TWI408500B - Photosensitive resin composition, laminate comprising the same, cured product of the same and method for forming pattern using the same (1) - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-sensitive photosensitive resin composition, with which a pattern of high-resolution and high aspect ratio can be formed. <P>SOLUTION: The photosensitive resin composition contains a polyfunctional epoxy resin (A) in a specified structure; and a cationic photopolymerization initiator (B) that is sulfonium-tris(pentafluoroethyl) trifluorophosphate. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

Photosensitive resin composition, laminate thereof, cured product thereof, and formation method of pattern using the composition (1)

The present invention relates to a pattern of a high-sensitivity, high aspect ratio pattern, and a photosensitive resin composition excellent in high sensitivity and liquid storage stability, a laminate thereof, a cured product thereof, and a pattern in which the composition is used. method.

The photoresist of photolithographic processing has recently been widely used in semiconductor or MEMS (Micro Electro Mechanical Systems) applications. This photolithography process is performed by patterning exposure on a substrate, followed by development. The liquid is developed to selectively remove the exposed or non-exposed areas. The photo-resistance (photoresist) that can be photolithographically processed has a positive or negative type, and is positively dissolved in the developing solution by exposure, and negative in insoluble. The advanced electropackage application requires a high aspect ratio. On the other hand, MEMS applications require uniform spin coating film formation and a thick film of 100 μm or more to maintain a straight shape, and high aspect ratio and photolithography. Light resistance. Among them, the aspect ratio is represented by the photoresist film thickness/pattern line width, and is an important characteristic indicating the performance of photolithography.

The positive-type photoresist of the prior art based on the reaction of the naphthoquinone-phenol novolak is not suitable for the use of a thick film requiring 50 μm or more, and has a limit when thick filming, because it is generally used for photoresist exposure. The dinaphthoquinone type (DNQ) photoreactive material with ultraviolet wavelength (350~450nm) has relatively high light absorption, and the DNQ type photoresist has different solubility due to the unique solubility of the exposed area and the non-exposed area in the developing solution. The shape is not linear but instead Now tilted shape. The light intensity can be gradually reduced by the light absorption at the top to the bottom of the film, but if the light absorption is too high, the bottom of the photoresist appears to be underexposed in comparison with the top, so that the side wall shape may have an inclined shape or a skewed shape.

Negative chemically enhanced thick film photolithographic composition, known to have very low light absorption in the 350-450 nm wavelength range, consisting of a polyfunctional bisphenol A novolac epoxy resin ( Resolution Polymer Product EPON SU-8 resin), photo-cationic polymerization initiator of CYRACURE UVI-6974 manufactured by Dow Chemical (this photo-cationic polymerization initiator is a propylene carbonate solution from aromatic hexafluoroantimonate) The photoresist composition is applied to various substrates by spin coating or curtain coating, and then the solvent is volatilized by baking to form a solid photoresist layer having a thickness of 100 μm or more. Then, using various exposure methods such as contact exposure, proximity exposure, and projection exposure, photolithography is performed by irradiating near ultraviolet light through a photomask, and then immersed in a developing solution to dissolve the non-exposed area. A negative image of the high resolution mask is formed on the substrate.

EPON SU-8 resin is a low molecular weight epoxy oligomer with excellent characteristics in thick film and high aspect ratio photolithography. (i) high epoxy functional group, (ii) high branching Degree, (iii) high transmittance of 350 to 450 nm, (iv) low molecular weight necessary for formation of solids; high epoxy functional group and high branching degree cause sufficient crosslinking under strong acid catalyst, high transmittance The system penetrates the thick film and is uniformly irradiated with light, and has a resistive pattern of a thick film having a thickness of 100 μm or more and an aspect ratio of 10 or more. can. Selecting a resin having a high epoxy functional group number and a high degree of branching is an important item for forming a side wall having a straight line and a structure having a high aspect ratio; selecting a low molecular weight resin can be formed on the substrate by a minimum number of coating stages. Thick film photoresist solid layer.

A photocationic polymerization initiator based on a phosphonium salt or an iodonium salt is well known, and a useful photocationic polymerization initiator having a suitable absorbance is disclosed, which contains a carbonyl-p-phenylene sulfide (Patent Document 1) And 2), and may also add a sensitizer such as 2-alkyl-9,10-dimethoxyanthracene or other anthracene, naphthalene, beryl or pyrryl compound, or may be introduced into the photo-induced Cationic polymerization initiator (Patent Document 3).

Negative photoresists based on compounds suitable for spin coating as disclosed above are sold by MICRO CHEM, in particular commercially used in MEMS device parts. For example, "SU-8 series" supplied by MICRO CHEM Co., Ltd. can be spin-coated at 1000 to 3000 rpm in order to form a film of 30 to 100 μm thick, and then exposed to ‧ development to form a film thickness of 100 μm or more and an aspect ratio of 10 The above pattern.

The use of a dry film photoresist coated on a substrate such as a polyester film is also disclosed (Patent Document 4).

A composition for a photosensitive cationically polymerizable flame retardant suitable for use as a solder mask (Patent Documents 5, 6, and 7) is disclosed, which is composed of 10 to 80% by weight of bisphenol A and epichlorohydrin. a mixture of condensates, starting from 20 to 90% by weight of bisphenol A novolac epoxy resin, 35 to 50% by weight of epoxidized tetrabromobisphenol A, 0.1 to 15% by weight of photocationic polymerization The composition of the agent.

Also disclosed are photopolymerizable compounds based on a hydroxyl group-containing additive, a photocationic polymerization initiator, and an epoxy resin having a functional group number of 15 or more. It has been reported to add a hydroxyl group-containing additive to increase flexibility or reduce 100 μm. Stress of thick film above thickness (Patent Document 8).

Patent Document 9 discloses a method of producing a hard epoxy resin in an EB-curable application, in which the main improvement point is the friability of the epoxy resin which is hardened by irradiation, and most of the structures or consumables are used. Resin (epoxy resin), in order to withstand years of strict use, must have sufficient strength and impact resistance, which reveals a wide range of tough materials including SU-8 resin, regarding the increased strength, in Patent Document 9 The effectiveness of the invention of the claims is expressed by the fracture toughness and the flexural modulus, which are composed of various thermoplastic plastics, hydroxyl-containing thermoplastic oligomers, epoxy-containing thermoplastic oligomers, and reactions. Sexual softness, elastomer, rubber and a mixture of these. However, the composition described in Patent Document 9 is applied to a composition of a film that is imaged by non-pattern EB irradiation, and is patterned by UV, X-ray, or EB irradiation. The properties of the substance cannot be used as a reference for sensitized use.

Many proposals have been made for an epoxy-containing photoresist composition (Patent Document 10) in which, for example, the necessity of modulating a photoresist composition suitable for a spin coating method is required, and rheological properties are required, plus here. The composition must have sufficient transmittance for exposure irradiation such as photodegradation of the photoinitiator after passing through the film thickness. Further, in order to withstand various applications, the photoresist composition must have appropriate physical and chemical properties such as solder resistance or ink resistance, deterioration of strength, or deterioration of adhesion. If this photoresist composition is made For other applications such as photoresist for etching, other characteristics are required, but the specific epoxy resin that satisfies all of the various requirements is currently absent, and many different combinations or various epoxy resins have been disclosed. Mixtures, well-known patents, describe various resins and photoinitiators for photohardenable compositions, most of which are photo-sensitive photoresists suitable for permanent film applications. However, none of these reveals the best we have tried to accomplish. For compositions that are suitable for MEMS applications, virtually all examples of plasticizers, softeners, and tougheners can degrade lithography performance.

[Patent Document 1] US Patent No. 5502083

[Patent Document 2] US Patent No. 6368769

[Patent Document 3] US Patent No. 5102772

[Patent Document 4] US Patent No. 4882245

[Patent Document 5] US Patent No. 5026624

[Patent Document 6] US Patent No. 5278010

[Patent Document 7] US Patent No. 5304457

[Patent Document 8] US Patent No. 4256828

[Patent Document 9] US Patent No. 5726216

[Patent Document 10] US Patent No. 5264325

A photosensitive resin composition of the prior art using a polyfunctional epoxy resin such as a novolac type epoxy resin, because the photocationic polymerization initiator contained therein has low sensitivity and requires a large amount of an initiator, In a short period of time, the reticle pattern faithfully reproduces the problem of the resin pattern. In addition, the photo-cationic polymerization initiator containing SbF ₆ ^- is relatively high-sensitivity, but it may be used for its toxicity problem. Restricted issues.

The present invention has been made in view of the above-described problems of the prior art, and an object of the invention is to provide a photosensitive resin composition which can form a pattern having high resolution and a high aspect ratio and which has high sensitivity and low toxicity.

In order to solve the above problems, the inventors of the present invention have repeatedly studied, experimented, and reviewed the results of high sensitivity and high resolution of the photosensitive resin composition, and found that a specific polyfunctional epoxy resin and a specific photocation are combined. The polymerization initiator prepares a photosensitive resin composition, and when the photosensitive resin composition is used to form a resin pattern, a resin pattern having high sensitivity and a high aspect ratio can be formed. That is, the constitution of the present invention is as follows.

(1) A photosensitive resin composition containing a photocationic polymerization initiator (A) of ruthenium (pentafluoroethyl)trifluorophosphonate and a specific structure represented by the following formula (1) Made of functional epoxy resin (B).

(2) The photosensitive resin composition according to the above (1), wherein the photocationic polymerization initiator (A) is a compound represented by the following formula (2).

(3) The photosensitive resin composition according to the above (1) or (2), which contains a reactive epoxy monomer (C).

(4) The photosensitive resin composition according to any one of the above (1) to (3), wherein the solid content of the photosensitive resin composition containing the solvent (D) is 5 to 95% by weight. .

(5) A photosensitive resin composition laminate according to any one of the above (1) to (4), wherein the photosensitive resin composition according to any one of the above (1) to (4) is used.

(6) A cured product comprising the photosensitive resin composition according to any one of the above (1) to (4).

(7) A pattern forming method comprising the photosensitive resin composition layer obtained by applying the photosensitive resin composition according to any one of the above (1) to (4) to a desired support. After drying, the film is exposed according to a predetermined pattern, baked after exposure, and the resin composition layer is developed, and the obtained resin pattern is heat-treated to obtain a cured resin pattern of a predetermined shape.

(8) A pattern forming method comprising the photosensitive resin composition layer remaining after the substrate is removed from the laminate according to the above (5), laminated on the desired support, and laminated. The photosensitive resin composition layer is exposed to a predetermined pattern, baked after exposure, and the resin composition layer is developed, and the obtained resin pattern is heat-treated to obtain a cured resin pattern having a predetermined shape.

(9) A photosensitive resin composition containing a photo-cationic polymerization initiator (A) of ruthenium (pentafluoroethyl)trifluorophosphonate and a specific structure represented by the following formula (3) Made of functional epoxy resin (B).

(10) The photosensitive resin composition according to the above (9), wherein the photocationic polymerization initiator (A) is a compound represented by the following formula (4).

(11) The photosensitive resin group as described in the above (9) or (10) A product containing a reactive epoxy monomer (C).

(12) The photosensitive resin composition according to any one of the above-mentioned (9), wherein the solid content of the photosensitive resin composition containing the solvent (D) is 5 to 95% by weight. .

(13) A photosensitive resin composition laminate according to any one of the above (1) to (12).

(14) A cured product comprising the photosensitive resin composition according to any one of the above (1) to (12).

(15) A pattern forming method comprising the photosensitive resin composition layer obtained by applying the photosensitive resin composition according to any one of the above (9) to (12) to a desired support. After drying, the film is exposed according to a predetermined pattern, baked after exposure, and the resin composition layer is developed, and the obtained resin pattern is heat-treated to obtain a cured resin pattern of a predetermined shape.

(16) A method of forming a pattern comprising a photosensitive resin composition layer remaining after removing a substrate from the laminate according to the above (13), and bonding the layer to the desired support, followed by lamination. The photosensitive resin composition layer is exposed to a predetermined pattern, baked after exposure, and the resin composition layer is developed, and the obtained resin pattern is heat-treated to obtain a cured resin pattern having a predetermined shape.

The photosensitive resin composition of the present invention is suitable for having a high aspect ratio The formation of the resin pattern of the outer shape is particularly suitable for resin molding having high dimensional stability in an electronic device of a fine size.

[Best Practice for Carrying Out the Invention]

Embodiments of the present invention will be described below.

The photosensitive resin composition of the present invention is characterized in that it contains a photo-cationic polymerization initiator (A) of a salt of cerium (pentafluoroethyl)trifluorophosphate ion of cerium, and a polyfunctional epoxy resin having a specific structure. (B) A resin pattern having a high sensitivity and a high aspect ratio can be formed, and the ability to form the above resin pattern is not deteriorated, and the characteristics which can be exhibited for a long period of time can be imparted. There are various possibilities for such a combination, and in particular, a light of a polyfunctional epoxy resin having a specific structure represented by the above formula (3) (for example, NC6300 manufactured by Nippon Kayaku Co., Ltd.) and a compound represented by the above formula (2) The combination of cationic polymerization initiators is optimal.

The photocationic cationic polymerization initiator of the present invention is subjected to irradiation with radiation of excimer laser, X-ray, electron beam or the like of ultraviolet rays, far ultraviolet rays, KrF, ArF or the like to generate cations, and the cation can be polymerized. The compound of the starting agent.

The photocationic polymerization initiator (A) is ruthenium (pentafluoroethyl)trifluorophosphate.

The ruthenium of the photocationic polymerization initiator may, for example, be triphenylsulfonium, tri-p-methylphenylphosphonium, tri-o-methylphenylphosphonium, stilbene (4-methoxyphenyl)fluorene or 1-naphthyl. Diphenyl hydrazine, 2-naphthyldiphenyl fluorene, stilbene (4-fluorophenyl) fluorene, tri-1-naphthyl anthracene, tri-2-naphthyl anthracene, ginseng (4-hydroxyphenyl) fluorene, 4-(phenylthio)phenyldiphenylphosphonium, 4-(p-tolylthio)phenyldi-p-methylphenyl, 4-(4-methoxyphenylthio)phenyl bis (4 -Methoxyphenyl)anthracene, 4-(phenylthio)phenylbis(4-fluorophenyl)anthracene, 4-(phenylthio)phenylbis(4-methoxyphenyl)anthracene, 4 -(phenylthio)phenyldi-p-tolylhydrazine, bis[4-(diphenylfluorenyl)phenyl] sulfide, bis[4-(bis[4-(2-hydroxyethoxy)) Phenyl]fluorenyl)phenyl] sulfide, bis(4-[bis(4-fluorophenyl)indenyl]phenyl) sulfide, bis(4-[bis(4-methylphenyl)fluorenyl) Phenyl) thioether, bis(4-[bis(4-methoxyphenyl)indenyl]phenyl) sulfide, 4-(4-benzylidene-4-chlorophenylthio)phenyl double (4-fluorophenyl)anthracene, 4-(4-benzhydrazin-4-chlorophenylsulfanyl)phenyldiphenylphosphonium, 4-(4-benzylidenephenylsulfonyl)phenylbis(4- Fluorophenyl)anthracene, 4-(4-benzylidenephenylthio)phenyldiphenylphosphonium, 4-isopropyl-4-oxo-10-thia-9,10-dihydroindole-2 - bis-p-tolylhydrazine, 7-isopropyl-9-oxo-10-thia-9,10-dihydroindol-2-yldi-phenylindole, 2-[(di-p) -tolyl)mercapto]thioxanthone, 2-[(diphenyl)indenyl]thioxanthone, 4-[4-(4-tert-butylbenzylidene)phenylthio]phenyldi- P-tolyl oxime, 4-[4 -(4-tert-butylbenzhydrazide)phenylthio]phenyldiphenylphosphonium, 4-[4-(benzhydrylphenylsulfonyl)]phenyldi-p-methylphenyl, 4-[ 4-(benzimidylthio)]phenyldiphenylphosphonium, 5-(4-methoxyphenyl)thiaanthrenium, 5-phenylthiaanthenium, 5-tolylthioanthenium, 5 -(4-ethoxyphenyl)thiaanthrenium, 5-(2,4,6-trimethylphenyl)thiaanthrenium, etc. triarylsulfonium; diphenylbenzoquinonemethylhydrazine, diphenyl a diaryl fluorene such as 4-nitrophenylhydrazine methyl hydrazine, diphenylbenzyl hydrazine or diphenylmethyl hydrazine; phenylmethylbenzyl hydrazine, 4-hydroxyphenylmethylbenzyl hydrazine, 4 -methoxy Phenylmethylbenzyl hydrazine, 4-ethyl hydrazine carbonyl phenyl methyl benzyl hydrazine, 2-naphthylmethyl benzyl hydrazine, 2-naphthylmethyl (1-ethoxycarbonyl) ethyl hydrazine Phenylmethylphenylhydrazine methylhydrazine, 4-hydroxyphenylmethylphenylhydrazinemethylhydrazine, 4-methoxyphenylmethylphenylhydrazinemethylhydrazine, 4-ethylhydrazinecarbonyloxyphenylenebenzene a monoaryl fluorene such as methyl hydrazine, 2-naphthylmethyl benzoquinone methyl hydrazine, 2-naphthyl octadecyl phenyl hydrazine methyl hydrazine, 9-fluorenylmethyl phenyl hydrazine methyl hydrazine; A trialkylhydrazine such as methyl benzoquinone methyl hydrazine, benzoquinone methyl tetrahydrothiophene hydrazine, dimethyl benzyl hydrazine, benzyl tetrahydrothiophene hydrazine or octadecylmethyl benzoquinone methyl hydrazine. These are described in the following documents.

Examples of the triaryl sulfonium include U.S. Patent No. 4,231,951, U.S. Patent No. 4,256,828, Japanese Patent Publication No. 4-61964, Japanese Patent Application No. Hei 8-165290, No. Hei No. Hei 7-10914, No. Hei 7-25922, and JP-A-8 -27208, special Kaiping 8-27209, special Kaiping 8-165290, special Kaiping 8-301991, special Kaiping 9-143212, special Kaiping 9-278813, special Kaiping 10-7680, special Kaiping 10- 287643, special Kaiping 10-245378, special Kaiping 8-157510, special Kaiping 10-204083, special Kaiping 8-245566, special Kaiping 8-157451, special Kaiping 7-324069, special Kaiping 9-268205 No. 9-278935, special opening 2001-288205, special Kaiping 11-80118, special Kaiping 10-182825, special Kaiping 10-330353, special Kaiping 10-152495, special Kaiping 5-239213 Japanese Patent Application Laid-Open No. Hei 7-333834, No. Hei 9-12537, No. Hei 8-325259, No. Hei 8-160606, No. 2000-186071 (U.S. Patent No. 6,368,769), and the like; Except for the special Kaikai 7-300504, special opening 64-45357 No. 64-29419, and the like. For the monoaryl hydrazine, JP-A-6-345726, JP-A-8-325225, JP-A-9-118663 (U.S. Patent No. 6,093,537), and JP-A No. 2 -196812, special Kaiping 2-1470, special Kaiping 2-196812, special Kaiping 3-237107, special Kaiping 3-17101, special Kaiping 6-228086, special Kaiping 10-152469, special Kaiping 7- 300505, JP-A-2003-277353, JP-A-2003-277352, etc.; for the trialkylsulfonium, JP-A-4-308563, JP-A-5-14010, JP-A-5-140209, and JP-A-5 -230189, Special Kaiping 6-271532, Special Kaikai 58-37003, Special Kaiping 2-178303, Special Kaiping 10-338688, Special Kaiping 9-328506, Special Kaiping 11-228534, Special Kaiping 8 No. -27,102, JP-A-H07-333834, JP-A No. 5-222167, No. Hei 11-21307

In particular, the ruthenium of the photocationic polymerization initiator is preferably triphenylphosphonium or 4-(phenylthio)phenyldiphenylphosphonium, 4-(phenylsulfate) represented by the following formula (2). Phenyldiphenylphosphonium is most preferred.

The polyfunctional epoxy resin (B) having the above specific structure in the present invention may be any polyfunctional epoxy resin having a sufficient epoxy group in a molecule for forming a thick film. The epoxy resin, such a polyfunctional epoxy resin having the above specific structure has an epoxy equivalent of 150 to 400, preferably less than this range, and is superior in hardening shrinkage to warpage or cracking of the cured product. On the other hand, when it is larger than this range, the crosslinking density becomes small, the strength of the cured film or the chemical resistance, heat resistance, and crack resistance are poor. A polyfunctional epoxy resin having a specific range as described above is particularly preferred as a polyfunctional epoxy resin having a specific structure as described above (for example, manufactured by Nippon Chemical Co., Ltd.).

The polyfunctional epoxy resin (B) having the above specific structure is represented by the following formula (3).

When the softening point of the polyfunctional epoxy resin is low, the mask is likely to adhere when patterning, and when used as a dry film photoresist, it is less preferred to soften at room temperature, and on the other hand, a multifunctional epoxy resin. When the softening point is high, when the dry film photoresist is laminated on the substrate, it is hard to soften, and the adhesion to the substrate is deteriorated, which is not preferable. For the above reasons, the polyfunctional epoxy resin preferably has a softening point of 40 to 120 ° C, more preferably 50 to 100 ° C.

The content of the photocationic polymerization initiator (A) in the photosensitive resin composition is too high, and when the content of the polyfunctional epoxy resin (B) having the specific structure described above is too low in the photosensitive resin composition The development of the resin composition is difficult, and the cured film becomes brittle, which is less preferable. On the contrary, the content of the above photo-cationic polymerization initiator (A) in the photosensitive resin composition is too low, and the content of the polyfunctional epoxy resin (B) having the above specific structure in the above-mentioned photosensitive resin composition is When it is too high, coating When the resin composition is on the substrate, the hardening time by the radiation exposure becomes longer and it is less preferable. In view of the above problems, the ratio of use of the photocationic polymerization initiator (A) to the polyfunctional epoxy resin (B) having the above specific structure is preferably 0.1:99.9 to 15:85, preferably 0.5:99.5. ~10:90.

In the photosensitive resin composition of the present invention, in order to further improve the performance of the pattern, a reactive epoxy monomer (C) having a miscibility may be added, and a reactive epoxy monomer may be used. For example, a glycidyl ether compound may be used. Diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, dimethylolpropane diglycidyl ether, polypropylene glycol diglycidyl ether (made by Asahi Kasei Co., Ltd., ED506), trimethylolpropane Triglycidyl ether (ED50, manufactured by Asahi Kasei Co., Ltd.), pentaerythritol tetraglycidyl ether, etc.; these may be used alone or in combination of two or more. The reactive epoxy monomer (C) component is used for improving the reactivity of the photoresist or the physical properties of the cured film. The reactive epoxy monomer component is more in liquid form, and when the component is in a liquid state, When the blending is more than 20% by weight, the film after the solvent is removed is liable to stick to the reticle, and is less suitable. From this point of view, when the reactive epoxy monomer component is blended, the blending is carried out. The total amount of the components (A), (B) and (C) is preferably 1 to 10% by weight, particularly 2 to 7 by weight, based on the solid content of the photoresist. % is more suitable.

When the viscosity of the photosensitive resin composition of the present invention is lowered, a solvent (D) which improves the coating property can be used, and a solvent can be used by using an organic solvent which is generally used and which can dissolve each component. Such an organic solvent can be exemplified. C a ketone such as a ketone, methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene or tetramethylbenzene; a glycol ether such as dipropylene glycol dimethyl ether or dipropylene glycol diethyl ether; Ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, etc., methanol, ethanol, cellosolve An alcohol such as a methyl cellosolve, an organic solvent such as an aliphatic hydrocarbon such as octane or decane, a petroleum solvent such as petroleum ether, naphtha, hydrogenated naphtha or solvent naphtha.

These solvents may be used singly or in combination of two or more. The purpose of the solvent component is to adjust the film thickness or coatability when applied to a substrate, in order to maintain proper solubility of the main component, volatility of the component, and composition. The liquid viscosity of the material is preferably from 5% by weight to 95% by weight, particularly preferably from 10% by weight to 90% by weight, based on the photosensitive resin composition.

In the photosensitive resin composition of the present invention, in order to further improve the adhesion of the composition to the substrate, a miscibility imparting agent having a miscibility may be used, and a decane coupling agent or a titanium coupling agent may be used as the adhesion imparting agent. The coupling agent is preferably a decane coupling agent.

The above decane coupling agent may, for example, be 3-chloropropyltrimethoxydecane, vinyltrichlorodecane, vinyltriethoxydecane, vinyltrimethoxydecane or vinyltrisole (2-methoxyethoxyl). Base) decane, 3-methacryloxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane , 3-mercaptopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, 3-anthracene Triethoxy decane and the like. These adhesion imparting agents may be used alone or in combination of two or more. Since the main component is unreacted, the adhesion imparting agent is present as a residual component in addition to the component acting on the interface of the substrate. Therefore, when used in a large amount, the physical properties are deteriorated, and the like. The difference in the amount of the material is preferably within a range that does not adversely affect the effect, and the use ratio is preferably 15% by weight or less based on the photosensitive resin composition, particularly preferably. It is 10% by weight or less.

In the photosensitive resin composition of the present invention, a sensitizer which absorbs ultraviolet light and supplies the absorbed light energy to the photocationic polymerization initiator may be further used as the sensitizer, preferably, for example, 9-position. And a hydrazine compound having an alkoxy group at the 10-position (9,10-dialkoxyfluorene derivative), and the alkoxy group may, for example, a C1 to C4 alkoxy group such as a methoxy group, an ethoxy group or a propoxy group. base. The 9,10-dialkoxyfluorene derivative may further have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a methyl group, an ethyl group, a propyl group or the like. An alkyl group or a sulfonic acid alkyl ester group or a carboxylic acid alkyl ester group of C1 to C4. The alkyl group of the alkyl sulfonate group or the alkyl carboxylate may, for example, be a C1 to C4 alkyl group such as a methyl group, an ethyl group or a propyl group, and the substitution position of these substituents is preferably 2 positions.

The 9,10-dialkoxypurine derivative may, for example, be 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-di Methoxy-2-ethyl hydrazine, 9,10-diethoxy-2-ethyl hydrazine, 9,10-dipropoxy-2-ethyl hydrazine, 9,10-dimethoxy-2 -chloropurine, 9,10-dimethoxyindole-2-sulfonic acid methyl ester, 9,10-diethoxyindole-2-sulfonic acid methyl ester, 9,10-dimethoxyanthracene- 2-carboxylic acid methyl ester or the like; these may be used singly or in combination of two or more. The sensitizer component, because a small amount can exert its effect, so it uses a proportional phase The photo-cationic polymerization initiator (A) is preferably 3% by weight or less, particularly preferably 1% by weight or less.

In the present invention, it is necessary to reduce the adverse effects caused by ions derived from the photocationic cationic starting polymerization agent (A), and it is also possible to add methoxy aluminum, ethoxylated aluminum, and isopropoxy aluminum. Aluminum alkoxide such as propoxydiethoxyaluminum or butylaluminum hydride; phenoxy aluminum such as phenoxy aluminum or para-methylphenoxy aluminum; Aluminum stearate, aluminum arsenate, aluminum propionate, aluminum acetonide, aluminum hexafluoroacetate, aluminum acetoacetate, diethyl acetonide acetonate An ion scavenger such as an organoaluminum compound such as aluminum or diisopropoxy (ethyl acetoacetate) aluminum; these components may be used singly or in combination of two or more kinds, and the blending amount thereof may be relative to The solid content is 10% by weight or less.

Further, in the case of the present invention, various additives such as a thermoplastic resin, a coloring agent, a tackifier, an antifoaming agent, and a leveling agent can be used. Examples of the thermoplastic resin include polyether oxime, polystyrene, and polycarbonate; and examples of the coloring agent include phthalocyanine blue, phthalocyanine green, iodine green, crystal violet, titanium oxide, carbon black, and naphthalene black. Examples of the tackifier include Orben, Pantone, and montmorillonite. Examples of the antifoaming agent include antifoaming agents such as polyoxyalkylene-based, fluorine-based, and polymeric. The amount of the additive to be used in the photosensitive resin composition of the present invention is, for example, about 0.1 to 30% by weight, which is an approximate simple standard, and can be appropriately increased or decreased depending on the purpose of use.

Further, in the present invention, an inorganic filler such as barium sulfate, barium titanate, cerium oxide, amorphous cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide or mica powder may be used. Blending ratio can be 0 to 60% by weight of the composition.

The photosensitive resin composition of the present invention is preferably added in the proportions shown in Table 1 below, and if necessary, the above-mentioned adhesion imparting agent, sensitizer, ion trapping agent, thermoplastic resin, coloring agent, and tackifier may be added. , antifoaming agent, coating agent and inorganic filler. The mixture may be mixed by a general method, or may be stirred only, and if necessary, it may be dispersed and mixed using a disperser such as a dissolver, a homogenizer or a 3-roller, and after mixing, it may be reused, filtered by a mesh sieve, a membrane filter or the like.

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, for example, it can be applied to a ruthenium wafer or a glass with a thickness of 0.1 to 1000 μm using a spin coater or the like. After heat treatment at 60 to 130 ° C for 5 to 60 minutes, the solvent is removed to form a photosensitive resin composition layer, and then a mask having a predetermined pattern is placed, and then ultraviolet rays are irradiated, and 50 to 130 ° C is performed for 1 to 50. After the heat treatment for about a minute, the unexposed portion is developed with a developing solution at room temperature to 50 ° C for about 1 to 180 minutes to form a pattern, and then heat-treated at 130 to 200 ° C to obtain a permanent protective film conforming to various characteristics. As the developer, for example, an organic solvent such as γ-butyrolactone, triethylene glycol dimethyl ether or propylene glycol monomethyl ether acetate, or a mixture of the above organic solvent and water may be used, and a development type may be used. Spray type, spray A developing device such as a shower type or the like can be subjected to ultrasonic irradiation if necessary.

The photosensitive resin composition of the present invention is coated with a roller coater, a die coater, a knife coater, a bar coater, a gravure coater, or the like. After drying on the base film, it is dried in a drying oven set at 45 to 100 ° C, by removing the amount of solvent, and if necessary, by laminating the outer layer film as a dry film photoresist. In this case, the thickness of the photoresist on the base film is adjusted to 2 to 100 μm, and the base film and the outer layer film may be films such as polyester, polypropylene, polyethylene, TAC, polyimide, etc., if necessary, such films are necessary. A film which is subjected to release treatment by an oxime release treatment agent or a non-oxime release treatment agent can be used. By using the dry film photoresist, for example, by peeling off the outer layer film by a manual roller, a laminator or the like, and transferring the substrate to the substrate at 40 to 100 ° C and a pressure of 0.05 to 2 MPa, the same exposure and post-exposure baking as described above can be performed. Bake, develop, heat treatment.

The above-mentioned photosensitive resin composition is supplied as a film, and the step of applying to the support and drying can be omitted, and pattern formation can be performed more easily.

The cured product of the resin composition of the present invention obtained by the above method is used as a permanent photoresist film for a MEMS component such as a jet recording head.

[Examples]

The embodiments of the present invention are described below, and the examples are merely illustrative of the present invention and are not intended to limit the invention.

Examples 1 to 3, Comparative Example 1 (Photosensitive resin composition)

The polyfunctional epoxy resin, the photocationic polymerization initiator, and other components were stirred and mixed at 60 ° C for 1 hour in a flask equipped with a stirrer according to the blending amount (unit: parts by weight) described in Table 2. A photosensitive resin composition was obtained.

(Picture of photosensitive resin composition)

The photosensitive resin composition was applied onto a ruthenium wafer by a spin coater and dried to obtain a photosensitive resin composition layer having a film thickness of 80 μm, and the photosensitive resin composition layer was passed through a hot plate. Prebaking at 65 ° C for 5 minutes and 95 ° C for 20 minutes, and then performing pattern exposure (soft contact, i-line) using an i-line exposure apparatus (mask alignment apparatus: manufactured by USHIO Electric Co., Ltd.) by heating The plate was subjected to post-exposure baking (PEB) at 95 ° C for 6 minutes, followed by development treatment at 23 ° C for 7 minutes by immersion using propylene glycol monomethyl ether acetate to obtain a hardened resin pattern on the substrate.

(Evaluation of photosensitive resin composition)

The following evaluation was carried out by the necessary exposure amount after development, and the results are shown in Table 2 below.

Optimum exposure: the photographic mask transfer precision is the best exposure

Aspect ratio: film thickness / the thinnest pattern width enclosed in the formed photoresist pattern

annotation:

(A): Photocationic polymerization initiator

(trade name: CPI-210S san-apro (share) system)

(B): The multifunctional epoxy resin of the present invention

(trade name: NC6300 Nippon Chemical Co., Ltd.)

(C): Reactive epoxy monomer

(trade name: ED506 Asahi Chemical Industry Co., Ltd.)

(D): Solvent cyclopentanone

(E): coating agent

(trade name: MEGAFAC F-470 Dainippon Ink Chemical Industry Co., Ltd.)

(F): decane coupling agent

(trade name: S-510 CHISSO (share) system)

(G): Photocationic polymerization initiator

(trade name: UVI-6974 50% propylene carbonate manufactured by Dow Chemical Co., Ltd. Alkene solution)

As shown in Table 2, Examples 1 to 3 are all good results.

Example 4 (Photosensitive resin composition)

100 parts by weight of the polyfunctional resin of the present invention (trade name: NC6300, manufactured by Nippon Chemical Co., Ltd.), and 4.6 parts by weight of a photopolymerization initiator (trade name: CPI-210S san-apro (manufactured by the company)), 4 A photosensitive epoxy resin composition (trade name: ED506, manufactured by Asahi Kasei Kogyo Co., Ltd.) and 30 parts by weight of methyl ethyl ketone were added in a weight ratio to obtain a photosensitive resin composition.

(Picture of photosensitive resin composition)

The photosensitive resin composition was uniformly applied onto a 60 μm polypropylene (PP) film (base film, manufactured by Toray Industries, Inc.), and subjected to a warm air convection dryer at 65 ° C for 10 minutes and at 80 ° C. After drying for 15 minutes, a PP film (outer film, manufactured by Toray Industries, Inc.) having a film thickness of 60 μm was laminated on the photosensitive resin composition layer to form a photosensitive resin composition laminate having a film thickness of 40 μm.

The outer layer film of the photosensitive resin composition laminate was peeled off, laminated on a ruthenium wafer at a roll temperature of 70 ° C, a gas pressure of 0.2 MPa, and a speed of 0.5 m/min, and the base film was peeled off, and this operation was repeated to obtain 80 μm. A photosensitive resin composition layer. On the photosensitive resin composition layer, pattern exposure (soft contact, i-line) was performed using an i-ray exposure apparatus (mask alignment apparatus: manufactured by USHIO Electric Co., Ltd.), and then, by a hot plate at 95 ° C. The PEB of the minute was then subjected to development treatment at 23 ° C for 7 minutes by immersion using propylene glycol monomethyl ether acetate to obtain a hardened resin pattern on the substrate. An excellent result of an optimum exposure amount of 350 mJ/cm ² and an aspect ratio of 9.1 was obtained.

From the comparison of the results of Examples 1 to 4 and Comparative Example 1, it is clear that a combination of a polyfunctional epoxy resin having a specific structure and a specific photocationic polymerization initiator can provide a high which cannot be obtained by other combinations. A resin pattern with a shape of sensitivity and a high aspect ratio.

[Industrial Availability]

As described above, the photosensitive resin composition according to the present invention is suitable for forming a resin pattern having an outer shape having a high aspect ratio, and is particularly suitable for resin molding having high dimensional stability such as an electronic device having a fine size.

Claims (8)

A photosensitive resin composition characterized by containing triphenylsulfonium pentoxide (pentafluoroethyl)trifluorophosphate or 4-(phenylsulfanyl)phenyldiphenylphosphonium pentoxide (pentafluoroethyl)trifluorophosphate The photocationic polymerization initiator (A) is formed of a polyfunctional epoxy resin (B) having a specific structure represented by the following formula (3). The photosensitive resin composition of the first aspect of the invention, wherein the photocationic polymerization initiator (A) is a compound represented by the following formula (2). A photosensitive resin composition according to claim 1 or 2, which is a reactive epoxy monomer (C) containing a glycidyl ether compound. The photosensitive resin composition of claim 1 or 2, wherein the photosensitive resin composition containing the solvent (D) has a solid content concentration of 5 to 95% by weight. A photosensitive resin composition laminate characterized in that the substrate is impregnated with the photosensitive resin composition according to any one of claims 1 to 4. A cured product comprising the photosensitive resin composition according to any one of claims 1 to 4 of the invention. A pattern forming method comprising a photosensitive resin composition layer obtained by applying a photosensitive resin composition according to any one of claims 1 to 4 to a desired support, after drying, According to the predetermined pattern exposure, post-exposure baking, development of the resin composition layer, and heat treatment of the obtained resin pattern, the step of obtaining a hardened resin pattern of a predetermined shape is carried out. A pattern forming method, which comprises a photosensitive resin composition remaining after removing a substrate from a laminate as disclosed in claim 5 The layer is bonded to the above-mentioned desired support and laminated, and the photosensitive resin composition layer is exposed according to a predetermined pattern, baked after exposure, developed a resin composition layer, and heat-treated to obtain a resin pattern. A step of obtaining a hardened resin pattern of a predetermined shape.