JP2016133661A - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having excellent opening property even when a fine opening is to be formed.SOLUTION: The photosensitive resin composition is to be used for a method for manufacturing such a structure that an insulation layer formed on a surface of a substrate having a conductor circuit has an opening and that a wiring part connected to the conductor circuit is formed in the opening. The photosensitive resin composition comprises a binder polymer, a specific photopolymerizable compound, and a photopolymerization initiator.SELECTED DRAWING: None

Description

  The present disclosure relates to a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a structure.

  In the field of manufacturing a printed wiring board which is one of structures having a conductor circuit, a photosensitive resin composition is widely known as a resist material used for etching or plating.

  A printed wiring board is, for example, a structure in which a plurality of wiring layers are formed on a core board, a copper clad laminate as a core board, an interlayer insulating material provided between each wiring layer, and a solder provided on the outermost surface. And a resist. A semiconductor element is usually mounted on a printed wiring board via a die bonding material or an underfill material. In addition, if necessary, the entire surface may be sealed with a transfer sealing material, or a metal cap (lid) for the purpose of improving heat dissipation may be attached. In recent years, semiconductor devices have become lighter and shorter, and the density of semiconductor elements and multilayer printed wiring boards has been increasing. Further, packaging forms such as a package-on-package in which a semiconductor device is stacked on a semiconductor device are actively performed, and it is expected that the mounting density of the semiconductor device will be further increased in the future.

  It is necessary to provide vias (openings) for electrically connecting the upper and lower wiring layers in the interlayer insulating material of the printed wiring board. If the number of flip chip pins mounted on a printed wiring board increases, it is necessary to provide openings corresponding to the number of pins. However, the conventional printed wiring board has a low mounting density, and the semiconductor to be mounted Since the number of pins of the element is designed from several thousand pins to around 10,000 pins, it is not necessary to provide openings with a small diameter and a narrow pitch.

  However, as miniaturization of semiconductor elements progresses and the number of pins increases from tens of thousands of pins to hundreds of thousands of pins, the openings formed in the interlayer insulating material of the printed wiring board are also narrowed in accordance with the number of pins of the semiconductor elements. There is a growing need. Recently, for example, as in the method shown in FIG. 1, development of a printed wiring board in which an opening is formed by a laser using a thermosetting resin material (for example, see Patent Documents 1 to 4 below).

  FIG. 1 is a schematic view showing a conventional method for manufacturing a multilayer printed wiring board. The multilayer printed wiring board 100 shown in FIG. 1F has a wiring pattern on the surface and inside. The multilayer printed wiring board 100 is obtained by laminating a copper-clad laminate, an interlayer insulating material, a metal foil, and the like and appropriately forming a wiring pattern by an etching method or a semi-additive method.

  A multilayer printed wiring board is manufactured as follows, for example. First, an interlayer insulating layer 103 is formed on both surfaces of a copper clad laminate 101 having a wiring pattern 102 on the surface (see FIG. 1A). As a method for forming the interlayer insulating layer 103, a thermosetting resin composition may be printed using a screen printer or a roll coater, or a film made of the thermosetting resin composition is prepared in advance, and a laminator is used. This film can also be attached to the surface of a printed wiring board. Next, an opening 104 is formed using a YAG laser or a carbon dioxide gas laser in a place that needs to be electrically connected to the outside, and a smear (residue) around the opening 104 is removed by a desmear process (FIG. 1B). reference). Next, the seed layer 105 is formed by an electroless plating method (see FIG. 1C). Further, a photosensitive resin composition is laminated on the seed layer 105 to form a photosensitive resin composition layer (photosensitive resin composition layer forming step). And the actinic ray is irradiated to the predetermined part of the photosensitive resin composition layer, and an exposure part is hardened (exposure process). Then, the pattern (resist pattern) 106 of the photosensitive resin layer which consists of the hardened | cured material of the photosensitive resin composition is formed by removing (developing) an unexposed part (development process, refer FIG.1 (d)). Next, a wiring pattern (circuit) 107 is formed by an electrolytic plating method (circuit formation step). And the hardened | cured material (pattern of the photosensitive resin layer) 106 of the photosensitive resin composition is peeled and removed with a peeling liquid (peeling process process). Further, the seed layer 105 is removed by etching (see FIG. 1E). The multilayer printed wiring board 100 can be manufactured by repeating the above and forming the solder resist 108 on the outermost surface (see FIG. 1F). In the multilayer printed wiring board 100 obtained in this way, semiconductor elements are mounted at corresponding locations, and electrical connection can be ensured.

  However, in the multilayer printed wiring board 100 manufactured by the method shown in FIG. 1, in addition to the need to introduce new equipment such as a laser, a large opening having a via diameter of 100 μm or more (for example, a cylindrical opening) In this case, the throughput decreases as the number of laser shots increases, and in the case of a minute opening (for example, a cylindrical opening) having a via diameter of 60 μm or less, a laser to be used in accordance with the opening diameter is selected. There are problems such as the necessity of proper use and the difficulty of providing a special shape. In addition, when forming an opening using a laser, each opening must be formed one by one. Therefore, it is time-consuming when it is necessary to provide a large number of fine openings, and resin residues around the openings. Therefore, unless the residue is removed, there is a problem that the reliability of the obtained multilayer printed wiring board is lowered.

  Thus, in order to solve the above-described problems, various photosensitive resin compositions have been conventionally studied (for example, see Patent Documents 5 and 6 below). In such a technique, a photosensitive resin composition that swells with an alkaline aqueous solution is used to form an opening that exposes a conductor circuit, and a photosensitive resin having an opening forming portion that is removed to form an opening. A resin layer is formed, and then the opening forming portion is removed by swelling and peeling with an alkaline aqueous solution to form an opening.

JP 08-279678 A JP-A-11-054913 JP 2001-217543 A Japanese Patent Laid-Open No. 2003-017848 International Publication No. 2013/054790 JP-A-11-274727

  However, in the photosensitive resin composition used in the technique described in Patent Document 5 or 6, when a finer opening (for example, a cylindrical opening having a diameter of 30 μm or less) is formed, it is alkaline to the fine opening forming portion. Since the aqueous solution is difficult to permeate, there is a problem that it is difficult to remove the opening forming part by swelling and peeling of the alkaline aqueous solution.

  As described above, the photosensitive resin composition for obtaining the resin layer in which the opening is formed has excellent opening property even when a fine opening (for example, an opening having a diameter of 30 μm or less) is formed. Is required.

  The present disclosure has been made in view of the above problems, and an object of the present disclosure is to provide a photosensitive resin composition having excellent opening properties even when a fine opening is formed. Moreover, this indication aims at providing the formation method of the photosensitive element using the said photosensitive resin composition, the resist pattern, and the structure.

［式（１）中、Ｒ^１１は、炭素数１〜２０のアルキレン基、炭素数１〜１０のシクロアルキレン基、又は、フェニレン基を示し、Ｒ^１２及びＲ^１３は、各々独立に水素原子又はメチル基を示し、Ｘ^１１及びＸ^１２は、各々独立に、オキシエチレン基及びオキシプロピレン基からなる群より選ばれる少なくとも１種を含むオキシアルキレン基又はポリオキシアルキレン基を示し、Ｘ^１１及びＸ^１２に含まれるオキシエチレン基及びオキシプロピレン基の総数が０〜８０である。］

［式（２）中、Ｒ^２１、Ｒ^２２及びＲ^２３は、各々独立に炭素数１〜２０のアルキレン基を示し、Ｒ^２４、Ｒ^２５及びＲ^２６は、各々独立に水素原子又はメチル基を示し、Ｘ^２１、Ｘ^２２及びＸ^２３は、各々独立に、オキシエチレン基及びオキシプロピレン基からなる群より選ばれる少なくとも１種を含むオキシアルキレン基又はポリオキシアルキレン基を示し、Ｘ^２１、Ｘ^２２及びＸ^２３に含まれるオキシエチレン基及びオキシプロピレン基の総数が０〜１２０である。］ The photosensitive resin composition according to the present embodiment has a structure in which an opening is provided in an insulating layer formed on the surface of a substrate having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening. A photosensitive resin composition used in a method for producing a body, comprising a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, wherein the photopolymerizable compound is represented by the following general formula (1): And at least one selected from the group consisting of compounds represented by the following general formula (2), wherein the method for producing the structure uses the photosensitive resin composition, and the conductor circuit A photosensitive resin layer forming step of forming a first photosensitive resin layer on the substrate so as to cover the substrate, and a first pattern that is patterned by subjecting the first photosensitive resin layer to exposure processing and development processing And the first photosensitive tree A thermosetting resin layer forming step of forming a thermosetting resin layer on the substrate so as to cover the pattern of the layer, and a part of the thermosetting resin layer is removed to remove the first photosensitive resin layer. A pattern exposing step of exposing a predetermined portion of the pattern from the thermosetting resin layer; and removing the predetermined portion of the pattern of the first photosensitive resin layer exposed from the thermosetting resin layer, to form the conductor circuit Forming an opening in the thermosetting resin layer.

[In Formula (1), R ¹¹ represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, or a phenylene group, and R ¹² and R ¹³ are each independently a hydrogen atom or Represents a methyl group, X ¹¹ and X ¹² each independently represent an oxyalkylene group or a polyoxyalkylene group containing at least one selected from the group consisting of an oxyethylene group and an oxypropylene group, and X ¹¹ and X ¹² The total number of oxyethylene groups and oxypropylene groups contained in is 0-80. ]

[In the formula (2), R ²¹ , R ²² and R ²³ each independently represents an alkylene group having 1 to 20 carbon atoms, and R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a methyl group. X ²¹ , X ²² and X ²³ each independently represent an oxyalkylene group or a polyoxyalkylene group containing at least one selected from the group consisting of an oxyethylene group and an oxypropylene group, and X ²¹ , X ²² the total number of oxyethylene groups and oxypropylene groups contained in and ^{X 23} is 0 to 120. ]

  The photosensitive resin composition according to the present embodiment is excellent in openability (removability) even when a fine opening (for example, a cylindrical opening having a diameter of 30 μm or less) is formed. The photosensitive resin composition which concerns on this embodiment can form opening, for example, suppressing generation | occurrence | production of the residue derived from the photosensitive resin composition. According to the photosensitive resin composition according to the present embodiment, it is possible to obtain a resist pattern having excellent openability, and sufficiently efficiently a structure having fine openings and excellent reliability. Can be obtained.

  In addition, according to the photosensitive resin composition according to the present embodiment, not only can a cylindrical opening be suitably formed, but an opening having another shape (for example, while suppressing generation of a residue derived from the photosensitive resin composition (for example, A line-shaped opening for obtaining a line-shaped conductor pattern can also be formed.

  The binder polymer may have a structural unit derived from a (meth) acrylic acid alkyl ester.

  The binder polymer may have an acid value of 60 to 250 mgKOH / g. The binder polymer may have a weight average molecular weight of 10,000 to 100,000.

  The photopolymerization initiator may include a 2,4,5-triarylimidazole dimer.

  The photosensitive resin composition according to the present embodiment may further contain a sensitizing dye.

  The photosensitive resin composition according to this embodiment may further contain a hydrogen donor.

  The photosensitive element which concerns on this embodiment is provided with a support body and the photosensitive resin layer formed on the said support body using the photosensitive resin composition which concerns on this embodiment.

  The method for forming a resist pattern according to this embodiment includes a step of forming a photosensitive resin layer on a substrate using the photosensitive resin composition according to this embodiment or the photosensitive element according to this embodiment, An exposure step of irradiating a predetermined portion of the photosensitive resin layer with actinic rays to cure the predetermined portion; and removing the portion other than the predetermined portion of the photosensitive resin layer from the substrate; And a development step of forming a resist pattern made of a cured product of the composition on the substrate.

  In the method for forming a resist pattern according to this embodiment, the wavelength of the actinic ray may be in the range of 340 to 430 nm.

  The structure manufacturing method according to the present embodiment has a structure in which an opening is provided in an insulating layer formed on the surface of a substrate having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening. A photosensitive resin composition according to the present embodiment or a photosensitive element according to the present embodiment, and a first photosensitive resin layer on the substrate so as to cover a conductor circuit. Forming a photosensitive resin layer, forming a pattern by subjecting the first photosensitive resin layer to exposure and development, and patterning the first photosensitive resin layer. A thermosetting resin layer forming step of forming a thermosetting resin layer on the substrate so as to cover, and a predetermined portion of the pattern of the first photosensitive resin layer by removing a part of the thermosetting resin layer Putter exposed from the thermosetting resin layer An opening for forming an opening in the thermosetting resin layer by removing the predetermined portion of the pattern of the first photosensitive resin layer exposed from the thermosetting resin layer and exposing the conductor circuit. Forming step. According to the structure manufacturing method according to the present embodiment, a structure having a fine opening and having excellent reliability can be manufactured sufficiently efficiently.

  The structure manufacturing method according to the present embodiment may further include a thermosetting step of thermosetting the thermosetting resin layer as a step between the thermosetting resin layer forming step and the pattern exposing step. .

  In the manufacturing method of the structure according to the present embodiment, a seed layer serving as a base of the wiring portion is formed by an electroless plating method so as to cover at least a part of the thermosetting resin layer after the opening is formed. Forming a seed layer, and forming a second photosensitive resin layer so as to cover the seed layer, and then subjecting the second photosensitive resin layer to exposure processing and development processing to pattern the second photosensitive resin layer Forming a wiring portion by electrolytic plating so as to cover at least a part of the seed layer, and then patterning the wiring portion by peeling the pattern of the second photosensitive resin layer You may further comprise a process and the seed layer removal process of removing the seed layer of the area | region in which the said wiring part is not formed.

  According to the present disclosure, it is possible to provide a photosensitive resin composition that is excellent in openability even when a fine opening is formed. Moreover, according to this indication, the photosensitive element using the said photosensitive resin composition, the formation method of a resist pattern, and the manufacturing method of a structure can be provided.

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

  Hereinafter, embodiments for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiment.

In the present specification, “(meth) acrylic acid” means at least one of acrylic acid and methacrylic acid, and “(meth) acrylate” means at least one of acrylate and methacrylate. The “(poly) oxyalkylene group” means at least one of an oxyalkylene group and a polyoxyalkylene group in which two or more alkylene groups are linked by an ether bond. The “(poly) oxyethylene group” means at least one of an oxyethylene group and a polyoxyethylene group in which two or more ethylene groups are connected by an ether bond. The “(poly) oxypropylene group” means at least one of an oxypropylene group and a polyoxypropylene group in which two or more propylene groups are connected by an ether bond. “EO-modified” means a compound having a (poly) oxyethylene group, “PO-modified” means a compound having a (poly) oxypropylene group, and “EO · PO” “Modified” means a compound having both a (poly) oxyethylene group and a (poly) oxypropylene group. The “oxyalkylene group” is a group represented by (—C _p H _2p —O—) (p: an integer of 1 or more), and the “oxyethylene group” is (—C ₂ H ₄ a group represented by -O-), a "oxypropylene _{group", (-} a group represented by _C 3 H 6 -O-).

  In this specification, the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. It is.

  The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. The content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

  The term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when observed as a plan view.

  The term “laminated” indicates that the layers are stacked, two or more layers may be bonded, or two or more layers may be removable.

<Photosensitive resin composition>
The photosensitive resin composition according to the present embodiment has a structure in which an opening is provided in an insulating layer formed on the surface of a substrate having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening. It is the photosensitive resin composition used for the manufacturing method of a body (structure which has a conductor circuit). The manufacturing method of the structure includes a photosensitive resin layer forming step of forming a first photosensitive resin layer on the substrate so as to cover a conductor circuit using the photosensitive resin composition according to the present embodiment; A first patterning step of patterning the first photosensitive resin layer by performing an exposure process and a developing process; and a thermosetting resin on the substrate so as to cover the pattern of the first photosensitive resin layer A thermosetting resin layer forming step of forming a layer, and a pattern for removing a part of the thermosetting resin layer and exposing a predetermined portion of the pattern of the first photosensitive resin layer from the thermosetting resin layer An exposure step; and an opening forming step of removing the first photosensitive resin layer exposed from the thermosetting resin layer and forming an opening in the thermosetting resin layer to expose the conductor circuit. .

  The photosensitive resin composition according to this embodiment includes (A) a binder polymer (hereinafter also referred to as “(A) component”) and (B) a photopolymerizable compound (hereinafter also referred to as “(B) component”). And (C) a photopolymerization initiator (hereinafter also referred to as “component (C)”). In the photosensitive resin composition according to the present embodiment, the component (B) is at least selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). Contains one species. The photosensitive resin composition according to the present embodiment may further contain other components as necessary.

［式（１）中、Ｒ^１１は、炭素数１〜２０のアルキレン基、炭素数１〜１０のシクロアルキレン基、又は、フェニレン基を示し、Ｒ^１２及びＲ^１３は、各々独立に水素原子又はメチル基を示し、Ｘ^１１及びＸ^１２は、各々独立に、オキシエチレン基及びオキシプロピレン基からなる群より選ばれる少なくとも１種を含む（ポリ）オキシアルキレン（オキシアルキレン基又はポリオキシアルキレン基）を示し、Ｘ^１１及びＸ^１２に含まれるオキシエチレン基及びオキシプロピレン基の総数（分子内の総数）が０〜８０である。オキシエチレン基及びオキシプロピレン基の双方が存在する場合、オキシエチレン基及びオキシプロピレン基は、ランダムに存在してもよく、ブロックを形成してもよい。］

[In Formula (1), R ¹¹ represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, or a phenylene group, and R ¹² and R ¹³ are each independently a hydrogen atom or X ¹¹ and X ¹² each independently represents a (poly) oxyalkylene (oxyalkylene group or polyoxyalkylene group) containing at least one selected from the group consisting of an oxyethylene group and an oxypropylene group. The total number of oxyethylene groups and oxypropylene groups contained in X ¹¹ and X ¹² (total number in the molecule) is 0-80. When both an oxyethylene group and an oxypropylene group are present, the oxyethylene group and the oxypropylene group may be present randomly or may form a block. ]

［式（２）中、Ｒ^２１、Ｒ^２２及びＲ^２３は、各々独立に炭素数１〜２０のアルキレン基を示し、Ｒ^２４、Ｒ^２５及びＲ^２６は、各々独立に水素原子又はメチル基を示し、Ｘ^２１、Ｘ^２２及びＸ^２３は、各々独立に、オキシエチレン基及びオキシプロピレン基からなる群より選ばれる少なくとも１種を含む（ポリ）オキシアルキレン（オキシアルキレン基又はポリオキシアルキレン基）を示し、Ｘ^２１、Ｘ^２２及びＸ^２３に含まれるオキシエチレン基及びオキシプロピレン基の総数（分子内の総数）が０〜１２０である。オキシエチレン基及びオキシプロピレン基の双方が存在する場合、オキシエチレン基及びオキシプロピレン基は、ランダムに存在してもよく、ブロックを形成してもよい。］

[In the formula (2), R ²¹ , R ²² and R ²³ each independently represents an alkylene group having 1 to 20 carbon atoms, and R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a methyl group. X ²¹ , X ²² and X ²³ each independently represents a (poly) oxyalkylene (oxyalkylene group or polyoxyalkylene group) containing at least one selected from the group consisting of an oxyethylene group and an oxypropylene group. The total number of oxyethylene groups and oxypropylene groups contained in X ²¹ , X ²² and X ²³ (total number in the molecule) is 0 to 120. When both an oxyethylene group and an oxypropylene group are present, the oxyethylene group and the oxypropylene group may be present randomly or may form a block. ]

((A): Binder polymer)
First, the binder polymer will be described.

  Although it does not specifically limit as a binder polymer, From a viewpoint of improving developability, it may be soluble in alkaline aqueous solution. The component (A) may have a structural unit derived from a polymerizable monomer described later, and can be produced, for example, by radical polymerization of a polymerizable monomer described later.

  Examples of the polymerizable monomer (monomer) include (meth) acrylic acid; (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid benzyl, and (meth) acrylic acid benzyl derivatives. , Furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, α-bromo (meta ) Acrylic acid, α-chloro (meth) acrylic acid, β-furyl (Meth) acrylic acid, (meth) acrylic acid esters such as β-styryl (meth) acrylic acid; styrene; styrene derivatives such as compounds substituted at the α-position or aromatic ring such as vinyltoluene and α-methylstyrene Acrylamide such as diacetone acrylamide; acrylonitrile; esters of vinyl alcohol such as vinyl-n-butyl ether; maleic acid; maleic anhydride; maleic monoester such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate; Examples include fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. The polymerizable monomers can be used alone or in any combination of two or more.

  The component (A) has a structural unit derived from a (meth) acrylic acid alkyl ester from the viewpoint of further improving the opening of the photosensitive resin layer with an alkaline aqueous solution when the conductor circuit is exposed and the opening is formed. Also good. For example, the component (A) may be obtained by radical polymerization of an alkyl (meth) acrylate.

  Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate and (meth) ) Dodecyl acrylate. The (meth) acrylic acid alkyl ester can be used alone or in combination of two or more.

  In the case where the component (A) has a structural unit derived from a (meth) acrylic acid alkyl ester, the content of the structural unit is that of the structural unit constituting the component (A) from the viewpoint of further excellent adhesion and openability. It may be 30 to 85% by mass, 40 to 80% by mass, or 50 to 75% by mass based on the total solid content. This content may be 30% by mass or more, 40% by mass or more, or 50% by mass or more from the viewpoint of further improving the adhesion. Moreover, this content may be 85 mass% or less, 80 mass% or less, or 75 mass% or less from the viewpoint of further improving the openability.

  When the component (A) has a structural unit derived from (meth) acrylic acid, the content of the structural unit is the solid content of the structural unit constituting the component (A) from the viewpoint of further improving adhesion and openability. 5-80 mass% may be sufficient on the basis of the total mass, 10-70 mass% may be sufficient, and 15-60 mass% may be sufficient. This content may be 5% by mass or more, 10% by mass or more, or 15% by mass or more from the viewpoint of further improving developability and openability. Moreover, this content may be 80 mass% or less, 70 mass% or less, and 60 mass% or less from a viewpoint which is further excellent in adhesiveness.

  The component (A) may have a structural unit derived from benzyl (meth) acrylate or a derivative thereof from the viewpoint of further improving openness and adhesion. When the component (A) has a structural unit derived from benzyl (meth) acrylate or a derivative thereof, the content of the structural unit is 5 based on the total solid mass of the structural unit constituting the component (A). -60 mass% may be sufficient, 10-55 mass% may be sufficient, and 20-50 mass% may be sufficient. This content may be 5% by mass or more, 10% by mass or more, or 20% by mass or more from the viewpoint of further excellent adhesion. Moreover, this content may be 60 mass% or less, 55 mass% or less, and 50 mass% or less from a viewpoint which is further excellent in opening property.

  The acid value of the component (A) may be 60 to 250 mgKOH / g, 100 to 250 mgKOH / g, or 100 to 230 mgKOH / g from the viewpoint of further improving developability and developer resistance. It may be 130-230 mgKOH / g. In addition, when performing solvent image development, you may adjust the polymerizable monomer (monomer) which has carboxyl groups, such as (meth) acrylic acid, to a small quantity. (A) The acid value of a component can be measured with reference to the measuring method of the Example mentioned later.

  When the weight average molecular weight (Mw) of the component (A) is measured by gel permeation chromatography (GPC) (converted by a calibration curve using standard polystyrene), from the viewpoint of further improving developability and developer resistance, It may be 10,000 to 100,000, 20000 to 80,000, or 25,000 to 70,000. The weight average molecular weight of the component (A) may be 100,000 or less, 80000 or less, or 70000 or less from the viewpoint of further improving developability. The weight average molecular weight of the component (A) may be 10,000 or more, 20000 or more, or 25000 or more from the viewpoint of excellent developer resistance. In addition, a weight average molecular weight can be measured with reference to the measuring method of the Example mentioned later.

  As the component (A), one type of binder polymer may be used alone, or two or more types of binder polymers may be used in any combination. As a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymer components (including different monomer units as copolymer components), two or more types of different weight average molecular weights Examples thereof include a binder polymer and two or more types of binder polymers having different degrees of dispersion. In addition, a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used.

  Even if content of (A) component is 30-70 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component from a viewpoint which is further excellent in film formation property, a sensitivity, and adhesiveness. It may be 40 to 70 parts by mass or 50 to 65 parts by mass.

((B): Photopolymerizable compound)
Next, the photopolymerizable compound will be described.

  In the photosensitive resin composition according to the present embodiment, as component (B), urethane di (meth) acrylate having a total number of structural units of oxyethylene groups and oxypropylene groups per functional group of 0 to 40, and functional groups It contains at least one photopolymerizable compound selected from the group consisting of isocyanurate-derived tri (meth) acrylates having a total number of structural units of oxyethylene groups and oxypropylene groups of from 0 to 40. As used herein, the functional group means a (meth) acryloyl group.

  Urethane di (meth) acrylate contains the compound represented by the general formula (1). The isocyanurate-derived tri (meth) acrylate includes a compound represented by the general formula (2). The isocyanurate-derived tri (meth) acrylate can be said to be a tri (meth) acrylate having a skeleton derived from isocyanurate. The photosensitive resin composition according to this embodiment comprises at least one photopolymerizable compound selected from the group consisting of a compound represented by the general formula (1) and a compound represented by the general formula (2). By containing, the openability can be improved when the conductor circuit is exposed and the openings are formed (for example, openings formed in the photosensitive resin layer with an alkaline aqueous solution).

In the general formula (1), X ¹¹ and X ¹² may be independently composed of an oxyethylene group and an oxypropylene group, and include an oxyalkylene group other than the oxyethylene group and the oxypropylene group. There may be. Examples of oxyalkylene groups other than oxyethylene groups and oxypropylene groups include oxybutylene groups. When an oxyalkylene group other than an oxyethylene group and an oxypropylene group is present, the oxyalkylene group and the oxyethylene group and / or oxypropylene group may be present randomly or may form a block. .

  The compound represented by the general formula (1) may be, for example, a compound represented by the following general formula (1a). The compound represented by the general formula (2) may be, for example, a compound represented by the following general formula (2a).

［式（１ａ）中、Ｒ^１１は、式（１）と同様に、炭素数１〜２０のアルキレン基、炭素数１〜１０のシクロアルキレン基、又は、フェニレン基を示し、Ｒ^１２及びＲ^１３は、式（１）と同様に、各々独立に水素原子又はメチル基を示し、Ａ^１Ｏ及びＢ^１Ｏは、各々独立にオキシエチレン基又はオキシプロピレン基を示し、（Ａ^１Ｏ）_ａ１、（Ｂ^１Ｏ）_ｂ１、（Ａ^１Ｏ）_ｃ１及び（Ｂ^１Ｏ）_ｄ１は、各々（ポリ）オキシエチレン基又は（ポリ）オキシプロピレン基を示す。オキシエチレン基及びオキシプロピレン基の双方が存在する場合、オキシエチレン基及びオキシプロピレン基は、ランダムに存在してもよく、ブロックを形成してもよい。ａ１、ｂ１、ｃ１及びｄ１は、対応する構造単位の構造単位数を示し、ａ１、ｂ１、ｃ１及びｄ１は、単一の分子においては整数値を示し、複数種の分子の集合体としては平均値である有理数を示す。以下、構造単位の構造単位数については同様である。ａ１＋ｂ１＋ｃ１＋ｄ１は、０〜８０である。ａ１、ｂ１、ｃ１及びｄ１は、各々独立に０〜８０の数値を採り得る。］

[In Formula (1a), R ¹¹ represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, or a phenylene group as in Formula (1), and R ¹² and R ¹³ Are each independently a hydrogen atom or a methyl group, and A ¹ O and B ¹ O are each independently an oxyethylene group or an oxypropylene group, and (A ¹ O) _a1 , (B ¹ O) _b1 , (A ¹ O) _c1 and (B ¹ O) _d1 each represent a (poly) oxyethylene group or a (poly) oxypropylene group. When both an oxyethylene group and an oxypropylene group are present, the oxyethylene group and the oxypropylene group may be present randomly or may form a block. a1, b1, c1 and d1 represent the number of structural units of the corresponding structural unit, a1, b1, c1 and d1 represent an integer value in a single molecule, and averaged as an aggregate of a plurality of types of molecules. Indicates a rational number that is a value. Hereinafter, the same applies to the number of structural units. a1 + b1 + c1 + d1 is 0-80. a1, b1, c1 and d1 can each independently take a numerical value of 0 to 80. ]

［式（２ａ）中、Ｒ^２１、Ｒ^２２及びＲ^２３は、各々独立に炭素数１〜２０のアルキレン基を示し、Ｒ^２１、Ｒ^２２及びＲ^２３は、無置換であってもよく、置換されていてもよく、当該置換基は、互いに同一であっても異なっていてもよく、Ｒ^２４、Ｒ^２５及びＲ^２６は、各々独立に水素原子又はメチル基を示し、Ａ^２Ｏ及びＢ^２Ｏは、各々独立にオキシエチレン基又はオキシプロピレン基を示し、（Ａ^２Ｏ）_ａ２、（Ｂ^２Ｏ）_ｂ２、（Ａ^２Ｏ）_ｃ２及び（Ｂ^２Ｏ）_ｄ２は、各々（ポリ）オキシエチレン基又は（ポリ）オキシプロピレン基を示す。オキシエチレン基及びオキシプロピレン基の双方が存在する場合、オキシエチレン基及びオキシプロピレン基は、ランダムに存在してもよく、ブロックを形成してもよい。ａ２、ｂ２、ｃ２、ｄ２、ｅ２及びｆ２は、対応する構造単位の構造単位数を示し、ａ２、ｂ２、ｃ２、ｄ２、ｅ２及びｆ２は、単一の分子においては整数値を示し、複数種の分子の集合体としては平均値である有理数を示す。ａ２＋ｂ２＋ｃ２＋ｄ２＋ｅ２＋ｆ２は、０〜１２０である。ａ２、ｂ２、ｃ２、ｄ２、ｅ２及びｆ２は、各々独立に０〜１２０の数値を採り得る。］

[In the formula (2a), R ²¹ , R ²² and R ²³ each independently represent an alkylene group having 1 to 20 carbon atoms, and R ²¹ , R ²² and R ²³ may be unsubstituted or substituted. The substituents may be the same as or different from each other, and R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group, and A ² O and B ² O independently represents an oxyethylene group or an oxypropylene group, and (A ² O) a ₂ , (B ² O) _{b 2} , (A ² O) _c ² and (B ² O) _{d 2} are each (poly) oxy An ethylene group or a (poly) oxypropylene group is shown. When both an oxyethylene group and an oxypropylene group are present, the oxyethylene group and the oxypropylene group may be present randomly or may form a block. a2, b2, c2, d2, e2 and f2 represent the number of structural units of the corresponding structural unit, a2, b2, c2, d2, e2 and f2 represent integer values in a single molecule, A rational number that is an average value is shown as an assembly of molecules. a2 + b2 + c2 + d2 + e2 + f2 is 0-120. a2, b2, c2, d2, e2, and f2 can each independently take a numerical value of 0 to 120. ]

In General Formula (1) and General Formula (1a), R ¹¹ is an alkylene group having 2 to 18 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, or a phenylene group from the viewpoint of further improving adhesion. May be an alkylene group having 2 to 15 carbon atoms, a cycloalkylene group having 3 to 7 carbon atoms, or a phenylene group, an alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, It may be a phenylene group. R ¹² and R ¹³ may be a methyl group from the viewpoint of improving adhesion. a1 + b1 + c1 + d1 may be 2 to 80 or 4 to 80 from the viewpoint of further improving developability and openability.

  Examples of the compound represented by the general formula (1) or the general formula (1a) include a compound represented by the following formula (3a) (UA-11 (trade name, manufactured by Hitachi Chemical Co., Ltd.): (EO) modification. Urethane dimethacrylate (ethylene oxide average 10 mol adduct)) and a compound represented by the following formula (3b) (UA-13 (trade name, manufactured by Hitachi Chemical Co., Ltd.): (EO) (PO) modified urethane dimethacrylate (Ethylene oxide average 2 mol, propylene oxide average 18 mol adduct)) is commercially available. These compounds can be used individually or in combination of 2 or more types.

In the general formula (2) and the general formula (2a), R ²¹ , R ²² and R ²³ may be an alkylene group having 2 to 18 carbon atoms from the viewpoint of further improving adhesion, and the number of carbon atoms is 2 -15 alkylene group may be sufficient and a C2-C10 alkylene group may be sufficient. R ²⁴ , R ²⁵ and R ²⁶ may be a methyl group from the viewpoint of improving adhesion. a2 + b2 + c2 + d2 + e2 + f2 may be 3 to 120 or 6 to 120 from the viewpoint of further improving the openability.

  As a compound represented by the general formula (2) or the general formula (2a), a compound represented by the following formula (4a) (UA-7100 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.): (EO) modification Isocyanurate-derived trimethacrylate (ethylene oxide average 27 mol adduct)) and a compound represented by the following formula (4b) (UA-21 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.): (EO) modified isocyanurate Derived trimethacrylate (ethylene oxide average 12 mol adduct)) is commercially available. These compounds can be used individually or in combination of 2 or more types.

  The content of each of the compound represented by the general formula (1) and the compound represented by the general formula (2) is 10 with respect to 100 parts by mass of the component (B) from the viewpoint of further improving the opening property. -100 mass parts may be sufficient, 20-100 mass parts may be sufficient, and 30-100 mass parts may be sufficient.

  The component (B) can contain a compound represented by the general formula (1) and other photopolymerizable compounds other than the compound represented by the general formula (2), and is capable of photocrosslinking. If there is no particular limitation, it can be used. For example, the component (B) can include a compound having an ethylenically unsaturated bond (excluding the compound represented by the general formula (1) and the compound represented by the general formula (2)). The compound having an ethylenically unsaturated bond includes a compound having one ethylenically unsaturated bond in the molecule, a compound having two ethylenically unsaturated bonds in the molecule, and three ethylenically unsaturated bonds in the molecule. And the like. The photopolymerizable compound other than the compound represented by the general formula (1) and the compound represented by the general formula (2) can be used alone or in combination of two or more.

  Examples of the compound having one ethylenically unsaturated bond in the molecule include nonylphenoxypolyethyleneoxyacrylate and fumaric acid compounds. The compounds having one ethylenically unsaturated bond in the molecule can be used alone or in combination of two or more. As commercially available products, M-114 (manufactured by Toagosei Co., Ltd., 4-normalnonylphenoxyoctaethyleneoxyacrylate), FA-MECH (manufactured by Hitachi Chemical Co., Ltd., γ-chloro-β-hydroxypropyl-) β′-methacryloyloxyethyl-o-phthalate) and the like.

  Examples of the compound having two ethylenically unsaturated bonds in the molecule include EO-modified urethane di (meth) acrylate other than the compound represented by the general formula (1), bisphenol type di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, 2,2-bis (4- (methacryloxypolyethoxy) phenyl) propane, and 2,2-bis (4- ( Methacryloxypolyethoxypolypropoxy) phenyl) propane. The compounds having two ethylenically unsaturated bonds in the molecule can be used alone or in combination of two or more.

  Examples of the compound having three ethylenically unsaturated bonds in the molecule include EO-modified isocyanurate-derived tri (meth) acrylates other than the compound represented by the general formula (2), PO-modified isocyanurate-derived tri (meth) Acrylate, EO / PO modified isocyanurate-derived tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO / PO modified Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, EO-modified pentaerythritol tri (meth) acrylate, PO-modified pentaerythritol tri (meth) acrylate, EO / PO-modified pentae Thritol tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, EO modified tetramethylol methane tri (meth) acrylate, PO modified tetramethylol methane tri (meth) acrylate, and EO / PO modified tetramethylol methane tri (meth) An acrylate is mentioned. Among these, commercially available products include A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd., tetramethylolmethane triacrylate), TMPT21E, TMPT30E (manufactured by Hitachi Chemical Co., Ltd., EO-modified trimethylolpropane trimethacrylate). ) And the like. Compounds having three ethylenically unsaturated bonds in the molecule can be used alone or in combination of two or more.

  The content of the component (B) may be 30 to 70 parts by mass or 30 to 60 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). -50 mass parts may be sufficient. When the content of the component (B) is 30 parts by mass or more, the sensitivity and adhesion tend to be further improved, and when the content is 70 parts by mass or less, the developability is further improved. Tend.

((C): Photopolymerization initiator)
Next, the photopolymerization initiator will be described.

  The component (C) is not particularly limited as long as it can polymerize the component (B) by irradiation with active light or the like, and can be appropriately selected from commonly used photopolymerization initiators.

  Examples of the component (C) include 4,4′-bis (diethylamino) benzophenone, benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- Aromatic ketones such as [4- (methylthio) phenyl] -2-morpholino-1-propanone; quinones such as alkylanthraquinones; benzoin ether compounds such as benzoin alkyl ether; benzoin compounds such as benzoin and alkylbenzoin; benzyldimethyl ketal Benzyl derivatives such as 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbis) Imidazole), 2- (o-chlorophenyl) -4,5-di (me Xylphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p- 2,4,5-triarylimidazole dimer such as methoxyphenyl) -4,5-diphenylimidazole dimer; acridine such as 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane Derivatives; N-phenylglycine; N-phenylglycine derivatives. (C) component can be used individually or in combination of 2 or more types.

  Moreover, the substituents of the two aryl groups of 2,4,5-triarylimidazole may give the same and symmetric compounds, or differently give asymmetric compounds. Moreover, (C) component may also contain a 2,4,5-triaryl imidazole dimer from a viewpoint which adhesiveness and a sensitivity improve further. (C) When a component contains a 2,4,5-triarylimidazole dimer, the content rate may be 10-100 mass parts with respect to 100 mass parts of solid content of (C) component. 30 to 100 parts by mass, or 50 to 100 parts by mass. There exists a tendency for a sensitivity and adhesiveness to improve further because content of (C) component is 10 mass parts or more.

  The content of the component (C) may be 0.1 to 10 parts by mass or 2 to 6 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). 3 to 5 parts by mass. (C) When the content of the component is 0.1 parts by mass or more, sensitivity and adhesion tend to be further improved, and when the content is 10 parts by mass or less, the shape of the opening forming part is further improved. Tend to be.

((D): sensitizing dye)
The photosensitive resin composition according to the present embodiment may further contain (D) a sensitizing dye (hereinafter also referred to as “component (D)”).

  Examples of the component (D) include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazines. Examples include compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. (D) component can be used individually or in combination of 2 or more types.

  As the component (D), a sensitizing dye having an absorption maximum at 340 to 430 nm can be used. In particular, when exposing the photosensitive resin layer using actinic rays of 340 to 430 nm, from the viewpoint of further improving sensitivity and adhesion, the component (D) is a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound, It may contain at least one sensitizing dye selected from the group consisting of a coumarin compound, a triarylamine compound, a thioxanthone compound and an aminoacridine compound. It may contain at least one selected from the group consisting of

  When the component (D) is contained, the content of the component (D) may be 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). 0.05 to 5 parts by mass, or 0.1 to 3 parts by mass. When the content of the component (D) is 0.01 parts by mass or more, the sensitivity and adhesion tend to be further excellent, and by being 10 parts by mass or less, the resist shape of the opening forming portion is There is a tendency to be even better.

((E): Hydrogen donor)
The photosensitive resin composition according to this embodiment may further contain (E) a hydrogen donor (hereinafter also referred to as “component (E)”). The component (E) can give hydrogen during the reaction in the exposed area. When the photosensitive resin composition according to the present embodiment further contains the component (E), the contrast between the exposed portion and the unexposed portion (also referred to as “imaging”) can be further improved.

  Examples of the component (E) include bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leucocrystal violet. (E) A component can be used individually or in combination of 2 or more types.

  When the component (E) is contained, the content of the component (E) may be 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). 0.05 to 5 parts by mass, or 0.1 to 2 parts by mass. When the content of the component (E) is 0.01 parts by mass or more, the sensitivity tends to be further improved. When the content is 10 parts by mass or less, the component (E) is a foreign substance after film formation. It tends to be difficult to precipitate as.

(Other ingredients)
If necessary, the photosensitive resin composition according to the present embodiment includes a photopolymerizable compound (such as an oxetane compound) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, malachite green, and the like. Dyes, photochromic agents such as tribromophenylsulfone and leucocrystal violet, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion imparting An agent, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent and the like may be further contained. These can be used alone or in combination of two or more. These contents may be 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B), respectively.

[Solution of photosensitive resin composition]
The photosensitive resin composition according to the present embodiment may contain a solvent to be described later in order to adjust the viscosity, if necessary. For example, the photosensitive resin composition according to the present embodiment is dissolved in the solvent. And it can be used as a solution (coating liquid) having a solid content of 30 to 60% by mass. Examples of the solvent include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, and a mixed solvent thereof.

  A photosensitive resin layer can be formed using the photosensitive resin composition according to the present embodiment by applying a coating solution on the surface of a support of a photosensitive element, which will be described later, a substrate, and the like and drying the coating solution.

  The thickness of the photosensitive resin layer varies depending on its use, but may be 2 to 50 μm in thickness after drying. The surface of the photosensitive resin layer may be covered with a protective layer. As a protective layer, polymer films, such as polyethylene and a polypropylene, are mentioned, for example.

<Photosensitive element>
The photosensitive element which concerns on this embodiment is provided with a support body and the photosensitive resin layer formed on the said support body using the photosensitive resin composition which concerns on this embodiment. By applying the photosensitive resin composition onto a support and drying it, a photosensitive resin layer can be formed on the support using the photosensitive resin composition. Thus, the photosensitive element which concerns on this embodiment provided with a support body and the said photosensitive resin layer formed on this support body is obtained. In addition, the photosensitive resin composition apply | coated on a support body may be the coating liquid mentioned above.

  As the support, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used.

  The photosensitive element may be provided with a protective layer that covers the surface of the photosensitive resin layer opposite to the support, if necessary.

  As a protective layer, the adhesive force with respect to the photosensitive resin layer may be smaller than the adhesive force with respect to the photosensitive resin layer of a support body, and the film of a low fish eye may be sufficient as it. Here, “fish eye” means that when a material is heat-melted, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are present in the film. It means what was taken in. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.

  As the protective layer, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used. Examples of commercially available products include polypropylene films such as Alphan MA-410 and E-200C manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and PS-25 polyethylene terephthalate such as Teijin DuPont Films Co., Ltd. A film is mentioned. The protective layer may be the same as the support.

  Specifically, for example, the photosensitive element can be manufactured as follows. The photosensitive element includes a step of preparing a coating liquid containing the photosensitive resin composition according to the present embodiment, a step of coating the coating liquid on a support to form a coating layer, and drying the coating layer. And a step of forming a photosensitive resin layer.

  Application of the photosensitive resin composition onto the support can be performed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating.

  There is no particular limitation on the drying of the coating layer as long as at least a part of the solvent can be removed from the coating layer. For example, the coating layer may be dried at 70 to 150 ° C. for 1 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin layer may be 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

  Moreover, although the thickness (after drying) of the photosensitive resin layer can be suitably adjusted as needed, it may be 2-50 micrometers, for example. When this thickness is 2 μm or more, it becomes easy to industrially form a photosensitive resin layer.

  The transmittance of the photosensitive resin layer with respect to ultraviolet rays may be 5 to 75%, 10 to 65%, or 15 to 55% with respect to ultraviolet rays having a wavelength of 365 nm. If this transmittance is 5% or more, sufficient adhesion tends to be obtained, and if it is 75% or less, sufficient adhesion tends to be obtained. The transmittance can be measured with a UV spectrometer. Examples of the UV spectrometer include a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

  The photosensitive element may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer.

  The obtained photosensitive element can be stored in the form of a sheet or a roll wound around a core. When winding in a roll shape, it may be wound so that the support is on the outside. Examples of the winding core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). On the end face of the roll-shaped photosensitive element roll thus obtained, an end face separator may be installed from the viewpoint of end face protection, or a moisture-proof end face separator may be installed from the viewpoint of edge fusion resistance. As a packing method, it may be wrapped in a black sheet with low moisture permeability.

<Method for forming resist pattern>
A resist pattern can be formed using the photosensitive resin composition or the photosensitive element. The resist pattern forming method according to this embodiment includes (i) a photosensitive resin layer forming step of forming a photosensitive resin layer on a substrate using the photosensitive resin composition or the photosensitive element, ii) an exposure process in which a predetermined portion of the photosensitive resin layer is irradiated with actinic rays to expose and cure the predetermined portion; and (iii) a portion other than the predetermined portion of the photosensitive resin layer is removed from the substrate. And a developing step of forming a resist pattern made of a cured product of the photosensitive resin composition on the substrate.

(I) Photosensitive resin layer formation process First, the photosensitive resin layer is formed on a board | substrate using the photosensitive resin composition or the photosensitive element. As the substrate, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used.

  As a method for forming the photosensitive resin layer on the substrate, for example, a method in which the photosensitive resin composition is applied on the substrate and then dried, and the photosensitive resin layer in the photosensitive element described above is transferred onto the substrate. (Lamination) is mentioned.

  Application of the photosensitive resin composition onto the substrate can be performed by a known method such as roll coating, comma coating, gravure coating, air knife coating, die coating, or bar coating.

  When using the photosensitive element, the lamination of the photosensitive resin layer on the substrate is performed, for example, by removing the protective layer of the photosensitive element and then pressing the photosensitive resin layer on the substrate while heating the photosensitive resin layer of the photosensitive element. Is done. Thereby, the laminated body which consists of a board | substrate, the photosensitive resin layer, and the support body, and these were laminated | stacked in order is obtained.

Lamination conditions can be appropriately adjusted as necessary, but the lamination may be performed under reduced pressure from the viewpoint of further improving adhesion and followability. The photosensitive resin layer and / or the substrate may be heated at a temperature of 70 to 130 ° C., or may be pressed at a pressure of 0.1 to 1.0 MPa (1 to 10 kgf / cm ² ). Although good, there are no particular restrictions on these conditions. If the photosensitive resin layer is heated to 70 to 130 ° C., it is not necessary to pre-heat the substrate in advance, but the substrate may be previously heated in the above temperature range in order to further improve the lamination property. .

(Ii) Exposure Step Next, a predetermined portion of the photosensitive resin layer on the substrate is irradiated with actinic rays to expose and cure the predetermined portion. At this time, when the support on the photosensitive resin layer is transmissive to actinic rays, it can be irradiated with actinic rays through the support, but when the support is light-shielding. After removing the support, the photosensitive resin layer is irradiated with actinic rays.

  Examples of the exposure method include a method of irradiating an image with active light through a negative or positive mask pattern called an artwork (mask exposure method). Alternatively, a method of irradiating actinic rays in an image form by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.

  As the actinic ray light source, a known light source can be used. For example, a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, a xenon lamp, a gas laser such as an argon laser, a solid laser such as a YAG laser, a semiconductor laser Those that effectively emit ultraviolet light, visible light, and the like are used.

  The wavelength of the actinic ray (exposure wavelength) may be 340 to 430 nm or 350 to 420 nm from the viewpoint of obtaining the effect of the present embodiment more reliably.

(Iii) Development process In a development process, the resist pattern which consists of hardened | cured material of the photosensitive resin composition is formed on a board | substrate by removing parts other than the said predetermined part of the photosensitive resin layer from a board | substrate. In the case where a support is present on the photosensitive resin layer, after removing the support, removal (development) of a portion (unexposed portion) other than the predetermined portion (exposed portion) is performed. Development methods include wet development and dry development, but wet development is widely used.

  In the case of wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. Examples of development methods include dipping, paddle, spraying, brushing, slapping, scrubbing, rocking immersion, etc. From the viewpoint of further improving resolution, the high-pressure spraying method is most suitable. ing. You may develop by combining these 2 or more types of methods.

  A developing solution is suitably selected according to the structure of the photosensitive resin composition. Examples of the developer include an alkaline aqueous solution and an organic solvent developer.

  The alkaline aqueous solution is safe and stable when used as a developer, and has good operability. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate; potassium phosphate, sodium phosphate Alkali metal phosphates such as sodium pyrophosphate and potassium pyrophosphate; borax (sodium tetraborate); sodium metasilicate; tetramethylammonium hydroxide; ethanolamine; ethylenediamine; diethylenetriamine; -Amino-2-hydroxymethyl-1,3-propanediol; 1,3-diamino-2-propanol; morpholine and the like are used.

  Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, a dilute solution of 0.1 to 5% by mass of sodium hydroxide, It may be a dilute solution of 1 to 5% by mass sodium tetraborate. The pH of the alkaline aqueous solution may be in the range of 9 to 11, and the temperature is adjusted according to the alkali developability of the photosensitive resin layer. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.

  Examples of the organic solvent used in the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. Water may be added to these organic solvents in an amount of 1 to 20% by mass to prevent ignition, and an organic solvent developer may be used.

In the method for forming a resist pattern according to this embodiment, after removing an unexposed portion, heating at 60 to 250 ° C. and / or exposure with an energy amount of 0.2 to 10 J / cm ² is performed as necessary. Therefore, you may further have the process of hardening a resist pattern.

<Method for manufacturing structure>
The photosensitive resin composition according to the present embodiment and the photosensitive element according to the present embodiment are suitably used for the manufacture of a structure (for example, a printed wiring board) for mounting a semiconductor element. It is preferably used for manufacturing a package substrate, and more preferably used for manufacturing a structure (a structure having a conductor circuit). In particular, in addition to the manufacture of printed wiring boards for mounting flip chip type semiconductor elements, in addition to coreless substrates, WLP (Wafer Level Package), eWLB (embedded Wafer Level Ball Grid Array) and other board-less package rewiring methods Can also be suitably used. Among them, the size of the semiconductor element to be mounted is large, and it is particularly suitable for a printed wiring board for electrically connecting to tens of thousands of bumps arranged in an area array on the surface of the semiconductor element.

  The structure according to the present embodiment is a structure in which an opening is provided in an insulating layer formed on the surface of a substrate having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening. The insulating layer is, for example, a thermosetting resin layer and / or a photosensitive resin layer. The structure manufacturing method according to the present embodiment uses the photosensitive resin composition according to the present embodiment or the photosensitive element according to the present embodiment to form a first photosensitive material on a substrate so as to cover a conductor circuit. A photosensitive resin layer forming step of forming a photosensitive resin layer, a first patterning step of patterning the first photosensitive resin layer by performing exposure processing and development processing, and a pattern of the first photosensitive resin layer A thermosetting resin layer forming step for forming a thermosetting resin layer on the substrate so as to cover the substrate, and removing a part of the thermosetting resin layer to heat a predetermined portion of the pattern of the first photosensitive resin layer. A pattern exposing step for exposing from the curable resin layer and a predetermined portion of the pattern of the first photosensitive resin layer exposed from the thermosetting resin layer are removed, and an opening for exposing the conductor circuit is formed in the thermosetting resin layer. An opening forming step to be formed. That is, according to the present disclosure, the multilayer printed wiring board shown in FIG. 1 can be manufactured without using a laser. As a manufacturing method of the structure, a manufacturing method described in Patent Document 5 may be used. In the present specification, as the “substrate having a conductor circuit”, a flexible substrate or a rigid substrate may be used. Further, the “conductor circuit” can also be referred to as a “conductor pattern” and a “wiring pattern”. The shape of the opening is not particularly limited, and may be, for example, an ellipse, a polygon, an irregular shape, or other shapes in addition to a circle and a line. In addition, when forming an opening using a stripping solution, when the stripping solution forms a line-shaped opening forming portion as compared to a circular, elliptical, polygonal, or irregular opening forming portion. , The stripping solution tends to penetrate more easily. In addition, the multilayer printed wiring board which can be manufactured by this indication is equipped with the insulating layer formed so that a conductor circuit may be covered on a board | substrate provided with a conductor circuit (wiring pattern). Furthermore, the insulating layer includes an opening formed so that at least a part of the conductor circuit on the substrate is exposed, and a conductor pattern can be formed in the opening.

  In this structure manufacturing method, various openings can be easily formed by patterning the first photosensitive resin layer in the first patterning step in accordance with the shape of the opening formed in the thermosetting resin layer. Can be formed. Also, in this method of manufacturing a structure (for example, a printed wiring board), unlike the case of forming openings with a laser, in addition to being able to form a plurality of openings at the same time, resin residues around the openings can be reduced. For this reason, even when the number of pins of the semiconductor element increases and a large number of fine openings need to be provided, a structure (eg, a printed wiring board) having excellent reliability can be efficiently manufactured. Further, even when an opening having a diameter of 30 μm or less is formed or a large opening having a diameter of 100 μm or more is formed, an opening having excellent insulation reliability can be more efficiently formed. it can.

  Moreover, the manufacturing method of a structure WHEREIN: As a process (For example, process immediately after a thermosetting resin layer formation process) between the said thermosetting resin layer formation process and the said pattern exposure process, a thermosetting resin layer is heat-processed. You may further provide the thermosetting process to harden | cure. In this case, for example, a part of the thermosetting resin layer after thermosetting is removed in the pattern exposure process, and the first photosensitive resin layer exposed from the thermosetting resin layer is removed in the opening forming process. Do. Examples of the method for removing a part of the thermosetting resin layer after thermosetting include mechanical polishing, plasma treatment, wet blasting, sand blasting, and chemical polishing. Examples of the method for removing the first photosensitive resin layer exposed from the thermosetting resin layer include chemical treatment (also referred to as “desmear treatment”), plasma treatment, wet blasting, and sand blasting.

  The method for removing a part of the thermosetting resin layer after the thermosetting may be mechanical polishing, and the method for removing the first photosensitive resin layer exposed from the thermosetting resin layer may be chemical treatment. . By removing a part of the thermosetting resin layer after thermosetting by mechanical polishing, the first photosensitive resin layer can be exposed more quickly, and residues around the opening can be more reliably reduced. By removing the first photosensitive resin layer exposed from the thermosetting resin layer by the chemical treatment, the residue around the opening can be more reliably reduced. Moreover, as a chemical | medical solution used for a chemical | medical solution process, it can peel with the aqueous solution which is stronger alkaline than the alkaline aqueous solution used for image development. Examples of the strong alkaline aqueous solution include a sodium permanganate aqueous solution, a sodium hydroxide aqueous solution, a potassium permanganate aqueous solution, and sulfuric acid. Further, as the chemical solution used for the chemical treatment, a developer composed of water or an alkaline aqueous solution and one or more organic solvents can be suitably used. Examples of the base of the alkaline aqueous solution include tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, and the organic solvent used together includes acetone, Examples include ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, and the like, and can be used alone or in combination of two or more bases. . In addition, these chemical | medical solutions can be used individually or in combination of 2 or more types as a liquid mixture.

  Further, a method of removing a part of the thermosetting resin layer after the thermosetting and a method of removing the first photosensitive resin layer exposed from the thermosetting resin layer include plasma treatment, wet blasting and sand blasting. It may be at least one selected from the group consisting of In this case, the first photosensitive resin layer can be exposed more quickly, and residues around the opening can be more reliably reduced.

  The method for removing a part of the thermosetting resin layer after the thermosetting and the method for removing the first photosensitive resin layer exposed from the thermosetting resin layer may be chemical treatment. . In this case, the first photosensitive resin layer can be exposed more quickly, and residues around the opening can be more reliably reduced. Moreover, as a chemical | medical solution used for a chemical | medical solution process, it can peel with the aqueous solution which is stronger alkaline than the alkaline aqueous solution used for image development. Examples of the strong alkaline aqueous solution include a sodium permanganate aqueous solution, a sodium hydroxide aqueous solution, a potassium permanganate aqueous solution, and sulfuric acid. Further, as the chemical solution used for the chemical treatment, a developer composed of water or an alkaline aqueous solution and one or more organic solvents can be suitably used. Examples of the base of the alkaline aqueous solution include tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, and the organic solvent used together includes acetone, Examples include ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, and the like, and can be used alone or in combination of two or more bases. . These chemical solutions can be used alone or as a mixed solution in combination of two or more.

  Further, in the thermosetting step, thermosetting may be performed in an inert gas atmosphere. By performing thermosetting in an inert gas atmosphere, copper oxidation on the surface of the conductor circuit can be suppressed in the thermosetting step.

  Further, the structure manufacturing method includes a seed layer forming step of forming a seed layer serving as a base of the wiring portion by an electroless plating method so as to cover at least a part of the thermosetting resin layer after the opening is formed. Forming a second photosensitive resin layer so as to cover the seed layer, and then patterning the second photosensitive resin layer by subjecting the second photosensitive resin layer to exposure and development, and at least one of the seed layer A wiring part patterning step in which the wiring part is formed by electrolytic plating so as to cover the part, and then the second photosensitive resin layer is peeled off by a peeling process to pattern the wiring part, and a region where the wiring part is not formed A seed layer removing step of removing the seed layer. By forming the seed layer, the wiring part can be formed by electrolytic plating, and the wiring part can be selectively patterned.

In the photosensitive resin layer forming step, the thickness T1 of the _first photosensitive resin layer may be 2 to 50 μm. When the thickness T1 of the _first photosensitive resin layer is 2 μm or more, the photosensitive resin composition used for forming the first photosensitive resin layer can be easily formed. ) Can be easily formed. When the thickness T1 of the _first photosensitive resin layer is 50 μm or less, it becomes easy to form a fine pattern on the first photosensitive resin layer.

In the thermosetting resin layer forming step, the thickness T2 of the thermosetting resin layer may be ₂ to 50 μm. If the thickness T ₂ of the thermosetting resin layer is 2μm or more, it becomes easier by forming a thermosetting resin composition used to form the thermosetting resin layer, the production of structures (e.g., printed circuit board) The film-like thermosetting resin composition used in the above can be easily produced. If the thickness T ₂ of the thermosetting resin layer is 50μm or less, it is easy to form a fine pattern in the thermosetting resin layer.

  Further, the structure according to the present embodiment is a structure (structure having a conductor circuit) manufactured by the above-described structure manufacturing method, and the diameter of the opening of the thermosetting resin layer is 30 μm or less. There may be. Compared with the conventional structure shown in FIG. 1, the structure manufactured by the above-described manufacturing method can have fine openings in the insulating layer and can have excellent reliability. In addition, since the diameter of the opening of the thermosetting resin layer in the structure is 30 μm or less, it is suitable for mounting a semiconductor element having a large number of pins having tens of thousands to hundreds of thousands of pins. It will be a thing.

  In addition, the thermosetting resin composition used in the method for producing a structure described above is not particularly limited as long as it can be cured by heat. However, an epoxy resin, a phenol resin, a cyanate ester resin, a polyamideimide resin, and a thermosetting resin are usable. It may be a resin composition containing at least one selected from the group consisting of curable polyimide resins. The thermosetting resin composition may contain an inorganic filler having a maximum particle size of 5 μm or less and an average particle size of 1 μm or less in a state dispersed in the thermosetting resin composition. By forming a thermosetting resin layer using such a thermosetting resin composition, the surface of the opening formed in the thermosetting resin layer becomes smooth, and it becomes easy to form a seed layer on the opening. Note that the maximum particle size of the inorganic filler in a state dispersed in the thermosetting resin composition is one measured using a microtrack method or a nanotrack method, for example, a dynamic light scattering nanotrack particle size distribution. The average value of the value measured using the total "UPA-EX150" (made by Nikkiso Co., Ltd.) and the laser diffraction scattering type micro track particle size distribution meter "MT-3100" (made by Nikkiso Co., Ltd.) is said.

  Hereinafter, although an example and an advantage of this indication are explained more concretely with an example, this indication is not limited to the following example.

<Synthesis of Binder Polymer (A-1)>
A polymerizable monomer (monomer) obtained by mixing 54 g of methacrylic acid, 150 g of methyl methacrylate and 96 g of ethyl acrylate (mass ratio 18/50/32) and 2.5 g of azobisisobutyronitrile. The solution was designated as “Solution a”.

  A solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 150 g of a mixed solution (mass ratio 3: 2) of 100 g of methyl cellosolve and 50 g of toluene was designated as “Solution b”.

  A flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas introduction tube was charged with 300 g of a mixture of 180 g of methyl cellosolve and 120 g of toluene (mass ratio 3: 2), and nitrogen gas was introduced into the flask. The mixture was heated with stirring while being blown, and the temperature was raised to 80 ° C.

  The solution a was added dropwise to the mixed solution in the flask over a period of 4 hours at a constant dropping rate, and then stirred at 80 ° C. for 2 hours. Next, the solution b was dropped into the solution in the flask at a constant dropping rate over 10 minutes, and then the solution in the flask was stirred at 80 ° C. for 3 hours. Further, the temperature of the solution in the flask was raised to 90 ° C. over 30 minutes and stirred at 90 ° C. for 2 hours. Then, the stirring was stopped and the solution was cooled to room temperature to obtain a binder polymer (A-1) solution. In this specification, room temperature means 25 ° C.

  The binder polymer (A-1) had a non-volatile content (solid content) of 44.6% by mass, a weight average molecular weight of 50,000, and an acid value of 117 mgKOH / g.

(Measurement method of weight average molecular weight)
The weight average molecular weight was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
(GPC conditions)
Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.)
Column: 3 in total, column specifications: 10.7 mmφ x 300 mm
Gelpack GL-R420
Gelpack GL-R430
Gelpack GL-R440 (Hitachi Chemical Co., Ltd., trade name)
Eluent: Tetrahydrofuran (hereinafter also referred to as “THF”)
Sample concentration: 120 mg of a binder polymer solution having a solid content of 42.8% by mass was sampled and dissolved in 5 mL of THF to prepare a sample.
Measurement temperature: 40 ° C
Injection volume: 200 μL
Pressure: 49Kgf / cm ² (4.8MPa)
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

(Measurement method of acid value)
About 1 g of the binder polymer synthesized in an Erlenmeyer flask is weighed, dissolved by adding a mixed solvent (mass ratio: toluene / methanol = 70/30), and then an appropriate amount of a phenolphthalein solution is added as an indicator, followed by 0.1N hydroxylation. The solution was titrated with an aqueous potassium solution, and the acid value was measured from the following formula.
x = 10 × Vf × 56.1 / (Wp × I)
In the formula, x represents an acid value (mgKOH / g), Vf represents a titration amount (mL) of a 0.1N KOH aqueous solution, Wp represents the mass (g) of the measured resin solution, and I was measured. The ratio (mass%) of the non volatile matter in a resin solution is shown.

<Synthesis of Binder Polymers (A-2) and (A-3)>
As the polymerizable monomer (monomer), the binder polymer (A-2) was obtained in the same manner as that for obtaining a solution of the binder polymer (A-1) except that the materials shown in Table 1 were used in the mass ratio shown in Table 1. ) And (A-3) were obtained.

<Preparation of photosensitive resin composition (coating liquid)>
The photosensitive resin compositions (coating solutions) of Examples and Comparative Examples were prepared by mixing the components shown in Tables 2 and 3 in the blending amounts (parts by mass) shown in Tables 2 and 3. The compounding quantity of the binder polymer in a table | surface is the mass (solid content) of a non volatile matter. Details of each component shown in Table 2 and Table 3 are as follows.

(A) Binder polymer Binder polymers (A-1) to (A-3) synthesized as described above were used.

(B) Photopolymerizable compound UA-13: (EO) (PO) -modified urethane dimethacrylate (ethylene oxide average 2 mol, propylene oxide average 18 mol adduct) (trade name, manufactured by Hitachi Chemical Co., Ltd.)
UA-7100: (EO) -modified isocyanurate-derived trimethacrylate (ethylene oxide average 27 mol adduct) (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)
TMPT-9EO: (EO) modified trimethylolpropane trimethacrylate (9 mol of ethylene oxide average adduct) (made by Shin-Nakamura Chemical Co., Ltd., trade name)
FA-024M: a vinyl compound (trade name, manufactured by Hitachi Chemical Co., Ltd.) in which R ⁵¹ and R ⁵² = methyl group, r5 = 6 (average value), and s51 + s52 = 12 (average value) in the following general formula (5) )
FA-321M: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (trade name, manufactured by Hitachi Chemical Co., Ltd.)
FA-MECH: γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate (trade name, manufactured by Hitachi Chemical Co., Ltd.)

(C) Photopolymerization initiator B-CIM: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole (trade name, manufactured by Hampford)

(D) Sensitizing dye EAB: 4,4′-bis (diethylamino) benzophenone (trade name, manufactured by Hodogaya Chemical Co., Ltd.)

(E) Hydrogen donor LCV: Leuco Crystal Violet (trade name, manufactured by Yamada Chemical Co., Ltd.)

Dye MKG: Malachite Green (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

<Preparation of printed wiring board having conductor circuit>
(Production of photosensitive element)
Each of the photosensitive resin compositions obtained above was applied on a 16 μm thick polyethylene terephthalate film (trade name “HTF-01” manufactured by Teijin Ltd.) (support film) so that the thickness was uniform. Then, using a hot air convection dryer, drying was performed at 70 ° C. for 1 minute and then at 110 ° C. for 1 minute to form a photosensitive resin layer having a film thickness after drying of 25 μm. Furthermore, a polyethylene film (manufactured by Tamapoly Co., Ltd., trade name “NF-15”) (protective layer) was laminated on the photosensitive resin layer, and a support film, a photosensitive resin layer, and a protective layer were laminated in order. As the photosensitive element, photosensitive elements according to Examples and Comparative Examples were obtained.

(Formation of photosensitive resin layer)
First, a copper clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name “MCL-E-679FG”) in which a copper foil having a thickness of 18 μm was adhered to both surfaces was prepared. The thickness of the copper clad laminate was 400 μm. The copper surface was roughened with a CZ treatment solution (trade name “MEC etch bond CZ-8100” manufactured by MEC Co., Ltd.). After heating this roughened copper substrate (hereinafter simply referred to as “substrate”) to 80 ° C., each of the photosensitive elements according to Examples and Comparative Examples was laminated on the copper surface of the substrate ( Layered). Lamination was performed under conditions of a temperature of 120 ° C. and a lamination pressure of 0.39 MPa so that the photosensitive resin layer of each photosensitive element was in close contact with the copper surface of the substrate while removing the protective layer. Subsequently, it cooled until it became room temperature, and the laminated substrate A by which the photosensitive resin layer and the support film were laminated | stacked on the copper surface of the board | substrate was obtained.

(Formation of photosensitive resin layer pattern)
Next, the multilayer substrate A is divided into two regions, and a circular pattern having a diameter of 30 μmφ, 40 μmφ, and 50 μmφ is arranged on a support film in one region at a pitch of 40 μm, 80 μm, and 100 μm, respectively. A photo tool made of PET was placed. The distance between the centers of two adjacent circular patterns is referred to as “pitch”. The exposure uses a parallel light exposure machine (trade name “EXM-1201”, manufactured by Oak Manufacturing Co., Ltd.) using a short arc UV lamp (trade name “AHD-5000R” manufactured by Oak Manufacturing Co., Ltd.) as a light source. The photosensitive resin layer was exposed through a PET phototool and a support film with an exposure amount (energy amount) that allows the diameter of a 30 μmφ circular pattern after development to be obtained as designed. For measurement of illuminance, an ultraviolet illuminance meter (trade name “UV-350SN type” manufactured by Oak Manufacturing Co., Ltd.) to which a 365 nm probe was applied was used.

  After the exposure, the support film is peeled off from the laminated substrate A, the photosensitive resin layer is exposed, and a 1% by mass sodium carbonate aqueous solution is sprayed at 30 ° C. and 0.2 MPa using a developing machine (manufactured by HMS). The exposed part was removed. The development time was set to twice the shortest development time of each photosensitive resin composition. Thus, the laminated substrate B was obtained by forming the cured film which consists of the hardened | cured material pattern (photosensitive resin layer pattern) of a photosensitive resin composition on the copper surface of a board | substrate. The shortest development time was a value obtained by measurement as follows. First, the laminated substrate A was cut into a size of 30 mm × 30 mm to obtain a test piece. After peeling off the support film from the test piece, spray development is performed at a pressure of 0.2 MPa using a 1% by mass sodium carbonate aqueous solution at 30 ° C., and the shortest time that can be visually confirmed that an unexposed portion of 1 mm or more has been removed. Was set as the shortest development time.

(Preparation of thermosetting film type resin composition)
As a thermosetting resin composition used for forming a thermosetting resin layer (interlayer insulating layer) of a printed wiring board, 70 parts by mass of an epoxy resin, 30 parts by mass (solid content), and an inorganic filler component The solution of the thermosetting resin composition was prepared by mixing. In addition, the inorganic filler component was blended so as to be 30% by mass with respect to the resin content.

  As the epoxy resin, a biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name “NC-3000H”) was used.

  As the curing agent, a curing agent solution obtained as follows was used. In a 2 L reaction vessel equipped with a thermometer, a stirrer, and a moisture quantifier with a reflux condenser, a volume of 2 L that can be heated and cooled, 26.40 g of bis (4-aminophenyl) sulfone: 2,2′-bis [4 -(4-Maleimidophenoxy) phenyl] propane: 484.50 g, p-aminobenzoic acid: 29.10 g, and dimethylacetamide: 360.00 g were added and reacted at 140 ° C. for 5 hours in the molecular main chain. A solution of a curing agent having a sulfone group and having an acidic substituent and an unsaturated N-substituted maleimide group was obtained.

  As the inorganic filler component, silica filler having an average particle size of 50 nm and silane coupling treatment with vinylsilane was used. The dispersion state was measured using a dynamic light scattering nanotrack particle size distribution analyzer “UPA-EX150” (manufactured by Nikkiso Co., Ltd.) and a laser diffraction scattering microtrack particle size distribution analyzer “MT-3100” (manufactured by Nikkiso Co., Ltd.). The maximum particle size was confirmed to be 1 μm or less.

  The solution of the thermosetting resin composition obtained as described above is uniformly applied onto a 16 μm-thick polyethylene terephthalate film (G2-16, manufactured by Teijin Ltd., trade name) as a support layer. A composition layer was formed. Thereafter, the thermosetting resin composition layer was dried at 100 ° C. for about 10 minutes using a hot air convection dryer to obtain a film-like thermosetting resin composition. The film-shaped thermosetting resin composition prepared the film thickness of 10-90 micrometers.

  Next, a polyethylene film (trade name “NF-15” manufactured by Tamapoly Co., Ltd.) is protected on the surface opposite to the side in contact with the support layer so that dust or the like does not adhere to the thermosetting resin composition layer. Bonding as a film gave a thermosetting film type resin composition.

(Opening formation)
A thermosetting resin layer was formed on the laminated substrate B using the obtained thermosetting film type resin composition. Specifically, first, only the protective film of the thermosetting film type resin composition made of the above thermosetting resin composition is peeled off, and heat is applied to both surfaces (on the photosensitive resin layer pattern and the conductor circuit) of the multilayer substrate B. A curable resin composition was placed. The thermosetting resin composition was laminated on the surface of the laminated substrate B using a press-type vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho, trade name). Regarding the pressing conditions, the hot plate temperature was 80 ° C., the evacuation time was 20 seconds, the laminating press time was 30 seconds, the atmospheric pressure was 4 kPa or less, and the pressing pressure was 0.4 MPa. Next, the thermosetting resin layer was thermoset at a predetermined temperature and a predetermined time in a clean oven.

  Thereafter, plasma treatment (plasma ashing) was performed under the conditions shown in Table 4, whereby the thermosetting resin layer was ground to form an exposed portion in the photosensitive resin layer pattern. Next, along the steps shown in Table 5, the exposed portion of the photosensitive resin layer pattern is removed, and a part of the thermosetting resin layer and the photosensitive resin layer is opened to form a via, thereby forming a printed wiring board. Got.

<Evaluation of openability>
The via opening (removability of the cylindrical resist) was evaluated based on the following criteria by observing vias having a diameter of 30 μmφ, 40 μmφ, and 50 μmφ with an electron microscope (SEM). The evaluation results are shown in Tables 6 and 7.
A: There is no residue derived from the photosensitive resin composition on the copper surface, and it can be peeled off and removed.
B: Residue derived from the photosensitive resin composition is generated in a portion where the via is formed (opening portion) less than 50% of the volume.
C: Residue derived from the photosensitive resin composition is generated at 50% or more of the volume in the via forming part (opening part).

  As is clear from Tables 6 and 7, it was found that the opening property was good even when the via diameter was 30 μm or less by using the photosensitive resin composition of the example. On the other hand, the opening property of the via obtained using the photosensitive resin composition of the comparative example was inferior to that of the example.

  A printed wiring board was produced in the same manner as in the above evaluation except that the diameter of the via was changed to 100 μm, and the evaluation was performed in the same manner as described above. Furthermore, a printed wiring board was produced in the same manner as in the above evaluation except that the via diameter was changed to 200 μm, and the evaluation was performed in the same manner as described above. In any case, when the photosensitive resin compositions of Examples 1 to 6 were used, it was found that even when the roughening time was shortened to 1/3, the opening was good and the throughput was excellent.

DESCRIPTION OF SYMBOLS 100 ... Multilayer printed wiring board, 101 ... Copper clad laminated board, 102 ... Wiring pattern, 103 ... Interlayer insulation layer, 104 ... Opening, 105 ... Seed layer, 106 ... Wiring pattern, 107 ... Wiring pattern, 108 ... Solder resist.

Claims (13)

A photosensitive resin composition used in a method for producing a structure in which an opening is provided in an insulating layer formed on a surface of a substrate having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening. Because
Containing a binder polymer, a photopolymerizable compound, and a photopolymerization initiator,
The photopolymerizable compound includes at least one selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2),
A manufacturing method of the structure is as follows:
Using the photosensitive resin composition, a photosensitive resin layer forming step of forming a first photosensitive resin layer on the substrate so as to cover a conductor circuit;
A first patterning step of patterning the first photosensitive resin layer by subjecting it to an exposure process and a development process;
A thermosetting resin layer forming step of forming a thermosetting resin layer on the substrate so as to cover the pattern of the first photosensitive resin layer;
A pattern exposure step of removing a part of the thermosetting resin layer to expose a predetermined portion of the pattern of the first photosensitive resin layer from the thermosetting resin layer;
Removing the predetermined portion of the pattern of the first photosensitive resin layer exposed from the thermosetting resin layer, and forming an opening in the thermosetting resin layer to expose the conductor circuit; A photosensitive resin composition comprising:

[In Formula (1), R ¹¹ represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, or a phenylene group, and R ¹² and R ¹³ are each independently a hydrogen atom or Represents a methyl group, X ¹¹ and X ¹² each independently represent an oxyalkylene group or a polyoxyalkylene group containing at least one selected from the group consisting of an oxyethylene group and an oxypropylene group, and X ¹¹ and X ¹² The total number of oxyethylene groups and oxypropylene groups contained in is 0-80. ]

[In the formula (2), R ²¹ , R ²² and R ²³ each independently represents an alkylene group having 1 to 20 carbon atoms, and R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a methyl group. X ²¹ , X ²² and X ²³ each independently represent an oxyalkylene group or a polyoxyalkylene group containing at least one selected from the group consisting of an oxyethylene group and an oxypropylene group, and X ²¹ , X ²² the total number of oxyethylene groups and oxypropylene groups contained in and ^{X 23} is 0 to 120. ]   The photosensitive resin composition of Claim 1 in which the said binder polymer has a structural unit derived from the (meth) acrylic-acid alkylester.   The photosensitive resin composition of Claim 1 or 2 whose acid value of the said binder polymer is 60-250 mgKOH / g.   The photosensitive resin composition as described in any one of Claims 1-3 whose weight average molecular weights of the said binder polymer are 10,000-100000.   The photosensitive resin composition as described in any one of Claims 1-4 in which the said photoinitiator contains a 2,4,5-triaryl imidazole dimer.   The photosensitive resin composition as described in any one of Claims 1-5 which further contains a sensitizing dye.   The photosensitive resin composition as described in any one of Claims 1-6 which further contains a hydrogen donor.   A photosensitive element provided with a support body and the photosensitive resin layer formed on the said support body using the photosensitive resin composition as described in any one of Claims 1-7. Forming a photosensitive resin layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 7 or the photosensitive element according to claim 8, and
An exposure step of irradiating a predetermined portion of the photosensitive resin layer with an actinic ray to cure the predetermined portion;
A development step of forming a resist pattern made of a cured product of the photosensitive resin composition on the substrate by removing portions other than the predetermined portion of the photosensitive resin layer from the substrate. Pattern formation method.   The method for forming a resist pattern according to claim 9, wherein the wavelength of the actinic ray is in a range of 340 to 430 nm. A method of manufacturing a structure in which an opening is provided in an insulating layer formed on a surface of a substrate having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening,
A photosensitive resin composition according to any one of claims 1 to 7, or a photosensitive element according to claim 8, wherein a first photosensitive resin is formed on the substrate so as to cover a conductor circuit. A photosensitive resin layer forming step of forming a layer;
A first patterning step of patterning the first photosensitive resin layer by subjecting it to an exposure process and a development process;
A thermosetting resin layer forming step of forming a thermosetting resin layer on the substrate so as to cover the pattern of the first photosensitive resin layer;
A pattern exposure step of removing a part of the thermosetting resin layer to expose a predetermined portion of the pattern of the first photosensitive resin layer from the thermosetting resin layer;
Removing the predetermined portion of the pattern of the first photosensitive resin layer exposed from the thermosetting resin layer, and forming an opening in the thermosetting resin layer to expose the conductor circuit; A structure manufacturing method comprising:   The manufacturing method of the structure of Claim 11 further equipped with the thermosetting process of thermosetting the said thermosetting resin layer as a process between the said thermosetting resin layer formation process and the said pattern exposure process. A seed layer forming step of forming a seed layer as a base of the wiring portion by an electroless plating method so as to cover at least a part of the thermosetting resin layer after the opening is formed;
A second patterning step of forming a second photosensitive resin layer so as to cover the seed layer and then patterning the second photosensitive resin layer by performing an exposure process and a development process;
A wiring part patterning step of patterning the wiring part by peeling the pattern of the second photosensitive resin layer after forming the wiring part by electrolytic plating so as to cover at least a part of the seed layer;
The structure manufacturing method according to claim 11, further comprising: a seed layer removing step of removing a seed layer in a region where the wiring portion is not formed.

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