Photoresist composition

Abstract

A photoresist composition comprising: a resin which has a structural unit represented by formula (I): ##STR00001##
wherein R.sup.1 represents a hydrogen atom, a halogen atom, or a C1 to C6 alkyl group which optionally has a halogen atom, and R.sup.2 represents a C1 to C42 hydrocarbon group which optionally has a substituent; an alkali-soluble resin; an acid generator; and a solvent.

Claims

1. A photoresist composition comprising: a resin (A1); a novolak resin (A2); another resin (A3); an acid generator; and a solvent, wherein the acid generator is a compound which has a structure represented by formula (B1): ##STR00082## where R.sup.b1 represents a C1-C18 hydrocarbon group which optionally has a fluorine atom and in which a methylene group optionally has been replaced by an oxygen atom or a carbonyl group, and wherein the resin (A1) consists of a structural unit represented by formula (I): ##STR00083## wherein R.sup.1 represents a hydrogen atom, a halogen atom, or a C1 to C6 alkyl group which optionally has a halogen atom, and R.sup.2 represents a C1 to C42 hydrocarbon group which optionally has a substituent; and at least one selected from the group consisting of a structural unit represented by formula (a1-1), a structural unit represented by formula (a1-2), a structural unit represented by formula (a2-2), a structural unit represented by formula (a2-3), a structural unit represented by formula (a2-4) and a structural unit having a lactone ring and no acid-labile group: ##STR00084## wherein R.sup.a1, R.sup.a2 and R.sup.a3 each independently represent a C1-C8 alkyl group or a C3 to C20 alicyclic hydrocarbon group, two of R.sup.a1, R.sup.a2 and R.sup.a3 together may represent one C2 to C20 divalent hydrocarbon group where a methylene group can be replaced by an oxygen atom or a sulfur atom, R.sup.a1′ and R.sup.a2′ each independently represent a hydrogen atom or a C1 to C12 hydrocarbon group, R.sup.a3′ represents a hydrogen atom or a C1 to C20 hydrocarbon group, and one of R.sup.a1′ and R.sup.a2′ together with R.sup.a3′ may represent one C2 to C20 divalent heterocyclic group where a methylene group can be replaced by an oxygen atom or a sulfur atom, R.sup.a4 and R.sup.a5 each independently represent a hydrogen atom or a methyl group, R.sup.a6 represents a C1 to C6 alkyl group or a C1 to C6 alkoxy group, and m represents an integer of 0 to 4; ##STR00085## wherein R.sup.a8 and R.sup.a9 each independently represent a hydrogen atom or a methyl group, R.sup.a11 represents a hydrogen atom, or a C1 to C20 primary or secondary hydrocarbon group, R.sup.a12 each independently represents a C1 to C6 primary or secondary alkyl group, L.sup.a1 each independently represents a C2 to C6 alkanediyl group where carbon atoms bonded to an oxygen atom is a primary or secondary carbon atom, and n represents an integer of 1 to 30; ##STR00086## wherein R.sup.a13 independently represents a hydrogen atom or a methyl group, R.sup.a14 represents a C1 to C6 alkyl group or a C1 to C6 alkoxy group, R.sup.a15 each independently represents a C1 to C12 primary or secondary hydrocarbon group where a methylene group can be replaced by an oxygen atom or a carbonyl group provided that the carbon group bonded to the oxygen atom neighboring the benzene ring is not replaced by an oxygen atom, m″ and m′″ each independently represent an integer of 0 to 4 provided that the sum of them is 5 or less, and wherein the another resin (A3) has a structural unit having an acid-labile group other than a structural unit represented by formula (I).

2. The photoresist composition according to claim 1, wherein R.sup.2 represents a C1 to C20 linear aliphatic hydrocarbon group, or a C3 to C20 branched aliphatic hydrocarbon group.

3. The photoresist composition according to claim 1, wherein the resin (A1) has a structural unit selected from the group consisting of a structural unit represented by formula (a2-2) and a structural unit represented by formula (a2-3) and a structural unit having a lactone ring and no acid-labile group.

4. The photoresist composition according to claim 3, wherein the resin (A1) has a structural unit selected from the group consisting of the structural unit represented by formula (a2-3) and the structural unit having a lactone ring and no acid-labile group.

5. The photoresist composition according to claim 1, wherein the weight of solvent accounts for 40% to 75% by weight of the total weight of the photoresist composition.

6. The photoresist composition according to claim 1, wherein the another resin (A3) has a structural unit represented by formula (a1-2): ##STR00087## wherein R.sup.a1′ and R.sup.a2′ independently each represent a hydrogen atom or a C1 to C12 hydrocarbon group, R.sup.a3′ represents a C1 to C20 hydrocarbon group, or R.sup.a3′ are bonded to R.sup.a1′ or R.sup.a2′ to form a C2 to C20 divalent heterocyclic group where a methylene group can be replaced by an oxygen atom or a sulfur atom, R.sup.a5 represents a hydrogen atom or a methyl group, R.sup.a6 independently each represents a C1 to C6 alkyl group or a C1 to C6 alkoxy group, and m represents an integer of 0 to 4.

7. A process for producing a photoresist pattern comprising: (1) a step of applying the photoresist composition according to claim 1 on a substrate, (2) a step of forming a photoresist composition film by drying the photoresist composition, (3) a step of exposing the photoresist composition film, and (4) a step of developing the exposed photoresist composition film.

Description

EXAMPLES

(1) The present invention will be described more specifically by Examples, which are not construed to limit the scope of the present invention.

(2) The “%” and “part(s)” used to represent the content of any component and the amount of any material used in the following examples and comparative examples are on a weight basis unless otherwise specifically noted.

(3) The weight-average molecular weight of any material used in the following examples is a value determined by gel permeation chromatography under the following conditions.

(4) Equipment: HLC-8120GPC type, manufactured by TOSOH CORPORATION

(5) Column: TSKgel Multipore H.sub.XL-M.sub.X 3 with guard column, manufactured by TOSOH CORPORATION

(6) Solvent: tetrahydrofuran

(7) Flow rate: 1.0 mL/min.

(8) Detector: RI Detector

(9) Column temperature: 40° C.

(10) Injection volume: 100 μL

(11) Standard reference material: standard polystyrene, manufactured by TOSOH CORPORATION

Synthesis Example 1

(12) In a reactor, 86 parts of methacrylic acid, 516 parts of tert-methylbutylether and 99.2 parts of chloromethylether were mixed and stirred. To the obtained mixture, 111.2 parts of triethylamine were dropped over a period of one hour on an ice bath, and then stirred at room temperature for six hours.

(13) To the reaction mixture, 172 parts of tert-methylbutylether and 260 parts of ion exchanged water were added, and then an organic layer was separated therefrom.

(14) To the organic layer, 260 parts of 1% oxalic acid was added and an organic layer was newly separated therefrom.

(15) To the newly separated organic layer, 260 parts of on exchanged water was added, and then washed organic layer was separated therefrom: the washing step was conducted three times. Then the obtained organic layer was concentrated and then dried under reduced pressure to give 131.3 parts of the compound represented by formula (A).

(16) ##STR00054##

Synthesis Example 2

(17) In a reactor, 60 parts of methacrylic acid, 480 parts of tert-methylbutylether and 103.6 parts of chloromethylcyclohexylether were mixed and stirred. To the obtained mixture, 74 parts of triethylamine were dropped over a period of one hour on an ice bath, and then stirred at room temperature for six hours.

(18) To the reaction mixture, 120 parts of tert-methylbutylether and 240 parts of ion-exchanged water were added, and then an organic layer was separated therefrom.

(19) To the organic layer, 240 parts of 1% oxalic acid was added, and an organic layer was newly separated therefrom.

(20) To the newly separated organic layer, 240 parts of ion exchanged water was added, and then washed organic layer was separated therefrom: the washing step was conducted three times. Then the obtained organic layer was concentrated and then dried under reduced pressure to give 135.4 parts of the compound represented by formula (B).

(21) ##STR00055##

Synthesis Example 3

(22) ##STR00056##

(23) By mixing 13.1 parts of the compound represented by formula (A), 15.7 parts of compound represented by formula (C), 0.137 parts of azobisisobutyronitrile and 12.8 parts of propyleneglycolmonomethylether acetate, Mixture (1) was obtained.

(24) Into a flask equipped with a thermometer and a stirrer, 27.7 parts of propyleneglycolmonomethylether acetate was fed and then increased its temperature to 80° C. Thereinto, Mixture (1) was dropped while being stirred over a period of one hour, and then heated at 80° C. for nine hours. Then the reaction mixture was cooled to 40° C. and then diluted with 30.4 parts of propyleneglycolmethylether acetate, and then 168 parts of methanol and 336 parts of ion-exchanged water, followed by collecting precipitated resin by filtration.

(25) To the precipitated resin, 129 parts of propyleneglycolmethylether acetate was added and stirred, followed by concentrating it to obtain 45.3 parts of resin solution (Solid content: 48% by weight).

(26) The obtained resin is referred to as “Resin A1-1”, the weight average molecular weight of which was 6.8×10.sup.4. Resin. A1-1 had the following structural units.

(27) ##STR00057##

Synthesis Example 4

(28) ##STR00058##

(29) By mixing 10.9 parts of the compound represented by formula (A), 19.6 parts of compound represented by formula (C), 0.142 parts of azobisisobutyronitrile and 13.9 parts of propyleneglycolmonomethylether acetate, Mixture (2) was obtained.

(30) Into a flask equipped with a thermometer and a stirrer, 29.6 parts of propyleneglycolmonomethylether acetate was fed and then increased its temperature to 80° C. Thereinto, Mixture (2) was dropped while being stirred over a period of one hour, and then heated at 80° C. for nine hours.

(31) Then the reaction mixture was cooled to 40° C. and then diluted with 32.5 parts of propyleneglycolmethylether acetate, and then 179 parts of methanol and 359 parts of ion-exchanged water, followed by collecting precipitated resin by filtration.

(32) To the precipitated resin, 138 parts of propyleneglycolmethylether acetate was added and stirred, followed by concentrating it to obtain 42.3 parts of resin solution (Solid content: 56.3% by weight).

(33) The obtained resin is referred to as “Resin A1-2”, the weight average molecular weight of which was 7.4×10.sup.4. Resin A1-2 had the following structural units.

(34) ##STR00059##

Synthesis Example 5

(35) ##STR00060##

(36) By mixing 25.1 parts of the compound represented by formula (A), 19.6 parts of compound represented by formula (C), 11.8 parts of compound represented by formula (D), 0.285 parts of azobisisobutyronitrile and 28.1 parts of propyleneglycolmonomethylether acetate, Mixture (3) was obtained.

(37) Into a Flask equipped with a thermometer and a stirrer, 56.4 parts of propyleneglycolmonomethylether acetate was fed and then increased its temperature to 80° C. Thereinto, Mixture (3) was dropped while being stirred over a period of one hour, and then heated at 80° C. for nine hours.

(38) Then the reaction mixture was cooled to 40° and then diluted with 62 parts of propyleneglycolmethylether acetate, and then 342 parts of methanol and 684 parts of ion-exchanged water, followed by collecting precipitated resin by filtration.

(39) To the precipitated resin, 263 parts of propyleneglycolmethylether acetate was added and stirred, followed by concentrating it to obtain 99 parts of resin solution (Solid content: 51.3% by weight).

(40) The obtained resin is referred to as “Resin A1-3”, the weight average molecular weight of which was 6×10.sup.4. Resin A1-3 had the following structural units.

(41) ##STR00061##

Synthesis Example 6

(42) ##STR00062##

(43) By mixing 10.9 parts of the compound represented by formula (A), 10.4 parts of compound represented by formula (C), 6.9 parts of compound represented by formula (E), 0.285 parts of azobisisobutyronitrile and 12.8 parts of propyleneglycolmonomethylether acetate, Mixture (4) was obtained.

(44) Into a flask equipped with a thermometer and a stirrer, 27.4 parts of propyleneglycolmonomethylether acetate was fed and then increased its temperature to 80° C. Thereinto, Mixture (4) was dropped while being stirred over a period of one hour, and then heated at 80° C. for nine hours.

(45) Then the reaction mixture was cooled to 40° C. and then diluted with 30.1 parts of propyleneglycolmethylether acetate, and then 178 parts of methanol and 178 parts of ion-exchanged water, followed by collecting precipitated resin by filtration.

(46) To the precipitated resin, 155 parts of propyleneglycolmethylether acetate was added and stirred, followed by concentrating it to obtain 53.1 parts of resin solution (Solid content: 34.1% by weight).

(47) The obtained resin is referred to as “Resin A1-4”, the weight average molecular weight of which was 16×10.sup.4. Resin A1-4 had the following structural units.

(48) ##STR00063##

Synthesis Example 7

(49) ##STR00064##

(50) By mixing 32.1 parts of the compound represented by formula (B), 24.3 parts of compound represented by formula (C) 5.5 parts of compound represented by formula (D), 0.186 parts of azobisisobutyronitrile and 30.8 parts of propyleneglycolmonomethylether acetate, Mixture (5) was obtained.

(51) Into a flask equipped with a thermometer and a stirrer, 61.8 parts of propyleneglycolmonomethylether acetate was fed and then increased its temperature to 80° C. Thereinto, Mixture (5) was dropped while being stirred over a period of one hour, and then heated at 80° C. for nine hours.

(52) Then the reaction mixture was cooled to 40° C. and then diluted with 68 parts of propyleneglycolmethylether acetate, and then 281 parts of methanol and 844 parts of ion-exchanged water, followed by collecting precipitated resin by filtration. To the precipitated resin, 288 parts of propyleneglycolmethylether acetate was added and stirred, followed by concentrating it to obtain 113.7 parts of resin solution (Solid content: 44.8% by weight).

(53) The obtained resin is referred to as “Resin A1-5”, the weight average molecular weight of which was 13.3×10.sup.4. Resin A1-5 had the following structural units.

(54) ##STR00065##

Synthesis Example 8

(55) ##STR00066##

(56) By mixing 26.1 parts of the compound represented by formula (A), 9.9 parts of compound represented by formula (C), 4.5 parts of compound represented by formula (D), 9.3 parts of compound represented by formula (F), 0.129 parts of azobisisobutyronitrile and 24.6 parts of propyleneglycolmonomethylether acetate, Mixture (6) was obtained.

(57) Into a flask equipped with a thermometer and a stirrer, 49.6 parts of propyleneglycolmonomethylether acetate was fed and then increased its temperature to 80° C. Thereinto, Mixture (6) was dropped while being stirred over a period of one hour, and then heated at 80° C. for nine hours.

(58) Then the reaction mixture was cooled to 40° C. and then diluted with 54.5 parts of propyleneglycolmethylether acetate, and then 271 parts of methanol and 632 parts of ion-exchanged water, followed by collecting precipitated resin by filtration.

(59) To the precipitated resin, 264 parts of propyleneglycolmethylether acetate was added and stirred, followed by concentrating it to obtain 97.7 parts of resin solution (Solid content: 39% by weight).

(60) The obtained resin is referred to as “Resin A1-6”, the weight average molecular weight of which was 9.1×10.sup.4. Resin A1-6 had the following structural units.

(61) ##STR00067##

Synthesis Example 9

(62) ##STR00068##

(63) By mixing 30.4 parts of the compound represented by formula (A), 11.4 parts of compound represented by formula (C), 15.5 parts of compound represented by formula (D), 0.164 parts of azobisisobutyronitrile and 28 parts of propyleneglycolmonomethylether acetate, Mixture (7) was obtained.

(64) Into flask equipped with a thermometer and a stirrer, 56.9 parts of propyleneglycolmonomethylether acetate was fed and then increased its temperature to 80° C. Thereinto, Mixture (7) was dropped while being stirred over a period of one hour, and then heated at 80° C. for nine hours.

(65) Then the reaction mixture was cooled to 40° C. and then diluted with 62.5 parts of propyleneglycolmethylether acetate, and then 310 parts of methanol and 724 parts of ion-exchanged water, followed by collecting precipitated resin by filtration.

(66) To the precipitated resin, 303 parts of propyleneglycolmethylether acetate was added and stirred, followed by concentrating it to obtain 144.2 parts of resin solution (Solid content: 34.8% by weight).

(67) The obtained resin is referred to as “Resin A1-7”, the weight average molecular weight of which was 8.4×10.sup.4. Resin. A1-7 had the following structural units.

(68) ##STR00069##

Synthesis Example 10

(69) ##STR00070##

(70) By mixing 21.3 parts of the compound represented by formula (A), 4.6 parts of compound represented by formula. (G), 42.3 parts of compound represented by formula (H), 0.261 parts of azobisisobutyronitrile and 29.1 parts of propyleneglycolmonomethylether acetate, Mixture (8) was obtained.

(71) Into a flask equipped with a thermometer and a stirrer, 58.5 parts of propyleneglycolmonomethylether acetate was fed and then increased its temperature to 80° C. Thereinto, Mixture (8) was dropped while being stirred over one and half hours, and then heated at 80° C. for nine hours.

(72) Then the reaction mixture was cord to 40° C. and then diluted with 88.3 parts of propyleneglycolmethylether acetate, and then 371 parts of methanol and 865 parts of ion-exchanged water, followed by collecting precipitated resin by filtration.

(73) To the precipitated resin, 362 parts of propyleneglycolmethylether acetate was added and stirred, followed by concentrating it to obtain 120.7 parts of resin solution (Solid content: 42.2% by weight).

(74) The obtained resin is referred to as “Resin A1-8”, the weight average molecular weight of which was 7.6×10.sup.4. Resin A1-8 had the following structural units.

(75) ##STR00071##

Synthesis Example 11

(76) ##STR00072##

(77) By mixing 27.5 parts of the compound represented by formula (A), 4.1 parts of compound represented by formula (G), 32.3 parts of compound represented by formula H), 0.232 parts of azobisisobutyronitrile and 27.5 parts of propyleneglycolmonomethylether acetate, Mixture (9) was obtained.

(78) Into a flask equipped with a thermometer and a stirrer, 55.8 parts of propyleneglycolmonomethylether acetate was fed and then increased its temperature to 80° C. Thereinto, Mixture (9) was dropped while being stirred over one and half hours, and then heated at 80° C. for nine hours.

(79) Then the reaction mixture was cooled to 40° C. and then diluted with 83.6 parts of propyleneglycolmethylether acetate, and then 351 parts of methanol and 819 parts of ion-exchanged water, followed by collecting precipitated resin by filtration.

(80) To the precipitated resin, 343 parts of propyleneglycolmethylether acetate was added and stirred, followed by concentrating it to obtain 114.3 parts of resin solution (Solid content: 44.6% by weight).

(81) The obtained resin is referred to as “Resin A1-9”, the weight average molecular weight of which was 8.3×10.sup.4. Resin A1-9 had the following structural units.

(82) ##STR00073##

Synthesis Example 12

(83) ##STR00074##

(84) By mixing 16.2 parts of the compound represented by formula (A), 3.5 parts of compound represented by formula (G), 27.64 parts of compound represented by formula (H), 20 parts of compound represented by formula (E), 0.199 parts of azobisisobutyronitrile and 28.9 parts of propyleneglycolmonomethylether acetate, Mixture (10) was obtained.

(85) Into a flask equipped with a thermometer and a stirrer, 58.2 parts of propyleneglycolmonomethylether acetate was fed and then increased its temperature to 80° C. Thereinto, Mixture (10) was dropped while being stirred over one and half hours, and then heated at 80° C. for nine hours.

(86) Then the reaction mixture was cooled to 40° C. and then diluted with 87.3 parts of propyleneglycolmethylether acetate, and then 367 parts of methanol and 856 parts of ion-exchanged water, followed by collecting precipitated resin by filtration.

(87) To the precipitated resin, 358 parts of propyleneglycolmethylether acetate was added and stirred, followed by concentrating it to obtain 119.4 parts of resin solution (Solid content: 44.8% by weight).

(88) The obtained resin is referred to as “Resin A1-10”, the weight average molecular weight of which was 10.8×10.sup.4. Resin A1-10 had the following structural units.

(89) ##STR00075##

Synthesis Example 13

(90) To a four-necked flask with a stirring device, a reflux condenser and a thermometer, 413.5 parts of 2,5-xylenol, 103.4 parts of salicylaldehyde, 20.1 parts of p-toluenesulfonic acid and 826.9 parts of methanol were poured, and heated to make the mixture refluxed and then the temperature of the mixture was kept for 4 hours. Then the obtained mixture was cooled, and 1320 parts of methylisobutylketone was fed thereto, followed by distilling 1075 parts of the mixture away under an ordinary pressure.

(91) Then 762.7 parts of m-cresol and 29 parts of 2-tert-butyl-5-methylphenol were added to the residues and heated to 65° C., followed by dropping 678 parts of 37% formalin thereto over a period of 1.5 hours while controlling the temperature of the mixture to be 87′C. at the end of dropping. Then the temperature of the mixture was kept at 87° C. for 10 hours, and then 1115 parts of methylisobutylketone was added to the obtained resin solution, followed by washing it with water three times. To the washed resin solution, 500 parts methylisobutylketone was added, followed by distilling it under reduced pressure until the amount of solution became 3435 parts. To the washed resin solution, 3796 parts of methylisobutylketone and 4990 parts of n-heptane were added and heated to 60° C., and then stirred for an hour, followed by separating therefrom the resin solution of the bottom layer.

(92) To the separated resin solution, 3500 parts of propyleneglycolmonomethylether acetate was added to dilute it, followed by distilling it under reduced pressure until the amount of solution became 1690 parts (43% of solid content). The obtained novolak resin is referred to as “Resin A2-1”, the weight average molecular weight of which was 7000.

Synthesis Example 14

(93) ##STR00076##

(94) By mixing 12 parts of the compound represented by formula (J), 21.4 parts of compound represented by formula (C), 0.141 parts of azobisisobutyronitrile and 16.7 parts of propyleneglycolmonomethylether acetate, Mixture (11) was obtained.

(95) Into a flask equipped with a thermometer and a stirrer, 33.4 parts of propyleneglycolmonomethylether was fed and then increased its temperature to 80° C. Thereinto, Mixture (11) was dropped while being stirred over a period of one hour, and then heated at 80° C. for nine hours.

(96) Then the reaction mixture was cooled to 40° C. and then diluted with 62.5 parts of propyleneglycolmethylether acetate, and then 203 parts of methanol and 406 parts of ion-exchanged water, followed by collecting precipitated resin by filtration.

(97) To the precipitated resin, 156 parts of propyleneglycolmethylether acetate was added and stirred, followed by concentrating it to obtain 53.9 parts of resin solution (Solid content: 40.4% by weight).

(98) The obtained resin is referred to as “Resin A3-1a”, the weight average molecular weight of which was 12×10.sup.4. Resin A3-1a had the following structural units.

(99) ##STR00077##

Synthesis Example 16

(100) Twenty (20) parts of polyvinylphenol (Trade name VP-15000, Product of Nippon Soda Co., Ltd.) was dissolved in 240 parts of methylisobutylketone, followed by concentrating it with an evaporator.

(101) To a four-necked flask with a stirring device, a reflux condenser and a thermometer, the concentrated mixture and 0.003 parts of p-toluenesulfonic acid dehydrates were poured and then 5.05 parts of ethylvinylether was dropped thereinto at a temperature of 20 to 25° C. over a period of 10 minutes. The obtained mixture was stirred at the above-mentioned temperature for 2 hours and then diluted with 200 parts of methylisobutylketone, followed by washing it with ion-exchanged water five times.

(102) The washed mixture was concentrated until its amount became 45 parts using an evaporator, and 150 parts of propyleneglycolmonomethylether acetate were added thereto, followed by concentrating it again to obtain 78 parts of propyleneglycolmonomethylether acetate solution (29% of solid content) of resin A3-2, the weight average molecular weight of which was 22100, and in which the content of the ethoxyethyl group were 38.5%. Resin. A3-2 has the following structural units.

(103) ##STR00078##

Synthesis Example 17

(104) In 95 parts of acetone, 10.3 parts of 3,5-dihydroxynaphthoic acid was dissolved.

(105) To the obtained mixture, 83.6 parts of potassium carbonate and 28.4 parts of dimethylsulfuric acid were added, followed by being stirred at 50° C. for 12 hours.

(106) The obtained reaction solution was filtrated to thereby remove a solid therefrom, and then the solvent therein was distilled off with an evaporator.

(107) To the obtained residue, 50 parts of ion-exchanged water, 40 parts of methanol and 10 parts of potassium hydroxide were added, and stirred at 65° C. for three hours.

(108) To the reaction solution, 100 parts of hydrochloric acid was added, followed by collecting the precipitated solid to obtain 20 parts of 3,5-dimethoxy-2-naphthoic acid.

(109) In 160 parts of thionyl chloride, 20 parts of 3,5-dimethoxy-2-naphthoic acid was added, and stirred at 80° C. for two hours.

(110) The obtained mixture was set under reduced pressure at 80° C. Then thionyl chloride and the hydrochloric acid, byproducts of the above-mentioned reaction, were distilled off to thereby obtain 20 parts of 3,5-dimethoxy-2-naphthoyl chloride. In 50 parts of methanol, 8.3 parts of N-methylhydroxyamine hydrochloride was dissolved. Into the obtained methanol solution, 60 gram of potassium hydroxide solution (10% in methanol) was dropped while being stirred at 0° C., to thereby obtain. Mixture (12). A solution in which 11.8 parts of 2-naphthoyl chloride was dissolved in 30 parts of THF was added to Mixture (12), followed by being stirred for one hour. The obtained reaction solution was left under room temperature, and then further stirred for one hour, followed by distilling off its solvent therefrom.

(111) The obtained residue was extracted with ethyl acetate and a saturated aqueous sodium chloride solution, followed by isolating an organic layer therefrom. Then, a solvent was distilled off therefrom to collect a white solid.

(112) In 75 parts of chloroform, 20 parts of the obtained solid and 3.8 parts of (+)-10-camphorsulfonyl chloride were dissolved.

(113) Into the obtained mixture, 3.4 parts of pyridine was dropped while being stirred at 0° C.

(114) The obtained mixture was stirred at 50° C. for 8 hours, followed by being extracted with a mixture of chloroform and ion-exchanged water. Then an organic layer was left under reduced pressure to thereby remove a solvent therefrom. Further, the obtained residue was recrystallized with methanol, 3.5 parts of compounds represented by the following formula

(115) ##STR00079##

Examples 1 to 5 and Comparative Examples 1 to 2

(116) (Preparation of Photoresist Pattern)

(117) The following components listed in Table 1 were mixed and dissolved in the solvent as mentioned below, and further filtrated through a fluorine resin having pore diameter of 5 μm to prepare photoresist compositions. The contents of the components in each example are shown in Table 1.

(118) The symbols recited in Table 1 represent the following components.

(119) <Resin>

(120) A1-1: Resin A1-1, A1-2: Resin A1-2, A1-3: Resin A1-3, A1-4: Resin A1-4, A1-5: Resin A1-5, A1-6: Resin A1-6, A1-7: Resin A1-7, A1-8: Resin A1-B, A1-9: Resin A1-9, A1-10: Resin A1-10, A2-1: Resin A2-1, A3-1a: Resin A3-1a A3-2: Resin A3-2

(121) <Acid Generator>

(122) B1: The compound represented by formula, trade name “NAI-105” product by Midori Kagaku, Co., Ltd.

(123) ##STR00080##

(124) B2: The compound represented by formula, prepared in the manner as Synthesis Example 17.

(125) ##STR00081##
<Quencher>

(126) C1: 2,4,5-triphenylimidazole (Product of Tokyo Chemical Industry, Co., Ltd.)

(127) <Surfactant>

(128) F1: Polyether denaturated silicone oil (DOW CORNING TORAY SH8400; Product of Toray Dow Corning, Co., Ltd.)

(129) F2: MEGAFACE F477 (brand name)

(130) <Solvent>

(131) D1: Propyleneglycolmonomethylether acetate

(132) TABLE-US-00001 TABLE 1 Acid Surfactant (I) Solvent Ex. Resin generator Quencher (parts) (parts) PB (° C.)/ No. (Kind/parts) (Kind/parts) (Kind/parts) (% by wt) (% by wt) PEB (° C.) 1 A1-1/6.075 B1/0.24 C1/0.05 F1/0.00025 D1/30 110/90 A2-1/7.425 (0.0006) (69) 2 A1-2/6.075 B1/0.24 C1/0.05 F1/0.00025 D1/30 110/90 A2-1/7.425 (0.0006) (69) 3 A1-3/7.425 B1/0.24 C1/0.05 F1/0.00025 D1/30 110/90 A2-1/6.075 (0.0006) (69) 4 A1-1/6.075 B2/0.37 C1/0.05 F1/0.00025 D1/30 110/90 A2-1/7.425 (0.0006) (69) 5 A1-4/4.725 B1/0.24 C1/0.05 F1/0.00025 D1/40 110/90 A2-1/8.775 (0.0005) (74) 6 A1-5/8.1 B1/0.07 C1/0.02 F1/0.00835 D1/16.2 110/90 A2-1/5.4 (0.028) (54) 7 A1-6/6.75 B1/0.07 C1/0.02 F2/0.00835 D1/15.4 110/70 A2-1/1.35 (0.0288) (53) A3-2/5.4 8 A1-7/1.35 B1/0.07 C1/0.02 F2/0.00835 D1/15.6 110/70 A2-1/3.375 (0.0277) (55) A3-2/8.775 9 A1-8/2.03 B1/0.07 C1/0.02 F1/0.00835 D1/15.2 110/70 A2-1/4.05 (0.0290) (53) A3-2/7.43 10 A1-9/2.03 B1/0.07 C1/0.02 F1/0.00835 D1/15.2 110/70 A2-1/4.05 (0.0290) (53) A3-2/7.43 11 A1-10/2.03 B1/0.07 C1/0.02 F1/0.00835 D1/15.2 110/70 A2-1/4.05 (0.0290) (53) A3-2/7.43 C1 A3-1a/6.075 B1/0.24 C1/0.05 F1/0.00025 D1/30 110/90 A2-1/7.425 (0.0006) (69) C2 A3-2/7.425 B1/0.24 C1/0.05 F1/0.00025 D1/25 110/90 A2-1/6.075 (0.0006) (64) C3 A3-2/7.425 B1/0.07 C1/0.02 F2/0.00835 D1/13.6 110/70 A2-1/6.075 (0.0307) (50) C4 A3-2/7.425 B1/0.07 C1/0.02 — D1/13.6 110/70 A2-1/6.075 (50) Note: The “C1”, “C2”, “C3” and “C4” represent respectively Comparative Examples 1, 2, 3 and 4.
(Preparation of Photoresist Pattern)

(133) Over the substrate (4 inches), each of the photoresist compositions prepared as above was spin-coated so that the thickness of the resulting film became 5 μm after drying. The substrates thus coated with the respective photoresist compositions were each prebaked on a direct hotplate at the temperature as shown in the columns “PB” of Table 1 for 180 seconds.

(134) Using an i-ray stepper (“NSR 1755i7A” manufactured by Nikon, NA=0.5) and a mask (line width: 3 μm) for forming a line-and-space pattern, each wafer thus formed with the respective film was subjected to exposure with the exposure quantity being varied stepwise.

(135) After exposure, each wafer was subjected to post-exposure baking on a hotplate at the temperature as shown in the columns “PEB” of Table 1 for 60 seconds.

(136) After the exposure, each wafer was subjected to paddle development for 180 seconds with an aqueous solution of 2.38 wt % tetramethylammonium hydroxide.

(137) (Evaluation)

(138) I. Uniformity of Thickness

(139) The thickness of the composition film after prebaking was measured at five points distant by 25 mm from the middle of the film, whose point-to-point distances were equal to each other, using a spectroscopic reflectometer [Lambda Ace, products made by SCREEN Semiconductor Solutions Co., Ltd.]. The film in which the maximum difference of thickness size was 0.2 μm or more was marked by “X” (bad). The film in which the maximum difference was less than 0.2 μm was marked by “ο” (good).

(140) The results of the evaluation are listed in Table 2.

(141) II. Resolution

(142) The photoresist patterns were prepared at the exposure quantity of ES. The minimum line width of the pattern free from the collapse of the line was determined as the value of “Resolution”.

(143) In this evaluation, the ES (Effective Sensitivity) means the exposure quantity that the ratio of width between the line and the space was 1:1 at the line width of 3 μm.

(144) The results of the evaluation are listed in Table 2.

(145) TABLE-US-00002 TABLE 2 Uniformity of Resolution thickness (μm) Ex. 1 ∘ 1 Ex. 2 ∘ 1 Ex. 3 ∘ 1 Ex. 4 ∘ 1 Ex. 5 ∘ 1 Comp. ∘ — (No pattern Ex. 1 formed) Comp. ∘ — (No pattern Ex. 2 formed)

Examples 6 to 11 and Comparative Examples 3 to 4

(146) (Preparation of Photoresist Pattern)

(147) The components listed in Table 1 were mixed and dissolved in the solvent as mentioned above, and further filtrated through a fluorine resin filter having pore diameter of 15 μm to prepare photoresist compositions. The contents of the components in each example are shown in Table 1.

(148) (Preparation of Photoresist Pattern)

(149) Over the substrate (4 inches), each of the photoresist compositions prepared as above was spin-coated so that the thickness of the resulting film became 50 μm after drying. The substrates thus coated with the respective photoresist compositions were each prebaked on a direct hotplate at the temperature as shown in the columns “PB” of Table 1 for 300 seconds.

(150) Using an i-ray stepper (“NSR 1755i7A” manufactured by Nikon, NA=0.5) and a mask for forming a line-and-space pattern, each wafer thus formed with the respective film was subjected to exposure with the exposure quantity being varied stepwise. After exposure, each wafer was subjected to post-exposure baking on a hotplate at the temperature as shown in the columns “PEB” of Table 1 for 180 seconds.

(151) (Evaluation)

(152) I. Uniformity of Thickness

(153) The thickness of the composition film after prebaking was measured at five points distant by 25 mm from the middle of the film, whose point-to-point distances were equal to each other, using a spectroscopic reflectometer [Lambda Ace, products made by SCREEN Semiconductor Solutions Co., Ltd.]

(154) The film in which the maximum difference of thickness size was 2 μm or more was marked by “χ” (bad). The film in which the maximum difference was less than 2 μm was marked by “ο” (good).

(155) The results of the evaluation are listed in Table 3.

(156) II. Resolution

(157) The photoresist patterns were prepared at the exposure quantity of ES. The minimum line width of the pattern free from the collapse of the line was determined as the value of “Resolution”.

(158) In this evaluation, the ES (Effective Sensitivity) means the exposure quantity that the ratio of width between the line and the space was 1:1 at the line width of 40 μm.

(159) The results of the evaluation are listed in Table 3.

(160) III. Resistance to Cracking

(161) Over the substrate (4 inches), each of the photoresist compositions prepared as above was spin-coated so that the thickness of the resulting film became 50 μm after drying. The substrates thus coated with the respective photoresist compositions were each prebaked on a direct hotplate at the temperature as shown in the columns “PB” of Table 1 for 300 seconds. Then the prebaked substrates were each baked on a hotplate at 130° C. for 300 seconds, followed by being cooled to 23° C. rapidly. The obtained film which had no crack was marked as “ο” (good), and the obtained film which had 10 or more of cracks was marked as “χ” (bad)

(162) The results of the evaluation are listed in Table 3.

(163) TABLE-US-00003 TABLE 3 Uniformity of Resolution Resistance thickness (μm) to cracking Ex. 6 ∘ 20 ∘ Ex. 7 ∘ 10 ∘ Ex. 8 ∘ 10 ∘ Ex. 9 ∘ 10 ∘ Ex. 10 ∘ 10 ∘ Ex. 11 ∘ 10 ∘ Comp. ∘ — (No pattern x Ex. 3 formed) Comp. x — (No pattern x Ex. 4 formed)

(164) The photoresist composition of the present invention can provide a photoresist film capable of forming a photoresist pattern with fine shape.