JP2017032827A - Treatment liquid, and method for producing structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide treatment liquid having an excellent opening property even when forming a fine opening.SOLUTION: The present invention provides a treatment liquid for removing a resin part embedded in an insulating layer to form an opening in the insulating layer, where the resin part has a cured product resulting by subjecting a photosensitive resin layer to exposure treatment and development treatment, and the treatment liquid has divalent metal ions, and the treatment liquid is used as at least one of treatment liquid for the development treatment and treatment liquid brought into contact with the cured product after the development treatment.SELECTED DRAWING: None

Description

  The present disclosure relates to a treatment liquid and a method for manufacturing a structure. In particular, the present disclosure relates to a treatment liquid that can be used to remove a resin portion embedded in an insulating layer and form an opening in the insulating layer, and a method of manufacturing a structure using the treatment liquid. . The present disclosure also includes a substrate having a conductor circuit, an insulating layer disposed on the surface of the substrate and having an opening formed therein, and a conductor portion formed in the opening and connected to the conductor circuit. The present invention relates to a treatment liquid that can be used in a method for producing a structure including the structure and a method for producing a structure using the treatment liquid.

  A printed wiring board that is a structure having a conductor circuit is, for example, a structure in which a plurality of wiring layers are formed on a core substrate, and a copper-clad laminate serving as a core substrate and an interlayer insulating material provided between each wiring layer And a solder resist provided on the outermost surface. In recent years, semiconductor devices have become lighter and thinner, 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.

  Vias (openings) for electrically connecting the upper and lower wiring layers need to be formed 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 form a number of openings corresponding to the number of pins, but the conventional printed wiring board has a low mounting density and is mounted. Since the number of pins of the semiconductor element is designed from several thousand pins to around 10,000 pins, it is not necessary to form openings with a small diameter and a narrow pitch.

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

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

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

  However, in the conventional method for manufacturing a multilayer printed wiring board shown in FIG. 1, in addition to the necessity of introducing new equipment such as a laser, the via is a large opening (for example, a cylindrical opening) having a diameter of 100 μm or more. In this case, there is a problem that the throughput decreases with an increase in the number of shots of the laser. When the via is a minute opening (for example, a cylindrical opening) having a diameter of 60 μm or less, it is matched with the opening diameter. There are problems that it is necessary to use different lasers, and that it is difficult to form a special shape. In addition, when forming an opening using a laser, each opening must be formed one by one. Therefore, there is a problem that it takes time when it is necessary to form a large number of fine openings. Therefore, there is also a problem that the reliability of the obtained multilayer printed wiring board is lowered unless the residue is removed.

  On the other hand, techniques using various photosensitive resin compositions have been studied (for example, see Patent Documents 5 and 6 below). In such a technique, a photosensitive resin composition that swells with an alkaline aqueous solution is used to form an opening that exposes a conductor circuit, and a photosensitive resin having an opening forming portion that is removed to form an opening. A resin layer is formed, and then the opening forming portion is removed by swelling and peeling with an alkaline aqueous solution to form an opening.

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

  However, in the technique described in Patent Document 5 or 6, when forming a finer opening (for example, a columnar opening having a diameter of 30 μm or less), it is difficult for the alkaline aqueous solution to penetrate into the fine opening forming portion. There is a problem that it becomes difficult to remove the opening forming part by swelling and peeling.

  As described above, a manufacturing method of a structure such as a printed wiring board is required to have excellent opening properties even when a fine opening (for example, a columnar opening having a diameter of 30 μm or less) is formed. Yes.

  The present disclosure has been made in view of the above problems, and provides a treatment liquid that has excellent opening properties even when a fine opening is formed, and a method of manufacturing a structure using the treatment liquid. With the goal.

  A processing liquid according to the present disclosure is a processing liquid for removing a resin portion embedded in an insulating layer to form an opening in the insulating layer, and the resin portion exposes and develops a photosensitive resin layer. A cured product obtained by performing a treatment, wherein the treatment liquid contains a divalent metal ion, and at least a treatment liquid for the development treatment and a treatment liquid that contacts the cured product after the development treatment Used as one.

  The treatment liquid according to the present disclosure is a case where a fine opening (for example, a columnar (columnar or the like) opening having a diameter of 30 μm or less. An opening formed by removing a resin portion embedded in an insulating layer) is formed. Even with excellent opening. For example, the treatment liquid according to the present disclosure can form an opening while suppressing generation of a residue derived from the photosensitive resin composition. According to the treatment liquid according to the present disclosure, it is possible to obtain a resin pattern with excellent openability (for example, a columnar resin pattern with a diameter of 30 μm or less), a fine opening, and excellent reliability. A structure can be obtained sufficiently efficiently.

  Further, according to the treatment liquid according to the present disclosure, not only the columnar opening can be suitably formed, but the opening of another shape (for example, a line-shaped conductor pattern is suppressed while suppressing generation of a residue derived from the photosensitive resin composition. A line-shaped opening) for obtaining the same.

  The treatment liquid according to the present disclosure is used in a method for manufacturing a structure including a substrate having a conductor circuit, the insulating layer, and a conductor portion formed in the opening, and the insulating layer is formed on the surface of the substrate. The conductive portion is connected to the conductor circuit, and the manufacturing method of the structure includes a photosensitive resin layer on the substrate so as to cover the conductor circuit using a photosensitive resin composition. And a step of applying an exposure process and a development process to the photosensitive resin layer to form a resin pattern including the cured product.

  A structure manufacturing method according to the present disclosure includes a substrate having a conductor circuit, an insulating layer disposed on a surface of the substrate and having an opening formed therein, and formed in the opening and connected to the conductor circuit. A process for forming a resin pattern including a cured product by subjecting a photosensitive resin layer to exposure processing and development processing, and embedding the resin pattern in the insulating layer. A step of forming a resin portion containing the cured product, and a step of removing the resin portion and forming the opening in the insulating layer, and a processing solution for the development processing, and the development processing after the development processing A treatment liquid containing a divalent metal ion is used as at least one of the treatment liquids in contact with the cured product.

  In the manufacturing method of the structure according to the present disclosure, the processing liquid according to the present disclosure is used. Thereby, it is possible to obtain the same effect as that of the treatment liquid according to the present disclosure. For example, even when a fine opening (for example, a columnar opening having a diameter of 30 μm or less) is formed, the opening property is excellent.

  The method for manufacturing a structure according to the present disclosure may further include a step of forming the photosensitive resin layer on the substrate so as to cover the conductor circuit using a photosensitive resin composition.

  The divalent metal ion may include at least one selected from the group consisting of calcium ion, magnesium ion, beryllium ion, strontium ion, and barium ion.

  The content of the divalent metal ion in the treatment liquid may be 10 to 1000 ppm.

  The photosensitive resin composition may contain a binder polymer, a photopolymerizable compound, and a photopolymerization initiator.

  The manufacturing method of the structure includes a step of forming a thermosetting resin layer on the substrate so as to cover the resin pattern, and removing a part of the thermosetting resin layer to form a predetermined portion of the resin pattern. The step of exposing from the thermosetting resin layer and the predetermined portion of the resin pattern exposed from the thermosetting resin layer are removed to form an opening in the thermosetting resin layer to expose the conductor circuit. And a process.

  According to the present disclosure, it is possible to provide a treatment liquid having excellent opening properties even when a fine opening (for example, a columnar opening having a diameter of 30 μm or less) is formed, and a structure manufacturing method using the treatment liquid. can do. According to the present disclosure, it is possible to provide an application of a treatment liquid to a method for manufacturing a structure including an insulating layer having an opening. According to the present disclosure, it is possible to provide an application of the treatment liquid to the manufacturing method of the structure including the step of forming the opening in the insulating layer by removing the resin portion embedded in the insulating layer. According to the present disclosure, a substrate having a conductor circuit, an insulating layer disposed on the surface of the substrate and having an opening, and a conductor portion formed in the opening and connected to the conductor circuit, The application of the treatment liquid to the manufacturing method of the structure provided can be provided.

It is a schematic diagram which shows the manufacturing method of the conventional multilayer printed wiring board. It is a mimetic diagram showing the manufacturing method of the structure concerning one embodiment of this indication. It is a mimetic diagram showing the manufacturing method of the structure concerning one embodiment of this indication. It is a mimetic diagram showing the manufacturing method of the structure concerning one embodiment of this indication.

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

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

  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.

  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. In the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.

  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.

<Processing liquid>
The processing liquid according to the present embodiment is a processing liquid for removing the resin portion embedded in the insulating layer to form an opening (via, through hole) in the insulating layer, and the resin portion is a photosensitive resin. A cured product obtained by subjecting the layer to exposure and development is included. The resin part is an opening forming part and is a place where an opening is formed by being removed. The treatment liquid according to the present embodiment is, for example, a substrate having a conductor circuit, an insulating layer disposed on the surface of the substrate and having an opening, and formed in the opening and connected to the conductor circuit. A treatment liquid used in a method for producing a structure (a structure having a conductor circuit) including a conductor part (wiring part or the like). That is, in the treatment liquid according to the present embodiment, for example, an opening is formed in an insulating layer formed on the surface of a substrate having a conductor circuit, and a conductor portion (a wiring portion or the like) connected to the conductor circuit is It is a processing liquid used for the manufacturing method of the structure (structure which has a conductor circuit) formed in opening. The manufacturing method of the structure according to the present embodiment includes a photosensitive resin layer forming step of forming a first photosensitive resin layer on a substrate using a photosensitive resin composition so as to cover a conductor circuit, and an exposure process. And developing the first photosensitive resin layer by patterning the first photosensitive resin layer by applying a development process to the first photosensitive resin layer, thereby forming a cured product (resin pattern) of the first photosensitive resin layer as a columnar resist. 1 patterning process may be further provided. In the first patterning step, a contact treatment (such as a water washing treatment) in which the treatment liquid is brought into contact with the cured product (resin pattern) of the first photosensitive resin layer may be performed after the development treatment.

  Moreover, the manufacturing method of the structure according to the present embodiment includes a thermosetting resin layer forming step of forming a thermosetting resin layer on the substrate so as to cover the resin pattern of the first photosensitive resin layer, A pattern exposing step of removing a part of the thermosetting resin layer to expose a predetermined portion of the resin pattern of the first photosensitive resin layer from the thermosetting resin layer, and exposing from the thermosetting resin layer An opening forming step of removing the predetermined portion of the resin pattern of the first photosensitive resin layer and forming an opening in the thermosetting resin layer to expose the conductor circuit may be further provided.

  The processing liquid according to the present embodiment contains a divalent metal ion and contacts the processing liquid for the development processing and the cured product (resin pattern or the like) of the first photosensitive resin layer after the development processing. Used as at least one of the treatment liquids. The processing liquid according to the present embodiment may be used as at least one of a processing liquid for development and a processing liquid for contact processing (such as a water-washing processing liquid) from the viewpoint of improving openness. Treatment liquid etc.). The washing treatment liquid is, for example, a liquid for washing the development treatment liquid adhering to the photosensitive resin layer during the development treatment.

  In the present embodiment, by using a treatment liquid containing a divalent metal ion, a fine opening (for example, a photosensitive resin embedded in a thermosetting resin layer using an alkaline aqueous solution when the structure is manufactured). Even when the photocured product of the resin layer is removed to form an opening formed in the thermosetting resin layer, the opening property is particularly excellent.

  The divalent metal ion may be at least one selected from the group consisting of calcium ion, magnesium ion, beryllium ion, strontium ion, and barium ion from the viewpoint of further improving the opening property. It may be at least one selected from the group consisting of ions. A divalent metal ion can be used individually or in combination of 2 or more types.

  The treatment liquid containing a divalent metal ion may be an aqueous solution derived from a salt containing a divalent metal ion (for example, an aqueous solution obtained by dissolving a salt containing a divalent metal ion in water). . Examples of the salt containing a divalent metal ion include calcium chloride, magnesium chloride, calcium sulfate, magnesium sulfate, beryllium sulfate, strontium sulfate, and barium sulfate. A divalent metal ion and an ion other than the divalent metal ion may be used in combination as long as the opening is excellent. Examples of ions other than divalent metal ions include monovalent ions, trivalent or higher ions, divalent nonmetallic ions, and the like.

  Examples of bases containing ions other than divalent metal ions include alkali chlorides such as lithium, sodium or potassium chloride; alkali hydroxides such as lithium, sodium or potassium hydroxide; lithium, sodium, potassium or Alkali carbonates such as ammonium carbonate or bicarbonate; alkali metal phosphates such as potassium phosphate and sodium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borax (sodium tetraborate ); Sodium metasilicate; tetramethylammonium hydroxide; ethanolamine; ethylenediamine; diethylenetriamine; 2-amino-2-hydroxymethyl-1,3-propanediol; 1,3-diamino-2-propanol; morpholine and the like. .

  The content of divalent metal ions in the treatment liquid (also referred to as “ion concentration”) may be 10 to 1000 ppm or 10 to 800 ppm from the viewpoint of further improving the opening property. It may be 10 to 500 ppm. When the content of the divalent metal ion is 10 ppm or more, the opening property of the first photosensitive resin layer is further improved, and when it is 1000 ppm or less, the solubility of the salt containing the divalent metal ion is improved. To do.

<Photosensitive resin composition>
The photosensitive resin composition according to this embodiment includes (A) a binder polymer (hereinafter also referred to as “(A) component”) and (B) a photopolymerizable compound (hereinafter also referred to as “(B) component”). And (C) a photopolymerization initiator (hereinafter also referred to as “component (C)”). The photosensitive resin composition according to the present embodiment may further contain other components as necessary.

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

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

  Examples of the polymerizable monomer (monomer) include (meth) acrylic acid; (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid benzyl, and (meth) acrylic acid benzyl derivatives. , Furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, α-bromo (meta ) Acrylic acid, α-chloro (meth) acrylic acid, β-furyl (Meth) acrylic acid, (meth) acrylic acid esters such as β-styryl (meth) acrylic acid; styrene; styrene such as compounds substituted at the α-position or aromatic ring, such as vinyltoluene and α-methylstyrene Derivatives; 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 Fumaric acid; cinnamic acid; α-cyanocinnamic acid; itaconic acid; crotonic acid; propiolic acid. A polymerizable monomer can be used individually or in combination of 2 or more types.

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

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

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

  When the component (A) has a structural unit derived from (meth) acrylic acid, the content of the structural unit is the solid content of the structural unit constituting the component (A) from the viewpoint of further improving adhesion and openability. 5-80 mass% may be sufficient on the basis of the total mass, 10-70 mass% may be sufficient, and 15-60 mass% may be sufficient.

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

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

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

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

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

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

  The component (B) can be used without particular limitation as long as it can be photocrosslinked. For example, the component (B) can include a compound having an ethylenically unsaturated bond. The compound having an ethylenically unsaturated bond includes a compound having one ethylenically unsaturated bond in the molecule, a compound having two ethylenically unsaturated bonds in the molecule, and three ethylenically unsaturated bonds in the molecule. And the like. (B) A component can be used individually or in combination of 2 or more types.

  Examples of the compound having one ethylenically unsaturated bond in the molecule include nonylphenoxypolyethyleneoxyacrylate and fumaric acid compounds. Among these, from the viewpoint of further improving the openability, (meth) acrylate having a fumaric acid-derived skeleton may be used.

  Examples of compounds having two ethylenically unsaturated bonds in the molecule include compounds having urethane bonds (EO-modified urethane di (meth) acrylate, PO-modified urethane di (meth) acrylate, EO / PO-modified urethane di (meth) acrylate, etc.) , Di (meth) acrylate having urethane bond, etc.), compound having isocyanurate bond (such as isocyanurate-derived di (meth) acrylate), bisphenol type di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, polybutylene glycol di (meth) acrylate, 2,2-bis (4- (methacryloxypolyethoxy) phenyl) propane, and 2,2-bis (4- (methacryloxypolyethoxypolypropylene) ) Phenyl) propane. Among these, from the viewpoint of further improving the openability, a compound having a urethane bond or a compound having an isocyanurate bond may be used, and a di (meth) acrylate having a urethane bond or an isocyanurate-derived di ( You may use a meth) acrylate. The isocyanurate-derived (meth) acrylate can also be said to be a (meth) acrylate having a skeleton derived from isocyanurate.

  Examples of the compound having three ethylenically unsaturated bonds in the molecule include a compound having a urethane bond, a compound having an isocyanurate bond (EO-modified isocyanurate-derived tri (meth) acrylate, PO-modified isocyanurate-derived tri (meta)). ) Acrylate, EO / PO-modified isocyanurate-derived tri (meth) acrylate, etc. isocyanurate-derived tri (meth) acrylate, etc.), 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 (meth) acrylate, tetramethylol methane tri (meth) acrylate, EO modified tetramethylol methane tri (meth) acrylate, PO modified tetramethylol methane Examples thereof include tri (meth) acrylate and EO / PO-modified tetramethylolmethane tri (meth) acrylate. Among these, from the viewpoint of further improving the openability, a compound having a urethane bond, or an isocyanurate-derived tri (meth) acrylate may be used, and an EO-modified isocyanurate-derived tri (meth) acrylate or PO-modified isocyanurate. Derived tri (meth) acrylate or EO / PO-modified isocyanurate-derived tri (meth) acrylate may be used.

  In the photosensitive resin composition according to the present embodiment, the component (B) is a urethane disiloxane having a total number of structural units of 0 to 40 oxyethylene groups and oxypropylene groups per functional group, from the viewpoint of further improving the openability. At least one photopolymerizable selected from the group consisting of (meth) acrylates and isocyanurate-derived tri (meth) acrylates having a total number of structural units of oxyethylene groups and oxypropylene groups per functional group of 0 to 40 A compound may be contained. As used herein, the functional group means a (meth) acryloyl group.

  Each content of the urethane di (meth) acrylate and the isocyanurate-derived tri (meth) acrylate may be 10 to 100 parts by mass with respect to 100 parts by mass of the component (B) from the viewpoint of further improving the openability. 20-100 mass parts may be sufficient and 30-100 mass parts may be sufficient.

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

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

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

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

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

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

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

  Examples of the component (D) include dialkylaminobenzophenone compounds (such as 4,4′-bis (diethylamino) benzophenone), pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, and thiazoles. Examples include compounds, benzothiazole compounds, triazole compounds, stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridine compounds. (D) A component can be used individually or in combination of 2 or more types.

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

  When the component (D) is used, the content of the component (D) may be 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). 05-5 mass parts may be sufficient and 0.1-3 mass parts may be sufficient. When the content of the component (D) is 0.01 parts by mass or more, the sensitivity and adhesion tend to be further excellent, and by being 10 parts by mass or less, the resist shape of the opening forming portion is There is a tendency to be even better.

((E): Hydrogen donor)
The photosensitive resin composition according to this embodiment may further contain (E) a hydrogen donor (hereinafter also referred to as “component (E)”). The component (E) can give hydrogen during the reaction in the exposed area. When the photosensitive resin composition according to this embodiment contains 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. (E) A component can be used individually or in combination of 2 or more types.

  When the component (E) is used, the content of the component (E) may be 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). 05-5 mass parts may be sufficient, and 0.1-2 mass parts may be sufficient. When the content of the component (E) is 0.01 parts by mass or more, the sensitivity tends to be further improved. When the content is 10 parts by mass or less, the component (E) is a foreign substance after film formation. It tends to be difficult to precipitate as.

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

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

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

<Photosensitive element>
The photosensitive element which concerns on this embodiment is provided with a support body and the photosensitive resin layer formed on the said support body using the photosensitive resin composition which concerns on this embodiment. The photosensitive resin layer of the photosensitive element according to the present embodiment contains the photosensitive resin composition according to the present embodiment. By applying the photosensitive resin composition onto a support and drying it, a photosensitive resin layer can be formed on the support using the photosensitive resin composition. 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 polyester such as polyethylene terephthalate (PET), polypropylene, and polyethylene can be used.

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

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

  As the protective layer, for example, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate (PET), polypropylene, and polyethylene can be used. The protective layer may be the same as the support.

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

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

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

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

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

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

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

<Method for manufacturing structure>
The treatment liquid, the photosensitive resin composition, and the photosensitive element according to this embodiment are suitably used for manufacturing a structure (for example, a printed wiring board) for mounting a semiconductor element, and in particular, manufacturing a high-density package substrate. It is more preferably used for the production of a structure (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 with tens of thousands of bumps arranged in an area array on the surface of the semiconductor element.

  The structure according to the present embodiment is a structure including an insulating layer having an opening, for example. The structure according to the present embodiment includes, for example, a substrate having a conductor circuit, an insulating layer disposed on the surface of the substrate and having an opening, and formed in the opening and connected to the conductor circuit. And a conductor part (wiring part or the like). That is, in the structure according to the present embodiment, for example, an opening is formed in an insulating layer formed on the surface of a substrate having a conductor circuit, and a conductor portion (wiring portion or the like) connected to the conductor circuit is an opening. It is a structure formed. The insulating layer is, for example, a thermosetting resin layer and / or a photosensitive resin layer.

  The structure manufacturing method according to the present embodiment covers, for example, the conductor circuit using the photosensitive resin composition according to the present embodiment or the photosensitive resin composition of the photosensitive element according to the present embodiment. Forming a first photosensitive resin layer on the substrate, and patterning the first photosensitive resin layer by subjecting the first photosensitive resin layer to an exposure process and a development process. And a first patterning step of forming a resin pattern of the first photosensitive resin layer as a resist. The structure manufacturing method according to the present embodiment may further include a preparatory step of preparing a substrate having a conductor circuit before the photosensitive resin layer forming step. Moreover, the manufacturing method of the structure which concerns on this embodiment WHEREIN: The thermosetting resin layer formation process (1st which forms a thermosetting resin layer on a board | substrate so that the resin pattern of a 1st photosensitive resin layer may be covered. A step of embedding the resin pattern of the photosensitive resin layer in the insulating layer to form a resin portion), and removing a part of the thermosetting resin layer to thermosetting a predetermined portion of the resin pattern of the first photosensitive resin layer A pattern exposing step for exposing from the resin layer, and removing the predetermined portion of the resin pattern of the first photosensitive resin layer exposed from the thermosetting resin layer, and opening the conductor circuit to expose the thermosetting resin layer And an opening forming step to be formed. As a manufacturing method of the structure, a manufacturing method described in Patent Document 5 may be used. That is, according to this embodiment, a multilayer printed wiring board can be manufactured without using a laser as shown in FIG.

  In the present specification, as the “substrate having a conductor circuit”, a flexible substrate or a rigid substrate may be used. Further, the “conductor circuit” can also be referred to as a “conductor pattern” and a “wiring pattern”. The shape of the opening is not particularly limited, and may be, for example, a circle (true circle, ellipse, etc.), a line, a polygon, an irregular shape, or other shapes. In the case where the opening is formed using the stripping solution, the stripping solution tends to easily penetrate into the line-shaped opening forming portion as compared with the opening forming portion having a circular shape, a polygonal shape, or an irregular shape. Note that the multilayer printed wiring board that can be manufactured according to the present embodiment may include an insulating layer formed on the substrate having the conductor circuit (wiring pattern) so as to cover the conductor circuit. Further, for example, the insulating layer includes an opening formed so that at least a part of the conductor circuit on the substrate is exposed, and a conductor pattern can be formed in the opening.

  In the structure manufacturing method according to the present embodiment, the first photosensitive resin layer is patterned in the first patterning process in accordance with the shape of the opening formed in the thermosetting resin layer. The opening can be easily formed. In addition, in the method of manufacturing a structure (for example, a printed wiring board) according to the present embodiment, unlike the case of forming openings with a laser, in addition to forming 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 formed, a structure (eg, a printed wiring board) having excellent reliability can be efficiently manufactured. . Further, even when an opening having a diameter of 30 μm or less is formed or a large opening having a diameter of 100 μm or more is formed, an opening having excellent insulation reliability can be more efficiently formed. it can.

  Hereinafter, with reference to FIGS. 2 to 4, an example of each step of the method for manufacturing the structure (multilayer printed wiring board or the like) 10 (see FIG. 4D) according to the present embodiment will be further described.

(Preparation process)
In the preparation step, as shown in FIG. 2A, a substrate (conductor circuit) having an insulating layer (support) 1 and conductor circuits (conductor layers) 2 disposed on both surfaces of the insulating layer 1 is provided. Substrate 3) is prepared. The conductor circuit 2 can be obtained by etching away unnecessary portions of the copper foil. The material of the conductor circuit is, for example, copper.

(Photosensitive resin layer forming step)
In the photosensitive resin layer forming step, as shown in FIG. 2B, the photosensitive resin layer 4 is formed on the substrate 3 so as to cover the conductor circuit 2 by using the photosensitive resin composition or the photosensitive element. . As a method for forming the photosensitive resin layer on the substrate, for example, a method in which the photosensitive resin composition is applied on the substrate and then dried, and the photosensitive resin layer in the photosensitive element described above is transferred onto the substrate. (Lamination) is mentioned.

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

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

Lamination conditions can be appropriately adjusted as necessary, but the lamination 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. Note that 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.

In the photosensitive resin layer forming step, the thickness T ₁ (see FIG. 2B) of the photosensitive resin layer 4 may be 2 to 50 μm. When the thickness T ₁ of the photosensitive resin layer 4 is 2 μm or more, the photosensitive resin composition used for forming the photosensitive resin layer 4 can be easily formed, so that the structure (for example, a printed wiring board) is manufactured. The photosensitive resin layer of the photosensitive element to be used can be easily formed. When the thickness T ₁ of the photosensitive resin layer 4 is 50 μm or less, it becomes easy to form a fine pattern on the photosensitive resin layer 4.

(First patterning step)
The first patterning step includes, for example, as shown in FIG. 2 (c), (a) an exposure step of irradiating a predetermined portion of the photosensitive resin layer with an actinic ray to expose and cure the predetermined portion; (B) The resin pattern of the photosensitive resin layer made of a photocured product of the photosensitive resin composition by removing a portion (unexposed portion) other than the predetermined portion (exposed portion) of the photosensitive resin layer from the substrate. And a developing step for forming 4a on the substrate. In the first patterning step, after the development step, (c) a contact treatment step of bringing the treatment liquid into contact with the cured product (resin pattern) of the photosensitive resin layer (for example, curing of the photosensitive resin layer during the development treatment) It may further have a water washing step for performing a water washing treatment for removing the developing processing solution adhering to the product (resin pattern). The contact treatment step is performed, for example, before the thermosetting resin layer forming step, the pattern exposing step, or the opening forming step. In the first patterning step, at least one of the processing solution for development used in the development step and the processing solution for contact processing (such as a washing solution for washing) used in the contact processing step contains a divalent metal ion. be able to.

[(A) Exposure step]
In the exposure step, 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 a light source of actinic light, 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 light, visible light, and the like are used.

  The wavelength of the actinic ray (exposure wavelength) is preferably 340 to 430 nm, more preferably 350 to 420 nm, from the viewpoint of obtaining the effects of the present disclosure more reliably.

[(B) Development step]
In the development step, the photosensitive resin layer is removed from the substrate by removing portions (unexposed portions) other than the predetermined portion (exposed portion; a portion corresponding to the opening forming position of the thermosetting resin layer) of the photosensitive resin layer. A resin pattern made of a photocured product of the composition is formed on the 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 can be performed by a known development method. Examples of development methods include dipping, paddle, spraying, brushing, slapping, scrubbing, rocking immersion, and the like. From the viewpoint of further improving resolution, the high-pressure spraying method is most suitable. Yes. You may develop by combining these 2 or more types of methods.

  As the processing solution for development, an alkaline aqueous solution can be used from the viewpoint of safety and stability and improved operability. Examples of the alkaline aqueous solution used for the processing solution 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, and a dilute solution of 0.1 to 5% by mass of sodium hydroxide. A dilute solution of 0.1 to 5% by 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.

[(C) Contact treatment step]
The contact processing solution (such as a washing processing solution) preferably has a lower alkalinity than the alkaline aqueous solution that can be used as the developing processing solution described above. That is, the concentration of the aqueous solution derived from the base may be low. Reliability can be improved by using such a treatment liquid for contact treatment.

  Contact treatment (such as washing with water) can be performed by a known method. Examples of contact methods (water washing methods, etc.) include dipping methods, paddle methods, spray methods, brushing, slapping, scrubbing, rocking immersion, etc. From the viewpoint of further improving resolution, high-pressure spraying The method is most suitable. You may develop by combining these 2 or more types of methods.

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

[Subsequent steps]
In the thermosetting resin layer forming step, as shown in FIG. 3A, the thermosetting resin layer 5 is formed on the substrate so as to cover the resin pattern 4a. In the pattern exposure step, as shown in FIG. 3B, a part of the thermosetting resin layer 5 is removed to expose a predetermined portion of the resin pattern 4 a from the thermosetting resin layer 5. In the opening forming step, as shown in FIG. 3C, the predetermined portion of the resin pattern 4a exposed from the thermosetting resin layer 5 is removed, and the opening 5h exposing the conductor circuit 2 is formed in the thermosetting resin layer. 5 to form.

In the thermosetting resin layer forming step, the thickness T ₂ (see FIG. 3A) of the thermosetting resin layer may be 2 to 50 μm. If the thickness T ₂ of the thermosetting resin layer is 2μm or more, it becomes easier by forming a thermosetting resin composition used to form the thermosetting resin layer, the production of structures (e.g., printed circuit board) The film-like thermosetting resin composition used in the above can be easily produced. If the thickness T ₂ of the thermosetting resin layer is 50μm or less, it is easy to form a fine pattern in the thermosetting resin layer.

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

  The method for removing a part of the thermosetting resin layer after the thermosetting may be mechanical polishing, and the method for removing the resin pattern of the first photosensitive resin layer exposed from the thermosetting resin layer is a chemical solution. It may be a process. By removing a part of the thermosetting resin layer after thermosetting by mechanical polishing, the resin pattern of the first photosensitive resin layer can be exposed more quickly, and the residue around the opening can be more reliably Can be reduced. By removing the resin pattern of the first photosensitive resin layer exposed from the thermosetting resin layer by chemical treatment, residues around the opening can be more reliably reduced. The chemical solution used for the chemical treatment can be peeled off with an aqueous solution that is more strongly alkaline than the alkaline aqueous solution used for development. Examples of the strong alkaline aqueous solution include a sodium permanganate aqueous solution, a sodium hydroxide aqueous solution, and a potassium permanganate aqueous solution. 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 like. Examples of the organic solvent used together include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, and the like. It can be used alone or in combination of two or more bases. In addition, these chemical | medical solutions can be used individually or in combination of 2 or more types as a liquid mixture.

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

  The method for removing a part of the thermosetting resin layer after the thermosetting and the method for removing the resin pattern of the first photosensitive resin layer exposed from the thermosetting resin layer may be chemical treatment. Good. In this case, the resin pattern of the first photosensitive resin layer can be exposed more quickly, and the residue around the opening can be more reliably reduced. The chemical solution used for the chemical treatment can be peeled off with an aqueous solution that is more strongly alkaline than the alkaline aqueous solution used for development. Examples of the strong alkaline aqueous solution include a sodium permanganate aqueous solution, a sodium hydroxide aqueous solution, and a potassium permanganate aqueous solution. 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 like. Examples of the organic solvent used together include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, and the like. It can be used alone or in combination of two or more bases. In addition, these chemical | medical solutions can be used individually or as a liquid mixture in combination of 2 or more types.

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

  In the structure manufacturing method according to the present embodiment, the seed layer 6 serving as a base of the wiring portion is formed by electroless plating so as to cover at least a part of the thermosetting resin layer 5 after the opening 5h is formed. Forming a seed layer (see FIG. 4A) and forming a second photosensitive resin layer so as to cover the seed layer 6, and then subjecting the second photosensitive resin layer to exposure processing and development processing to form a pattern The second patterning step (see FIG. 4B) for forming the resin pattern 7 of the second photosensitive resin layer by forming, and wiring by electrolytic plating so as to cover at least a part of the seed layer 6 After forming the portion 8 (see FIG. 4C), patterning the wiring portion to form the wiring pattern 8a by patterning the wiring portion 8 by peeling the resin pattern 7 of the second photosensitive resin layer by a peeling process. The process and the wiring part 8 are not formed The seed layer removing step of removing the seed layer 6 in the region (see FIG. 4 (d)), may further comprise a. By forming the seed layer, the wiring part can be formed by electrolytic plating, and the wiring part can be selectively patterned.

  The structure according to the present embodiment is a structure (structure having a conductor circuit) manufactured by the structure manufacturing method described above, and the diameter of the opening of the thermosetting resin layer is 30 μm or less. Also good. 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.

  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, but epoxy resin, phenol resin, cyanate ester resin, polyamideimide resin, and thermosetting resin. It may be a resin composition containing at least one selected from the group consisting of polyimide resins. The thermosetting resin composition may contain an inorganic filler having a maximum particle size of 5 μm or less and an average particle size of 1 μm or less in a state dispersed in the thermosetting resin composition. By forming a thermosetting resin layer using such a thermosetting resin composition, the surface of the opening formed in the thermosetting resin layer becomes smooth, and it becomes easy to form a seed layer on the opening. Note that the maximum particle size of the inorganic filler in a state dispersed in the thermosetting resin composition is one measured using a microtrack method or a nanotrack method, for example, a dynamic light scattering nanotrack particle size distribution. The average value of the value measured using the total "UPA-EX150" (made by Nikkiso Co., Ltd.) and the laser diffraction scattering type micro track particle size distribution meter "MT-3100" (made by Nikkiso Co., Ltd.) is said.

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

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

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

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

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

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

(Measurement method of weight average molecular weight)
The weight average molecular weight was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
{GPC condition}
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 44.6% by mass was collected and dissolved in 5 mL of THF to prepare a sample.
Measurement temperature: 40 ° C
Injection volume: 200 μL
Pressure: 49Kgf / cm ² (4.8MPa)
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

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

<Synthesis of binder polymer (A-2)>
As the polymerizable monomer (monomer), except that the materials shown in Table 1 were used in the mass ratio shown in Table 1, the binder polymer (A- A solution of 2) was obtained.

  The binder polymer (A-2) had a non-volatile content (solid content) of 42.8% by mass, a weight average molecular weight of 45,000, and an acid value of 183 mgKOH / g. In the measurement of the weight average molecular weight, 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.

<Preparation of photosensitive resin composition (coating liquid)>
Photosensitive resin compositions (H-1) and (H-2) were prepared by mixing the components shown in Table 2 in the blending amounts (parts by mass) shown in Table 2. The compounding quantity of the binder polymer in Table 2 is the mass (solid content) of non-volatile content. Details of each component shown in Table 2 are as follows.

(A) Binder polymer Binder polymers (A-1) and (A-2) synthesized as described above were used.

(B) Photopolymerizable compound UA-13: (EO) (PO) -modified urethane dimethacrylate (ethylene oxide average 2 mol, propylene oxide average 18 mol adduct) (trade name, manufactured by Hitachi Chemical Co., Ltd.)
UA-7100: (EO) -modified isocyanurate-derived trimethacrylate (ethylene oxide average 27 mol adduct) (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.)

(C) Photopolymerization initiator B-CIM: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (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 (Yamada Chemical Industries, trade name)

(dye)
MKG: Malachite Green (Osaka Organic Chemical Co., Ltd., trade name)

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

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

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

  After the exposure, the support film is peeled off from the laminated substrate A to expose the photosensitive resin layer, and using a developing machine (manufactured by HMS), a developing processing solution (1 mass% sodium carbonate aqueous solution) shown in Table 3 is 30. Spraying was carried out at 0.2 ° C. and 0.2 MPa, and then the unwashed portion was removed by spraying the treatment liquid for washing shown in Table 4 at 30 ° C. and 0.2 MPa. The spray time of each of the development time and the water washing time was set to twice the shortest development time of each photosensitive resin composition. Thus, the laminated substrate B was obtained by forming the photocured material pattern (resin pattern of the photosensitive resin layer) of the photosensitive resin composition on the copper surface of a board | substrate. The photocured product pattern was a cylindrical pattern having diameters of 30 μmφ, 40 μmφ, 50 μmφ, and 100 μmφ. The height of the photocured product pattern was 25 μm. The shortest development time was a value obtained by measurement as follows. First, the laminated substrate A was cut into a size of 30 mm × 30 mm to obtain a test piece. After peeling off the support film from the test piece, spray development is performed at a pressure of 0.2 MPa using a 1% by mass sodium carbonate aqueous solution at 30 ° C., and the shortest time that can be visually confirmed that an unexposed portion of 1 mm or more has been removed. Was set as the shortest development time. Tables 3 and 4 display constituent components other than pure water, and the pure water constitutes the remainder excluding the constituent components shown in each table.

  Tables 3 to 7 show developing processing solutions, washing processing solutions and photosensitive resin compositions used in Examples and Comparative Examples, respectively. In Table 5, in Example 1, the photosensitive resin composition (H-1) was used to form a photosensitive resin layer, which was then sprayed with a developing processing solution (F-2), and then washed with water. It means that it sprayed with (G-1).

In addition, the following substances were used as components of the treatment liquid.
・ Pure water (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
・ CaCl ₂ : Calcium chloride (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
・ NaCl: Sodium chloride (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
・ Na ₂ CO ₃ : Sodium carbonate (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)
MgCl ₂ : Magnesium chloride (made by Wako Pure Chemical Industries, Ltd., trade name)
・ MgSO ₄ : Magnesium sulfate (trade name, manufactured by Wako Pure Chemical Industries, Ltd.)

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

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

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

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

  The thermosetting resin composition layer obtained by uniformly coating the solution of the thermosetting resin composition obtained as described above on a 16 μm thick polyethylene terephthalate film (G2-16, manufactured by Teijin Ltd., trade name). Formed. Thereafter, the thermosetting resin composition layer was dried at 100 ° C. for about 10 minutes using a hot air convection dryer to obtain a film-like thermosetting resin composition. A film-shaped thermosetting resin composition having a film thickness of 25 μm was prepared.

  Next, a polyethylene film (trade name “NF-15” manufactured by Tamapoly Co., Ltd.) on the surface opposite to the side in contact with the polyethylene terephthalate film so that dust or the like does not adhere to the thermosetting resin composition layer. Were bonded together as a protective film to obtain a thermosetting film type resin composition.

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

  Thereafter, the thermosetting resin layer is ground by plasma treatment (plasma ashing) under the conditions shown in Table 8 to expose a part of the resin pattern of the photosensitive resin layer, whereby the resin pattern of the photosensitive resin layer is exposed. An exposed portion was formed. Next, along the steps shown in Table 9, the exposed portion of the resin pattern of the photosensitive resin layer is removed, and a via is formed by opening part of the resin pattern of the thermosetting resin layer and the photosensitive resin layer. As a result, a printed wiring board was obtained. Note that pure water was used in the water washing step and the drag-out step shown in Table 9.

The details of the treatment liquid in swelling, roughening and neutralization in Table 9 are as follows.
Swelling dip securigant P (Atotech): Mixture of diethylene glycol monobutyl ether and ethylene glycol Concentrate compact CP (Atotech): Concentrate compact (sodium permanganate), sodium hydroxide and water mixture Reduction Solution securigant P500 (manufactured by Atotech): Reduction securigant (hydroxyamine sulfate), sulfuric acid and water mixture

<Evaluation of openability>
The via opening (removability of the columnar resist) was evaluated based on the following criteria by observing vias having a diameter of 30 μmφ, 40 μmφ, 50 μmφ and 100 μmφ with an electron microscope (SEM). For the 100 μmφ via, only the example was evaluated. The evaluation results are shown in Tables 10 to 12.
A: There is no residue derived from the photosensitive resin composition on the copper surface, and it can be peeled off and removed.
B: Residue derived from the photosensitive resin composition is generated in a portion where the via is formed (opening portion) less than 50% of the volume.
C: Residue derived from the photosensitive resin composition is generated at 50% or more of the volume in the via forming part (opening part).

  As is apparent from Tables 10 to 12, it was found that by using the treatment liquids of the examples, the openability was good even when the via diameter was 30 μm or less. On the other hand, the opening of vias obtained using the treatment liquid of the comparative example was inferior to that of the example.

  A printed wiring board was produced in the same manner as in the above evaluation except that the diameter of the via was changed to 100 μm or more, and the evaluation was performed in the same manner as described above. In the case where the treatment liquids of Examples 1 to 16 were used, it was found that even if the roughening time was shortened to one third, the opening property was good and the throughput was excellent.

  DESCRIPTION OF SYMBOLS 1 ... Insulating layer, 2 ... Conductor circuit, 3 ... Board | substrate, 4 ... 1st photosensitive resin layer, 4a ... Resin pattern (columnar resist) of 1st photosensitive resin layer, 5 ... Thermosetting resin layer, 5h , 104 ... opening, 6, 105 ... seed layer, 7 ... resin pattern of the second photosensitive resin layer, 8 ... wiring part (conductor part), 8a, 102, 107 ... wiring pattern, 10 ... structure, 100 ... Multilayer printed wiring board, 101... Copper-clad laminate, 103. Interlayer insulating layer, 106... Resin pattern, 108.

Claims (12)

A treatment liquid for removing the resin portion embedded in the insulating layer and forming an opening in the insulating layer,
The resin part includes a cured product obtained by subjecting the photosensitive resin layer to an exposure process and a development process,
The processing liquid contains a divalent metal ion and is used as at least one of the processing liquid for the development processing and the processing liquid that contacts the cured product after the development processing.   The treatment liquid according to claim 1, wherein the divalent metal ion includes at least one selected from the group consisting of calcium ion, magnesium ion, beryllium ion, strontium ion, and barium ion.   The processing liquid according to claim 1 or 2, wherein the content of the divalent metal ion is 10 to 1000 ppm. A substrate having a conductor circuit, the insulating layer, and a conductor portion formed in the opening are used in a method for manufacturing a structure,
The insulating layer is disposed on a surface of the substrate;
The conductor portion is connected to the conductor circuit;
A manufacturing method of the structure is as follows:
Using the photosensitive resin composition, forming a photosensitive resin layer on the substrate so as to cover the conductor circuit;
A process liquid according to any one of claims 1 to 3, further comprising a step of subjecting the photosensitive resin layer to an exposure process and a development process to form a resin pattern including the cured product.   The processing liquid according to claim 4, wherein the photosensitive resin composition contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator. A manufacturing method of the structure is as follows:
Forming a thermosetting resin layer on the substrate so as to cover the resin pattern;
Removing a part of the thermosetting resin layer to expose a predetermined portion of the resin pattern from the thermosetting resin layer;
The method further comprises the step of removing the predetermined portion of the resin pattern exposed from the thermosetting resin layer and forming an opening in the thermosetting resin layer to expose the conductor circuit. The process liquid as described in. A method of manufacturing a structure comprising: a substrate having a conductor circuit; an insulating layer disposed on a surface of the substrate and having an opening; and a conductor portion formed in the opening and connected to the conductor circuit. Because
A step of subjecting the photosensitive resin layer to exposure treatment and development treatment to form a resin pattern containing a cured product;
Embedding the resin pattern in the insulating layer to form a resin portion containing the cured product;
Removing the resin portion and forming the opening in the insulating layer,
The manufacturing method of a structure using the processing liquid containing a bivalent metal ion as at least one of the processing liquid of the said development processing, and the processing liquid which contacts the said hardened | cured material after the said development processing.   The method for producing a structure according to claim 7, wherein the divalent metal ion includes at least one selected from the group consisting of calcium ion, magnesium ion, beryllium ion, strontium ion, and barium ion.   The manufacturing method of the structure of Claim 7 or 8 whose content of the said bivalent metal ion in the said process liquid is 10-1000 ppm.   The manufacturing of the structure according to any one of claims 7 to 9, further comprising a step of forming the photosensitive resin layer on the substrate so as to cover the conductor circuit using a photosensitive resin composition. Method.   The manufacturing method of the structure of Claim 10 in which the said photosensitive resin composition contains a binder polymer, a photopolymerizable compound, and a photoinitiator. Forming a thermosetting resin layer on the substrate so as to cover the resin pattern;
Removing a part of the thermosetting resin layer to expose a predetermined portion of the resin pattern from the thermosetting resin layer;
The method further comprises the step of removing the predetermined portion of the resin pattern exposed from the thermosetting resin layer and forming an opening in the thermosetting resin layer to expose the conductor circuit. The manufacturing method of the structure as described in any one of these.

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