JP2016070978A - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for producing structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that can increase a residual ratio of a part where an opening is to be formed.SOLUTION: The photosensitive resin composition is used for a method for producing a structure in which an opening is formed in an insulation layer formed on a surface of a support having a conductor circuit, and a wiring part to be connected to the conductor circuit is formed in the opening. The photosensitive resin composition comprises: a binder polymer; a photopolymerizable compound containing a bisphenol di(meth)acrylate having 8 to 30 in total of structural units of an oxyethylene group and an oxypropylene group; and a photopolymerization initiator.SELECTED DRAWING: None

Description

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

  A printed wiring board, which is one of the structures having conductor circuits, has a plurality of wiring layers formed on a core board, and a copper-clad laminate that serves as the core board and interlayer insulation provided between each wiring layer. And a solder resist provided on the outermost surface. 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.

  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.

  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). The interlayer insulating layer 103 may be printed with a thermosetting resin composition using a screen printer or a roll coater, or a film made of the thermosetting resin composition is prepared in advance, and this film is formed using a laminator. Can also be attached to the surface of the printed wiring board. Next, an opening 104 is formed using a YAG laser or a carbon dioxide gas laser 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, a seed layer 105 is formed by an electroless plating method (see FIG. 1C). A photosensitive resin composition is laminated on the seed layer 105, and a predetermined portion is exposed and developed to form a photosensitive resin layer pattern 106 (see FIG. 1D). Next, the wiring pattern 107 is formed by an electrolytic plating method, and the cured product of the photosensitive resin composition is removed by a peeling solution, and then the seed layer 105 is removed by etching (see FIG. 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.

  Incidentally, 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 the 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 number of pins of the semiconductor element to be mounted is designed from several thousand pins to around 10,000 pins, so there is no need to provide openings with a small diameter and a narrow pitch. It was.

  However, as miniaturization of semiconductor elements progresses and the number of pins increases from tens of thousands to hundreds of thousands of pins, the openings formed in the interlayer insulating material of the printed wiring board are also narrowed to match the number of pins of the semiconductor elements. The need to do is increasing. Recently, development of a printed wiring board in which an opening is provided by a laser using a thermosetting resin material has been advanced (for example, see Patent Documents 1 to 4 below).

  However, the multilayer printed wiring board 100 manufactured by the method shown in FIG. 1 requires introduction of a new facility such as a laser, and it is difficult to provide a relatively large opening or a minute opening of 60 μm or less. There are problems that it is necessary to use different lasers according to the aperture diameter, and it is difficult to provide 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.

  Therefore, in order to solve the above-described problem, a method using a photosensitive resin composition has been proposed as a method of providing an opening without using a laser (see, for example, Patent Document 5 below).

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

  However, when the diameter of the opening is further reduced to a fine region of 30 μm or less, a photosensitive resin layer is formed on the conductor circuit using a conventional photosensitive resin composition, and then an opening forming portion is formed using an alkaline aqueous solution. When patterning so as to remain, it becomes difficult to sufficiently leave the opening forming portion formed using the photosensitive resin composition, which may cause defects, and adversely affects the subsequent steps. is there. In particular, in the design of opening formation with a wide width between the openings (also referred to as “pitch”), there is a problem that the remaining ratio of the opening forming portion is likely to be lowered.

  This invention is made | formed in view of the said subject, and it aims at providing the photosensitive resin composition which can raise the residual rate of an opening formation part. Another object of the present invention is to provide a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for producing a structure.

  The photosensitive resin composition according to the present invention has a structure in which an opening is provided in an insulating layer formed on the surface of a support 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 and a bisphenol di (meth) acrylate having a total number of structural units of oxyethylene groups and oxypropylene groups of 8 to 30 A compound and a photopolymerization initiator, wherein the manufacturing method of the structure uses the photosensitive resin composition to form a first photosensitive resin layer on the support so as to cover a conductor circuit. A photosensitive resin layer forming step to be formed; a first patterning step of patterning the first photosensitive resin layer by exposing and developing the first photosensitive resin layer; and covering the pattern of the first photosensitive resin layer like A thermosetting resin layer forming step of forming a thermosetting resin layer on the support, and removing a part of the thermosetting resin layer to provide a predetermined portion of the pattern of the first photosensitive resin layer A pattern exposing step of exposing 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 expose the conductor circuit And an opening forming step formed in the thermosetting resin layer.

  According to the photosensitive resin composition according to the present invention, it is possible to increase the remaining ratio of the opening forming portion formed using the photosensitive resin composition. Moreover, the photosensitive resin composition according to the present invention is excellent in adhesion to the substrate, has a sufficiently high mechanical strength after exposure (after curing), and hardly breaks.

［式（１）中、Ｒ^１１及びＲ^１２はそれぞれ独立に、水素原子又はメチル基を示し、ＸＯ及びＹＯはそれぞれ独立に、オキシエチレン基又はオキシプロピレン基を示し、ｍ１、ｍ２、ｎ１及びｎ２はそれぞれ独立に、０〜３０を示す。］ The photopolymerizable compound preferably includes a compound represented by the following general formula (1).

[In the formula (1), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, XO and YO each independently represent an oxyethylene group or an oxypropylene group, m1, m2, n1 and n2 Each independently represents 0-30. ]

  The binder polymer preferably has a structural unit derived from at least one polymerizable monomer selected from the group consisting of benzyl (meth) acrylate, a benzyl (meth) acrylate derivative, styrene, and a styrene derivative.

  The acid value of the binder polymer is preferably 80 to 250 mgKOH / g. The binder polymer preferably has a weight average molecular weight of 10,000 to 100,000.

  The photopolymerizable compound preferably includes a compound having an ethylenically unsaturated bond. The photopolymerizable compound preferably includes a compound having three or more ethylenically unsaturated bonds as the compound having an ethylenically unsaturated bond.

  The photopolymerization initiator preferably contains a 2,4,5-triarylimidazole dimer.

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

  The photosensitive resin composition according to the present invention may further contain a hydrogen donor.

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

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

  In the method for forming a resist pattern according to the present invention, the wavelength of the actinic ray is preferably in the range of 340 to 430 nm.

  In the structure manufacturing method according to the present invention, an opening is provided in an insulating layer formed on the surface of a support 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 invention or a photosensitive element according to the present invention, wherein a first photosensitive resin layer is formed on the support so as to cover a conductor circuit. A photosensitive resin layer forming step to be formed; a first patterning step of patterning the first photosensitive resin layer by exposing and developing the first photosensitive resin layer; and covering the pattern of the first photosensitive resin layer The thermosetting resin layer forming step of forming a thermosetting resin layer on the support, and a predetermined portion of the pattern of the first photosensitive resin layer by removing a part of the thermosetting resin layer Exposing the pattern from the thermosetting resin layer Comprising a degree, by removing the first photosensitive resin layer exposed from the thermosetting resin layer, and a opening forming step of forming an opening for exposing the conductor circuit in the thermosetting resin layer.

  The structure manufacturing method according to the present invention 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. preferable.

  In the structure manufacturing method according to the present invention, 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. Seed layer forming step and second patterning step of 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 And a wiring part patterning step of patterning the wiring part by peeling off 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 And a seed layer removing step of removing a seed layer in a region where the wiring portion is not formed.

  ADVANTAGE OF THE INVENTION According to this invention, the residual rate of the opening formation part formed using the photosensitive resin composition can be raised.

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

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

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) 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 “oxyethylene group” is a group represented by (—C ₂ H ₄ —O—), and the “oxypropylene group” is represented by (—C ₃ H ₆ —O—). It is a group.

  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 of the present embodiment has a structure in which an opening is provided in an insulating layer formed on the surface of a support 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 method for producing the structure includes a photosensitive resin layer forming step of forming a first photosensitive resin layer on the support so as to cover a conductor circuit using the photosensitive resin composition of the present embodiment, A first patterning step of patterning the first photosensitive resin layer by exposing and developing, and thermosetting on the support so as to cover the pattern of the first photosensitive resin layer; A thermosetting resin layer forming step for forming a resin layer, and a part of the thermosetting resin layer is removed to expose a predetermined portion of the pattern of the first photosensitive resin layer from the thermosetting resin layer. A pattern exposing 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. Prepare.

  The photosensitive resin composition of the present 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”). (C) a photopolymerization initiator (hereinafter also referred to as “component (C)”). In the photosensitive resin composition of the present embodiment, the component (B) contains a bisphenol di (meth) acrylate having a total number of structural units of oxyethylene groups and oxypropylene groups of 8 to 30. The photosensitive resin composition of this embodiment may further contain other components as necessary.

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

  The binder polymer as component (A) is not particularly limited, but is preferably soluble in an 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. These may be used alone or in any combination of two or more.

  (A) It is preferable that a component has a structural unit derived from (meth) acrylic acid from a viewpoint which is further excellent in developability and peelability. In addition, the component (A) is at least one polymer selected from the group consisting of benzyl (meth) acrylate, benzyl (meth) acrylate, styrene and styrene derivatives, from the viewpoint of further improving the adhesion to the substrate. It is preferable to have a structural unit derived from a polymerizable monomer, and it is more preferable to have a structural unit derived from a polymerizable monomer selected from the group consisting of styrene and styrene derivatives. The component (A) is derived from a structural unit derived from at least one selected from the group consisting of benzyl (meth) acrylate and benzyl (meth) acrylate, and at least one selected from the group consisting of styrene and a styrene derivative. It is more preferable that both structural units are included. The component (A) preferably has a structural unit derived from these polymerizable monomers, and more preferably is obtained by radical polymerization of these polymerizable monomers.

  In the case where the component (A) has a structural unit derived from benzyl (meth) acrylate or a derivative thereof, the content of the structural unit is more polymerizable and constitutes the component (A) in terms of further excellent resolution and peelability. It is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 60% by mass based on the total solid content of the monomer. This content is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more in terms of further excellent resolution. In addition, this content is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less from the viewpoint of further excellent peelability.

  In the case where the component (A) has a structural unit derived from styrene or a derivative thereof, the content of the structural unit is that of the polymerizable monomer constituting the component (A) in that the adhesive unit and the peelability are further excellent. It is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, and still more preferably 20 to 50% by mass based on the total solid content. This content is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more in terms of further excellent adhesion. Moreover, this content is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less from the viewpoint of further excellent peelability.

  Moreover, it is preferable that (A) component has a structural unit derived from (meth) acrylic-acid alkylester from a viewpoint of improving alkali developability and peelability.

  When the component (A) has a structural unit derived from a (meth) acrylic acid alkyl ester, the content of the structural unit is a polymer that constitutes the component (A) in that the peelability, resolution, and adhesion are further excellent. It is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, and still more preferably 3 to 50% by mass, based on the total solid content of the functional monomer. This content is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more in terms of excellent peelability. In addition, this content is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less in terms of further excellent resolution and adhesion.

  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. These may be used alone or in any combination of two or more.

  The acid value of the component (A) is preferably 80 to 250 mgKOH / g, more preferably 90 to 250 mgKOH / g, and more preferably 100 to 230 mgKOH / g in terms of further improving developability and developer resistance. It is more preferable that it is 110-210 mgKOH / g, and it is very preferable that it is 120-200 mgKOH / g. In addition, when performing solvent image development, it is preferable to adjust the polymerizable monomer (monomer) which has carboxyl groups, such as (meth) acrylic acid, to a small quantity.

  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), it is further excellent in developability and developer resistance. It is preferably 10,000 to 100,000, more preferably 20,000 to 80,000, still more preferably 25,000 to 70,000. The weight average molecular weight of the component (A) is preferably 100,000 or less, more preferably 80000 or less, and still more preferably 70000 or less, from the viewpoint of further improving developability. The weight average molecular weight of the component (A) is preferably 10,000 or more, more preferably 20,000 or more, and further preferably 25,000 or more from the viewpoint of further excellent developer resistance.

  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 of the binder polymer include two or more 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.

  The content of the component (A) is preferably 30 to 70 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) in terms of further excellent film formability, sensitivity, and resolution. It is more preferably 35 to 65 parts by mass, and still more preferably 40 to 60 parts by mass.

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

  In the photosensitive resin composition of the present embodiment, the component (B) is a bisphenol di (meta) having a total number of structural units of oxyethylene groups and oxypropylene groups (total number of structural units in one molecule) of 8 to 30. ) Contains acrylate. The component (B) preferably contains a compound represented by the following general formula (1) as the bisphenol-type di (meth) acrylate.

［式（１）中、Ｒ^１１及びＲ^１２はそれぞれ独立に、水素原子又はメチル基を示す。ＸＯ及びＹＯはそれぞれ独立に、オキシエチレン基又はオキシプロピレン基を示す。式（１）で表される化合物の分子内において、ＸＯ及びＹＯは、それぞれ連続してブロック的に存在してもよく、ランダムに存在してもよい。（ＸＯ）_ｍ１、（ＸＯ）_ｍ２、（ＹＯ）_ｎ１及び（ＹＯ）_ｎ２は、それぞれ（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。ｍ１＋ｍ２＋ｎ１＋ｎ２が８〜３０であって、ｍ１、ｍ２、ｎ１及びｎ２はそれぞれ独立に、０〜３０の数値を採り得る。ＸＯがオキシエチレン基、ＹＯがオキシプロピレン基である場合、例えば、ｍ１＋ｍ２は１〜３０であり、ｎ１＋ｎ２は０〜２０である。ＸＯがオキシプロピレン基、ＹＯがオキシエチレン基である場合、例えば、ｍ１＋ｍ２は０〜２０であり、ｎ１＋ｎ２は１〜３０である。ｍ１、ｍ２、ｎ１及びｎ２は構造単位の構造単位数を示す。従って、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。］

[In formula (1), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group. XO and YO each independently represent an oxyethylene group or an oxypropylene group. In the molecule of the compound represented by the formula (1), XO and YO may be continuously present in blocks or may be present randomly. (XO) _m1 , (XO) _m2 , (YO) _n1 and (YO) _n2 each represent a (poly) oxyethylene group or a (poly) oxypropylene group. m1 + m2 + n1 + n2 is 8-30, and m1, m2, n1, and n2 can each independently take a numerical value of 0-30. When XO is an oxyethylene group and YO is an oxypropylene group, for example, m1 + m2 is 1-30 and n1 + n2 is 0-20. When XO is an oxypropylene group and YO is an oxyethylene group, for example, m1 + m2 is 0-20 and n1 + n2 is 1-30. m1, m2, n1, and n2 represent the number of structural units. Therefore, an integer value is shown in a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, the same applies to the number of structural units. ]

  By using the compound represented by the general formula (1) as the component (B), the mechanical strength after exposure of the photosensitive resin composition can be sufficiently increased, and the opening diameter is 30 μm or less and the pitch. Even when a wide opening forming portion is formed, the remaining ratio of the opening forming portion is further improved.

  In the general formula (1), the number of structural units of the structural unit of the oxyethylene group is preferably independently 8 to 30, preferably 8 to 28, from the viewpoint of further improving developability and removability. It is preferable that it is 8-25, and it is still more preferable. In addition, the number of structural units of the oxypropylene group is preferably 0 to 30, more preferably 0 to 25, and more preferably 0 to 20 from the viewpoint of further improving the adhesion. More preferably.

  As a compound represented by General formula (1), a commercially available thing may be used and what was synthesize | combined may be used. These can be used alone or in any combination of two or more. As a compound represented by the general formula (1), 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) or FA-321M. 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane (trade name, manufactured by Hitachi Chemical Co., Ltd.) is 2 as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). , 2-bis (4- (methacryloxyoctadecaethoxy) phenyl) propane is commercially available as BPE-900 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). These may be used alone or in any combination of two or more.

  The content of the compound represented by the general formula (1) is preferably 10 to 90% by mass, more preferably 10 to 80% by mass with respect to the mass of the entire component (B), and 20 to 20%. More preferably, it is 60 mass%.

  (B) A component can contain other photopolymerizable compounds other than the compound represented by General formula (1), and if it can photocrosslink, it can be especially used without a restriction | limiting. For example, component (B) is a compound having an ethylenically unsaturated bond (excluding compounds corresponding to bisphenol di (meth) acrylates having a total number of structural units of oxyethylene groups and oxypropylene groups of 8 to 30). Can be included. 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 an ethylenically unsaturated bond in the molecule. Examples thereof include compounds having three or more (for example, three).

  Examples of the compound having one ethylenically unsaturated bond in the molecule include nonylphenoxypolyethyleneoxyacrylate and fumaric acid compounds.

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

  Examples of the compound having three or more ethylenically unsaturated bonds in the molecule include 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 pentaerythritol tri (meta) ) Acrylate, tetramethylol methane tri (meth) acrylate, EO modified tetramethylol methane tri (meth) acrylate, PO modified tetramethylol methane tri (meth) acrylate, E · PO-modified tetramethylolmethane tri (meth) acrylate, EO-modified isocyanurate derived trimethacrylate, PO-modified isocyanurate derived trimethacrylate, and include EO · PO-modified isocyanurate derived trimethacrylate. Among these, commercially available products include, for example, A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd., tetramethylolmethane triacrylate), TMPT21E, TMPT30E (manufactured by Hitachi Chemical Co., Ltd., EO-modified trimethylolpropane). Trimethacrylate), M-114 (manufactured by Toagosei Co., Ltd., 4-normalnonylphenoxyoctaethyleneoxyacrylate), and FA-MECH (manufactured by Hitachi Chemical Co., Ltd., γ-chloro-β-hydroxypropyl-β′-methacryloyl). Oxyethyl-o-phthalate). Photopolymerizable compounds other than the compound represented by the general formula (1) can be used alone or in combination of two or more.

  Moreover, it is preferable that (B) component contains polyalkylene glycol di (meth) acrylate from a viewpoint of further improving the flexibility of the hardened | cured material (cured film) of the photosensitive resin composition. The polyalkylene glycol di (meth) acrylate is preferably a compound represented by the following general formula (2), (3) or (4). These can be used alone or in combination of two or more. The content of the polyalkylene glycol di (meth) acrylate is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and more preferably 10 to 30% by mass with respect to the mass of the entire component (B). % Is more preferable.

In the above general formulas (2), (3) and (4), R ²¹ , R ²² , R ³¹ , R ³² , R ⁴¹ and R ⁴² each independently represent a hydrogen atom or a methyl group, and EO represents an oxyethylene group PO represents an oxypropylene group. r21, r22, r3 and r4 represent the number of structural units of the oxyethylene group, and s2, s31, s32 and s4 represent the number of structural units of the oxypropylene group. In one molecule, the number of structural units of the oxyethylene group “r21 + r22”, r3 and r4 (average value) are each independently 1-30, and the number of structural units of the oxypropylene group s2, “s31 + s32” and s4 (average value) ) Each independently represents 1 to 30.

  In the compound represented by the general formula (2), (3) or (4), the number of structural units of the oxyethylene group “r21 + r22”, r3 and r4 are 1 to 30, preferably 1 to 10, More preferably, it is 4-9, More preferably, it is 5-8. When the number of structural units is 30 or less, there is a tendency that sufficient resolution, adhesion, and resist shape can be easily obtained.

  In the compound represented by the general formula (2), (3) or (4), the number of structural units s2, “s31 + s32” and s4 of the oxypropylene group is 1 to 30, preferably 5 to 20. More preferably, it is 8-16, More preferably, it is 10-14. When the number of structural units is 30 or less, it is easy to obtain a sufficient resolution, and sludge tends not to be generated.

As the compound represented by the general formula (2), R ²¹ and R ²² = methyl group, r21 + r22 = 6 (average value), s2 = 12 (average value) vinyl compound (manufactured by Hitachi Chemical Co., Ltd., product) Name FA-023M). As the compound represented by the general formula (3), R ³¹ and R ³² = methyl group, r3 = 6 (average value), s31 + s32 = 12 (average value) vinyl compound (manufactured by Hitachi Chemical Co., Ltd., product) Name FA-024M). As the compound represented by the above general formula (4), R ⁴¹ and R ⁴² = hydrogen atom, r4 = 1 (average value), s4 = 9 (average value) vinyl compound (manufactured by Shin-Nakamura Chemical Co., Ltd.) , Sample name NK ester HEMA-9P) and the like. These can be used alone or in combination of two or more.

  The content of the component (B) is preferably 30 to 70 parts by mass, more preferably 35 to 65 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). More preferably, it is 40-60 mass parts. When the content of the component (B) is 30 parts by mass or more, the sensitivity and resolution tend to be further improved, and when the content is 70 parts by mass or less, the resist shape is further improved. Tend to be.

((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- Acridine such as 2,4,5-triarylimidazole dimer such as methoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane Derivatives, N-phenylglycine, N-phenylglycine derivatives, coumarin compounds and the like can be mentioned. These are used alone or in combination of two or more.

  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, it is more preferable that (C) component contains a 2,4,5-triarylimidazole dimer from a viewpoint which adhesiveness improves further. When the 2,4,5-triarylimidazole dimer is contained, the content is preferably 10 to 100% by mass, more preferably 30 to 100% by mass based on the total solid content of the component (C). 50-100 mass% is still more preferable. When the content is 10% by mass or more, sensitivity and resolution tend to be further improved.

  The content of the component (C) is preferably 0.1 to 10 parts by mass and more preferably 2 to 6 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). Preferably, the amount is 2.5 to 5 parts by mass. When the content is 0.1 parts by mass or more, sensitivity and resolution tend to be improved, and when the content is 10 parts by mass or less, the shape of the opening forming part tends to be further improved. is there.

((D): sensitizing dye)
The photosensitive resin composition of 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. These can be used alone or in combination of two or more.

  As the component (D), a sensitizing dye having an absorption maximum at 340 to 430 nm can be used. In particular, when the photosensitive resin layer is exposed 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 preferably contains at least one sensitizing dye selected from the group consisting of a coumarin compound, a triarylamine compound, a thioxanthone compound and an aminoacridine compound, and among them, a dialkylaminobenzophenone compound, a pyrazoline compound, an anthracene compound and a triarylamine compound More preferably, at least one selected from the group consisting of:

  When (D) component is contained, it is preferable that content of (D) component is 0.01-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, 0 More preferably, the content is 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass. When the content is 0.01 parts by mass or more, the sensitivity and resolution tend to be further improved, and when the content is 10 parts by mass or less, the resist shape of the opening forming portion is further improved. Tend to be.

((E): Hydrogen donor)
The photosensitive resin composition of this embodiment may further contain (E) a hydrogen donor (hereinafter also referred to as “component (E)”). Hydrogen can be supplied during the reaction of the exposed part. By further containing the component (E), the contrast (also referred to as “imaging”) between the exposed portion and the unexposed portion can be further improved.

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

  When the component (E) is included, the content of the component (E) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). More preferably, it is 05-5 mass parts, and it is still more preferable that it is 0.1-2 mass parts. When the content 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 less likely to precipitate as foreign matter after film formation. Tend to be.

(Other ingredients)
If necessary, the photosensitive resin composition of 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. Dye, photochromic agent such as tribromophenylsulfone, leucocrystal violet, thermochromic inhibitor, plasticizer such as p-toluenesulfonamide, pigment, filler, antifoaming agent, flame retardant, stabilizer, adhesion promoter , 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 are used alone or in combination of two or more. It is preferable that these content is 0.01-20 mass parts, respectively with respect to 100 mass parts of total amounts of (A) component and (B) component.

[Solution of photosensitive resin composition]
The photosensitive resin composition of this embodiment may contain the solvent mentioned later in order to adjust a viscosity as needed, for example, melt | dissolve the photosensitive resin composition of this embodiment in a solvent. It can be used as a solution (coating solution) 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 of the present embodiment by applying a coating liquid on the surface of a support of a photosensitive element, which will be described later, a substrate, and the like, and then drying.

  Although the thickness of the photosensitive resin layer varies depending on its use, it is preferably 2 to 50 μm in thickness after drying. The surface of the photosensitive resin layer may be covered with a protective layer. Examples of the protective layer include polymer films such as polyethylene and polypropylene.

<Photosensitive element>
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 of 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.

  The protective layer preferably has a lower adhesive strength to the photosensitive resin layer than the adhesive strength of the support to the photosensitive resin layer, and is preferably a low fish eye film. 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 comprises a step of preparing a coating solution containing the photosensitive resin composition of the present embodiment, a step of coating the coating solution on a support to form a coating layer, and drying the coating layer to sensitize the photosensitive element. And a step of forming a conductive 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.

  Although the application layer is not particularly limited as long as at least a part of the solvent can be removed from the application layer, for example, it is preferably performed at 70 to 150 ° C. for 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin layer is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.

  Moreover, although the thickness of the photosensitive resin layer can be suitably adjusted as needed, it is preferable that it is 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 is preferably 5 to 75%, more preferably 10 to 65%, and still more preferably 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 resolution 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 it winds up in roll shape, it is preferable to wind up so that a support body may become an outer side. 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). From the viewpoint of end face protection, it is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll thus obtained, and it is preferable to install a moisture-proof end face separator from the standpoint of edge fusion resistance. As a packaging method, it is preferable to wrap and package in a black sheet with low moisture permeability.

<Method for forming resist pattern>
A resist pattern can be formed using the photosensitive resin composition. The resist pattern forming method of 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, and (ii) ) An exposure step of irradiating a predetermined portion of the photosensitive resin layer with actinic rays to expose and cure the predetermined portion; and (iii) removing portions other than the predetermined portion of the photosensitive resin layer 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 a photosensitive resin layer on a substrate, for example, a method in which a photosensitive resin composition is applied on a substrate and then dried, and the photosensitive resin layer in the photosensitive element described above is formed on the substrate. A method of transferring (laminating) may be 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 is preferably performed under reduced pressure from the viewpoint of further improving adhesion and followability. The photosensitive resin layer and / or the substrate is preferably heated at a temperature of 70 to 130 ° C. during the pressure bonding, and may be pressure bonded at a pressure of 0.1 to 1.0 MPa (1 to 10 kgf / cm ² ). Although preferred, these conditions are not particularly limited. 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, etc. Those that effectively emit ultraviolet rays, visible light, and the like are used.

  The wavelength of the actinic ray (exposure wavelength) is preferably 340 to 430 nm, and more preferably 350 to 420 nm, from the viewpoint of obtaining the effects of the present invention 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 the developing method include a method using a dipping method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, and the like. From the viewpoint of improving resolution, the high pressure spray method is most suitable. 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, A dilute solution of 1 to 5 mass% sodium tetraborate is preferred. The pH of the alkaline aqueous solution is preferably 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. In order to prevent flammability, it is preferable to add water in the range of 1 to 20% by mass to these organic solvents to obtain an organic solvent developer.

In the resist pattern forming method of the present 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. The method may further include a step of curing the resist pattern.

<Method for manufacturing structure>
The photosensitive resin composition of the present embodiment and the photosensitive element of the present embodiment are suitably used for the manufacture of a structure (for example, a printed wiring board) for mounting a semiconductor element. And is 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.

  A structure manufactured by a method for manufacturing a structure has a structure in which an opening is provided in an insulating layer formed on a surface of a support having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening. Is the body. The manufacturing method of a structure forms the 1st photosensitive resin layer on a support body so that a conductive circuit may be covered using the photosensitive resin composition of this embodiment, or the photosensitive element of this embodiment. A photosensitive resin layer forming step, a first patterning step of patterning by subjecting the first photosensitive resin layer to exposure and development, and a support so as to cover the pattern of the first photosensitive resin layer A thermosetting resin layer forming step for forming a thermosetting resin layer thereon, a part of the thermosetting resin layer is removed, and a predetermined portion of the pattern of the first photosensitive resin layer is removed from the thermosetting resin layer. A pattern exposing step for exposing, and an opening forming step for removing a predetermined portion of the pattern of the first photosensitive resin layer exposed from the thermosetting resin layer and forming an opening for exposing the conductor circuit in the thermosetting resin layer And comprising. As a manufacturing method of the structure, a manufacturing method described in Patent Document 5 may be used. In the present specification, the “support having a conductor circuit” can be said to be a “substrate having a conductor circuit”. Also, the “conductor circuit” can be said to be a “conductor pattern”.

  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. Even when an opening having a diameter of 30 μm or less is formed or an opening having a large diameter is formed, an opening having excellent insulation reliability can be formed more efficiently.

  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. It is preferable to further comprise a thermosetting step for curing. 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.

  Preferably, the method for removing a part of the thermosetting resin layer after the thermosetting is mechanical polishing, and the method for removing the first photosensitive resin layer exposed from the thermosetting resin layer is a 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 as Acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, etc. are used, and used alone or in combination of two or more kinds of 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 is preferably 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.

  Moreover, it is preferable that the method of removing a part of the thermosetting resin layer after the thermosetting and the method of removing the first photosensitive resin layer exposed from the thermosetting resin layer are chemical treatments. . 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 as Acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, etc. are used, and used alone or in combination of two or more kinds of bases. . These chemical solutions can be used alone or as a mixed solution in combination of two or more.

  Moreover, it is preferable to perform thermosetting in the atmosphere of an inert gas in a thermosetting process. 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. 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; and at least one seed layer. A wiring part patterning step of patterning the wiring part by peeling off the second photosensitive resin layer by a peeling process after forming the wiring part by electrolytic plating so as to cover the part, and the wiring part is not formed And a seed layer removing step of removing the seed layer in the region. 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 T ₁ of the first photosensitive resin layer is preferably 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.

Also, keep thermosetting resin layer forming step, it is preferable that the thickness T ₂ of the thermosetting resin layer is 2 to 50 [mu] m. 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.

  Moreover, the structure of this 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. It is preferable. 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. A resin composition containing at least one selected from the group consisting of curable polyimide resins is preferred. The thermosetting resin composition preferably contains 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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to an Example.

<Synthesis of Binder Polymer (A-1)>
A polymerizable monomer (monomer) 78 g of methacrylic acid, 75 g of benzyl methacrylate, 15 g of methyl methacrylate and 132 g of styrene (mass ratio 26/25/5/44) and 2.5 g of azobisisobutyronitrile. The solution obtained by mixing was designated as “Solution a”.

  A solution obtained by dissolving 1.2 g of azobisisobutyronitrile in 150 g of a mixed solution (mass ratio 2: 1) 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 42.8% by mass, a weight average molecular weight of 43,000, and an acid value of 170 mgKOH / g.

The weight average molecular weight was measured by gel permeation chromatography (GPC) and 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.)

<Preparation of photosensitive resin composition (coating liquid)>
The photosensitive resin composition (coating liquid) of Examples 1-2 and Comparative Examples 1-2 was produced by mixing each component shown in Table 1 with the compounding quantity (part by mass) shown in Table 1. The compounding quantity of the binder polymer (A-1) in a table | surface is the mass (solid content) of a non volatile matter. Details of each component shown in Table 1 are as follows.

(A) Binder polymer The binder polymer (A-1) synthesized as described above was used.

(B) Photopolymerizable compound-TMPT-9EO: (EO) -modified trimethylolpropane trimethacrylate (ethylene oxide average 9 mol 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 ³¹ and R ³² = methyl group, r3 = 6 (average value), s31 + s32 = 12 (average value) in the following general formula (3) )
M-114: 4-normalnonylphenoxyoctaethyleneoxyacrylate (manufactured by Toagosei Co., Ltd., trade name)
FA-321M: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (manufactured by Hitachi Chemical Co., Ltd., trade name), total number of structural units of oxyethylene group and oxypropylene group: 10
BPE-900: 2,2-bis (4- (methacryloxyoctadecaethoxy) phenyl) propane (made by Shin-Nakamura Chemical Co., Ltd., trade name), total number of structural units of oxyethylene group and oxypropylene group: 18
-BPE-200: Total number of structural units of 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (made by Shin-Nakamura Chemical Co., Ltd., trade name), oxyethylene group and oxypropylene group: 4
BPE-100: 2,2-bis (4- (methacryloxyethoxy) phenyl) propane (made by Shin-Nakamura Chemical Co., Ltd., trade name), total number of structural units of oxyethylene group and oxypropylene group: 2.6

(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.)

<Production of photosensitive element>
The photosensitive resin composition obtained above was applied on a 16 μm thick polyethylene terephthalate film (trade name “HTF-01”, manufactured by Teijin Ltd.) (support) 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 bonded onto the photosensitive resin layer, and the support, the photosensitive resin layer, and the protective layer were laminated in this order. As the photosensitive element, the photosensitive elements according to Examples 1-2 and Comparative Examples 1-2 were obtained.

<Preparation of printed wiring board having conductor circuit>
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 12 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., the photosensitive elements according to Examples 1 and 2 and Comparative Examples 1 and 2, respectively, Lamination was performed on the copper surface. 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 to room temperature and obtained the laminated substrate by which the photosensitive resin layer and the support body were laminated | stacked on the copper surface of the board | substrate.

<Evaluation>
(Evaluation of circular pattern formation)
The laminated substrate was divided into two regions, and a phototool having a design in which circular patterns with a diameter of 20 μmφ were arranged at a pitch of 100 μm was placed on a support in one region. 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 phototool and a support with an exposure amount (energy amount) of 180 mJ / cm ² . At this time, other areas not used were covered with a black sheet. Moreover, it exposed with the exposure amount of 250 mJ / cm < ² > by the same method with respect to each different area | region. 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 is peeled off from the laminated substrate, the photosensitive resin layer is exposed, and a 1% by mass aqueous sodium carbonate solution is sprayed at 30 ° C. and 0.2 MPa by using a developing machine (manufactured by HMS). Part was removed. The development time was set to twice the shortest development time of each photosensitive resin composition. Thus, the cured film which consists of hardened | cured material of the photosensitive resin composition was formed on the copper surface of a board | substrate. The shortest development time was a value obtained by measurement as follows. First, the laminated base material was cut into a size of 30 mm × 30 mm to obtain a test piece. After peeling off the support from the test piece, using a 1% by mass aqueous sodium carbonate solution at 30 ° C., spray development is performed at a pressure of 0.2 MPa, and the shortest possible to visually confirm that an unexposed portion of 1 mm or more has been removed. This time was defined as the shortest development time.

  After development, the space portion (unexposed portion) is removed without residue, and the circular pattern portion (exposed portion) (resist) is missing, and the pattern formed without causing defects such as collapse is left as a remaining circle. A resist was used. The circular resist was observed by measuring the remaining number of circular resists at a measurement area of 12 areas in the vertical direction, 16 in the horizontal direction, and a total of 192 areas. The converted rate was defined as the residual rate (formation rate). The higher this value, the better the residual rate. The results are shown in Table 2. The remaining number of circular resists was counted by magnifying at a magnification of 200 times using a microscope (manufactured by Keyence Corporation, trade name “Digital Microscope VHX-2000”) to check for defects. did.

(Evaluation of defective formation of circular patterns)
In the evaluation of the formability, a failure mode (resist shape) that could not be formed was evaluated by the following procedure. First, the region where the circular resist is formed is specified from the formed circular resist, and the region where the circular resist is not formed is identified by a microscope (manufactured by Keyence Corporation, trade name “Real Surface View Microscope VE-8800”). ) And magnified and observed at a magnification of 1500 times. Subsequently, the area | region where the circular resist was not formed was observed, and the factor used as the formation defect was evaluated on the following references | standards. The results are shown in Table 2. If the circular resist remains on the substrate, the cause of the formation failure is `` break '', and if the circular resist does not remain on the substrate, the cause of the formation failure is `` "Peeling". In addition, when the resist could not be formed due to fracture, the adhesion between the resist and the substrate was sufficient, but it was considered that the mechanical strength was not sufficient, and when the resist could not be formed by peeling, the resist and It can be determined that the adhesion to the substrate was not sufficient.
A: The failure of the resist is rupture.
B: Stripping is a cause of resist failure.

(Evaluation of mechanical strength)
First, a Teflon (registered trademark) sheet was fixed to the support substrate. Next, the photosensitive resin layer of the photosensitive element according to Example 1 was laminated on the Teflon sheet. Further, after peeling the support to expose the photosensitive resin layer, the photosensitive element according to Example 1 is laminated again on the photosensitive resin layer so that the photosensitive resin layers are in contact with each other. A laminate for mechanical strength evaluation was obtained in which a photosensitive resin layer having a thickness of 50 μm and a support were laminated on the sheet. Further, using the photosensitive elements according to Example 2 and Comparative Examples 1 and 2, laminates for evaluating mechanical strength were obtained in the same manner as in Example 1. In addition, the lamination is performed at a temperature of 120 ° C. and a lamination pressure of 0.39 MPa so that the photosensitive resin layer of each photosensitive element is in close contact with the surface of the Teflon sheet or the surface of the photosensitive resin layer while removing the protective layer. Performed under conditions.

A photomask that transmits light in a rectangular shape having a width of 2 cm and a length of 10 cm was disposed on a support of a test piece for evaluating mechanical strength. Then, using 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, 500 mJ The photosensitive resin layer was exposed through a phototool and a support with an exposure amount (energy amount) of / cm ² . After the exposure, the support is peeled off from the laminate for mechanical strength evaluation, the photosensitive resin layer is exposed, and a 1% by mass aqueous sodium carbonate solution is sprayed at 30 ° C. and 0.2 MPa using a developing machine (manufactured by HMS). This removed the unexposed part. The development time was set to twice the shortest development time of each photosensitive resin composition. In this way, a test piece for measuring the mechanical strength was obtained. Thereafter, a tensile test was performed under the following conditions, and the breaking energy, which is an integrated value of elongation and breaking strength, was calculated. The results are shown in Table 2.
Test equipment: Shimadzu Autograph AGS-5kNG
Film sample thickness: 0.05mm
Width: 20mm
Distance between chucks: 20mm
Pulling speed: 5mm / min
Measurement temperature: 23 ° C

  As is apparent from Table 2, by using the photosensitive resin compositions of Examples 1 and 2, openings having a sufficiently high mechanical strength after exposure, an opening diameter of 30 μm or less, and a wide pitch are provided. Even when it was formed, it was found that the remaining ratio of the opening formation portion was good. On the other hand, the photosensitive resin compositions of Comparative Examples 1 and 2 were inferior to the photosensitive resin compositions of Examples 1 and 2 in the mechanical strength and the remaining ratio of the opening forming portion.

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

Claims (16)

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 support having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening. A thing,
A binder polymer, a photopolymerizable compound containing a bisphenol-type di (meth) acrylate having a total number of structural units of oxyethylene groups and oxypropylene groups of 8 to 30, and a photopolymerization initiator,
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 support 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 support 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: The photosensitive resin composition of Claim 1 in which the said photopolymerizable compound contains the compound represented by following General formula (1).

[In the formula (1), R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group, XO and YO each independently represent an oxyethylene group or an oxypropylene group, m1, m2, n1 and n2 Each independently represents 0-30. ]   The binder polymer has a structural unit derived from at least one polymerizable monomer selected from the group consisting of benzyl (meth) acrylate, a benzyl (meth) acrylate derivative, styrene, and a styrene derivative. Or the photosensitive resin composition of 2.   The photosensitive resin composition as described in any one of Claims 1-3 whose acid value of the said binder polymer is 80-250 mgKOH / g.   The photosensitive resin composition as described in any one of Claims 1-4 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 1-5 in which the said photopolymerizable compound contains the compound which has an ethylenically unsaturated bond.   The photosensitive resin composition of Claim 6 in which the said photopolymerizable compound contains the compound which has 3 or more of ethylenically unsaturated bonds as a compound which has the said ethylenically unsaturated bond.   The photosensitive resin composition as described in any one of Claims 1-7 in which the said photoinitiator contains a 2,4,5-triaryl imidazole dimer.   The photosensitive resin composition as described in any one of Claims 1-8 which further contains a sensitizing dye.   The photosensitive resin composition as described in any one of Claims 1-9 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 1-10. Forming a photosensitive resin layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 10 or the photosensitive element according to claim 11;
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 12, wherein the wavelength of the actinic ray is within 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 support having a conductor circuit, and a wiring portion connected to the conductor circuit is formed in the opening,
Using the photosensitive resin composition according to any one of claims 1 to 10 or the photosensitive element according to claim 11, a first photosensitive property on the support so as to cover a conductor circuit. A photosensitive resin layer forming step of forming a resin 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 support 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;
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. Production method.   The manufacturing method of the structure of Claim 14 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 14, further comprising: a seed layer removing step of removing a seed layer in a region where the wiring part is not formed.

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