JP6543882B2 - PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE ELEMENT, SEMICONDUCTOR DEVICE, AND METHOD FOR FORMING RESIST PATTERN - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive element, a semiconductor device, and a method of forming a resist pattern.

  In the production of semiconductor elements or printed wiring boards, for example, a negative photosensitive resin composition is used to form a fine pattern. In this method, a photosensitive layer is formed on a substrate (a chip in the case of a semiconductor element, a substrate in the case of a printed wiring board) by application of a photosensitive resin composition or the like, and an actinic ray is irradiated through a predetermined pattern. Cure the exposed area. Furthermore, the resist pattern which is a cured film of the photosensitive resin composition is formed on a base material by selectively removing an unexposed part using a developing solution. Therefore, the photosensitive resin composition is required to be excellent in having high sensitivity to an actinic ray, being able to form a fine pattern (resolution), and the like. Therefore, a photosensitive resin composition containing a novolak resin, an epoxy resin and a photoacid generator soluble in an alkaline aqueous solution, an alkali-soluble epoxy compound having a carboxyl group, a photosensitive resin composition containing a cationic photopolymerization initiator, etc. Have been proposed (see, for example, Patent Documents 1 and 2).

  Furthermore, insulation reliability such as heat resistance, electrical characteristics, mechanical characteristics, etc. is required for the surface protective film and the interlayer insulating film used for the semiconductor element. Then, the photosensitive resin composition which further contains a crosslinkable monomer in the said photosensitive resin composition is proposed (for example, refer patent document 3).

  Further, by forming the interlayer insulating film thick, the insulation between the interconnections in the thickness direction of the layer can be improved, and a short circuit of the interconnections can be prevented, so that the reliability regarding the insulation between the interconnections is improved. Further, when the chip is mounted, since the stress applied to the pads of the solder bumps can be relieved by the semiconductor element having a thick interlayer insulating film, connection failure hardly occurs at the time of mounting. Therefore, from the viewpoint of insulation reliability and productivity when mounting a chip, it is also required to be able to form a film of a thick photosensitive resin composition exceeding 20 μm.

  In addition, a metal layer formed on a substrate used in the manufacture of semiconductor devices is formed using a sputtering technique in order to use a seed layer forming technique. The surface of the metal layer formed using the sputtering technique has a very high smoothness, as compared to the metal layer formed using conventional electroless plating. Since the adhesion between the metal layer having very high smoothness and the photosensitive resin composition may be lowered, the photosensitive resin composition to be used is required to have high adhesion to the metal layer.

Japanese Patent Application Laid-Open No. 09-087366 International Publication No. 2008/010521 Unexamined-Japanese-Patent No. 2003-215802

  However, for example, in the case of the photosensitive resin composition described in Patent Document 1, when the thickness of the coating film is 50 μm, the resolution is about 40 μm in the space width, which is not suitable for highly integrated semiconductor devices. It is enough. Moreover, in the photosensitive resin composition of patent document 2, sufficient heat resistance may not be able to be expressed. Moreover, in the photosensitive resin composition described in Patent Document 3, when the thickness of the coating film is 10 μm, good resolution having a space width of about 5 μm can be obtained, but when thickened Good resolution can not be obtained.

  Furthermore, in the conventional photosensitive resin composition, sufficient adhesiveness may not be obtained with respect to the metal layer which has the very high smoothness formed using the technique of sputtering etc. FIG.

  The object of the present invention is to solve the problems associated with the prior art as described above, and even when a coating film having a thickness of more than 20 μm is formed, the adhesion to the metal layer is excellent and sufficient. It is an object of the present invention to provide a photosensitive resin composition capable of forming a resist pattern having resolution and heat resistance.

  As a result of intensive studies to solve the above problems, the present inventors have found a photosensitive resin composition having excellent properties. That is, the photosensitive resin composition of the present invention comprises (A) component: resin having a phenolic hydroxyl group, (B) component: a compound having two or more oxirane rings, a compound having a methylol group and an alkoxyalkyl group. It is characterized in that it is a photosensitive resin composition containing one or more compounds selected from the group consisting of compounds, (C) component: a photosensitive acid generator, and (D) component: a compound having a siloxane bond. There is.

  It is preferable to contain 20-90 mass parts of said (B) components with respect to 100 mass parts of said (A) components.

  The compound having two or more oxirane rings preferably has two or more glycidyl ether groups.

  The compound having two or more oxirane rings preferably has three or more glycidyl ether groups.

  The component (D) is preferably an inorganic filler having a siloxane bond.

  The average particle diameter of the inorganic filler having a siloxane bond is preferably 80 nm or less.

  The inorganic filler having a siloxane bond is preferably silica.

  The component (D) is preferably a silane compound having a siloxane bond.

  The silane compound having a siloxane bond preferably has one or more glycidyl ether groups.

  The silane compound having a siloxane bond preferably has one or more trimethoxysilyl groups or triethoxysilyl groups.

  The component (D) is preferably an alkoxy oligomer.

  The present invention also provides a photosensitive element comprising a support and a photosensitive layer formed from the photosensitive resin composition provided on the support.

  Furthermore, the present invention provides a semiconductor device comprising the cured product of the photosensitive resin composition as a surface protective film or an interlayer insulating film. The cured product can be suitably used as a solder resist or an interlayer insulating layer.

  In the present invention, the photosensitive resin composition is applied onto a substrate, and the applied photosensitive resin composition is dried to form a photosensitive layer, and the photosensitive layer is exposed to light in a predetermined pattern, and then exposed. A resist comprising a step of performing post-heating treatment (hereinafter, this heating treatment is also referred to as “post-exposure baking”), and a step of developing the photosensitive layer after the heating treatment and heating the obtained resin pattern. Provide a method of forming a pattern.

  Furthermore, the present invention comprises the steps of forming the photosensitive layer of the photosensitive element on a substrate, exposing the photosensitive layer to a predetermined pattern, and performing post-exposure heat treatment, and the photosensitive layer after the heat treatment. And D. heat treating the obtained resin pattern, and providing a method for forming a resist pattern.

  According to the photosensitive resin composition of the present invention, even when a coating film having a thickness of more than 20 μm is formed, it has excellent adhesion to the metal layer and has sufficient resolution and heat resistance. It is possible to form a resist pattern.

It is a schematic diagram which shows the manufacturing method of the multilayer printed wiring board of this embodiment.

  Hereinafter, although one embodiment of the present invention is described concretely, the present invention is not limited to this.

  In the present specification, the term “layer” includes the structure of a shape formed in part, in addition to the structure of a shape formed on the entire surface when observed as a plan view. In the present specification, the term "process" is not limited to an independent process, and even when it can not be clearly distinguished from other processes, the term "process" is used for this term if the intended purpose of the process is achieved. included. In the present specification, a numerical range indicated by using “to” indicates a range including numerical values described before and after “to” as the minimum value and the maximum value, respectively. As used herein, the term "siloxane bond" refers to a bond between a silicon atom and an oxygen atom, i.e., a "Si-O bond".

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment includes (A) component: resin having a phenolic hydroxyl group, (B) component: a compound having two or more oxirane rings, a compound having a methylol group and a compound having an alkoxyalkyl group. And at least one compound selected from the group consisting of (C) component: a photosensitive acid generator and (D) component: a compound having a siloxane bond.

  Moreover, the photosensitive resin composition of this embodiment can also contain (E) component: solvent, (F) component: leveling agent, (G) component, etc. as needed.

<(A) component>
Although it does not specifically limit as resin which has phenolic hydroxyl group which is (A) component, It is preferable that it is resin soluble in alkaline aqueous solution, and novolak resin is especially preferable. The novolac resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst.

  Examples of the above-mentioned 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 and the like can be mentioned.

  Moreover, as said aldehydes, formaldehyde, paraformaldehyde, an acetaldehyde, benzaldehyde etc. are mentioned, for example.

  Specific examples of the novolac resin include phenol / formaldehyde condensation novolac resin, cresol / formaldehyde condensation novolac resin, phenol-naphthol / formaldehyde condensation novolac resin and the like.

  Examples of the component (A) other than novolac resin include polyhydroxystyrene and copolymers thereof, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, etc. Be Component (A) can be used singly or in combination of two or more.

  The component (A) preferably has a weight average molecular weight of 100,000 or less, and more preferably 1,000 to 8,000, from the viewpoint of resolution of the insulating film to be obtained, developability, thermal shock resistance, heat resistance, etc. 2000 to 50000 is more preferable, 2000 to 20 000 is particularly preferable, and 5000 to 15000 is very preferable.

  30-90 mass parts is preferable with respect to 100 mass parts of whole photosensitive resin compositions except (D) and (E) component, and, as for content of (A) component, 40-80 mass parts is more preferable. The film | membrane formed using the photosensitive resin composition obtained as the ratio of (A) component is the said range is excellent by the developability by aqueous alkali solution.

<(B) component>
The component (B) is at least one compound selected from the group consisting of a compound having two or more oxirane rings, a compound having a methylol group and a compound having an alkoxyalkyl group.

  The compound having two or more oxirane rings is preferably an aliphatic or alicyclic epoxy compound, and more preferably an epoxy compound having a weight average molecular weight of 1000 or less. The compound having two or more oxirane rings is preferably a compound having two or more glycidyl ether groups, and more preferably a compound having three or more glycidyl ether groups. In addition, an "aliphatic or an alicyclic epoxy compound" is that whose main skeleton is an aliphatic skeleton and / or an alicyclic skeleton, and does not contain an aromatic ring and a heterocyclic ring.

  When the photosensitive resin composition of the present embodiment contains a compound having two or more oxirane rings, the inventors believe that the reason why a pattern with high resolution can be formed is as follows. First, in the unexposed area, the solubility of the resin having a phenolic hydroxyl group (A) in the developer is significantly improved by the addition of the component (B). Next, in the exposed area, the acid generated from the photosensitive acid generator (C) not only reacts and crosslinks two or more oxirane rings in the component (B) but also reacts with the phenolic hydroxyl group of the component (A) And the solubility of the composition in the developer decreases significantly. As a result, when the image is developed, sufficient resolution is obtained due to the remarkable difference in the solubility of the unexposed area and the exposed area in the developer, and the reaction between the components (B) is caused by the heat treatment of the pattern after development. The present inventors speculate that the reaction between the component (B) and the component (A) further proceeds and sufficient heat resistance can be obtained.

  Examples of compounds having two or more oxirane rings include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, glycerin diglycidyl ether, pentaerythritol tetraglycidyl ether, trimethylol ethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol propoxylate triglycidyl ether, dicyclopentadiene dioxide, 1, 2, 5, 6 Diepoxycyclooctane, 1,4-cyclohexanedimethanol diglycidyl ether, di- Rishijiru 1,2-cyclohexane dicarboxylate, 3,4-epoxycyclohexylmethyl 3 ', 4'-epoxycyclohexane carboxylate, and a bis (3,4-epoxycyclohexylmethyl) adipate and cyclohexene oxide type epoxy resin.

  Among the compounds having two or more oxirane rings, compounds having three oxirane rings are preferable, and trimethylolethane triglycidyl ether or trimethylolpropane triglycidyl ether is more preferable, in terms of excellent sensitivity and resolution.

  The compounds having the two or more oxirane rings are, for example, Epolight 40E, Epolight 100E, Epolight 70P, Epolight 200P, Epolight 1500 NP, Epolight 1600, Epolight 80 MF, Epolight 100 MF (all manufactured by Kyoeisha Chemical Co., Ltd., trade names) Alkyl-type epoxy resin ZX-1 542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L and Denacol EX-850L (all are Nagase Chem Commercially available as Tech Co., Ltd. (trade name).

  The compounds having two or more oxirane rings can be used singly or in combination of two or more.

  When the photosensitive resin composition of the present embodiment contains a compound having a methylol group or a compound having an alkoxyalkyl group, the inventors consider that the reason why a pattern with high resolution can be formed is as follows. There is. First, as described later, when the photosensitive resin composition contains the component (C), an acid is generated by irradiation with an actinic ray or the like. By the catalytic action of the generated acid, a negative pattern is obtained by reacting alkoxyalkyl groups in component (B) or alkoxyalkyl groups in component (B) with component (A) with dealcoholation. Can be formed. Further, due to the catalytic action of the generated acid, the methylol groups in (B) component or the methylol group in (B) component and the (A) component react with dealcoholization to give a negative pattern. It can be formed. Next, when the photosensitive layer after resin pattern formation is heated and cured, the component (B) reacts with the component (A) to form a crosslinked structure, preventing the resin pattern from becoming brittle and the resin pattern from being denatured. be able to. Therefore, even if a resist pattern with high resolution is formed, defects such as meandering and falling of the resist pattern can be reduced, and the present inventors speculate that sufficient heat resistance can be obtained. Do.

  Specifically as a compound having a methylol group or a compound having an alkoxyalkyl group, a compound having a phenolic hydroxyl group (however, the component (A) is not included) or a compound having a hydroxymethylamino group is preferably used. be able to.

  The “compound having a phenolic hydroxyl group” used as the component (B) can increase the dissolution rate of the unexposed area when developing with an aqueous alkali solution, and can improve the sensitivity. The molecular weight of the compound having a phenolic hydroxyl group is preferably 94 to 2000 as a weight average molecular weight, and 108 to 2000, in consideration of the balance of solubility in an aqueous alkaline solution, photosensitivity, mechanical properties, etc. More preferably, it is 108-1500.

［一般式（１）中、Ｚは単結合又は２価の有機基を示し、Ｒ^１及びＲ^２はそれぞれ独立に水素原子又は１価の有機基を示し、Ｒ^３及びＲ^４はそれぞれ独立に１価の有機基を示し、ａ及びｂはそれぞれ独立に１〜３の整数を示し、ｃ及びｄはそれぞれ独立に０〜３の整数を示す。］ Although a conventionally well-known thing can be used as a compound which has the said phenolic hydroxyl group, The compound represented by following General formula (1) is a resin pattern of the resin pattern after hardening by heating enhancement of the unexposed part, and heating It is preferable from being excellent in the balance of the effect which prevents a deformation | transformation.

[In general formula (1), Z represents a single bond or a divalent organic group, R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, and R ³ and R ⁴ each independently represent And a and b each independently represent an integer of 1 to 3; c and d each independently represent an integer of 0 to 3; ]

  In the general formula (1), a compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. Further, as the divalent organic group represented by Z, an alkylene group having 1 to 10 carbon atoms such as methylene, ethylene and propylene; an alkylidene group having 2 to 10 carbons such as ethylidene; An arylene group having 6 to 30 carbon atoms, such as a phenylene group; a group in which part or all of hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom; a sulfonyl group; a carbonyl group; an ether bond; An amide bond and the like. Among these, Z is preferably a divalent organic group represented by the following general formula (2).

［一般式（２）中、Ｘは、単結合、アルキレン基（例えば、炭素数が１〜１０のアルキレン基）、アルキリデン基（例えば、炭素数が２〜１０のアルキリデン基）、それらの水素原子の一部又は全部をハロゲン原子で置換した基、スルホニル基、カルボニル基、エーテル結合、チオエーテル結合又はアミド結合を示す。Ｒ^５は、水素原子、ヒドロキシル基、アルキル基又はハロアルキル基を示し、ｅは１〜１０の整数を示す。複数のＲ^５は互いに同一でも異なっていてもよい。］

[In general formula (2), X is a single bond, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), an alkylidene group (for example, an alkylidene group having 2 to 10 carbon atoms), their hydrogen atoms The group which substituted one part or all part by the halogen atom, a sulfonyl group, a carbonyl group, an ether bond, a thioether bond, or an amide bond is shown. R ⁵ represents a hydrogen atom, a hydroxyl group, an alkyl group or a haloalkyl group, and e represents an integer of 1 to 10. The plurality of R ⁵ may be the same or different. ]

  Examples of the compound having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N) -A nitrogen-containing compound etc. which alkyl-etherified all or one part of methylol groups, such as-hydroxymethyl) urea, etc. are mentioned. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component formed by partial self condensation. Specifically, hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl) urea and the like can be mentioned.

  The compound having a methylol group and the compound having an alkoxyalkyl group can be used singly or in combination of two or more.

  The content of the component (B) is preferably 20 to 90 parts by mass, more preferably 25 to 85 parts by mass, particularly preferably 40 to 75 parts by mass with respect to 100 parts by mass of the component (A). preferable. When the content of the component (B) is 20 parts by mass or more, the reaction of the exposed portion proceeds sufficiently and the resolution tends to be more excellent, and when the content is 90 parts by mass or less It becomes easy to form a resin composition on a desired support, and the resolution tends to be further improved.

<(C) component>
The photosensitive acid generator which is the component (C) is a compound which generates an acid upon irradiation with an actinic ray or the like, and not only the components (B) react with each other by the catalytic effect of the generated acid, but (B) The component also reacts with the phenolic hydroxyl group of the component (A), and the solubility of the composition in the developer decreases significantly.

  The component (C) is not particularly limited as long as it is a compound capable of generating an acid upon irradiation with an actinic ray or the like, and, for example, onium salt compounds, halogen containing compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfoneimide compounds, diazomethane compounds Etc. Among them, it is preferable to use an onium salt compound or a sulfoneimide compound from the viewpoint of easy availability. In particular, when a solvent is used as the component (E), it is preferable to use an onium salt compound from the viewpoint of solubility in the solvent. Hereinafter, the specific example is shown.

Onium salt compounds:
As onium salt compounds, for example, iodonium salts, sulfonium salts, phosphonium salts, diazonium salts and pyridinium salts can be mentioned. Specific examples of preferred onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, and diaryliodonium salts such as diphenyliodonium tetrafluoroborate; triphenylsulfonium Triarylsulfonium salts such as trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate and the like; 4-t-butylphenyl-diphenylsulfonium trifluoromethanesulfonate; 4-t-butylphenyl-diphenylsulfonium p- Toluene sulfonate; 4, 7 And di -n- butoxy naphthyl tetrahydrothiophenium trifluoromethanesulfonate, and the like.

Sulfonimide compound:
Specific examples of sulfonimide compounds include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) -1,8- Naphthalimide and N- (10-camphorsulfonyloxy) -1,8-naphthalimide are mentioned.

  In the present embodiment, the component (C) is preferably a compound having a trifluoromethanesulfonate group, a hexafluoroantimonate group, a hexafluorophosphate group or a tetrafluoroborate group from the viewpoint of excellent sensitivity and resolution. Moreover, (C) component can be used individually by 1 type or in mixture of 2 or more types.

  The content of the component (C) is 0.1 to 15 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of securing the sensitivity, resolution, pattern shape etc. of the photosensitive resin composition of the present embodiment. Part is preferable and 0.3-10 mass parts is more preferable.

<(D) component>
The photosensitive resin composition of the present embodiment contains a compound having a siloxane bond as the component (D). By containing the compound having a siloxane bond, adhesion to a highly smooth seed metal layer (titanium and / or a titanium compound) formed by using a sputtering technique can be significantly improved.

  The compound having a siloxane bond is not particularly limited as long as it has a siloxane bond, and examples of the inorganic filler and the silane compound include a compound having a siloxane bond, and an alkoxy oligomer. By using a photosensitive resin composition containing a compound having a siloxane bond, an interaction between Ti present on the surface of the seed metal layer and Ti-O-Si can be obtained, so the metal layer and the photosensitive resin composition Adhesion with objects is improved.

  Component (D) can be used singly or in combination of two or more.

  The average particle diameter of the inorganic filler used in the present embodiment is preferably 100 nm or less, more preferably 80 nm or less, and particularly preferably 50 nm or less from the viewpoint of photosensitivity. When the average particle size exceeds 100 nm, the resin composition becomes cloudy, exposure light does not pass through the resin composition, the unexposed area can not be removed, and the resolution may be lowered.

  The average particle size of the inorganic filler is an average particle size of the inorganic filler in a dispersed state in the photosensitive resin composition, and is a value obtained by measurement as follows. First, after the photosensitive resin composition is diluted (or dissolved) 1000 times with methyl ethyl ketone, it conforms to international standard ISO13321 using a submicron particle analyzer (trade name: N5, manufactured by Beckman Coulter Co., Ltd.) Then, the particles dispersed in the solvent with a refractive index of 1.38 are measured, and the particle diameter at an integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle diameter. Further, the particle diameter at an integrated value of 99.9% (volume basis) in the above particle size distribution is taken as the maximum particle diameter. In addition, even the photosensitive layer provided on the support or the cured film of the photosensitive resin composition may be diluted (or dissolved) 1000 times (volume ratio) with the solvent as described above, and then the sub It can be measured using a micron particle analyzer.

  When an inorganic filler having an average primary particle diameter of 100 nm or less is contained as the component (D), the thermal expansion coefficient of the film obtained by heating and curing the photosensitive layer after pattern formation is the filling amount of the component (D) Can be reduced accordingly. Here, when any inorganic filler is dispersed in the resin composition, the maximum particle diameter is dispersed to 2 μm or less.

  When the inorganic filler is contained as the component (D), the inorganic filler is preferably a silica such as fused spherical silica, fused and crushed silica, fumed silica, sol-gel silica and the like. In addition, the inorganic filler may have a siloxane bond by treating the inorganic filler with a silane compound, and as the inorganic filler other than silica, for example, aluminum oxide, aluminum hydroxide, calcium carbonate, calcium hydroxide, sulfuric acid Inorganic fillers derived from mines such as barium, barium carbonate, magnesium oxide, magnesium hydroxide, talc, mica and the like can be mentioned. These are pulverized by a pulverizer, optionally classified, and dispersed with a maximum particle diameter of 2 μm or less.

When an inorganic filler is contained as component (D), the type of inorganic filler is not particularly limited as long as it has a siloxane bond, but as the inorganic filler, the thermal expansion coefficient is 5.0 × 10 ⁻⁶ / ° C. The following are preferable, and from the viewpoint of particle diameter, fused spherical silica, fumed silica, sol-gel silica and the like are preferable. Among them, fumed silica and sol-gel silica are more preferable. Moreover, it is preferable to use what is called nano silica which has an average primary particle diameter in the range of 5 nm to 100 nm. These tend to be easily dispersed in the photosensitive resin composition with the maximum particle diameter of 2 μm or less. At this time, a silane compound may be used to disperse in the resin without aggregation.

  When a silane compound is contained as the component (D), there is no particular limitation as long as the silane compound has a siloxane bond, but, for example, alkylsilane, alkoxysilane, vinylsilane, epoxysilane, aminosilane, acrylsilane, methacrylsilane, Mercaptosilane, sulfide silane, isocyanate silane, sulfurasilane, styrylsilane, alkylchlorosilane can be used.

  The silane compound which is the component (D) preferably contains a compound represented by the following general formula (3).

In general formula (3), R ⁶ is an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl and propyl, R ⁷ is a monovalent organic group, and n is an integer of 0 to 3. When n is 0, 1 or 2, a plurality of R ⁶ may be the same or different. When n is 2 or 3, plural R ^{7 s} may be the same as or different from each other. From the viewpoint of better resolution, R ⁶ is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms. When treating with a silane compound in order to improve the dispersibility of the filler, n is preferably 0 to 2 and more preferably 0 to 1 from the viewpoint of further improving the dispersibility of the filler.

  Specific compound names of the silane compounds which are the component (D) are methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxy Silane, diisopropyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxy Silane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylto Ethoxysilane, 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) propyldisulfide Ethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethyldiethylsilane) Examples include butylidene) -3-aminopropyltriethoxysilane and the like.

  The silane compound preferably has a functional group capable of reacting with the (A) component or the (B) component. The functional group capable of reacting with the component (A) or the component (B) is preferably an epoxy group, an amino group, a mercapto group or an isocyanate group. Among them, from the viewpoint of being more excellent in the stability of the photosensitive resin composition, an epoxy group is more preferable, and an epoxysilane having one or more glycidyl ether groups is more preferable from the viewpoint of being more excellent in resolution.

  The alkoxy oligomer which is the component (D) is a compound having an organic group and an alkoxysilyl group, for example, X-41-1053, X-41-1059A, X-41-1056, X-40-2655A, KR- 513, KC-513, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR- 9218 and KR-213 (all manufactured by Shin-Etsu Silicone Co., Ltd., trade names) and the like.

  The content of the compound having a siloxane bond is 1% by mass to 70% by mass, and preferably 3% by mass to 65% by mass, based on the total mass of the solid content of the photosensitive resin composition. The photosensitive resin composition obtained as it is this range can improve adhesiveness with a metal layer more, maintaining sufficient resolution.

<(E) component>
The photosensitive resin composition of the present embodiment further contains a solvent as a component (E) in order to improve the handleability of the photosensitive resin composition or to adjust the viscosity and storage stability. Can. The component (E) is preferably an organic solvent. The type of the organic solvent is not particularly limited as long as it can exhibit the above-mentioned performance, and examples thereof include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether Propylene glycol monoalkyl ether such as propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; Propylene glycol dialkyl ether such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; Propylene glycol monomethyl ether Propylene glycol monoalkyl ether acetates such as cetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; Cellosolve such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; methyl lactate, lactic acid Ethyl, lactic acid esters such as n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate Aliphatic carboxylic acid esters such as isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-eth Other esters such as methyl cypropionate, ethyl 3-ethoxypropionate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone And ketones such as cyclohexanone; amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; and lactones such as γ-butyrolactone. The organic solvents may be used singly or in combination of two or more.

30-200 mass parts is preferable with respect to 100 mass parts of whole photosensitive resin compositions except (E) component, and, as for content of (E) component, 60-120 mass parts is more preferable.
<(F) component>
The photosensitive resin composition of the present embodiment may further contain a leveling agent as the component (F), if necessary. Component (F) can be used singly or in combination of two or more. The film thickness uniformity of a coating film can be improved by containing (F) component.

  0.01-1.5 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (F) component, 0.05-0.5 mass parts is more preferable.

<(G) component>
The photosensitive resin composition of the present embodiment may further contain a sensitizer as the component (G), if necessary. Examples of the sensitizer include 9,10-dibutoxyanthracene. Moreover, (G) component can be used individually by 1 type or in mixture of 2 or more types. By containing the component (G), the photosensitivity of the photosensitive resin composition can be improved.

  0.01-1.5 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (G) component, 0.05-0.5 mass parts is more preferable.

  The photosensitive resin composition of the present embodiment may contain, in addition to the component (A), a phenolic low molecular weight compound having a molecular weight of less than 1000 (hereinafter referred to as "phenol compound (a)"). . For example, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylether, 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) And the like. 1) 1-methylethyl} phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane and the like. These phenol compounds (a) can be contained in an amount of 0 to 40 parts by mass, particularly 0 to 30 parts by mass, per 100 parts by mass of the component (A).

[Photosensitive element]
Next, the photosensitive element of the present embodiment will be described.

  The photosensitive element which concerns on this embodiment is provided with a support body and the photosensitive layer formed from the above-mentioned photosensitive resin composition provided on this support body. A protective layer may be further provided on the photosensitive layer to cover the photosensitive layer.

  As said support body, the polymer film which has heat resistance and solvent resistance, such as a polyethylene terephthalate, a polypropylene, polyethylene, polyester, can be used, for example. The thickness of the support (polymer film) is preferably 5 to 25 μm. The polymer film may be used by laminating one on a support and the other on a photosensitive layer as a protective layer.

  As said protective layer, the polymer film which has heat resistance and solvent resistance, such as a polyethylene terephthalate, a polypropylene, polyethylene, polyester, can be used, for example.

  The photosensitive layer can be formed by applying the photosensitive resin composition on a support or a protective layer. Examples of the coating method include dipping, spraying, bar coating, roll coating, spin coating, and the like. The thickness of the photosensitive layer varies depending on the application, but is preferably 10 to 100 μm, more preferably 15 to 60 μm, and particularly preferably 20 to 50 μm after drying the photosensitive layer.

[Method of forming resist pattern]
Next, a method of forming a resist pattern according to the present embodiment will be described.

  First, a photosensitive layer formed of the above-mentioned photosensitive resin composition is formed on a substrate (a resin-coated copper foil, a copper-clad laminate, a silicon wafer provided with a metal sputter film, an alumina substrate, etc.) on which a resist is to be formed. Form. As a method of forming a photosensitive layer, a method of coating a photosensitive resin composition on a substrate and drying to volatilize a solvent etc. to form a coating film (photosensitive layer), the photosensitive layer in the above-mentioned photosensitive element There is a method of transferring onto a substrate.

  As a method of apply | coating the said photosensitive resin composition to a base material, application methods, such as a dipping method, a spray method, a bar coat method, a roll coat method, a spin coat method, can be used, for example. Moreover, the thickness of a coating film can be suitably controlled by adjusting solid content concentration and viscosity of an application | coating means and the photosensitive resin composition.

Next, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. Examples of actinic rays used for exposure include: rays of g-line steppers; ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and i-line steppers; electron beams; laser beams; Although it selects suitably by the thickness etc. of a coating film, in the case of the ultraviolet irradiation from a high pressure mercury lamp, for example, in thickness of 10-50 micrometers of a coating film, it is about 100-5000 mJ / cm < ² >.

  Further, heat treatment (post-exposure bake) is performed after the exposure. Post-exposure baking can accelerate the curing reaction of the components (A) and (B) due to the generated acid. Although the conditions for post-exposure baking vary depending on the content of the photosensitive resin composition, the thickness of the coating film, etc., it is usually preferable to heat at 70 to 150 ° C. for 1 to 60 minutes, and 1 to 60 at 80 to 120 ° C. It is more preferable to heat for a minute.

  Then, the coating film subjected to exposure and / or post-exposure baking is developed with an alkaline developer to dissolve and remove the area other than the cured area (unexposed area) to obtain a desired resist pattern. Examples of the development method in this case include a shower development method, a spray development method, an immersion development method, and a paddle development method. The development conditions are, for example, 1 to 20 minutes at 20 to 40 ° C.

  Examples of the alkaline developing solution include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, or choline is dissolved in water to a concentration of 1 to 10% by mass, ammonia water, etc. Alkaline aqueous solution of An appropriate amount of, for example, a water-soluble organic solvent such as methanol or ethanol, or a surfactant can be added to the alkaline developer. After development with the alkaline developer, the film is washed with water and dried. The alkaline developing solution is preferably tetramethylammonium hydroxide from the viewpoint of excellent resolution.

  Furthermore, a cured film (resist pattern) of the photosensitive resin composition is obtained by performing a heat treatment to develop insulating film characteristics. Although the curing conditions of the photosensitive resin composition are not particularly limited, it may be heated at 50 to 250 ° C. for 30 minutes to 10 hours to cure the photosensitive resin composition depending on the application of the cured product. it can.

  In addition, heating can be performed in two steps in order to sufficiently advance curing or to prevent deformation of the obtained resin pattern shape. For example, it may be cured by heating at 50 to 120 ° C. for 5 minutes to 2 hours in the first step, and further heating at 80 to 200 ° C. for 10 minutes to 10 hours in the second step.

  If it is the above-mentioned hardening conditions, there is no restriction in particular as heating equipment, and a common oven, an infrared furnace, etc. can be used.

[Multilayer printed wiring board]
The cured product formed from the photosensitive resin composition of the present embodiment may be suitably used, for example, as a surface protective film or an interlayer insulating film of a semiconductor element, or as a solder resist and / or an interlayer insulating film in a multilayer printed wiring board. it can. FIG. 1 is a view showing a method of manufacturing a multilayer printed wiring board including a cured product of the photosensitive resin composition of the present embodiment as a solder resist and / or an interlayer insulating material. The multilayer printed wiring board 100A shown in FIG. 1 (f) has a wiring pattern on the surface and inside. The multilayer printed wiring board 100A is obtained by laminating a copper-clad laminate, an interlayer insulating material, a metal foil or the like and appropriately forming a wiring pattern by an etching method or a semi-additive method. Hereinafter, a method of manufacturing the multilayer printed wiring board 100A will be briefly described based on FIG.

  First, interlayer insulating layers 103 are formed on both surfaces of a copper-clad laminate 101 having a wiring pattern 102 on the surface (see FIG. 1A). The interlayer insulating layer 103 may be formed by printing a photosensitive resin composition using a screen printer or a roll coater, or the photosensitive element described above may be prepared in advance, and the photosensitive layer may be formed using a laminator. The photosensitive layer in the element may be attached to the surface of the printed wiring board. Next, an opening 104 is formed using a YAG laser or a carbon dioxide gas laser at a place where it is necessary to electrically connect to the outside (see FIG. 1B). Smear (residue) around the opening 104 is removed by desmearing. Next, the seed layer 105 is formed by electroless plating (see FIG. 1C). A photosensitive layer formed of the photosensitive resin composition described above is laminated on the seed layer 105, and predetermined portions are exposed and developed to form a wiring pattern 106 (see FIG. 1D). An adhesion layer, for example, a titanium layer having a thickness of about 30 nm is formed on the seed layer, and a copper layer having a thickness of about 100 nm is further formed. These seed layers can be formed by sputtering. Next, the wiring pattern 107 is formed by electrolytic plating, and the cured product of the photosensitive resin composition is removed by a peeling solution, and then the seed layer 105 is removed by etching (see FIG. 1 (e)). The multilayer printed wiring board 100A can be produced by repeatedly performing the above operation and forming the solder resist 108 formed of the cured product of the photosensitive resin composition described above on the outermost surface (see FIG. 1 (f)).

  The multilayer printed wiring board 100A obtained in this manner can be a semiconductor device in which a semiconductor element is mounted at a corresponding position, and electrical connection can be thereby secured.

EXAMPLES Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples. In the following examples and comparative examples, parts are used in the meaning of parts by mass unless otherwise specified. The following Examples 1 to 8 and 13 correspond to Reference Examples.

<Preparation of Photosensitive Resin Composition>
(Examples 1 to 13 and Comparative Examples 1 to 5)
Compound having two or more oxirane rings, compound having methylol group or compound having alkoxyalkyl group (B-1 to B-6), 100 parts by mass of novolac resin (A-1 to A-2), light The photosensitive acid generator (C-1), the compound having a siloxane bond (D-1 to D-4), the solvent (E-1) and the sensitizer (G-1) were added to the predetermined amounts shown in Table 1 The mixture was blended to obtain a photosensitive resin composition.

<Preparation of Photosensitive Element>
The above photosensitive resin composition is coated on a polyethylene terephthalate film (manufactured by Teijin DuPont Film Co., Ltd., trade name: Purex A53) (support) so as to have a uniform thickness, and dried at 90 ° C. with a hot air convection system. The film was dried for 10 minutes to form a photosensitive layer having a thickness of 25 μm after drying. Then, a photosensitive layer having a thickness of 40 μm after drying was formed on the support by the method described above. A protective layer (manufactured by Tamapoly Co., Ltd., trade name: NF-15) is laminated on the photosensitive layer of each film thickness, and a photosensitive element in which a support, a photosensitive layer, and a protective layer are sequentially laminated is provided. Obtained.

<Evaluation of resolution>
While peeling off the protective layer on a silicon wafer having a diameter of 6 inches, the photosensitive element having a film thickness of 25 μm obtained above was laminated such that the photosensitive layer was in contact with the silicon surface. The support was then peeled off to obtain uniform photosensitive layers each having a thickness of 25 μm on a silicon wafer. In addition, lamination was performed at a pressure of 0.4 MPa and a roll speed of 1.0 m / min using a heat roll at 120 ° C. Using the i-line stepper (trade name: FPA-3000iW, manufactured by Canon Inc.), the produced coating film was subjected to reduction projection exposure through an i-line (365 nm) through a mask. As a mask, a mask having a pattern in which the width of the exposed portion and the unexposed portion is 1: 1 is used in an interval of 2 μm: 2 μm to 30 μm: 30 μm. The exposure amount is in the range of 100~3000mJ / cm ^2, was subjected to the reduction projection exposure while changing by 100 mJ / cm ^2.

Next, the exposed coating film is heated at 65 ° C. for 1 minute, then at 95 ° C. for 4 minutes (post exposure bake), and a minimum developing time (unexposed area is obtained) using a 2.38 mass% tetramethylammonium hydroxide aqueous solution. The unexposed area was removed by immersion for a time corresponding to twice the minimum time to be removed) (development process). After development, the formed resist pattern was observed using a metallurgical microscope. The smallest space width in the range of 100 to 3000 mJ / cm ² of the pattern in which the space portion (unexposed portion) is removed cleanly and the line portion (exposed portion) is formed without meandering or chipping The value of was evaluated as the minimum resolution.

<Evaluation of heat resistance>
The protective layer of the photosensitive element having a film thickness of 40 μm is peeled off, and then the exposure energy amount is 3000 mJ / cm ² using an exposure machine having a high pressure mercury lamp (trade name: EXM-1201 manufactured by Oak Manufacturing Co., Ltd.). The photosensitive layer was exposed to be The exposed photosensitive layer was heated on a hot plate at 65 ° C. for 2 minutes, and then at 95 ° C. for 8 minutes (post exposure bake). Furthermore, heat treatment was performed at 180 ° C. for 60 minutes in a hot air convection dryer, and then the support was peeled off to obtain a cured film. Subsequently, the cured film was cut into a length of 20 mm and a width of 2 mm to prepare a test piece. Furthermore, using a thermomechanical analyzer (trade name: TMA / SS6000, manufactured by Seiko Instruments Inc.), the amount of thermal expansion of the cured film is measured when the temperature is raised at a temperature rising rate of 5 ° C./min. The inflection point obtained from the curve was determined as the glass transition temperature Tg. In addition, the measurement conditions of the amount of thermal expansion are shown below.
Sample width: 2 mm
Sample length: 10 mm
Chuck distance: 10 mm
Load: 5 gf (0.05 N)
Measurement temperature range: 18 to 420 ° C

<Evaluation of adhesive strength (peel strength)>
While peeling off the protective layer on a silicon wafer having a diameter of 6 inches, the photosensitive element having a film thickness of 25 μm obtained above was laminated such that the photosensitive layer was in contact with the silicon surface. Next, the support was peeled off to obtain uniform photosensitive layers each having a thickness of 25 μm on a silicon wafer. Next, the photosensitive layer was exposed to an irradiation energy of 3000 mJ / cm ² using an exposure machine (trade name: EXM-1201, manufactured by Oak Corporation) having a high pressure mercury lamp. The exposed photosensitive layer was heated on a hot plate at 65 ° C. for 2 minutes, and then at 95 ° C. for 8 minutes (post exposure bake). Furthermore, heat treatment was performed at 180 ° C. for 60 minutes in a hot air convection dryer to obtain a cured resin film on a silicon wafer. A sputtered metal film (seed metal layer) of titanium was formed to a thickness of 0.1 μm on the upper surface of the resin film using a sputtering apparatus, and then a sputtered metal film of copper was formed to a thickness of 0.1 μm. Furthermore, copper sulfate electrolytic plating was performed, and then annealing treatment was performed at 180 ° C. for 60 minutes to form a conductor layer (titanium layer and copper layer) having a thickness of 20 μm on the cured film. An area of 10 mm in width and 50 mm in length was formed in the conductor layer by etching, and one end of this area was peeled off by 10 mm at the interface between the seed metal layer (titanium layer) and the cured resin film. Next, the peeled resin film is gripped with a clamp and the load (peel strength) when peeled off at room temperature is measured five times at a tensile speed of 50 mm / min in the thickness direction (vertical direction) of the silicon wafer, and measured five times. The average value was calculated from the values and used as an index of adhesive strength. In addition, evaluation of peeling strength was performed based on JISC5016 (1994-peeling strength of a conductor). Moreover, in this specification, room temperature shows 25 degreeC. The evaluation results are shown in Table 1.

Ａ−１：クレゾールノボラック樹脂（旭有機材工業（株）製、商品名：ＥＰ４０２０Ｇ）
Ａ−２：ノボラック樹脂（旭有機材工業（株）製、商品名：ＭＸＰ５５６０ＢＦ、重量平均分子量＝７８００）
Ｂ−１：１，４−シクロヘキサンジメタノールジグリシジルエーテル（アルドリッチ社製、商品名）
Ｂ−２：ネオペンチルグリコールジグリシジルエーテル（共栄社化学（株）製、商品名：エポライト１５００ＮＰ）
Ｂ−３：トリメチロールプロパントリグリシジルエーテル（新日鉄住金化学（株）製、商品名：ＺＸ−１５４２、下記式（４）参照）

A-1: Cresol novolak resin (Asahi Organic Material Industry Co., Ltd., trade name: EP 4020 G)
A-2: Novolak resin (manufactured by Asahi Organic Materials Co., Ltd., trade name: MXP 5560 BF, weight average molecular weight = 7800)
B-1: 1,4-cyclohexanedimethanol diglycidyl ether (manufactured by Aldrich, trade name)
B-2: neopentyl glycol diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Epolite 1500 NP)
B-3: trimethylolpropane triglycidyl ether (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: ZX-1542, see the following formula (4))

Ｂ−４：４,４’−（１,１,１,３,３,３−ヘキサフルオロイソプロピリデン）ビス[２,６−ビス（ヒドロキシメチル）フェノール]（本州化学工業（株）製、商品名：ＴＭＬ−ＢＰＡＦ）
Ｂ−５：１,３,４,６−テトラキス（メトキシメチル）グリコールウリル（（株）三和ケミカル製、商品名：ＭＸ−２７０）
Ｂ−６：エチルグリシジルエーテル（東京化成工業（株）製、商品名）
Ｃ−１：トリアリールスルホニウム塩（サンアプロ（株）社製、商品名：ＣＰＩ-１１０Ｂ）
Ｄ−１：３−グリシドキシプロピルトリメトキシシラン（信越シリコーン（株）製、商品名：ＫＢＭ−４０３）
Ｄ−２：シランカップリング剤（信越シリコーン（株）製、商品名：Ｘ−１２−９８１）
Ｄ−３：３−メタクリロキシプロピルトリメトキシシランでカップリング処理した平均一次粒子径が１５ｎｍであるシリカ。
Ｄ−４：シリコーンアルコキシオリゴマー（信越シリコーン（株）製、商品名：ＫＣ−８９Ｓ）
Ｅ−１：メチルエチルケトン（和光純薬工業（株）製、商品名：２−ブタノン）
Ｇ−１：９，１０−ブトキシアントラセン（川崎化成工業（株）製、商品名：ＤＢＡ）

B-4: 4,4 '-(1,1,1,3,3,3-hexafluoroisopropylidene) bis [2,6-bis (hydroxymethyl) phenol] (manufactured by Honshu Chemical Industry Co., Ltd., a product Name: TML-BPAF)
B-5: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: MX-270)
B-6: Ethyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., trade name)
C-1: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-110B)
D-1: 3-glycidoxypropyl trimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., trade name: KBM-403)
D-2: Silane coupling agent (manufactured by Shin-Etsu Silicone Co., Ltd., trade name: X-12-981)
D-3: Silica having an average primary particle size of 15 nm that has been subjected to coupling treatment with 3-methacryloxypropyltrimethoxysilane.
D-4: silicone alkoxy oligomer (manufactured by Shin-Etsu Silicone Co., Ltd., trade name: KC-89S)
E-1: methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 2-butanone)
G-1: 9, 10-butoxyanthracene (manufactured by Kawasaki Kasei Kogyo Co., Ltd., trade name: DBA)

  As is clear from Table 1, in Comparative Examples 4 and 5, after the exposure, all of the resist pattern was dissolved in the developer, so that the resolution could not be evaluated. Moreover, although the comparative examples 1 and 2 showed the outstanding resolution of 5 micrometers, and high Tg, peel strength (adhesion strength of the interface of a seed metal layer (titanium layer) and a resin film) has Examples 1-13. It was significantly lower compared to. In addition, in Comparative Example 3, the peel strength could not be evaluated because swelling occurred after the annealing treatment. On the other hand, Examples 1 to 13 exhibited an excellent resolution of 9 μm or less and a high Tg, and the peel strength showed a high value of 0.17 kN / m or more.

  The photosensitive resin composition of the present invention is applied as a solder resist of a wiring board material or an interlayer insulating film, or a material used for a surface protective film (overcoat film) or an interlayer insulating film (passivation film) of a semiconductor element or the like. . In particular, since the photosensitive resin composition is excellent in adhesion to a metal layer, and has sufficient resolution and heat resistance, it is suitably used for a high density package substrate etc. which is thinned and densified. .

  100A: multilayer printed wiring board, 101: copper-clad laminate, 102, 106, 107: wiring pattern, 103: interlayer insulating layer, 104: opening, 105: seed layer, 108: solder resist.

Claims (9)

(A) Component: novolak resin,
Component (B): a compound having three or more glycidyl ether groups ,
Component (C): a photosensitive acid generator, and (D): an inorganic filler having a Si-O bond,
The component (C) is at least one compound selected from the group consisting of onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfoneimide compounds, and diazomethane compounds,
The average particle diameter of the inorganic filler having the Si-O bond is 50 nm or less,
A photosensitive resin composition containing 20 to 90 parts by mass of the component (B) with respect to 100 parts by mass of the component (A), but a resin composition containing particles composed of a crosslinked polymer except.).   The photosensitive resin composition of Claim 1 whose inorganic filler which has the said Si-O coupling | bonding is a silica. (A) Component: novolak resin,
Component (B): a compound having two or more oxirane rings, a compound having a methylol group and a phenolic hydroxyl group, a compound having a hydroxymethylamino group, a compound having an alkoxymethyl group and a phenolic hydroxyl group, and a hydroxymethylamino group At least one compound selected from the group consisting of nitrogen-containing compounds obtained by alkylating all or part of methylol groups of the compound having
Component (C): a photosensitive acid generator, and (D): a silicone alkoxy oligomer,
The component (C) is at least one compound selected from the group consisting of onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfoneimide compounds, and diazomethane compounds,
A photosensitive resin composition containing 20 to 90 parts by mass of the component (B) based on 100 parts by mass of the component (A) (excluding a resin composition containing particles made of a crosslinked polymer) ). The photosensitive resin composition according to claim 3 , wherein the compound having two or more oxirane rings has two or more glycidyl ether groups. The photosensitive resin composition of Claim 3 or 4 in which the compound which has the said 2 or more oxirane ring has 3 or more glycidyl ether groups.   The photosensitive element provided with a support body and the photosensitive layer formed from the photosensitive resin composition as described in any one of Claims 1-5 provided on this support body.   The semiconductor device provided with the hardened | cured material of the photosensitive resin composition as described in any one of Claims 1-5 as a surface protective film or an interlayer insulation film. The process of apply | coating the photosensitive resin composition as described in any one of Claims 1-5 on a base material, drying the said photosensitive resin composition, and forming a photosensitive layer,
Exposing the photosensitive layer to a predetermined pattern and performing post-exposure heat treatment;
And D. developing the photosensitive layer after the heat treatment and subjecting the obtained resist pattern to a heat treatment. Forming a photosensitive layer of the photosensitive element according to claim 6 on a substrate;
Exposing the photosensitive layer to a predetermined pattern and performing post-exposure heat treatment;
And D. developing the photosensitive layer after the heat treatment and subjecting the obtained resist pattern to a heat treatment.

Images