WO2008010521A1

WO2008010521A1 - Photosensitive resin composition

Info

Publication number: WO2008010521A1
Application number: PCT/JP2007/064192
Authority: WO
Inventors: Nao Honda; Satoshi Mori; Harris Miller
Original assignee: Nippon Kayaku Kabushiki Kaisha; Microchem Corp.
Priority date: 2006-07-21
Filing date: 2007-07-18
Publication date: 2008-01-24
Also published as: JP4913143B2; TW200830042A; JPWO2008010521A1; TWI418934B

Abstract

Disclosed is a photosensitive resin composition containing a cationic photopolymerization initiator (A) composed of sulfonium tris(pentafluoroethyl)trifluorophosphate and an alkali-soluble epoxy compound (B) which is obtained by reacting a polybasic acid anhydride (c) with a reaction product (I) between an epoxy compound (a) having two or more epoxy groups in a molecule and a compound (b) having one or more carboxyl groups and one or more hydroxyl groups in a molecule.

Description

Specification

Photosensitive resin composition

Technical field

[0001] The present invention relates to a chemically amplified negative-type thick film resist. In more detail, it is suitable for precision processing such as bump formation, metal post formation, wiring formation, etc. performed in the manufacture of MEMS parts, micromachine parts, μ-TAS (micro total analysis system) parts, microreactor parts, electronic parts, etc. The present invention relates to a photosensitive resin composition capable of alkali development.

Background art

[0002] A device in which minute mechanical elements, electronic circuits, and optical elements are integrated is called MEMS (micro eletromechanical system) or micromachine, and many applications have been studied and put into practical use (Non-patent Document 1) reference). These devices are small parts based on semiconductor manufacturing technology, but are generic names for devices that perform complex and advanced functions. Various sensors, printer heads, disk heads, communication optical switches, biochips, etc. It is an important part that holds the key to the micro system. In this field, unlike normal semiconductor manufacturing, there is a need for a resist that can be patterned with a high aspect ratio (the aspect ratio means the height Z width of the structure).

[0003] As a method for producing a high aspect ratio structure, a pattern forming method by X-ray lithography (see Non-Patent Document 2) of a photosensitive resin composition called “LIGA process” is often employed. However, the LIGA process requires expensive X-ray equipment and has the drawback that X-ray irradiation takes a long time, and demands for resource saving, energy saving, workability improvement, productivity improvement, etc. Therefore, application of UV (ultraviolet) lithography system that is inexpensive and highly productive is attracting attention.

[0004] However, conventional positive resists based on the dinaphthoquinone-novolak reaction in UV lithography systems are not suitable for applications requiring thick films of 50 μm or more. There is a limit in thick film formation, compared with dinaphthoquinone type (DNQ) photoreactants in the near-ultraviolet region wavelength (350 to 450 nm) generally used for resist exposure. By having a relatively high light absorption. DNQ-type photoresists also have a slope shape rather than a straight sidewall due to the unique solubility difference between the exposed and unexposed areas in the developer. Due to light absorption, the irradiation intensity decreases when the film's top force also approaches the bottom. However, if this light absorption is too high, the resist bottom will be underexposed compared to the top, so the sidewall shape will be a slope shape. Or it becomes a distorted shape.

[0005] On the other hand, a negative-type chemically amplified type consisting of a polyfunctional bisphenol A novolac epoxy resin, a photopower thione polymerization initiator, and a propylene carbonate solution of an aromatic sulfo-hexafluoroantimonate. Thick film resist compositions are known to have very low light absorption in the 350-450 nm wavelength region. This resist composition is spin-coated or curtain-coated on various substrates, and then the solvent is evaporated by baking to form a solid photoresist layer having a thickness of 100 m or more. Photolithography is performed by irradiating near-ultraviolet light through a photomask using various exposure methods such as oral exposure and process exposure. Subsequently, by dipping in a developing solution and dissolving the non-exposed areas, a high-resolution photomask negative image can be formed on the substrate, and a dry coating coated on a substrate such as a polyester film can be formed. An application such as a film resist is also disclosed (Patent Document 1). However, an organic solvent is used for the development of this composition, and development of a resist for forming a high aspect ratio that can be developed with an alkali is desired because of its influence on the environment. Patent Documents 2 and 3 disclose resist compositions that can be developed with an aqueous alkaline solution as a chemically amplified thick film resist. High aspect ratio can be achieved and it has excellent properties such as heat resistance and matt resistance, but storage stability decreases due to the mixture of alkali-soluble groups and reactive crosslinking groups. Tend.

[0006] Non-Patent Document 1: Micromachine, published by Industrial Technology Service Center Co., Ltd. (2002) Non-Patent Document 2: Polymer, No. 43, 564 (1994)

Patent Document 1: US Pat. No. 4,882,245

Patent Document 2: Japanese Patent No. 3698499

Patent Document 3: US Publication No. 20050147918

Disclosure of the invention Problems to be solved by the invention

[0007] In a conventional photosensitive resin composition using a polyfunctional epoxy resin such as a novolac-type epoxy resin or an alkali-soluble epoxy compound, the sensitivity of the light-powered thione polymerization initiator contained is low. There are problems that it is necessary to contain an initiator, and that the mask pattern cannot be faithfully reproduced in the resin pattern in a short time. Also, SbF —

6 Although the light-powered thione polymerization initiator contained is relatively sensitive, there is a problem that its use is limited. The present invention has been made in view of the above-described conventional circumstances, and its problem is to provide a photosensitive resin composition that can form a pattern with high resolution and high aspect ratio and is highly sensitive. It is to provide.

Means for solving the problem

[0008] In order to solve the above problems, the present inventors have increased the sensitivity of a photosensitive resin composition.

, Earnestly experimented and studied about high resolution. As a result, a photosensitive resin composition was prepared by combining a specific alkali-soluble epoxy compound and a specific photopower thione polymerization initiator, and a resin pattern was formed using this photosensitive resin composition. It has been found that a resin pattern with high sensitivity and high aspect ratio can be formed.

That is, the configuration of the present invention is as follows.

(1) Photo-thion polymerization initiator (A), which is sulfo-umtris (pentafluoroethyl) trifluorophosphate, and an epoxy compound having two or more epoxy groups in one molecule (a) And an alkali-soluble epoxy compound obtained by reacting a polybasic acid anhydride (c) with a reaction product (I) of a compound (b) having one or more carboxyl groups and one or more hydroxyl groups in one molecule A photosensitive resin composition comprising (B).

(2) The photosensitive resin composition according to the above (1), wherein the alkali-soluble epoxy compound (B) is represented by the following general formula (1).

[0010] [Chemical 1]

(In Formula (1), m and n are average values, each independently represents a real number of 0 or more, and the sum is a real number from 0 to 30. Also, even if D and D are the same, Even if they are different

1 2

Often selected from the group consisting of the groups shown below! )

[Chemical 2]

(3) Photopower thione polymerization initiator (A) Power The photosensitive resin composition according to the above (1) or (2), which is the compound (A-1) represented by the following formula (2).

[Chemical 3]

[0013] (4) The photosensitive resin composition according to any one of (1) to (3) above, which contains phenolic resin (C).

(5) The photosensitive resin composition according to any one of (1) to (4) above, wherein the solid content concentration of the photosensitive resin composition containing the solvent (D) is 5 to 95% by weight. A rosin composition.

(6) A photosensitive resin composition laminate in which the photosensitive resin composition according to any one of (1) to (5) above is sandwiched between substrates.

(7) A cured product comprising the photosensitive resin composition according to any one of (1) to (5) above.

(8) A photosensitive resin composition obtained by applying the photosensitive resin composition according to any one of the above (1) to (5) onto a desired support. After drying, the layer is exposed to a predetermined pattern, subjected to beta after exposure, the resin composition layer is developed, and the resulting resin pattern is heated to obtain a cured resin pattern having a predetermined shape. A pattern forming method comprising:

(9) The photosensitive resin composition layer remaining after the substrate is removed in addition to the laminate strength described in (6) above is laminated on a desired support, and the photosensitive resin composition layer is laminated. A pattern forming method comprising exposing to a predetermined pattern, beta-exposure after exposure, developing the resin composition, and heat-treating the obtained resin pattern to obtain a cured resin pattern having a predetermined shape .

The invention's effect

The photosensitive resin composition of the present invention can form a pattern with a high aspect ratio by development with an alkaline aqueous solution. Furthermore, since it is highly sensitive, it is advantageous in the manufacturing process and has low toxicity compared to SbF-. BEST MODE FOR CARRYING OUT THE INVENTION

[0015] The present invention is described in detail below.

The photosensitive resin composition of the present invention comprises a photothion polymerization initiator (A) that is sulfoyutris (pentafluoroethyl) trifluorate phosphate and an alkali-soluble epoxy resin represented by the general formula (1). It contains compound (B). According to the photosensitive resin composition, a high-sensitivity and high aspect ratio resin pattern can be formed.

[0016] The photopower thione polymerization initiator in the present invention generates cations upon irradiation with excimer lasers such as ultraviolet rays, far ultraviolet rays, KrF and ArF, X-rays, and electron beams, and the cations are generated. It is a compound that can be a polymerization initiator.

[0017] The light-power thione polymerization initiator (A) is sulfoyulium tris (pentafluoroethyl) trifluorophosphate.

[0018] The sulfone of the photoactive thione polymerization initiator includes triphenyl sulfone, tri-p-tolyl sulfone, tri-o-tolyl sulfone, tris (4-methoxyphenol) s. Norejoum, 1 Naftinoresihue-Noresnorehonum, 2-Naphtinoresihue-Noresnorehonum, Tris (4 Funoleo mouth-Fuel), Snorehonum, Tri 1 1-Naftinolesnorehoum, Tri —2 Naphthyl sulfone, Tris (4 hydroxyphenol) sulfur, 4 -— (Phenolthio) phenol disulfol, 4 -— (p-Tolylthio) phenol p-Tolylsulfome 4- (4-methoxyphenylthio) phenolbis (4-methoxyphenyl) sulfur, 4- (phenolthio) phenolbis (4-fluorophenyl) sulfurium, 4- (phenol -Luthio) Ferrubis (4-Met (Sulfur) sulfur, 4— (feruol) farge p-tolylsulfurum, bis [4— (diphenylsulfo-phenol) sulfur], bis [4— (bis [ 4- (2-Hydroxyethoxy) phenyl] sulfo-phenol) sulfide, bis (4- [bis (4-fluorophenyl) sulfo-phenyl] sulfide), bis (4 [bis (4 methylphenol) -L) sulfo- [io] phenole) sulfide, bis (4 [bis (4-methoxyphenol) sulfo-o] phenol) sulfide, 4-((4-benzoyl-4-sulfone) -norethio ) Ferbis (4-Funoreo-Fu) Snelephonium, 4- (4-Benzoyl 4-FloroFuerthio) Fuel disulfosulfo, 4- (4-Benzo-Fuerthio) Phenylbis (4-Fluorophenyl) sulfurium, 4-one (4-benzoate) L-phenylthio) phenyl disulfol sulfone, 4-isopropyl 4- 4-oxo 1 thia 9, 10 dihydroanthracene 2-yl di-p-tolyl sulfo 7-isopropyl 9 9-oxo 10 9, 10 Dihydroanthracene 2-yldiphenyl sulfone, 2-[(di-p-tolyl) sulfo-o] thioxanthone, 2 -— [(diphenyl) sulfo-o] thioxanthone, 4 [4 4 tert-butylbenzoyl) phenolthiol p-tolylsulfol, 4 [4- (tert-butylbenzoyl) phenylthio] phenol disulfol, 4 [4 (benzoylthiol)] -Russy p Tolylsulfum, 4— [4— (Benzylphenylthio)] phenoldisulfol, 5 -— (4-Methoxyphenyl) thiaanthrhenium, 5—Felthiaanthrhenium, 5— Triaryls such as tritylthanthanthrenium, 5- (4-ethoxyphenyl) thiaanthrhenium, 5- (2,4,6 trimethylphenol) thiaanthrhenium; -Rum, Diphenol Nole 4 -Trofenacinoles Nole Home, Diphenyl Penicylsulfum, Diphenylmethylsulfom, etc. —Hydroxyphenylmethylbenzyl sulfone, 4-methoxyphenylmethylbenzyl sulfone, 4-acetocarboxylphenyl methylbenzyl sulfone, 2-naphthylmethylbenzyl sulfone, 2 -Naphtylmethyl (1-ethoxycarbol) ethyl sulfone, Phenylmethylphenacyl sulfone, 4-Hydroxyphenol methylphenol Silsulfol, 4-methoxyphenylmethylphenacylsulfol, 4-acetocarboxoxyphenylmethylphenacylsulfol, 2-naphthylmethylphenacylsulfol, 2-naphthylocta Monoarylsulfomes such as decylphenacylsulfoum, 9 anthracelsulfene, dimethylphenacylsulfur, phenacyltetrahydrothiofum, dimethylbenzylsulfum , Trialkylsulfome such as benzyltetrahydrothiophene and octadecylmethylphenacylsulfo. These light thione polymerization initiators may be used alone or in combination of two or more. These are described in the following documents. Regarding triarylsulfo-um, U.S. Pat. No. 4,231,951, U.S. Pat.No. 4,256,828, JP-A-7-61964, JP-A-8-165290, JP-A-7-10914, column JP-A-7-25922, JP-A-8-27208, JP-A-8-27209, JP-A-8-165290, JP-A-8-301991, JP-A-9-143212, JP-A-9-278813, JP-A-10 — 7680, JP-A-10-287643, JP-A-10-245378, JP-A-8-157510, JP-A-10-203, JP-A-8-245566, JP-A-8-157451, JP 7-324069, JP-A-9-268205, JP-A-9-278935, JP-A-2001-288205, JP-A-11-80118, JP-A-10-182825, JP-A-10-330353, JP-A-10 — 152495, JP-A-5-239213, JP-A-333834, JP-A-9-12537, JP-A-8-325259, JP-A-8-160606, JP2000-186071 (US Pat. No. 6,368,769) In the case of dialylsulfo-um, JP-A-7-300504, JP-A-64-45357, JP-A-64-29419, etc .; in the case of monoarylsulfo-um, JP-A-6-345726, Kaihei 8-325225, JP-A-9-118663 (US Pat. No. 6093753), JP-A-2-196812, JP-A-2-1470, JP-A-2-196812, JP-A-3-237107, JP-A-3-17101, JP-A-6-228086, JP-A-10-152469, JP-A-7-300505, JP-A-2003-277353, JP-A-2003-277352, etc .; JP-A-4-308563, JP-A-5-140210, JP-A-5-140209, JP-A-5-230189, JP-A-6-271532, JP-A-58-37003, JP-A-2- 178303, JP-A-10-33688, JP-A-9-328506, JP-A-11-228534, JP-A-8-27102, JP-A-7-333834, JP-A-5-222167, JP-A-11- 21307, JP-A-11 35613, US Pat. No. 6,310,014 and the like.

[0020] In particular, as the sulfone of the light-power thione polymerization initiator, triphenyl sulfone and 4 (phenylthio) phenyl disulfol sulfome are more preferable in the above formula (2). The most preferred is 4 (Fuerthio) Fuel Disulfosulfum (A-1) as shown!

[0021] The alkali-soluble epoxy compound (B) in the present invention includes an epoxy compound ( _a ) having two or more epoxy groups in one molecule, one or more carboxyl groups and one or more in one molecule. An epoxy compound obtained by reacting a polybasic acid anhydride (c) with the reaction product (I) of the compound (b) having a hydroxyl group is preferably used.

Here, as the epoxy compound (a), for example, novolac type epoxy resin, bisphenol These include epoxy type epoxy resins, trisphenol methane type epoxy resins, tris (2,3-epoxypropyl) isocyanurate, biphenyl diglycidyl ether, alicyclic epoxy resins, and copolymerized epoxy resins.

Examples of the novolak type epoxy resin include novolaks obtained by reacting phenols such as phenol, cresol, halogenated phenol and alkylphenol with formaldehyde in the presence of an acidic catalyst, epichlorohydrin, Z or methyl. And the like obtained by reacting with epichlorohydrin. Examples of such epoxy resin include EOCN-103, EOCN-104S, EOCN-102, EOCN-1027, EOCN-4400H, EPPN-201, BREN-S; manufactured by Nippon Kayaku Co., Ltd. , DEN-431, DEN-439; Dainippon Ink & Chemicals, N-730, N-770, N-865, N-665, N-673, VH-4150, etc. . Examples of bisphenol type epoxy resin include bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A, and epichlorohydrin and Z or methylepoxyhydrin. And those obtained by reacting a diglycidyl ether of bisphenol A or bisphenol F with a condensate of the above bisphenols with epichlorohydrin and Z or methyl epichlorohydrin. As such epoxy resin, commercially available products such as Epicoat 1004, Epicoat 1002, Epicoat 4002, and Epicoat 4004 manufactured by Yuka Shell Epoxy Co., Ltd. are available. Examples of the trisphenol methane type epoxy resin include those obtained by reacting trisphenol methane, tristarzole methane and the like with epichlorohydrin and Z or methyl epichlorohydrin. Such epoxy resin is available as Nippon Kayaku Co., Ltd., EPP N-501, EPPN-502, etc. Examples of alicyclic epoxy resin include Daicel Chemical Industries, Celoxide 2021, Yuka Shell Epoxy, E-10 31S, Nippon Soda Co., Ltd., EPB-13, EPB-27, Commercial products such as Daicel Chemical Industries, Ltd. and EHPE 3150 are available. Examples of the copolymer type epoxy resin include Nippon Oil & Fats Co., Ltd., which is a copolymer of glycidyl metatalylate, styrene and methylstyrene, CP-50OM, CP-50S, or glycidyl metatalylate and cyclohexylmaleimide. And the like. Others, Epomic VG-3 manufactured by Mitsui Petrochemical Industries, Ltd. It is also possible to use an epoxy compound having a special structure such as 101.

[0024] Specific examples of the compound (b) include, for example, dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, polyhydroxymonocarboxylic acids such as dimethylolcaproic acid, hydroxybivalic acid, p-hydroxyl. And monohydroxy monocarboxylic acids such as benzoic acid. Two or more of these may be used in combination.

[0025] The reaction between the epoxy compound (a) and the compound (b) having one or more carboxyl groups and one or more hydroxyl groups in one molecule is equivalent to 1 equivalent of the epoxy group of the epoxy compound (a). On the other hand, the carboxylic acid of the compound (b) is preferably 0.01 to 0.5 mol force S, particularly preferably 0.1 to 0.3 mol. The reaction temperature may be 60-150 ° C. The reaction time is usually 5 to 30 hours. In this way, the reaction product (I) can be obtained.

[0026] Next, the reaction between the reactant (I) and the polybasic acid anhydride (c) is carried out by reacting the polybasic acid anhydride (c) with respect to one hydroxyl group equivalent to the hydroxyl group in the reactant (I). Is preferably reacted in an amount of 0.1 to 1.0 equivalent. The reaction time is preferably 60 to 150 ° C, and the reaction time is usually 3 to 24 hours. Here, specific examples of the polybasic acid anhydride (c) include, for example, compounds represented by the following formula, and two or more of these may be used.

[0027] [Chemical 4]

In the above reaction, as diluents, ketones such as ethyl methyl ketone, cyclohexanone and cyclopentanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, dipropylene glycol dimethyl ether, dipropylene glycol jetyl ether Glycol ethers such as tellurium, esters such as ethyl acetate, butyl acetate, butylcetosolvate, carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha It is preferable to use organic solvents such as petroleum solvents. Further, it is preferable to use a catalyst (for example, triphenylphosphine, benzyldimethylamine, methyltriethylamine chloride, triphenylstibine, chromium octoate, etc.) to accelerate the reaction. In addition, after the reaction is completed, the catalytic activity is substantially inactivated by oxidizing the used catalyst with an organic peroxide or the like. The amount of the catalyst used is preferably 0.1 to 10% by weight based on the reaction raw material mixture. Polymerization inhibitors to prevent polymerization during the reaction (For example, hydroquinone, methylhydroquinone, p-methoxyphenol, catechol, pyrogallol, etc.)

The preferred cocn is 0.01-1% by weight.

[0029] The alkali-soluble epoxy compound (B) thus obtained is preferably an epoxy compound represented by the above formula (1). Such alkali-soluble epoxy compounds include epoxy compound (a), cresol novolac epoxy resin (commercially available from Nippon Kayaku Co., Ltd., EOCN-103, EOCN-104S, EOCN-4400H Dimethylolpropionic acid as a compound (b) having one or more carboxyl groups and one or more hydroxyl groups in one molecule, and polybasic acid anhydride (c) below. It can be obtained by reacting any of the anhydrides according to the above.

[0030] [Chemical 5]

»

[0031] Furthermore, it is particularly preferable that the alkali-soluble epoxy compound is an epoxy compound represented by the following formula (3)!

[0032] [Chemical 6]

[0033] To the photosensitive resin composition of the present invention, phenol resin (C) may be added in order to further improve liquid storage stability. Phenolic resin (C) is a nopolac resin obtained by addition condensation of an aromatic compound having a phenolic hydroxyl group and an aldehyde under an acid catalyst, and a homopolymer of vinyl phenol (including hydrogenated products). )) And the ability of copolymerization with components that can be copolymerized with buenphenol. The selected bulufenol polymers (including hydrogenated products) and the like are preferably used. In the present invention, the phenol resin (C) can be used alone or in combination of two or more.

Specific examples of the aromatic compound having a phenolic hydroxyl group include phenol, o-cresol monole, m crezo monole, p crezo mono nore, o ethino leuenore, m-ethino leuhe nore, p ethenyl phenol, o butyl. Phenols, m-Butinolephenol, p-Butylphenol, o Xylenol, 2, 3 Xylenol, 2, 4 Xylenol, 2, 5 Xylenol, 3, 4 Xylenol, 3, 5 Xylenol, 2, 3, 5 Trimethylphenol Diol, 3, 4, 5-trimethylphenol, p-phenolphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, bisphenolanol A, tenolepen skeleton-containing diphenol, gallic acid, gallic acid ester, a naphthol, j8-naphthol Etc. Examples of the aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetoaldehyde.

[0034] Specific examples of the component copolymerizable with bulufenol include acrylic acid or its Derivatives, styrene or derivatives thereof, maleic anhydride, vinyl acetate, acrylonitrile and the like.

[0035] The phenolic resin (C) hardly participates in the crosslinking reaction upon curing by photopower thione polymerization. Therefore, when a large amount of phenol resin (C) is used (specifically, an amount exceeding 80% by weight), the degree of crosslinking is insufficient, and patterning with an aspect ratio of 5 or more becomes difficult. Therefore, the blending ratio of the phenolic resin (C) is preferably 1 to 50% by weight, particularly preferably 5 to 25% by weight in the photosensitive resin composition of the present invention.

[0036] The photosensitive resin composition of the present invention may be diluted with a solvent (D) for use. Examples of such a solvent (D) include ketones such as ethyl methyl ketone, cyclohexanone, cyclopentanone and y-butyrolatatone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, dipropylene glycol, and the like. Glycol ethers such as dimethyl ether and dipropylene glycol jetyl ether, ethyl acetate, butyl acetate, butyl cellosolve acetate, esters such as carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated Examples thereof include organic solvents such as petroleum solvents such as petroleum naphtha and solvent naphtha. These solvents (D) can be used alone or in admixture of two or more.

[0037] The solvent (D) is added for the purpose of adjusting the film thickness and coating properties when applied to the substrate. In order to appropriately maintain the solubility of each of the above components, the volatility of the solvent (D) itself, and the liquid viscosity of the photosensitive resin composition, it is 1 to 100 parts by weight of the photosensitive resin composition of the present invention. ˜99 parts by weight is preferred, particularly preferably 10 to 90 parts by weight.

[0038] In the present invention, a reactive monomer (E) can be added to the photosensitive resin composition of the present invention as necessary. As the reactive monomer (E), a polyfunctional glycidyl ether compound can be used. Specifically, for example, diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, dimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether and the like can be used. These can be used alone or in admixture of two or more.

[0039] Many of these reactive monomer components are liquid. Sensitive when the component is liquid It is not preferable to add more than 20 parts by weight with respect to the water-soluble resin composition because the film after removal of the solvent tends to be sticky and mask sticking is likely to occur. From this point, when a reactive monomer component is added, the addition ratio is preferably 10 parts by weight or less, particularly 8 parts by weight or less, with respect to 100 parts by weight of the photosensitive resin composition of the present invention. Is preferred.

[0040] In the present invention, a sensitizer may be used to absorb ultraviolet light and to supply the absorbed light energy to the photopower thione polymerization initiator. As the sensitizer, for example, an anthracene compound (9, 10 dialkoxy-anthracene derivative) having an alkoxyl group at the 9th and 10th positions is preferable. Examples of the alkoxyl group include C1-C4 alkoxyl groups such as methoxyl group, ethoxyl group and propoxyl group. The 9, 10 dialkoxy-anthracene derivative may further have a substituent. Examples of the substituent include a fluorine atom, a halogen atom such as a chlorine atom, a bromine atom, and an iodine atom, a C1-C4 alkyl group such as a methyl group, an ethyl group, and a propyl group, a sulfonic acid alkyl ester group, and a carboxylic acid group. Examples include an alkyl ester group. Examples of the alkyl in the sulfonic acid alkyl ester group and the carboxylic acid alkyl ester include C1-C4 alkyl such as methyl, ethyl, and propyl. The substitution position of these substituents is preferably the 2-position! /.

[0041] Specific examples of 9, 10 dialkoxy-anthracene derivatives include 9, 10 dibutoxy anthracene, 9, 10 dimethoxy anthracene, 9, 10 jetoxy anthracene, 9, 10 dipropoxy anthracene, 9, 10 dimethoxy 2 Ethyl-anthracene, 9, 10 Diethoxy 2 Ethyl-anthracene, 9, 10 Dipropoxy 2 Ethyl anthracene, 9, 10 Dimethoxy-2 chloro-anthracene, 9, 10 Dimethoxyanthracene 2-sulfonic acid methyl ester, 9, 10 Jetoxyanthracene 2 -Sulphonic acid methyl ester, 9,10 Dimethoxyanthracene 2-Strength ruvic acid methyl ester. These can be used alone or in combination of two or more.

[0042] The sensitizer component is effective even in a small amount. For this reason, the use ratio is preferably 5 parts by weight or less, particularly preferably 2 parts by weight or less, based on 100 parts by weight of the photodynamic thione polymerization initiator (B). In the present invention, an adhesion-imparting agent may be used for the purpose of improving the adhesion of the composition to the substrate. Examples of the adhesion-imparting agent include 3-chloropropylpropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl'tris (2-methoxyethoxy) silane, and 3-methacryloxypropyltrimethoxy. Silane, 2- (3, Xoxysilane, 3-Mercaptopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, N-2- (Aminoethyl) 3-Aminopropyltrimethoxysilane, 3 Ureidopropyltriethoxysilane, etc. These adhesion-imparting agents can be used alone or in combination of two or more.

[0044] The adhesion-imparting agent does not show reactivity with the main component in the photosensitive resin composition of the present invention. For this reason, components other than those that act at the substrate interface are present in the cured product as residual components after curing. When used in large amounts (over 10 parts by weight with respect to 100 parts by weight of the photosensitive resin composition), the physical properties deteriorate. There are concerns about adverse effects such as. Depending on the substrate, it is appropriate to use it within a range that does not adversely affect it, since it can be effective even in a small amount (more than 0.5 parts by weight with respect to 100 parts by weight of the photosensitive resin composition). The use ratio is preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less, with respect to 100 parts by weight of the photosensitive resin composition of the present invention.

[0045] In the present invention, when it is necessary to reduce the adverse effect of ions derived from the photopower thione polymerization initiator, trismethoxyaluminum, trisethoxyoxyaluminum, trisoxypolyoxyaluminum, isopropoxydiethoxyaluminum, tris Alkoxy aluminum such as butoxyaluminum, phenoxyaluminum such as trisphenoxyaluminum, trisparamethylphenoxyaluminum, trisacetoxyaluminum, tris stearate aluminum, trisbutyrato aluminum, trisp ported pionato aluminum Triacetyl acetylacetonate aluminum, Tristrifluoroacetylacetonate aluminum, Tricetyl acetylacetonate aluminum, Dicetyl acetonate dipivaloylmethanatoal - © beam, diisopropoxy may be added (E chill § Seto § Seta g) an organic aluminum compound such as aluminum. These components can be used alone or in combination of two or more. The amount added is 1 with respect to 100 parts by weight of the photosensitive resin composition of the present invention. 0 parts by weight or less.

[0046] In the present invention, for example, barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, acid aluminum, hydroxide aluminum aluminum, mica powder Inorganic fillers such as can be used. The blending ratio is 0 to 60 parts by weight with respect to 100 parts by weight of the photosensitive resin composition of the present invention.

[0047] Further, in the present invention, various additives such as thermoplastic rosin, colorant, thickener, antifoaming agent, leveling agent and the like can be used as necessary. Examples of the thermoplastic resin include polyethersulfone, polystyrene, and polycarbonate. Examples of the colorant include phthalocyanine blue, phthalocyanine green, Iodine 'green, tartar violet, titanium oxide, carbon black, naphthalene black and the like. Examples of the thickener include olben, benton and montmorillonite. Examples of the antifoaming agent include silicone-based, fluorine-based and polymer-based antifoaming agents. When these additives are used, the amount used is about 0.5 to 30 parts by weight, for example, with respect to 100 parts by weight of the photosensitive resin composition of the present invention. Force Can be increased or decreased appropriately according to the purpose of use.

[0048] The photosensitive resin composition of the present invention may be prepared by simply mixing and stirring the above components. If necessary, the photosensitive resin composition may be dispersed and mixed using a disperser such as a dissolver, a homogenizer, or a three-roll mill. Also good. Further, after mixing, filtration may be performed using a mesh, a membrane filter or the like.

[0049] The photosensitive resin composition of the present invention is suitable as a resist composition for application as a thick film on a substrate, but the range of use is not limited thereto. For example, it can be used as a protective film during etching of various substrates such as copper, chromium, iron, and glass substrates, as a resist mold during electrolytic plating, and as a resist for manufacturing semiconductors.

[0050] Formation of bumps using the photosensitive resin composition of the present invention as a thick film resist film is performed, for example, as follows.

(1) Formation of coating film: A desired coating film is formed by applying a solution of the photosensitive resin composition prepared as described above on a predetermined substrate and removing the solvent by heating. Application methods on the substrate to be processed include spin coating, roll coating, and screen printing. A method such as an applicator method can be employed. The prebeta conditions of the coating film of the photosensitive resin composition of the present invention vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc., but are usually 40 to 150 ° C., preferably 60 to It is about 2-60 minutes at 120 ° C.

[0051] (2) Irradiation: Wiring that forms bumps by irradiating the obtained coating film with radiation, for example, ultraviolet rays or visible rays having a wavelength of 300 to 500 nm through a mask having a predetermined pattern. Only the pattern portion is exposed. As these radiation sources, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal nitride lamp, an argon gas laser, or the like can be used. Here, radiation means ultraviolet rays, visual rays, far ultraviolet rays, X-rays, electron beams, and the like. The amount of radiation irradiation varies depending on the type of each component in the composition, the blending amount, the film thickness of the coating film, etc., but is, for example, 100 to 2000 miZcm ² when using an ultrahigh pressure mercury lamp.

(3) Heating: After exposure, heating is performed using a known method.

[0052] (4) Development: As a development method after radiation irradiation, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, leaving only the radiation irradiated portions. As the developer, an alkaline aqueous solution such as TMAH, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and the like can be used. An aqueous solution obtained by adding a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer. The development time varies depending on the type of each component of the composition, the blending ratio, and the dry film thickness of the composition, but the development conditions are usually 0.5 to 10% by weight of developer, temperature 15 to 30 ° C, The time is from 1 to 30 minutes, and the developing method may be any of a liquid filling method, a dubbing method, a paddle method, a spray developing method, and the like. After development, wash with running water for 30 to 180 seconds and dry using an air gun or oven.

It should be noted that the plating process method is not particularly limited, and various plating methods known per se can be employed. As the plating solution, nickel plating, solder plating, and copper plating solution are particularly preferably used.

[0054] The film thickness obtained by the photosensitive resin composition of the present invention is usually 2 to 150 μm, preferably 20 to 120 μm, more preferably 40 to 90 μm. [0055] The photosensitive resin composition of the present invention is a coating obtained from a photosensitive resin composition using a roll coater, a die coater, a knife coater, a bar coater, a gravure coater or the like on a base film. After applying the solution, dry it in a drying oven set at 60 to 100 ° C to remove a predetermined amount of solvent, and if necessary, make a dry film resist by laminating a cover film etc. Can do. At this time, the thickness of the resist on the base film is adjusted to 2 to 100 m. As the base film and the cover film, for example, a film of polyester, polypropylene, polyethylene or the like is used. To use this dry film resist, for example, the cover film is peeled off and transferred to the substrate, and exposure, Development and heat treatment may be performed.

[0056] According to the present invention, there can be provided a photosensitive resin composition capable of forming a pattern with a high aspect ratio by development with an alkaline aqueous solution and having high sensitivity. The photosensitive resin composition of the present invention is suitable for precision processing such as bump formation, metal post formation, and wiring formation.

Example

[0057] Hereinafter, the present invention will be described more specifically with reference to Examples.

[0058] Synthesis example of alkali-soluble epoxy compound

Cresolol novolac-type epoxy resin (manufactured by Nippon Shakuyaku Co., Ltd., EOCN-4400H, Epoxy equivalent 189) 1890 parts by weight (10 equivalents), dimethylolpropionic acid 301.8 parts by weight (2.25 moles) Then, 99.4 parts by weight of cyclopentanone was added, and the mixture was heated to 80 ° C and stirred to dissolve the mixture. Next, the obtained liquid was cooled to 60 ° C, charged with 8.0 parts by weight (0.03 mol) of triphenylphosphine, and heated to 100 ° C. The mixture was allowed to react for about 10 hours, and when the acid value (mgKOHZg) became 0.5 mgKOHZg or less, it was cooled to 50 ° C. Next, tetrahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid TH) was charged with 555.6 parts by weight (3.68 moles) and cyclopentanone 555.6 parts by weight and reacted at 95 ° C for 10 hours. A cyclopentanone solution containing 70% by weight of the alkali-soluble epoxy compound (B-1) represented by the formula (3) where m = 0.9 and n = 2.1 was obtained. The acid value of the product (solid content) was 75 (mgK OHZg). The values of m and n are calculated as follows. Molecular weight of epoxy resin / Molecular weight of repeating unit X DMPA charge (mol) Equivalent number of epoxy resin = m, Molecular weight of epoxy resin. Molecular weight of Z repeating unit m— l = n. Here, the number of equivalents of epoxy resin = amount of epoxy resin charged (parts by weight) Z epoxy equivalent, the molecular weight was measured by GPC, the number average molecular weight was measured, and the method described in Epoxy equivalent IS K-7236 Measure with 7.

[0059] Examples 1 to 3, Comparative Example 1

(Photosensitive resin composition)

According to the blending amount shown in Table 1 (unit is parts by weight), alkali-soluble epoxy resin, photocationic polymerization initiator, and other ingredients are stirred for 1 hour at 60 ° C in a flask equipped with a vortexer. Thus, a photosensitive composition was obtained.

[0060] (Patterning of photosensitive resin composition)

This photosensitive resin composition was coated on a silicon wafer with a spin coater and dried to obtain a photosensitive resin composition layer having a thickness of 80 μm. This photosensitive resin composition layer was prebetated on a hot plate at 65 ° C for 5 minutes and at 95 ° C for 20 minutes. After that, pattern exposure (soft contact, i-line) is performed using an i-line exposure system (mask aligner: manufactured by Usio Electric Co., Ltd.), and after exposure, beta (PEB) is performed at 95 ° C for 6 minutes. 2. A development process was performed for 7 minutes at 23 ° C by immersion using 38% TMA H aqueous solution to obtain a resin pattern cured on the substrate.

[0061] (Evaluation of photosensitive resin composition)

After the development, the following evaluation was performed according to the required exposure amount. The results are shown in Table 1 below.

[0062] Optimum exposure amount: exposure amount with the best mask transfer accuracy

Aspect ratio: Film thickness / The finest pattern width closely adhered in the formed resist pattern

[0063] [Table 1] Examples Comparative Examples Ingredients

1 2 3 1

Al force resoluble epoxidation

B-1 100 80 100 100 Compound

A-1 GP 1 -21 OS 3.5 5 3. 5 2. 1

Light power thione polymerization initiator

G U I -6974 7 Phenolic resin C P H M-C 20

Solvent D C P 30 30 30 30 Repelling agent E F-4 7 0 0. 06 0. 06 0. 06 0. 06 Coupling agent F S-510 2 2 2 2

Suitable dew; 7ti, m J / cm 350 400 500 500 Aspect ratio 5. 6 5. 3 5. 5 5. 1

[0064] Note:

(A-1): Photon thione polymerization initiator (trade name: CPI-210S manufactured by Sanpro Corporation)

(B-1): Alkali-soluble epoxy compound synthesized according to the synthesis example

(C): Hydrogenated product of polybutanol (trade name: Marcarinkaichi PHM—C Maruzen Petrochemical Co., Ltd.)

(D): Solvent cyclopentanone

(E): Fluorine leveling agent (trade name MegaFuck F-470, manufactured by Dainippon Ink, Inc.)

(F): Silane coupling agent (trade name S-510 manufactured by Chisso Corporation)

(G): Photopower thione polymerization initiator (trade name UVI—6974 50% propylene carbonate solution manufactured by Dow Chemical Company)

[0065] As shown in Table 1, in Examples 1 to 3, the deviation was also good.

[0066] Example 4

(Photosensitive resin composition)

100 parts by weight of an alkali-soluble epoxy compound (B-1) synthesized according to the synthesis example, 4.6 parts by weight of a light-powered thione polymerization initiator (trade name CPI-210S manufactured by Sanya Pro), and 40 parts by weight of MEK To obtain a photosensitive composition.

(Patterning of photosensitive resin composition)

This photosensitive resin composition is uniformly applied onto a 60 μm-thick polypropylene (PP) film (base film, manufactured by Toray Industries, Inc.), and heated at 65 ° C for 10 minutes and 80 ° C using a hot air convection dryer. After drying at C for 15 minutes, a PP film (cover film) with a film thickness of 60 μm is laminated on the exposed surface. To form a photosensitive resin composition laminate having a thickness of 40 m.

[0067] The cover film of this photosensitive resin composition laminate is peeled off, laminated on a silicon wafer at a roll temperature of 70 ° C, an air pressure of 0.2 MPa, and a speed of 0.5 mZmin, and this is repeated twice. A photosensitive resin composition layer having a thickness of 80 m was obtained. The photosensitive resin composition layer was subjected to pattern exposure (soft contact, i-line) using an i-line exposure apparatus (mask aligner: manufactured by Usio Electric Co., Ltd.). After that, PEB was performed for 6 minutes at 95 ° C with a hot plate, and 2. Development process was performed for 7 minutes at 23 ° C by immersion using 38% TMAH aqueous solution to obtain a cured resin pattern on the substrate. . Good results were obtained with an optimal exposure of 350 mjZcm ² and an aspect ratio of 5.3.

[0068] From the comparison of the evaluation results of Examples 1 to 4 and Comparative Example 1, it was found that the combination of a specific alkali-soluble epoxy resin and a specific light-power thione polymerization initiator resulted in high sensitivity that cannot be obtained by other combinations. It has been found that a high aspect profile resin pattern can be obtained Industrial applicability

[0069] As described above, the photosensitive resin composition useful in the present invention is useful for forming a resin pattern having a high aspect profile, and is particularly dimensionally stable in a fine-sized electronic device. Suitable for highly efficient resin molding. More specifically, this photosensitive resin composition is a bump type used in the manufacture of MEMS parts, micromachine parts, μ-TAS (micro total analysis system) parts, microreactor parts, electronic parts, etc. It is suitably used for precision processing such as formation, metal post formation, and wiring formation.

Claims

Claims [1] Photopower chain polymerization initiator (A), which is sulfo-umtris (pentafluoroethyl) trifluorophosphate, and an epoxy compound having two or more epoxy groups in one molecule (A) and an alkali-soluble product obtained by reacting polybasic acid anhydride (c) with reaction product (I) of compound (b) having one or more carboxyl groups and one or more hydroxyl groups in one molecule A photosensitive resin composition comprising an epoxy compound (B). [2] The photosensitive resin composition according to claim 1, wherein the alkali-soluble epoxy compound (B) is represented by the following general formula (1). [Chemical 1]

(In Formula (1), m and n are average values, each independently representing a real number of 0 or more, and the sum thereof is a real number from 0 to 30. Also, D 1 and D 2 are the same. Or may be different and is selected from the group consisting of the groups shown below! / Indicates any group.)

[Chemical 2]

[3] Photosensitive thione polymerization initiator (A) power The photosensitive resin composition according to claim 1 or 2, which is a compound (A-1) represented by the following formula (2).

[Chemical 3]

[4] The photosensitive resin composition according to any one of claims 1 to 3, which contains phenolic resin (C).

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the photosensitive resin composition containing the solvent (D) has a solid content concentration of 5 to 95% by weight.

[6] A photosensitive resin composition laminate in which the photosensitive resin composition according to any one of claims 1 to 5 is sandwiched between substrates.

[7] A cured product comprising the photosensitive resin composition according to any one of claims 1 to 5.

[8] A photosensitive resin composition layer obtained by applying a photosensitive resin composition according to claim 1 or 5 of any one of claims 1 to 5 on a desired support. , Drying, exposing to a predetermined pattern, post-exposure beta, developing the resin composition layer, and heat-treating the obtained resin pattern to obtain a cured resin pattern having a predetermined shape. A pattern forming method.

[9] Laminate strength according to claim 6 The photosensitive resin composition layer remaining after the substrate is removed is laminated on a desired support, and the photosensitive resin composition layer is formed into a predetermined pattern. A pattern forming method comprising: exposing, betaing after exposure, developing the resin composition, and heat-treating the obtained resin pattern to obtain a cured resin pattern having a predetermined shape.