JP6631026B2 - Dry film, cured product, semiconductor device, and method of forming resist pattern - Google Patents

Description

  The present invention relates to a dry film, a cured product, a semiconductor device, and a method for 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 base material (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. Further, a resin pattern is formed on the base material by selectively removing the unexposed portions using a developing solution. For this reason, the photosensitive resin composition is required to have a short development time (developability), excellent sensitivity to actinic rays, excellent fine pattern formation (resolution), and the like. Therefore, a photosensitive resin composition containing a novolak resin, an epoxy resin and a photoacid generator soluble in an aqueous alkali solution, a photosensitive resin composition containing an alkali-soluble epoxy compound having a carboxyl group and a photocationic polymerization initiator, etc. (For example, see Patent Documents 1 to 3).

  Further, from the viewpoint of workability in forming a photosensitive layer on a substrate, the photosensitive resin composition is also required to have excellent sticking properties (tack properties) to the substrate. When a photosensitive resin composition that does not have sufficient tackiness is used, the photosensitive layer in the exposed area is easily removed by the development treatment, and the adhesion between the base material and the resist pattern tends to deteriorate.

  Further, the surface protection film and the interlayer insulating film used for the semiconductor element are required to have insulation reliability such as heat resistance, electric characteristics, and mechanical characteristics. Therefore, a photosensitive resin composition further containing a crosslinkable monomer in the photosensitive resin composition has been proposed (for example, see Patent Document 4).

  Further, by forming the interlayer insulating film to be thick, the insulation between the wirings in the layer thickness direction is improved, and the short circuit of the wirings can be prevented, so that the reliability regarding the insulation between the wirings is improved. When a chip is mounted, since the semiconductor element has a thick interlayer insulating film, the stress applied to the pad of the solder bump can be reduced, so that a connection failure does not easily occur at the time of mounting. Therefore, from the viewpoints of insulation reliability and productivity in mounting a chip, it is also required that a thick film of the photosensitive resin composition exceeding 20 μm can be formed.

JP 06-059444 A JP-A-09-087366 WO 2008/010521 JP 2003-215802 A

  However, the photosensitive resin compositions described in the above-mentioned prior art documents have excellent insulation reliability and the like, but have difficulty in increasing the resolution when the film is made thick. For example, in the photosensitive resin composition described in Patent Document 2, when the thickness of the coating film is 50 μm, the space width is about 40 μm, which is insufficient for a highly integrated semiconductor element. is there. Further, the photosensitive resin composition described in Patent Document 3 may not be able to exhibit sufficient heat resistance. Further, in the photosensitive resin composition described in Patent Document 1 or 4, when the thickness of the coating film is 10 μm, good resolution with a space width of about 5 μm is obtained, but when the film is thickened. Does not provide good resolution.

  Further, as a method for forming a photosensitive layer on a printed wiring board, there is a method of applying a solution of a photosensitive resin composition by spin coating or a method of printing, and thereafter, drying of a solvent is required. On the other hand, a dry film can easily form a photosensitive layer having a uniform thickness by lamination.

  An object of the present invention is to solve the problems associated with the prior art as described above, and to have excellent resolution and heat resistance even when a coating film (photosensitive layer) having a thickness exceeding 20 μm is formed. An object of the present invention is to provide a dry film capable of forming a resist pattern and having excellent handleability of the film. Another object of the present invention is to provide a cured product obtained by using a photosensitive layer in the dry film, a semiconductor device using the cured product, and a method for forming a resist pattern using the dry film. It is in.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found a dry film having excellent characteristics. That is, the present invention is a dry film comprising a photosensitive layer formed using a photosensitive resin composition and a protective layer in this order, wherein the photosensitive resin composition comprises a component (A): a phenolic hydroxyl group. And a resin having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring, and an alicyclic ring, and having a methylol group or an alkoxyalkyl group, and a component (G). : One or both components of a silane coupling agent and component (C): an aliphatic compound having two or more functional groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group and a hydroxyl group. And a (D) component: a photosensitive acid generator, and a sample cut out from the dry film into a width of 2 cm and a length of 8 cm is provided with the protective layer on the surface side. Immobilized on sea urchin pedestal temperature 23 ° C. the protective layer from the sample, the photosensitive layer at the time of peeled off from the longitudinal end of the sample in 180 ° direction at a tensile rate of 5 cm / min and the protective layer and A dry film having a peel force of 0.5 to 10 N / m.

  According to the dry film of the present invention, since the photosensitive layer is a layer formed using the photosensitive resin composition containing each of the above-described components, a coating film (photosensitive layer) having a thickness exceeding 20 μm is formed. Even with this, it is possible to form a resist pattern having excellent resolution and heat resistance. Further, the protective layer is provided on the photosensitive layer having the above configuration, and the peeling force between the photosensitive layer and the protective layer is within the above range, the photosensitive layer is broken during handling of the dry film, and The destruction of the photosensitive layer when the protective layer is peeled from the photosensitive layer can be prevented, and the handleability of the dry film is improved. Further, since the destruction of the photosensitive layer during handling of the dry film is prevented, excellent resolution at the time of forming a resist pattern can be maintained.

  In the dry film of the present invention, the peeling force between the photosensitive layer and the protective layer is preferably 0.5 to 6 N / m. In this case, the destruction of the photosensitive layer when the protective layer is separated from the photosensitive layer can be more sufficiently prevented.

  In the dry film of the present invention, the photosensitive resin composition preferably contains 20 to 70 parts by mass of the component (C) based on 100 parts by mass of the component (A).

  The component (C) preferably has three or more functional groups.

  The present invention also provides a cured product obtained by using the photosensitive layer in the dry film of the present invention.

  The present invention also provides a semiconductor device comprising the cured product of the present invention as a surface protective film or an interlayer insulating film.

  The present invention further includes a step of forming a photosensitive layer on a substrate using the dry film of the present invention, a step of exposing the photosensitive layer to a predetermined pattern, and a heat treatment after exposure; And a heat treatment of the obtained resin pattern. According to such a method for forming a resist pattern, even when a coating film (photosensitive layer) having a thickness exceeding 20 μm is formed, it is possible to form a resist pattern having excellent resolution and heat resistance. .

  According to the present invention, even when a coating film (photosensitive layer) having a thickness of more than 20 μm is formed, a resist pattern having excellent resolution and heat resistance can be formed, and the handleability of the film can be improved. An excellent dry film can be provided. Further, according to the present invention, it is possible to provide a cured product obtained by using a photosensitive layer in the dry film, a semiconductor device using the cured product, and a method for forming a resist pattern using the dry film. .

FIG. 1 is a schematic sectional view showing a dry film according to one embodiment of the present invention. It is a mimetic diagram showing a manufacturing method of a multilayer printed wiring board of one embodiment of the present invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the following description, the same or corresponding parts will be denoted by the same reference characters, without redundant description.

[Dry film]
The dry film of the present embodiment will be described with reference to FIG. FIG. 1 is a schematic sectional view of a dry film 10 according to the present embodiment. As shown in FIG. 1, a dry film 10 according to the present embodiment includes a support 1, a photosensitive layer 3 formed using a photosensitive resin composition, and a protective layer 5 covering the photosensitive layer 3. It prepares in this order.

In the dry film 10 of the present embodiment, a sample cut out from the dry film 10 to a width of 2 cm × a length of 8 cm is fixed on a pedestal with a double-sided tape or the like so that the protective layer 5 is on the front side, and is protected from the sample. Peeling force between the photosensitive layer 3 and the protective layer 5 when peeling the layer 5 from one end in the longitudinal direction of the sample at a temperature of 23 ° C. and a pulling speed of 5 cm 2 / min (peak of peeling force at the time of measurement) Strength) is 0.5 to 10 N / m. Here, the peeling force can be measured using, for example, a force gauge. When the peeling force is 10 N / m or less, tack (stickiness) during handling is appropriately suppressed, and the protective layer 5 can be easily peeled from the photosensitive layer 3. Further, it is possible to prevent the photosensitive layer 3 from being destroyed when the protective layer 5 is peeled off. On the other hand, when the peeling force is 0.5 N / m or more, the protective layer 5 can be easily attached to the photosensitive layer 3 at the time of producing a dry film, and the protective layer 5 is prevented from spontaneously peeling. Thus, it is possible to prevent the photosensitive layer 3 from being broken due to a winding deviation when the dry film 10 is wound. The peeling force is preferably 0.5 to 6 N / m from the viewpoint of more sufficiently obtaining the above-described effects.

  As a method for adjusting the above-mentioned peeling force within the above-mentioned range, for example, in a method for producing a dry film 10 described later, an application speed when applying the photosensitive resin composition onto the support 1 and drying conditions (drying temperature, (Drying time), a method of appropriately adjusting the material, surface treatment, and the like of the support 1 to be used. Further, as a method for adjusting the peeling force within the above range, the material and surface treatment of the protective layer 5 to be used, and the composition and viscosity of the photosensitive resin composition forming the photosensitive layer 3 are appropriately adjusted. There are also methods.

  Hereinafter, each layer constituting the dry film 10 of the present embodiment will be described.

<Support>
As the support 1, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. The thickness of the support (polymer film) 1 is preferably 5 to 25 μm. The above-mentioned polymer film may be used by laminating one on the both sides of the photosensitive layer 3 so as to sandwich the photosensitive layer 3 with one serving as the support 1 and the other serving as the protective layer 5.

  At least one surface of the support 1 may be surface-treated from the viewpoint of improving the releasability from the photosensitive layer 3. Here, the surface treatment means that a silicone-based surfactant, a silicone-based compound such as a silicone resin, a fluorine-based surfactant, a fluorine-containing compound such as a fluorine-containing resin, an alkyd resin, or the like is thinly applied (coated) on the surface of the support 1. ), Or physical treatment such as corona treatment of the surface of the support 1.

  When applying (coating) the above-mentioned surfactant or resin to the support 1, it is preferable to apply (coat) thinly as long as the releasing effect can be obtained. After application (coating), the above-mentioned surfactant or resin may be fixed to the support 1 by heat or UV treatment. It is more preferable to apply an undercoat layer to the support 1 before applying (coating) the surfactant or the resin.

  From the viewpoint of applicability of the photosensitive resin composition and releasability of the photosensitive layer 3, the surface tension (wetting tension) at 23 ° C. of the surface-treated surface of the support 1 may be 20 to 45 mN / m. Preferably, it is 30 to 45 mN / m, more preferably 35 to 45 mN / m. The surface tension was measured by applying a commercially available wet tension test mixture (manufactured by Wako Pure Chemical Industries, Ltd.) to the release-treated surface of the support film using a cotton swab at 23 ° C. The minimum value of the test mixture liquid that wets or wets without liquid is defined as surface tension (wet tension).

From the viewpoint of the peelability of the photosensitive layer 3, the 180 ° peel strength of the surface-treated surface of the support 1 at 23 ° C. is 5 to 300 gf / inch (1.97 to 118 gf / cm or 19.3 to 1156). preferably .4 × a ¹⁰ -3 N / cm), it is 5～200Gf / inch (1.97~78.7gf / cm or 19.3~771.3 × ¹⁰ -3 N / cm) And more preferably 100 to 200 gf / inch (39.4 to 78.7 gf / cm or 386.1 to 771.3 × 10 ⁻³ N / cm). The 180 ° peel strength can be measured by a general method (for example, a method based on JIS K6854-2) using an adhesive tape (trade name: “NITTO31B” manufactured by Nitto Denko Corporation). it can.

  The preferred thickness of the layer made of the above surfactant or resin (hereinafter referred to as “surface treatment layer”) is about 0.005 to 1 μm, particularly preferably 0.01 to 0.1 μm. When the thickness of the surface treatment layer is within the above range, the adhesion between the support 1 and the surface treatment layer becomes good.

  Examples of the PET film of which at least one surface is surface-treated with the above surfactant or resin include, for example, trade names “Purex A53”, “A31-25”, and “A51-25” manufactured by Teijin DuPont Films Limited. And "A53-38" are commercially available ("Purex" is a registered trademark).

<Photosensitive layer>
The photosensitive layer 3 can be formed using a photosensitive resin composition described below. The thickness of the photosensitive layer 3 is preferably from 1 to 50 μm, more preferably from 5 to 25 μm.

<Protective layer>
As the protective layer 5, for example, a polymer film such as polyethylene, polypropylene, polyethylene terephthalate, and polyester can be used. Further, similarly to the support 1, a polymer film which has been subjected to a surface treatment with a surfactant or a resin may be used. From the viewpoint of flexibility in winding the dry film into a roll, the protective layer 5 is particularly preferably a polyethylene film. In addition, the protective layer 5 is preferably a low fisheye film so that dents on the surface of the photosensitive layer 3 can be reduced.

  The thickness of the protective layer 5 is preferably from 10 to 100 μm, particularly preferably from 15 to 80 μm.

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment has a component (A): a resin having a phenolic hydroxyl group and a component (B): at least one selected from the group consisting of an aromatic ring, a heterocyclic ring, and an alicyclic ring. And a compound having a methylol group or an alkoxyalkyl group, and a component (G): one or both components of a silane coupling agent, and a component (C): an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and a hydroxyl group. And an aliphatic compound having two or more functional groups selected from the group consisting of (A) and (D): a photosensitive acid generator. Further, the photosensitive resin composition of the present embodiment may contain, if necessary, a component (E): a solvent, a component (F): an inorganic filler, a component (H): a sensitizer, a component (I): an amine, The component (J) may include an organic peroxide, and the component (K) may include a leveling agent.

  The present inventors consider that the photosensitive resin composition of the present embodiment can form a resin pattern having excellent resolution and heat resistance as follows. First, in the unexposed area, the solubility of the component (A) in the developing solution is significantly improved by the addition of the component (C). Next, in the exposed portion, the acid generated from the component (D) causes not only the methylol group or the alkoxyalkyl group in the component (B) to react with the component (C), but also to the phenolic hydroxyl group in the component (A). In addition, the solubility of the photosensitive resin composition in a developing solution is significantly reduced. Thereby, when developed, sufficient resolution is obtained due to a remarkable difference in solubility of the unexposed portion and the exposed portion in the developing solution. Further, by the heat treatment of the pattern after development, the reaction of the component (B) and the component (G) with the component (C) or the component (A) further proceeds to obtain a resin pattern having sufficient heat resistance. The present inventors speculate.

<(A) component>
The resin having a phenolic hydroxyl group as the component (A) is not particularly limited, but is preferably a resin soluble in an aqueous alkali solution, and particularly preferably a novolak resin from the viewpoint of improving resolution. Such a novolak resin is obtained by condensing phenols and aldehydes in the 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 and the like.

  Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.

  Specific examples of such a novolak resin include a phenol / formaldehyde condensed novolak resin, a cresol / formaldehyde condensed novolak resin, and a phenol-naphthol / formaldehyde condensed novolak resin.

  The component (A) other than the novolak resin includes, for example, polyhydroxystyrene and a copolymer thereof, a phenol-xylylene glycol condensed resin, a cresol-xylylene glycol condensed resin, a phenol-dicyclopentadiene condensed resin, and the like. Can be The component (A) can be used alone or in combination of two or more.

  The component (A) preferably has a weight average molecular weight of 100,000 or less, more preferably 1,000 to 80,000, from the viewpoint of further improving the resolution, developability, thermal shock resistance, heat resistance, and the like of the obtained resin pattern. More preferably, it is more preferably 2,000 to 50,000, particularly preferably 2,000 to 20,000, and most preferably 5,000 to 15,000. "Weight average molecular weight" refers to a value measured using a calibration curve with standard polystyrene according to a gel permeation chromatography (GPC) method, and more specifically, a pump (manufactured by Hitachi, Ltd., L -6200), columns (TSKgel-G5000HXL and TSKgel-G2000HXL, both manufactured by Tosoh Corporation, trade name) and a detector (Hitachi, Ltd., model L-3300RI) using tetrahydrofuran as an eluent. The measurement is performed at a temperature of 30 ° C. and a flow rate of 1.0 mL / min.

  In the photosensitive resin composition of the present embodiment, the content of the component (A) is based on 100 parts by mass of the total amount of the photosensitive resin composition (excluding the component (E) when the component (E) is used). It is preferably from 30 to 90 parts by mass, more preferably from 40 to 80 parts by mass. When the content of the component (A) is within this range, the photosensitive layer formed using the obtained photosensitive resin composition tends to have more excellent developability with an aqueous alkaline solution.

<(B) component>
The photosensitive resin composition of the present embodiment contains at least one of the component (B) and the component (G). The photosensitive resin composition of the present embodiment preferably contains both the component (B) and the component (G) from the viewpoint of adjusting the adhesive strength to the protective layer. The component (B) is a compound having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring, and an alicyclic ring, and having a methylol group or an alkoxyalkyl group. Here, the aromatic ring means a hydrocarbon group having aromaticity (for example, a hydrocarbon group having 6 to 10 carbon atoms), and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic ring means a cyclic group having at least one hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom (for example, a cyclic group having 3 to 10 carbon atoms), for example, a pyridine ring, an imidazole ring, Examples include a pyrrolidinone ring, an oxazolidinone ring, an imidazolidinone ring and a pyrimidinone ring. The alicycle means a cyclic hydrocarbon group having no aromaticity (for example, a cyclic hydrocarbon group having 3 to 10 carbon atoms), such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring and And a cyclohexane ring. An alkoxyalkyl group means a group in which an alkyl group is bonded to an alkyl group via an oxygen atom. The two alkyl groups may be different from each other, for example, an alkyl group having 1 to 10 carbon atoms.

  By containing the component (B), when the photosensitive layer after the formation of the resin pattern is heated and cured, the component (B) reacts with the component (A) to form a bridged structure, and the resin pattern becomes brittle. And deformation of the resin pattern can be prevented, and heat resistance can be improved. As the component (B), specifically, a compound further having a phenolic hydroxyl group or a compound further having a hydroxymethylamino group or an alkoxymethylamino group can be preferably used, and the components (A) and (C) The component is not included in the component (B). The component (B) can be used alone or in combination of two or more.

  As will be described later, when the photosensitive resin composition contains the component (D), an acid is generated by irradiation with actinic rays or the like. Due to the catalytic action of the generated acid, the alkoxyalkyl groups in the component (B) or the alkoxyalkyl groups in the component (B) react with the component (A) with dealcoholation to form a negative pattern. can do. Further, by the catalytic action of the generated acid, the methylol groups in the component (B) or the methylol groups in the component (B) react with the component (A) with dealcoholation, thereby forming a negative pattern. Can be formed. Incidentally, depending on the structure of the component (C), a negative pattern can be formed even if the photosensitive resin composition does not contain the component (B). From the viewpoint of forming a negative pattern having higher heat resistance, the photosensitive resin composition preferably contains the component (B).

  The “compound further having a phenolic hydroxyl group” used as the component (B) has a methylol group or an alkoxyalkyl group, and thus can be used not only for the reaction with the component (C) or the component (A) but also for development with an aqueous alkali solution. Can increase the dissolution rate of the unexposed portion of the film, thereby improving the sensitivity. The molecular weight of the compound having a phenolic hydroxyl group is preferably from 94 to 2,000 in terms of weight-average molecular weight, and from 108 to 2,000 in consideration of improving the solubility in an aqueous alkali solution, photosensitivity, and mechanical properties in a well-balanced manner. Is more preferable, and it is more preferable that it is 108-1500. When it is difficult to measure a compound having a low molecular weight by the above-described method for measuring the weight average molecular weight, the molecular weight can be measured by another method and the average can be calculated.

一般式（１）中、Ｚは単結合又は２価の有機基を示し、Ｒ^２４及びＲ^２５はそれぞれ独立に水素原子又は１価の有機基を示し、Ｒ^２６及びＲ^２７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。ここで、１価の有機基としては、例えば、メチル基、エチル基、プロピル基等の炭素原子数が１〜１０であるアルキル基；ビニル基等の炭素原子数が２〜１０であるアルケニル基；フェニル基等の炭素原子数が６〜３０であるアリール基；これら炭化水素基の水素原子の一部又は全部をフッ素原子等のハロゲン原子で置換した基が挙げられる。Ｒ^２４〜Ｒ^２７が複数ある場合には、互いに同一でも異なっていてもよい。 As the compound having a phenolic hydroxyl group, a conventionally known compound can be used. However, the compound represented by the following general formula (1) has a dissolving promoting effect on an unexposed portion and an effect upon curing of the photosensitive resin film. It is preferable because the balance of the effect of preventing melting is excellent.

In the general formula (1), Z represents a single bond or a divalent organic group, R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a monovalent organic group, and R ²⁶ and R ²⁷ each independently represent 1 A and b each independently represent an integer of 1 to 3; c and d each independently represent an integer of 0 to 3; Here, 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 a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms. When there are a plurality of R ^{24 to} R ²⁷ , they may be the same or different.

一般式（２）中、Ｘ^１は単結合又は２価の有機基を示し、複数のＲは、それぞれ独立にアルキル基（例えば、炭素原子数が１〜１０のアルキル基）を示す。 The compound represented by the general formula (1) is preferably a compound represented by the general formula (2).

In Formula (2), X ¹ represents a single bond or a divalent organic group, and a plurality of Rs each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

一般式（３）中、複数のＲは、それぞれ独立にアルキル基（例えば、炭素原子数が１〜１０のアルキル基）を示す。 Further, as the compound having a phenolic hydroxyl group, a compound represented by the general formula (3) may be used.

In the general formula (3), a plurality of Rs each independently represents an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

  In the general formula (1), the compound in which Z is a single bond is a biphenol (dihydroxybiphenyl) derivative. 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; and 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; a group in which some or all of the hydrogen atoms of these hydrocarbon groups have been substituted with halogen atoms such as a fluorine atom; a sulfonyl group; a carbonyl group; A sulfide bond; an amide bond. Among them, Z is preferably a divalent organic group represented by the following general formula (4).

一般式（４）中、Ｘ^２は、単結合、アルキレン基（例えば、炭素原子数が１〜１０のアルキレン基）、アルキリデン基（例えば、炭素原子数が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、スルフィド結合又はアミド結合を示す。Ｒ^２８は、水素原子、水酸基、アルキル基（例えば、炭素原子数が１〜１０のアルキル基）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^２８及びＸ^２は互いに同一でも異なっていてもよい。ここで、ハロアルキル基とは、ハロゲン原子で置換されたアルキル基を意味する。

In the general formula (4), X ² represents 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), A group in which part or all of hydrogen atoms are substituted with halogen atoms, a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond, or an amide bond. R ²⁸ represents a hydrogen atom, a hydroxyl group, an alkyl group (for example, 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 R ²⁸ and X ² may be the same or different from each other. Here, the haloalkyl group means an alkyl group substituted with a halogen atom.

  Examples of the compound having a hydroxymethylamino group or an alkoxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (Poly) (N-hydroxymethyl) urea and the like. Further, a nitrogen-containing compound in which all or a part of the hydroxymethylamino group of these compounds is alkyl-etherified may be used. Here, the alkyl group of the alkyl ether includes a methyl group, an ethyl group, a butyl group or a mixture thereof, and may contain an oligomer component which is partially self-condensed. Specific examples include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, and tetrakis (methoxymethyl) urea.

一般式（５）中、複数のＲは、それぞれ独立にアルキル基（例えば、炭素原子数が１〜１０のアルキル基）を示す。

一般式（６）中、複数のＲは、それぞれ独立にアルキル基（例えば、炭素原子数が１〜１０のアルキル基）を示す。 Specifically, the compound having an alkoxymethylamino group is preferably a compound represented by the general formula (5) or a compound represented by the general formula (6).

In Formula (5), a plurality of Rs each independently represent an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms).

In the general formula (6), a plurality of Rs each independently represents an alkyl group (for example, 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, and more preferably 10 to 35 parts by mass with respect to 100 parts by mass of the component (A). Is particularly preferred. When the content of the component (B) is 5 parts by mass or more, the reaction in the exposed portion becomes sufficient, so that the resolution is not easily reduced, and the chemical resistance and the heat resistance tend to be good. When the content is less than the above, the photosensitive resin composition is easily formed on a desired support, and the resolution tends to be good.

<(C) component>
Component (C): an aliphatic compound having two or more functional groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and a hydroxyl group is an adhesive between the photosensitive resin composition and the support. Properties, that is, tackiness. Further, it is possible to increase the dissolution rate of an unexposed portion when developing with an alkaline aqueous solution, thereby improving the resolution. The component (C) may have two or more different types of functional groups one by one, or may have two or more types of functional groups. From the viewpoints of tackiness and solubility in an aqueous alkali solution, the molecular weight of the component (C) is preferably 92 to 2000, more preferably 106 to 1500, and more preferably 134 to 1500 in terms of weight average molecular weight in consideration of the balance. Particularly preferred is 1300. The “aliphatic compound” refers to a compound whose main skeleton is an aliphatic skeleton and does not contain an aromatic ring or an aromatic heterocyclic ring.

［一般式（７）〜（１０）中、Ｒ^１、Ｒ^５、Ｒ^１６及びＲ^１９は、それぞれ水素原子、メチル基、エチル基、水酸基又は一般式（１１）で表される基を示し、Ｒ^２１は水酸基、グリシジルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を示し、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１７、Ｒ^１８及びＲ^２０は、それぞれ水酸基、グリシジルオキシ基、アクリロイルオキシ基、メタクリロイルオキシ基、一般式（１２）で表される基又は一般式（１３）で表される基を示し、Ｒ^２２及びＲ^２３はそれぞれ水酸基、グリシジルオキシ基、アクリロイルオキシ基又はメタクリロイルオキシ基を示し、ｎ及びｍはそれぞれ１〜１０の整数である。］ 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, and even more preferably an acryloyloxy group. The component (C) preferably has three or more of the above functional groups. The upper limit of the number of the functional groups is not particularly limited, but is, for example, twelve. Specific examples of the component (C) include compounds represented by general formulas (7) to (10).

[In the general formulas (7) to (10), R ¹ , R ⁵ , R ¹⁶ and R ¹⁹ each represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group or a group represented by the general formula (11); R ²¹ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, and R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ^{12 13} , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ²⁰ are each a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the general formula (12) or a general formula (13) a group represented, respectively, R ²² and R ²³ represents a hydroxyl group, a glycidyloxy group, acryloyloxy group or methacryloyloxy indicates an oxy group, an integer der respectively n and m 1 to 10 . ]

  Examples of the compound having a glycidyloxy group include, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl. Ether, glycerin diglycidyl ether, dipentaerythritol hexaglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, glycerin triglycidyl ether, Glycerol propoxylate Triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, and the like diglycidyl 1,2-cyclohexane dicarboxylate. These compounds having a glycidyloxy group can be used alone or in combination of two or more.

  Among the compounds having a glycidyloxy group, trimethylolethane triglycidyl ether or trimethylolpropane triglycidyl ether is preferable in terms of excellent sensitivity and resolution.

  Compounds having a glycidyloxy group include, for example, Epolite 40E, Epolite 100E, Epolite 70P, Epolite 200P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.), alkyl epoxy Resin ZX-1542 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, and Denacol EX-850L (Nagase Chemtech Co., Ltd.) (Trade name, product name).

  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, and 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 Trimethylol B bread acrylate, trimethylolpropane acrylate, EO-modified glycerol tri acrylate, PO-modified glycerol triacrylate, glycerin triacrylate. These compounds having an acryloyloxy group can be used alone or in combination of two or more. 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 ditrimethylolpropanetetramethacrylate, and 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 DOO, PO-modified trimethylolpropane dimethacrylate, trimethylolpropane dimethacrylate, EO modified glycerol trimethacrylate, PO-modified glycerol trimethacrylate, glycerine trimethacrylate and the like. These compounds having a methacryloyloxy group can be used alone or in combination of two or more. EO represents an ethyleneoxy group, and PO represents a propyleneoxy group.

  Examples of the compound having a hydroxyl group include polyhydric alcohols such as dipentaerythritol, pentaerythritol and glycerin. These compounds having a hydroxyl group can be used alone or in combination of two or more.

  The content of the component (C) is preferably 20 to 70 parts by mass, more preferably 25 to 65 parts by mass, and more preferably 35 to 55 parts by mass with respect to 100 parts by mass of the component (A). Is particularly preferred. When the content of the component (C) is at least 20 parts by mass, crosslinking in the exposed portion will be sufficient, and the peeling force between the protective layer and the photosensitive layer tends to be sufficient. It becomes easy to form a film of the resin composition on a desired support, and the resolution is not easily reduced.

<(D) component>
The photosensitive acid generator as the component (D) is a compound that generates an acid upon irradiation with actinic rays or the like. Further, not only do the components (B) react with each other due to the generated acid, but also the component (B) also reacts with the component (A) or the component (C), thereby lowering the solubility of the photosensitive resin composition in a developing solution. By doing so, a negative pattern can be formed. In the case where the component (C) is a compound having an acryloyloxy group or a methacryloyloxy group, the radical polymerization of the acryloyloxy group or the methacryloyloxy group proceeds by irradiation with actinic rays or the like.

  The component (D) is not particularly limited as long as it is a compound capable of generating an acid upon irradiation with actinic rays or the like. And the like. Especially, it is preferable to use an onium salt compound or a sulfonimide compound from a viewpoint of 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, specific examples thereof will be described.

Onium salt compounds:
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 diaryliodonium salts such as diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, and diphenyliodonium tetrafluoroborate; triphenylsulfonium Triarylsulfonium salts such as trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate and triphenylsulfonium hexafluoroantimonate; 4-t-butylphenyl-diphenylsulfonium trifluoromethanesulfonate; 4-t-butylphenyl-diphenylsulfonium p- Toluenesulfonate; 4,7 And di -n- butoxy naphthyl tetrahydrothiophenium trifluoromethanesulfonate, and the like.

Sulfonimide compound:
Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, and N- (trifluoromethylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (p-toluenesulfonyloxy) -1,8- And 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 that the sensitivity and the resolution are more excellent. . The component (D) can be used alone or in combination of two or more.

  The content of the component (D) is from 0.1 to 100 parts by mass of the component (A) from the viewpoint of improving the sensitivity, resolution, pattern shape, and the like of the photosensitive resin composition of the present embodiment. It is preferably from 1 to 15 parts by mass, more preferably from 0.3 to 10 parts by mass.

<(E) component>
The photosensitive resin composition of the present embodiment may further contain a solvent as the component (E) in order to improve the handleability of the photosensitive resin composition and to adjust the viscosity and storage stability. it can. The component (E) is preferably an organic solvent. The type of such an organic solvent is not particularly limited as long as it can exert the above-mentioned performance, but, for example, 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 dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, and propylene glycol dibutyl ether Propylene glycol dialkyl ethers such as propylene glycol Propylene glycol monoalkyl ether acetates such as coal 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 esters such as methyl lactate, ethyl lactate, n-propyl lactate, and isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, and propionate Aliphatic carboxylic acid esters such as n-butyl acid and isobutyl propionate; methyl 3-methoxypropionate, 3-methoxy Other esters such as ethyl lopionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; 2-butanone, 2-heptanone, 3 Ketones such as -heptanone, 4-heptanone and cyclohexanone; amides such as N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone. These organic solvents can be used alone or in combination of two or more.

  The content of the component (E) is preferably from 30 to 200 parts by mass, more preferably from 60 to 120 parts by mass, based on 100 parts by mass of the photosensitive resin composition excluding the component (E). preferable.

<(F) component>
The photosensitive resin composition of this embodiment can reduce the thermal expansion coefficient of the obtained cured film according to the content of the component (F) by including an inorganic filler as the component (F). As the component (F), one type can be used alone, or two or more types can be used in combination. When any of the inorganic fillers is dispersed in the resin composition, it is preferable that the maximum particle diameter is dispersed to 2 μm or less.

  Examples of the inorganic filler include aluminum compounds such as aluminum oxide and aluminum hydroxide; alkali metal compounds; alkaline earth metal compounds such as calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, and magnesium hydroxide; talc And inorganic compounds derived from mines such as mica; silica such as fused spherical silica, fused and ground silica, fumed silica, and sol-gel silica. These can be pulverized by a pulverizer, classified in some cases, and dispersed with a maximum particle diameter of 2 μm or less.

Any kind of inorganic filler can be used, but silica is preferable as the inorganic filler. The silica preferably has a coefficient of thermal expansion of 5.0 × 10 ⁻⁶ / ° C. or less. From the viewpoint of the particle size, silica such as fused spherical silica, fumed silica, and sol-gel silica is preferable, and fumed silica is preferable. Alternatively, sol-gel silica is more preferred. As silica, it is desirable to use silica (nano-silica) having an average primary particle diameter in the range of 5 nm to 100 nm. These are preferably dispersed in the photosensitive resin composition at a maximum particle size of 2 μm or less. At that time, a silane coupling agent can be used to disperse the resin in the resin without agglomeration.

  When measuring the particle size of each inorganic filler, it is desirable to use a known particle size distribution meter. For example, irradiating a particle group with laser light and calculating the particle size distribution by calculation from the intensity distribution pattern of the diffracted and scattered light emitted from the particle group. A particle size distribution analyzer for nanoparticles for which the distribution is to be obtained can be used. In addition, the maximum particle diameter is a maximum particle diameter of the inorganic filler in a state of being dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows. First, after diluting (or dissolving) the photosensitive resin composition 1000-fold with methyl ethyl ketone, using a submicron particle analyzer (trade name: N5, manufactured by Beckman Coulter, Inc.) in accordance with the international standard ISO 13321. The particles dispersed in the solvent are measured at a refractive index of 1.38, and the particle diameter at an integrated value of 99.9% (by volume) in the particle size distribution is defined as the maximum particle diameter. Further, even if the photosensitive layer or the cured film of the photosensitive resin composition provided on the support is diluted (or dissolved) to 1000 times (volume ratio) with a solvent as described above, It can be measured using a micron particle analyzer.

  The content of the component (F) is preferably from 1% by mass to 70% by mass, and more preferably from 3% by mass to 65% by mass, based on the total amount of the photosensitive resin composition excluding the component (E). Is more preferable.

  The inorganic filler used in this embodiment preferably has an average primary particle size of 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 primary particle size is 100 nm or less, the resin composition is less likely to be clouded, exposure light is more likely to pass through the resin composition, unexposed portions are more easily removed, and resolution tends not to be reduced. There is.

  The average primary particle diameter is a value obtained by conversion from the BET specific surface area.

<(G) component>
The photosensitive resin composition of the present embodiment contains at least one of the component (B) and the component (G). The photosensitive resin composition of the present embodiment preferably contains both the component (B) and the component (G) from the viewpoint of adjusting the adhesive strength to the protective layer. When the photosensitive resin composition contains a silane coupling agent as the component (G), the adhesive strength between the photosensitive layer and the substrate after the formation of the resin pattern can be improved.

  As the component (G), generally available ones can be used, for example, alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acryloyl silane, methacryloyl silane, mercapto silane, sulfide silane, isocyanate silane, Sulfur silane, styryl silane and alkyl chloro silane can be used.

  Specific examples of the component (G) include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, and isobutyl. Trimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, Diphenyldimethoxysilane, triphenylsilanol, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, n-octyl Methylchlorosilane, 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, Nyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane, aminosilane, and the like.

  As the component (G), an epoxysilane having one or more glycidyloxy groups is preferable, and an epoxysilane having a trimethoxysilyl group or a triethoxysilyl group is more preferable. Further, acryloylsilane or methacryloylsilane may be used.

  The content of the component (G) is preferably 1 to 20 parts by mass, more preferably 3 to 10 parts by mass, per 100 parts by mass of the component (A).

<(H) component>
The photosensitive resin composition of the present embodiment may contain a sensitizer as the component (H). Examples of the sensitizer include 9,10-dibutoxyanthracene. The component (H) can be used alone or in combination of two or more. By containing the component (H), the photosensitivity of the photosensitive resin composition can be improved.

  The content of the component (H) is preferably from 0.01 to 1.5 parts by mass, more preferably from 0.05 to 0.5 parts by mass, per 100 parts by mass of the component (A). .

  Further, the photosensitive resin composition of the present embodiment contains, in addition to the component (A), a phenolic low-molecular compound having a molecular weight of less than 1,000 (hereinafter, referred to as “phenol compound (a)”). Is also good. Examples of the phenol compound (a) include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenylether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenyl Ethane, 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 and the like. These phenol compounds (a) can be contained in the range of 0 to 40% by mass, particularly 0 to 30% by mass, based on the component (A).

  Further, the photosensitive resin composition of the present embodiment may contain other components other than the above-described components. Examples of the other components include an inhibitor for a reaction accompanying irradiation with actinic rays, an adhesion aid, and the like.

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

  First, a photosensitive layer is formed on a substrate on which a resist is to be formed (a copper foil with a resin, a copper-clad laminate, a silicon wafer with a metal sputtered film, an alumina substrate, etc.) using the above-described photosensitive resin composition. I do. Examples of the method of forming the photosensitive layer include a method of transferring the photosensitive layer in the above-described dry film onto a substrate.

Next, the photosensitive layer is exposed to a predetermined pattern through a predetermined mask pattern. The actinic rays used for exposure include, for example, rays of a g-ray stepper; ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and an i-ray stepper; an electron beam; a laser beam; The thickness is appropriately selected depending on the thickness of the photosensitive layer and the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the thickness is about 100 to 5000 mJ / cm ² when the thickness of the photosensitive layer is 10 to 50 μm.

  Further, a heat treatment (post-exposure bake) is performed after the exposure. By performing post-exposure baking, the curing reaction between the component (A) and the component (B) by the generated acid can be promoted. The conditions of the post-exposure bake vary depending on the composition of the photosensitive resin composition, the content of each component, the thickness of the photosensitive layer, and the like, but it is usually preferable to heat at 70 to 150 ° C. for 1 to 60 minutes, It is more preferable to heat at a temperature of 1 to 60 minutes.

  Next, the exposed and / or post-exposure-baked photosensitive layer is developed with an alkaline developer to dissolve and remove the unexposed area to obtain a desired resin pattern. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The development conditions are usually 20 to 40 ° C. for 1 to 10 minutes.

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

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

  In addition, heating can be performed in two stages in order to allow the curing to proceed sufficiently or to prevent deformation of the obtained resin pattern shape. For example, in the first stage, heating may be performed at 50 to 120 ° C for 5 minutes to 2 hours, and in the second stage, heating may be performed at 80 to 200 ° C for 10 minutes to 10 hours for curing.

  As long as the curing conditions are as described above, the heating equipment is not particularly limited, and a general oven, an infrared furnace, or the like can be used.

[Multilayer printed wiring board]
The cured product containing the photosensitive resin composition of the present embodiment can be suitably used, for example, as a solder resist and / or an interlayer insulating film in a multilayer printed wiring board. FIG. 2 is a diagram illustrating 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. 2F has a wiring pattern on the surface and inside. Hereinafter, a method of manufacturing the multilayer printed wiring board 100A according to an embodiment of the present disclosure will be briefly described with reference to FIG.

  First, an interlayer insulating film 103 is formed on both surfaces of a substrate 101 having a wiring pattern 102 on the surface (see FIG. 2A). The interlayer insulating film 103 may be formed by printing the photosensitive resin composition using a screen printing machine or a roll coater, or preparing the above-described dry film in advance and using a laminator to form the dry film. The photosensitive layer can also be formed by adhering to the surface of a 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. 2B). Smear (residue) around the opening 104 is removed by desmear processing. Next, the seed layer 105 is formed by an electroless plating method (see FIG. 2C). A photosensitive layer containing a photosensitive resin composition for semi-additive is laminated on the seed layer 105, and a predetermined portion is exposed and developed to form a resin pattern 106 (see FIG. 2D). An adhesion layer, for example, a titanium layer having a thickness of about 30 nm is formed on the seed layer, and a Cu layer having a thickness of about 100 nm is further formed. These adhesion layers can be formed by a sputtering method. Next, a wiring pattern 107 is formed by electroplating on a portion of the seed layer 105 where the resin pattern 106 is not formed, and after removing the resin pattern 106 by peeling off the liquid, the seed layer 105 is removed by etching (FIG. 2 (e)). The above operation is repeated to form a solder resist 108 made of a cured product of the above-described photosensitive resin composition on the outermost surface, whereby the multilayer printed wiring board 100A can be manufactured (see FIG. 2F).

  In the multilayer printed wiring board 100A obtained in this way, a semiconductor element is mounted at a corresponding portion, and electrical connection can be secured.

  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, “parts” is used to mean “parts by mass” unless otherwise specified.

(Examples 1 to 10 and Comparative Examples 1 to 4)
<Preparation of photosensitive resin composition>
Compound (B-1, B-2) having two or more methylol groups or alkoxyalkyl groups and having an aromatic ring, a heterocyclic ring or an alicyclic ring per 100 parts by mass of the novolak resin (A-1, A-2). -2), epoxy resin, acryloyl compound and methacryloyl compound (C-1, C-2, C-3), photosensitive acid generator (D-1), solvent (E-1), inorganic filler (F- 1) and the silane coupling agent (G-1) were blended in the predetermined amounts shown in Table 1 to obtain photosensitive resin compositions used for producing dry films of Examples 1 to 10 and Comparative Examples 1 to 4. Was.

<Preparation of dry film>
The photosensitive resin composition is coated on a polyethylene terephthalate film (manufactured by Teijin DuPont Films, product name: Purex A53) (support) so that the thickness of the photosensitive resin composition is uniform, It was dried for 10 minutes with a hot air convection dryer at 90 ° C. to form a photosensitive layer having a thickness of 25 μm or 40 μm after drying. On this photosensitive layer, a polyethylene film (manufactured by Tamapoly Co., Ltd., product name: NF-15) was laminated as a protective layer, and the support, the photosensitive layer, and the protective layer were laminated in this order. Dry films of No. 10 and Comparative Examples 1 to 4 were obtained.

<Evaluation of peeling force>
From the obtained dry film (thickness of the photosensitive layer: 25 μm), a sample having a width of 2 cm and a length of 8 cm was cut out. The samples were fixed with double-sided tape on the pedestal so protective layer is surface side, force gauge (RHEOTECH Co., product name: RT C -3010D-CW) the protective layer from the sample using a 23 The peeling force between the photosensitive layer and the protective layer when the sample was peeled from one end in the longitudinal direction at 180 ° C. at a pulling speed of 5 cm / min at a temperature of 5 ° C. was measured. The measurement was performed five times, and the average value was obtained. Table 1 shows the results.

<Evaluation of film handling>
The above-mentioned dry film (thickness of the photosensitive layer: 25 μm) having a width of 560 mm and a length of 10 m was prepared, wound around a winding core having an outer diameter of 83 mm, and collected. Thereafter, the dry film was unwound and the protective layer was peeled off. When the destruction of the photosensitive layer was observed at the time of peeling of the protective layer, it was evaluated as "x", and when it was not observed, as "o". Table 1 shows the results.

<Evaluation of developability and resolution>
The dry film was laminated on a 6-inch silicon wafer so that the photosensitive layer was in contact with the silicon surface while peeling off the protective layer of the dry film (photosensitive layer thickness: 25 μm). Next, the support was peeled off to form a uniform photosensitive layer having a thickness of 25 μm on the silicon. Lamination was performed using a 120 ° C. heat roll at a pressure of 0.4 MPa and a roll speed of 1.0 m / min. The formed photosensitive layer was subjected to reduced projection exposure with an i-line (365 nm) through a mask using an i-line stepper (trade name: FPA-3000iW, manufactured by Canon Inc.). As the mask, a mask having a pattern in which the width of the exposed portion and the unexposed portion was 1: 1 from 2 μm: 2 μm to 30 μm: 30 μm in steps of 1 μm was used. 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 was heated at 65 ° C. for 1 minute and then at 95 ° C. for 4 minutes (post-exposure bake), and the shortest development time using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (the unexposed portion was Developing by immersion for a time corresponding to twice the shortest time of removal (the shortest time to be removed), the unexposed part was removed, and development processing was performed. After the development, the formed resin pattern was observed using a metallographic microscope. The smallest space width in the range where the exposure amount is 100 to 3000 mJ / cm ² , of the pattern in which the space portion (unexposed portion) is cleanly removed and the line portion (exposed portion) is formed without meandering or chipping. Was evaluated as the minimum resolution. Table 1 shows the results.

<Evaluation of heat resistance>
The protective layer of the dry film in which the thickness of the photosensitive layer was 40 μm was peeled off, and the irradiation energy was 3000 mJ using an exposure machine (manufactured by Oak Manufacturing Co., Ltd., trade name: EXM-1201) having a high-pressure mercury lamp. / Cm ² to expose the photosensitive layer. The exposed photosensitive layer is heated on a hot plate at 65 ° C. for 2 minutes, then at 95 ° C. for 8 minutes, and heated at 180 ° C. for 60 minutes in a hot air convection dryer, and the support is peeled off and cured. A membrane was obtained. Using a thermomechanical analyzer (manufactured by Seiko Instruments Inc., trade name: TMA / SS6000), the amount of thermal expansion of the cured film when the temperature was increased at a heating rate of 5 ° C./min was measured, and the curve was obtained. Was obtained as the glass transition temperature Tg. Table 1 shows the results.

A-1: Cresol novolak resin (trade name: TR4020G, manufactured by Asahi Organic Materials Industry Co., Ltd.)
A-2: Cresol novolak resin (trade name: TR4080G, manufactured by Asahi Organic Materials Industry Co., Ltd.)
B-1: 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name: MX-270)
B-2: 4,4 '-(1,1,1,3,3,3-hexafluoroisopropylidene) bis [2,6-bis (hydroxymethyl) phenol] (commercially available from Honshu Chemical Industry Co., Ltd.) (Name: TML-BPAF)
C-1: Trimethylolpropane triglycidyl ether (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name: ZX-1542, see the following formula (14))

C-2: Trimethylolpropane triacrylate (trade name: TMPTA, manufactured by Nippon Kayaku Co., Ltd.)
C-3: pentaerythritol triacrylate (trade name: PET-30, manufactured by Nippon Kayaku Co., Ltd.)
D-1: Triarylsulfonium salt (manufactured by San Apro Co., Ltd., trade name: CPI-310B)
E-1: methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd., trade name: 2-butanone)
G-1: 3-glycidoxypropyltriethoxysilane (Shin-Etsu Silicone Co., Ltd., trade name: KBM-403).

  As is clear from Table 1, the dry films of Comparative Examples 1 to 3 had a peeling force between the photosensitive layer and the protective layer outside the range of 0.5 to 10 N / m, and had a problem in handling. In addition, since the dry film of Comparative Example 3 could not form a pattern, Tg was not measured. In the dry film of Comparative Example 4, the cured film of the photosensitive layer had a low Tg, and had insufficient heat resistance. On the other hand, in the dry films of Examples 1 to 10, the peeling force between the photosensitive layer and the protective layer was in the range of 0.5 to 10 N / m, the handleability was good, and the thickness of the photosensitive layer was 20 μm. It has been confirmed that the composition has excellent developability and resolution which can form a fine pattern having a space width of 9 μm or less even when the thickness exceeds the limit, and has high heat resistance (Tg).

  The dry film of the present invention is applied as a material used for 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 element or the like. In particular, since the dry film has good resolution and heat resistance after curing, the dry film is suitably used for a high-density package substrate or the like having a thinner and higher density.

  DESCRIPTION OF SYMBOLS 1 ... Support, 3 ... Photosensitive layer, 5 ... Protective layer, 10 ... Dry film, 100A ... Multilayer printed wiring board, 101 ... Base material, 102, 107 ... Wiring pattern, 103 ... Interlayer insulating film, 104 ... Opening, 105: seed layer; 106: resin pattern; 108: solder resist.

Claims (6)

A dry film comprising a support, a photosensitive layer formed using the photosensitive resin composition, and a protective layer in this order,
The photosensitive resin composition,
(A) component: a resin having a phenolic hydroxyl group;
Component (B): a compound having at least one selected from the group consisting of an aromatic ring, a heterocyclic ring, and an alicyclic ring, and having a methylol group or an alkoxyalkyl group ;
(G) component: a silane coupling agent ,
Component (C): an aliphatic group represented by the following general formulas (7) to (10) having at least two functional groups selected from an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and a hydroxyl group. A compound;
(D) component: a photosensitive acid generator,
Containing
The photosensitive resin composition contains 20 to 70 parts by mass of the component (C) based on 100 parts by mass of the component (A),
A sample cut into a width of 2 cm and a length of 8 cm from the dry film was fixed on a pedestal such that the protective layer was on the front side, and the protective layer was cut from the sample at a temperature of 23 ° C. and a pulling rate of 5 cm / min. A dry film, wherein a peeling force between the photosensitive layer and the protective layer when peeled off from one end in a length direction of the sample in a direction of 180 ° is 0.5 to 10 N / m.

[In the general formulas (7) to (10), R ¹ , R ⁵ , R ¹⁶ and R ¹⁹ each represent a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group or a group represented by the general formula (11); R ²¹ represents a hydroxyl group, a glycidyloxy group, an acryloyloxy group or a methacryloyloxy group, and R ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ^{12 13} , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ and R ²⁰ are each a hydroxyl group, a glycidyloxy group, an acryloyloxy group, a methacryloyloxy group, a group represented by the general formula (12) or a general formula (13) a group represented, respectively, R ²² and R ²³ represents a hydroxyl group, a glycidyloxy group, acryloyloxy group or methacryloyloxy indicates an oxy group, an integer der respectively n and m 1 to 10 . ]   The dry film according to claim 1, wherein the peeling force between the photosensitive layer and the protective layer is 0.5 to 6 N / m. The component (C) has the functional group of three or more, dry film according to claim 1 or 2. Cured product obtained by using a photosensitive layer in a dry film of any one of claims 1-3. A semiconductor device comprising the cured product according to claim 4 as a surface protective film or an interlayer insulating film. A step of forming a photosensitive layer on a substrate using the dry film according to any one of claims 1 to 3 ,
Exposing the photosensitive layer to a predetermined pattern, and performing a heat treatment after exposure,
Developing the photosensitive layer after the heat treatment, and heat-treating the obtained resin pattern,
And a method of forming a resist pattern.

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