1. A corneal imaging device provided with an optical system for photographing a corneal portion of an eye, the optical system including an illumination optical system configured to irradiate illumination light toward a cornea and a light receiving optical system placed in a position inclined with respect to an optical axis of the illumination optical system configured to receive reflection light from the cornea by a photodetector,
wherein the corneal imaging device includes a light-limiting part provided in an optical path of the optical system for photographing the corneal portion of the eye and configured to limit light asymmetrically with respect to an optical axis.
2. The corneal imaging device according to claim 1, wherein the light-limiting part is placed in a position away from a condensing point of the light.
3. The corneal imaging device according to claim 1, wherein the light-limiting part is configured to allow light having passed through a central part of an objective lens provided in the light receiving optical system to pass toward the photodetector, but asymmetrically limit light having passed through a peripheral part of the objective lens.
4. The corneal imaging device according to claim 1, wherein the optical system for photographing the corneal portion is an optical system to photograph endothelial cells of the cornea, the illumination optical system is configured to irradiate the illumination light to the cornea from an oblique direction, and the light receiving optical system is configured to receive the reflection light from the cornea in a specular direction at the cornea.
5. The corneal imaging device according to claim 1, wherein
the illumination optical system and the light receiving optical system are arranged symmetrically with respect to a central axis,
the light-limiting part is configured to:
allow the light having passed through the central part of the objective lens provided in the light receiving optical system to pass through toward the photodetector; and
allow a light part of the light having passed through the peripheral part of the objective lens on a side close to the central axis to pass through and limit a light part of the light having passed through the peripheral part of the objective lens on an opposite side to the central axis side.
6. The corneal imaging device according to claim 1, wherein
the illumination optical system and the light receiving optical system are arranged symmetrically with respect to a central axis,
the light-limiting part is configured to:
allow the light having passed through the central part of the objective lens provided in the light receiving optical system to pass through toward the photodetector; and
allow a light part of the light having passed through the peripheral part of the objective lens on an opposite side to a side close to the central axis to pass through and limit a light part of the light having passed through the peripheral part of the objective lens on the central axis side.
7. The corneal imaging device according to claim 1, further including an observation optical system configured to observe a front image of an anterior segment of an examinee’s eye,
wherein the illumination optical system and the light receiving optical system are arranged symmetrically with respect to a central axis, and
an observation optical axis of the observation optical system is the central axis.
8. The corneal imaging device according to claim 1, wherein the light-limiting part is placed in the light receiving optical system to asymmetrically limit the reflection light from the cornea.
9. The corneal imaging device according to claim 1, wherein the light-limiting part is placed in the illumination optical system to asymmetrically limit the illumination light.
10. The corneal imaging device according to claim 1, wherein the light-limiting part is provided with an aperture portion formed with an asymmetric aperture with respect to the optical axis and a light shielding portion formed outside the aperture portion.
11. The corneal imaging device according to claim 1, wherein the light-limiting part is one of an asymmetric diaphragm, a lens holder having an asymmetric opening, and an asymmetric coating to an optical member.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
We claim:
1. A polymer prepared by polymerizing a mixture of monomers, comprising:
at least one monomer having an acid labile group; and
at least one -oxo ester containing monomer which is free of a lactone group.
2. A polymer according to claim 1, wherein said -oxo ester containing monomer comprises from about 2 to about 20% by weight of the polymer.
3. A polymer according to claim 1, wherein said -oxo ester containing monomer has an ethylenically unsaturated ester portion and a -oxo group containing portion covalently bonded to the oxygen of the ester group of said ethylenically unsaturated ester portion through a covalent bond between the oxygen of the ethylenically unsaturated ester portion and the CHR1 group of the -oxo group containing portion, said covalent bond being represented as follows:
OCHR1
wherein R1 is selected from the group consisting of: alkyl, haloalkyl and an alkylene residue.
4. A polymer according to claim 3, wherein said ethylenically unsaturated ester portion is represented by formula 3 or formula 4:
44
wherein R is selected from the group consisting of: hydrogen, C1-4 alkyl group, CH2CN, CH2OR4, CH2C(O)OR4, CH2OC(O)R4, wherein R4 is selected from the group consisting of: substituted or unsubstituted C1-C10 linear, branched, or cyclic alkyl; substituted or unsubstituted C1-C10 linear, branched, cyclic or alicyclic alkylene group; and n is an integer of from 0 to 2; and
wherein said covalently bonded -oxo group containing portion is represented by the formulas 5, 6a, 6b, 7, 8, 9 or 10:
45
wherein in formula 5, R1 and R2 together represent an alkylene group of 2 to 5 carbon atoms to form a 4-, 5-, 6- or 7-membered ring having a -oxo group; wherein in formula 6a, R2 is selected from the group consisting of: hydrogen and a C1-4 alkyl group and R1 represents an alkylene group of 1 to 4 carbon atoms to form a 4-, 5-, 6- or 7-membered ring having a -oxo group;
wherein in formula 6b, R1 is selected from the group consisting of: hydrogen and a C1-4 alkyl group and R2 represents an alkylene group of 2 to 5 carbon atoms to form a 4-, 5-, 6- or 7-membered ring having a -oxo group;
wherein in formula 7, each of R1 and R2 is independently selected from the group consisting of: hydrogen, substituted or unsubstituted linear, branched, cyclic C1-10 alkyl group; C1-C10 fluoroalkyl and substituted or unsubstituted linear, branched, cyclic or alicyclic C7-15 alkylene group;
wherein in formula 8, each of R1, R2 and R3 is independently selected from the group consisting of: hydrogen, substituted or unsubstituted linear, branched, cyclic C1-C10 alkyl group; C1-C10 fluoroalkyl and substituted or unsubstituted linear, branched, cyclic or alicyclic C7-15 alkylene group;
wherein in formula 9, each of R1, R2 and R3 is independently selected from the group consisting of: hydrogen, substituted or unsubstituted linear, branched, cyclic C1-10 alkyl group; C1-C10 fluoroalkyl and substituted or unsubstituted linear, branched, cyclic or alicyclic C7-15 alkylene group; and
wherein in formula 10, each of R1 and R2 is independently selected from the group consisting of: hydrogen, substituted or unsubstituted linear, branched, cyclic C1-10 alkyl group; C1-C10 fluoroalkyl and substituted or unsubstituted linear, branched, cyclic or alicyclic C7-15 alkylene group.
5. A polymer according to claim 4, wherein said R group in said ethylenically unsaturated ester portion in formula 4 is selected from the group consisting of: hydrogen, methyl, ethyl, n-butyl, i-butyl, n-propyl, i-propyl, CH2CN, CH2OMe, CH2O-adamantyl, CH2OCH2-adamantyl, CH2O-cyclohexyl, CH2O-norbornyl, CH2OCF3, CH2C(O)OMe, CH2C(O)O-cyclopentyl, CH2C(O)O-i-propyl, CH2C(O)CF3, CH2C(O)OCH2-cyclohexyl, CH2OC(O)CH2Br, CH2OC(O)CH2Cl, CH2OC(O)CF3, CH2OC(O)Me, CH2OC(O)-norbornyl, CH2OC(O)-adamantyl, CH2OC(O)-cyclohexyl and CH2OC(O)-tert-butyl.
6. A polymer according to claim 4, wherein said covalently bonded -oxo group containing portion in formula 6a is selected from the group consisting of:
46
7. A polymer according to claim 4, wherein said covalently bonded -oxo group containing portion in formula 6b is selected from the group consisting of:
47
8. A polymer according to claim 4, wherein each of said R1 and R2 groups in said formula 7 is selected from the group consisting of: hydrogen, methyl, ethyl, t-butyl, butyl, propyl, i-propyl, amyl, t-amyl, sec-amyl, octyl, cyclohexyl, cyclohexylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexylethyl, 4-methoxybutyl, trifluoromethyl, 1,1,1-trifluoroethyl, nonafluorobutyl and norbornyl.
9. A polymer according to claim 8, wherein said covalently bonded -oxo group containing portion in formula 7 is selected from the group consisting of:
48
10. A polymer according to claim 4, wherein each of said R1 and R2 groups in said formula 8 is selected from the group consisting of: hydrogen, methyl, ethyl, t-butyl, butyl, propyl, i-propyl, amyl, t-amyl, sec-amyl, octyl, cyclohexyl, cyclohexylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexylethyl, 4-methoxybutyl, trifluoromethyl, 1,1,1-trifluoroethyl, nonafluorobutyl and norbornyl; and R3 is selected from the group consisting of: methyl, ethyl, t-butyl, butyl, propyl, i-propyl, amyl, t-amyl, sec-amyl, octyl, cyclohexyl, cyclohexylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexylethyl, 4-methoxybutyl, trifluoromethyl, 1,1,1-trifluoroethyl, nonafluorobutyl, adamantyl and norbornyl.
11. A polymer according to claim 10, wherein said covalently bonded -oxo group containing portion in formula 8 is selected from the group consisting of:
49
12. A polymer according to claim 4, wherein each of said R1 and R2 groups in said formula 9 is selected from the group consisting of: hydrogen, methyl, ethyl, t-butyl, butyl, propyl, i-propyl, amyl, t-amyl, sec-amyl, octyl, cyclohexyl, cyclohexylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexylethyl, 4-methoxybutyl, trifluoromethyl, 1,1,1-trifluoroethyl, nonafluorobutyl and norbornyl; and R3 is selected from the group consisting of: methyl, ethyl, t-butyl, butyl, propyl, i-propyl, amyl, t-amyl, sec-amyl, octyl, cyclohexyl, cyclohexylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexylethyl, 4-methoxybutyl, trifluoromethyl, 1,1,1-trifluoroethyl, nonafluorobutyl, adamantyl and norbornyl.
13. A polymer according to claim 12, wherein said covalently bonded -oxo group containing portion in formula 8 is selected from the group consisting of:
50
14. A polymer according to claim 4, wherein each of said R1 and R2 groups in said formula 10 is selected from the group consisting of: hydrogen, methyl, ethyl, t-butyl, butyl, propyl, i-propyl, amyl, t-amyl, sec-amyl, octyl, cyclohexyl, cyclohexylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexylethyl, 4-methoxybutyl, trifluoromethyl, 1,1,1-trifluoroethyl, nonafluorobutyl and norbornyl; and R3 is selected from the group consisting of: methyl, ethyl, t-butyl, butyl, propyl, i-propyl, amyl, t-amyl, sec-amyl, octyl, cyclohexyl, cyclohexylmethyl, cyclopentyl, cyclopentylmethyl, cyclohexylethyl, 4-methoxybutyl, trifluoromethyl, 1,1,1-trifluoroethyl, nonafluorobutyl, adamantyl and norbornyl.
15. A polymer according to claim 14, wherein said covalently bonded -oxo group containing portion in formula 10 is selected from the group consisting of:
51
16. A polymer according to claim 4, wherein said -oxo ester containing monomer is selected from the group consisting of:
52
17. A polymer according to claim 4, wherein said -oxo ester-containing monomer is selected from the group consisting of: 3-acryloyl-2-butanone, ethyl lactate acrylate, tetrahydrofurfuryl norbornene carboxylate, tetrahydrofurfuryl acrylate, ethyl ethoxy norbornene carboxylate and ethyl lactyl norbornene carboxylate.
18. A polymer according to claim 1, wherein said mixture of monomers, further comprises:
at least one comomomer selected from the group consisting of: styrene, naphthalene acrylate, naphthalene methacrylate, vinyl acetate, vinyl chloride, allyltrimethyl silane, vinyltrimethyl silane, norbornene, cyclohexene, maleic anhydride, dialkyl fumarate, maleimide, N-alkylmaleimide, N-arylmaleimide, sulfur dioxide, carbon monoxide, acrylamide, acrylate ester, methacrylate ester and mixtures thereof.
19. A polymer according to claim 18, wherein said mixture of monomers comprises at least one monomer selected from the group consisting of: maleic anhydride, norbornene, t-butyl acrylate, allyltrimethylsilane, naphthalene methacrylate, and methylcyclohexyl norbornene carboxylate.
20. A polymer according to claim 1, selected from the group consisting of: poly(norbornene-maleic anhydride-t-butylacrylate-3-acrolyl-2-butanone), poly(norbornene-maleic anhydride-t-butylacrylate-tetrahydrofurfuryl acrylate), poly(norbornene-maleic anhydride-t-butylacrylate-ethyl lactate acrylate), poly(norbornene-maleic anhydride-t-butylacrylate-diethylene glycol acrylate), poly(allyltrimethylsilane-maleic anhydride-t-butylacrylate-3-acryloyl-2-butanone), poly(allyltrimethylsilane-maleic anhydride-t-butylacrylate-1-naphthalene methylacrylate-3-acryloyl-2-butanone), poly(allyltrimethylsilane-maleic an hydride-t-butylacrylate-1-naphthalene methylacrylate-tetrahyurofurfuryl acrylate), poly(tetrahydrofurfuryl norbornene carboxylate-maleic anhydride-methylcyclohexyl norbornene carboxylate), poly(ethoxyethyl norbornene carboxylate-maleic anhydride-methylcyclohexyl norbornene carboxylate, poly(ethyl lactate norbornene carboxylate-maleic anhydride-methylcyclohexyl norbornene carboxylate) and mixtures thereof.
21. A radiation sensitive photoresist composition comprising:
(a) a polymer prepared by polymerizing a mixture of monomers, comprising: at least one monomer having an acid labile group; and at least one -oxo ester containing monomer which is free of a lactone group;
(b) a photoacid generator compound; and
(c) a solvent capable of dissolving components (a) and (b).
22. A radiation sensitive photoresist composition according to claim 21, wherein said polymer is selected from the group consisting of: poly(norbornene-maleic anhydride-t-butylacrylate-3-acrolyl-2-butanone), poly(norbornene-maleic anhydride-t-butylacrylate-tetrahydrofurfuryl acrylate), poly(norbornene-maleic anhydride-t-butylacrylate-ethyl lactate acrylate), poly(norbornene-maleic anhydride-t-butylacrylate-diethylene glycol acrylate), poly(allyltrimethylsilane-maleic anhydride-t-butylacrylate-3-acryloyl-2-butanone), poly(allyltrimethylsilane-maleic anhydride-t-butylacrylate-1-naphthalene methylacrylate-3-acryloyl-2-butanone), poly(allyltrimethylsilane-maleic anhydride-t-butylacrylate-1-naphthalene methylacrylate-tetrahydrofurfuryl acrylate), poly(tetrahydrofurfuryl norbornene carboxylate-maleic anhydride-methylcyclohexyl norbornene carboxylate), poly(ethoxyethyl norbornene carboxylate-maleic anhydride-methylcyclohexyl norbornene carboxylate, poly(ethyl lactate norbornene carboxylate-maleic anhydride-methylcyclohexyl norbornene carboxylate) and mixtures thereof.
23. A method of producing a resist image on a substrate, comprising:
coating said substrate with a radiation sensitive photoresist composition comprising:(a) a polymer prepared by polymerizing a mixture of monomers, comprising: at least one monomer having an acid labile group; and at least one -oxo ester containing monomer which is free of a lactone group; (b) a photoacid generator compound; and (d) a solvent capable of dissolving components (a) and (b);
imagewise exposing said radiation sensitive photoresist composition to actinic radiation to produce an exposed photoresist composition;
developing said exposed photoresist composition with a developer to produce a resist image.
24. A method of producing a resist image on a substrate according to claim 23, wherein said polymer in said radiation sensitive photoresist composition is selected from the group consisting of: poly(norbornene-maleic anhydride-t-butylacrylate-3-acrolyl-2-butanone), poly(norbornene-maleic anhydride-t-butylacrylate-tetrahydrofurfuryl acrylate), poly(norbornene-maleic anhydride-t-butylacrylate-ethyl lactate acrylate), poly(norbornene-maleic anhydride-t-butylacrylate-diethylene glycol acrylate), poly(allyltrimethylsilane-maleic anhydride-t-butylacrylate-3-acryloyl-2-butanone), poly(allyltrimethylsilane-maleic anhydride-t-butylacrylate-1-naphthalene methylacrylate-3-acryloyl-2-butanone), poly(allyltrimethylsilane-maleic anhydride-t-butylacrylate-1-naphthalene methylacrylate-tetrahydrofurfuryl acrylate), poly(tetrahydrofurfuryl norbornene carboxylate-maleic anhydride-methylcyclohexyl norbornene carboxylate), poly(ethoxyethyl norbornene carboxylate-maleic anhydride-methylcyclohexyl norbornene carboxylate, poly(ethyl lactate norbornene carboxylate-maleic anhydride-methylcyclohexyl norbornene carboxylate) and mixtures thereof.
25. A resist image on a substrate, prepared by the method of claim 23.