Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Radiation sensitive composition or product or process of making
Reexamination Certificate
1998-10-07
2001-02-13
Hamilton, Cynthia (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Imaging affecting physical property of radiation sensitive...
Radiation sensitive composition or product or process of making
C430S288100, C430S018000, C430S330000, C430S326000, C522S026000, C204S478000
Reexamination Certificate
active
06187509
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to positive type electrodeposition photoresist compositions, as well as to formation processes, using the compositions, for pattern useful to circuit formation of electronic devices, materials for printing etc.
2. Description of the Prior Art
Currently, positive type photoresists are widely used for formation of circuit patterns of electronic devices etc. As positive type aqueous resist compositions used for these applications, in many cases, resins, which dissolve or disperse in water by neutralization and chemically bound with a quinone diazide compound, are used in the form of aqueous solution or dispersion.
These compositions form a resist film by utilizing a reaction in which the quinone diazide group is photo-decomposed when irradiated with an ultraviolet light and forms an indenecarboxylic acid via a ketene.
The resist compositions using quinone diazide compound, however, are weakly photoreactive to a visible light and hence, there are problems of insufficient resolution etc. in case a formation of a very fine pattern is necessary. Moreover, the quinone diazide group is unstable in aqueous systems, and hence, there is a difficulty in using the composition containing a quinone diazide group in applications that require prolonged stability of the composition in a bath as in the electrodeposition coating process.
The present inventors previously proposed, as positive type electrodeposition photoresist compositions replacing these, a composition sensitive also to a visible light comprising a polymer having carboxyl group(s) and occasionally phenolic hydroxyl group(s), a compound having a plurarity of vinyl ether groups, and a compound which is decomposed and generates an acid when irradiated with an actinic ray (U.S. Pat. No. 5,527,656; Japanese Laid-open Patent Publications No. 313134/1994, 313135/1994, and 313136/1994. These compositions are photosensitive electrodeposition compositions which function according to a mechanism that the film formed from them becomes insoluble in solvents and aqueous alkaline solutions through crosslinking by an addition reaction between carboxyl group(s) and vinyl ether group(s) when heated, and when it is further irradiated with an actinic ray and then heated, the exposed portions become soluble in solvents and aqueous alkaline solutions again as the crosslinked structure is severed by the catalytic action of the acid generated by the irradiation.
These compositions have advantages such as having high transparency to actinic rays, because they need not contain a large amount of a functional group of high extinction coefficient unlike resists using quinone diazide as a photosensitizer and having high sensitivity as positive type photosensitive composition because the acid generated at the exposed portions acts as catalyst, when heated, to sever the crosslinked structure in the form of a chain reaction.
However, the heating time is required to be shortened in respect of productivity, when these photosensitive electrodeposition compositions are coated on a substrate and heated for crosslinking. When a shortening of the time is tried by heating at a higher temperature than 100° C., there is the problem that the compound, which generates an acid when irradiated with an actinic ray, existing in said photosensitive electrodeposition composition, generates an acid already before being irradiated by a visible light and thus the whole formed film is dissolved when developed. Therefore, an improvement of the thermal stability of said photosensitive electrodeposition composition is strongly demanded in said technical field.
SUMMARY OF THE INVENTION
The present inventors made an intensive study to solve problems the above-mentioned photosensitive electrodeposition compositions have. As a result, they have found that the above-mentioned problems can be solved by using naphthalimidylsulphonate, as the compound which is decomposed and generates an acid when irradiated with a visible light, in combination with a sensitizing dye and completed the present invention.
Thus, according to an aspect of the present invention, there is provided a positive type electrodeposition photoresist composition characterized by neutralizing by a basic compound and dissolving or dispersing in an aqueous medium a composition comprising (A) a polymer having 0.5-10 equivalents of carboxyl group(s) and optionally having more than 1 equivalent of hydroxy-phenyl group(s) per kg polymer; (B) a compound having at least two vinyl ether groups per molecule; (C) a compound, which generates an acid when irradiated with a visible light, represented by the general formula wherein R represents
wherein R represent
group (where R
1
, R
2
and R
3
each independently represents hydrogen atom or fluorine atom),
and (D) a sensitizing dye;
as well as a process for pattern formation using such a composition.
Furthermore, according to another aspect of the present invention, there is provided a positive type electrodeposition photoresist composition characterized by neutralizing by a basic compound and dissolving or dispersing in an aqueous medium a composition comprising (A′) a polymer having 0.5-10 equivalents of carboxyl group(s) per kg polymer; (A″) a polymer having more than 1 equivalent of hydroxyphenyl group(s) per kg polymer;
(B) a compound having at least two vinyl ether groups per molecule; (C) a compound, which generates an acid when irradiated with a visible light, represented by the above-mentioned general formula (I); and (D) a sensitizing dye; as well as a process for pattern formation using such a composition.
The compositions of the present invention are highly sensitive to a visible light, especially to Ar laser having stable emission of radiation in a visible area of wavelength 488 nm or 514.5 nm, have even no problem of film dissolution during development in the pattern formation procedure due to a high thermal stability, have an excellent contrast of the formed pattern, and are useful for such applications as positive type photoresist, printing materials etc.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is hereinafter described in more detail.
(A) Polymer having Carboxyl Group(s) and Optionally having Hydroxyphenyl Group(s)
The polymer (A) used in the positive type electrodeposition photoresist composition according to the first aspect of the present invention is a film-forming polymer having at least one carboxyl group per molecule and optionally having hydroxyphenyl group(s). The polymers having only carboxyl group(s) include, for example, homopolymers of a carboxyl group-containing polymerizable unsaturated monomer; copolymers of said carboxyl group-containing monomer and another monomer copolymerizable therewith; a resin of polyester type, polyurethane type, polyamide type or other types having carboxyl group(s) in the molecular chain or at the molecular end(s). The polymers having both carboxyl group(s) and hydroxyphenyl group(s) include, for example, copolymers of a hydroxystyrene such as p-hydroxystyrene and a carboxyl group-containing polymerizable unsaturated monomer; copolymers of a hydroxystyrene and said carboxyl group-containing monomer, and another copolymerizable monomer and the like.
The above-mentioned carboxyl group-containing polymerizable unsaturated monomers include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid etc. The other monomers copolymerizable with these carboxyl group-containing polymerizable unsaturated monomers and/or a hydroxystyrene include, for example, C
1
-C
12
alkyl esters of (meth)acrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate and the like; C
2
-C
6
hydroxyalkyl esters of (meth)acrylic acid, such as hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate a
Hasegawa Takeya
Imai Genji
Kogure Hideo
Hamilton Cynthia
Kansai Paint Co. Ltd.
Wenderoth , Lind & Ponack, L.L.P.
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