Radiation imagery chemistry: process – composition – or product th – Radiation modifying product or process of making – Screen other than for cathode-ray tube
Reexamination Certificate
2000-11-29
2002-12-17
McPherson, John A. (Department: 1756)
Radiation imagery chemistry: process, composition, or product th
Radiation modifying product or process of making
Screen other than for cathode-ray tube
C430S281100, C430S288100, C522S008000, C522S009000, C522S013000, C522S016000, C522S018000, C106S031130
Reexamination Certificate
active
06495298
ABSTRACT:
FIELD OF TECHNOLOGY
This invention relates to photopolymerizable resin compositions which are useful for applications such as insulating films for semiconductors, resists for semiconductors, protective films for color filters, colored films, and insulating spacers for touch panels.
BACKGROUND TECHNOLOGY
Photopolymerizable resin compositions are exposed to light, generally with the use of UV as light source, in their applications to letterpress, relief images, photoresists, and the like and the resin compositions of this type contain a resin component which constitutes the main body of an image to be formed and a photopolymerization initiator which, upon exposure to light such as UV, generates an active species for polymerization.
From the standpoint of environmental problems and ease of obtaining a large difference in solubility before and after exposure to light in recent years, there is a preference for an aqueous solution of alkali to an organic solvent in the development step in the application of photopolymerizable resin compositions. In such a case, a combination of an addition-polymerizable compound containing an ethylenically unsaturated group and a resin soluble in an aqueous solution of alkali is used preferentially for the resin component which constitutes the main body of an image. There is a demand for higher sensitivity for this type of photopolymerizable resin compositions and numerous studies are in progress on photopolymerization initiators in order to enhance the sensitivity.
Many substances are known already for photopolymerization initiators; for example, benzoin and its derivatives and substituted and unsubstituted quinones [Photopolymer Handbook, Chapter 6, edited by Photopolymer Konwakai (in Japanese)]. These compounds, however, are not sufficiently sensitive to the i-line (365 nm), h-line (405 nm) and g-line (437 nm) mainly emitted by a commonly used mercury vapor lamp.
A combination of benzophenone, a diaminobenzophenone compound, and an N-phenylglycine compound has been proposed for use as a photopolymerization initiator in order to obtain photopolymerizable resin compositions with enhanced sensitivity in the range 300-450 nm [Japan Tokkyo Koho Hei 4-27541 (1992)].
However, when a photopolymerizable resin composition containing this combination of benzophenone, a diaminobenzophenone compound, and an N-phenylglycine compound is exposed to light whose main component is the i-line, the composition lacks sufficient sensitivity to undergo curing on the surface when the film thickness is less than 10 &mgr;m during exposure to light. On the other hand, when the film thickness exceeds 10 &mgr;m during exposure to light, the addition of the diaminobenzophenone compound is diminished in order to advance the photocuring in the inside until the adherence of a pattern during development is secured; then the generation of radicals from the photopolymerization initiator diminishes, which leads to the hindrance of the surface curing and roughening of the surface of the film after development.
Methods for incorporating a halomethyltriazine as photopolymerization initiator into colored photopolymerizable compositions for use in color filters are known [Japan Tokkyo Koho Sho 59-28328 (1984), Japan Tokkyo Koho Hei 5-88243 (1993), Japan Kokai Tokkyo Koho Hei 6-167808 (1994), and Japan Kokai Tokkyo Koho Hei 6-27662 (1994)].
The aforementioned photopolymerizable compositions containing a halomethyltriazine are colored yellow, although highly sensitive, and posed a problem of reducing the transmission of blue filters in particular and the compound in question was a cause of extensive discoloration during heating.
There is a demand for displays with high color purity and brightness for color liquid crystal displays in recent years. In the case of color filters with high color purity, light in the ultraviolet region reaches the deep part of the film with difficulty and this poses problems such as poor adhesion of a pattern due to insufficient curing in the deep part of the film and peeling off of a pattern during development. Moreover, absorption of the photopolymerization initiator and yellowing after heat treatment sometimes diminished the brightness of color filters.
Accordingly, an object of this invention is to provide a photopolymerizable resin composition which excels in resolution, development latitude and surface curability and shows enhanced sensitivity particularly to the i-line and, furthermore, to provide a photopolymerizable resin composition which is curable even at a film thickness of, say, 10 &mgr;m or more and, when used in a colored polymerizable composition, is highly transparent and does not significantly affect the color characteristics. Another object of this invention is to provide a photopolymerizable resin composition which is highly sensitive to UV, not only to the i-line but also to lines in the range to the g-line.
A further object of this invention is to provide a blue ink with excellent color characteristics. A still further object of this invention is to provide a film to be obtained by applying the aforementioned photopolymerizable resin composition or a blue ink followed by curing and to provide a color filter containing said film as blue filter or protective film.
DISCLOSURE OF THE INVENTION
Thus, this invention relates to a photopolymerizable resin composition comprising a resin and/or a resin-forming ingredient as component (A) and a photopolymerization initiator (B), wherein the component (A) comprises an addition-polymerizable compound (A1) which shows a boiling point of 100° C. or higher at normal pressure and has at least 2 ethylenically unsaturated groups in the molecule and the component (B) comprises a diaminobenzophenone compound (B1) represented by the following general formula (1)
(in which R is a hydrogen atom or an alkyl group with 1-3 carbon atoms, either identical with or different from each other), an N-phenylglycine compound (B2) represented by the following general formula (2)
(in which R is an alkyl group with 1-8 carbon atoms, R′ is a hydrogen atom or an alkyl group with 1-8 carbon atoms, n is an integer in the range 0-5, and R may be identical with or different from each other when n is 2 or more), and at least one kind of compound selected from a group of a 3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3) represented by the following general formula (3)
(in which R is an alkyl group with 1-8 carbon atoms, identical with or different from each other), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), and a 1,3,5-triazine derivative (B5) containing at least one trihalomethyl group as substituent.
This invention also relates to the aforementioned photopolymerizable resin composition wherein the component (A) composed of a resin and/or a resin-forming ingredient comprises the addition-polymerizable compound (A1) and an alkali-soluble resin (A2) and the ratio (A1)/(A2) by weight is 10/90-90/10.
This invention further relates to the aforementioned photopolymerizable resin composition which comprises 100 parts by weight of the component (A), 0.05-2.0 parts by weight of a diaminobenzophenone compound (B1), 0.2-2 parts by weight of an N-phenylglycine compound (B2), 0-2.5 parts by weight of a 3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3), 0-5 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), and 0-1 part by weight of a 1,3,5-triazine derivative (B5). Likewise, this invention relates to the aforementioned photopolymerizable resin composition which comprises 100 parts by weight of the component (A), 0.05-2.0 parts by weight of a diaminobenzophenone compound (B1), 0.2-2 parts by weight of an N-phenylglycine compound (B2), 0.1-2.5 parts by weight of a 3,3′,4,4′-tetra(alkylperoxycarbonyl)benzophenone (B3), 1-5 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (B4), and 0-0.5 part by weight of a 1,3,5-triazine derivative (B5). Still more, this
Fujishiro Koichi
Higashi Manabu
McPherson John A.
Nippon Steel Chemical Co. Ltd.
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