# Patent

## Title
Photosensitive resin composition, photosensitive element, semiconductor device and method for forming resist pattern

## Abstract

A photosensitive resin composition comprises: a component (A): a resin having a phenolic hydroxyl group; a component (B): a compound having a methylol group or an alkoxyalkyl group; a component (C): an aliphatic compound having two or more functional groups, the functional groups being one or more types selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group; and a component (D): a photosensitive acid generator.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a U.S. national phase application filed under 35 U.S.C. §371 of International Application No. PCT/JP2014/075925, filed Sep. 29, 2014, designating the United States, which claims priority from Japanese Patent Application No. 2013-203628 and 2013-251324, filed Sep. 30, 2013, and Dec. 4, 2013, respectively, which are hereby incorporated herein by reference in their entirety.
TECHNICAL FIELD
The present invention relates to a photosensitive resin composition, a photosensitive element, and a method for forming a resist pattern.
BACKGROUND ART
In order to form fine patterns in manufacturing semiconductor devices or printed wiring boards, for example, a negative type photosensitive resin composition has been used. In the method, a photosensitive layer formed on a base material (a chip for semiconductor device, and a substrate for printed wiring board) by application of a photosensitive resin composition or the like is irradiated with active rays through a specified pattern so as to cure the exposed portion. Further, the unexposed portion is selectively removed by a developer so as to form a resist pattern as cured film of the photosensitive resin composition on the base material. The photosensitive resin composition is therefore required to have a short development time (developability) and to be excellent in the sensitivity to active rays, the formability of fine patterns (resolution) and the like. Accordingly, a photosensitive resin composition comprising a novolac resin soluble in alkaline aqueous solution, an epoxy resin and a photo-acid generator, a photosensitive resin composition comprising an alkali-soluble epoxy compound having a carboxyl group and a photo-cationic polymerization initiator, and the like have been proposed (for example, refer to Patent Literatures 1 to 3).
Moreover, from the viewpoint of the workability in forming the photosensitive layer on a base material, a photosensitive resin composition is also required to be excellent in stickiness to the base material (tackiness). When a photosensitive resin composition not having sufficient tackiness is used, the photosensitive layer in an exposed portion is easily removed by developing treatment, so that the adhesion between the base material and a resist pattern tends to worsen.
Further, a surface protective film and an interlayer insulating film for use in a semiconductor device are required to have insulation reliability such as heat resistance, electrical properties, mechanical properties and the like. Accordingly, a photosensitive resin composition which further comprises a cross-linkable monomer has been proposed (for example, refer to Patent Literature 4).
Further, when the interlayer insulating film having an increased thickness is formed, the insulation between wirings in the thickness direction of the layer can be enhanced to prevent short circuiting of wiring, and therefore the reliability of the insulation between wirings is improved. Further, in a case of mounting a chip, when a semiconductor device has a thick interlayer insulating film, the stress applied to the pad from a solder bump can be relaxed, so that connection failures hardly occur in mounting. Accordingly, in terms of the insulation reliability and the productivity in mounting a chip, a thick film of photosensitive resin composition with a thickness more than 20 μm is also required to be formed.
CITATION LIST
Patent Literature
Patent Literature 1: JP H6-059444 A
Patent Literature 2: JP H9-087366 A
Patent Literature 3: WO 2008/010521
Patent Literature 4: JP 2003-215802 A
SUMMARY OF INVENTION
Technical Problem
However, although the photosensitive resin compositions described in the cited literatures are excellent in insulation reliability and the like, a high resolution cannot be achieved when a thick film is made therefrom. For example, the photosensitive resin composition described in Patent Literature 2 has a resolution with a space width of about 40 μm when a coating film has a thickness of 50 μm, which is insufficient for a highly integrated semiconductor device. The photosensitive resin composition described in Patent Literature 3 cannot exhibit sufficient heat resistance in some cases. Further, the photosensitive resin composition described in Patent Literature 1 or 4 provides excellent resolution with a space width of about 5 μm when a coating film has a thickness of 10 μm, but excellent resolution cannot be obtained when a thick film is made therefrom.
An object of the present invention is to solve the above problems associated with the conventional arts and to provide a photosensitive resin composition which enables a resist pattern excellent in resolution and heat resistance to be formed even when a coating film having a thickness more than 20 μm is formed.
Solution to Problem
As a result of extensive studies to solve the above problems, the present inventors have found a photosensitive resin composition having excellent properties. Namely, the photosensitive resin composition of the present invention comprises a component (A): a resin having a phenolic hydroxyl group; a component (B): a compound having a methylol group or an alkoxyalkyl group; a component (C): an aliphatic compound having two or more functional groups, which are one or more groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group; and a component (D): a photosensitive acid generator.
Preferably the component (B) is a compound which further has at least one selected from the group consisting of an aromatic ring, a heterocycle and an alicycle.
The photosensitive resin composition of the present invention preferably contains 20 to 70 parts by mass of the component (C) relative to 100 parts by mass of the component (A).
In the photosensitive resin composition of the present invention, the component (C) preferably has three or more of the functional groups.
The present invention also provides a photosensitive element comprising a supporting material and a photosensitive layer formed on the supporting material, the photosensitive layer being formed of the photosensitive resin composition.
The present invention further provides a cured product of the above described photosensitive resin composition. The cured product can be suitably used as a solder resist or an interlayer insulating film.
The present invention provides a method for forming a resist pattern comprising: a step of applying the photosensitive resin composition onto a substrate and drying the applied photosensitive resin composition so as to form a photosensitive layer, a step of exposing the photosensitive layer to an active ray in order to form a predetermined pattern and performing a heat-treatment after exposure (hereinafter, this heat-treatment is also referred to as “post-exposure baking”), and a step of developing the photosensitive layer after heat-treatment and heat-treating the obtained resin pattern.
The present invention further provides a method for forming a resist pattern comprising: a step of forming the photosensitive layer of the photosensitive element on a substrate, a step of exposing the photosensitive layer to an active ray in order to form a predetermined pattern and performing a heat-treatment after exposure, and a step of developing the photosensitive layer after heat-treatment and heat-treating the obtained resin pattern.
Advantageous Effects of Invention
The photosensitive resin composition of the present invention allows a resist pattern with excellent resolution and heat resistance to be formed, even when a coating film having a thickness more than 20 μm is formed.



BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a schematic view illustrating the manufacturing method of a multi-layered printed wiring board in an embodiment of the present invention.



DESCRIPTION OF EMBODIMENTS
An embodiment of the present invention will be more specifically described in the following, though the present invention is not limited thereto.
[Photosensitive Resin Composition]
The photosensitive resin composition of the present embodiment comprises: (A) a resin having a phenolic hydroxyl group; (B) a compound having a methylol group or an alkoxyalkyl group; a component (C): an aliphatic compound having two or more functional groups, which are one or more groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group; and a component (D): a photosensitive acid generator. The photosensitive resin composition of the present embodiment may also comprise: a component (E): a solvent, a component (F): an inorganic filler, a component (G): a silane coupling agent, a component (H): a sensitizer, a component (I): amine, a component (J): an organic peroxide, a component (K): a leveling agent, and the like, if necessary.
The present inventors presume the reason that a resin pattern with excellent resolution and heat resistance can be formed from the photosensitive resin composition of the present embodiment is as follows. First, the solubility of the component (A) in a developer is drastically improved with addition of the component (C) in the unexposed portions. Second, in the exposed portion, due to the acid generated from the component (D), the methylol group or the alkoxyalkyl group of the component (B) reacts not only with the component (C), but also with the phenolic hydroxyl group of the component (A), so that the solubility of the photosensitive resin composition in the developer decreases drastically. Therefore, due to the remarkable difference in solubility in a developer between an unexposed portion and an exposed portion when developing, sufficient resolution can be obtained. In addition, the present inventors presume that due to heat treatment of the developed pattern, the reaction between the component (B) and the component (C) or the component (A) further proceeds, so that a resin pattern with sufficient heat resistance can be obtained.
<Component (A)>
Examples of the resin having a phenolic hydroxyl group as component (A) preferably include a resin soluble in an alkali aqueous solution, particularly preferably a novolac resin, though not specifically limited. The novolac resin can be obtained from condensation of phenols and aldehydes under presence of a catalyst.
Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol, etc.
Further, the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, etc.
Specific examples of the novolac resin include a phenol/formaldehyde condensation novolac resin, a cresol/formaldehyde condensation novolac resin, a phenol-naphthol/formaldehyde condensation novolac resin, etc.
Further, examples of the component (A) other than novolac resins include polyhydroxystyrene and a copolymer thereof, a phenol-xylylene glycol condensation resin, a cresol-xylylene glycol condensation resin, a phenol-dicyclopentadiene condensation resin, etc. One of the component (A) may be used singly, or a mixture of two or more kinds of the components (A) may be used.
From the viewpoints of the further excellent resolution, developability, thermal shock, heat resistance, etc., of a cured film to be obtained, the component (A) has a weight average molecular weight of preferably 100000 or less, more preferably 1000 to 80000, furthermore preferably 2000 to 50000, particularly preferably 2000 to 20000, extremely preferably 5000 to 15000.
In the photosensitive resin composition of the present embodiment, the content of the component (A) is preferably 30 to 90 parts by mass, more preferably 40 to 80 parts by mass, relative to 100 parts by mass of the total of the photosensitive resin composition (excluding the component (E) when used). With a content of the component (A) in this range, the film formed from the photosensitive resin composition to be obtained tends to have further excellent developability in an alkali aqueous solution.
<Component (B)>
The photosensitive resin composition of the present embodiment comprises a compound having a methylol group or an alkoxyalkyl group as the component (B). The component (B) is preferably a compound further having at least one selected from the group consisting of an aromatic ring, a heterocycle, and an alicycle. Herein, the aromatic ring means a hydrocarbon group having aromaticity (e.g. a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring. The heterocycle means a cyclic group having at least one hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom (e.g. a cyclic group having 3 to 10 carbon atoms), and examples thereof include a pyridine ring, an imidazole ring, a pyrrolidinone ring, an oxazolidinone ring, an imidazolidinone ring and a pyrimidinone ring. Further, the alicycle means a cyclic hydrocarbon group having no aromaticity (e.g. a cyclic hydrocarbon group having 3 to 10 carbon atoms), and example thereof include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. The alkoxyalkyl group means an alkyl group bonded to another alkyl group through an oxygen atom. The two alkyl groups may be different from each other, and examples thereof include an alkyl group having 1 to 10 carbon atoms.
Inclusion of the component (B) prevents the resin pattern from being embrittled and deformed when the photosensitive layer is cured by heating after formation of the resin pattern, and the heat resistance can be improved due to formation of a cross-linked structure resulting from the reaction of the component (B) with the component (A). Specifically, a compound further having a phenolic hydroxyl group or a compound further having a hydroxymethylamino group can be preferably used, but the component (A) and the component (C) are not included in the component (B). One of the component (B) may be used singly, or a mixture of two or more of the components (B) may be used.
As described below, due to the inclusion of the component (D) in a photosensitive resin composition, an acid is generated by irradiation of active rays or the like. Due to the catalytic action of the generated acid, the alkoxyalkyl groups in the component (B) can react each other, or the alkoxyalkyl group in the component (B) and the component (A) can react accompanying with dealcoholization, to thereby form a pattern of negative type. Further, due to the catalytic action of the generated acid, the methylol groups in the component (B) can react each other, or the methylol group in the component (B) and the component (A) can react accompanying with dealcoholization, to thereby form a pattern of negative type.
Due to having a methylol group or an alkoxyalkyl group, the “compound further having a phenolic hydroxyl group” for use as the component (B) not only reacts with the component (C) or the component (A) but also increases the dissolution rate of the unexposed portion when developed in an alkali aqueous solution so as to improve the sensitivity. The weight average molecular weight of the compound having a phenolic hydroxyl group is preferably 94 to 2000, more preferably 108 to 2000, furthermore preferably 108 to 1500, in consideration of the well-balanced improvement of the solubility in an alkali aqueous solution, the photosensitivity, the mechanical properties and the like.
Although a conventionally known compound can be used as the compound having a phenolic hydroxyl group, a compound represented by the following formula (1) is preferred due to excellent balance between the effect of enhancing dissolution of an unexposed portion and the effect of preventing the photosensitive resin film from melting during curing.




In the formula (1), Z represents a single bond or a divalent organic group, R24 and R25 each independently represent a hydrogen atom or a monovalent organic group, R26 and R27 each independently represent a monovalent organic group, a and b each independently represent an integer of 1 to 3, and c and d each independently represent an integer of 0 to 3. Herein, examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, and a propyl group; an alkenyl group having 2 to 10 carbon atoms such as a vinyl group; an aryl group having 6 to 30 carbon atoms such as a phenyl group; and the above-described hydrocarbon groups of which a part or all of the hydrogen atoms are substituted with a halogen atom such as fluorine atom.
The compound represented by the formula (1) is preferably a compound represented by the formula (2).




In the formula (2), X1 represents a single bond or a divalent organic group, and R represents an alkyl group (e.g. an alkyl group having 1 to 10 carbon atoms).
As the compound having a phenolic hydroxyl group, a compound represented by the formula (3) may be used.




In the formula (3), R represents an alkyl group (e.g. an alkyl group having 1 to 10 carbon atoms).
The compound with a single bond as Z in the formula (1) is a biphenol(dihydroxy biphenyl) derivative. Further, examples of the divalent organic group represented by Z include: an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, and a propylene group; an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group; an arylene group having 6 to 30 carbon atoms such as a phenylene group; the above-described hydrocarbon groups of which a part or all of the hydrogen atoms are substituted with a halogen atom such as fluorine atom; a sulfonyl group; a carbonyl group; an ether bond; a sulfide bond; and an amide bond. Among these, Z is preferably a divalent organic group represented by the following formula (4).




In the formula (4), X2 represents a single bond, an alkylene group (e.g. an alkylene group having 1 to 10 carbon atoms), an alkylidene group (e.g. an alkylidene group having 2 to 10 carbon atoms), the above-described groups of which a part or all of the hydrogen atoms are substituted with a halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond or an amide bond. R28 represents a hydrogen atom, a hydroxyl group, an alkyl group (e.g. an alkyl group having 1 to 10 carbon atoms) or a haloalkyl group, and e represents an integer of 1 to 10. A plurality of R28 may be the same or different from each other. Herein, the haloalkyl group means an alkyl group substituted with a halogen atom.
Examples of the compound having a hydroxymethylamino group include (poly)(N-hydroxymethyl)melamine, (poly)(N-hydroxymethyl)glycoluril, (poly)(N-hydroxymethyl)benzoguanamine, and (poly)(N-hydroxymethyl)urea. Alternatively, nitrogen-containing compounds, i.e. the above-described compounds of which a part or all of the hydroxymethylamino groups are alkyletherified, may be used. Herein, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, and a mixture thereof, and also these compounds may be an oligomer component formed by partial self-condensation. Specific examples thereof include hexakis(methoxymethyl)melamine, hexakis(butoxymethyl)melamine, tetrakis(methoxymethyl)glycoluril, tetrakis(butoxymethyl)glycoluril, and tetrakis(methoxymethyl)urea.
Specifically, the compound having a hydroxymethylamino group is preferably a compound represented by the formula (5) or the formula (6).




In the formula (5), R represents an alkyl group (e.g. an alkyl group having 1 to 10 carbon atoms).




In the formula (6), R represents an alkyl group (e.g. an alkyl group having 1 to 10 carbon atoms).
The content of the component (B) is preferably 5 to 60 parts by mass, more preferably 10 to 45 parts by mass, particularly preferably 10 to 35 parts by mass, relative to 100 parts by mass of the component (A). With a content of component (B) of 5 parts by mass or more, the reaction sufficiently proceeds in the exposed portion, so that the resolution hardly decreases and the chemical resistance and the heat resistance tend to be improved. With a content of 60 parts by mass or less, film formation of the photosensitive resin composition can be easily performed on a desired supporting material and the resolution tends to be improved.
<Component C>
Component (C): An aliphatic compound having two or more functional groups, which are one or more groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group, improves the adhesion between the photosensitive resin composition and a supporting material, i.e., the tackiness. Furthermore, the dissolution rate of an unexposed portion can increase in development in an alkali aqueous solution to improve the resolution. From the viewpoints of tackiness and solubility in an alkali aqueous solution and in consideration of the balance, the weight average molecular weight of the component (C) is preferably 92 to 2000, more preferably 106 to 1500, particularly preferably 134 to 1300. Herein, the “aliphatic compound” means a compound having an aliphatic skeleton as main skeleton and including no aromatic ring and no heterocycle.
The functional group of the component (C) is preferably a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, more preferably a glycidyloxy group or an acryloyl group, furthermore preferably an acryloyloxy group. Further, the component (C) preferably has three or more of the above-described functional groups. The upper limit of the number of the functional groups is, for example, 12, though not particularly limited. Specific examples of the component (C) include the compounds represented by the formulas (7) to (10).




[In the formulas (7) to (10), R1, R5, R16 and R19 each represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group or a group represented by the formula (11); R21 represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group; R2, R3, R4, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R17, R18 and R20 each represent a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the formula (12), or a group represented by the formula (13); R22 and R23 each represent a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group; and n and m each are an integer of 1 to 10.]
Examples of the compound having a glycidyloxy group include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerol triglycidyl ether, glycerol propoxylate triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, and diglycidyl 1,2-cyclohexane-dicarboxylate. One of these compounds having a glycidyloxy group may be used singly, or a mixture of two or more thereof may be used.
Among the compounds having a glycidyloxy group, trimethylolethane triglycidyl ether or trimethylolpropane triglycidyl ether is preferred from the viewpoints of the excellent sensitivity and resolution.
Examples of the compound having a glycidyloxy group include EPOLIGHT 40E, EPOLIGHT 100E, EPOLIGHT 70P, EPOLIGHT 200P, EPOLIGHT 1500NP, EPOLIGHT 1600, EPOLIGHT 80MF, and EPOLIGHT 100MF (all the above are made by Kyoeisha Chemical Co., Ltd., trade names), an alkyl-type epoxy resin ZX-1542 (made by Nippon Steel and Sumikin Chemical Co., Ltd., trade name), DENACOL EX-212L, DENACOL EX-214L, DENACOL EX-216L, DENACOL EX-321L, and DENACOL EX-850L (all the above made by Nagase ChemteX Corporation, trade names).
Examples of the compound having an acryloyloxy group include EO-modified dipentaerythritol hexaacrylate, PO-modified dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, EO-modified ditrimethylolpropane tetraacrylate, PO-modified ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetraacrylate, EO-modified pentaerythritol tetraacrylate, PO-modified pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, EO-modified pentaerythritol triacrylate, PO-modified pentaerythritol triacrylate, pentaerythritol triacrylate, EO-modified trimethylolpropane acrylate, PO-modified trimethylolpropane acrylate, trimethylolpropane acrylate, EO-modified glycerol triacrylate, PO-modified glycerol triacrylate, and glycerol triacrylate. One of these compounds having an acryloyloxy group may be used singly, or a mixture of two or more thereof may be used. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.
Examples of the compound having a methacryloyloxy group include EO-modified dipentaerythritol hexamethacrylate, PO-modified dipentaerythritol hexamethacrylate, dipentaerythritol hexamethacrylate, EO-modified ditrimethylolpropane tetramethacrylate, PO-modified ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetramethacrylate, EO-modified pentaerythritol tetramethacrylate, PO-modified pentaerythritol tetramethacrylate, pentaerythritol tetramethacrylate, EO-modified pentaerythritol trimethacrylate, PO-modified pentaerythritol trimethacrylate, pentaerythritol trimethacrylate, EO-modified trimethylolpropane methacrylate, PO-modified trimethylolpropane methacrylate, trimethylolpropane methacrylate, EO-modified glycerol trimethacrylate, PO-modified glycerol trimethacrylate, and glycerol trimethacrylate. A single kind of these compounds having a methacryloyloxy group, or a mixture of two or more kinds thereof may be used. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.
Examples of the compound having a hydroxyl group include a polyalcohol such as dipentaerythritol, pentaerythritol, and glycerol. One of these compounds having a methacryloyloxy group may be used singly, or a mixture of two or more kinds thereof may be used.
The content of the component (C) is preferably 20 to 70 parts by mass, more preferably 25 to 65 parts by mass, particularly preferably 35 to 55 parts by mass, relative to 100 parts by mass of the component (A). With a content of the component (C) of 20 parts by mass or more, sufficient cross-linking occurs in an exposed portion, and the tackiness tends to be sufficient. With a content of 70 parts or less, film formation of the photosensitive resin composition can be easily performed on a desired supporting material and the resolution tends to hardly decrease.
<Component (D)>
The photosensitive acid generator as component (D) is a compound which generates an acid by irradiation of active rays or the like. The generated acid allows the component (B) to react not only with each other, but also with the component (A) or the component (C), so that the solubility of the photosensitive resin composition decreases in a developer. Consequently a pattern of negative type can be formed. In the case of the component (C) of a compound having an acryloyloxy group or a methacryloyloxy group, a radical polymerization of the acryloyloxy group or the methacryloyloxy group also proceeds by the irradiation of active rays or the like.
The component (D) is not specifically limited as long as being a compound which generates an acid with irradiation of active rays or the like, and examples thereof include an onium salt compound, a halogen-containing compound, a diazoketone compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound, etc. Among them, use of a sulfonimide compound or an onium salt compound is preferred from the viewpoint of easy availability. In particular, when a solvent is used as the component (E), an onium salt compound is preferably used from the viewpoint of the solubility in the solvent. Specific examples thereof are as follows.
Onium Salt Compound:
Examples of the onium salt compound include an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt and a pyridinium salt. Preferred specific examples of the onium salt compound include a diaryliodonium salt such as a diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate; a triarylsulfonium salt such as triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, and triphenylsulfonium hexafluoroantimonate; 4-t-butylphenyl-diphenysulfonium trifluoromethanesulfonate; 4-t-butylphenyl-diphenylsulfonium p-toluenesulfonate; and 4,7-di-n-butoxynaphthyl-tetrahydrothiophenium trifluoromethanesulfonate.
Sulfonimide Compound:
Specific examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthalimide, N-(p-toluenesulfonyloxy)-1,8-naphthalimide, and N-(10-camphorsulfonyloxy)-1,8-naphthalimide.
In the present embodiment, the component (D) is preferably a compound having a trifluoromethanesulfonate group, a hexafluoroantimonate group, a hexafluorophosphate group, or a tetrafluoroborate group, in terms of having further excellent sensitivity and resolution. Incidentally, one of the component (D) may be used singly, or a mixture of two or more kinds of the components (D) may be used.
The content of the component (D) is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, relative to 100 parts by mass of the component (A), from the viewpoint of further improving the sensitivity, the resolution, the pattern shape, and the like of the photosensitive resin composition of the present embodiment.
<Component (E)>
The photosensitive resin composition of the present embodiment may further comprise a solvent as the component (E), in order to improve the handling properties of the photosensitive resin composition or in order to adjust the viscosity and the storage stability. The component (E) is preferably an organic solvent. The kind of the organic solvent is not specifically limited as long as capable of exhibiting the performance above-mentioned, and examples thereof include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve, carbitols such as butyl carbitol; lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, and isopropyl lactate; aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate and isobutyl propionate; other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; amides such as N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and lactones such as γ-butyrolactone. One of the organic solvent may be used singly, or a mixture of two or more kinds of the organic solvents may be used.
The content of the component (E) is preferably 30 to 200 parts by mass, more preferably 60 to 120 parts by mass, relative to 100 parts by mass of the total amount of the photosensitive resin composition except for the component (E).
<Component (F)>
When the photosensitive resin composition of the present embodiment comprises an inorganic filler as the component (F), the thermal expansion coefficient of the cured film obtained by heating the photosensitive layer after pattern formation can be decreased corresponding to the content of the component (F). One of the component (F) may be used singly, or a mixture of two or more of the components (F) may be used. Any of the inorganic fillers dispersed in the resin composition preferably has a maximum particle diameter of 2 μm or less.
Examples of the inorganic filler include: aluminum compounds such as aluminum oxide and aluminum hydroxide; alkali metal compounds; alkali earth metal compounds such as calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, and magnesium hydroxide; inorganic compounds derived from mining such as talc and mica; and silica such as fused spherical silica, fused crushed silica, fumed silica, and sol-gel silica. These may be crushed by a crusher and classified in some cases, enabling dispersion with a maximum particle diameter of 2 μm or less.
Although any type of inorganic filler can be used, silica is preferred as inorganic filler. The thermal expansion coefficient of silica is preferably 5.0×10−6/° C. or less. From the viewpoint of the particle diameter, silica such as fused spherical silica, fumed silica, and sol-gel silica is preferred, and fumed silica or sol-gel silica is more preferred. It is desirable to use silica (nanosilica) with an average primary particle diameter in the range of 5 nm to 100 nm. These are preferably dispersed to have a maximum particle size of 2 μm or less in the photosensitive resin composition. On this occasion, in order to achieve dispersion in the resin without aggregation, a silane coupling agent may be used.
In measuring the particle diameter of each of the inorganic fillers, it is desirable to use a known particle size analyzer. Examples thereof include a laser diffraction scattering particle size analyzer which obtains the particle size distribution by calculation based on the intensity distribution pattern of the diffracted and scattered light emitted from the particles irradiated with laser beams, and a nanoparticle size analyzer which obtains the particle size distribution using frequency analysis by a dynamic light scattering method.
The content of the component (F) is 1 mass % or more and 70 mass % or less, preferably 3 mass % or more and 65 mass % or less, relative to the total amount of the photosensitive resin composition excluding the component (E).
The inorganic filler for use in the present embodiment has an average primary particle diameter of preferably 100 nm or less, more preferably 80 nm or less, and particularly preferably 50 nm or less from the viewpoint of photosensitivity. With an average primary particle diameter of 100 nm or less, the resin composition hardly becomes cloudy, so that the exposure light is easily transmitted through the resin composition. Consequently the unexposed portion is easily removed, and the resolution tends not to decrease.
The average primary particle diameter is a value obtained by conversion from the BET specific surface area.
<Component (G)>
The photosensitive resin composition of the present embodiment may comprise a silane coupling agent as the component (G). The inclusion of the component (G) allows the adhesion strength between the photosensitive layer and the base material to be improved after formation of the resin pattern.
A commonly available compound can be used as the component (G), and examples of the compound include alkylsilane, alkoxysilane, vinylsilane, epoxysilane, aminosilane, acryloylsilane, methacryloylsilane, mercaptosilane, sulfide silane, isocyanatosilane, sulfur silane, styrylsilane, alkylchlorosilane.
Specific examples of the component (G) include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, triphenylsilanol, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, n-octyldimethylchlorosilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, bis(3-(triethoxysilyl)propyl)disulfide, bis(3-(triethoxysilyl)propyl)tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N-(1,3-dimethylbutylidene)-3-aminopropyltriethoxysilane, and aminosilane.
As the component (G), an epoxysilane having one or more glycidyloxy groups is preferred, and an epoxysilane having a trimethoxysilyl group or a triethoxysilyl group is more preferred. Alternatively, acryloylsilane or methacryloylsilane may be used.
The content of the component (G) is preferably 1 to 20 parts by mass, and more preferably 3 to 10 parts by mass, relative to 100 parts by mass of the component (A).
<Component (H)>
The photosensitive resin composition of the present embodiment may comprise a sensitizer as component (H). Examples of the sensitizer include 9,10-dibutoxyanthracene. One of the component (H) may be used singly, or a mixture of two or more of the components (H) may be used. The inclusion of the component (H) allows the photosensitivity of the photosensitive resin composition to be improved.
The content of the component (H) is preferably 0.01 to 1.5 parts by mass, more preferably 0.05 to 0.5 parts by mass, relative to 100 parts by mass of the component (A).
The photosensitive resin composition of the present embodiment may further comprise a low-molecular weight phenolic compound having a molecular weight less than 1000 (hereinafter referred to as “phenol compound (a)”) in addition to the component (A). Examples thereof include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, tris(4-hydroxyphenyl)ethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)-1-[4-{1-(4-hydroxyphenyl)-1-methylethyl}phenyl]ethane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, etc. These phenol compounds (a) can be contained in the range of 0 to 40 mass %, particularly 0 to 30 mass %, relative to the component (A).
The photosensitive resin composition of the present embodiment may comprise components other than the components described above. Examples of the other components include an inhibitor of the reaction caused by the irradiation of active rays, an adhesion aid, and the like.
<Photosensitive Element>
The photosensitive element of the present embodiment will be described in the following.
The photosensitive element of the present embodiment includes a supporting material and a photosensitive layer of the above-described photosensitive resin composition formed on the supporting material. A protective layer for covering the photosensitive layer may be further provided on the photosensitive layer.
Examples of the above-described supporting material for use include a polymer film of polyethylene terephthalate, polypropylene, polyethylene, polyester, or the like, having heat resistance and solvent resistance. The thickness of the supporting material (polymer film) is preferably set to 5 to 25 μm. Incidentally, one of the polymer films may be used as a supporting material and the other one as a protective film, so as to be laminated on each side of the photosensitive layer to sandwich the photosensitive layer.
Examples of the above-described protective layer for use include a polymer film of polyethylene terephthalate, polypropylene, polyethylene, polyester, or the like, having heat resistance and solvent resistance.
The photosensitive layer may be formed by applying the photosensitive resin composition on a supporting material or a protective layer. Examples of the coating method include dipping, spraying, bar coating, roll coating, spin coating, etc. Although the thickness of a photosensitive layer is different according to the use, the dried photosensitive layer has a thickness of preferably 10 to 100 μm, more preferably 15 to 60 μm, particularly preferably 20 to 50 μm.
[Method for Forming Resist Pattern]
The method for forming a resist pattern of the present embodiment is described in the following.
First, a photosensitive layer comprising the above-described photosensitive resin composition is formed on a substrate (a copper foil coated with a resin, a copper-clad laminate, a silicon wafer coated with a metal-sputtered film, an alumina substrate, etc.) on which a resist is to be formed. Examples of the method for forming the photosensitive layer include: a method of applying a photosensitive resin composition to a substrate and drying so as to evaporate the solvent and the like to form a coating film (photosensitive layer); and a method of transferring the photosensitive layer of the above-described photosensitive element onto a substrate; etc.
Examples of the method for use in applying the photosensitive resin composition to a substrate include an application method such as dipping, spraying, bar coating, roll coating, spin coating, etc. The thickness of the coating film can be appropriately controlled by adjusting the coating means, and the solid content and viscosity of the photosensitive resin composition.
Subsequently, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. Examples of the active rays for use in exposure include rays from a g-line stepper; ultraviolet rays from a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an i-line stepper; electron beams; laser beams; etc. The exposure amount is appropriately selected depending on the light source used and the thickness of a coating film, and the like, and may be, for example, about 100 to 5000 mJ/cm2 for a coating film thickness of 10 to 50 μm with ultraviolet irradiation from a high pressure mercury lamp.
Further, a heat treatment is performed after exposure (post-exposure baking). The post-exposure baking can accelerate the curing reaction between the component (A) and the component (B) due to the generated acid. Although the conditions for the post-exposure baking are different depending on the content of the photosensitive resin composition, the thickness of the coating film, and the like, heating at 70 to 150° C. for about 1 to 60 minutes is typically preferred, and heating at 80 to 120° C. for about 1 to 60 minutes is more preferred.
Subsequently, the coating film subjected to exposure and/or post-exposure baking is developed in an alkali developer to dissolve and remove a region other than a cured portion (unexposed portion), so that a desired resist pattern can be obtained. Examples of the development method in this case include shower developing, spray developing, dip developing, paddle developing, etc. Development conditions at 20 to 40° C. for about 1 to 10 minutes are typical.
Examples of the alkali developer include an alkali aqueous solution comprising an alkali compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, etc., dissolved in water at a concentration of about 1 to 10 mass %, an alkali aqueous solution such as an aqueous ammonia solution, etc. A water soluble organic solvent such as methanol and ethanol, a surfactant, or the like in an appropriate amount may be added to the alkali aqueous solution. After development with the alkali developer, washing with water and drying are performed. Tetramethylammonium hydroxide aqueous solution is preferred as the alkali developer, in terms of achieving excellent resolution.
Further, through a heat treatment for imparting insulating film properties, a cured film (resist pattern) of the photosensitive resin composition is obtained. Curing conditions of the photosensitive resin composition are not specifically limited, so that the photosensitive resin composition can be cured by heating at 50 to 250° C. for 30 minutes to 10 hours, corresponding to the use of the cured product.
Further, the heat treatment may be performed in two stages for sufficient progress of curing and prevention of deformation of the obtained shape of a resin pattern. For example, curing may be performed by heating at 50 to 120° C. for 5 minutes to 2 hours in a first stage, and at 80 to 200° C. for 10 minutes to 10 hours in a second stage.
Heating facilities are not specifically limited as long as the above-described conditions are satisfied, so that an oven in common use, an infrared furnace, etc., may be used.
[Multi-Layered Printed Wiring Board]
The cured product comprising the photosensitive resin composition of the present embodiment can be suitably used as a solder resist and/or an interlayer insulating film in a multi-layered printed wiring board. FIG. 1 is a schematic view illustrating the manufacturing method of a multi-layered printed wiring board which includes the cured product formed from the photosensitive resin composition of the present embodiment as a solder resist and/or an interlayer insulating material. The multi-layered printed wiring board 100A shown in FIG. 1(f) has wiring patterns on the surface and on the inside. The multi-layered printed wiring board 100A is obtained by stacking a copper-clad laminate, an interlayer insulating material, and a metal foil, etc., and appropriately forming wiring patterns by etching or a semi-additive method. The manufacturing method of a multi-layered printed wiring board 100A is briefly described in the following with reference to FIG. 1.
First, interlayer insulating films 103 are respectively formed on each side of the copper-clad laminate 101 having a wiring pattern 102 on the surface (refer to FIG. 1(a)). The interlayer insulating films 103 may be formed by printing with a screen printing machine or a roll coater using the photosensitive resin composition, or by previously preparing the photosensitive element and sticking the photosensitive layer of the photosensitive element to the surface of a printed wiring board with a laminater. Subsequently, an openings 104 are formed at portions required to be electrically connected to the outside with YAG laser or carbon dioxide laser (refer to FIG. 1(b)). Smears (residues) around the openings 104 are removed by a desmearing treatment. Subsequently, a seed is formed by electroless plating (refer to FIG. 1(c)). A photosensitive layer comprising the above-described photosensitive resin composition is laminated on the seed layer 105, and predetermined portions are subjected to exposure and developing treatment so as to form a wiring pattern 106 (refer to FIG. 1(d)). Adhesion layers are formed on the seed layer; for example, a titanium layer having a thickness of about 30 nm is formed and a Cu layer having a thickness of about 100 nm is further formed. These adhesion layers can be formed by sputtering. Subsequently, a wiring pattern 107 is formed by electrolytic plating, and the cured product of the photosensitive resin composition is removed with a stripping solution. The seed layer 105 is then removed by etching (refer to FIG. 1(e)). The above-described operations are repeated, so that a solder resist 108 formed of the cured product of the photosensitive resin composition is formed on the outermost surface. Consequently the multi-layered printed wiring board 100A can be thus formed (refer to FIG. 1(f)).
The thus obtained multi-layered printed wiring board 100A allows the semiconductor elements mounted at corresponding positions to have ensured electrical connection.
EXAMPLES
The present invention will be illustrated in detail with reference to Examples as follows, but the present invention is not limited to the Examples in any way. In the following Examples and Comparative Examples, “part” means “part by mass” unless otherwise specified.
<Preparation of Photosensitive Resin Composition>
A compound having two or more methylol groups or alkoxyalkyl groups (B-1 to B-3), an epoxy resin, an acryloyl compound and a methacryloyl compound (C-1 to C-8, and C′-9 to C′-10), a photosensitive acid generator (D-1), a solvent (E-1) and an inorganic filler (F-1) in specified amounts shown in Table 1 were blended with 100 parts by mass of a novolac resin (A-1 and A-2) so as to obtain a photosensitive resin composition.
<Preparation of Photosensitive Element>
The photosensitive resin composition was applied on a polyethylene terephthalate film (made by Teijin DuPont Films Ltd., trade name: PUREX A53) (supporting material) so as to have a uniform thickness, and dried for 10 minutes with a hot air convection dryer at 90° C., so that a photosensitive layer having a thickness of 25 μm or 40 μm after drying was formed. A polyethylene film (made by Tamapoly Co., Ltd., trade name: NF-15) as a protective layer was laminated on each of the photosensitive layer so as to obtain the photosensitive elements including the supporting material, the photosensitive layer, and the protective layer laminated in this order, respectively.
<Evaluation on Tackiness>
The interface between the photosensitive layer and the protective layer of the photosensitive element was visually observed. The tackiness was evaluated by appearance, that is, in case of an element with both of the layers adhering to each other, the element was recorded as “◯”, and in case of an element with the occurrence of peeling, the element was recorded as “X”.
<Evaluation on Developability and Resolution>
While peeling the protective layer of the photosensitive element having the photosensitive layer with a thickness of 25 μm, the photosensitive element was laminated on a 6-inch silicon wafer such that the photosensitive layer came in contact with the silicon surface. Subsequently, the respective supporting material was peeled off, so that a uniform photosensitive layer having a thickness of 25 μm on silicon was obtained. The lamination was performed using a heat roll at 120° C. with a compressive pressure of 0.4 MPa at a roll speed of 1.0 m/min.
The prepared coating film was subjected to reduction projection exposure to i-line (365 nm) through a mask, using an i-line stepper (made by Canon Inc., trade name: FPA-3000iW). The mask for use had patterns with a width ratio between an exposed portion and an unexposed portion of 1:1, in the range from 2 μm:2 μm to 30 μm:30 μm at an interval of 1 μm. In the reduction projection exposure, the exposure amount was changed in the range of 100 to 3000 mJ/cm2 at an interval of 100 mJ/cm2.
Subsequently, the exposed coating film was heated at 65° C. for 1 minute, and then at 95° C. for 4 minutes (post-exposure baking), and developed by immersing in 2.38 mass % tetramethylammonium hydroxide aqueous solution for a time corresponding to twice the shortest developing time (the shortest time for removing the unexposed portion) for removal of the unexposed portion. On this occasion, the developability was evaluated so that in case of the coating film with a shortest development time less than 10 minutes, the coating film was recorded as “◯”, and in case of the coating film with a shortest development time of 10 minutes or more, the coating film was recorded as “X”. After the development treatment, the resist pattern formed was observed with a metallurgical microscope. Among the formed patterns with a space portion (unexposed portion) cleanly removed and with a line portion (exposed portion) having no meandering or missing, the smallest space width value was evaluated as the smallest resolution for the exposure amount in the range of 100 to 3000 mJ/cm2.
<Evaluation on Heat Resistance>
The protective layer of the photosensitive element having the photosensitive layer with a thickness of 40 μm was peeled off and the photosensitive layer was then exposed with an exposure machine having a high-pressure mercury lamp (made by ORC Manufacturing Co., Ltd., trade name: EXM-1201) so that the amount of the irradiation energy is 3000 mJ/cm2. The exposed photosensitive layer was heated on a hot plate at 65° C. for 2 minutes and then at 95° C. for 8 minutes, and subjected to heat treatment at 180° C. for 60 minutes with a hot air convection dryer, and then the supporting material was peeled off to obtain a cured film. Using a thermomechanical analyzer (made by Seiko Instruments Inc., trade name: TMA/SS6000) the thermal expansion amount of the cured film was measured when the temperature was raised at a rate of temperature rise of 5° C./min. The inflection point obtained from the measurement curve was determined as the glass transition temperature Tg. Further, the thermal expansion coefficient was calculated from the thermal expansion amount for a tensile load of 5 gf in the range from 40° C. to 150° C.









TABLE 1









Comparative



Example
Example

























Item
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1
2
3





A-1
100
—
100
100
100
100
100
100
100
100
—
 50
100
100
100
100
100
100


A-2
—
100
—
—
—
—
—
—
—
—
100
 50
—
—
—
—
—
—


B-1
 28
 28
—
 28
 28
 28
 28
 28
 28
 28
 28
 28
 28
 28
—
 28
 28
 28


B-2
—
—
—
—
—
—
—
—
—
—
—
—
—
 5
—
—
—
—


B-3
—
—
 28
—
—
—
—
—
—
—
—
—
—
—
 28
—
—
—


C-1
 43
 43
 43
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—


C-2
—
—
—
 43
—
—
—
—
—
—
—
—
—
—
—
—
—
—


C-3
—
—
—
—
 43
—
—
—
—
—
—
—
—
—
—
—
—
—


C-4
—
—
—
—
—
 43
—
—
—
—
—
—
—
—
—
—
—
—


C-5
—
—
—
—
—
—
 43
—
—
—
—
—
—
—
—
—
—
—


C-6
—
—
—
—
—
—
—
 43
—
—
 43
 43
 43
 43
 43
—
—
—


C-7
—
—
—
—
—
—
—
—
 43
—
—
—
—
—
—
—
—
—


C-8
—
—
—
—
—
—
—
—
—
 43
—
—
—
—
—
—
—
—


C′-9
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
 43
—


C′-10
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
 43


D-1
 8
 8
 8
 8
 8
 8
 8
 8
 8
 8
 8
 8
 8
 8
 8
 8
 8
 8


E-1
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100


G-1
—
—
—
—
—
—
—
—
5—
—
—
—
 10
—
—
—
—
—


Tackiness
◯
◯
◯
◯
◯
◯
◯
◯
◯
◯
◯
◯
◯
◯
◯
X
◯
◯


Developability
◯
◯
◯
◯
◯
◯
◯
◯
◯
◯
◯
◯
◯
◯
◯
X
X
X


Minimum
 5
 5
 6
 6
 8
 8
 8
 9
 9
 7
 7
 8
 8
 7
 8
 10
—*1
—*1


resolution




















(μm)




















Tg (° C.)
207
206
178
206
209
209
213
215
209
202
212
216
210
218
180
216
—
—





*1Unmeasurable due to inability to form a resin pattern.


A-1: cresol novolac resin (made by Asahi Organic Chemicals Industry Co., Ltd., trade name: TR4020G);


A-2: cresol novolac resin (made by Asahi Organic Chemicals Industry Co., Ltd., trade name: TR4080G)


B-1: 1,3,4,6-tetrakis(methoxymethyl)glycoluril (made by Sanwa Chemical Co., Ltd., trade name: MX-270)


B-2: methylated urea resin (made by Sanwa Chemical Co., Ltd., trade name: MX-280)


B-3: 4,4′-(1,1,1,3,3,3-hexafluoroisopropylidene)bis[2,6-bis(hydroxymethyl)phenol] (made by Honshu Chemical Industry Co., Ltd., trade name: TML-BPAF)


C-1: trimethylolpropane triglycidyl ether (made by Nippon Steel and Sumikin Chemical Co., Ltd., trade name: ZX-1542, refer to the following formula (14))


[Chemical Formula 14]





C-2: trimethylolethane triglycidyl ether (made by Sigma-Aldrich Co.)


C-3: pentaerythritol polyglycidyl ether (made by Nagase ChemteX Corporation, trade name: EX-411)


C-4: trimethylolpropane (made by Wako Pure Chemical Industries, Ltd.)


C-5: trimethylolpropane triacrylate (made by Nippon Kayaku Co., Ltd., trade name: TMPTA)


C-6: pentaerythritol triacrylate (made by Nippon Kayaku Co., Ltd., trade name: PET-30)


C-7: dipentaerythritol hexaacrylate (made by Kyoeisha Chemical Co., Ltd., trade name: LIGHT ACRYLATE DPE-6A)


C-8: EO-modified trimethylolpropane trimethacrylate (made by Hitachi Chemical Co., Ltd., trade name: FA-137M)


C′-9: EO-modified bisphenol A dimethacrylate (made by Hitachi Chemical Co., Ltd., trade name: FA-324M)


C′-10: EO-modified bisphenol A dimethacrylate (made by Hitachi Chemical Co., Ltd., trade name: FA-320M)


D-1: triarylsulfonium salt (made by San-Apro Ltd., trade name: CPI-310B)


E-1: methyl ethyl ketone (made by Wako Pure Chemical Industries, Ltd., trade name: 2-BUTANONE)


G-1: silica subjected to coupling treatment with 3-methacryloyloxypropyltrimethoxysilane, having an average primary particle diameter of 15 nm.






As clearly shown in Table 1, Comparative Examples 1 to 3 had low developability and a poor resolution of 10 μm or more. In contrast, Examples 1 to 15 had good tackiness and developability, exhibiting excellent patternability with a resolution of 9 μm or less and high heat resistance (Tg).
Examples 16 to 18 and Comparative Examples 4 and 5
A cross-linking agent (B-1 and B-3), an epoxy compound (C-1 and C′-11), a photosensitive acid generator (D-2), a solvent (E-1) and a sensitizer (H-1) in specified amounts shown in Table 2 were blended with 100 parts by mass of a novolac resin (A-3 and A-4) so as to obtain a photosensitive resin composition.
The photosensitive resin composition was applied on a polyethylene terephthalate film (made by Teijin DuPont Films Ltd., trade name: PUREX A53) (supporting material) so as to have a uniform thickness, and dried for 10 minutes with a hot air convection dryer at 90° C., so that a photosensitive element having a thickness of a photosensitive layer of 25 μm after drying was formed.
<Evaluation on Solubility>
A 6-inch silicon wafer was spin-coated with the photosensitive resin composition, which was heated at 65° C. for 2 minutes and then at 95° C. for 8 minutes on a hot plate, so that a uniform coating film having a thickness of 25 mm was prepared. The prepared coating film was immersed in 2.38 mass % tetramethylammonium hydroxide aqueous solution at 23° C. in a Petri dish. The solubility was evaluated according to the following criteria. The evaluation results are shown in Table 2.
(Evaluation Criteria)
◯: uniformly dissolved.
Δ: dissolved, accompanied by turbidity.
X: undissolved.
<Evaluation on Resolution>
The photosensitive element was laminated on a 6-inch silicon wafer using a heat roll at 100° C. with a compressive pressure of 0.4 MPa at a roll speed of 1.0 m/min. The prepared coating film was subjected to reduction projection exposure to i-line (365 nm) through a mask by using an i-line stepper (made by Canon Inc., trade name: FPA-3000iW). The mask for use had patterns with a ratio of exposed portions to unexposed portions of 1:1 at 1 μm intervals from 2 μm:2 μm to 30 μm:30 μm. Further, reduction projection exposure was performed with changing the exposure amount at an interval of 100 mJ/cm2 in the range of 100 to 3000 mJ/cm2.
Subsequently the exposed coating film was heated at 65° C. for 1 minute and then at 95° C. for 4 minutes (post-exposure baking), and then immersed in 2.38 mass % tetramethylammonium hydroxide aqueous solution for a time period 1.5 times the shortest developing time period (the shortest time period for removal of unexposed portions) for development, and unexposed portions were removed in the developing treatment. After developing treatment, the formed resist pattern was observed with a metallurgical microscope. The smallest space width of the patterns having clearly removed space portions (unexposed portions) and line portions (exposed portions) formed without occurrence of meandering or chipping was assumed to be the minimum resolution, and the exposure amount on that occasion was evaluated.
<Evaluation of Heat Resistance>
The photosensitive resin composition in each of Examples 16 to 18 and Comparative Examples 4 and 5 was applied on a polyethylene terephthalate film (made by Teijin DuPont Films Ltd., trade name: PUREX A53) (supporting material) so as to have a uniform thickness, and dried for 10 minutes with a hot air convection dryer at 90° C., so that a photosensitive element having a thickness of a photosensitive layer of 40 μM after drying was formed. Subsequently, the photosensitive layer was exposed with an exposure machine having a high-pressure mercury lamp (made by ORC Manufacturing Co., Ltd., trade name: EXM-1201) so that the amount of the irradiated energy is 3000 mJ/cm2. The exposed photosensitive layer was heated at 65° C. for 2 minutes and then at 95° C. for 8 minutes on a hot plate, subjected to a heat treatment at 180° C. for 60 minutes with a hot air convection dryer so as to obtain a cured film. Using a thermomechanical analyzer (made by Seiko Instruments Inc., trade name: TMA/SS6000), the thermal expansion coefficient of the cured film with temperature increase at a rate of temperature rise of 5° C./min was measured. From the measurement curve, an inflection point was obtained as the glass transition temperature Tg. The evaluation results are shown in Table 2.












TABLE 2






Example
Example
Example
Comparative
Comparative


Item
16
17
18
Example 4
Example 5




















A-3
—
—
100
—
—


A-4
100
100
—
100
100


B-1
28
—
28
—
28


B-3
—
28
—
—
—


C-1
43
43
43
43
—


C′-11
—
—
—
—
43


D-2
7
7
7
7
7


E-1
110
110
110
110
110


H-1
0.07
0.07
0.07
0.07
0.07


Solubility
◯
◯
◯
◯
X


Minimum
5
5
5
5
—


resolution (μm)







Tg (° C.)
205
176
200
155
—





A-3: novolac resin (made by Asahi Organic Chemicals Industry Co., Ltd., trade name: MXP5560BF, weight-average molecular weight: 7800)


A-4: cresol novolac resin (made by Asahi Organic Chemicals Industry Co., Ltd., trade name: EP4020G)


B-1: 1,3,4,6-tetrakis(methoxymethyl)glycoluril (made by Sanwa Chemical Co., Ltd., trade name: MX-270)


B-3: 4,4′-(1,1,1,3,3,3-hexafluoroisopropylidene)bis[2,6-bis(hydroxymethyl)phenol] (made by Honshu Chemical Industry Co., Ltd., trade name: TML-BPAF)


C-1: trimethylolpropane triglycidyl ether (made by Nippon Steel and Sumikin Chemical Co., Ltd., trade name: ZX-1542, refer to Formula (14))


C′-11: tris(4-hydroxyphenyl)methane triglycidyl ether (made by Sigma-Aldrich Co., trade name)


D-2: triarylsulfonium salt (made by San-Apro Ltd., trade name: CPI-101A)


E-1: Methyl ethyl ketone (made by Wako Pure Chemical Industries, Ltd., trade name: 2-BUTANONE)


H-1: 9,10-dibutoxyanthracene (made by Kawasaki Kasei Chemicals Ltd., trade name: DBA)






As clearly shown in Table 2, Examples 16 to 18 comprising a cross-linking agent having a methylol group or an alkoxyalkyl group had a good heat resistance of 160° C. or higher. In contrast, Comparative Example 4 not comprising the component (B) had an insufficient heat resistance lower than 160° C., and Comparative Example 5 blended with an aromatic epoxy compound having two or more oxirane rings instead of the component (C) allowed the solubility to decrease. It was found that Examples 16 to 18 had more excellent balance between the resolution and the heat resistance in compared with Comparative Examples 4 and 5.
INDUSTRIAL APPLICABILITY
The photosensitive resin composition of the present invention is applied as a material for use in a solder resist or an interlayer insulating film of a wiring board material, or a surface protective film (overcoat film) or an interlayer insulating film (passivation film) of a semiconductor device or the like. In particular, due to excellent in any of the resolution and the heat resistance after curing, the photosensitive resin composition is suitably used for a high-density package substrate having thinned wiring and high density.
REFERENCE SIGNS LIST
100A: MULTI-LAYERED PRINTED WIRING BOARD; 101: COPPER-CLAD LAMINATE; 102, 106, AND 107: WIRING PATTERN; 103: INTERLAYER INSULATING FILM; 104: OPENING; 105: SEED LAYER; 108: SOLDER RESIST

## Claims

1. A photosensitive resin composition comprising:
a component (A): a resin having a phenolic hydroxyl group, the component (A) comprising a novolac resin;
a component (B): a compound having a methylol group or an alkoxyalkyl group;
a component (C): an aliphatic compound having two or more functional groups, the functional groups being one or more groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group; and
a component (D): a photosensitive acid generator, the component (D) comprising at least one compound selected from the group consisting of an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonimide compound, and a diazomethane compound.

2. The photosensitive resin composition according to claim 1, wherein the component (B) comprises a compound having at least one selected from the group consisting of an aromatic ring, a heterocycle and an alicycle, and having a methylol group or an alkoxyalkyl group.

3. The photosensitive resin composition according to claim 1, wherein the content of the component (C) is 20 to 70 parts by mass relative to 100 parts by mass of the component (A).

4. The photosensitive resin composition according to claim 1, wherein the component (C) has three or more of the functional groups.

5. A photosensitive element comprising a supporting material and a photosensitive layer formed on the supporting material,
wherein the photosensitive layer comprises the photosensitive resin composition according to claim 1.

6. A cured product of the photosensitive resin composition according to claim 1.

7. A semiconductor device comprising the cured product of the photosensitive resin composition according to claim 6 as a surface protective film or an interlayer insulating film.

8. A method for forming a resist pattern, comprising:
a step of applying the photosensitive resin composition according to claim 1 onto a substrate and drying the applied photosensitive resin composition so as to form a photosensitive layer;
a step of exposing the photosensitive layer to an active ray in order to form a predetermined pattern and performing a heat-treatment after exposure; and
a step of developing the photosensitive layer after the heat-treatment and heat-treating the obtained resin pattern.

9. A method for forming a resist pattern, comprising:
a step of forming the photosensitive layer of the photosensitive element according to claim 5 on a substrate;
a step of exposing the photosensitive layer to an active ray in order to form a predetermined pattern and performing a heat-treatment after the exposure; and
a step of developing the photosensitive layer after the heat-treatment and heat-treating the obtained resin pattern.

10. The photosensitive resin composition according to claim 2, wherein the content of the component (C) is 20 to 70 parts by mass relative to 100 parts by mass of the component (A).

11. The photosensitive resin composition according to claim 2, wherein the component (C) has three or more of the functional groups.

12. The photosensitive resin composition according to claim 3, wherein the component (C) has three or more of the functional groups.

13. A photosensitive element comprising a supporting material and a photosensitive layer formed on the supporting material,
wherein the photosensitive layer comprises the photosensitive resin composition according to claim 2.

14. A photosensitive element comprising a supporting material and a photosensitive layer formed on the supporting material,
wherein the photosensitive layer comprises the photosensitive resin composition according to claim 3.

15. A photosensitive element comprising a supporting material and a photosensitive layer formed on the supporting material,
wherein the photosensitive layer comprises the photosensitive resin composition according to claim 4.

16. A cured product of the photosensitive resin composition according to claim 2.

17. A cured product of the photosensitive resin composition according to claim 3.

18. A cured product of the photosensitive resin composition according to claim 4.

19. A semiconductor device comprising the cured product of the photosensitive resin composition according to claim 17 as a surface protective film or an interlayer insulating film.

20. A semiconductor device comprising the cured product of the photosensitive resin composition according to claim 18 as a surface protective film or an interlayer insulating film.