TW201009497A - Photosensitive resin composition for MEMS and cured product thereof - Google Patents

Abstract

Disclosed is a photosensitive resin composition for an MEMS, which comprises (A) a photo-cationic polymerization initiator and (B) an epoxy resin having two or more epoxy groups on average per molecule, wherein the photo-cationic polymerization initiator (A) is a photo-cationic polymerization initiator (A-1) represented by formula (1).

Description

[Technical Field] The present invention relates to an epoxy resin composition for forming a photosensitive image and a permanent hardening product thereof, which can be processed by ultraviolet (UV: Ultraviolet) lithography Or use hot stamping for stamping, and in MEMS (Microelectromechanical System) parts, micro-tool parts, micro-fluid parts, μ-TAS (micro-integrated system) parts, inkjet printers Parts, microreactor parts, conductive layers, LIGA (lithographic electroformed) parts, micro-injection forming and hot stamping models and impressions, screens or stencils for fine-printing applications, MEMS package parts, semiconductors A useful component, a laminate thereof, and a cured product thereof for use in packaging parts, BioMEMS (bio-micro electromechanical systems), biophotonic devices, and printed wiring boards. [Prior Art] Photoresist that can be used for lithography has recently been widely used in semiconductor or MEMS and micro-tooling applications. In this application, the lithography process is performed by forming a pattern on a substrate and exposing it, followed by development with a developer to selectively remove the exposed or non-exposed areas. The photoresist that can be subjected to lithography (photoresist: Photoresist) has a positive type and a negative type, and is dissolved in the developing solution by exposure to a positive type, and insoluble is a negative type. In advanced electronic package applications or MEMS applications, not only the formation energy of a uniform spin coating film but also a high aspect ratio, a straight sidewall shape of a thick film, and high adhesion to a substrate are required. Here, the aspect ratio is calculated by the film thickness of the light -5 - 201009497 / the line width of the pattern, and is an important characteristic indicating the performance of the lithography. Such photoresists are known by a polyfunctional bisphenol A phenolic epoxy resin (trade name EPON SU-8 resin, manufactured by Resolution Performance Products) and CYRACURE UVI-6974 by Dow Chemical. A negative-type chemically amplified photoresist composition formed of a starter (this photocationic polymerization initiator is formed from a solution of an aromatic sulfonium salt hexafluoroantimonate propylene carbonate). Since the photoresist composition has extremely low light absorption in a wavelength region of 3 50 nm to 450 nm, it is known as a photoresist composition for lithographic processing of a thick film. The photoresist composition can be spin-coated or curtain coated on various substrates, and then volatilized by baking to form a solid photoresist layer having a thickness of ΙΟΟμπι or more, and then using contact exposure, proximity exposure or projection. Various exposure methods such as exposure are performed by illuminating near-ultraviolet light through a photomask to perform lithography. Next, it is immersed in a developing solution to dissolve the non-exposed areas, thereby forming a negative image of a high-resolution photomask on the substrate. For example, Patent Document 1 discloses that by blending a specific epoxy resin, it is possible to maintain good image resolution, thermal stability, chemical resistance, and solvent properties of the EPON SU-8 resin-based formulation, and at the same time, improve adhesion. Characters such as sex, interlaminar peeling, cracking, white spots, stress and softness. However, the photocationic polymerization initiator contained in the composition of the present invention is not described, and the adhesion after the pressure cooker test (PCT) due to the difference in photocationic polymerization initiator is not mentioned. On the other hand, in the field of MEMS parts or MEMS and semiconductor packages, etc., in the field of -6-201009497, it is known that the physical properties of the package material have a large influence on the reliability of the device. MEMS and semiconductor components are greatly affected by changes in ambient temperature or humidity or fine dust, which causes deterioration of this characteristic and is easily broken by mechanical vibration or impact. In order to protect MEMS and semiconductor components from such external factors, it is known that they are sealed by a ceramic case or resin and used as a package. In the manufacture of this hollow form of the package, when it is sealed with metal or ceramic gas, it is essentially non-permeable to moisture, but has disadvantages such as high manufacturing cost and poor dimensional accuracy. On the other hand, when the resin is packaged, the manufacturing cost is relatively low, and the dimensional accuracy is also high, but the resin basically has a water diffusion coefficient, and gradually passes moisture over time, resulting in deterioration of characteristics of the semiconductor element, penetration into the retention. The moisture inside the airtight package is condensed on the glass surface, and has a problem of lack of reliability (Patent Document 2). [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent Publication No. 2007-522531 [Patent Document 2] Japanese Patent Application Publication No. 2005-2 1 72 1 2 [Description of the Invention] In the conventional photosensitive resin composition using a polyfunctional epoxy resin such as a phenolic epoxy resin, since the photocationic polymerization initiator contained therein has low sensitivity, it is necessary to contain a large amount of an initiator. It has the problem that it is impossible to faithfully reproduce the mask pattern in the resin pattern in a short time. In addition, in 201009497, although the photocationic polymerization initiator containing hexafluoroantimonate ion (SbF6·) has a relatively high sensitivity, it has a problem of limited use due to toxicity. On the other hand, in the field of MEMS parts, MEMS, and semiconductor packages, the adhesion of the resin composition is lowered with time due to the moisture resistance of the resin composition, and the reliability of the device is greatly reduced. The present invention has been made in view of the above-described conventional circumstances, and the object of the present invention is to provide a good image resolution, thermal stability, chemical resistance, and solvent solubility, which is high in sensitivity and is applied to a substrate after a pressure cooker test (PCT). The purpose of the photosensitive resin composition in which the adhesion is not lowered is for the purpose. (Means for Solving the Problems) The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a photosensitive resin composition having a specific epoxy resin and a specific photocationic polymerization initiator is combined. When the resin pattern is formed by using the photosensitive resin composition, it is possible to form a pattern in which the adhesion to the substrate after the pressure cooker test is not lowered. In other words, the present invention relates to: (1) A photosensitive resin composition for MEMS, which is an epoxy resin containing a photocationic polymerization initiator (A) and an average of two or more epoxy groups in one molecule ( B) The photosensitive resin composition for MEMS, the photocationic polymerization initiator (A) is a photocationic polymerization initiator (A*l) represented by the following formula (1), -8 - 201009497

F+F o=s=o

^S>F ❹

(2) The photosensitive resin composition for MEMS according to the above item (1), wherein the photosensitive resin composition for MEMS is used for packaging; (3) the MEMS according to the above (1) or (2) A photosensitive resin composition, wherein the epoxy resin (B) has a softening point of 40 ° C or more and 120 ° C or less, and an epoxy equivalent of 15 Å to 500 / eq.; (4) as described in (1) to ( The photosensitive resin composition for MEMS according to any one of item 3, wherein the epoxy resin (B) is an epoxy resin (B-1) represented by the following formula (3);

(wherein R independently represents a glycidyl group or a hydrogen atom. k is an average number of repetitions, and represents a real number in the range of 0 to 30); and an epoxy resin represented by the following formula (4) (B-2) ); -9 - 201009497 【化3】

(wherein, each of Ri, R2 and R3 independently represents a hydrogen atom or a hospital group having 1 to 4 carbon atoms. p is an average repeat number, which represents a real number in the range of uo): and the following formula (5) Epoxy resin (B_3); φ [Chemical 4]

(wherein η and m are the average repeating numbers, and each independently represents a real number in the range of 1 to 30. R4 and R5 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group. Base); and

An epoxy resin (b-4) represented by the following formula (6);

(wherein η is an average repeat number, which is a real number of the formula of 1 to 30); and an epoxy resin represented by the following formula (7) (Β - 5 ); -10- 201009497 [Chem. 6]

And an epoxy resin (B-6) obtained by reacting a polyprotonic acid anhydride with the following reactants, wherein the reactant is an epoxy compound having at least an average of two or more epoxy groups in one molecule. a compound having at least one or more hydroxyl groups and one carboxyl group in one molecule is reacted; and an epoxy resin (B-7) represented by the following formula (9);

Q (where n is the average number of repetitions is a real number in the range in which it is located); and an epoxy resin (B_8) represented by the formula (10);

201009497 (wherein π is the average repeat number) means a real number in the range of 〇1 to 5); and an epoxy resin (B-9) represented by the following formula (1 1 );

(wherein, l, m and η are the average repeating numbers, which are real numbers in the range of l + m + n = 2 to 60): and the epoxy resin represented by the following formula (1 2 ) (; b - 1) 0 ); 【化1 0】

P (12)

LJ η (wherein η is an average repeat number, which represents a real number in the range of 0.16); and a compound represented by the following formula (1 3 ) and/or the following formula (i 4 ) and the following formula (1) 5) and/or one or more epoxy resins selected from the group consisting of epoxy resins (BU) of a cocondensate of a compound represented by the following formula (16); -12- 201009497 1

Och3 ShOCH3 OCH, (13)

OCH3 I 3 Si-OCH3 OCH3 (14) 【化1 2

Or och3 Si-OCH3 0CH3 (15) OCH3 H3C-Si-〇CH3 (16) OCH3 (5) A cured product of the MEMS photosensitive resin according to any one of the above items (1) to (4) The composition is hardened and produced. (6) A laminated body obtained by sandwiching the photosensitive resin composition for MEMS according to any one of the above items (1) to (4). (7) A cured product obtained by hardening the laminate of the above item (6). Advantageous Effects of Invention The photosensitive resin composition of the present invention has excellent image resolution, thermal stability, chemical resistance, and solvent solubility, and is highly sensitive and adheres to a substrate after a pressure cooker test (PCT). Since it does not deteriorate, it is suitable as a photosensitive resin composition for MEMS. [Embodiment] Hereinafter, embodiments of the present invention will be described. The photosensitive resin composition of the present invention is characterized by containing the photocationic polymerization initiator (A-1) represented by the above formula (1) and having an average of two or more epoxy groups in one molecule from 13 to 201009497. The epoxy resin (B) can form a pattern of high sensitivity and the adhesion to the substrate after the pressure cooker test is not lowered. Further, since the above composition does not contain a highly toxic quinone compound, the load on the human body and the environment can be reduced. The photocationic polymerization initiator (A-1) of the present invention generates cations by irradiation with excimer lasers such as ultraviolet rays, deep ultraviolet rays KrF or ArF, X-rays, and electron beams, and the cations can be generated. A compound which becomes a polymerization initiator, also referred to as a myoelectric acid generator. Next, the above epoxy resin (B) will be described. The epoxy resin (B) of the present invention is not particularly limited as long as it is an epoxy resin having an average of two or more epoxy groups in one molecule. When the epoxy group having one molecule has an average of less than two, the chemical resistance or heat resistance of the cured product is remarkably lowered, and the use as a permanent film may not be withstood. Specific examples of the epoxy resin (B) include a phenolic epoxy resin obtained by reacting a phenolic aldehyde with an epichlorohydrin and/or a methyl epichlorohydrin-like halogen alcohol, or a compound having an olefin. An epoxy compound obtained by an oxidation reaction, wherein the phenolic compound is a phenol (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) under an acidic catalyst. It is prepared by reacting with formaldehyde. The epoxy equivalent of the epoxy resin (B) is preferably 150 to 500 g/eq., and when it is smaller than this range, the hardening shrinkage becomes large and the warpage or crack of the cured product is likely to occur. Look, it is less ideal. On the other hand, when it is larger than this range, the crosslinking density is lowered, and the strength, chemical resistance, heat resistance, and crack resistance of the cured film are deteriorated, which is not preferable. -14- 201009497 The epoxy equivalent in the present invention means an epoxy equivalent measured by a method in accordance with JIS K7236. Further, when the softening point is too low, the mask is liable to be viscous when the pattern is formed, and when it is used as a dry film resist, it is softened at room temperature, which is not preferable. On the other hand, when the softening point of the epoxy resin (B) is too high, the dry film resist is hardly softened when it is laminated on the substrate, and the adhesion to the substrate is deteriorated, which is not preferable. For the above reasons, the desirable softening point of the polyfunctional epoxy resin (B) is 40 to 120 ° C, more preferably 50 to 100 ° C. The softening point in the present invention means a softening point measured by the method according to JIS K7234. From the above description, the photosensitive resin composition of the present invention preferably has an epoxy resin having an epoxy equivalent of from 40 ° C to 120 ° C and an epoxy equivalent of from 15 0 to 50 (?/64. Specific examples of the epoxy resin (8) satisfying the above range include, for example, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1 020, EOCN-4400H, EPPN-201, EPPN-501 ❹, EPPN-502 ' XD-1 000, BREN-S, NER-7604, NER-7403, NER-1302, NER-7516, NC-3000 (all product names, 曰本化药(股))' Epikote 157S70 (Product name , Japan Epoxy Resin (share) system, ΕΗPE3 1 5 0 (trade name, Daice 1 chemical industry (stock) system), etc. Among these epoxy resins (B), the resistance of the cured film, the plasma withstand It is preferable that the epoxy resin (Bl), (B-2), (B-3), (B-4), (the above) are high in properties and transparency, and the cured product is low in hygroscopicity. B-5), (B-6), (B-7), (B-8), (B-9 -15- 201009497), (Β·10), (B-ll) 所谓The so-called formula in the present invention (3) The epoxy resin represented by ~(12), etc. means The epoxy resin containing the epoxy resin as a main component may contain a by-product formed when the epoxy resin is produced, or a high molecular weight body of the epoxy resin, etc. The above formula (3) Specific examples of the epoxy resin (Β-1) are shown, for example, Epikotel 57 (trade name, JER company, epoxy equivalent 180 to 25 0 g/eq., softening point 80 to 90 ° C), EPON-SU- 8 (product name, manufactured by Resolution Performance Products: epoxy equivalent: 195 to 230 g/eq. 'softening point: 80 to 90 ° C), etc. Specific examples of the epoxy resin (B-2) represented by the above formula (4) For example, there is NC-3000 (trade name: manufactured by Nippon Kayaku Co., Ltd.: epoxy equivalent: 270 to 300 g/eq., softening point: 55 to 75 ° C). Epoxy resin represented by the above formula (5) (B-3) Specific examples include NER-7604, NER-7403, NER-1302, and NER-7016 (all of which are manufactured under the trade name 'Nippon Chemical Co., Ltd.: Epoxy Equivalent 200~500g/eq.' Softening Point 55~75) Specific examples of the epoxy resin (B-4) represented by the above formula (6) include, for example, e〇CN-1020 (trade name, manufactured by Nippon Kayaku Co., Ltd.: epoxy equivalent 19 0~210g/eq_, softening point 55~85°C), EOCN-103S (product name, manufactured by Nippon Kayaku Co., Ltd.: epoxy equivalent 209~2 1 9g/eq., softening point 8 1~85. (:). Specific examples of the epoxy resin (B-5) represented by the above formula (7) include, for example, NC-6300 (trade name: manufactured by Nippon Kayaku Co., Ltd.: epoxy equivalent 230 to 235 g/eq., softening point 70 to 72) °C). The epoxy resin (Β·6) is, for example, a polycarboxylic acid epoxy compound described in the method of Japanese Patent No. 3698499, which has an epoxy equivalent and a softening point of 201009497, which can be used as an epoxy resin (B-6). The epoxy resin of the raw material or the introduction rate of the introduced substituent is variously adjusted. Specific examples of the epoxy resin (b-7) represented by the above formula (9) include, for example, EPPN-201-L (trade name 'Nippon Chemical Co., Ltd.; epoxy equivalent 180 to 200 g/eq., softening point 65 ～78. (:). Specific examples of the epoxy resin (B-8) represented by the above formula (1) include, for example, EPPN-501H (trade name 'Nippon Chemical Co., Ltd.: epoxy equivalent 162 to 172 g /eq., softening point 51~57°c), EPPN-501HY (trade name, manufactured by Nippon Kayaku Co., Ltd.: epoxy equivalent 163~175g/eq·, softening point 57~63°C), EPPN-502H ( Product name, manufactured by Nippon Kayaku Co., Ltd.: Epoxy equivalent: 158 to 178 g/eq. 'Softening point: 60 to 72 ° C.) Specific examples of the epoxy resin (B-9) represented by the above formula (11), for example EHPE3150 (product name: Daicel Chemical Industry Co., Ltd.: epoxy equivalent: 170 to 190 g/eq., softening point: 70 to 85 ° C). Specific examples of the epoxy resin (B-1 〇) represented by the above formula (12) 'For example, there is XD-1 000 (trade name, Nippon Kayaku Co., Ltd.: epoxy equivalent 245 to 260 g/eq., softening point 68 to 78 ° C). The above formula (13) and / or formula (14) a compound expressed as described above ( The epoxy resin (B-ll) of 15) and/or the cocondensate of the compound represented by the following formula (16) can be produced by the method described in JP-A-2007-29 1263. The ratio of the components of the photosensitive resin composition of the present invention to the photocationic polymerization initiator (A) of the photosensitive resin composition of the present invention (hereinafter also referred to simply as "(A) component") When the total amount of the epoxy resin (B) having an average of two or more epoxy groups in the molecule (i) is only 100% by mass, the total amount of the epoxy resin (B) is hereinafter referred to as "(B) component). In general, the ratio of the component (A) is 0.1 to 15% by mass, and the component (B) is 85 to 99.9% by mass. The photocationic polymerization initiator used in the photosensitive resin composition of the present invention ( A) 'Because the molar absorption coefficient at a wavelength of 30,000 to 3 80 nm is high, it is necessary to adjust the film thickness to a suitable blending ratio in accordance with the film thickness of the photosensitive resin composition. The photosensitive resin composition of the present invention, Additive reactions can also be added to improve the performance of the pattern The epoxy monomer (C) (hereinafter also referred to as "(C) component). The reactive epoxy monomer may be a glycidyl ether compound such as diethylene glycol diglycidyl ether or Glycol diglycidyl ether, dimethylolpropane diglycidyl ether, polypropylene glycol diglycidyl ether ("ED506" made by ADEKA), trimethylolpropane triglycidyl ether (made by ADEKA, ED5) 0 5 ), trimethylolpropane triglycidyl ether (low chlorine type, manufactured by Nagase Chemtex Co., Ltd., EX321L), neopentyl alcohol tetraglycidyl ether, and the like. Since these epoxy monomers generally have a high chlorine content, it is preferred to use a low chlorine type which has been subjected to a low chlorine production method or a purification step. These may be used singly or in combination of two or more. The reactive epoxy monomer (C) component is used for the purpose of improving the reactivity of the photoresist or the physical properties of the cured film. The reactive epoxy monomer component is mostly liquid, and when the component is liquid, the relative component is relatively When the total amount of the photosensitive resin composition is more than 20% by mass, it is less appropriate to form a thick film on the film after solvent removal and easily cause the mask to become viscous. In this regard, when the monomer component is blended, when the total of the component (A), the component -18 - 201009497 (B), and the component (C) is a solid component of the photoresist, the blending ratio is higher in the solid fraction. It is preferably 10% by mass or less, and more preferably 7% by mass or less. A solvent (D) can also be used in order to lower the viscosity of the photosensitive resin composition of the present invention to improve the film properties. The solvent can be used as long as it is an organic solvent generally used for inks, paints, and the like, and can dissolve each component. Examples of such an organic solvent include φ ketones such as acetone, methyl ethyl ketone, cyclohexanone, and cyclopentanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether; And other glycol ethers; ethyl acetate, butyl acetate, Butyl Cello solve acetate, carbitol acetate, propylene glycol methyl ether acetate and r-butyrolactone; Alcohols such as methanol, ethanol, 赛路苏, methyl 赛路苏; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum light oil, hydrogenated petroleum light oil and solvent light oil Wait. These solvents may be used singly or in combination of two or more. The solvent-based Q component is added for the purpose of adjusting the film thickness or coatability when applied to a substrate, and is used to appropriately maintain the solubility of the main component, the volatility of the component, and the liquid viscosity of the composition. The amount of the photosensitive resin composition is preferably 95% by mass or less, more preferably 10 to 90% by mass. In the photosensitive resin composition of the present invention, an adhesion-promoting agent having blendability can be used for the purpose of improving the adhesion of the composition to the substrate. As the adhesion imparting agent, for example, a coupling agent such as a decane coupling agent or a titanium coupling agent can be used, and a decane coupling agent is preferred. The above decane coupling agent is, for example, 3-chloropropyltrimethoxydecane, ethyl-5-201009497 alkenyltrichloromethane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethyl) Oxymethane, 3-methylpropenyloxypropyltrimethoxydecane' 2-(3,4·epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3 - thiopropylpropyltrimethoxy decane, 3-aminopropyltriethoxy decane, N-2-(aminoethyl)-3-aminopropyltrimethoxy decane, 3-ureidopropyltriethoxy decane, and the like. These adhesion imparting agents may be used singly or in combination of two or more. Since the adhesion imparting agent is also unreactive with the main component, it is present as a residual component in addition to the component acting at the interface of the substrate, and if it is used in a large amount, adverse effects such as deterioration in physical properties are caused. . In view of the difference in the amount of the substrate, it is preferable to use it in a range which does not cause adverse effects, and it is preferable that the ratio is 15% by mass based on the photosensitive resin composition. Hereinafter, it is more preferably 5% by mass or less. In the photosensitive resin composition of the present invention, a sensitizer which absorbs ultraviolet rays and supplies the absorbed light energy to the photocationic polymerization initiator can be further used. The sensitizer is preferably, for example, Thioxanthone, an anthracene compound having an oxime at the 9th and 10th positions (9,10-dialkoxyanthracene derivative). The alkoxy group may, for example, be a C1 to C4 alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group. The 9,10-dialkoxyfluorene derivative may further have a substituent. The substituent may, for example, be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a C1 to C4 alkyl group such as a methyl group, an ethyl group or a propyl group; or a sulfonic acid alkyl ester group or a carboxylic acid alkyl ester group. The alkyl group in the alkyl sulfonate group or the alkyl carboxylate group may, for example, be a C1-C4 alkyl group such as a methyl group, an ethyl group -20-201009497 or a propyl group. The substitution position of these substituents is preferably 2 positions. Specific examples of the thioxanthone include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,-chlorothioxanthone, 2,4·diisopropylthioxanthone, and the like. More preferably, it is 2,4-diethylthioxanthone (trade name: 1^7&(^1^6〇£丁和-8, manufactured by Nippon Kayaku Co., Ltd.), 2-isopropylthioxanthone 9,10-Dialkyloxyfluorene derivatives, for example, 9,10-dimethoxyanthracene, 0,1〇-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10 -dibutoxy oxime, 9,10-dimethoxy-2-ethyl hydrazine, 9,10-diethoxy-2-ethyl hydrazine, 9.10-dipropoxy-2-ethyl hydrazine, 9,10-dibutoxy-2-chloroindole, methyl 9,10-dimethoxyindole-2-sulfonate, methyl 9,10-diethoxyindole-2-sulfonate, 9.10- Methyl dimethoxy hydrazine-2-carboxylate, etc. These may be used singly or in combination of two or more, but it is most preferred to use 2,4-diethylthioxanthone and 9,10-dimethoxy The sensitizer component is preferably used in an amount of 30% by mass or less, more preferably 20% by mass, based on the photo-Q cationic polymerization initiator (A). % or less. In the present invention, when necessary When reducing the adverse effects caused by the ions of the photocationic polymerization initiator (A), trimethoxy aluminum, triethoxy aluminum, triisopropoxy aluminum, isopropoxy diethoxy aluminum and three may be added. Aluminum alkoxide such as butoxy aluminum; phenoxy aluminum such as triphenyloxy aluminum and tris(p-methylphenoxy) aluminum; aluminum trisulphate aluminum tristearate, aluminum trisuccinate , aluminum tripropionate, aluminum triacetate, aluminum tris(trifluoroacetamidine), aluminum triethylacetate, aluminum diacetate, potassium pimelate, and diisopropoxy (ethyl ethyl) 21 - 201009497 An ion trapping agent such as an organic aluminum compound such as ruthenium acetate), such as aluminum (A), (B), and (C). When the total amount of the components is a solid content of the photoresist, the compounding amount is 10% by mass or less based on the solid content. Further, in the present invention, a thermoplastic resin, a coloring agent, a tackifier, and defoaming may be added as necessary. Various additives such as a agent, a leveling agent, etc. The thermoplastic resin is, for example, polyether maple, polystyrene, polycarbonate, or the like. The coloring agent is, for example, phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium dioxide, carbon black, naphthalene black, etc., and the tackifier is, for example, organic bentonite, bentonite, Montestone, etc., and the antifoaming agent is, for example, polyfluorene. An antifoaming agent such as an oxyalkylene, a fluorine or a polymer. When the additives are used, the amount of the photosensitive resin composition of the present invention is approximately 0.1 to 30% by mass, respectively, which can be used for the purpose of use. Further, in the present invention, for example, barium sulfate, barium titanate, cerium oxide, amorphous vermiculite, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica may be used. In the inorganic resin composition such as powder, the blending ratio is 〇60% by mass in the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention is preferably formulated in the ratio of the following first table, and the adhesion imparting agent, the sensitizer, the ion trapping agent, the thermoplastic resin, the coloring agent, and the tackifying agent may be added as necessary. The agent, the antifoaming agent, the leveling agent and the inorganic chelating agent are prepared by mixing and stirring by a general method. Or, if necessary, dispersing and mixing using a disperser such as a dissolver, a homogenizer, or a three-roll mill. Further, it can be filtered by using a sieve or a membrane filter after mixing. -22- 201009497 [Table 1] Mass 0.1~15.0 85.0~99.9 1.0~1 0.0 5.8 ~2090.0 Ingredient name Photocationic polymerization initiator (A) Epoxy resin (B) Reactive epoxy monomer (C) Solvent (D) The photosensitive resin composition of the present invention is preferably used in the form of a liquid. When the photosensitive resin composition of the present invention is used, it can be applied to a metal substrate such as ruthenium, aluminum or copper at a thickness of 0.1 to 1000 μm using a spin coater or the like; lithium molybdate, glass, yttrium oxide lanthanum nitride a ceramic substrate; a substrate such as polyimide or polyethylene terephthalate, which is subjected to heat treatment at 60 to 130 ° C for 5 to 60 minutes to remove a solvent to form a photosensitive resin composition, and then Place a mask with a specific pattern and irradiate the UV light for heat treatment at 50 to 130 ° C for 1 to 50 minutes, then use the developer to apply the unexposed portion at room temperature to 50 ° C for 1 to 180 minutes. The development is patterned into a pattern, followed by heat treatment at 1 to 30 ° C to thereby produce a permanent protective film that satisfies the characteristics. As the developer, for example, an organic solvent such as 7-butyrolactone, triethylene glycol dimethyl ether or propylene glycol methyl ether acetate; or a mixture of the above organic solvent and water may be used. For development, a developing device such as a stirring type, a spray type, or a shower type can be used, and ultrasonic irradiation can be performed as necessary. When the photosensitive resin composition of the present invention is used, the preferred metal substrate is, for example, aluminum. The resin composition of the present invention is coated on the base film by coating the composition -23-201009497 with a roll coater, a die coater, a knife coater, a bar coater, a gravure coater or the like. Drying is carried out in a drying oven set at 45 to 100 ° C to remove a specific amount of solvent, and a cover film or the like may be laminated as necessary to form a dry film photoresist. At this time, the thickness of the photoresist on the base film is adjusted to 2 to 100 μm. As the base film and the cover film, for example, a film of polyester, polypropylene, polyethylene, TAC (Triacetyl Cellulose: cellulose triacetate) or polyimine can be used. These films may be used as a film obtained by a release treatment such as a polyoxyalkylene-based release treatment agent or a non-polyoxyalkylene-based release treatment agent, if necessary. When the dry film resist is used, for example, the cover film can be peeled off, and transferred to a substrate at a temperature of 40 to 100 ° C and a pressure of 0.05 to 2 MPa by a manual roll or a laminator to form a liquid photosensitive resin. The exposure is similarly performed, post-exposure baking, development, and heat treatment. When the photosensitive resin composition is supplied as a dry film as described above, the step of applying and drying the support can be omitted, and the photosensitive resin composition of the present invention can be more easily used for pattern formation. . When used as a MEMS package or a semiconductor package, it can be used by forming a coating or forming a hollow structure by the photosensitive resin composition of the present invention. For the MEMS and semiconductor package substrates, a metal film such as aluminum, gold, copper, chromium, or titanium can be formed into a film of various shapes by sputtering or vapor deposition at a film thickness of 10 to 5000 Å. A substrate obtained by finely processing the metal by an etching method or the like on a wafer. Depending on the situation, a film of ruthenium oxide or tantalum nitride is formed as a protective film of inorganic film with a film thickness of 1 〇 to 1 。. Next, a MEMS or semiconductor device is fabricated or disposed on the substrate, and in order to block the device from the external environment, it is necessary to form a coating or to fabricate a hollow structure. When the photosensitive resin composition of the present invention is formed by coating -24 - 201009497, it can be produced by the aforementioned method. In addition, at the time of manufacture, a spacer method can be formed on the substrate by the above method, and a pattern can be formed on the upper layer to form a laminate and a film on the partition wall, thereby forming a hollow package structure, which can be used in response to 130 to 200. The 10~ process is performed in °C to obtain MEMS body package parts that can satisfy various characteristics.所谓 The so-called “package” is a method for sealing gases and liquids that are used to block the external environment in order to maintain the substrate and the properties. The so-called package described in the present invention has a driving unit such as a ME MS, or a hollow package of SAW, and a surface protection or resin sealing for preventing deterioration of a semiconductor substrate, printing, or the like, and the like. Characteristics of the resin composition, such as resolution, thermal stability, drug resistance, and solvent dissolution φ. Adhesion to the substrate after the pressure cooker test (PCT), for example, can be applied to MEMS (Micro Electro Mechanical Systems) parts, microfluids. Parts, μ-TAS (micro-integrated parts, inkjet printer parts, micro-reactor parts, micro-injection forming and screen or stencils for hot stamping models and printing applications, MEMS package parts, BioMEMS and bio Photonic devices, printing, etc. Among them, in particular, MEMS package parts and semi-conductors are made into hollow walls, and then dried by the above-mentioned cover. In addition, 120 minutes of heating package parts, semi-wires, components, etc. are produced. The denseness of the security of the device, such as the brush wiring board and the wiring system used to seal the device, etc., have good image quality, and are highly sensitive and will not Low, so parts, micro-tools analysis system) zero, conductive layer, LIGA impression, useful for fine-grained, semiconductor package zero-wiring wiring board production package -25-201009497 [Embodiment] The following is implemented by The invention is described in detail by way of example only, and is not intended to limit the invention. Examples 1 to 3 and Comparative Example 1 (Preparation of photosensitive resin composition) According to the blending amount (unit: mass parts) described in Table 2, a polyfunctional ring was introduced at 60 ° C by a flask equipped with a stirrer. The oxygen resin, the photocationic polymerization initiator and other components were stirred and mixed for 1 hour to obtain a photosensitive resin composition of the present invention and comparative use. (Formation of Pattern of Photosensitive Resin Composition) Each of the photosensitive resin compositions of Examples 1 to 3 and Comparative Example 1 was applied onto a ruthenium wafer by a spin coater, and then dried to obtain a second The film thickness shown in the table (the "thickness after coating" in the second table means the film thickness after coating and drying) is a photosensitive resin composition layer. This photosensitive resin composition layer was subjected to prebaking at 65 ° C for 5 minutes and at 15 ° C for 15 minutes by means of a hot plate. Then, pattern exposure (soft contact, i-ray) was performed using an i-ray exposure apparatus (mask aligner: manufactured by Ushio Electric Co., Ltd.), and post-exposure baking was performed at 95 ° C for 6 minutes by a hot plate (described below). In the case of "PEB", propylene glycol methyl ether acetate (hereinafter referred to as "PGMEA") was used and developed by a dipping method at 23 t for 5 minutes to obtain a cured resin pattern on a substrate (tantalum wafer). -26-201009497 (Evaluation of Sensitivity of Photosensitive Resin Composition) In the above-mentioned pattern exposure, the sensitivity of each photosensitive resin composition was evaluated by using the exposure amount which is the most excellent in the transfer precision of the mask as the optimum exposure amount. The smaller the optimum exposure, the higher the sensitivity. The results are shown in Table 2 below. (Evaluation of Analytical Property of Photosensitive Resin Composition) Analytical property: In the pattern exposure described above, a photomask having a line of 1, 5, 10, and 20 μm and a pitch was used, and the photoresist pattern was analyzed without generating residue. The thinnest pattern width that is in close contact with the substrate is measured. The results are as shown in the following Table 2 (Evaluation of PCT Acceptability of Photosensitive Resin Composition). A 1000 Å aluminum film is formed on a ruthenium wafer by sputtering, and φ is used in the substrate. Each of the photosensitive resin compositions obtained in Examples 1 to 3 and Comparative Example 1 was formed into the same pattern as described above. Using a warm air convection oven, each test piece was subjected to 15 (TC, 30 minutes hard baking. Then each test piece was placed in a HAST (Highly Accelerated Stress Test) room ( In Espec, it was set at 121 t:, 100% RH, 2 atm, and kept in a constant temperature and humidity state (PCT) for 20 hours. The test piece was taken out and the shape of the pattern shown in Fig. 1 was measured. The adhesion of the pattern is used to evaluate the PCT tolerance. In addition, the shearing force is used to apply force from the side of the pattern, and the shear strength at the time of peeling from the substrate in the -27-201009497 pattern is the adhesion. 〇(Excellent): The adhesion is 50gf or more △(good): the adhesion is 5gf or more and less than 50gf X (not): the adhesion is less than 5 gf (measuring margin is γ [Table 2]

Formulation Composition Example Comparative Example 1 53.5· ος π 1 2 ---- 3 Multifunctional epoxy resin B-1 EPON SU-8 53.5 100 100 B-2 NC-3000H 25.0 B-3 NER-7604 15.0 15.0 Photocation Polymerization initiator A-1 GSID26-1 3.0 2.0 — 4.0 PAG-1 CPI-101A 8 0 Reactive epoxy monomer C EX-321L 5.0 ------ 5.0 Solvent D CP 54.5 39.0 39.0 J 52.0 Homogenization Agent E F-470 0.15 0.06 0.06 0.15 Coupler F S-510 1.5 1.5 Film thickness after coating Γμιηΐ 25 50 50 25 Sensitivity (optimal exposure) rmJ/cm2l 100 130 40 250 Minimum resolution line width _ 5 5 5 10 PCT withstand 〇〇〇X (A -1 ) to (F ) of Table 2 are as follows. (A-1): Photocationic polymerization initiator (product name: GSID26-1, manufactured by Chiba Specialty Chemicals) (Bl) represented by the above formula (1): epoxy resin represented by the above formula (3) -28- 201009497 EPON-SU-8 * Resolution Performance Products Co., Ltd. · Epoxy equivalent 2 1 Og/eq. 'Softening point 85 °C · (B-2): Epoxy resin represented by the above formula (4) (Product name: NC-300 0H' manufactured by Nippon Kayaku Co., Ltd.: epoxy equivalent: 285 g/eq., softening point: 65.) (B-3): Epoxy resin represented by the above formula (5) (trade name NER- 7 6 04, manufactured by Nippon Kayaku Co., Ltd.: epoxy equivalent 347g/eq·, softening point ^ 7 1°C) (PAG-1): photocationic polymerization initiator (biphenyl [4-(phenylthio))benzene Base 铳 = = hexafluoroantimonate, trade name CPI-101A, made by San-Apro, 50% propylene carbonate solution) (C): Reactive epoxy monomer (trade name EX-321L, Nagase Chemtex ()): Solvent cyclopentanone (CP)

(E): a fluorine-based leveling agent (trade name: Megafac F-470, manufactured by DIC Corporation) (F): a decane coupling agent (trade name: S-510 'manufactured by Chisso Co., Ltd.) As shown in Table 2, the present invention The photosensitive resin composition (Examples 1 to 3) was higher in sensitivity than Comparative Example 1, and the PCT withstandability (the adhesion to the substrate was not lowered) was high. Example 4 (Photosensitive Resin Composition Laminate) -29- 201009497 The upper layer was coated on a Tor ay public clock and a photosensitive tree having a thickness of 3 8 μm η g (the sensation was separated, and the laminate was rolled over the chopped resin) U shi 〇 曝光 ( ( ( ( ( ( ( ( ( ( 软 软 软 软 软 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Polypropylene (pp) film (base film, manufactured by Sis), laminated with a film HJPP film on a heated surface by a warm air convection dryer at 65. (: 5 minutes at 80 ° C for 20 minutes. (cover film) to prepare a film composition of a film thickness of 15 μm. The pattern of the photoreceptor composition laminate is formed by the film peeling temperature of the obtained photosensitive resin composition laminate. 70 ° C, air pressure 〇 2 MPa, speed 0.5 m / min on the wafer, repeat this operation 6 times to obtain a photosensitive layer of 80 μπι. Using an i-ray exposure device (mask aligner: manufactured by the company) , the photosensitive resin composition layer is patterned , i-ray). Then, PEB was performed at 95 ° C by a hot plate, PGMEA was used, and 4 shadow treatment was performed at 23 ° C by dipping, and a hardened resin was obtained on the substrate (矽 wafer) to obtain an optimum exposure amount. 130mJ/cm2, fine line close to 5μηι, good example 5~14 Preparation, pattern formation, sensitivity evaluation, evaluation of PCT tolerance of optical resin composition) Formed by the blending ingredients described in Tables 3 and 4 The present photo-resin composition is obtained by the methods according to Examples 1 to 3.

-30- 201009497 to assess sensitivity, analyticity and PCT affordability. The results are shown in Tables 3 and 4 below. [Table 3]

Formulation Composition Example 5 6 7 8 9 Multifunctional Epoxy Test B-1 EPON SU-8 53.5 50 B-2 NC-3000H 25.0 50 B-3 NER-7604 15.0 100 B-4 EOCN-103S 100 B-4 EOCN-4400H 100 Photocationic polymerization initiator A-1 GSID26-1 1.0 1.0 1.0 1.0 1.0 Reactive epoxy monomer C EX-321L 5.0 Solvent D CP 50.0 50.0 50.0 50.0 50.0 Homogenizer E F-470 0.06 0.06 0.06 0.06 0.06 Coupling agent F S-510 1.5 Film thickness after coating Γμπιΐ 25 25 25 25 25 Sensitivity (optimal exposure) [mJ/cm2l 250 140 70 100 350 Minimum resolution line width ίμπιΐ 5 5 5 5 5 PCT withstandability〇 Δ 〇〇Δ -31 - 201009497 [Table 4] Formulation Ingredient Example 10 11 12 13 14 Multifunctional epoxy resin B-1 EPON SU-8 90 90 B-5 NC-6300H 100 B-6 EP3698499 100 B- 7 EPPN-201-L 100 B-8 EPPN-502H 10 B-10 XD-1000 10 Photocationic polymerization initiator A-1 GSID26-1 1.0 1.0 1.0 1.0 1.0 Solvent D CP 50.0 50.0 50.0 50.0 50.0 Homogenizer E F-470 0.06 0.06 0.06 0.06 0.06 Film thickness after coating 25 25 25 25 25 Sensitivity (optimal exposure) fmJ/cm2l 70 140 80 180 90 Minimum resolution line width Γμιηΐ 5 10 5 5 5 PCT withstandability Δ 〇 Δ Δ Δ Tables 3 and 4 (Bl), (B-2), (B-3), (A-1), (C), (D), (E), and (F) are the same as those of the users of Examples 1 to 3. (B - 4) ~ (B - 8) and (B - 1 0 ) are as follows. (B-4): an epoxy resin represented by the above formula (6) (trade name: EOCN-103S, manufactured by Nippon Kayaku Co., Ltd.: epoxy equivalent: 214 g/eq·, softening point: 83 ° C; and trade name EOCN-4400H) , manufactured by Sakamoto Chemical Co., Ltd.: Epoxy equivalent 190g/eq., softening point 6〇°c) (B-5): Epoxy resin represented by the above formula (7) (trade name NC-6300H 'Japan Chemicals Company system: epoxy equivalent 232 g/eq, softening point 70 〇C) (B-6): Epoxy resin synthesized according to Synthesis Example -32-201009497 2 of Japanese Patent No. 3698499 (sample name EP3 698499 'loop Oxygen equivalent 3 50 g/eq.) (B-7): an epoxy resin represented by the above formula (9) (trade name: EPPN-201-L > 曰本化制药公司: epoxy equivalent: 190 g/eq·, Softening point 72.) (B-8): Epoxy resin represented by the above formula (10) (trade name EPPN-502H, manufactured by Nippon Kayaku Co., Ltd.: epoxy equivalent: 168 g/eq·, softening point 60°) C) (B-10): an epoxy resin represented by the above formula (12) (trade name XD-1000, manufactured by Nippon Kayaku Co., Ltd.: epoxy equivalent 252 g/eq·, softening point 73〇C) as in the third Table and Table 4 and Examples 5 to 14 The photosensitive resin composition of the present invention has high sensitivity and high PCT resistance (the adhesion to the substrate is not lowered) as compared with Comparative Example 1. Industrial Applicability: The photosensitive resin composition of the present invention has high sensitivity for maintaining good image resolution, thermal stability, chemical resistance, and solvent solubility, and is applied to a substrate after a pressure cooker test (PCT). It is useful to form a resin pattern in which the adhesion is not lowered, and in particular, in the fields of MEMS parts, MEMS package parts, and semiconductor packages, it is suitable for forming a resin having high dimensional stability and high durability. [Simplified illustration] -33- 201009497 Figure 1 is a cross-sectional view showing the test piece used in the PCT tolerance evaluation. [Description of main component symbols] In Fig. 1, 1: cured material of a laminate of a photosensitive resin composition after removing a cover film and a base film: cured product of a photosensitive resin composition ❻ 3 : aluminum film (thickness 1 000A) 4 : 矽 wafer (thickness 500^1111) -34-

Claims (1)

201009497 VII. Patent application scope: 1 · A photosensitive resin composition for MEMS, which is an epoxy resin containing a photocationic polymerization initiator (A) and an average of two or more epoxy groups in one molecule (B) The photosensitive resin composition for MEMS, characterized in that the photocationic polymerization initiator (A) is a photocationic polymerization initiator (A-1) represented by the following formula (1); 2. The photosensitive resin composition for MEMS according to the first aspect of the patent application, wherein the photosensitive resin composition for MEMS is used for encapsulation. 3. The photosensitive resin composition for MEMS according to claim 1 or 2, wherein the epoxy resin (B) has a softening point of 40 ° C or more and 120 ° C or less, and an epoxy equivalent of 150 to 500 / eq. ·. 4. The photosensitive resin composition for MEMS according to any one of claims 1 to 3, wherein the epoxy resin (B) is an epoxy resin (B-1) represented by the following formula (3); -35- 201009497 3 (wherein 'R each independently represents a glycidyl group or a hydrogen atom; k is an average number of repeats' means a real number in the range of 〇~30); and an epoxy resin represented by the following formula (4) -2 ); ΐ化3] (4) R3 (wherein R', R2 and R3 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; P is an average repeat number, which means a real number in the range of 1 to 30); And the epoxy resin (B_3) represented by the following formula (5); [Chemical 4] ^ /=ν.〇ΛΔ R5 W〇° (5) (wherein 'n and m are average repeat numbers' are each independently representing a real number in the range of 1 to 30; R4 and R5 each independently represent a hydrogen atom, and have a ❹ -36- 201009497 1 An alkyl group of ~4 carbon atoms or a trifluoromethyl group; and an epoxy resin represented by the following formula (6) (B_4) (wherein η is the average repeat number, which is a real number in the range of 1 to 30); and an epoxy resin (Β_5 ) represented by the following formula (7); And an epoxy resin (Β-6) obtained by reacting a polyprotonic acid anhydride with the following reactants, the reactant being an epoxy compound having at least an average of 2 or more epoxy groups in one molecule A compound having at least one or more hydroxyl groups and one carboxyl group in one molecule is reacted; and an epoxy resin represented by the following formula (9) (Β-7); -37- 201009497 [Chem. 7] (wherein η is the average repeat number, which is a real number in the range of 1 to 10), and an epoxy resin (Β-8) represented by the following formula (1 〇 ); (where η is the average number of repetitions, which means that it is in the range of 0.1 to 5 And the epoxy resin (Β-9) represented by the following formula (1 1 ) (wherein, l, m and η are the average repeating numbers, which are real numbers in the range of -38 to 201009497 l + m + n = 2 to 60), and the epoxy resin represented by the following formula (1 2 ) (B-1 0 [Chemical 1 0] (12) (wherein η is the average repeat number, which is a real number in the range of 〇1 to 6): and a compound represented by the following formula (1 3 ) and/or the following formula (丨4) and the following formula (1 5 ) And/or one or more epoxy resins selected from the group consisting of epoxy resins (Β-11) of the cocondensate of the compound represented by the following formula (6); [1 1] Och3 shoch3 och3 (13) Och3 Si-〇CH3 OCH3 (14) [Chemical 1 2] /=\ 〇ch3 ^ SrOCH3 (15) 0CH3 och3 H3C-S1-OCH3 (16 ) OCH3 5. A kind of hardened material, which makes the scope of patent application l The MEMS photosensitive resin composition of any one of the four items is obtained by curing. 6. A laminate of the MEMS photosensitive resin composition according to any one of claims 1-4 to 4, which is a substrate. 7. A hardened material obtained by hardening a laminate of the scope of claim 6 - 39 - 201009497. -40-