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
1999-09-07
2001-02-06
Baxter, Janet (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
C430S281100, C430S325000
Reexamination Certificate
active
06183935
ABSTRACT:
TECHNICAL FIELD
The present invention relates to inorganic substance-containing photosensitive resin compositions useful for forming minute inorganic patterns, a process for producing the same, and a process for forming inorganic patterns.
BACKGROUND ART
As materials for forming inorganic patterns, there have been known photosensitive pastes made up with a photosensitive resin filled with or comprising inorganic particulates. Such photosensitive paste is coated or applied on a substrate (or base), and the coat layer is exposed patternwise through a given mask, developed, and baked or calcinated for eliminating an organic component(s) to form an inorganic pattern. Photosensitive pastes of such type are required to have a high inorganic component content and high sensitivity, and to be able to give high resolution. However, in a photosensitive paste, the concentration of inorganic particulates (filling factor) and photosensitive properties (e.g., sensitivity, resolution) are incompatible with each other. Therefore, when the filling factor of the inorganic particulates is low, upon heat-baking for elimination of organic components, an inorganic pattern largely shrinks or becomes much smaller in volume and is separated from the substrate, resulting in deterioration in adhesion. In addition, the profile of the pattern is deformed and the resolution is consequently deteriorated. On the other hand, when the content of the inorganic particulates is raised, exposed light is absorbed, reflected or scattered by the inorganic particulates and therefore the sensitivity and resolution are reduced. Moreover, it is difficult to form minute inorganic patterns having highly rectangular profiles and high aspect ratios with high precision using the above photosensitive paste.
To improve the dispersibility of inorganic particulates and thereby to improve the sensitivity and resolution, treatment over the surfaces of the inorganic particulates has been proposed. However, the dispersibility has not reached a sufficient level yet and the contrast between the exposed areas and non-exposed areas (the difference between the solubilities thereof to a developer) is low, and such surface treatment is not sufficient as to improve the resolution.
Accordingly, an object of the present invention is to provide a inorganic substance-containing photosensitive resin composition which is highly sensitive and capable of providing an inorganic pattern of high resolution even with a high inorganic component content, a process for producing the same, and a process for forming inorganic patterns.
Another object of the present invention is to provide an inorganic substance-containing photosensitive composition useful for forming an inorganic pattern which shows a sharply defined rectangular profile and has a high aspect ratio, a process for producing the same, and a process for forming inorganic patterns.
DISCLOSURE OF INVENTION
The inventors of the present invention did intensive research and found that the sensitivity of a photosensitive resin composition and the resolution of a pattern formed therefrom, even with a high inorganic component filling factor, can be maintained at high levels by improving the dispersibility of an inorganic component contained therein, and that the dispersibility can be improved by using a photosensitive resin, a condensable (hydrolytic polymerizable) organic metal compound and inorganic particulates having a functional group showing for example reactivity and photosensitivity in combination. The present invention is achieved based on the above findings.
To summarize, the inorganic substance-containing photosensitive resin composition of the present invention comprises (A) a photosensitive organic oligomer or polymer, (B) a condensable (hydrolytic polymerizable) organic metal compound or a condensate thereof, and (C) an inorganic filler having a functional group. The photosensitive organic oligomer or polymer (A) may be constituted of an oligomer or a polymer and a photosensitizer. The condensable organic metal compound (B) may be constituted of a silicon-containing compound or a silane coupling agent having a photosensitive group, or a condensate thereof. The functional group of the above inorganic filler (C) may be a photosensitive group and the inorganic filler (C) may be a monodispersed colloidal silica having a mean particle size of 2 to 100 nm.
The present invention includes a process for producing an inorganic substance-containing photosensitive resin composition which comprises mixing (A) a photosensitive organic oligomer or polymer, (B) a hydrolytic polymerizable organic metal compound or a condensate thereof, and (C) an inorganic filler having a functional group, and a process for forming an inorganic pattern which comprises coating or applying the above-described inorganic substance-containing photosensitive resin composition on a substrate or base, exposing the coated layer, developing the exposed layer to form a pattern, and baking the pattern.
BEST MODE FOR CARRYING OUT THE INVENTION
Photosensitive Polymer
The photosensitive organic oligomer or polymer (A) (hereinafter, referred to simply as a photosensitive polymer) may be constituted of (A1) an oligomer or polymer which itself has photosensitivity, or (A2) a photosensitive resin composition containing an oligomer or polymer and a photosensitizer. The latter, i.e., the photosensitive resin composition (A2) is usually employed.
Examples of (A1) the oligomer or polymer having sensitivity are diazonium salt group-containing polymers, azido group-containing polymers, and polymers having a photodimerizable functional group such as cinnamoyl group or cinnamylidene group (e.g., polyvinyl cinnamates).
As an oligomer or polymer constituting the photosensitive polymer (A2), use can be made of a variety of polymers having a polar or nonpolar group. The preferable photosensitive polymer has a polar group, for example, hydroxyl group, an alkoxy group, carboxyl group, an ester group, an ether group, a carbonate group, amide group or an N-substituted amide group (e.g., —NHC(O)—, >NC(O)—), nitrile group, glycidyl group, or a halogen atom. The photosensitive polymer may be a polymerizable oligomer or polymer having a polymerizable group such as (meth)acryloyl group and allyl group.
Examples of the hydroxyl group-containing polymer and a derivative thereof are polyvinyl alcohol-series polymers, polyvinyl acetals, ethylene-vinylalcohol copolymers, phenolic resins, novolak resins, methylolmelamine, and derivatives thereof (e.g., acetalized polymers or compounds, hexamethoxymethylmelamine). Examples of the carboxyl group-containing polymer and a derivataive thereof are homopolymers and copolymers containing a polymerizable unsaturated carbonic acid such as (meth)acrylic acid, maleic anhydride, and itaconic acid, and esters thereof. Examples of the ester group-containing polymers are homopolymers and copolymers containing a monomer such as a vinyl ester (e.g., vinyl acetate) and a (meth)acrylic acid ester (e.g.,methyl methacrylate), (e.g., polyvinyl acetate, ethylene-vinyl acetate copolymer, and (meth)acrylic resins); saturated polyesters; unsaturated polyesters; vinyl ester resins; diallyl phthalate resins; and cellulose esters. As a polymer having an ether group, there may be exemplified polyalkylene oxides, polyoxyalkylene glycols, polyvinyl ethers, and silicone resins. As a carbonate group-containing polymer, there may be exemplified bisphenol A-based polycarbonates.
As the above polymers having an amide group or a substituted amide group, there may be exemplified polyoxazoline or N-acylated polyalkylene imines (polymers corresponding to the above polyoxazoline, such as polymers having an N-acylamino group such as N-acetylamino group and N-polypropionylamino group); poly(vinylpyrrolidone) and derivatives thereof; polyurethane-series polymers; polyureas; nylons or polyamide-series polymers; polymers having a biuret bond; polymers having an allophanate bond; and protein such as gelatin.
As a monomer which constitutes the above polyoxazoline,
Hanabata Makoto
Yasuda Tokugen
Ashton Rosemary
Baxter Janet
Kansai Research Institute
Pillsbury Madison & Sutro LLP
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