WO2008007762A1

WO2008007762A1 - Photosensitive resin composition, layered product thereof, cured object therefrom, and method of forming pattern from the composition (2)

Info

Publication number: WO2008007762A1
Application number: PCT/JP2007/063954
Authority: WO
Inventors: Ryo Sakai; Satoshi Mori; Nao Honda; Donald Johnson; Harris Miller
Original assignee: Nippon Kayaku Kabushiki Kaisha; Microchem Corp.
Priority date: 2006-07-14
Filing date: 2007-07-13
Publication date: 2008-01-17
Also published as: JP4913141B2; TW200813627A; TWI406088B; JPWO2008007762A1

Abstract

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

Description

Photosensitive resin composition, laminate thereof, cured product thereof, and pan forming method using the composition (2)

Technical field

The present invention relates to a photosensitive resin composition capable of forming a pattern with high resolution and a high aspect ratio, a laminate thereof, a cured product thereof, and a pattern forming method using the composition.

Background art

Photoresistable resists have recently been used extensively in semiconductor and MEMS (microelectro-mechanical systems) applications. In such an application, photolithography is performed by patterning exposure on a substrate, and then it is achieved by selectively removing an exposed area or a non-exposed area by developing with a developer. Resist that can be photolithographically processed (photoresist) is either positive or negative type, and those that dissolve in the developer upon exposure are positive types and those that become insoluble are negative types. High-aspect ratios are required for leading-edge electoric package applications, while in MEMS applications, the ability to form a uniform spin-coating film, a straight shape with a thickness of 100 m or more, and high-aspect ratio photo Lithographic resist is required. Here, the aspect ratio is an important characteristic expressed by resist film thickness Z pattern line width and showing the performance of photolithography.

] Conventional positive resists based on the dinaphthoquinone-novolak reaction are not suitable for applications requiring thick films of 50 μm or more. There is a limit in thick film formation because the dinaphthoquinone type (DNQ) photoreactant in the near ultraviolet region wavelength (350 to 450 nm) generally used for resist exposure is relatively high! By having. The DNQ type photoresist also has a slope shape rather than a straight shape due to the unique solubility difference between the exposed and unexposed areas in the developer. The top force of the film due to light absorption. The force that reduces the irradiation intensity toward the bottom. If the light absorption is too high, the bottom of the resist is underexposed compared to the top. Or distorted shape.

[0004] It is known that a negative chemically amplified thick film photolithography processable yarn and composite has very low light absorption in the 350 to 450 nm wavelength region. The composition of this resist is a polyfunctional bisphenol A novolak epoxy resin (Resolution 'Performance' EPON SU-8 resin manufactured by Podakku), Dow Chemical's CYRACURE UVI-6974, a light-powered thione polymerization initiator (this The photopower thione polymerization initiator consists of a propylene carbonate solution of an aromatic sulfo-hexafluoroantimonate). This photoresist composition is spin-coated or curtain-coated on various substrates, then the solvent is volatilized by baking to form a solid photoresist layer having a thickness of 100 m or more, contact exposure, Photolithography is performed by irradiating near ultraviolet light through a photomask using various exposure methods such as proximity exposure and projection exposure. Then, it is immersed in a developing solution, the non-exposed area is dissolved, and a high-resolution photomask negative image is formed on the substrate.

[0005] EPON SU-8 resin is a low molecular weight epoxy oligomer having superior characteristics in photolithography processing with a high aspect ratio in a thick film. Its superior features are (1) high epoxy functionality, (2) high branching, (3) high transmittance at 350-450 nm, and (4) low molecular weight necessary and sufficient to form solids. is there. High number of epoxy functional groups and high degree of branching cause sufficient cross-linking under strong acid catalyst, and high transmittance is uniformly irradiated through the thick film, forming a pattern with an aspect ratio of 10 or more with a thick film of 100 m or more. Has resist performance. The selection of a resin having a high number of epoxy functional groups and a high degree of branching is an important item for forming a high aspect ratio structure with straight sidewalls. The selection of a low molecular weight resin allows a solid layer of thick film photoresist to be performed with a minimum number of coating steps to form a solid layer on the substrate.

[0006] Photopower thione polymerization initiators based on sulfo-um salt or ododonium salt are well known, and useful light-power thione polymerization initiators having appropriate absorbance are disclosed. p-Phenol-lentioether is contained (Patent Documents 1 and 2). In addition, sensitizers such as 2-alkyl-9,10-dimethoxyanthracene or other anthracene, naphthalene, peryl or pyrilil compounds can be added to initiate photo-thion polymerization. Even if it is introduced into the agent (Patent Document 3).

[0007] Negative resists based on the disclosed compounds as described above, suitable for spin coating, are sold by MicroChem and are used commercially, especially in MEMS device components. For example, the “SU-8 Series” provided by Micro-Chem is spin-coated at 1000-3000 rpm to form a film with a thickness of 30-100 μm, and then exposed to 100 m or more after imaging. A pattern with an aspect ratio of 10 or more can be formed.

[0008] An application such as a dry film resist coated on a substrate such as a polyester film is also disclosed (Patent Document 4).

[0009] A photoimageable cationic polymerizable flame retardant composition suitable for use as a solder mask is disclosed (Patent Documents 5, 6, and 7). This bisphenol A and the condensation product of Epiku port Ruhidorin consists of a mixture containing 10 to 80 wt ^_0/0, bisphenol A climb Kkuepokishi榭脂20 to 90 weight ^_0/0, epoxidized tetrabromobisphenol bisphenol A Thus, a compositional power containing 35 to 50% by weight and 0.1 to 15% by weight of a light power thione polymerization initiator is also obtained.

A photopolymerizable compound based on a hydroxyl group-containing additive, a light-power thione polymerization initiator, and an epoxy resin having a functional group number of 1.5 or more is also disclosed. Hydroxyl-containing additives have been reported to increase flexibility and reduce stress in thick films of 100 μm or more (Patent Document 8).

[0011] Patent Document 9 discloses a method of producing a hard epoxy resin system in an EB curable application. The main improvement here is the brittleness of the radiation-cured epoxy resin. Many structural and consumer resins (epoxy resins) must have sufficient strength and impact resistance to withstand years of rigorous service. A wide range of tough materials including SU-8 resin is disclosed herein. Regarding the increased strength, the effectiveness of the invention described in Patent Document 9 is shown by fracture toughness and flexural modulus. The tough material described in Patent Document 9 also has various thermoplastics, hydroxyl group-containing thermoplastic oligomers, epoxy-containing thermoplastic oligomers, reactive flexible materials, elastomers, rubbers, and mixtures thereof. However, the composition described in Patent Document 9 is a composition applied to a film imaged by non-patterned EB irradiation. Therefore, the characteristics of these compositions when exposed to patterning by UV, X-ray, and EB irradiation. Sex is not a reference for photoimaging applications.

Many proposals have been made regarding a photoresist composition containing an epoxy (Patent Document 10). Here, for example, the necessity of adjusting a resist composition applied to a spin coating method is disclosed, and rheological characteristics are required. In addition, the composition here must have a sufficient transmittance for exposure irradiation that photodegrades the photoinitiator through the film thickness. In addition, this photoresist composition has appropriate physical properties such as solder resistance or ink resistance or strength, significant deterioration, or reduced adhesion to withstand various applications. You must have it. If this photoresist composition is used for other applications such as a photoresist for etching, other characteristics are required. However, there are currently no specific epoxy resins that satisfy all of the various requirements. Many different combinations or mixtures of various epoxy resins have already been disclosed, and all the prominent patents describe various resins, photoinitiators for photocured compositions. Many of them will be useful as photoimageable resists as permanent film applications. However, none of these disclose the optimum thread and composition for our intended MEMS application, and in fact most examples of plasticizers, softeners and tougheners reduce lithographic performance.

[0013] Patent Document 1: USP5502083

Patent Document 2: USP6368769

Patent Document 3: USP5102772

Patent Document 4: USP4882245

Patent Document 5: USP5026624

Patent Document 6: USP5278010

Patent Document 7: USP5304457

Patent Document 8: USP4256828

Patent Document 9: USP5726216

Patent Document 10: USP5264325

Disclosure of the invention Problems to be solved by the invention

[0014] In a conventional photosensitive resin composition using a polyfunctional epoxy resin such as a novolak-type epoxy resin, the sensitivity of the light-powered thione polymerization initiator is low, and therefore a large amount of initiator is included. There is a problem that a mask pattern cannot be faithfully reproduced in a short time. In addition, the photopower thione polymerization initiator containing SbF6— has relatively high sensitivity, but has the problem of toxicity and limited use.

[0015] The present invention has been made in view of the above-described conventional circumstances, and an object thereof is to provide a photosensitive resin composition capable of forming a pattern with high resolution and high aspect ratio. Means for solving the problem

[0016] In order to solve the above-mentioned problems, the present inventors have intensively conducted experiments and examinations regarding high sensitivity and high resolution in a photosensitive resin composition, and as a result, specific polyfunctional epoxy resin. And a specific photoactive thione polymerization initiator are combined to prepare a photosensitive resin composition, and using this photosensitive resin composition, a resin pattern is formed. The present inventors have found that a greaves pattern with a high ratio can be formed. That is, the present invention provides (1) an epoxy resin having a biphenyl structure represented by the following general formula (1) (A-1)

[0017] [Chemical 1]

[In the formula, R and R are each an independent hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

1 2

n is an average value and is a real number from 1 to 30. )

And a polyfunctional epoxy resin represented by the following general formula (2) (A-2)

[0019] [Chemical 2]

[0020] (wherein R and R each independently represent a hydrogen atom or a methyl group, t, u and V are

1 2

Each is an average value and independently represents a real number of 1 or more, and the sum is a real number of 3 to 30. ) One or more types of epoxy resin (A) whose power is also selected, and one or more bisphenol A novolac type polyfunctional epoxy resins (B) represented by the following general formula (3)

[0021] [Chemical 3]

(In the formula, each R is an independent glycidyl group or a hydrogen atom, and n is an average value and is a real number of 1 to 30.)

And a photopolymerization initiator (C) that is sulfomutris (pentafluoroethyl) trifluorophosphate.

(2) The photoactive thione polymerization initiator (C) is a compound represented by the following formula (4) (A-1)

[0023] [Chemical 4]

[0024] The photosensitive resin composition according to the above (1), wherein

(3) The photosensitive resin composition according to (1) or (2) above, which contains one or more reactive epoxy monomers (D).

(4) The photosensitive resin composition according to any one of (1) to (3) above, which contains the solvent (E) and has a solid content concentration of 5 to 95% by weight.

(5) A photosensitive resin composition laminate in which any one of the photosensitive resin compositions of (1) to (4) is sandwiched between substrates.

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

(7) The photosensitive resin composition layer obtained by applying any one of the photosensitive resin compositions of (1) to (4) above onto a desired support, and after drying, into a predetermined pattern A pattern forming method comprising exposing to light, performing beta after exposure, developing the resin composition layer, and heat-treating the obtained resin pattern to obtain a cured resin pattern having a predetermined shape.

(8) The photosensitive resin composition layer remaining after the substrate is removed in addition to the laminate strength described in (5) above is laminated on a desired support, and the photosensitive resin composition layer is laminated. Pattern formation comprising exposing to a predetermined pattern, beta after exposure, developing the resin composition, and heat-treating the obtained resin pattern to obtain a cured resin pattern of a predetermined shape Method.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described.

The photosensitive resin composition of the present invention includes an epoxy resin (A-1) having a bifur structure represented by the general formula (1) and a polyvalent resin represented by the general formula (2). Functional epoxy resin (A-2) Force is also selected One or more epoxy resin (A) and one or more bisphenol A represented by the above general formula (3) Functional epoxy It contains a fat (B) and a photocationic polymerization initiator (C) that is sulfo-umtris (pentafluoroethyl) trifluorophosphate, and has a high sensitivity and high aspect ratio resin pattern. Can be formed. Various combinations of these are possible, but in particular, biphenyl novolac type epoxy resin (eg, NC3000H Nippon Gyaku Co., Ltd.) and multifunctional epoxy resin (eg, NER7604 Nippon Kayaku) (Made by Co., Ltd.) One or more types of epoxy resin selected for its power, and 8-functional bisphenol A novolac type epoxy resin (eg, EPON SU-8 manufactured by Resolution “Performance” products) and the above formula (4 A combination with a photopower thione polymerization initiator which is a compound represented by

[0026] In the present invention, the epoxy resin (A) is a polyfunctional epoxy resin (A-1) having a biphenyl structure and a polyfunctional epoxy resin (A-2) force selected from one kind or more Many epoxy resins.

[0027] The polyfunctional epoxy resin (A-1) having a biphenyl structure in the present invention has a biphenyl structure containing enough epoxy groups in one molecule to form a thick film pattern. Any epoxy resin may be used as long as it is a polyfunctional epoxy resin. These may be used alone or in combination of two or more. The epoxy equivalent of the polyfunctional epoxy resin having a biphenyl structure is preferably from 150 to 400. If the epoxy equivalent is smaller than this range, the curing shrinkage is largely unfavorable. On the other hand, if it is larger than this range, the crosslinking density is small. I like it. A bifunctional epoxy resin having a biphenyl structure satisfying the above range is particularly preferably a biphenol-nonopolak type epoxy resin (eg, NC3000H manufactured by Nippon Gyaku Co., Ltd.). Here, n in the general formula (1) represents the number of repeating units, and is a value obtained by dividing the average molecular weight measured by GPC by the repeating unit molecular weight.

[0028] The polyfunctional epoxy resin (A-1) having the biphenyl structure is represented by the following general formula (1).

[0029] [Chemical 5]

(Wherein R 1 and R 2 are each independently an hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

1 2

n is an average value and is a real number from 1 to 30. )

[0031] The polyfunctional epoxy resin (A-2) in the present invention is a thick, alcoholic property of bisphenol F type epoxy resin containing an epoxy group sufficient in one molecule to form a film pattern. Any epoxy resin obtained by reaction of hydroxyl group with epichlorohydrin and epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin with epichlorohydrin It may be greaves. These can be used alone or in combination of two or more. The epoxy equivalent of these polyfunctional epoxy resins (A-2) is preferably 150 to 400, and is less than this range, and is not preferable because the curing shrinkage is large and warping and cracks of the cured product are likely to occur. On the other hand, if it is larger than this range, the crosslinking density becomes low, and the strength of the cured film is unfavorable due to poor chemical resistance, heat resistance and crack resistance. As the polyfunctional epoxy resin (A-2) satisfying the above range, NER-7604 (epoxy equivalent 325) and NER-1320 (epoxy equivalent 315) (manufactured by Nippon Kayaku Co., Ltd.) are particularly preferable. Here, t, u and V in the general formula (2) represent the number of repeating units, and are values obtained by dividing the average molecular weight measured by GPC by the repeating unit molecular weight.

[0032] The polyfunctional epoxy resin (A-2) is represented by the following general formula (2).

[0033] [Chemical 6]

[0034] (wherein R and R each independently represent a hydrogen atom or a methyl group, t, u and V are

1 2

Each is an average value and independently represents a real number of 1 or more, and the sum is a real number of 3 to 30. [0035] The bisphenol A novolak type polyfunctional epoxy resin (B) in the present invention is a bisphenol A novolak type polyfunctional epoxy resin containing a sufficient number of epoxy groups in one molecule to form a film pattern. Any epoxy resin may be used as long as it is a functional epoxy resin. These can be used alone or in admixture of two or more. Specific examples of bisphenol A novolac type polyfunctional epoxy resin include EPON SU—8 (Resolution 'Performance' Megumi Dakut Co., Ltd.), Epicoat 157S70, Epicoat 157S65 (Japan Epoxy Resin Co., Ltd.), YD—128 (Toto Kasei Co., Ltd.), Epiclon N—885, Epiclon N—865, Epicron 2055 (Dainippon Ink Chemical Industries, Ltd.) ). The epoxy equivalent of these bisphenol A novolac type polyfunctional epoxy resins is preferably 150 to 400 force, smaller than this range, and is preferable in terms of large curing shrinkage and easy occurrence of warping and cracking of the cured product. . On the other hand, when it is larger than this range, the crosslink density becomes small, and the strength of the cured film is not preferable because the chemical resistance, heat resistance and crack resistance are poor. As the bisphenol A novolak type polyfunctional epoxy resin satisfying the above range, EPON SU-8 (Resolution 'Performance. Products') Epicoat 157S70 (Japan Epoxy Resin Co., Ltd.) is particularly preferred.

The bisphenol A novolac type polyfunctional epoxy resin (B) is represented by the following general formula (3). Here, n in the general formula (3) represents the number of repeating units, and is a value obtained by dividing the average molecular weight measured by GPC by the repeating unit molecular weight.

[0037] [Chemical 7]

[In the formula, each R is an independent glycidyl group or a hydrogen atom, and n is a real number of 1 to 30.]

[0039] If the epoxy resin (A) and the bisphenol A novolac polyfunctional epoxy resin (B) have a low soft spot, mask sticking is likely to occur during patterning. When used as a dry film resist, it is not preferable because it softens at room temperature. On the other hand, when the soft point of the polyfunctional epoxy resin having a biphenyl structure is high, When laminating a dry film resist to a substrate, it is not preferable because it is difficult to soften and adheres to the substrate. For the above reasons, the preferred softening point of the polyfunctional epoxy resin is 40 to 120 ° C, more preferably 50 to 100 ° C.

[0040] The photopower thione polymerization initiator in the present invention generates cations upon irradiation with excimer lasers such as ultraviolet rays, far ultraviolet rays, KrF and ArF, X-rays and electron beams, and the cations are generated. It is a compound that can be a polymerization initiator.

[0041] The light-power thione polymerization initiator (C) is sulfoyulium tris (pentafluoroethyl) trifluorophosphate.

[0042] Examples of the sulfone of the photoactive thione polymerization initiator include triphenyl sulfone, tri-p-tolyl sulfone, tri-o-tolyl sulfome, tris (4-methoxyphenol) s. Norejoum, 1 Naftinoresihue-Noresnorehonum, 2-Naphtinoresihue-Noresnorehonum, Tris (4 Funoleo mouth-Fuel), Snorehonum, Tri 1 1-Naftinolesnorehoum, Tri —2 Naphthyl sulfone, Tris (4 hydroxyphenol) sulfur, 4 -— (Phenolthio) phenol disulfol, 4 -— (p-Tolylthio) phenol p-Tolylsulfome 4- (4-methoxyphenylthio) phenolbis (4-methoxyphenyl) sulfur, 4- (phenolthio) phenolbis (4-fluorophenyl) sulfurium, 4- (phenol -Luthio) Ferrubis (4-Met (Sulfur) sulfur, 4— (feruol) farge p-tolylsulfurum, bis [4— (diphenylsulfo-phenol) sulfur], bis [4— (bis [ 4- (2-Hydroxyethoxy) phenyl] sulfo-phenol) sulfide, bis (4- [bis (4-fluorophenyl) sulfo-phenyl] sulfide), bis (4 [bis (4 methylphenol) -L) sulfo- [io] phenole) sulfide, bis (4 [bis (4-methoxyphenol) sulfo-o] phenol) sulfide, 4-((4-benzoyl-4-sulfone) -norethio ) Ferbis (4-Funoreo-Fu) Snelephonium, 4- (4-Benzoyl 4-FloroFuerthio) Fuel disulfosulfo, 4- (4-Benzo-Fuerthio) Phenylbis (4-Fluorophenyl) sulfurium, 4-one (4-benzoylphenol) ) Fuel disulfol sulfone, 4-Isopropyl 4-4-oxo 1 Thia 9, 10 Dihydroanthracene 2-yldi-tolyl sulfome 7-Isopropyl 1 9-oxo 10 Thia 9, 10 Dihydroanthracene 1 2-ildiphenol Rusulforum, 2 — [(di-p-tolyl) sulfo-o] thioxanthone, 2 — [(Diphenyl) sulfo-thio] thioxanthone, 4 [4 (4-tert-butylbenzoyl) phenolthio] Ruzy-p-tolylsulfum, 4 [4- (tert-butylbenzoyl) phenolthiol] -phenyldisulfosulfone, 4 [4 (Benzyl-phenylthio)] phenol-tri-sulfurium, 4 — [4— (Benzylphenylthio)] phenyldisulfol, 5- (4-methoxyphenyl) thiaanthrhenium, 5-phenolthanthanthrenium, 5-trilthiaanthrhenium, 5- (4 —Ethoxyphenol) thiaanthrenium, 5— (2, 4, 6 trimethylphenol) thiaanthrenium and other triaryls noordome; Diphenorenocinoles noreform, Diphne nore 4- Trofenacino Diaryl sulfones such as snoor form, diphenyl pendyl sulfone, diphenyl methyl sulfone; 4-methoxyphenylmethylbenzyl sulfone, 4-acetocarboxoxyphenyl methylbenzyl sulfone, 2-naphthylmethylbenzyl sulfone, 2-naphthylmethyl (1-ethoxycarbole) ethylsulfo -Hum, phenylmethylphenacyl sulfone, 4-hydroxyphenyl methylphenacyl sulfone, 4-methoxyphenyl methylphenacyl sulfome, 4-acetocarboxylphenol Methylphenacyl sulfone, 2-naphthylmethylphenacyl sulfone, 2 naphthyloctadecylphenacylsulfurium, 9A Monoarylsulfomes such as tracermethyl rufenacylsulfome; dimethylphenacylsulfum, phenacyltetrahydrothiophum, dimethylbenzylsulfome, benzyltetrahydrothiophene And trialkylsulfo-um such as octadecylmethylphenacylsulfo-um, which are described in the following literature!

Regarding triarylsulfo-um, U.S. Pat. No. 4,231,951, U.S. Pat.No. 4,256,828, JP-A-7-61964, JP-A-8-165290, JP-A-7-10914, JP-A-7-25922. JP-A-8-27208, JP-A-8-27209, JP-A-8-165290, JP-A-8-301991, JP-A-9-143212, JP-A-9-278813, JP-A-10-7680, Kaihei 10-287643, JP-A-10-245378, JP-A-8-157510, JP-A-10-204083, JP-A-8-245566, JP-A-8-157451, Special Kaihei 7-324069, JP 9-268205, JP 9-278935, JP 2001-288205, JP 11-80118, JP 10-182825, JP 10-33035 3, Special Kaihei 10-152495, JP-A-5-239213, JP-A-333834, JP-A-9-12537, JP-A-8-325259, JP-A-8-160606, JP-A-2000-186071 (US Patent No. 1) No. 6368769), etc .;

— 300504, JP-A-64-45357, JP-A-64-29419, etc .; For monoaryl sulfone, JP-A-6-345726, JP-A-8-325225, JP-A-9-11 No. 8663 (US Pat. No. 6093753), JP-A-2-196812, JP-A-2-1470, JP-A-2-196812, JP-A-3-237107, JP-A-3-17101, JP-A-6- 2 28086, JP-A-10-152469, JP-A-7-300505, JP-A-2003-277353, JP-A-2003-277352, etc .; with regard to trialkyl sulfone, JP-A-4-30563 Kaihei 5-140210, JP-A-5-140209, JP-A-5-230189, JP-A-6-271532, JP-A-58-37003, JP-A-2-178303, JP-A-10

— 338688, JP-A-9-328506, JP-A-11-228534, JP-A-8-27102, JP-A-7-333834, JP-A-5-222167, JP-A-11-21307, JP-A-11 35613 No., US Pat. No. 6,310,014 and the like.

[0044] In particular, as the sulfone of the light-power thione polymerization initiator, triphenyl sulfone and 4 (ferthio) phenyl disulfol sulfome are more preferred, represented by the following formula (4): The most preferred is 4 (Fuerthio) Fuel Disulfosulfum (A-1) as shown!

[0045] [Chemical 8]

[0046] The total content of the epoxy resin (A) and the bisphenol A novolac type polyfunctional epoxy resin (B) is too low with respect to the photosensitive resin composition, and the photopower thione polymerization starts. When the content of the agent (c) in the photosensitive resin composition is too high, it is not preferable because the resin composition is difficult to develop and the film after curing becomes brittle. Conversely, the epoxy resin

(A) and the bisphenol A novolak-type polyfunctional epoxy resin (B) in a total content of the photosensitive resin composition is too high, and the photosensitive resin of the photopower thione polymerization initiator (C) When the content with respect to the composition is too low, it is not preferable because the curing time by radiation exposure of the resin composition becomes long when coated on a substrate. Considering these, the ratio of the total of epoxy resin (A) and bisphenol A novolak type polyfunctional epoxy resin (B) to the photopower thione polymerization initiator (C) is preferably 0.1: 99. 9-15: 85, more preferably 0.5: 99. 5-: LO: 90.

[0047] To the photosensitive resin composition of the present invention, a reactive epoxy monomer (D) having miscibility may be added to further improve the performance of the pattern. As the reactive epoxy monomer, a glycidyl ether compound can be used. For example, diethylene glycol diglycidyl ether, hexanediol diglycidyl ether, dimethylolpropane diglycidyl ether, polypropylene glycol diglycidyl ether (Asahi Denka Kogyo Co., Ltd., ED506) ), Trimethylolpropane triglycidyl ether (manufactured by Asahi Denshi Kogyo Co., Ltd., ED505), pentaerythritol tetraglycidyl ether, and the like. These may be used alone or in combination of two or more. The reactive epoxy monomer (D) component is used for the purpose of improving the reactivity of the resist and the physical properties of the cured film. Reactive epoxy monomer Many components are in liquid form. If the component is in liquid form, adding more than 20% by weight tends to cause stickiness on the film after removal of the solvent, and mask sticking. There is a problem and it is inappropriate. From this point, when the monomer component is blended, the blending ratio is the solid content when the sum of the components (A), (B), (C) and (D) is the solid content of the resist. 1 to LO weight percent is preferred, especially 2 to 7 weight percent is preferred.

[0048] A solvent (E) can be used to lower the viscosity of the photosensitive resin composition of the present invention and improve the coating properties. As the solvent (E), any commonly used organic solvent capable of dissolving each component can be used. Such organic solvents include acetone, ethyl methyl ketone, ketones such as cyclohexanone, toluene, xylene, tetramethyl. Aromatic hydrocarbons such as benzene, glycol ethers such as dipropylene glycol dimethyl ether and dipropylene glycol jetyl ether, ethyl acetate, butyl acetate, butyl acetate sorb acetate, carbitol acetate, propylene glycol monomethyl ether acetate, y Esters such as butyrolatatane, alcohols such as methanol, ethanol, ceresolve, and methyl ceresolve, aliphatic hydrocarbons such as octane and decane, petroleum ethers such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha Examples include organic solvents.

[0049] These solvents may be used alone or in combination of two or more. The solvent component is added for the purpose of adjusting the film thickness and applicability when applied to the base material, and in order to maintain the solubility of the main component, the volatility of the component, and the liquid viscosity of the composition properly. Further, it is preferably 5 to 95% by weight based on the photosensitive resin composition, particularly preferably 10 to 90% by weight.

[0050] In the photosensitive resin composition of the present invention, a miscible adhesion-imparting agent may be used for the purpose of further improving the adhesion of the composition to the substrate. As the adhesion-imparting agent, a coupling agent such as a coupling agent silane coupling agent or a titanium coupling agent can be used, and a silane coupling agent is preferable.

[0051] Examples of the silane coupling agent include 3-chloropropyl methoxysilane, butyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl'tris (2-methoxyethoxy) silane, and 3-methacryloxypropyltrimethoxy. Silane, 2— (3,4 epoxy

Examples include 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane. These adhesion promoters can be used alone or in combination of two or more. Since the adhesion-imparting agent is non-reactive with the main component, components other than those that act at the substrate interface are present as residual components after curing, and if used in large amounts, adverse effects such as deterioration of physical properties will occur. Depending on the base material, it can be used within a range that does not adversely affect the effect even in a small amount, and the use ratio is preferably 15% by weight or less based on the photosensitive resin composition. Particularly preferably 5% by weight or less It is below.

[0052] In the photosensitive resin composition of the present invention, a sensitizer may be further used to absorb ultraviolet light and to supply the absorbed light energy to the photothion polymerization initiator. As the sensitizer, for example, anthracene compounds having an alkoxyl group at the 9th and 10th positions (9, 10 dialkoxyanthracene derivatives) are preferable. Examples of the alkoxyl group include C1-C4 alkoxyl groups such as a methoxy group, an ethoxy group, and a propoxy group. The 9, 10 dialkoxyanthracene derivative may further have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, C1-C4 alkyl group such as methyl group, ethyl group and propyl group, sulfonic acid alkyl ester group, and carboxylic acid alkyl ester group. Etc. Examples of the alkyl in the sulfonic acid alkyl ester group and the carboxylic acid alkyl ester include C1-C4 alkyl such as methyl, ethyl and propyl. The substitution position of these substituents is preferably the 2-position.

[0053] Examples of the 9, 10 dialkoxyanthracene derivatives include 9, 10 dimethoxyanthracene, 9, 10 jetoxyanthracene, 9,10 dipropoxyanthracene, 9,10 dimethoxy-2-ethylanthracene, 9,10 diethoxy-2 Ethylanthracene, 9,10 Dipropoxy-2 Ethylanthracene, 9,10 Dimethoxy-2-chloroanthracene, 9,10 Dimethoxyanthracene 2-sulfonic acid methyl ester, 9,10 Jetxanthracene mono-2-sulfonic acid methyl ester, 9, 10 Dimethoxyanthracene 2-carboxylic acid methyl ester. These can be used alone or in admixture of two or more. Since the sensitizer component exerts its effect in a small amount, its use ratio is preferably 3% by weight or less, particularly preferably 1% by weight or less, based on the light-power thione polymerization initiator (C) component.

[0054] In the present invention, when it is necessary to reduce the adverse effects of ions derived from the photopower thione polymerization initiator (C), trismethoxy aluminum, trisethoxy aluminum, trisisopropoxy aluminum, iso Alkoxyaluminum such as propoxydiethoxyaluminum and trisbutoxyaluminum, phenoxyaluminum such as trisphenoxyaluminum and trisparamethylphenoxyaluminum, triacetoxyaluminum, tris Tearate Aluminum, Trisbutyrate Aluminum, Trisp Ported Pionato Aluminum, Triacetylacetylacetonate Aluminum, Tristrifluoracetylacetonate Aluminum, Tricetylacetate Aluminum, Dicetylacetonate Didipivalo These components can be added alone or in combination of two or more of them, such as organic aluminum compounds such as rumethanatoaluminum yuum and diisopropoxy (ethylacetoacetato) aluminum. Can be used. The blending amount is 10% by weight or less based on the solid content.

[0055] Further, in the present invention, various additives such as a thermoplastic rosin, a colorant, a thickener, an antifoaming agent and a leveling agent can be used as necessary. Examples of the thermoplastic resin include polyethersulfone, polystyrene, and polycarbonate. Examples of the colorant include phthalocyanine blue, phthalocyanine green, iodine 'green, crystal violet, titanium oxide, carbon black, and naphthalene black. Examples of the thickener include olven, benton, and montmorillonite. Examples of the antifoaming agent include antifoaming agents such as silicone, fluorine, and polymer. These additives. In the photosensitive resin composition of the present invention, the amount used is, for example, about 0.1 to 30% by weight in each case, but may be appropriately increased or decreased depending on the purpose of use.

[0056] In the present invention, for example, barium sulfate, barium titanate, silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, acid aluminum, hydroxide aluminum aluminum, mica powder Inorganic fillers such as the above can be used, and the blending ratio is 0 to 60% by weight in the composition.

[0057] The photosensitive resin composition of the present invention is preferably blended in the proportions shown in Table 1 below, and if necessary, the adhesion-imparting agent, sensitizer, ion catcher, thermoplastic resin, colorant, sensitizer. You may add a sticky agent, an antifoamer, a leveling agent, and an inorganic filler. Just mixing and stirring by ordinary methods, it is possible to disperse and mix using a disperser such as a dissolver, a homogenizer, or a three-roll mill if necessary. Also, after mixing, filter with a mesh or membrane filter.

[0058] [Table 1] Parts by weight

Epoxy resin (A) 1 to 70

Bisphenol A Nopolac type epoxy resin (B) 1 5-98. Θ

Light power thione polymerization initiator (C) 0.1-1 5

Reactive epoxy monomer (D) 1 ~ 1 0

Solvent (E) 5. 8-2090

[0059] The photosensitive resin composition of the present invention is preferably used in liquid form. In order to use the photosensitive resin composition of the present invention, for example, it is applied onto a substrate such as silicon wafer or glass using a spin coater or the like at a thickness of 0.1 to LOO of 0 μm, and 60 to 130 Then, heat treatment is performed for about 5 to 60 minutes to remove the solvent and form a photosensitive resin composition layer. Then, a mask having a predetermined pattern is placed and irradiated with ultraviolet rays, and at 50 to 130 ° C, 1 to After heat treatment for about 50 minutes, the unexposed part is developed with a developer at room temperature to 50 ° C for about 1 to 180 minutes to form a pattern, and then heated at 130 to 200 ° C. By processing, a permanent protective film that satisfies various properties can be obtained. As the developer, for example, an organic solvent such as γ-petit-mouth rataton, triethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, or a mixed solution of the organic solvent and water can be used. For development, a paddle type, spray type, shower type, or other developing device may be used, and ultrasonic irradiation may be performed as necessary.

[0060] The resin composition of the present invention is obtained by applying the yarn composition on a base film using a roll coater, die coater, knife coater, bar coater, gravure coater, etc., and then 45 to 100 ° C. It can be made into a dry film resist by drying in a drying oven set to, removing a predetermined amount of solvent, and laminating a cover film or the like as necessary. At this time, the thickness of the resist on the base film is adjusted to 2 to: LOO / zm. As the base film and the cover film, for example, a film of polyester, polypropylene, polyethylene, TAC, polyimide or the like is used. If necessary, these films may be processed with a release agent such as a silicon release treatment agent or a non-silicon release treatment agent. In order to use this dry film resist, for example, the cover film is peeled off, and a hand roll, a laminator, etc. are used, a temperature of 40 ° C. to 100 ° C. and a pressure of 0.05 to 2 MPa. Transfer to a substrate and exposure, post-exposure beta, development, and heat treatment may be performed in the same manner as the photosensitive resin composition described in paragraph [0059] immediately above.

[0061] As described above, if the photosensitive resin composition is supplied as a film, it can be applied onto a support.

And the drying step can be omitted, and pattern formation using the photosensitive resin composition of the present invention can be performed more easily.

[0062] The cured product of the resin composition of the present invention obtained by the above method is used, for example, as a permanent resist film, for example, for MEMS parts such as an inkjet recording head.

Example

[0063] Examples of the present invention will be described below, but these examples are merely examples for suitably explaining the present invention, and do not limit the present invention.

(Examples 1 to 3 and Comparative Example 1)

(Photosensitive resin composition)

According to the blending amount shown in Table 2 (unit is parts by weight), polyfunctional epoxy resin, light-power thione polymerization initiator, and other components should be mixed for 1 hour at 60 ° C in a flask equipped with a vortexer. The mixture was mixed to obtain a photosensitive composition.

[0065] (Patterning of photosensitive resin composition)

(Examples 1 to 3 and Comparative Example 1)

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

[0066] (Evaluation of photosensitive resin composition)

After the development, the following evaluation was performed according to the required exposure amount. The results are shown in Table 2 below.

[0067] Optimum exposure amount: exposure amount with the best mask transfer accuracy

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

(B): Bisphenol A novolac type polyfunctional epoxy resin (trade name EPON SU-8, n

= 8, Resolution 'Performance' made by Products)

(C-1): Light power thione polymerization initiator (trade name: CPI-210S manufactured by Sanpro Corporation)

(D): Reactive epoxy monomer (trade name ED506, manufactured by Asahi Denka Kogyo Co., Ltd.)

(E): Solvent cyclopentanone

(F): Fluorine-based leveling agent (trade name: Mega-Fac F-470, manufactured by Dainippon Ink and Company)

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

(H): Light power thione polymerization initiator (trade name: UVI-6974, 50% propylene carbonate solution manufactured by Dow Chemical Co., Ltd.)

[0070] As shown in Table 2, in Examples 1 to 3, the deviation was also good.

[Example 4]

(Photosensitive resin composition)

20 parts by weight of polyfunctional epoxy resin (trade name: NER— 7604 made by Nippon Gyaku Co., Ltd.), bisphenol A novolac type multifunctional epoxy resin (trade name: EPON SU—8 Resolution “Performance Products”) 80 parts by weight, 4.6 parts by weight of light thione polymerization initiator (trade name C PI-210S Sanpro Co., Ltd.) and 4 parts of reactive epoxy monomer (trade name E D506 made by Asahi Denka Kogyo Co., Ltd.) A photosensitive composition in which 40 parts by weight of MEK and 40 parts by weight of MEK were mixed was obtained.

(Patterning of photosensitive resin composition)

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

[0072] The cover film of the photosensitive resin composition laminate is peeled off and laminated on a silicon wafer at a roll temperature of 70 ° C, an air pressure of 0.2 MPa, and a speed of 0.5 mZmin, and this is repeated once more. An 80 m photosensitive resin composition layer was obtained. This photosensitive resin composition layer was subjected to pattern exposure (soft contour, i-line) using an i-line exposure apparatus (mask aligner: manufactured by Usio Electric Co., Ltd.). Then, PEB for 4 minutes at 95 ° C using a hot plate, and PGMEA Using this, a development process was performed at 23 ° C for 4 minutes by an immersion method to obtain a cured resin pattern on the substrate. Optimum exposure OmjZcm ² Aspect ratio 9.6 and good results were obtained.

[0073] As is clear from the comparison of the results of Examples 1 to 4 and the comparative example, a combination of a specific polyfunctional epoxy resin and a specific light-power thione polymerization initiator is not obtained in other combinations. Sensitivity and high aspect ratio of resin pattern found to be available Industrial applicability

[0074] As described above, the photosensitive resin composition useful in the present invention is useful for forming a resin pattern having a high aspect profile, and is particularly dimensionally stable in a fine-sized electronic device. Suitable for high-performance resin molding.

Claims

The scope of the claims

Epoxy resin having biphenyl structure represented by the following general formula (1) (A

(In the formula, R and R are each an independent hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

1 2

n is an average value and is a real number from 1 to 30. )

[Chemical 2]

(Wherein R and R each independently represent a hydrogen atom or a methyl group, t, u and V are

1 2

Each is an average value and independently represents a real number of 1 or more, and the sum is a real number of 3 to 30. ) One or more epoxy resins (A) selected from: and one or more bisphenol A novolac type polyfunctional epoxy resins (B) represented by the following general formula (3):

[Chemical 3]

(In the formula, R is an independent glycidyl group or a hydrogen atom, and n is an average value and is a real number of 1 to 30.)

The light thione polymerization initiator (C) is a compound represented by the following formula (4) (C-1)

[Chemical 4]

The photosensitive resin composition according to claim 1, wherein

[3] The photosensitive resin composition according to claim 1 or 2, comprising one or more reactive epoxy monomers (D).

[4] The photosensitive resin composition according to any one of [1] to [3], which contains the solvent (E) and has a solid content concentration of 5 to 95% by weight.

[5] A photosensitive resin composition laminate in which the photosensitive resin composition according to any one of claims 1 to 4 is sandwiched between substrates.

[6] A cured product comprising the photosensitive resin composition according to any one of claims 1 to 4.

[7] A photosensitive resin composition layer obtained by coating the photosensitive resin composition according to any one of claims 1 to 4 on a desired support is dried, and then a predetermined amount is obtained. A non-turn forming method comprising: exposing to a pattern, performing beta after exposure, developing the resin composition layer, and heat-treating the obtained resin pattern to obtain a cured resin pattern having a predetermined shape.

[8] Laminate strength according to claim 5 The photosensitive resin composition layer remaining after the substrate is removed is laminated on a desired support, and the photosensitive resin composition layer is formed into a predetermined pattern. A pattern forming method comprising: exposing, betaing after exposure, developing the resin composition, and heat-treating the obtained resin pattern to obtain a cured resin pattern having a predetermined shape.