Radiation imagery chemistry: process – composition – or product th – Diazo reproduction – process – composition – or product – Composition or product which contains radiation sensitive...
Reexamination Certificate
2002-05-30
2004-01-13
Chu, John S. (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Diazo reproduction, process, composition, or product
Composition or product which contains radiation sensitive...
C430S191000, C430S193000
Reexamination Certificate
active
06677099
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a photosensitive material useful for electric/electronic devices, particular for semiconductor devices. More particularly, it relates to a positive type photosensitive polyimide resin composition excellent in the adhesion to a substrate, the developability, etc.
BACKGROUND ART
As a method for imparting photosensitivity to a polyimide resin, there may, for example, be mentioned a method of chemically bonding a crosslinkable group to a soluble polyimide precursor as disclosed in e.g. JP-A-54-116216 and JP-A-54-116217, or a method of mixing crosslinkable monomers as disclosed in JP-A-54-145794 and JP-A-57-168942.
The above methods are of a negative type wherein an exposed portion is crosslinked and made insoluble by light, and they have a problem with respect to safety as an organic solvent is used for development, and further have a drawback that it is difficult to carry out fine processing at a high resolution, since the exposed portion will be swelled by a developing solution.
Whereas, recently, a positive type photosensitive resin material has been developed and has attracted an attention, which can be developed by an aqueous alkaline solution. For example, JP-A-64-60630 discloses a method of mixing an o-quinonediazide compound to an organic solvent-soluble polyimide resin having hydroxyl groups introduced. Further, JP-A-3-209478 discloses a method wherein a resin excellent in transparency is used as an organic solvent-soluble polyimide resin, and accordingly, by mixing an o-quinonediazide compound, a very high sensitivity and a high resolution can be attained.
However, these methods have had a problem that the adhesion to a substrate of e.g. silicon, is not adequate, and if no pretreatment of the substrate with a silane coupling agent or the like is carried out at the time of forming a pattern, the resin is likely to peel from the substrate during the development or after curing. Further, a solvent-soluble polyimide resin having the alkali affinity extremely lowered, is used in order to suppress the alkali solubility of a non-exposed portion and to make a large difference in the solubility rate from an exposed portion, when an o-quinonediazide is mixed thereto.
Thus, while they had excellent characteristics, conventional positive type photosensitive polyimide resins were not fully satisfactory from the viewpoint of a process in view of e.g. the low adhesion or low developability.
DISCLOSURE OF THE INVENTION
The present invention has been made in view of the above-mentioned situations and is intended to provide a positive type photosensitive resin composition which can be developed with an aqueous alkaline solution and which is excellent in the developability and the adhesion to a substrate.
The present inventors have conducted an extensive study to solve the above-mentioned problems and have finally arrived at the present invention.
The present invention relates to a positive type photosensitive polyimide resin composition characterized by comprising 100 parts by weight of a solvent-soluble polyimide having repeating units represented by the formula (1):
(wherein repeating units n is an integer of from 3 to 1000, R
1
represents a bivalent organic group constituting a diamine, R
2
represents a tetravalent organic group constituting a tetracarboxylic acid or its derivative, and R
1
is a bivalent organic group wherein from 1 to 90 mol % of the diamine component has one or plural groups of at least one type selected from the group consisting of a phenolic hydroxyl group, a carboxyl group, a thiophenol group and a sulfonic group, and from 10 to 99 mol % has no phenolic hydroxyl, carboxylic, thiophenol or sulfonic group) and from 1 to 50 parts by weight of a polyimide precursor having repeating units represented by the formula (2):
(wherein repeating units m is an integer of from 3 to 1000, R
3
is a bivalent organic group constituting a diamine, and R
4
is a tetravalent organic group constituting a tetracarboxylic acid or its derivative), and by further containing an o-quinonediazide compound in an amount of from 1 to 100 parts by weight per 100 parts by weight of the total amount of the repeating units represented by the formula (1) and the repeating units represented by the formula (2).
In one embodiment of the present invention, the bivalent organic group constituting a diamine for R
3
in the polyimide precursor having the repeating units represented by the formula (2), is such that from 1 to 100 mol % of the diamine component is a silicone diamine, and further, it relates to the positive type photosensitive polyimide resin composition, wherein in the solvent-soluble polyimide resin having repeating units represented by the formula (1) and in the polyimide precursor having repeating units represented by the formula (2), R
2
and R
4
are cyclobutane moieties.
Now, the present invention will be described in detail.
The diamine constituting R
1
in the above formula (1) of the present invention is not particularly limited so long as from 1 to 90 mol % of the diamine component is a bivalent organic group having one or plural groups of at least one type selected from the group consisting of a phenolic hydroxyl group, a carboxyl group, a thiophenol group and a sulfonic group, and from 10 to 99 mol % is a bivalent organic group having no phenolic hydroxyl, carboxylic, thiophenol or sulfonic group.
Further, the above diamine component of from 1 to 90 mol %, and the diamine component of from 10 to 99 mol % may, respectively, be single or plural. As its specific examples, the diamine having a phenolic hydroxyl group, a carboxyl group, a thiophenol group and/or a sulfonic group, may, for example, be a diamine having a phenolic hydroxyl group, such as 1,3-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, 1,3-diamino-2-hydroxybenzene, 1,4-diamino-2,5-dihydroxybenzene, bis(3-amino-4-hydroxyphenyl)ether, bis(4-amino-3-hydroxyphenyl)ether, bis(4-amino-3,5-dihydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methane, bis(4-amino-3-hydroxyphenyl)methane, bis(4-amino-3,5-dihydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(4-amino-3,5-dihydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl)hexafluoropropane, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxy-5,5′-dimethylbiphenyl, 4,4′-diamino-3,3′-dihydroxy-5,5′-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis(4-amino-3-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]sulfone, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]propane, or 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane; a diamine having a carboxyl group, such as 1,3-diamino-4-carboxybenzene, 1,3-diamino-5-carboxybenzene, 1,3-diamino-4,6-dicarboxybenzene, 1,4-diamino-2-carboxybenzene, 1,4-diamino-2,5-dicarboxybenzene, bis(4-amino-3-carboxyphenyl)ether, bis(4-amino-3,5-dicarboxyphenyl)ether, bis(4-amino-3-carboxyphenyl)sulfone, bis(4-amino-3,5-dicarboxyphenyl)sulfone, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,5′-dimethylbiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,5′-dimethoxybiphenyl, 1,4-bis(4-amino-3-carboxyphenoxy)benzene, 1,3-bis(4-amino-3-carboxyphenoxy)benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone, bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, or 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane; a diamine having a thiophenol group, such as 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl)ether, or 2,2-bis(3-amino-4-mercaptophenyl)hexafluoropropane; a diamine having a sulfonic group, such as 1,3-diaminobenzene-4-sulfonic acid,
Fukuro Hiroyoshi
Ishii Kazuhisa
Nakayama Tomonari
Nihira Takayasu
Chu John S.
Nissan Chemical Industries Ltd.
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