TW200813627A - Photosensitive resin composition, laminate comprising the same, cured product of the same and method for forming pattern using the same (2) - Google Patents

Abstract

A photosensitive resin composition which can form a pattern having high resolution and a high aspect ratio and has high sensitivity. The photosensitive resin composition comprises one or more epoxy resins (A) selected among epoxy resins (A-1) having a biphenyl structure and polyfunctional epoxy resins (A-2), a polyfunctional bisphenol-A novolak epoxy resin (B), and a cationic photopolymerization initiator (C) which is sulfonium tris(pentafluoroethyl) trifluorophosphate.

Description

[Technical Field] The present invention relates to a photosensitive resin composition capable of forming a high resolution, high aspect ratio pattern, a laminate thereof, a cured product thereof, and a pattern using the composition. The method of formation. [Prior Art] Photoresistive photo-resistance has recently been widely used in semiconductor or MEMS (Micro-Electro-Mechanical Systems) applications. Such lithography is performed on a substrate by pattern exposure. Then, development is carried out with a developing solution to selectively remove the exposed or non-exposed areas. The photo-resistance (photoresist) processed by photolithography has a positive or negative type, and is dissolved in the developing solution by exposure to a positive type, and insoluble is a negative type. The advanced electropackage application requires a high aspect ratio. On the other hand, the MEMS application requires uniform spin coating film formation and a thick film above ΙΟΟμηη to maintain a straight shape, and high aspect ratio and photolithography. Light resistance. Among them, the aspect ratio is represented by the thickness of the photoresist film/line width, and is an important characteristic indicating the performance of photolithography. The prior art positive photoresist based on the naphthoquinone-novolac reaction is not suitable for applications requiring a thick film of 50 μm or more, and has a limit when thick filming, because it is generally used for photoresist exposure. The dinaphthoquinone type (DNQ) photoreactive material with ultraviolet wavelength (3 5 0~4 5 Onm) has relatively high light absorption, and the DNQ type photoresist has special solubility due to exposed and non-exposed areas in the developing solution. Different, so the shape of the side wall is not linear but instead presents a shape of tilt 200813627. The light intensity can be gradually reduced by the light absorption at the top to the bottom of the film, but if the light absorption is too high, the bottom of the photoresist appears to be underexposed in comparison with the top, so the side wall shape will have a slanted shape or a skewed shape. Negative chemically enhanced thick film photolithographic composition, known to have very low light absorption in the wavelength range of 3 5 0 to 45 nm, the composition of this photoresist consists of polyfunctional bisphenol A phenolic Varnish epoxy resin (Reponsive Performance Product EPON SU-8 Shuyue), photo-cationic polymerization initiator of CYRACURE UVI-6974 manufactured by Dow Chemical (this photo-cationic polymerization initiator is derived from aromatic hexafluoroantimony) The bismuth acrylate carbonate solution is formed by spin coating or shower coating on various substrates, and then volatilizing the solvent by baking to form ΙΟΟμιη or the number 値The above-mentioned solid photoresist layer of thickness is subjected to photolithography by irradiating near-ultraviolet light through a photomask by various exposure methods such as contact exposure, proximity exposure, and projection exposure. , immersed in the developer to dissolve the non-exposed areas, and form a negative image of the highly resolved mask on the substrate. EPON SU-8 resin is a low molecular weight epoxy oligomer with excellent characteristics in thick film and high aspect ratio photolithography. This excellent feature is (1) high epoxy functional group and (2) high branch chain. Degree, (3) 3 5 0~45 0nm high transmittance ' (4) low molecular weight necessary for the formation of solids; high epoxy functional group and high branching degree cause sufficient cross-linking under strong acid catalyst, high The transmittance is transmitted through a thick film and is uniformly irradiated with light, and has a resistive property of a pattern having a thickness of 1 〇〇μηη or more and an aspect ratio of 10 or more. Selecting a resin with a high epoxy-6 - 200813627 functional group and a high degree of branching is an important item for forming a side wall having a straight line and a structure having a high aspect ratio; selecting a low molecular weight resin, the number of minimum coating stages available A thick film photoresist layer is formed on the substrate. A photo-cationic polymerization initiator based on a mirror salt or an iodine salt is well known, and a useful photo-cationic polymerization initiator having a suitable absorbance is disclosed, which contains a carbonyl-P-phenylene sulfide (Patent Document 1) And 2), and may also add a sensitizer such as 2-alkyl-9,10-dimethoxyanthracene or other anthracene, naphthalene, beryl or pyrryl compound, or may be introduced into the photo-induced Cationic polymerization initiator (Patent Document 3). Negative photoresists based on compounds suitable for spin coating as disclosed above are sold by MICRO CHEM, particularly commercially for use in MEMS device parts. For example, the "SU-8 series" supplied by MICRO CHEM Co., Ltd. can be spin-coated at 1000 to 3000 rpm in order to form a film having a thickness of 30 to ΙΟΟμη, and then exposed and developed to have a film thickness of ΙΟΟμηη or more and an aspect ratio of 1 〇The above pattern. The use of a dry film photoresist coated on a substrate such as a polyester film is also disclosed (Patent Document 4). A composition suitable for use as a solder resist (3〇1 (1^11^31〇, a photosensitive cationically polymerizable flame retardant) (Patent Documents 5, 6, and 7) is disclosed as being contained in an amount of 10 to 80% by weight. a mixture of bisphenol hydrazine and epichlorohydrin condensate, comprising 20 to 90% by weight of bisphenol A novolac epoxy resin, 35 to 50% by weight of epoxidized tetrabromobisphenol A, 0.1 to 15 by weight a photopolymerizable compound based on a hydroxyl group-containing additive, a photocationic polymerization initiator, and an epoxy resin having a functional group number of 5.4 or more, as disclosed in 200813627. It has been reported that a hydroxyl group-containing additive is added to increase the flexibility or to reduce the stress of a thick film having a thickness of 1 ΟΟμιη or more (Patent Document 8). Patent Document 9 discloses the use of a hard epoxy resin in the use of a hardenable resin. The main method for the production, the friability of the epoxy resin that has been hardened by irradiation, and the resin (epoxy resin) used for most structures or consumables must be adequate in order to withstand the rigorous use for many years. Strength and resistance Impact, which discloses a wide range of tough materials including SU-8 resin, and the effectiveness of the invention claimed in Patent Document 9 regarding the increased strength is expressed by the fracture toughness and the flexural modulus, the tough material It is composed of various thermoplastic plastics, hydroxyl-containing thermoplastic plastic oligomers, epoxy-containing thermoplastic plastic oligomers, reactive softness, elastomers, rubber, and the like. However, Patent Document 9 describes The composition is applied to a composition of a film which is imaged by irradiation with a non-pattern, and when it is subjected to pattern exposure by irradiation with UV, X-ray or krypton, the characteristics of these compositions cannot be used as a photosensitive object. A number of proposals are made for epoxy-containing photoresist compositions (Patent Document 1), in which, for example, the necessity of modulating a photoresist composition suitable for spin coating is required, and rheological properties are required, plus The composition herein must have sufficient transmittance for exposure irradiation such as photo-decomposition photoinitiator after film thickness. In addition, the photoresist composition must be used for various purposes. Appropriate physical and chemical properties that are not resistant to soldering or ink resistance or strength, or that do not degrade in adhesion. If the photoresist composition is used, -8-200813627 is used as a photoresist for etching. For other uses, other characteristics are required. However, the specific epoxy resin that satisfies all of the various requirements is not present at present, and many different combinations or mixtures of various epoxy resins have been disclosed, and well-known patents are described. Various resins and photoinitiators for photohardenable compositions, most of which are sensitized photoresists suitable for use as permanent films, but none of which reveals the composition that we are trying to accomplish that is most suitable for MEMS applications. In fact, most of the examples of the plasticizer, the softener, and the toughener can reduce the lithography performance. [Patent Document 1] USP 5 5 020 83 [Patent Document 2] USP 6368769 [Patent Document 3] USP 5 1 02772 [Patent Document 4 USP 4,882,245 [Patent Document 5] USP 5026624 [Patent Document 6] USP5278010 [Patent Document 7] USP 5 3 0445 7 [Patent Document 8] USP 4256828 [Patent Document 9 US Pat. No. 5,264, the disclosure of which is hereby incorporated by reference. The subject of the present invention is to use a photosensitive resin composition of the prior art using a polyfunctional epoxy resin such as a novolac type epoxy resin. The cationic polymerization initiator has low sensitivity and requires a large amount of initiator. Therefore, there is a problem that the mask pattern cannot be faithfully reproduced in the resin pattern in the short period of -9-200813627. In addition, the SbF is contained.光 Photoinduced cationic polymerization initiators are more sensitive to high sensitivity, but there are problems in their use due to their toxicity problems. The present invention has been made in view of the above-described problems of the prior art. The subject of the invention is to provide a photosensitive resin composition which can form a pattern of high resolution and high aspect ratio and which has high sensitivity and low toxicity. [Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have found that the combination of specific sensitivity and high resolution is repeated, and the results of careful investigation, experimentation, and review are repeated. The epoxy resin and a specific photocationic polymerization initiator prepare a photosensitive resin composition, and when the photosensitive resin composition is used to form a resin pattern, a resin pattern having high sensitivity and a high aspect ratio can be formed. That is, the constitution of the present invention is as follows. (1) A photosensitive resin composition comprising: an epoxy resin (A-1) having a biphenyl structure represented by the following general formula (1) and a general formula (2): One or more than one epoxy resin (A) of the polyfunctional epoxy resin (A-2), and one or more than one of the above-described general formula (3) of the biguanide A novolac a polyfunctional epoxy resin (B), and a photocationic polymerization initiator (C) of ruthenium (pentafluoroethyl)trifluorophosphonium phosphate; -10- 200813627

(wherein Rr R2 is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; η represents an average enthalpy, and is a real number of 1 to 30.) [Chemical 2]

〇CJh (2) (wherein, RPR2 is each independently a hydrogen atom or a methyl group; t, u, and v each represent an average enthalpy, and are independently a real number of 1 or more, and the sum is a real number of 3 to 30.) 3]

-11 - 200813627 (wherein R is each independently a glycidyl group or a hydrogen atom; and n represents an average enthalpy, which is a real number of 1 to 30.). (2) The photosensitive resin composition as described in the above (1) wherein the photo-cationic polymerization initiator (c) is a compound (C-1) represented by the following formula (4). 【化4】

(3) The photosensitive resin composition according to the above (1) or (2), which contains one or more than one reactive epoxy monomer (D). (4) The photosensitive resin composition according to any one of the above (1) to (3) which contains a solvent (E) and has a solid content concentration of 5 to 95% by weight. (5) A photosensitive resin composition laminate according to any one of the above (1) to (4). (6) A cured product comprising the photosensitive resin composition as recited in any one of the above (1) to (4). (7) A method for forming a pattern comprising a photosensitive resin composition obtained by applying the photosensitive resin composition according to any one of the above (1) to (4) to a desired support. After the layer is dried, it is exposed to a predetermined pattern, and after exposure and baking, the resin composition layer is developed, and the obtained resin pattern is heat-treated, and a step of obtaining a cured resin pattern having a predetermined shape is obtained. (8) A method for forming a pattern comprising a photosensitive resin composition layer remaining after removing a substrate from the laminate of 200813627 described in (5), and bonding the layer to the desired support layer The photosensitive resin composition layer is exposed to a predetermined pattern, baked after exposure, and the resin composition layer is developed, and the obtained resin pattern is heated to obtain a cured resin pattern of a predetermined shape. . [Best Mode for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described. The photosensitive resin composition of the present invention is characterized by containing an epoxy resin (A-1) having a biphenyl structure represented by the following general formula (1) and a general formula (2): One or more epoxy resins (A) of the functional epoxy resin (A-2), and one or more than one bisphenol A novolak type represented by the following general formula (3) The photo-cationic polymerization initiator (C) of the polyfunctional epoxy resin (B) and the ginseng (pentafluoroethyl) trifluorophosphate mirror can form a resin pattern of high sensitivity and high aspect ratio. There are various possibilities for such a combination, but in particular, a biphenol novolak type epoxy resin (for example, NC3 000H Nippon Chemical Co., Ltd.), and a polyfunctional epoxy resin (for example, NER7604 Nippon Chemical Co., Ltd.) One or more types of epoxy resins, and an 8-functional bisphenol A novolac type epoxy resin (for example, EPON SU-8 resin manufactured by Resolution Performance Product), and a compound represented by the above formula (4) The combination of photocationic polymerization initiators is optimal. The epoxy resin (A) of the present invention is one or more than one epoxy selected from the group consisting of a polyfunctional epoxy resin (A-1) having a biphenyl structure and a polyfunctional epoxy resin (A-2). Resin. -13- 200813627 The polyfunctional epoxy resin (A" having a biphenyl structure of the present invention may be a polyfunctional epoxy resin containing a sufficient amount of biphenyl in one of the patterns for forming a thick film, Any epoxy resin may be used alone or in combination of two or more. The epoxy equivalent of the polyfunctional epoxy resin having a biphenyl structure is preferably 150 to 400, and the hardening shrinkage is less than this range. Larger and less preferable. On the other hand, when it is larger than this range, the crosslinking density becomes smaller and it is less. The polyfunctional epoxy resin having a biphenyl structure in accordance with the above range is a biphenyl aldehyde varnish type epoxy resin. (For example, NC3 000H 曰 化 制 制 ) 。 。 。 。 。 。 NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC NC The polyfunctional epoxy resin (A _ 1 ) of the biphenyl structure is represented by the following formula (1).

(wherein, Ri and R2 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and η is a real number of 1 to 30 of the average enthalpy.) The polyfunctional epoxy resin (Α-2) of the present invention is as long as An epoxy resin obtained by reacting an alcoholic hydroxyl group of a bisphenol F type epoxy resin having a sufficient epoxy group in a molecule for forming a thick film with epichlorohydrin, and by double In the reaction of the alcoholic hydroxyl group of the phenolphthalein type epoxy resin with epichlorohydrin, the epoxy resin of 200813627 is obtained, and any epoxy resin may be used. These may be used alone or in combination of two or more. The epoxy equivalent of the polyfunctional epoxy resin (A-2) is preferably from 150 to 400, and is less than this range, and is not preferable from the viewpoint of large hardening shrinkage and easy warpage or cracking of the cured product. On the other hand, when it is larger than this range, the crosslinking density becomes small, the strength of the cured film or the chemical resistance, the heat resistance, and the crack resistance are poor. The polyfunctional epoxy resin (A-2) in the above range is particularly preferably NER-7604 (epoxy equivalent 3 2 5 ) or NER-1 320 (epoxy equivalent 315) (manufactured by Nippon Kayaku Co., Ltd.). Among them, t, u and v in the general formula (2) represent the number of repeating units, which are obtained by dividing the average molecular weight measured by GPC by the molecular weight of the repeating unit. The above polyfunctional epoxy resin (A-2) is represented by the following formula (2). 【化6】

(2) (wherein R1 and R2 are each independently a hydrogen atom or a methyl group, and t, U and V are each independently a real number of 1 or more of an average enthalpy, and the sum is a real number of 3 to 30.) The present invention The bisphenol A novolac type polyfunctional epoxy resin (B) may be a bisphenol A novolak type polyfunctional epoxy resin having a sufficient epoxy group in a molecule for forming a thick film. Any epoxy resin may be used alone or in combination of two or more. Specific examples of such bisphenol A novolak-type polyfunctional epoxy resins include epon 200813627 SU-8 (manufactured by R es ο 1 uti ο n Performance Product), EPIKOTE 157S70, and EPIKOTE 157S65 (manufactured by Sakamoto Epoxy Co., Ltd.) ), YD-128 (manufactured by Tosho Kasei Co., Ltd.), EPICLON N- 8 8 5, EPICLON N-865, and EPICLON 2055 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.). The bisphenol A novolac type polyfunctional epoxy resin preferably has an epoxy equivalent of from 150 to 400, and is less than this range, and is less excellent from the viewpoint of large hardening shrinkage and easy occurrence of warpage or cracking of the cured product. On the other hand, when it is larger than this range, the crosslinking density is small, the strength of the cured film or the chemical resistance, the heat resistance, and the crack resistance are poor. A bisphenol A novolac type polyfunctional epoxy tree which is in the above range is preferably EPON SU-8 (Resolution Performance Product) or EPIKOTE 157S70 (manufactured by Nippon Epoxy Co., Ltd.). The polyfunctional epoxy tree (B) is represented by the following formula (3). Wherein, η in the general formula (3) represents the number of repeating units, which is obtained by dividing the average molecular weight measured by GP C by the molecular weight of the repeating unit. 【化7】

(wherein R is each independently a glycidyl group or a hydrogen atom' η is a real number of 1 to 30 of an average 値 -16 - 200813627.). When the softening point of the epoxy resin (A) and the bisphenol A novolac type polyfunctional epoxy resin (B) is low, the mask is likely to adhere when patterning is formed, and when used as a dry film photoresist, Softening at room temperature is less preferred. On the other hand, when the softening point of the polyfunctional epoxy resin having a biphenyl structure is high, the dry film photoresist is not easily softened when laminated on the substrate, and the adhesion to the substrate is deteriorated. Therefore, it is not good. For the above reasons, the polyfunctional epoxy resin preferably has a softening point of 40 to 120 ° C, more preferably 50 to 100 ° C. The photocationic cationic polymerization initiator of the present invention is subjected to irradiation with radiation of excimer laser, X-ray, electron beam or the like of ultraviolet rays, far ultraviolet rays, KrF, ArF or the like to generate cations, and the cation can be polymerized. The compound of the starting agent. The photocationic polymerization initiator (C) is ruthenium (pentafluoroethyl)trifluorophosphate. The mirror of the photocationic polymerization initiator may, for example, be triphenylsulfonium, tris-P-tolylhydrazine, tris-fluorenyltolylhydrazine, stilbene (4-methoxyphenyl)fluorene or 1-naphthyl. Diphenylanthracene, 2-naphthyldiphenylphosphonium, stilbene (4-fluorophenyl)anthracene, tri-1-naphthylfluorene, tris-2-naphthyl anthracene, ginseng (4-hydroxyphenyl)anthracene, 4-(phenylthio)phenyldiphenylphosphonium, 4-(p-tolylthio)phenyldi-P-tolyl mirror, 4-(4-methoxyphenylthio)phenyl bis (4) -Methoxyphenyl)anthracene, 4-(phenylthio)phenylbis(4-fluorophenyl)anthracene, 4-(phenylthio)phenylbis(4-methoxyphenyl)anthracene, 4 -(phenylthio)phenyldi-P-tolylhydrazine, bis[4-(diphenylfluorenyl)phenyl] sulfide, bis[4-(bis[4-(2-hydroxyethoxy)) Phenyl]fluorenyl)phenyl] sulfide, bis(4-[bis(4-fluorophenyl)indenyl]phenyl) sulfide, bis(4_[bis(4-methylphenyl)indenyl] -17- 200813627 Phenyl) sulfide, bis(4-[bis(4-methoxyphenyl)indenyl]phenyl) sulfide, 4-(4-benzoguanidine-4-chlorophenyl sulfide) Phenyl bis(4-fluorophenyl) mirror, 4-(4-benzhydrazin-4-chlorophenylthio)phenyldiphenylanthracene, 4-(4-benzamide) Phenylthio)phenylbis(4-fluorophenyl)anthracene, 4-(4-benzylidenephenylthio)phenyldiphenylphosphonium, 4-isopropyl-4-oxo-10-thio- 9,10-dihydroinden-2-yldi-P-tolylhydrazine, 7·isopropyl-9-oxo-10thioindole-9,10 - _^ 恩-2-yl-yl-based Mirror, 2-[(-.-p-tolyl)indolyl]thioxanthone, 2-[(diphenyl)indenyl]thioxanthone, 4-[4-(4-tert-butylbenzene)醯)phenylthio]phenyldi-P-tolylhydrazine, 4-[4-(4-tert-butylbenzylidene)phenylsulfonyl]phenyldiphenylphosphonium, 4-[4-(benzene Methyl phenyl thio)]phenyl di-P-tolyl fluorene, 4-[4-(benzylidene phenylthio)]phenyldiphenyl fluorene, 5-(4-methoxyphenyl) sulphide Anthrenium, 5-phenylthiaanthenium, 5-tolylthiaanthenium, 5-(4-ethoxyphenyl)thiaanthenium, 5-(2,4,6-trimethylphenyl)sulfide a triaryl sulfonium such as an anthranium; a diphenyl hydrazine methyl hydrazine; a diphenyl 4-nitrophenyl hydrazine methyl hydrazine; a diphenyl benzyl hydrazine; a diphenylmethyl hydrazine; Phenylmethylbenzyl hydrazine, 4-hydroxyphenylmethylbenzyl hydrazine, 4-methoxyphenylmethylbenzyl hydrazine, 4-ethyl hydrazine carbonyl Phenylmethylbenzyl hydrazine, 2-naphthylmethylbenzyl hydrazine, 2-naphthylmethyl(1-ethoxycarbonyl)ethyl hydrazine, phenylmethylphenylhydrazine methyl hydrazine, 4-hydroxyl Phenylmethylphenylhydrazine methylhydrazine, 4-methoxyphenylmethylphenylhydrazinemethylhydrazine, 4-ethylhydrazine carbonyloxyphenylmethylphenylhydrazinemethylhydrazine, 2-naphthylmethylbenzoquinone a monoaryl fluorene such as fluorenyl, 2-naphthyl octadecyl phenyl hydrazine methyl hydrazine or 9-fluorenylmethyl phenyl hydrazine methyl hydrazine; dimethyl phenyl hydrazine methyl hydrazine, phenyl hydrazine methyl tetrahydro hydride A three-hospital base such as a thiophene key, a dimethylbenzyl hydrazine, a benzyl tetrahydrothiophene key, or an 18-yard methyl hydrazine methyl hydrazine. These are described in the following -18-200813627. As for the triaryl sulfonium, there are exemplified by U.S. Patent No. 4 2 3 1 591, U.S. Patent No. 4,258,682, U.S. Patent No. 7-6, No. 1,964, Japanese Patent Laid-Open No. Hei. 10914, Special Kaiping 7-25922, Special Kaiping 8-27208, Special Kaiping 8-27209, Special Kaiping 8-1 65290, Special Kaiping 8-301991, Special Kaiping 9-143212, Special Kaiping 9- No. 278813, special Kaiping 1 0-7680, special Kaiping 1 0-287643, special Kaiping 10-245 3 7 8 , special Kaiping 8 - 1 5 7 5 1 0, special Kaiping 1 0-2040 83, Special Kaiping No. 8-245 5 66, Special Kaiping No. 8-1 5 74 5 1 , Special Kaiping No. 7-324069, Special Kaiping No. 9-268205, Special Kaiping 9-27893 No. 5, Special Opening No. 2001-288205, Special Kaiping 11-80118, Special Kaiping 10-1 8282 5, Special Kaiping 1 0-3 3 03 5 3, Special Kaiping 1 0- 1 52495, Special Kaiping 5-23 92 1 3, Special Kaiping 7 -3 3 3 8 3 No. 4, Special Kaiping 9-1 25 3 No. 7, Special Kaiping 8 -3 2 525 9 , Special Kaiping 8 - 1 60606, Special Opening 2000_ 1 8607 1 (US Patent No. 63 68769 No.); for the diaryl sulfonium, it can be cited as No. 7-3 00504, and No. 64-4 5 3 5 7 , JP-A-64-294, No. 9 and the like; for the monoaryl sulfonium, JP-A-6-345726, JP-A-8-325225, and JP-A-9-186663 (U.S. Patent No. 6,093,753) , Special Kaiping 2- 1 968 1 2, Special Kaiping 2-1470, Special Kaiping 2- 1 968 1 2, Special Kaiping 3 -23 7 1 07, Special Kaiping 3-17 101, Special Kaiping 6- No. 228086, special Kaiping 1 0- 1 52469, special Kaiping 7-3 005 05, special open 2003 - 2773 5 3, special open 2003 - 2773 52, etc.; for trialkyl mirrors, can be listed as special Kaiping 4 -3 08 5 63, special Kaiping 5-14010, special Kaiping 5-140209, special Kaiping 5--19-200813627 23 0 1 89, special Kaiping 6-27 1 5 3 2, special opening 5 8-3 7003, special Kaiping 2- 1 7 83 03, special Kaiping 1 0-3 3 8 68 8 , special Kaiping 9-3 28 5 06, special Kaiping 1 1 -228 5 3 4, special Kaiping 8-27 1 02, Special Kaiping 7-3 3 3 8 3 4, Special Kaiping 5-222 1 67, Special Kaiping 11-21307, Special Kaiping 1 1 -3 5 6 1 3, US Patent No. 603 1 0 1 4 and so on. In particular, the ruthenium of the photocationic polymerization initiator is preferably triphenylphosphonium or 4-(phenylthio)phenyldiphenylphosphonium, and phenylsulfanylphenyl represented by the following formula (4). Phenylhydrazine (A-1) is the best. 【化8】

The total amount of the epoxy resin (A) and the bisphenol A novolak type polyfunctional epoxy resin (B) is too low relative to the content of the photosensitive resin composition, and the photocationic polymerization initiator (C) When the content in the photosensitive resin composition is too high, development of the resin composition is difficult, and the cured film becomes brittle, which is not preferable. On the other hand, the total amount of the epoxy resin (A) and the bisphenol A novolak type polyfunctional epoxy resin (B) is too high relative to the content of the photosensitive resin composition, and the photocationic polymerization initiator is used. (C) When the content in the photosensitive resin composition is too low, the curing time of the resin composition by radiation exposure becomes long when applied to a substrate, which is less preferable. Considering the above problems, the ratio of the above epoxy resin-20-200813627 (A) and the bisphenol A novolak type polyfunctional epoxy resin (B) to the photocationic polymerization initiator (c) is 〇.1 : 99.9~15 : 85 is better, preferably 〇·5 : 99.5~10 : 90. In the photosensitive resin composition of the present invention, in order to further improve the performance of the pattern, a reactive reactive epoxy monomer (D) may be added, and a reactive epoxy monomer may be used. For example, a glycidyl ether compound may be used. Diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, dimethylolpropane diglycidyl ether, polypropylene glycol diglycidyl ether (made by Asahi Kasei Co., Ltd., ED506), trimethylolpropane Triglycidyl ether (manufactured by Asahi Kasei Co., Ltd., ED5 05), pentaerythritol tetraglycidyl ether, etc.; these may be used alone or in combination of two or more. The reactive epoxy monomer (D) component is used for improving the reactivity of the photoresist or the physical properties of the cured film. The reactive epoxy monomer component is more in liquid form, and when the component is in a liquid state, When the blending is more than 20% by weight, it is less likely to cause sticking of the film after the solvent is removed, causing adhesion of the mask, etc., and thus, when the reactive epoxy monomer component is blended, The blending ratio is a combination of the (A) component, the (B) component, the (c) component, and the (D) component, and the solid component of the photoresist is preferably 1 to 10% by weight based on the solid component, particularly It is more suitable for 2 to 7 wt%. When the viscosity of the photosensitive resin composition of the present invention is lowered, a solvent (E) which improves the coating property can be used, and the solvent (E) can be used by using an organic solvent which is generally used and can dissolve various components. Examples of the solvent include ketones such as acetone, methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether; Glycol ethers, esters of ethyl acetate, butyl acetate, butyl cellosolve B-21-200813627 acid ester, carbitol acetate, propylene glycol monomethyl ether acetate, r-butyrolactone, etc. Alcohols such as methanol, ethanol, cellosolve, methyl cellosolve, aliphatic hydrocarbons such as octane and decane, petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, etc. Such as organic solvents and the like. These solvents may be used singly or in combination of two or more. The purpose of the solvent component is to adjust the film thickness or coatability when applied to a substrate, in order to maintain proper solubility of the main component, volatility of the component, and composition. The liquid viscosity of the material is preferably from 5% by weight to 95% by weight, particularly preferably from 10% by weight to 90% by weight, based on the photosensitive resin composition. In the photosensitive resin composition of the present invention, in order to further improve the adhesion of the composition to the substrate, a miscibility imparting agent having a miscibility may be used, and a decane coupling agent or a titanium coupling agent may be used as the adhesion imparting agent. The coupling agent is preferably a decane coupling agent. The above decane coupling agent may, for example, be 3-chloropropyltrimethoxydecane, vinyltrichlorodecane, vinyltriethoxydecane, vinyltrimethoxydecane or vinylquinone (2-methoxyethoxyl). Base) decane, 3-methacryloxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane , 3_mercaptopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-2_(aminoethyl)-3-aminopropyltrimethoxydecane, 3-anthracene Triethoxy decane and the like. These adhesion imparting agents may be used singly or in combination of two or more. Since the main component is unreactive, the adhesion imparting agent exists as a residual component after hardening, in addition to the component acting on the interface of the substrate. Therefore, if it is used in a large amount, it will cause a bad influence such as a decrease in physical properties. Depending on the substrate, it is more appropriate to use it in a range that does not cause adverse effects from the viewpoint that even a small amount of -22-200813627 can exert its effect. The use ratio is preferably 5% by weight or less based on the photosensitive resin composition, and particularly preferably 5% by weight or less. In the photosensitive resin composition of the present invention, a sensitizer which absorbs ultraviolet light and supplies the absorbed light energy to the photocationic polymerization initiator may be further used as the sensitizer, preferably, for example, 9-position. And a fluorene compound having alkoxy group at the 1-position (9,10-dialkoxyfluorene derivative), and the alkoxy group may, for example, be a C1 to C4 alkane such as a methoxy group, an ethoxy group or a propoxy group. Oxygen. The 9,10-dialkoxyfluorene derivative may further have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a methyl group, an ethyl group, a propyl group or the like. An alkyl group or a sulfonic acid alkyl ester group of C1 to C 4 or a carboxylic acid ester group or the like. The sulfonate sulfonate group or the decyl phthalate ester group may, for example, be a C1 to C4 alkyl group such as a methyl group, an ethyl group or a propyl group, and the substitution position of these substituents is preferably 2 positions. The 9,10-dialkoxypurine derivative may, for example, be 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-di Methoxy-2-ethyl hydrazine, 9,10-diethoxy-2-ethyl hydrazine, 9,10-dipropoxy-2-ethyl hydrazine, 9,10-dimethoxy-2 -chloropurine, 9,10-dimethoxyindole-2-sulfonic acid methyl ester, 9,10-diethoxyindole-2-sulfonic acid methyl ester, 9,10-dimethoxyanthracene- 2-carboxylic acid methyl ester or the like; these may be used singly or in combination of two or more. The sensitizer component is effective in a small amount, and therefore the ratio is preferably 3% by weight or less, particularly preferably 1% by weight or less, based on the photocationic polymerization initiator (C). In the present invention, it is necessary to reduce the adverse effects of ions derived from the photocationic cationic starting polymerization agent -23-200813627 (A), and it is also possible to add methoxy aluminum, ethoxylated aluminum, and isopropyl isopropoxide. Aluminum alkoxide such as aluminum, isopropoxy diethoxy aluminum or butyl aluminum oxide; phenoxy aluminum such as phenoxy aluminum or para-methylphenoxy aluminum; Base aluminum, ginseng aluminum stearate, aluminum arsenate, aluminum propionate, aluminum acetonide, aluminum hexaacetate, aluminum acetoacetate, aluminum acetoacetate, diethyl acetonide An ion scavenger such as an organoaluminum compound such as aluminum formate or diisopropoxy (ethyl acetoacetate) aluminum; these components may be used singly or in combination of two or more kinds, and the blending amount thereof is It may be 1% by weight or less based on the solid content. Further, in the case of the present invention, various additives such as a thermoplastic resin, a colorant, a tackifier, an antifoaming agent, and a leveling agent can be used. Examples of the thermoplastic resin include polyether oxime, polystyrene, and polycarbonate; and examples of the coloring agent include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, naphthalene black, and the like. Examples of the tackifier include Orben, Pantone, and montmorillonite. Examples of the antifoaming agent include antifoaming agents such as polysiloxanes, fluorines, and polymers. The use of such an additive or the like is used in the photosensitive resin composition of the present invention, for example, each of which is a simple standard of about 0.1 to 30% by weight, and can be appropriately increased or decreased depending on the purpose of use. Further, in the present invention, an inorganic chelating agent such as barium sulfate, barium titanate, cerium oxide, amorphous cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, oxidized magnesium, aluminum hydroxide or mica powder may be used. The blending ratio may be 0 to 60 weight/min in the composition. The photosensitive resin composition of the present invention is preferably added in the proportions shown in Table 1 below, and if necessary, the above-mentioned adhesion imparting agent, sensitizer, and from -24 to 200813627 sub-capture, thermoplastic resin, and colorant may be added. , tackifiers, defoamers, coating agents and inorganic chelating agents. The mixture may be mixed in a usual manner, or may be stirred only, and if necessary, it may be dispersed, mixed, and reused by a disperser such as a dissolver, a homogenizer or a 3-roller, and filtered by a mesh sieve or a membrane filter.

Parts by weight epoxy resin (A) 1 r\ I~/ u Bisphenol A novolak type epoxy resin (B) I5~98.9 Photocationic polymerization initiator (c) 0· I ~ I 5 Reactive epoxy (D) I to 10 Solvent (E) 5.8 to 2090 The photosensitive resin composition of the present invention is preferably used in the form of a liquid, and when the photosensitive resin composition of the present invention is used, for example, a spin coater or the like can be used. It is applied to a substrate such as a ruthenium wafer or a glass at a thickness of 0.1 to 100 μm, and heat-treated at 60 to 130 ° C for about 5 to 60 minutes to remove a solvent to form a photosensitive resin composition layer, and then placed thereon. After the mask of the predetermined pattern is irradiated with ultraviolet rays, heat treatment is performed at 50 to 130 ° C for about 1 to 50 minutes, and then the unexposed portion is developed with a developer at room temperature to 50 ° C for about 1 to 180 minutes. The pattern is then heat treated at 130 to 200 ° C to obtain a permanent protective film that meets the characteristics. As the developer, an organic solvent such as r-butyrolactone, triethylene glycol dimethyl ether or propylene glycol monomethyl ether acetate, or a mixture of the above organic solvent and water can be used, and a development type can also be used. A developing device such as a spray type or a shower type may be subjected to ultrasonic irradiation if necessary. -25-200813627 The photosensitive resin composition of the present invention is coated with a roll coater, a die coater, a knife coater, a bar coater, a gravure coater, or the like. After the composition was applied to the base film, it was dried by a drying oven set at 45 to 100 ° C, by removing the amount of the solvent, and if necessary, by laminating the outer layer film as a dry film photoresist. At this time, the thickness of the photoresist on the base film is adjusted to 2 to ΙΟΟμιη, and the base film and the outer layer film can be, for example, a film of polyester, polypropylene, polyethylene, TAC, polyimine or the like. A film which is subjected to release treatment by an oxime release treatment agent or a non-oxime release treatment agent can be used. By using the dry film photoresist, for example, by peeling the outer layer film by a manual roller, a laminator or the like, the substrate is transferred to the substrate at 40 ° C to 1 0 0 ° C and a pressure of 0. 05 to 2 MPa. The exposure, post-exposure baking, development, and heat treatment are carried out in the same manner as the photosensitive resin composition described in one paragraph. The above-mentioned photosensitive resin composition is supplied as a film, and the step of applying to the support and drying can be omitted, and pattern formation can be performed more easily. The cured product of the resin composition of the present invention obtained by the above method is used, for example, as a permanent photoresist film for a MEM S component such as a jet recording head. [Embodiment] [Embodiment] The embodiments of the present invention are described below, and the examples are merely illustrative of the present invention and are not intended to limit the present invention. -26-200813627 (Examples 1 to 3, Comparative Example 1) (Photosensitive resin composition) The polyfunctional epoxy resin and photocationic polymerization were polymerized according to the blending amount (unit: parts by weight) described in Table 2 The initiator and other components were stirred and mixed at 60 ° C for 1 hour in a flask equipped with a stirrer to obtain a photosensitive resin composition. (Picture of photosensitive resin composition) (Examples 1 to 3, Comparative Example 1) This photosensitive resin composition was applied onto a tantalum wafer by a spin coater and dried to obtain 80 μm. a photosensitive resin composition layer having a film thickness, and the photosensitive resin composition layer is prebaked by a hot plate at 65 ° C for 5 minutes and 95 t for 20 minutes, and then an i-line exposure device (photomask) is used. Alignment device: manufactured by USHIO Electric Co., Ltd.) pattern exposure (soft contact, i-line), post-exposure bake (PEB) at 95 °C for 6 minutes using a hot plate, followed by propylene glycol monomethyl ether acetate The ester was subjected to development treatment at 23 ° C for 7 minutes by a dipping method to obtain a cured resin pattern on the substrate (evaluation of the photosensitive resin composition). After development, the following evaluation was performed by the necessary exposure amount, and the results are shown in Table 2 below. Optimum exposure: the optimum precision of the reticle transfer precision: the film thickness / the thinnest pattern of the formed photoresist pattern -27-200813627 [3嗽] Comparative Example TH Ο <Ν(N 〇\ inch 〇moo (N 300 σ> Example m Ο ο Ό inch inch 〇m VO oo <N 180 ο (N Ο (Ν 〇〇〇 inch ο moo (N 200 〇 \ 〇\ ο CN inch inch ο moo <N 180 OS blended ingredients!_ NC3000H NER7604 EPON SU-8 CPI-2 1 0S UVI-6974 ED506 CP F-470 〇rH 1 m Optimum exposure (mJ/cm2) Width ratio rH 1 < (Ν I < PQ U ffi Q (Jh O as 秘 秘 {ππ carboxy 擀 polyfunctional epoxy resin m m 狻 photo photo cation initiator reactive epoxy monomer solvent Coating Agent Coupler-28 - 200813627 Notes: (Al): Biphenylphenol varnish type multifunctional epoxy resin (trade name NC3 000H, n = 5, manufactured by Nippon Kayaku Co., Ltd.) (A-2): Functional epoxy resin (trade name: NER-7604, t+u+v = 6, manufactured by Sakamoto Chemical Co., Ltd.) (B): Bisphenol A novolac type multifunctional epoxy resin (trade name EP ON SU- 8 , n = 8, Resolution Performance Product) (Cl): photo-cationic polymerization initiator (trade name: CPI-210S san-apro) (D): Reactive epoxy monomer (trade name: ED5 06 Asahi (Electrical Chemical Co., Ltd.) (E): Solvent cyclopentanone (F): Fluorine coating agent (trade name · MEGAFAC F-470 Dainippon Ink Chemical Industry Co., Ltd.) (G) : decane coupling agent (trade name: manufactured by S_510 CHISSO Co., Ltd.) (H): Photocationic polymerization initiator (trade name: 50% propylene carbonate solution manufactured by Dow Chemical Co., Ltd.) As shown in Table 2, Examples 1 to 3 (Example 4) (Photosensitive resin composition) 20 parts by weight of a polyfunctional resin (trade name: NER-7604, manufactured by Nippon Kayaku Co., Ltd.) and 80 parts by weight of bisphenol a phenol aldehyde were mixed. Varnish-type polyfunctional ring and tree|Japan (Shangkoukou name EPON SU-8' Resolution Performance -29- 200813627

Product system), 4.6 parts by weight of photopolymerization initiator (trade name: CPI-21 OS san-apro (manufactured by the company)), 4 parts by weight of reactive epoxy monomer (trade name ED506 Asahi Chemical Industry Co., Ltd.) And 40 parts by weight of MEK to obtain a photosensitive resin composition. (Picture of the photosensitive resin composition) This photosensitive resin composition was uniformly applied to a 60 μm polypropylene film (base film, manufactured by Toray Co., Ltd.), and dried by warm air convection. After drying at 65 t for 10 minutes and at 80 ° C for 15 minutes, a PP film (outer film, manufactured by Toray Industries, Inc.) having a film thickness of 60 μm was laminated on the photosensitive resin composition layer to form a film having a film thickness of 40 μm. Resin composition laminate. The outer layer film of the photosensitive resin composition laminate was peeled off, laminated on a sand wafer at a roller temperature of 70 ° C, a gas pressure of 0.2 MPa, and a speed of 0.5 m/min, and the base film was peeled off, and this operation was repeated once more. Thus, a photosensitive resin composition layer of 80 μm was obtained. On the photosensitive resin composition layer, pattern exposure (soft contact, i line) was performed using an i-ray exposure apparatus (mask alignment apparatus: manufactured by USHIO Electric Co., Ltd.), and then, at 95 ° C by a heating plate. 4 minutes of PEB, followed by PGMEA, was subjected to development treatment at 23 ° C for 4 minutes by dipping, and a hardened resin pattern was obtained on the substrate. Excellent results were obtained in which the optimum exposure amount is OmJ/cm2 and the aspect ratio is 9.6. From the comparison of the results of Examples 1 to 4 and Comparative Example 1, it is clear that a combination of a polyfunctional epoxy resin having a specific structure and a specific photocationic polymerization initiator can provide a high which cannot be obtained by other combinations. Resin pattern with a shape of -30-200813627 aspect ratio. [Industrial Applicability] As described above, the photosensitive resin composition according to the present invention is suitable for forming a resin pattern having an outer shape having a high aspect ratio, and is particularly suitable for a high dimensional stability of an electronic device having a fine size. Resin molding. -31 -

Claims (1)

200813627 X. Patent Application No. 1 A photosensitive resin composition characterized by comprising an epoxy resin (A-ι) having a biphenyl structure represented by the following general formula (1) and the following general formula (2) One or more epoxy resins (A) of the polyfunctional epoxy resin (A-2) and one or more than one of the following general formula (3) a bisphenol A novolac type polyfunctional epoxy resin (B), and a photo-cationic polymerization initiator (C) of a quinone (pentafluoroethyl) trifluorophosphate mirror; (wherein R1 and R2 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; n represents an average enthalpy, and is a real number of 1 to 30). (wherein, Ri and R2 are each independently a hydrogen atom or a methyl group; and t, U and V each represent an average enthalpy, and independently a real number of 1 or more 'the sum is a real number of 3 to 30) -32 - 200813627 3] (wherein R is each independently a glycidyl group or a hydrogen atom; and η represents an average 値, which is a real number of 1 to 30). 2. The photosensitive resin composition of the first aspect of the invention, wherein the photocationic polymerization initiator (C) is a compound represented by the following formula (4) (Ο-ΐ) 3. The photosensitive resin composition according to claim 1 or 2, which contains one or more than one reactive epoxy monomer (D). 4. The photosensitive resin composition according to any one of claims 1 to 3, which contains a solvent (Ε) and has a solid content concentration of 5 to 9.5 wt%. A photosensitive resin composition laminate characterized by using the substrate to be incorporated into the photosensitive resin composition of any one of claims 1 to 4 to -33 - 200813627 6 · a cured product, The composition is obtained by the photosensitive resin composition according to any one of claims 1 to 4. And a photosensitive resin composition layer obtained by coating the photosensitive resin composition of any one of claims 1 to 4 on the desired support, After drying, it is exposed to a predetermined pattern, baked after exposure, and the resin composition layer is developed, and the obtained resin pattern is heat-treated to obtain a cured resin pattern of a predetermined shape. 8. A method for forming a pattern, comprising the step of laminating a photosensitive resin composition layer remaining after removing a substrate from the laminate of claim 5, and laminating the laminate on the desired support. The photosensitive resin composition layer is exposed to a predetermined pattern, baked after exposure, and the resin composition layer is developed to form a resin pattern obtained by heat treatment, and then a step of obtaining a cured resin pattern having a predetermined shape is obtained. -34- 200813627 VII. Designated representative map (1) The designated representative figure of this case is: None (2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: none