CN102532544B - Light-sensitive polyimide - Google Patents

Light-sensitive polyimide Download PDF

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CN102532544B
CN102532544B CN 201110460714 CN201110460714A CN102532544B CN 102532544 B CN102532544 B CN 102532544B CN 201110460714 CN201110460714 CN 201110460714 CN 201110460714 A CN201110460714 A CN 201110460714A CN 102532544 B CN102532544 B CN 102532544B
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周孟彦
李传宗
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Changxing Material Industry Limited-Liability Co
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Eternal Chemical Co Ltd
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Abstract

The invention relates to light-sensitive polyimide modified by using an epoxide. The polyimide has excellent heat resistance, ageing resistance and flexibility, and can be applied to liquid-state photoresistors or dry film photoresistors or solder resists, covering films or printed circuit boards.

Description

Light sensitive polyimide
Patent application of the present invention is to be on December 11st, 2008 applying date, and application number is 200810183103.0, and denomination of invention is divided an application for the application for a patent for invention of " light sensitive polyimide ".
Technical field
The present invention system is about a kind of light sensitive polyimide, and it can be applicable to liquid photoresistance or dry film photoresistance, or supplies the usefulness of solder resist, mulch film or printed circuit board (PCB).
Background technology
Because electronic product is emphasized gently, thin, short, little, various electronics spare parts also must be followed and do littler and littler in recent years.Under this development trend, light, thin, high temperature resistant and mass producible flexible printed wiring board has just had more development space.For example, present popular electronic product such as mobil phone, LCD, PLED and OLED etc. the trace that all can see flexible printed wiring board.Flexible printed wiring board is good pliability because more traditional silicon substrate or glass substrate are arranged, and can be described as soft board again, is made up of insulating substrate, solid and copper conductor substantially.Simultaneously, generally avoid the ambient temperature and humidity influence for the copper wire oxidation and the protection circuit that prevent flexible printed wiring board, also can add last layer mulch film (coverlay) on its substrate usually and protect, this mulch film system usually is made up of insulating substrate and solid.
And at present with regard to the material of mulch film (coverlay film), can be divided into three major types, the first kind is photosensitive type mulch film (photosensitive coverlay), second class is non-photosensitive type mulch film (non-photosensitive coverlay), and the 3rd class then is thermoplastics type's mulch film (thermal plastic coverlay).And with regard to first kind photosensitive type mulch film, can divide into again with polyimide (polyimide, PI) be the mulch film (non-PI based coverlay) of matrix for the mulch film of matrix (PI based coverlay) and with non-polyimide, it wherein is the mulch film of base material with non-polyimide, because relatively poor and thermal expansivity (the coefficient of thermal expansion of thermotolerance, CTE) more high factor, it is subjected to more restriction in application.The non-photosensitive type mulch film of second class is because processing procedure than photosensitive type mulch film complexity, therefore is not so good as the photosensitive type mulch film in practicality.As for thermoplastics type's mulch film, it needs pore-forming to make processing procedure processing afterwards, is poor than the photosensitive type mulch film also on convenience therefore.
General traditional light sensitive polyimide is made up of its polyamic acid or polyesteramide precursor, but owing to need high temperature roasting firmly (approximately greater than 300 ° of C high temperature), its copper cash Louis produces oxidation, for electrical properties and the reliability of product detrimentally affect is arranged all.In order to solve the roasting firmly copper wire problem of oxidation that can produce of high temperature, Japan one disclosed patent application case 2003-345007 has disclosed a kind of light sensitive polyimide that does not need the hard baking journey of high temperature, it is to utilize acrylate monomer and the major key have the 3rd amido to have-the solubility pi generation ion bond of COOH group, form negative photosensitive type pi (negative type photosensitive polyimide, Negative-type PSPI).But if need to use thicker polyimide, mulch film or soft board, this method just has its restriction during application.
Summary of the invention
Therefore, first purpose of the present invention is intended to provide a kind of can hardens the light sensitive polyimide that can be prepared into thick film and have preferable reactivity, stability and thermostability under low temperature.
Second purpose of the present invention provides a kind of photosensitive compoistion that comprises above-mentioned light sensitive polyimide; it can be used as the protective membrane material or is photoresistance; photosensitive compoistion of the present invention has good electrical specification, thermotolerance, flexibility and endurance after film forming.Therefore, photosensitive compoistion of the present invention can be used solder resist, mulch film material and the printed circuit board (PCB) as the protective membrane material.
First aspect present invention provides the light sensitive polyimide of a kind of tool with following formula (I) structure:
Figure GDA00003228054200021
Wherein:
A is for containing at least one modification group R 1Quadrivalent organic radical group;
B and D are identical or different divalent organic group;
C is not for containing modification group R 1Quadrivalent organic radical group,
M is the integer greater than 0; And
N equals 0 or greater than 0 integer,
Wherein, modification group R 1For being selected from the group that following groups constitutes:
Figure GDA00003228054200031
Figure GDA00003228054200032
Or
Figure GDA00003228054200033
Wherein, R 2For containing the unsaturated group of vinyl.
Second aspect present invention provides a kind of photosensitive compoistion, and it comprises light sensitive polyimide of the present invention, and at least one light trigger.
Embodiment
The structure of light sensitive polyimide polymkeric substance cording following formula of the present invention (I):
Formula (I)
Wherein,
A is for containing at least one modification group R 1Quadrivalent organic radical group;
B and D are identical or different divalent organic group;
C is not for containing modification group R 1Quadrivalent organic radical group;
M is the integer greater than 0, and preferably, m is for greater than 0 and be less than or equal to 2000 integer; And
N equals 0 or greater than 0 integer, and preferably, n is for greater than 0 and be less than or equal to 2000 integer;
Wherein, modification group R 1For being selected from the group that following groups constitutes:
Figure GDA00003228054200041
Figure GDA00003228054200042
Or
Wherein, R 2For containing the unsaturated group of vinyl, preferably, the described unsaturated group system of containing vinyl is selected from following group:
Figure GDA00003228054200044
Or
Figure GDA00003228054200045
Wherein, R 3Be hydrogen or methyl, and o and p respectively be 0 to 6 integer, more preferably, o and p respectively are 2 to 4 integer.
Quadrivalent organic radical contained in the light sensitive polyimide polymkeric substance of formula of the present invention (I) is rolled into a ball A and C, there is no particular restriction, for example can be tetravalence aromatic group or tetravalence aliphatic group, the preferably, and A system is selected from group that following groups constitutes respectively:
Figure GDA00003228054200051
Figure GDA00003228054200052
Or
Figure GDA00003228054200053
Wherein,
R 1For being selected from following organic group:
Or
Figure GDA00003228054200056
Wherein, R 2The definition that cording is mentioned above;
R 4For-CH 2-,-O-,-S-,-CO-,-SO 2-,-C (CH 3) 2-or-C (CF 3) 2-;
R 5For-H or-CH 3And
X is-O-,-NH-or-S-.
A in the above-mentioned formula (I) is better to be selected from by group that following groups constitutes:
Figure GDA00003228054200061
Wherein, R 1The definition that cording is mentioned above.
The C system of above-mentioned formula (I) is selected from group that following groups constitutes respectively:
Figure GDA00003228054200071
Figure GDA00003228054200072
Or
Figure GDA00003228054200073
Wherein, R 4, R 5And X is person as hereinbefore defined; And
R 6Be OH, COOH or NH 2
C in the above-mentioned formula (I) is better to be selected from by group that following groups constitutes:
Figure GDA00003228054200081
Figure GDA00003228054200092
Or
Figure GDA00003228054200093
B and D are divalent organic group, the preferably, and it is to be selected from the following group that constitutes group respectively:
Figure GDA00003228054200094
Figure GDA00003228054200101
Or
Figure GDA00003228054200102
Wherein, R 7Be H, methyl or ethyl;
R 8Be-H, C1-C4 alkyl, C1-C4 perfluoroalkyl, methoxyl group, oxyethyl group, halogen, OH, COOH, NH 2Or SH;
A is the integer greater than 0, and preferably, a is for greater than 0 and be less than or equal to 6 integer;
B is the integer greater than 0, and preferably, b is for greater than 0 and be less than or equal to 6 integer;
C is 0 to 4 integer;
D is 0 to 4 integer; And
R 9For covalent linkage or be selected from following group:
Figure GDA00003228054200103
Wherein, w and x respectively do for oneself greater than 0 integer, and preferably, w is for greater than 0 and be less than or equal to 10 integer; X is greater than 0 and is less than or equal to 4 integer, and R11 is-S (O) 2-,-C (O)-, covalent linkage or be the organic group with C1-C18 that is substituted or is unsubstituted.
Better person, B and D system are selected from group that following groups constitutes respectively:
Figure GDA00003228054200111
Wherein, y is 1 to 12 integer, is more preferred from the integer of 1-6.
For making polyimide have photosensitive group, in order to polymer application photocuring mechanism, the present invention uses a kind of epoxide (epoxy) that contains photosensitive group with the modified polyimide polymkeric substance, makes it have photosensitive group after modification, for example has the two keys of C=C.The used epoxide of the present invention can with polyimide polymer in hydroxyl (OH), carboxyl (COOH) isoreactivity radical reaction, and then polyimide polymer given modification.Epoxide preferably used in the present invention is contained but is not limited to following structure:
Figure GDA00003228054200121
Wherein, R 3Be hydrogen or methyl, o and p respectively are 0 to 6 integer, and more preferably, o and p respectively are 2 to 4 integer.
But light sensitive polyimide mat persond having ordinary knowledge in the technical field of the present invention of the present invention polymerization process known obtains, and for example can make by the method that comprises the following step:
(a) make a tool formula H 2N-P-NH 2Diamine monomer and a tool formula
Figure GDA00003228054200122
Dianhydride monomer and another tool formula
Figure GDA00003228054200123
Dianhydride monomer react, form the compound of tool following formula (1):
Wherein, G is reactive functional group, as OH Ji ﹑ COOH base or NH 2Base.
As if being example with COOH, ensuing reactions steps is:
(b) add epoxy compounds in the product of step (a), (glycidyl methacrylate) is example with glycidyl methacrylate, then forms as shown in the formula the compound shown in (2):
Figure GDA00003228054200131
Wherein, f+g=i.
In the above-mentioned method for preparing the light sensitive polyimide polymkeric substance, spendable diamine monomer, such as but not limited to following monomer:
Figure GDA00003228054200141
Wherein,
R 7Be H, methyl or ethyl;
R 8Be-H, C1-C4 alkyl, C1-C4 perfluoroalkyl, methoxyl group, oxyethyl group, halogen, OH, COOH, NH 2Or SH;
A is the integer greater than 0, and preferably, a is for greater than 0 and be less than or equal to 6 integer;
B is the integer greater than 0, and preferably, b is for greater than 0 and be less than or equal to 6 integer;
C is 0 to 4 integer;
D is 0 to 4 integer; And
R 9For covalent linkage or be selected from following group:
Figure GDA00003228054200142
Wherein, w and x are the integer greater than 0, and preferably, w is for greater than 0 and be less than or equal to 10 integer; X is greater than 0 and is less than or equal to 4 integer, and R11 is-S (O) 2-,-C (O)-, covalent linkage or be the organic group with C1-C18 that is substituted or is unsubstituted.
Preferably, above-mentioned diamine monomer is to be selected from following diamines or its mixture that constitutes group:
Figure GDA00003228054200161
Wherein, y is 1 to 12 integer, is more preferred from the integer of 1-6.
In the above-mentioned method for preparing the light sensitive polyimide polymkeric substance, the anhydride monomers of tool reactive functional group base can be selected from group that following compound constitutes or its mixture:
Figure GDA00003228054200162
Wherein,
R 4For-CH 2-,-O-,-S-,-CO-,-SO 2-,-C (CH 3) 2-or-C (CF 3) 2-;
R 5For-H or-CH 3-;
R 6Be OH, COOH or NH 2And
X is-O-,-NH-or-S-.
In the above-mentioned method for preparing the light sensitive polyimide polymkeric substance, employed another kind of anhydride monomers there is no particular restriction, and it can have or not have reactive functional group.Can be used for the anhydride monomers that does not have reactive functional group of the present invention, is to be familiar with this technical field person to know, its such as, but not limited to:
Figure GDA00003228054200171
Wherein,
E, F and H respectively represent covalent linkage or saturated or unsaturated, the ring-type with C1-C20 or acyclic organic group for being substituted or being unsubstituted;
R 20For covalent linkage or be selected from following groups:
Figure GDA00003228054200181
The preferably, the anhydride monomers that does not have reactive functional group that can be used among the present invention can be selected from the group that following compound constitutes:
The present invention provides a kind of photosensitive compoistion in addition, can be applicable to liquid photoresistance, dry film photoresistance, mulch film, solder resist or printed circuit board (PCB), and it comprises at least about 1% light sensitive polyimide and light trigger and the solvent of formula (I) structure as described above.In the above-mentioned photosensitive compoistion, the weight percent that each is formed, visual product demand adjusts.Generally speaking, the content of formula (I) light sensitive polyimide polymkeric substance, in whole constituent gross weight, at least about 1 weight %, it is preferable between 5-90 weight %; The content of light trigger, in whole constituent gross weight, at least about 0.001 weight %, preferable between about 0.01-10 weight %.
Be applicable to that the light trigger in the above-mentioned constituent there is no particular restriction, it can be benzophenone (benzophenone), bitter almond oil camphor (benzoin), 2-hydroxy-2-methyl-1-Propiophenone (2-hydroxy-2-methyl-1-phenyl-propan-1-one), 2,2-dimethoxy-1,2-phenylbenzene second-1-ketone (2,2-dimethoxy-1,2-diphenylethan-1-one), 1-hydroxy-cyclohexyl phenyl ketone (1-hydroxy cyclohexyl phenyl ketone), 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (2,4,6-trimethylbenzoyl diphenyl phosphine oxide), N-phenyl glycine (N-phenylglycine), 9-phenylacridine (9-phenylacridine), benzyl dimethyl ketal (benzyldimethylketal), 4, two (diethylamide) benzophenone (4 of 4'-, 4'-bis (diethylamine) benzophenone), 2,4,5-triarylimidazoles dipolymer (2,4,5-triarylimidazole dimers) or its mixture; Preferable light trigger is 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (2,4,6-trimethylbenzoyl diphenyl phosphine oxide).
Be applicable to that the solvent in the above-mentioned constituent there is no particular restriction, it can be but is not limited to N-N-methyl 2-pyrrolidone N-(NMP), N,N-DIMETHYLACETAMIDE (DMAC), dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), toluene (toluene), dimethylbenzene (xylene) or its mixture.
Further, for increasing the photo-crosslinking degree, make its film-forming properties better, photosensitive compoistion of the present invention optionally adds reactive monomer or short chain oligomer, makes molecule and intermolecular formation crosslinked (crosslinking).Be applicable to that reactive monomer or oligopolymer in the constituent there is no particular restriction, it for example can be diacrylate 1,6-hexylene glycol ester (1,6-hexanediol diacrylate), diacrylic acid pentyl diol ester (neopentyl glycol diacrylate), ethylene glycol diacrylate (ethylene glycol diacrylate), diacrylate pentaerythritol ester (pentaerythritoldiacrylate), trimethyol propane triacrylate (trimethylolpropane triacrylate), pentaerythritol triacrylate (pentaerythritol triacrylate), six vinylformic acid dipentaerythritol ester (dipentaerythritol hexaacrylate), tetrapropylene acid tetra methylol propane ester (tetramethylolpropane tetraacrylate), diacrylate TEG ester (tetraethylene glycol diacrylate), dimethacrylate 1,6-hexylene glycol ester (1,6-hexanediol dimethacrylate), dimethacrylate DOPCP (neopentyl glycol dimethacrylate), Ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), dimethacrylate pentaerythritol ester (pentaerythritol dimethacrylate), trihydroxy methyl propane trimethyl acrylate (trimethylolpropane trimethacrylate), trimethylammonium vinylformic acid pentaerythritol ester (pentaerythritol trimethacrylate), hexamethyl vinylformic acid dipentaerythritol ester (dipentaerythritol hexamethacrylate), tetramethyl-vinylformic acid tetra methylol propane ester (tetramethylolpropane tetramethacrylate), dimethacrylate TEG ester (tetraethylene glycol dimethacrylate), methacrylic acid methoxy base binaryglycol ester (methoxydiethylene glycol methacrylate), methacrylic acid methoxy base macrogol ester (methoxypolyethylene glycol methacrylate), phthalandione Beta-methyl acryloxy ethyl hydrogen diene ester (β-methacryloyloxyethylhydrodiene phthalate), succsinic acid Beta-methyl acryloxy ethyl hydrogen diene ester (β-methacryloyloxyethylhydrodiene succinate), methacrylic acid 3-chloro-2-hydroxypropyl acrylate (3-chloro-2-hydroxypropyl methacrylate), methacrylic acid stearate (stearyl methacrylate), phenoxyethyl acrylate (phenoxyethyl acrylate), vinylformic acid phenoxy group binaryglycol ester (phenoxydiethylene glycol acrylate), vinylformic acid phenoxy group macrogol ester (phenoxypolyethylene glycol acrylate), succsinic acid β-acryloxy ethyl hydrogen diene ester (β-acryloyloxyethylhydrodiene succinate), lauryl acrylate (lauryl acrylate), Ethylene glycol dimethacrylate (ethylene glycol dimethacrylate), diethyleneglycol dimethacrylate(DEGDMA) (diethylene glycol dimethacrylate), dimethacrylate triglycol ester (triethylene glycol dimethacrylate), dimethacrylate macrogol ester (polyethylene glycol dimethacrylate), dimethacrylate-1,3-butanediol ester (1,3-butylene glycol dimethacrylate), dimethacrylate polypropylene glycol ester (polypropylene glycol dimethacrylate), 2-hydroxyl-1,3-dimethyl allene oxygen base propane (2-hydroxy-1,3-dimethacryloxypropane), 2,2-two [4-(metacryloxy oxyethyl group) phenyl] propane (2,2-bis[4-(methacryloxyethoxy) phenyl] propane), 2,2-two [4-(metacryloxy diethoxy) phenyl] propane (2,2-bis[4-(methacryloxydiethoxy) phenyl] propane), 2,2-two [4-(methylpropenyl polyethoxye) phenyl] propane (2,2-bis[4-(methacryloxypolyethoxy) phenyl] propane), diacrylate macrogol ester (polyethylene glycol diacrylate), diacrylate tripropylene glycol ester (tripropylene glycol diacrylate), diacrylate polypropylene glycol ester (polypropylene glycol diacrylate), 2,2-two [4-(propenyloxy group diethoxy) phenyl] propane (2,2-bis[4-(acryloxydiethoxy) phenyl] propane), 2,2-two [4-(propenyloxy group polyethoxye) phenyl] propane (2,2-bis[4-(acryloxypolyethoxy) phenyl] propane), 2-hydroxyl-1-propenyloxy group-3-metacryloxy propane (2-hydroxy-1-acryloxy-3-methacryloxypropane), trihydroxy methyl propane trimethyl acrylate (trimethylolpropane trimethacrylate), three vinylformic acid tetramethylol methane esters (tetramethylolmethane triacrylate), tetrapropylene acid tetramethylol methane ester (tetramethylolmethane tetraacrylate), methacrylic acid methoxy base dipropylene glycol ester (methoxydipropylene glycol methacrylate), vinylformic acid methoxyl group triglycol ester (methoxytriethylene glycol acrylate), vinylformic acid Nonylphenoxy macrogol ester (nonylphenoxypolyethylene glycol acrylate), vinylformic acid Nonylphenoxy polypropylene glycol ester (nonylphenoxypolypropylene glycol acrylate), 2-phthalic acid-1-acryloxy propyl group-ester (1-acryloyloxypropyl-2-phthalate), vinylformic acid isostearate (isostearyl acrylate), vinylformic acid polyethylene oxide alkyl ether-ether (polyoxyethylene alkyl ether acrylate), vinylformic acid Nonylphenoxy glycol ester (nonylphenoxyethylene glycol acrylate), vinylformic acid polypropylene glycol dimethyl esters (polypropylene glycol dimethacrylate), dimethacrylate-1,4-butanediol ester (1,4-butanediol dimethacrylate), dimethacrylate-3-methyl isophthalic acid, 5-pentadiol ester (3-methyl-1,5-pentanediol dimethacrylate), methacrylic acid-1,6-hexylene glycol ester (1,6-hexanediol methacrylate), methacrylic acid-1,9-nonanediol ester (1,9-nonanediol methacrylate), dimethacrylate-2,4-diethyl-1,5-pentadiol ester (2,4-diethyl-1,5-pentanediol dimethacrylate), dimethacrylate-1,4-cyclohexanedimethanoester ester (1,4-cyclohexanedimethanol dimethacrylate), dipropylene glycol diacrylate (dipropylene glycol diacrylate), diacrylate tristane front three alcohol ester (tricyclodecanedimethanol diacrylate), 2,2-dihydro two [4-propenyloxy group polyethoxye] phenyl] propane (2,2-hydrogenated bis[4-acryloxypolyethoxy] phenyl) propane), 2,2-two [the 4-propenyloxy group gathers propoxy-] phenyl] propane (2,2-bis[4-acryloxypolypropoxy] phenyl) propane), diacrylate-2,4-diethyl-1,5-pentadiol ester (2,4-diethyl-1,5-pentanediol diacrylate), three vinylformic acid ethoxyquin trihydroxymethylpropanyl esters (ethoxylated trimethylolpropane triacrylate), three vinylformic acid, the third oxidation trihydroxymethylpropanyl ester (propoxylated trimethylolpropane triacrylate), three (ethane vinylformic acid) isocyanuric acid ester (isocyanuric acid tri (ethaneacrylate)), pentaerythritol tetracrylate (pentaerythritol tetraacrylate), tetrapropylene acid ethoxyquin pentaerythritol ester (ethoxylated pentaerythritol tetraacrylate), the tetrapropylene acid third oxidation pentaerythritol ester (propoxylated pentaerythritol tetraacrylate), tetrapropylene acid two trihydroxymethylpropanyl esters (ditrimethylolpropane tetraacrylate), polyacrylic acid dipentaerythritol ester (dipentaerythritol polyacrylate), triallyl isocyanurate (triallyl isocyanurate), glycidyl methacrylate (glycidyl methacrylate), glycidyl allyl ether (allyl glycidylether), 1,3,5-three acryloyls six hydrogen-s-triazine (1,3,5-triacryloylhexahydro-s-triazine), 1,3,5-phenylformic acid triallyl (triallyl1,3,5-benzenecarboxylate), triallylamine (triallylamine), citric acid triallyl (triallyl citrate), triallyl phosphate (triallyl phosphate), Allobarbitone (allobarbital), diallyl amine (diallylamine), diallyl dimethylsilane (diallyldimethylsilane), diallyl disulfide (diallyl disulfide), diallyl ether (diallyl ether), cyanogen urea diallyl phthalate (diallyl cyanurate), diallyl isophthalate (diallyl isophthalate), terephthalic acid diallyl (diallyl terephthalate), 1,3-two allyloxys-2-propyl alcohol (1,3-diallyloxy-2-propanol), diallyl sulfide (diallyl sulfide), diallyl maleate (diallyl maleate), dimethacrylate-4,4 '-isopropylidene biphenyl phenolic ester (4,4 '-isopropylidenediphenol dimethacrylate) or diacrylate-4,4 '-isopropylidene biphenyl phenolic ester (4,4 '-isopropylidenediphenol diacrylate).The employed reactive monomer of photosensitive composition of the present invention or oligopolymer are when existing, and in whole constituent gross weight, its consumption system is preferably between 0.1-30 weight % at least about 0.1 weight %.
Following examples will the present invention is described further, only non-in order to limiting the scope of the invention, and anyly is familiar with the technology of the present invention field person, without prejudice to spirit of the present invention following the modification of being reached and variation, all belongs to scope of the present invention.
In following examples, employed abbreviation is defined as follows:
DA1:
Figure GDA00003228054200231
DA2:
Figure GDA00003228054200232
DA3:
DA4:
Figure GDA00003228054200242
DA5:
Figure GDA00003228054200243
DA6:
Figure GDA00003228054200244
6FDA:4,4'-hexafluoroisopropyli,ene two phthalandione dianhydrides (4,4'-hexafluoroisopropylidene-2,2-bis-(phthalic acid anhydride)
DMDB:2,2'-dimethyl diphenyl-4, the 4'-diamines (2,2'-dimethylbiphenyl-4,4'-diamine)
ODA:4, and 4'-oxygen pentanoic (4,4'-oxydianiline)
GMA: glycidyl methacrylate (glycidyl methacrylate)
TBAB: bromination tributyl ammonium (tert-butylammonium bromide)
MEHQ: methyl hydroquinone (methylhydroquinone)
DMAc: N,N-DIMETHYLACETAMIDE (dimethyl acetamide)
NMP:N-methyl-2-pyrrolidone (N-methylpyrrolidone)
Example 1: the polyimide (P1) of synthetic GMA modification
Weigh the DA1 of 64.85g (0.2mol) and the DMDB of 42.46g (0.2mol), add 300ml NMP, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.015g TBAB and the 0.06g MEHQ of 6.11g (0.05mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, get final product P1.
Example 2: the polyimide (P2) of synthetic GMA modification
Weigh the DA2 of 73.256g (0.2mol) and the DMDB of 42.46g (0.2mol), add 350ml NMP, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.015g TBAB and the 0.06g MEHQ of 6.11g (0.05mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, get final product P2.
Example 3: the polyimide (P3) of synthetic GMA modification
Weigh the DA3 of 100.074g (0.2mol) and the DMDB of 42.46g (0.2mol), add 450ml NMP, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.015g TBAB and the 0.06g MEHQ of 6.11g (0.05mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, get final product P3.
Example 4: the polyimide (P4) of synthetic GMA modification
Weigh the DA4 of 124.1g (0.2mol) and the DMDB of 42.46g (0.2mol), add 550ml NMP, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.03g TBAB and the 0.06g MEHQ of 12.22g (0.1mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, get final product P4.
Example 5: the polyimide (P5) of synthetic GMA modification
Weigh the DA5 of 126.9g (0.2mol) and the DMDB of 42.46g (0.2mol), add 550ml NMP, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.03g TBAB and the 0.06g MEHQ of 12.22g (0.1mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, get final product P5.
Example 6: the polyimide (P6) of synthetic GMA modification
Weigh the DA6 of 115.7g (0.2mol) and the DMDB of 42.46g (0.2mol), add 500ml NMP, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.015g TBAB and the 0.06g MEHQ of 6.11g (0.05mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, get final product P6.
Example 7: the polyimide (P7) of synthetic GMA modification
Weigh the DA1 of 64.85g (0.2mol) and the ODA of 40.05g (0.2mol), add 300ml DMAc, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.015g TBAB and the 0.06gMEHQ of 6.11g (0.05mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, get final product P7.
Example 8: the polyimide (P8) of synthetic GMA modification
Weigh the DA2 of 73.26g (0.2mol) and the ODA of 40.05g (0.2mol), add 350ml DMAc, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.015g TBAB and the 0.06g MEHQ of 6.11g (0.05mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, namely reach and to get P8.
Example 9: the polyimide (P9) of synthetic GMA modification
Weigh the DA3 of 100.074g (0.2mol) and the ODA of 40.05g (0.2mol), add 450ml DMAc, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.015g TBAB and the 0.06g MEHQ of 6.11g (0.05mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, get final product P9.
Example 10: the polyimide (P10) of synthetic GMA modification
Weigh the DA4 of 124.1g (0.2mol) and the ODA of 40.05g (0.2mol), add 550ml DMAc, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.03g TBAB and the 0.06g MEHQ of 12.22g (0.1mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, get final product P10.
Example 11: the polyimide (P11) of synthetic GMA modification
Weigh the DA4 of 126.9g (0.2mol) and the ODA of 40.05g (0.2mol), add 550ml DMAc, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.03g TBAB and the 0.06g MEHQ of 12.22g (0.1mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, get final product P11.
Example 12: the polyimide (P12) of synthetic GMA modification
Weigh the DA4 of 115.7g (0.2mol) and the ODA of 40.05g (0.2mol), add 550ml DMAc, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.015g TBAB and the 0.06g MEHQ of 6.11g (0.05mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, get final product P12.
Example 13: the polyimide (P13) of synthetic GMA modification
Weigh DA4,44.42g (0.1mol) 6FDA of 57.85g (0.1mol) and the ODA of 40.05g (0.2mol), add 500ml DMAc, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.015g TBAB and the 0.06g MEHQ of 6.11g (0.05mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, get final product P13.
Example 14: the polyimide (P14) of synthetic GMA modification
Weigh DA5,44.42g (0.1mol) 6FDA of 63.45g (0.1mol) and the ODA of 40.05g (0.2mol), add 500ml DMAc, under room temperature, stirred 1 hour, stirred 4 hours after being warming up to 50 ° of C again.After 4 hours, add 50ml toluene, under 130 ° of C, dewater with Dien-Stark (dean-stark) device.After waiting to dewater fully, solution is down to room temperature, adds GMA, 0.015g TBAB and the 0.06g MEHQ of 6.11g (0.05mol) again.After adding solution is warming up to 90 ° of C, stirred 12 hours, get final product P14.

Claims (7)

1. a tool is with the light sensitive polyimide of following formula (I) structure:
Figure FDA00003228054100011
Wherein,
A is for containing at least one modification group R 1Quadrivalent organic radical group, be selected from the group that following groups constitutes:
Figure FDA00003228054100012
Figure FDA00003228054100013
Or
Figure FDA00003228054100015
Wherein,
Modification group R 1For being selected from the group that following groups constitutes:
Figure FDA00003228054100016
Wherein, R 2For containing the unsaturated group of vinyl, be to be selected from following group:
Figure FDA00003228054100021
R wherein 3Be hydrogen or methyl, and o and p respectively are 0 to 6 integer;
R 4System-CH 2-,-O-,-S-,-CO-,-SO 2-,-C (CH 3) 2-or-C (CF 3) 2-;
R 5System-H or-CH 3And
X system-O-,-NH-or-S-;
B and D are identical or different divalent organic group, are to be selected from separately by group that following groups constitutes:
Figure FDA00003228054100022
Wherein,
R 7Be H, methyl or ethyl;
R 8System-H, C1-C4 alkyl, C1-C4 perfluoroalkyl, methoxyl group, oxyethyl group, halogen, OH, COOH, NH 2Or SH;
A is the integer greater than 0;
B is the integer greater than 0;
C is 0 to 4 integer;
D is 0 to 4 integer; And
R 9For covalent linkage or be selected from the group that following groups constitutes:
Figure FDA00003228054100031
Wherein, w and x respectively do for oneself greater than 0 integer, and R11 is-S (O) 2-,-C (O)-, covalent linkage or be the organic group with C1-C18 that is substituted or is unsubstituted;
C is not for containing modification group R 1Quadrivalent organic radical group, be to be selected from group that following groups constitutes respectively:
Figure FDA00003228054100041
Or
Figure FDA00003228054100044
Wherein, R 4, R 5And X system as the preceding middle definien of institute; And
R 6System-OH ,-COOH or NH 2
M is for greater than 0 and be less than or equal to 2000 integer; And
N is for greater than 0 and be less than or equal to 2000 integer.
2. light sensitive polyimide as claimed in claim 1, wherein A system is selected from the group that following groups constitutes:
Figure FDA00003228054100051
Wherein,
R 1Cording has definition as claimed in claim 1.
3. light sensitive polyimide as claimed in claim 1, wherein C system is selected from group that following groups constitutes respectively:
Figure FDA00003228054100061
Figure FDA00003228054100071
4. light sensitive polyimide as claimed in claim 1, wherein the divalent organic group of B and D system is selected from respectively by group that following groups constitutes:
Figure FDA00003228054100081
Wherein, y is 1 to 12 integer.
5. photosensitive compoistion, it comprises light sensitive polyimide as claimed in claim 1, and at least one light trigger.
6. photosensitive compoistion as claimed in claim 5 wherein also comprises one and has reactive monomeric or oligopolymer.
7. photosensitive compoistion as claimed in claim 5, it is the usefulness that is applied to liquid photoresistance or dry film photoresistance.
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JP2000147761A (en) * 1998-11-11 2000-05-26 Hitachi Ltd Photosensitive polyimide composition and pattern forming method by using same
TW567198B (en) * 1999-12-28 2003-12-21 Kaneka Corp Epoxy-modified polyimide, photosensitive composition, coverlay film, solder resist, and printed wiring board using the epoxy-modified polyimide
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