA0000380676580000172
wherein:
r4 and R5 are each H or a substituted or unsubstituted alkyl group having C1-C5, and
r6 is a covalent bond or a substituted or unsubstituted organic group having C1-C20;
r1 mentioned above is a group selected from:
Figure BDA0000380676580000181
wherein:
o, p, q and r are each 0 or an integer greater than 0;
r4, R5 and R6 have the definitions described above;
r7 is H or a substituted or unsubstituted organic group having C1-C12; and
r8 is a covalent bond or is selected from organic groups having:
Figure BDA0000380676580000182
the invention also provides a photosensitive composition, which comprises at least 1% of photosensitive polyimide polymer with the structure of the formula (I), a photoinitiator and a solvent. The photosensitive composition of the present invention can be used for a liquid photoresist or a dry film photoresist, or for a solder resist, a coverlay film or a printed wiring board. The weight percentage of each component in the photosensitive composition can be adjusted according to the product requirement, generally speaking, the content of the photosensitive polyimide polymer of the formula (I) is at least 1 weight percent, preferably 10-50 weight percent based on the total weight of the whole composition; the photoinitiator is present in an amount of at least 0.001 wt%, preferably between 0.01 and 1 wt%, based on the total weight of the overall composition.
The photoinitiator suitable for use in the above composition according to the present invention is not particularly limited, and may be selected from the group consisting of: benzophenone (benzophenone), benzoin, 2-hydroxy-2-methyl-1-phenylpropanone (2-hydroxy-2-methyl-1-phenyl-propan-1-one), 2-dimethoxy-1,2-diphenylethan-1-one (2,2-dimethoxy-1,2-diphenylethan-1-one), 1-hydroxycyclohexylphenylketone (1-hydroxycyclohexylphenylketone), 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (2,4, 6-trimethylbenzoyldiphenylphosphine oxide), N-phenylglycine, 9-phenylacridine (9-phenylacridine), benzyldimethyl ketal (benzyldimethyllketone), 4' -bis (diethylamine) benzophenone, 2,4,5-triarylimidazole dimers (2,4,5-triarylimidazole dimers) and mixtures thereof; the preferred photoinitiator is benzophenone.
According to the present invention, the solvent suitable for use in the above composition is not particularly limited, and is, for example, but not limited to, selected from the group consisting of: n-methylpyrrolidone (NMP), Dimethylacetamide (DMAC), Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), toluene (tolumene), xylene (xylene), and mixtures thereof.
To increase the degree of photocrosslinking, the photosensitive composition of the present invention may optionally be added with an amount of reactive monomer or short chain oligomer to form crosslinks (Crosslinking) between molecules. According to the present invention, the reactive monomer or oligomer suitable for use in the above composition is not particularly limited, and may be selected from the group consisting of: 1,6-hexanediol diacrylate (1,6-hexanediol diacrylate), neopentyl glycol diacrylate (neopentylglycol diacrylate), ethylene glycol diacrylate (ethylene glycol diacrylate), pentaerythritol diacrylate (pentaerythrityl diacrylate), trimethylolpropane triacrylate (trimethylolpropane triacrylate), pentaerythritol triacrylate (pentaerythrityl triacrylate), dipentaerythritol hexaacrylate (dipentaerythrityl methacrylate), tetramethylolpropane tetraacrylate (tetramethylolpropane tetraacrylate), tetraethylene glycol diacrylate (tetraethylene glycol diacrylate), 1,6-hexanediol dimethacrylate (1,6-hexanediol diacrylate), neopentyl glycol dimethacrylate (neopentyl glycol dimethacrylate), pentaerythritol dimethacrylate (trimethylolpropane dimethacrylate), pentaerythritol dimethacrylate (trimethacrylate), pentaerythritol dimethacrylate (trimethylolpropane dimethacrylate), pentaerythritol methacrylate (trimethacrylate), pentaerythritol methacrylate (trimethacrylate), pentaerythritol methacrylate (trimethacrylate (trimethylolpropane triacrylate (trimethacrylate), pentaerythritol methacrylate (trimethylolpropane triacrylate (pentaerythritol methacrylate), pentaerythritol methacrylate, pentaerythritol, Dipentaerythritol hexamethacrylate, tetramethylpropylene tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β -methacryloyloxyethylhydrodienoate, 3-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxyphenylmethacrylate, methacryloyloxypropylmethacrylate, and methoxypolyethylene glycol methacrylate, and polyoxyethylene glycol methacrylate, and polyoxyethylene glycol methacrylate, and polyoxyethylene methacrylate, Beta-acryloxyethylhydrogensuccinate (beta-acryloxyethylhydrogensuccinate), laurylacrylate (laurylacrylate), ethyleneglycol dimethacrylate (ethyleneglycol dimethacrylate), diethyleneglycol dimethacrylate (diethyleneglycol dimethacrylate), triethyleneglycol dimethacrylate (triethyleneglycol dimethacrylate), polyethyleneglycol dimethacrylate (polyethyleneglycol dimethacrylate), 1, 3-butyleneglycol dimethacrylate (1, 3-butylglycol dimethacrylate), polypropyleneglycol dimethacrylate (polypropyleneglycoldimethacrylate), 2-hydroxy-1, 3-dimethylpropyleneoxy propane (2-hydroxy-1, 3-dimethoxypropane), 2-bis [4- (methacryloxyethoxy) phenyl ] propane (2, 2-dioxy [4- (2, 2-dioxy) phenyl ] propane (2,2-bis [4- (2, 4-dimethoxyphenyl ] propane), 2-bis [4- (2, 4-dimethoxyphenyl ] propane (2, 2-dimethoxyphenyl) propane (2, 2-dimethoxypropyl) propane, 2-bis [4- (methacryloxypolyethoxy) phenyl ] propane, 2-bis [4- (methacryloxypolyethoxy) phenyl ] propane (2,2-bis [4- (methacryloxypolyethoxy) phenyl ] propane), polyethylene glycol diacrylate (polyethylene glycol diacrylate), tripropylene glycol diacrylate (tripropylene glycol diacrylate), polypropylene glycol diacrylate (polypropyleneglycol diacrylate), 2-bis [4- (acryloxydiethoxy) phenyl ] propane (2,2-bis [4- (acryloxyethoxy) phenyl ] propane), 2-bis [4- (acryloxypolyethoxy) phenyl ] propane (2,2-bis [4- (acryloxypolyethoxy) phenyl ] propane), 2-hydroxy-1-3-methyl-3-propylene-2-bis [4- (acryloxypolyethoxy) phenyl ] propane (2,2-bis [4- (acryloxypolyethoxy) phenyl ] propane), Trimethylolpropane trimethacrylate (trimethylolpropane trimethacrylate), tetramethylolmethane triacrylate (tetramethylolmethane tetraacrylate), methoxypropylene glycol methacrylate (methoxypropylene glycol methacrylate), methoxytriethylene glycol acrylate (monomethylolmethane glycol acrylate), nonylphenoxypolyethylene glycol acrylate (nonylphenoxypolyethylene glycol acrylate), polyoxyethylene glycol acrylate (polyoxyethylene glycol acrylate), polyoxyethylene-2-acrylate (polyoxyethylene glycol acrylate), isopropylethylene glycol acrylate (polyoxyethylene glycol acrylate), polyoxyethylene-4-butylene glycol methacrylate (polyoxyethylene-1-polyoxyethylene glycol acrylate), polyoxyethylene-4-polyoxyethylene glycol acrylate (polyoxyethylene-4-polyoxyethylene glycol methacrylate), polyoxyethylene-4-polyoxyethylene glycol methacrylate (polyoxyethylene-1-polyoxyethylene glycol methacrylate), polyoxyethylene-4-polyoxyethylene glycol acrylate (polyoxyethylene-4-polyoxyethylene glycol methacrylate), 5-pentanediol dimethacrylate (3-methyl-1,5-pentanediol dimethacrylate), 1,6-hexanediol methacrylate (1,6-hexanediol methacrylate), 1,9-nonanediol methacrylate (1,9-nonanediol methacrylate), 2,4-diethyl-1,5-pentanediol dimethacrylate (2, 4-diethylene-1, 5-pentanediol dimethacrylate), 1,4-cyclohexanedimethanol dimethacrylate (1, 4-cyclohexanedimethanoldimethacrylate), dipropylene glycol diacrylate (dipropylene glycol diacrylate), tricyclodecanetrimethacrylate (tricyclohexylenediacrylate), 2-dihydrobis [4-acryloxypolyethoxy ] phenyl ] propane (2, 2-dihydrobis [4-acryloxy ] phenyl ] propane (2, 2-dihydrophenoxy [ 4-propoxy ] propane), 2-propenedioxy ] propane (2, 4-propenyloxyphenoxy [ 2, 4-propenyloxypropylpropane (2, 2-propenyloxypropylphenoxy ] propane), 2-bis [ 4-acryloxypropylphenyl ] propane), 2,4-diethyl-1,5-pentanediol diacrylate (2,4-diethyl-1,5-pentanediol diacrylate), ethoxylated trimethylolpropane triacrylate (ethoxylated trimethylolpropane triacrylate), propoxylated trimethylolpropane triacrylate (ethoxylated trimethylolpropane triacrylate), tris (ethacrylate) (isocyanuric acid), pentaerythritol tetraacrylate (pentaerythrityl tetraacrylate), ethoxylated pentaerythritol tetraacrylate (ethoxylated pentaerythritol tetraacrylate), propoxylated pentaerythritol tetraacrylate (pentaerythritol tetraacrylate), pentaerythritol tetraacrylate (allyl methacrylate), pentaerythritol tetraacrylate (pentaerythritol tetraacrylate), pentaerythritol tetraacrylate (pentaerythritol methacrylate), pentaerythritol tetraacrylate (pentaerythritol tetraacrylate), pentaerythritol tetraacrylate (pentaerythritol methacrylate), pentaerythritol tetraacrylate (allyl methacrylate), pentaerythritol tetraacrylate (pentaerythritol tetraacrylate), pentaerythritol tetraacrylate (pentaerythritol methacrylate), pentaerythritol tetraacrylate (pentaerythritol tetraacrylate), pentaerythritol tetraacrylate (pentaerythritol methacrylate), pentaerythritol tetraacrylate (pentaerythritol tetraacrylate), pentaerythritol (pentaerythritol methacrylate), pentaerythritol (pentaerythritol methacrylate), pentaerythritol (pentaerythritol methacrylate), pentaerythritol (pentaerythritol methacrylate), pentaerythritol, 1,3, 5-triacrylhexahydro-s-tris (1,3,5-triacryloylhexahydro-s-triazine), triallyl1,3, 5-benzoate (triallyl1,3, 5-benzazole), triallylamine (triallylamine), triallyl citrate (triallyl citrate), triallyl phosphate (triallyl phosphate), alloparbital (allophanatal), diallylamine (diallylamine), diallyldimethylsilane (diallyldimethacrylate), diallyldisulfide (diallyl disulfide), diallylether (diallyl ether), diallyl cyanurate (diallyl cyanurate), diallyl isopropoxide (diallyl isopropoxide), diallyl terephthalate (diallyl maleate), 1, 3-diallyl-2 (diallyl-2-diallyl-maleate), diallyl maleate (diallyl maleate), diallyl-2-diallyl maleate, diallyl maleate (diallyl maleate), diallyl-diallyl maleate, diallyl-2-diallyl maleate, diallyl maleate (diallyl maleate), diallyl maleate, diallyl-maleate, diallyl-maleate, diallyl-maleate, diallyl-diallyl, 4,4'-isopropylidene diphenol dimethacrylate (4,4' -isopropylidene diphenol) and 4,4'-isopropylidene diphenol diacrylate (4,4' -isopropylidene diphenol). The reactive monomers or oligomers used in the photosensitive composition of the invention, when present, are present in an amount of at least 0.1% by weight, preferably from 0.1 to 20% by weight, based on the total weight of the total composition.
The following examples are intended to illustrate the present invention without limiting the scope thereof, and any changes and modifications that can be made by one skilled in the art without departing from the spirit of the present invention are intended to be included within the scope thereof.
In the examples, the abbreviations used are defined as follows:
and (3) PMDA: pyromellitic dianhydride (pyromellitic dianhydride)
DABA: 3, 5-diaminobenzoic acid (3,5-diamino benzoic acid)
6 FDA: 4,4'-hexafluoroisopropylidene diphthalic dianhydride (4,4' -hexafluoroisopropylidene-2,2-bis- (phthalic acid anhydride)
BAPA: 2,2'-bis (3-amino-4-hydroxyphenyl) propane (2,2' -bis (3-amino-4-hydroxyphenyl) propane)
MBAA: bis (4-amino-3-carboxyphenyl) methane (bis (4-amino-3-carboxyphenyl) methane)
MEMG: bis (4-aminophenoxy) methane
TAB-E: 3,3',4,4' -Tetraaminodiphenyl ether (3,3',4,4' -tetraaminodiphenylether)
IEM: 2-Isocyanatoethyl methacrylate (2-Isocyanoethyl methacrylate)
1-MI: 1-methylimidazole (1-methylimidazole)
HEMA: 2-hydroxyethyl methacrylate (2-hydroxyhexyl methacrylate)
HMC: 4'-hydroxy-4-methoxychalcone (4' -hydroxy-4-methoxychalcone)
TMDC: tetramethylene diisocyanate (tetramethylene diisocyanate)
IPDI: isophorone diisocyanate (isophoron diisocyanate)
PTZ: phenothiazine (phenothiazine)
DMAC: dimethylacetamide (dimethyl acetamide)
NMP: n-methylpyrrolidone (N-methylpyrrolidinone)
Example 1: synthesis of polyimide having carboxyl group (P1)
43.62g (0.2mol) of PMDA and 30.43g (0.2mol) of DABA were weighed, 300mL of NMP was added thereto, and the mixture was stirred at room temperature for 1 hour, then heated to 50 ℃ and stirred for 4 hours. After 4 hours, 50mL of xylene were added and water was removed at 150 ℃ with a dean-stark apparatus. After the water removal was completed, a polyimide solution having an acid group (P1) was obtained.
Example 2: synthesis of carboxyl isocyanate-modified polyimide (I-P1)
370g of P1 was weighed, and 1-MI1.4g, IEM15.5g and PTZ0.1g were added thereto, followed by stirring at room temperature for 1 hour. After 1 hour, the temperature was raised to 60 ℃ and the mixture was stirred for 6 hours to obtain a polyimide (I-P1) in which the desired carboxyl group was modified with an isocyanate.
Example 3: synthesis of polyimide having hydroxyl group (P2)
88.85g (0.2mol) of 6FDA and 57.26g (0.2mol) of BAPA were weighed, 300mL of NMP was added, and the mixture was stirred at room temperature for 1 hour, then heated to 50 ℃ and stirred for 4 hours. After 4 hours, 50mL of xylene were added and water was removed at 150 ℃ with a dean-stark apparatus. After the water removal was completed, a polyimide solution having a hydroxyl group (P2) was obtained.
Example 4: synthesis of polyimide with hydroxyl group modified with isocyanate (I-P2)
440g of P2 was weighed, and 1-MI1.67g, IEM36.86g and PTZ0.12g were added thereto, followed by stirring at room temperature for 1 hour. After 1 hour, the temperature was raised to 60 ℃ and the mixture was stirred for 6 hours to obtain a polyimide (I-P2) in which the desired hydroxyl group was modified with an isocyanate.
Example 5: synthesis of polyimide having carboxyl group modified with diisocyanate (DI-P1)
370g of P1 was weighed, and 1-MI1.4g, HEMA13.01g, TMDC14.01g and PTZ0.1g were added thereto, followed by stirring at room temperature for 1 hour. After 1 hour, the temperature was raised to 60 ℃ and the mixture was stirred for 6 hours to obtain a desired carboxyl group diisocyanate-modified polyimide (DI-P1).
Example 6: synthesis of polyimide with hydroxyl group modified with diisocyanate (DI-P2)
440g of P2 was weighed, and 1-MI1.67g, HEMA13.01g, TMDC14.01g and PTZ0.12g were added thereto and stirred at room temperature for 1 hour. After 1 hour, the temperature was raised to 60 ℃ and the mixture was stirred for 6 hours to obtain a polyimide (DI-P2) in which the desired hydroxyl group was modified with a diisocyanate.
Example 7: synthesis of polyimide having carboxyl group (P3)
43.62g (0.2mol) of PMDA, 15.22g (0.1mol) of DABA and 23.03g (0.1mol) of MEMG were weighed, 300mL of NMP was added thereto, and the mixture was stirred at room temperature for 1 hour, then heated to 50 ℃ and stirred for 4 hours. After 4 hours, 50mL of xylene were added and water was removed at 150 ℃ with a dean-stark apparatus. After the water removal was completed, a polyimide solution having a carboxyl group (P1) was obtained.
Example 8: synthesis of carboxyl isocyanate-modified polyimide (I-P3)
420g of P3 was weighed, and 1-MI0.7g, IEM7.75g and PTZ0.1g were added thereto, followed by stirring at room temperature for 1 hour. After 1 hour, the temperature was raised to 60 ℃ and the mixture was stirred for 6 hours to obtain a polyimide (I-P3) in which the desired carboxyl group was modified with an isocyanate.
Example 9: synthesis of polyimide having carboxyl group modified with diisocyanate (DI-P3)
420g of P3 was weighed, and 1-MI0.7g, HEMA6.5g, TMDC7g and PTZ0.11g were added thereto, followed by stirring at room temperature for 1 hour. After 1 hour, the temperature was raised to 60 ℃ and the mixture was stirred for 6 hours to obtain a desired carboxyl group diisocyanate-modified polyimide (DI-P3).
Example 10: synthesis of polyimide having hydroxyl group (P4)
88.85g (0.2mol) of 6FDA and 28.63g (0.1mol) of BAPA and 23.03g (0.1mol) of MEMG are weighed out, 300mL of NMP are added, stirred at room temperature for 1 hour, warmed to 50 ℃ and stirred for 4 hours. After 4 hours, 50mL of xylene were added and water was removed at 150 ℃ with a dean-stark apparatus. After the water removal was completed, a polyimide solution having a hydroxyl group (P4) was obtained.
Example 11: synthesis of polyimide with hydroxyl group modified with diisocyanate (DI-P4)
490g of P4 was weighed, and 1-MI0.85g, HEMA6.51g, IPDI11.12g and PTZ0.11g were added thereto, followed by stirring at room temperature for 1 hour. After 1 hour, the temperature was raised to 60 ℃ and the mixture was stirred for 6 hours to obtain a polyimide (DI-P4) in which the desired hydroxyl group was modified with a diisocyanate.
Example 12: synthesis of polyimide with hydroxyl group modified with diisocyanate (DI-P5)
490g of P4 were weighed, and 1-MI0.85g, HMC25.43g, IPDI22.23g and PTZ0.11g were added thereto, followed by stirring at room temperature for 1 hour. After 1 hour, the temperature was raised to 60 ℃ and the mixture was stirred for 6 hours to obtain a polyimide (DI-P5) in which the desired hydroxyl group was modified with a diisocyanate.
Example 13: synthesis of polyimide having amino group (P6)
43.62g (0.2MOL) of PMDA, 23.03g (0.1MOL) of TAB-E and 28.63g (0.1MOL) of DABA were weighed, 300mL of NMP was added thereto, and the mixture was stirred at room temperature for 1 hour, then heated to 50 ℃ and stirred for 4 hours. After 4 hours, 50mL of xylene were added and water was removed at 150 ℃ with a dean-stark apparatus. After the water removal was completed, a polyimide solution having an amino group (P6) was obtained.
Example 14: synthesis of amino isocyanate-modified polyimide (I-P6)
440g of P6 was weighed, and 1-MI0.85g, IEM15.5g and PTZ0.1g were added thereto, followed by stirring at room temperature for 1 hour. After 1 hour, the temperature was raised to 60 ℃ and the mixture was stirred for 6 hours to obtain a polyimide (I-P6) in which the desired amino group was modified with an isocyanate.
Example 15: synthesis of amino diisocyanate-modified polyimide (DI-P6)
440g of P6 was weighed, 1-MI1.45g, HEMA6.51g, IPDI11.12g and PTZ0.11g were added, and the mixture was stirred at room temperature for 1 hour. After 1 hour, the temperature was raised to 60 ℃ and the mixture was stirred for 6 hours to obtain a desired amino diisocyanate-modified polyimide (DI-P6).

Claims (13)

1. A photosensitive polyimide polymer with the structure of formula (I),
Figure FDA0000380676570000011
formula (I)
Wherein:
a and C may be the same or different and are each independently a tetravalent organic group;
b is at least one selected from
Figure FDA0000380676570000012
Figure FDA0000380676570000013
A divalent organic group of (a);
wherein R represents an unsaturated group containing a vinyl group or a group selected from:
wherein:
r1 is a substituted or unsubstituted saturated or unsaturated organic group having C1-C20, and
r2 is a vinyl-containing unsaturated group;
each D is independently a divalent organic group;
n is an integer greater than 0, and
m is equal to 0 or an integer greater than 0.
2. A photosensitive polyimide polymer as defined in claim 1, wherein the vinyl group-containing unsaturated group is a group selected from:
Figure FDA0000380676570000021
wherein:
r4 and R5 are each H or substituted or unsubstituted alkyl having C1-C5, and
r6 is a covalent bond or a substituted or unsubstituted organic group having C1-C20.
3. A photosensitive polyimide polymer as defined in claim 1, wherein the vinyl group-containing unsaturated group is a group selected from:
Figure FDA0000380676570000022
wherein z is an integer of 0 to 6.
4. A photosensitive polyimide polymer as claimed in claim 1, wherein R1 is a group selected from:
Figure FDA0000380676570000031
wherein:
o, p, q and r are each 0 or an integer greater than 0;
r4, R5 and R6 have the definitions as set forth in claim 2;
r7 are each H or a substituted or unsubstituted organic group having C1-C12; and is
R8 is a covalent bond or is selected from organic groups having:
Figure FDA0000380676570000041
5. a photosensitive polyimide polymer as claimed in claim 4, wherein R1 is a group selected from:
Figure FDA0000380676570000042
6. a photosensitive polyimide polymer according to claim 1, wherein a and C are each selected from the group consisting of:
Figure FDA0000380676570000043
Figure FDA0000380676570000051
7. a photosensitive polyimide polymer according to claim 1, wherein the divalent organic groups of B are each selected from the group consisting of:
Figure FDA0000380676570000052
wherein:
r' is selected from
Figure FDA0000380676570000053
Wherein R has the definition as defined in claim 1;
r9 is H, methyl or ethyl;
s is an integer of 1 to 4;
t is an integer of 0 to 5;
u is equal to 0 or an integer greater than 0;
v is an integer greater than 0; and is
R11 each represents a covalent bond or a group selected from;
wherein:
w and x are each an integer greater than 0, and
r12 is a covalent bond or a substituted or unsubstituted organic group having C1-C18.
8. A photosensitive polyimide polymer according to claim 7, wherein the divalent organic group of B is selected from the group consisting of:
Figure FDA0000380676570000062
Figure FDA0000380676570000071
wherein R' has the meaning as defined in claim 7.
9. A photosensitive polyimide polymer according to claim 1, wherein D is selected from the group consisting of:
Figure FDA0000380676570000072
r' is-H, C1-C4 alkyl, C1-C4 perfluoroalkyl, methoxy, ethoxy, halogen, OH, COOH, NH2Or SH;
r9 and R11 have the definitions as set forth in claim 7;
c is an integer of 0 to 4;
a is an integer greater than 0; and is
b is an integer greater than 0.
10. A photosensitive polyimide polymer according to claim 9, wherein D is selected from the group consisting of:
Figure FDA0000380676570000081
wherein y is an integer of 1 to 12.
11. A photosensitive composition comprising at least 1% of the photosensitive polyimide polymer of claim 1, and at least one photoinitiator, based on the total weight of the composition.
12. The photosensitive composition of claim 11, further comprising a reactive monomer or oligomer.
13. The photosensitive composition according to claim 11 or 12, which is used for a liquid photoresist or a dry film photoresist.
CN201310413998.3A 2008-01-25 2008-01-25 Photosensitive polyimide Pending CN103524735A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05232701A (en) * 1992-02-20 1993-09-10 Hitachi Chem Co Ltd Photosensitive resin compound
US5472823A (en) * 1992-01-20 1995-12-05 Hitachi Chemical Co., Ltd. Photosensitive resin composition
JP2006169409A (en) * 2004-12-16 2006-06-29 Kaneka Corp Polyimide precursor and photosensitive resin composition using it
CN101068852A (en) * 2004-12-16 2007-11-07 日本化药株式会社 Unsaturated group-containing polyimide resin, photosensitive resin composition containing same, and cured product thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5472823A (en) * 1992-01-20 1995-12-05 Hitachi Chemical Co., Ltd. Photosensitive resin composition
JPH05232701A (en) * 1992-02-20 1993-09-10 Hitachi Chem Co Ltd Photosensitive resin compound
JP2006169409A (en) * 2004-12-16 2006-06-29 Kaneka Corp Polyimide precursor and photosensitive resin composition using it
CN101068852A (en) * 2004-12-16 2007-11-07 日本化药株式会社 Unsaturated group-containing polyimide resin, photosensitive resin composition containing same, and cured product thereof

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