Radiation imagery chemistry: process – composition – or product th – Diazo reproduction – process – composition – or product – Composition or product which contains radiation sensitive...
Reexamination Certificate
2000-11-15
2002-04-16
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...
C430S165000, C430S190000, C430S192000, C430S193000, C430S325000
Reexamination Certificate
active
06372403
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a photosensitive resin composition. More particularly, the present invention relates to a photosensitive resin composition useful for forming protective or insulating films for, for example, semiconductor devices, flat panel displays, liquid crystal devices, and especially for color filters and thin film transistors (hereinafter referred to as “TFTs”) etc.
2. Related Art
Heretofore, mixtures of novolak resins and diazidonaphthoquinone have generally been used as positive photoresists useful in the production of flat panel displays (hereinafter referred to as “FPDs”) or semiconductor devices. However, films formed by using these mixtures are sometimes insufficient in transparency. In case these films are intended to use as protective or insulating films which are applied to the surfaces of semiconductor devices, FPDs or liquid crystal devices, such insufficient transparency causes disadvantageousness. In particular, some problems occur due to such insufficient transparency when these films are used for such devices as color filters or TFTs through which light is allowed to pass. Why these conventional photoresist films cannot have sufficiently high transparency is chiefly due to the nature of novolak resins used as resin components in the photoresists. In case high transparency is required for such films, acrylic or polyhydroxystyrene (hereinafter referred to as “PHS”) resins which can give films having higher transparency have been used. However, even in this case, some improvements other than its transparency are needed.
Namely, since acrylic or PHS resins are poor in compatibility with copolymers of benzophenone compounds and 1,2-diazidonaphthoquinone, which are photosensitizers usually used in photoresists to be used for the above-described purposes, it is sometimes difficult to obtain high contrast between exposed area and unexposed area after development.
Therefore, photosensitive resin compositions capable of forming films having sufficiently high transparency, and of imparting satisfactorily high contrast to images to be formed in the films after development are still needed.
SUMMARY OF THE INVENTION
A photosensitive resin composition of the present invention comprises the following components:
(a) a photosensitizer having in its structure 1,2-diazidonaphthoquinone structure, and a methylene-bridged structure composed of two or more methyl-substituted phenol derivatives;
(b) a polymer having both hydroxyl group and carboxyl group, or a combination of a polymer having hydroxyl group and a polymer having carboxyl group;
(c) a crosslinking agent capable of crosslinking hydroxyl group and carboxyl group; and
(d) a solvent.
Further, an article of the present invention comprises a protective or insulating film made from the aforementioned photosensitive resin composition.
Moreover, a method for forming patterns of the present invention comprises the following process;
(a) a process for coating the aforementioned photosensitive resin composition on a substrate,
(b) a process for exposing the coated photosensitive resin composition on the substrate for making an image on it; and
(c) a process for developing the exposed photosensitive resin composition on the substrate.
Furthermore, an another aspect of the present invention is an use of the aforementioned photosensitive resin composition for manufacturing a protective or insulating film.
By using the photosensitive resin composition of the present invention, it is possible to obtain films having high transparency. Moreover, patterns having high contrast can be obtained when the composition of the invention is used as a photoresist.
DETAILED DESCRIPTION OF THE INVENTION
1. Photosensitizer
The photosensitizer for use in the photosensitive resin composition of the present invention has in its structure 1,2-diazidonaphthoquinone structure and a methylene-bridged structure composed of two or more methyl-substituted phenol derivatives. In general, methyl-substituted phenol derivatives are phenol derivatives in which any of hydrogens attached to carbons on phenol structure is substituted with methyl group. However, in the present invention, they also encompass those compounds which are not substituted with methyl group, that is, phenols themselves. Therefore, the methylene-bridged structure composed of two or more methyl-substituted phenol derivatives can be defined as a structure in which two or more phenol structures are connected by methylene group, and any of hydrogens on the phenol structure is substituted with methyl group.
In the present invention, the photosensitizer has in its structure two or more methyl-substituted phenol derivatives; and the number of the methyl-substituted phenol derivatives present in the structure is preferably from 2 to 5, particularly 4.
In the present invention, the photosensitizer may contain a plurality of 1,2-diazidonaphthoquinone structures. It is enough that at least one 1,2-diazidonaphthoquinone structure is present in the structure of the photosensitizer. However, this structure can exist in any number, the maximum number being equal to the number of hydroxyl groups present in the methylene-bridged structure composed of methyl-substituted phenol derivatives; the number is preferably from 1 to 5, particularly from 2 to 4.
Of photosensitizers fulfilling the above-described requirements, those ones represented by the following formulae are particularly preferred as the photosensitizer for use in the photosensitive resin composition of the present invention:
wherein D is
or H, provided that at least one of Ds present in each formula is not H.
Of the photosensitizers re presented by the above formulae, those ones in which three of four Ds are esterified with 1,2-diazidonaphthoquinonesulfonic acid are most preferred.
Such photosensitizers can be obtained by condensation polymerization reaction between methylene-bridged products of methyl-substituted phenol derivatives and compounds having 1,2-diazidonaphthoquinone structure; and polymers obtained in this manner are preferred.
Any methyl-substituted phenol derivative and any compound having 1,2-diazidonaphthoquinone structure can be used for the condensation polymerization as long as they can give, when condensation-polymerized, a photosensitizer that can be used for the photosensitive resin composition of the present invention. Further, this condensation polymerization reaction can be carried out by any conventional method.
Examples of compounds having 1,2-diazidonaphthoquinone structure that can be subjected to the above condensation polymerization include 1,2-diazidobenzoquinonesulfonic ester, 1,2-diazidonaphthoquinonesulfonic ester, 1,2-diazidobenzo-quinonesulfonamide, and 1,2-diazidonaphthoquinonesulfonamide. More specifically, the following compounds can be mentioned: phenyl 1,2-diazidobenzoquinone-4-sulfonate, 1,2,1′1,2′-di-(diazidobenzoquinone-4-sulfonyl)-dihydroxybiphenyl, 1,2-diazidobenzoquinone-4-(N-ethyl-N-&bgr;-naphthyl)-sulfonamide, cyclohexyl 1,2-diazidonaphthoquinone-5-sulfonate, 1-(1,2-diazidonaphthoquinone-5-sulfonyl) -3,5-dimethylpyrazole, 1,2-diazidonaphthoquinone-5-sulfonic acid-4′-hydroxy-diphenyl-4″-azo-&bgr;-naphthol ester, N,N-di-(1,2-diazidonaphthoquinone-5-sulfonyl)-aniline, 2′-(1,2-diazidonaphthoquinone-5-sulfonyloxy)-1-hydroxyanthraquinone, 1,2-diazidonaphthoquinone-5-sulfonic acid-2,3,4-trihydroxy-benzophenone ester, 1,2-diazidonaphthoquinone-5-(N-dihyroabietyl)sulfonamide, a condensation product of 1,2-diazidonaphthoquinone-5-sulfonic acid chloride(2 moles) and 4,4′-diaminobenzophenone (1 mole), a condensation product of 1,2-diazidonaphthoquinone-5-sulfonic acid chloride (2 moles) and 4,4′-dihydroxy-1,1′-diphenylsulfone (1 mole), and a condensation product of 1,2-diazidonaphthoquinone-5-sulfonic acid chloride (1 mole) and purpurogallin (1 mole). In addition, the compounds having 1,2-diazidonaphthoquinone structure described in the following documents may also be used: Japanese Patent
Fukuzawa Junichi
Harada Takamasa
Kudo Takanori
Kurisaki Minoru
Takeda Takashi
Banerjee Krishna
Chu John S.
Clariant Finance (BVI) Limited
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