More preferred is a homopolymer of p-hydroxystyrene. generation, Chemically amplified positive resist composition, Acid-labile group protected hydroxystyrene polymers or copolymers thereof and their application to radiation sensitive materials, <- Previous Patent (Radiation sensitive ...). Newly-devel op e d positive photoresist X P m r-P 15 AV, which [...] is viscous, UV-sensitive and can be developed in aqueous/alkaline medium, has a perpendicular edge profile with an aspect ratio of up to 6. This resin had a weight-average molecular weight of 9,800. Chem. Soc., 91, 145 (1969), A. L. Maycok et al., J. Org. A positive photoresist composition is disclosed which comprises (a) a resin obtained from an alkali-soluble resin containing phenolic hydroxyl groups by replacing from 10 to 80% of the phenolic hydroxyl groups each with a group having a specific structure, (b) a compound which generates an acid upon irradiation with actinic rays or a radiation, and (c) a solvent. The resin used in the present invention, which is obtained by protecting phenolic hydroxyl groups (alkali solubilizing groups) of the alkali-soluble resin with specific acid-decomposable groups represented by general formula (I), is a novel resin, having groups which decompose by the action of an acid to enhance solubility in an alkaline developing solution. 339,049 and 410,201, JP-A-2-150,848, and JP-A-2-296,514; the sulfonium salts described in, e.g., J. V. Crivello et al., Polymer J., 17, 73 (1985), J. V. Crivello et al., J. Org. ##STR17##. Alkali-soluble resins C-1 to C-4 having substituents which are not a group represented by the general formula (I) according to the present invention were obtained from the alkali-soluble resins shown in Table 1 and from ethyl vinyl ether (Y-1), isobutyl vinyl ether (Y-2), or chloroethyl vinyl ether (Y-3). The chemically amplified positive resist compositions described above are roughly divided into three groups: three-component systems comprising an alkali-soluble resin, a compound which generates an acid upon exposure to a radiation (photo-acid generator), and a dissolution inhibitive compound for the alkali-soluble resin which has acid-decomposable groups; two-component systems comprising a resin having groups which decompose upon reaction with an acid to render the resin alkali-soluble and a photo-acid generator; and hybrid systems comprising a resin having groups which decompose upon reaction with an acid to render the resin alkali-soluble, a low-molecular dissolution inhibitive compound having an acid-decomposable group, and a photo-acid generator. For example, such a photo-acid generator is represented by general formula (PAG3) or (PAG4) wherein Ar1, Ar2, and R203 to R205 each represents a substituted or unsubstituted aryl group and Z- is an anion which, when converted to an acid upon irradiation with light, has relatively low diffusibility in the resist film. ##STR12##. A resin having the substituents described above can be obtained by synthesizing a vinyl ether corresponding to the substituent and reacting the ether by a known method with the alkali-soluble resin containing phenolic hydroxyl groups which has been dissolved in an appropriate solvent, e.g., tetrahydrofuran. As a developing solution for the chemically amplified positive resist composition of the present invention, an aqueous solution of an alkali can be used. This alkali-soluble resin not containing acid-decomposable groups (hereinafter referred to simply as "alkali-soluble resin") needs to be alkali-soluble. (μm) Depression Substrate. Sym., Vol. Ed., 17, 2877 (1979), European Patents 370,693, 3,902,114, 233,567, 297,443, and 297,442, U.S. Pat. Hallo und Herzlich Willkommen auf unserem Portal. This mixture was heated with refluxing for 1 hour to hydrolyze the resin. Examples of this polymeric compound are given in, e.g., M. E. Woodhouse et al., J. Chem. Nos. Specific examples thereof are given below, but the compounds represented by general formula (PAG5) or (PAG6) should not be construed as being limited thereto. Thereafter, the resultant mixture was added dropwise to 5 L of ultrapure water with vigorous agitation to conduct reprecipitation. The main monomer for novolak resins should not be construed as being limited to the above examples. Each resist solution thus obtained was applied to a silicon wafer with a spin coater, and the coating was dried at 130° C. for 60 seconds with a vacuum holding type hot plate to obtain a resist film having a thickness of 0.8 μm. (3) Disulfone derivatives represented by the following general formula (PAG5) and iminosulfonate derivatives represented by the following general formula (PAG6). The mechanism by which unexposed DNQ inhibits novolac dissolution is not well understood, but is believed to be related to hydrogen bonding (or more exactly diazocoupling in the … General Information. Preferred substituents for the aryl group include alkoxy groups having 1 to 8 carbon atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups, nitro, carboxyl, mercapto, hydroxy, and halogen atoms. Photochem., 36, 85, 39, 317 (1987), B. Amit et al., Tetrahedron Lett., (24) 2205 (1973), D. H. R. Barton et al., J. Chem Soc., 3571 (1965), P. M. Collins et al., J. Chem. It is possible to incorporate an alkali-soluble resin not containing acid-decomposable groups into the composition of the present invention to thereby improve sensitivity. Furthermore, JP-A-8-253534 discloses a photoresist composition containing a partly crosslinked polymer having groups substituted with acetal groups. ##STR5##. PHOTOPOSIT SP 24 Photoresist has also been formulated for use in a wide variety of etching applications. No. Improved resist adhesion to all common substrate materials Broad process parameter window for stable and reproducible litho-processes The resin thus obtained was dried in a vacuum dryer at 70° C. for 12 hours to obtain alkali-soluble resin B-1 having substituents according to the present invention. Thus, the resist has low sensitivity to give only a tapered pattern. Nos. ##STR8##, (2) Iodonium salts represented by the following general formula (PAG3) and sulfonium salts represented by the following general formula (PAG4). Therefore, the photoresist film must be thick enough to resist etching and ensure that there is no vacuum. Another means for eliminating the problem described hereinabove is a system which is stable over long at room temperature but decomposes upon heating in the presence of an acid to become alkali-soluble. Other examples of the compound which generates an acid upon irradiation with actinic rays or a radiation for use in the present invention include onium salts such as: the diazonium salts described in, e.g., S. I. Schlesinger, Photogr. The photo-acid generators and organic basic compounds used in the Examples are shown below. 3,779,778, and European Patent 126,712. Hence, further improvements have been desired. A satisfactory resist pattern can be obtained by applying the chemically amplified positive resist composition described above on a substrate such as those for use in the production of precision IC elements (e.g., silicon/silicon dioxide coating) by an appropriate coating means, e.g., a spinner or coater, exposing the coating to light through a mask, and then baking and developing the coating. The results given in Table 3 show that the positive photoresist compositions obtained in the Examples according to the present invention each gave satisfactory results, whereas the photoresist compositions obtained in the Comparative Examples were unsatisfactory in threshold resolution, pattern top depressions, and adhesion to substrate. Preferred examples of the aryl group include phenyl, tolyl, xylyl, mesityl, and cumenyl, with phenyl being more preferred. ����?�M�(��[6�N�ݬU��H���� ��ӯ�P�����U;���a` v�z�#X�����-B���M4�����n���������%����Vݽܿ In 100 ml of tetrahydrofuran were dissolved 35.25 g (0.2 mol) of p-tert-butoxystyrene and 5.21 g (0.05 mol) of styrene which both had been purified by dehydration and distillation in an ordinary way. But optimism quickly turned to frustration.The problem is that… If the addition amount of the compounds decomposing upon irradiation with actinic rays or a radiation to generate an acid is smaller than 0.001% by weight, sensitivity is reduced. Chem., Rapid Commun., 9, 625 (1988), Y. Yamada et al., Makromol. This resin was taken out by filtration, washed with water, dried, and then dissolved in 200 ml of tetrahydrofuran to give a solution, which was added dropwise to 5 L of ultrapure water with vigorous agitation to conduct reprecipitation. Especially preferred alkali-soluble resins for use in the present invention are novolak resins, alkali-soluble resins comprising p-hydroxystyrene units (more preferably poly(p-hydroxystyrene), p-hydroxystyrene/m-hydroxystyrene copolymers, p-hydroxystyrene/o-hydroxystyrene copolymers, and p-hydroxystyrene/styrene copolymers), alkyl-substituted hydroxy resins such as 4-hydroxy-3-methylstyrene resins and 4-hydroxy-3,5-dimethylstyrene resins, resins obtained from the above resins by converting OH groups thereof into alkyl or acetyl groups, partially hydrogenated poly(hydroxystyrene) resins, poly(hydroxystyrene) resins, partially hydrogenated novolak resins, and partially hydrogenated poly(hydroxystyrene) resins. The resultant reaction mixture was poured into 1,200 ml of hexane to precipitate a white resin. AZ® PL 177 can be used in all those places, where layouts are directly to be copied onto and … The dry film photoresist is way easier to apply and a lot cheaper. & Terms of Use. In the above formulae, R201 represents a substituted or unsubstituted aryl or alkenyl group; R202 represents a substituted or unsubstituted aryl, alkenyl, or alkyl group or --C(Y)3 ; and Y represents a chlorine or bromine atom. In the present invention, it is essential to use a resin obtained from the above-described alkali-soluble resin containing phenolic hydroxyl groups by replacing from 10 to 80% of the hydroxyl groups each with a group represented by general formula (I) given above. (4) The positive photoresist composition as described in any one of (1) to (3) above, wherein the alkali-soluble resin containing phenolic hydroxyl groups is poly(p-hydroxystyrene). Examples thereof include perfluoroalkanesulfonate anions, e.g., BF4-, AsF6-, PF6-, SbF6-, SiF62-, ClO4-, and CF3 SO3-, a pentafluorobenzenesulfonate anion, fused-ring aromatic sulfonate anions, e.g., a naphthalene-1-sulfonate anion, an anthraquinonesulfonate anion, and dyes containing a sulfonate group. Soc. In the present invention, the compound which generates an acid upon irradiation with actinic rays or a radiation is preferably an onium salt, a disulfone, a 4-DNQ sulfonic ester, or a triazine compound. PHOTOPOSIT SP 24 Photoresist is a positive-working photoresist designed primarily for the low-cost production of PWB innerlayers as part of a print and etch process. A positive photoresist composition is disclosed which comprises (a) a resin obtained from an alkali-soluble resin containing phenolic hydroxyl groups by replacing from 10 to 80% of the phenolic hydroxyl groups each with a group having a specific structure, (b) a compound which generates an acid upon irradiation with actinic rays or a radiation, and (c) a solvent. 95 (commercial names, products of Kyoeisha Yushi Kagaku Kogyo K.K.). These solvents may be used alone or as a mixture thereof. The resin obtained had a weight-average molecular weight of 10,000. �n>|���{�7eeۦ=�f�x; cm��Yn�9� ։z��&"�ٝ����ǯ2�M��������[���Q#��n�׶1��AۺmwP[�uOU]Vlb0֓9��ԇj�����;ط} R8lx�Gn2��;9v .�f�����y4���ce�dt? Nos. ����y?���zg��Fo��'�40}�j���qXp��,V>"��{ooc+vJ;>�����O�3b��\��U�9�4B$���J��_�c:����i����F���-N>XB\n/�3��_��&���L��|}���%�o%"�[�PWpH����,W΀?-8�ܩ��tz��:��ąC���-��f���!Ȋ��R�g8���;�cM��ܡ�9�b%�G��6iGvr�&\�"x���W�&/�-ջP��E���P��x�P4-�B. �Dvk9>V�xT]ܺU ~�_�Q��dQ�� This resin was taken out by filtration, washed with water, dried, and then dissolved in 200 ml of tetrahydrofuran to give a solution, which was added dropwise to 5 L of ultrapure water with vigorous agitation to conduct reprecipitation. Positive Photoresists for UV lithography (mask aligner, laser, greyscale exposure) and e-beam lithography. Alkali-soluble resin A-4, obtained in Synthesis 20 g Example II-4 Tetrahydrofuran 80 ml Vinyl ether X-1, obtained in Synthesis Example I-1 7.58 g, Results of Resin Syntheses Molecu- Alkali-soluble lar resin Vinyl ether Molecu- weight Synthesis Resin Amount Amount lar distri- Example No. Preferred organic basic compounds that can be used in the present invention are compounds having higher basicity than phenol. Am. The chemically amplified positive resist composition can further contain surfactants, dyes, pigments, plasticizers, spectral sensitizers, compounds having two or more phenolic OH groups, which can promote the dissolution in a developing solution, and the like, if needed. 3-140109; and the disulfone compounds described in, e.g., JP-A-61-166544. Among the compounds enumerated above which generate an acid upon irradiation with actinic rays or a radiation, especially effective compounds are explained below. n represents a natural number of from 1 to 4. Curing, 13 (4), W. J. Mijs et al., Coating Technol., 55 (697), 45 (1983), Akzo, H. Adachi et al., Polymer Preprints, Japan, 37 (3), European Patents 0,199,672, 84,515, 199,672, 044,115, and 0,101,122, U.S. Pat. The present invention relates to a positive photoresist composition for use in the production of semiconductor IC elements, masks for IC production, printed circuit boards, liquid-crystal panels, etc. 69. (1) A positive photoresist composition which comprises (a) a resin obtained by replacing from 10 to 80% of the phenolic hydroxyl groups contained in an alkali-soluble resin containing phenolic hydroxyl groups with a group represented by the following general formula (I), (b) a compound which generates an acid upon irradiation with actinic rays or a radiation, and (c) a solvent, ##STR1## wherein R1 represents a substituent selected from alkyl groups having 1 to 4 carbon atoms, W is an organic residue containing at least one atom selected from oxygen, nitrogen, sulfur, phosphorus, and silicon atoms or an atomic group selected from the group consisting of an amino group, an ammonium group, and a mercapto group, and. The resin thus obtained was dried in a vacuum dryer at 120° C. for 12 hours to obtain a p-hydroxystyrene/styrene copolymer as alkali-soluble resin A-2. More preferred is methyl. A polymerization technique such as anionic polymerization is preferably used for obtaining a polymer having a molecular weight distribution in the above range. This mixture was heated with refluxing for 3 hours to hydrolyze the resin. Preferred examples of the solvent that can be used include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and tetrahydrofuran. The resin thus obtained was dried in a vacuum dryer at 120° C. for 12 hours to obtain a p-hydroxystyrene/methyl methacrylate copolymer as alkali-soluble resin A-3. The present invention provides a positive photoresist composition which has any of the following constitutions. The organic residue represented by W is constituted of at least one atom selected from oxygen, nitrogen, sulfur, phosphorus, and silicon atoms and at least one carbon atom. This reprecipitation operation was repeated three times. Ar1 and Ar2 may be bonded to each other likewise. The addition amount of these compounds which decompose upon irradiation with actinic rays or a radiation to generate an acid is generally from 0.001 to 40% by weight, preferably from 0.01 to 20% by weight, more preferably from 0.1 to 5% by weight, based on the total amount of the photosensitive composition (excluding the solvent). The onium salts represented by general formulae (PAG3) and (PAG4) are known. Preferred examples of the linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms as the group represented by R2 or R3 include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, and cyclohexyl. 4,069,055 and 4,069,056; the iodonium salts described in, e.g., J. V. Crivello et al., Macromorecules, 10 (6), 1307 (1977), Chem. Examples thereof include Oil Yellow #101, Oil Yellow #103, Oil Pink #312, Oil Green BG, Oil Blue BOS, Oil Blue #603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries Ltd., Japan), crystal violet (CI 42555), methyl violet (CI 42535), rhodamine B (CI 45170B), malachite green (CI 42000), and methylene blue (CI 52015). Chem. Examples of such preferred compounds include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridines, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomorpholine, and substituted or unsubstituted aminoalkylmorpholines. This reprecipitation operation was repeated three times. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, and 2,833,827, and German Patents 2,904,626, 3,604,580, and 3,604,581; the selenonium salts described in, e.g., J. V. Crivello et al., Macromorecules, 10 (6), 1307 (1977) and J. V. Crivello et al., J. Polymer Sci., Polymer Chem. Photosensitive Film Photographic Film for 5m Portable Photosensitive Dry Film for Circuit Production Photoresist Sheet . W is a group selected from the group consisting of the following substituents: ##STR19## wherein R2 represents a hydrogen atom or a substituent selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 6 carbon atoms, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group, provided that when W is ##STR20## or --OR2, then R2 represents a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms; R3 represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkoxy group having 1 to 6 carbon atoms, or a substituent selected from the group consisting of a halogen atom, a nitro group, an amino group, a hydroxyl group, and a cyano group; m represents a natural number of from 1 to 4; and. Entspricht der Photoresist der Qualität, die ich als Kunde für diesen Preis erwarten kann? No. Chem. 4,491,628 and European Patent 29,139. This mixture was heated with refluxing at 80 to 90° C. for 8 hours. Imaging Sci., 30 (5), 218 (1986), S. Kondo et al., Makromol. Chem., 43, 3055 (1978), W. R. Watt et al., J. Polymer Sci., Polymer Chem. Examples of the acid catalyst include sulfuric acid, formic acid, acetic acid, and oxalic acid. The resin obtained was dried and then dissolved in 150 ml of methanol. Examples of the alkali-soluble resin for use in the present invention include novolak resins, hydrogenated novolak resins, acetone-pyrogallol resins, poly(hydroxystyrene), alkyl-substituted poly(hydroxystyrene)s, hydroxystyrene/N-substituted maleimide copolymers, partially O-alkylated or O-acylated poly(hydroxystyrene)s, styrene/maleic anhydride copolymers, carboxylated methacrylic resins and derivatives thereof, styrene/polyhydroxystyrene copolymers, and hydrogenated poly(hydroxystyrene)s. However, the alkali-soluble resin for use in the present invention should not be construed as being limited to these examples. The resin obtained had a weight-average molecular weight of 15,000. The amount of the surfactant is preferably from 0.0005 to 0.01 part by weight, per 100 parts by weight of the composition (excluding the solvent). Z- represents a counter anion. Technol., 130 (6), F. M. Houlihan et al., Macromolecules, 21, 2001 (1988), European Patents 0,290,750, 046,083, 156,535, 271,851, and 0,388,343, U.S. Pat. Thus, such too high or too low degrees of replacement are unusable for the present invention. The following ingredients were mixed together in a flask. @k�cg�z���F��(� �=@��c��� �U��Q� ��cmqn���k�R�uk�>�����ʺ/�zDv��r���`��e�Z�����ƪ�cB��yc�Ƕ�?�D��ڤBx�i�9��h([�h,� �M���f����}ӈ��:�FN`j�y8��#J3/g���=���8E/�y��әj�o�3 In the above formulae, Ar1 and Ar2 each independently represents a substituted or unsubstituted aryl group. Preferred examples of the halogen atom include fluorine, chlorine, bromine, and iodine. In 200 ml of tetrahydrofuran was dissolved 50 g of the resin A-4. Its advantages include reduced process times, reduced UV light intensity exposure, and uniform photoresist thickness. This ether extract was added to the reaction mixture, and the ether and the chloroethyl vinyl ether remaining unreacted were removed with an evaporator. H��W˖۸��C�Yuϴd$����c�Ll��$��@$Ҧ@ݭ|}� Specific examples thereof are given below, but the compounds represented by general formula (PAG1) or (PAG2) should not be construed as being limited thereto. Preferred examples of the linear, branched, or cyclic alkoxy group having 1 to 6 carbon atoms as the group represented by R3 include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, and hexyloxy. From 10 to 80% of the phenolic hydroxyl groups of the alkali-soluble resin should be replaced with substituents represented by general formula (I) according to the present invention. The desired degree of the replacement by the substituent can be achieved by controlling the charged amount of the ether. Auf welche Faktoren Sie beim Kauf Ihres Photoresist Aufmerksamkeit richten sollten. The purple signifies photoresist, and black and white represents the dark and transparent parts of a photomask respectively. Three 0.033 g portions of azobisisobutyronitrile (AIBN) were added at an interval of 2.5 hours to the solution with stirring at 80° C. in a nitrogen stream and stirring was thereafter continued for 5 hours, whereby polymerization reaction was conducted. One very common positive photoresist used with the I, G and H-lines from a mercury-vapor lamp is based on a mixture of diazonaphthoquinone (DNQ) and novolac resin(a phenol formaldehyde resin). In JP-A-2-19847 is disclosed a resist composition characterized by containing a resin obtained from poly(p-hydroxystyrene) by protecting all or part of the phenolic hydroxyl groups each with a tetrahydropyranyl group. DuPont™ Riston® dry film photoresist revolutionized the way printed circuit boards were fabricated when it was invented by DuPont 40 years ago. One or more photo-acid generators are suitably selected from those and used alone or as a mixture thereof. 4.0 out of 5 stars 2. Andererseits wird das Mittel zwar auch gelegentlich etwas negativ bewertet, aber summa summarum genießt es einen ungemein guten Ruf. Specific example thereof are given below, but the compounds represented by general formula (PAG3) or (PAG4) should be construed as being limited thereto. Three 0.033 g portions of azobisisobutyronitrile (AIBN) were added at an interval of 2.5 hours to the solution with stirring at 80° C. in a nitrogen stream and stirring was thereafter continued for 5 hours, whereby polymerization reaction was conducted. The degree of this replacement is preferably from 15 to 60%, more preferably from 20 to 40%. Rad. Examples of the compound having two or more phenolic OH groups capable of accelerating dissolution in a developing solution include polyhydroxy compounds. Thereto was added an aqueous solution prepared by dissolving 7.7 g (0.19 mol) of sodium hydroxide in 50 ml of water. If the degree of replacement of the phenolic hydroxyl groups with groups represented by general formula (I) is lower than 10%, a sufficient difference in the rate of dissolution in alkali cannot be obtained between exposed and unexposed areas, resulting in reduced resolution. 2,807,648 and 4,247,473, and JP-A-53-101331. This process is called photolithographyand it can be summarized by Figure 1. Soc., Perkin I, 1695 (1975), M. Rudinstein et al., Tetrahedron Lett., (17), 1445 (1975), J. W. Walker et al., J. However, the counter anion should not be construed as being limited to these examples. This resin was taken out by filtration, washed with water, dried, and then dissolved in 200 ml of tetrahydrofuran to give a solution, which was added dropwise to 5 L of ultrapure water with vigorous agitation to conduct reprecipitation. Photoresist films are commonly used as a mask against ion implantation in MOS integrated circuits production. Sci. The present invention has been completed based on this finding. Especially preferred are compounds containing both at least one substituted or unsubstituted amino group and at least one nitrogen-containing ring structure and compounds having at least one alkylamino group. Ed., 18, 2677 (1980), U.S. Pat. Thereafter, the reaction mixture was diluted with 200 ml of water and neutralized with hydrochloric acid to precipitate a white resin.