Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2001-03-14
2002-04-02
Barts, Samuel (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C560S205000, C560S211000, C568S665000, C568S664000, C568S667000
Reexamination Certificate
active
06365771
ABSTRACT:
TECHNICAL FIELD
The present invention relates to tricyclo[5.2.1.0
2,6
]decane compound or tricyclo[5.2.1.0
2,6
]dece-3-ene compound shown in the formula [1] below and the curable resin composition containing said compound described above
wherein A
1
and A
2
are independently hydrogen; or acryloyl group or methacryloyl group shown in the formula [2] below
wherein R
1
is hydrogen or C
1
-C
4
alkyl; and R
2
and R
3
are independently hydrogen or C
1
-C
10
alkyl; or 2-vinyloxyethyl group shown in the formula [3] below
—CH
2
CH
2
OCH═CH
2
[3]
wherein the dotted line is a single bond or double bond with the proviso that A
1
and A
2
are not hydrogen at the same time.
The compound in the present invention relates to the monomer used in the field of pattern style materials suitable for the lithography with active light radiation such as ultraviolet rays, far ultraviolet rays, electron rays, ion beam and X-rays, and the curable resin composition containing said monomer. Further, the compound in the present invention relates to the monomer raw materials agent, optical materials and adhesive agents by having reactive ehtylenic unsaturated groups within the molecule as well as the highly heat resistant tricyclodecane structure, and the curable resin composition containing said monomer.
BACKGROUND ART
Up to now, the compound shown in the formula below is known as the compound having more than one unsaturated groups in the molecule of alicyclic compound or as the main component of monomer raw materials for the overcoat agent composition for optical disk (JP Laid-Open Hei 1-121370).
The resin composition for optical raw materials consisting of the compound shown in the formula below as the main component of said composition is also known (JP Laid-Open Hei 2-115205).
In addition, the inventor of the present invention had already filed the patent application relating to tricyclo[5.2.1.0
2,6
]dece-3-ene-8,9-dicarboxylic acid diallyl (abbreviated as TDEA) shown in the formula below (JP Laid-Open Sho 60-156683).
However, polyester using TDEA have shown low reactivity of polymerization of allyl group and therefore the satisfactory result was not obtained in using said resin composition for acrylic optical raw materials.
Copolymer having adamantylmethacrylate unit of alicyclic polymer as a polymer compound with the clarity at 193 nm wavelength and yet with dry etching resistance [Takechi, S. et al., Journal of Photopolymer Science and Technology, 5 (3):439-446 (1992); and JP Laid-Open Hei 5-265212], poly (norbornylmethacrylate) [Endo, M. et al., Proceedings of IEDM], CA14-18, San Francisco (1992)] or copolymer having poly (isobornylmethacrylate) unit [Wallraff, G. M. et al., Journal of Vacuum Science and Technology, B11 (6):2783-2788 (1993)], and copolymer having poly (menthylmethacrylate) unit [JP Laid-Open Hei 8-82925] have been proposed.
On the other hand, aromatic derivatives such as 2,2-bis(4-(2-vinyloxy)ethoxy)phenyl)propane shown in the formula below
or aliphatic vinylether derivatives such as bis(2-vinyloxyethyl)ether, 1,2-bis[(2-vinyloxy)ethoxy]ethane and the like are well known as vinylether derivatives heretofore [Chemistry of Materials, 6 (10): 1854-1860 (1994)].
However, alicyclic derivatives having vinyloxyethyloxymethyl group at 8 and 9 positions of tricyclo[5.2.1.0
2,6
]dece-3-ene or tricyclo[5.2.1.0
2,6
]decane were not known at all.
The existing art described above do not contain residues which can manifest the difference in solubility before and after the light exposure within the residue unit of alicyclic group (adamantyl, norbornyl, isobornyl or menthyl) which result in dry etching resistance, and therefore the use as the resin component for the resist by preparing copolymer with co-monomer such as t-butylmethacrylate or tetrahydropyranylmethacrylate which can manifest the difference in solubility has been employed in the pertinent art heretofore. However, the patterning has been employed in the pertinent art heretofore. However, the patterning requires about 30-50% co-monomer content, and as a result, the effect of dry etching resistance due to alicyclic group structure was drastically reduced and their utility have been questionable.
The existing art heretofore in use do not have any polar site within the molecules and therefore adhesion to the silicon substrate is poor. In addition, sensitivity is low because of low solubility in alkaline developing aqueous solution, and furthermore, there is a shortcoming of dregs left in the developing solution in all likelihood.
DISCLOSURE OF INVENTION
The object of the present invention is to prepare the novel alicyclic compound suitable as photo-monomer for the resist raw materials by having high clarity at short wavelength ultraviolet light and by excelling in dry etching resistance due to tricyclo ring structure, and by showing adhesion for the substrate and high solubility in alkaline developing solution in addition to high sensitivity and greater resolution, as monomer for optic raw materials and disk overcoat materials by having high clarity, low birefringence and low water absorption rate, and as monomer for the coating raw materials such as EB curable coating by having high reactivity, high wear characteristics and water resistance and to provide the curable resin composition containing said compound.
The present inventors made the utmost effort in solving the problems described above. The present invention have been completed after the selection of tricyclodecanyl group as an alicyclic group in order to obtain high clarity and high dry etching resistance and the introduction of hydroxymethyl group as a polar substituent in order to achieve good adhesion for the substrate and high solubility in alkaline developing solution in addition to high sensitivity and greater resolution.
Thus, the present invention relates to tricyclo[5.2.1.0
2,6
]decane compound or tricyclo[5.2.1.0
2,6
]dece-3-ene compound shown in the formula [1] below
wherein A
1
and A
2
are independently hydrogen; or acryloyl group or methacryloyl group shown in the formula [2] below
wherein R
1
is hydrogen or C
1
-C
4
alkyl; and R
2
and R
3
are independently hydrogen or C
1
-C
10
alkyl; or 2-vinyloxyethyl group shown in the formula [3] below
—CH
2
CH
2
OCH═CH
2
[3]
wherein the dotted line is single bond or double bond with the proviso that A
1
and A
2
are not hydrogen at the same time, and the curable resin composition containing said compound therein.
C
1
-C
4
alkyl group in the definition of R
1
is straight or branched alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl and the like.
C
1
-C
10
alkyl group in the definition of R
2
and R
3
is also straight or branched alkyl group such as 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, nonyl, decyl and the like in addition to groups described above.
Following compounds described below may be abbreviated as shown in the left.
DOL: 8,9-bis(hydroxymethyl)tricyclo[5.2.1.0
2,6
]dece-3-ene
DH-DOL: 8,9-bis(hydroxymethyl)tricyclo[5.2.1.0
2,6
]decane
DH-DOLMA: acryloyloxymethyl-9-hydroxymethyltricyclo[5.2.1.0
2,6
]decane
DH-DOLMM: 8-methacryloyloxymethyl-9-hydroxymethyltricyclo[5.2.1.0
2,6
]decane
DH-DOLDA: 8,9-bis(acryloyloxymethyl)tricyclo[5.2.1.0
2,6
]decane
DH-DOLDM: 8,9-bis(methacryloyloxymethyl)tricyclo[5.2.1.0
2,6
]decane
DOLMV: 8(or 9)-hydroxymethyl-9(or 8)-(2-vinyloxyethyl)oxymethyl-tricyclo[5.2.1.0
2,6
]dece-3-ene
DH-DOLMV: 8-hydroxymethyl-9-(2-vinyloxyethyl)oxymethyl-tricyclo[5.2.1.0
2,6
]decane
DOLVE: 8,9-bis[(2-vinyloxyethyl)oxymethyl]tricyclo[5.2.1.0
2,6
]dece-3-ene
DH-DOLVE: 8,9-bis&l
Nihira Takayasu
Suzuki Hideo
Takigawa Shinichiro
Barts Samuel
Nissan Chemical Industries Ltd.
Price Elvis O.
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