JP6664473B2 - Method for manufacturing insulating layer and method for manufacturing multilayer printed circuit board - Google Patents

Description

[Cross-reference of related applications]
This application claims the benefit of priority from Korean Patent Application No. 10-2016-0150510 filed on November 11, 2016 and Korean Patent Application No. 10-2017-0144765 filed on November 1, 2017. All the contents disclosed in the Korean patent application literature are included as a part of this specification.

  The present invention relates to a method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board. More specifically, it can be manufactured in a faster and simpler manner, improving process efficiency, easily adjusting the thickness of an insulating layer, and forming a high-resolution via hole without physical damage. The present invention relates to a method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board using the insulating layer obtained by the method for manufacturing an insulating layer.

  Recent electronic devices are becoming smaller, lighter, and more sophisticated. For this reason, the use of multi-layer printed circuit boards is rapidly increasing due to the rapid expansion of the field of application of build-up printed circuit boards (PCBs), mainly for small devices.

  The multilayer printed circuit board is capable of three-dimensional wiring from planar wiring. In particular, in the field of industrial electronics, the integration degree of functional devices such as integrated circuits (ICs) and large scale integrations (LSIs) is improved, and the integration of electronic devices is improved. It is a product that is advantageous for miniaturization, weight reduction, high functionality, structural electrical function integration, reduction of assembly time and cost reduction.

  The build-up PCB used in such an application area always requires connection between layers, and therefore, uses a method of forming a via hole corresponding to an electric connection path between layers of a multilayer printed circuit board. However, there is a limit in reducing the diameter of the via hole, and there is a limit that it is difficult to achieve high density.

  Therefore, there has been proposed a method of using a fine protrusion having a diameter smaller than that of a via hole and using the protrusion as an interlayer electrical connection passage of a multilayer printed circuit board. However, in the conventional method, after forming fine protrusions of a metal component on a single circuit, the fine protrusions are covered with an insulating layer, and the insulating layer is physically removed until the fine protrusions are exposed on the surface. Most of the methods have limitations in that the insulating layer is easily broken during the physical removal process, and it is difficult to adjust a desired thickness easily.

  The present invention can be manufactured in a faster and simpler method, can improve the efficiency of the process, easily adjust the thickness of the insulating layer, and form a high-resolution via hole without physical damage. It is intended to provide a method for manufacturing an insulating layer that can be used.

  The present invention also provides a method for manufacturing a multilayer printed circuit board using an insulating layer obtained by the method for manufacturing an insulating layer.

  In this specification, the step of sealing a semiconductor device having a metal protrusion on the surface with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder; the step of sealing the semiconductor device having the metal protrusion on the surface Forming a pattern on the polymer resin layer while maintaining the state; first curing the polymer resin layer on which the pattern is formed; etching the surface of the cured polymer resin layer with an alkaline aqueous solution to form a metal A method of manufacturing an insulating layer, comprising: exposing projections; and secondary curing the polymer resin layer with the metal projections exposed.

  In addition, the present specification provides a method of manufacturing a multilayer printed circuit board, including a step of forming a metal pattern layer on an insulating layer manufactured by the method of manufacturing an insulating layer.

  Hereinafter, a method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board according to specific embodiments of the present invention will be described in more detail.

  According to one embodiment of the present invention, the step of sealing a semiconductor device having a metal protrusion on a surface with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder; the semiconductor device having a metal protrusion on the surface Forming a pattern on the polymer resin layer while maintaining the hermetically sealed state; first curing the polymer resin layer on which the pattern is formed; and curing the surface of the cured polymer resin layer with an alkaline aqueous solution. A method of manufacturing an insulating layer may include providing a step of exposing metal protrusions by etching; and a step of second curing the polymer resin layer with the metal protrusions exposed.

  The present inventors, when using the manufacturing method of the insulating layer of the embodiment, by exposing the metal projections sealed by the polymer resin layer through chemical etching with an aqueous alkali solution, the physical properties of the insulating layer In addition to preventing damage to the insulation layer, the thickness of the insulation layer can be easily adjusted to a desired range, and the insulation layer can be manufactured through an easier process in a shorter time. Confirmed and completed the invention.

  In particular, in the method of manufacturing an insulating layer according to the embodiment, a metal protrusion is easily exposed on the surface of the insulating layer by applying a polymer resin of a novel component capable of performing stable etching at an appropriate level with a specific alkaline aqueous solution. Therefore, there is an advantage that a multilayer circuit board can be easily manufactured through exposed metal protrusions.

  In addition, the method of manufacturing an insulating layer according to the one embodiment includes forming a pattern on the polymer resin layer while maintaining a sealed state of the semiconductor element having the metal protrusions formed on the surface thereof. A high-resolution fine opening (via hole) can be formed without affecting the element and without physically damaging the polymer resin layer. In the method for manufacturing a multilayer printed circuit board, which will be described later, by filling the fine opening (via hole) with metal, it can serve as an electrical path between the lower substrate and the upper substrate with respect to the insulating layer. Therefore, the degree of integration on a circuit board having a multilayer structure can be improved.

  More specifically, the method for manufacturing an insulating layer according to the embodiment includes a step of sealing a semiconductor element having a metal protrusion formed on a surface thereof with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder; Forming a pattern on the polymer resin layer while keeping the semiconductor element having the metal protrusions sealed; first curing the polymer resin layer on which the pattern is formed; The method may include: exposing the metal protrusions by etching the surface of the molecular resin layer with an alkaline aqueous solution; and secondary curing the polymer resin layer while the metal protrusions are exposed.

  First, in a step of sealing a semiconductor device having a metal protrusion on a surface with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder, the semiconductor device may have a metal protrusion formed on a surface. The method of forming the metal protrusions on the surface of the semiconductor element is not particularly limited. For example, a plating step or an adhesive step using an adhesive for an opening of the photosensitive resin layer pattern may be used. it can.

  As a specific example of the plating process for the opening of the photosensitive resin layer pattern, a step of laminating a photosensitive resin layer on a semiconductor element; a step of forming a pattern on the photosensitive resin layer; A method for forming a metal projection including the metal protrusion can be used.

  More specifically, the photosensitive resin layer can exhibit photosensitivity and alkali solubility. Therefore, the deformation of the molecular structure is promoted by the exposure step of irradiating the photosensitive resin layer with light, and the resin layer can be etched or removed by the development step of contacting with an alkaline developer.

  Therefore, when the photosensitive resin layer is selectively exposed to a portion and then subjected to alkali development, the exposed portion is not developed, and only the unexposed portion is selectively etched and removed. be able to. In this way, a part of the photosensitive resin layer which remains without being alkali-developed by exposure is referred to as a photosensitive resin pattern.

That is, to give an example of a method of exposing the photosensitive resin layer, a photomask having a predetermined pattern formed on the photosensitive resin layer is irradiated with ultraviolet light or a predetermined mask contained in the mask. After the pattern is imaged through the projection objective lens, the pattern can be selectively exposed through ultraviolet irradiation, or by direct imaging using a laser diode as a light source and then irradiated with ultraviolet light. At this time, as an example of the ultraviolet irradiation condition, irradiation with a light amount of 5 mJ / cm ^{2 to} 600 mJ / cm ² may be mentioned.

  Examples of the method of performing alkali development after exposure of the photosensitive resin layer include a method of treating an alkali developer. Examples of the alkali developer include, but are not particularly limited to, for example, an alkali aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, and amines. Can be used by adjusting the concentration and temperature, and an alkaline developer sold as a commercial product can also be used. Although the specific amount of the alkali developer used is not particularly limited, it is necessary to adjust the concentration and temperature so as not to damage the photosensitive resin pattern. For example, sodium carbonate 0.5% to 3% at 25 ° C. to 35 ° C. % Aqueous solution can be used.

  On the other hand, in the electroplating step, examples of a plating method include a dry deposition process or a wet deposition process, and specific examples of the dry deposition process include vacuum deposition, ion plating, and a sputtering method. Can be

  On the other hand, specific examples of the wet deposition process include electroless plating of various metals. Electroless copper plating is generally used, and may further include a roughening process before or after deposition.

  The roughening process also includes a dry process and a wet process depending on conditions. Examples of the dry process include vacuum, normal pressure, plasma treatment by gas, and excimer UV treatment by gas. As an example of the method, desmearing can be used. Through such a roughening process, the surface roughness of the metal thin film can be increased to improve the adhesion to the metal deposited on the metal thin film.

  The method may further include removing the photosensitive resin layer after the electroplating to leave only the metal protrusions. When removing the photosensitive resin pattern, it is preferable to use a method that removes only the photosensitive resin layer without removing the lower semiconductor element and metal protrusion as much as possible.

  As a specific example of the method of stripping the photosensitive resin pattern, a photoresist stripper may be treated, a desmear process or plasma etching may be performed, and the above methods may be mixed. .

  On the other hand, as a specific example of the bonding process using the adhesive, a metal protrusion is formed on the surface of a passive device such as MLCC or an active device such as a semiconductor chip, and then the metal protrusion is formed on the opposite side of the formed metal protrusion. Can be used to adhere to the surface of the semiconductor element using an insulating adhesive or the like. At this time, as the method of forming the metal protrusion on the surface of the passive element or the active element, the above-described method of the plating process for the opening of the photosensitive resin layer pattern can be used as it is. For example, a method may be used in which a photosensitive resin layer pattern is formed on the surface of a passive element or an active element, and then a metal is plated in an opening of the pattern.

  The thickness of the polymer resin layer may be 1 μm to 500 μm, or 3 μm to 500 μm, or 3 μm to 200 μm, or 1 μm to 60 μm, or 5 μm to 30 μm, and the metal protrusion may have a height of 1 μm to 20 μm and It may have a cross-sectional diameter of 3 μm to 30 μm. The cross-sectional diameter means a diameter of a cross-section obtained by cutting the metal protrusion in a direction perpendicular to a height direction of the metal protrusion, or a maximum diameter. For example, examples of the shape of the metal projection include a circular column, a truncated cone, a polygonal column, a truncated polygon, a truncated cone, and a truncated polygon. Further, examples of the metal component contained in the metal protrusion are not particularly limited, and for example, a conductive metal such as copper and aluminum can be used.

  The semiconductor element having the metal projection formed on the surface can be sealed with a polymer resin layer. More specifically, the semiconductor element may exist in a state formed on a substrate including a semiconductor material such as a circuit board, a sheet, a multilayer printed wiring board, and a silicon wafer such as a copper-clad laminate at a lower portion. is there. In order to form the semiconductor element on the substrate, it is possible to apply an adhesive layer on the surface of the substrate and bond the semiconductor element, or to apply a method of forming an adhesive layer on the semiconductor element and bonding it to the substrate without any limitation. it can.

  Examples of the adhesive layer are not particularly limited, and various adhesive layers widely known in the field of semiconductor devices and electric / electronic materials can be used without limitation. For example, a debonding type temporary fixing adhesive ( A Debondable Temporary Adhesive or a die bonding film (Die Attach Film, DAF) can be used. As described above, in a state where the semiconductor element is present on the base material, the conductive wiring can be sealed through a method of forming a polymer resin layer on the base material.

  Examples of the method of forming the polymer resin layer on the substrate are not particularly limited, for example, directly coating the polymer resin composition for forming the polymer resin layer on the substrate, or on the carrier film After forming a polymer resin layer by applying a polymer resin composition to the base material, a method of laminating the base material and the polymer resin layer can be used.

  The semiconductor element having the metal protrusions formed on the surface thereof is sealed with a polymer resin layer, so that the semiconductor element has a structure in which all parts except the part that contacts the base material and the part that contacts the metal protrusion are formed. Can come into contact with the polymer resin layer. In addition, all surfaces of the metal protrusions formed on the surface of the semiconductor element may be sealed by the polymer resin layer and contact the polymer resin layer.

  The polymer resin layer refers to a film formed by drying a polymer resin composition including an alkali-soluble resin and a thermosetting binder. The polymer resin layer may include 1 to 150 parts by weight, or 10 to 100 parts by weight, or 20 to 50 parts by weight of a thermosetting binder based on 100 parts by weight of the alkali-soluble resin. . If the content of the thermosetting binder is too large, the developability of the polymer resin layer is reduced, and the strength can be reduced. On the contrary, when the content of the thermosetting binder is too small, not only the polymer resin layer is excessively developed but also the uniformity during coating can be reduced.

  The thermosetting binder is a thermosetting functional group, an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyanide group, a maleimide group, and at least one functional group selected from the group consisting of a benzoxazine group and an epoxy group. Can be included. That is, the thermosetting binder necessarily contains an epoxy group, and in addition to the epoxy group, an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyanide group, a maleimide (maleimide) group, a benzoxazine (benzoxazine) group, or A mixture of two or more of these may be included. Such a thermosetting binder can form a cross-linking with an alkali-soluble resin or the like by thermosetting, thereby ensuring heat resistance or mechanical properties of the insulating layer.

  More specifically, as the thermosetting binder, a polyfunctional resin compound containing two or more functional groups described above in a molecule can be used.

  The polyfunctional resin compound may include a resin containing two or more cyclic ether groups and / or cyclic thioether groups (hereinafter, referred to as cyclic (thio) ether groups) in a molecule.

  The thermosetting binder containing two or more cyclic (thio) ether groups in the molecule is preferably one or two of a cyclic ether group having a 3, 4 or 5-membered ring, or a cyclic thioether group in the molecule. May be included.

  Examples of the compound having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., Ltd.

  Further, the polyfunctional resin compound may be a polyfunctional epoxy compound containing at least two or more epoxy groups in a molecule, a polyfunctional oxetane compound containing at least two or more oxetanyl groups in a molecule, or two The above-mentioned episulfide resin containing a thioether group, a polyfunctional cyanate ester compound containing at least two or more cyanide groups in a molecule, or a polyfunctional benzoxazine compound containing at least two or more benzoxazine groups in a molecule are also included. Good.

  Specific examples of the polyfunctional epoxy compound include, for example, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and novolak Epoxy resin, phenol novolak epoxy resin, cresol novolac epoxy resin, N-glycidyl epoxy resin, bisphenol A novolak epoxy resin, bixylenol epoxy resin, biphenol epoxy resin, chelate epoxy resin, glyoxal epoxy Resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, Tiger glycidyl xylenoyl yl ethane resins, silicone-modified epoxy resins, such as ε- caprolactone-modified epoxy resin. Further, in order to impart flame retardancy, those having atoms such as phosphorus introduced into the structure may be used. These epoxy resins are cured by heat to improve the properties of the cured film such as adhesion, solder heat resistance, and electroless plating resistance.

  Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, and 1,4-bis [(3-methyl -3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) ) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), cardo bisphenol , Calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxy group such as silsesquioxane and the like. Other examples include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

  Examples of the polyfunctional cyanate ester compound include bisphenol A type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol M type cyanate ester resin, and novolak type cyanate ester Resins, phenol novolak type cyanate ester resins, cresol novolak type cyanate ester resins, novolak type cyanate ester resins of bisphenol A, biphenol type cyanate ester resins, and oligomers or copolymers thereof.

  Examples of the polyfunctional maleimide compound include 4,4'-diphenylmethane bismaleimide, phenylmethane bismaleimide, m-phenylmethane bismaleimide, and m-phenylmethane bismaleimide. Bisphenol A diphenyl ether bismaleimide (bisphenol A diphenylethyl bismaleimide), 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide (3,3′-dimethyl-5,5′-diethyl-4) , 4'-diphenylmethyl bismaleimide), 4 Methyl-1,3-phenylene bismaleimide (4-methyl-1,3-phenylene bismaleimide), 1,6′-bismaleimide- (2,2,4-trimethyl) hexane (1,6′-bismaleimide- (2 , 2,4-trimethyl) hexane) and the like.

  Examples of the polyfunctional benzoxazine compound include bisphenol A benzoxazine resin, bisphenol F benzoxazine resin, phenolphthalein benzoxazine resin, thiodiphenol benzoxazine resin, dicyclopentadiene benzoxazine resin, , 3 ′-(Methylene-1,4-diphenylene) bis (3,4-dihydro-2H-1,3-benzoxazine (3,3 ′-(methylene-1,4-diphenylene) bis (3,4- dihydro-2H-1,3-benzoxazine) resin and the like.

  More specific examples of the polyfunctional resin compound include YDCN-500-80P manufactured by Kokuto Chemical Co., Ltd., phenol novolak type cyanate ester resin PT-30S manufactured by Lonza Japan Co., Ltd., and Daiwa Chemical Industry Co., Ltd. ), A Pd-type benzoxazine resin manufactured by Shikoku Chemicals Co., Ltd., and the like.

  Meanwhile, the alkali-soluble resin may include at least two or more acidic functional groups and at least two cyclic imide functional groups substituted with amino groups. Examples of the acidic functional group are not particularly limited, but may include, for example, a carboxy group or a phenol group. The alkali-soluble resin contains at least two or more acidic functional groups so that the polymer resin layer exhibits higher alkali developability and can control the developing speed of the polymer resin layer.

  The cyclic imide functional group substituted with the amino group includes an amino group and a cyclic imide group in the functional group structure, and may include at least two or more. Since the alkali-soluble resin contains at least two or more cyclic imide functional groups substituted with the amino group, the alkali-soluble resin has a structure in which a large number of active hydrogens contained in the amino group are present. In addition, it is possible to increase the curing density while improving the reactivity with the thermosetting binder at the time of curing, thereby improving the heat resistance and the mechanical properties.

  In addition, since a large number of the cyclic imide functional groups are present in the alkali-soluble resin, the polarity is increased by the carbonyl group and the tertiary amine group contained in the cyclic imide functional group, and the interfacial adhesive force of the alkali-soluble resin is increased. Can be increased. Accordingly, the polymer resin layer containing the alkali-soluble resin can have a higher interfacial adhesive force with the metal layer laminated thereon.

  More specifically, the cyclic imide functional group substituted with the amino group may include a functional group represented by the following Chemical Formula 1.

In Formula 1, R ₁ is an alkylene group or alkenyl group having 1 to 10, or 1 to 5, or 1 to 3 carbon atoms, and “ ^* ” means a bonding point. The alkylene group is a divalent functional group derived from an alkane, and includes, for example, a linear, branched or cyclic methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, Examples include a tert-butylene group, a pentylene group, and a hexylene group. One or more hydrogen atoms contained in the alkylene group may be substituted with a different substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms. Alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 12 carbon atoms, heteroaryl group having 2 to 12 carbon atoms, arylalkyl group having 6 to 12 carbon atoms, halogen atom, cyano group, amino group, amidino group , A nitro group, an amide group, a carbonyl group, a hydroxy group, a sulfonyl group, a carbamate group, and an alkoxy group having 1 to 10 carbon atoms.

  The term “substituted” means that another functional group is bonded instead of a hydrogen atom in a compound, and the position to be substituted is the position where the hydrogen atom is substituted, that is, the substituent is substitutable. There is no limitation as long as it is a position. When two or more substituents are substituted, the two or more substituents may be the same or different from each other.

  The alkenyl group means that one or more carbon-carbon double bonds are contained in the middle or at the terminal of the above-mentioned alkylene group, and examples thereof include ethylene, propylene, butylene, hexylene, and acetylene. One or more hydrogen atoms of the alkenyl group can be substituted with the same substituents as in the case of the alkylene group.

  Preferably, the cyclic imide functional group substituted with the amino group may be a functional group represented by the following Chemical Formula 2.

In Formula 2, " ^* " means a bonding point.

  As described above, the alkali-soluble resin contains a cyclic imide functional group substituted with an amino group together with an acidic functional group, and specifically, has an acidic functional group on at least one terminal of the cyclic imide functional group substituted with the amino group. Groups can be attached. At this time, the cyclic imide functional group and the acidic functional group substituted with the amino group can be bonded via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, for example, a cyclic group substituted with the amino group. An acidic functional group can be bonded to the terminal of the amino group contained in the imide functional group through a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and to the cyclic imide functional group substituted with the amino group. An acidic functional group can be bonded to the terminal of the contained imide functional group via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group.

  More specifically, the terminus of the amino group contained in the cyclic imide functional group substituted with the amino group means a nitrogen atom contained in the amino group in the above Chemical Formula 1, and is substituted with the amino group. The terminus of the imide functional group contained in the obtained cyclic imide functional group means a nitrogen atom contained in the cyclic imide functional group in Chemical Formula 1.

  The alkylene group is a divalent functional group derived from an alkane, and includes, for example, a linear, branched or cyclic methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, Examples include a tert-butylene group, a pentylene group, and a hexylene group. One or more hydrogen atoms contained in the alkylene group may be substituted with a different substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms. Alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 12 carbon atoms, heteroaryl group having 2 to 12 carbon atoms, arylalkyl group having 6 to 12 carbon atoms, halogen atom, cyano group, amino group, amidino group , A nitro group, an amide group, a carbonyl group, a hydroxy group, a sulfonyl group, a carbamate group, and an alkoxy group having 1 to 10 carbon atoms.

  The arylene group is a divalent functional group derived from arene, and includes, for example, a cyclic phenyl group and a naphthyl group. One or more hydrogen atoms contained in the arylene group may be substituted with a different substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms. Alkynyl group having 2 to 10 carbon atoms, aryl group having 6 to 12 carbon atoms, heteroaryl group having 2 to 12 carbon atoms, arylalkyl group having 6 to 12 carbon atoms, halogen atom, cyano group, amino group, amidino group , A nitro group, an amide group, a carbonyl group, a hydroxy group, a sulfonyl group, a carbamate group, and an alkoxy group having 1 to 10 carbon atoms.

  Examples of the method for producing the alkali-soluble resin are not particularly limited. For example, it can be produced through a reaction of a cyclic unsaturated imide compound; and an amine compound. At this time, at least one of the cyclic unsaturated imide compound and the amine compound may include a terminally substituted acidic functional group. That is, the cyclic unsaturated imide compound, the amine compound, or any of these two compounds can have an acidic functional group substituted at the terminal. The content of the acidic functional group is as described above.

  The cyclic imide compound is a compound containing the above-described cyclic imide functional group, and the cyclic unsaturated imide compound is a compound containing at least one unsaturated bond, that is, a double bond or a triple bond in the cyclic imide compound. Means

  The alkali-soluble resin may be prepared by reacting an amino group contained in the amine compound with a double bond or triple bond contained in the cyclic unsaturated imide compound.

  Examples of the weight ratio of reacting the cyclic unsaturated imide compound and the amine compound are not particularly limited. For example, the amine compound is 10 to 80 parts by weight, or 30 to 30 parts by weight, based on 100 parts by weight of the cyclic unsaturated imide compound. 60 parts by weight can be mixed and reacted.

  Examples of the cyclic unsaturated imide compound include an N-substituted maleimide compound. N-substituted means that a functional group is bonded instead of a hydrogen atom bonded to a nitrogen atom contained in the maleimide compound, and the N-substituted maleimide compound is a N-substituted maleimide compound. Depending on the number, they are classified into monofunctional N-substituted maleimide compounds and polyfunctional N-substituted maleimide compounds.

  The monofunctional N-substituted maleimide compound is a compound in which a functional group is substituted on a nitrogen atom contained in one maleimide compound, and the polyfunctional N-substituted maleimide compound is a compound having two or more maleimide compounds. It is a compound in which the contained nitrogen atom is bonded via a functional group.

  In the monofunctional N-substituted maleimide compound, the functional group substituted by the nitrogen atom contained in the maleimide compound may include various known aliphatic, alicyclic or aromatic functional groups without limitation. The functional group substituted by the nitrogen atom may include an aliphatic, alicyclic or aromatic functional group in which an acidic functional group is substituted. The content of the acidic functional group is as described above.

  Specific examples of the monofunctional N-substituted maleimide compound include o-methylphenylmaleimide, p-hydroxyphenylmaleimide, p-carboxyphenylmaleimide, and dodecylmaleimide.

  In the polyfunctional N-substituted maleimide compound, the functional group that mediates the bond between nitrogen atoms contained in each of the two or more maleimide compounds may be any of various known aliphatic, alicyclic or aromatic functional groups. They can be included without limitation, and specific examples include 4,4′-diphenylmethane functional groups. The functional group substituted by the nitrogen atom may include an aliphatic, alicyclic or aromatic functional group in which an acidic functional group is substituted. The content of the acidic functional group is as described above.

  Specific examples of the polyfunctional N-substituted maleimide compound include 4,4′-diphenylmethane bismaleimide (BMI-1000, BMI-1100 manufactured by Daiwa Chemical Industry Co., Ltd.), phenylmethane bismaleimide, m- Phenylenemethane bismaleimide, bisphenol A diphenylether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6 ′ -Bismaleimide- (2,2,4-trimethyl) hexane and the like.

As the amine compound, a primary amine compound containing at least one amino group (—NH ₂ ) in a molecular structure can be used, and more preferably, a carboxylic acid compound substituted with an amino group, and Or a polyfunctional amine compound containing an amino group or a mixture thereof.

  In the carboxylic acid compound substituted with the amino group, the carboxylic acid compound is a compound containing a carboxylic acid (—COOH) functional group in a molecule, and is an aliphatic compound depending on the type of hydrocarbon bonded to the carboxylic acid functional group. , Alicyclic or aromatic carboxylic acids. The developability of the alkali-soluble resin can be improved while the carboxylic acid compound substituted with the amino group contains a large number of carboxylic acid-functional groups in the alkali-soluble resin.

  Specifically, the alkali-soluble resin produced through the reaction between the carboxylic acid compound substituted with the amino group and the cyclic unsaturated imide compound has an acid value determined by KOH titration of 50 mg KOH / g to 250 mg KOH. / G, or 70 mg KOH / g to 200 mg KOH / g. An example of the method for measuring the acid value of the alkali-soluble resin is not particularly limited. For example, the following method can be used. A 0.1 N KOH solution (solvent: methanol) is prepared as a base solvent, and alpha-naphtholbenzein (pH: 0.8 to 8) is used as an indicator. .2 yellow, 10.0 blue green) were prepared. Next, about 1 to 2 g of the alkali-soluble resin of the sample was collected and dissolved in 50 g of dimethylformaldehyde (DMF) solvent, and after adding a label, titration was performed with a base solvent. The acid value was determined in mg KOH / g by the amount of base solvent used at the time of completion of the titration.

  If the acid value of the alkali-soluble resin is excessively reduced to less than 50 mg KOH / g, the developability of the alkali-soluble resin may be low, and the development step may be difficult to proceed. If the acid value of the alkali-soluble resin exceeds 250 mg KOH / g and increases too much, phase separation from other resins may occur due to an increase in polarity.

  The term “substituted” means that another functional group is bonded instead of a hydrogen atom in the compound, and the position where the amino group is substituted in the carboxylic acid compound is the position where the hydrogen atom is substituted. If it is, there is no limitation, and the number of amino groups to be substituted may be one or more.

  Specific examples of the carboxylic acid compound substituted with the amino group include about 20 kinds of α-amino acids, 4-aminobutanoic acid, 5-aminopentanoic acid, 6-aminohexanoic acid, -Aminoheptanoic acid, 8-aminooctanoic acid, 4-aminobenzoic acid, 4-aminophenylacetic acid, 4-aminocyclohexanecarboxylic acid and the like.

Further, the polyfunctional amine compound containing two or more amino groups is a compound containing two or more amino groups (—NH ₂ ) in a molecule, and depending on the type of hydrocarbon bonded to the amino group, the fatty acid may be a fatty acid. It can include all aromatic, cycloaliphatic or aromatic polyfunctional amines. Through the polyfunctional amine compound containing two or more amino groups, the flexibility and toughness of the alkali-soluble resin, the adhesion of the copper foil, and the like can be improved.

  Specific examples of the polyfunctional amine compound containing two or more amino groups include 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) -cyclohexane, 1,4 -Bis (aminomethyl) -cyclohexane, bis (aminomethyl) -norbornene, octahydro-4,7-methanoindene-1 (2), 5 (6) -dimethanamine, 4,4'-methylenebis (cyclohexylamine), 4, 4'-methylenebis (2-methylcyclohexylamine), isophoronediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,3,5,6- Tetramethyl-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-phenylene Diamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 4,6-diaminoresinol, 2,5-diamino-1,4-benzenedithiol, 3-aminobenzylamine, 4- Aminobenzylamine, m-xylenediamine, p-xylenediamine, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 2,6-diaminoanthraquinone, m-tolidine, o-tolidine, 3,3 ′, 5 5′-tetramethylbenzidine (TMB), o-dianisidine, 4,4′-methylenebis (2-chloroaniline), 3,3′-diaminobenzidine, 2,2′-bis (trifluoromethyl) -benzidine, 4,4'-diaminooctafluorobiphenyl, 4,4'-diamino-p-terphenyl, 3,3'-diaminodiphenyl Methane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-methylenebis (2-ethyl-6-methylaniline), 4,4'-methylenebis (2,6-diethylaniline), 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-ethylenedianiline, 4,4'-diamino-2,2 '-Dimethylbibenzyl, 2,2'-bis (3-amino-4-hydroxyphenyl) propane, 2,2'-bis (3-aminophenyl) -hexafluoropropane, 2,2'-bis (4- Aminophenyl) -hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) -hexafluoropropane, 2,2′- Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,1'-bis (4-aminophenyl) -cyclohexane, 9,9'-bis (4-aminophenyl) -fluorene, 9,9'-bis (4-amino-3- Chlorophenyl) fluorene, 9,9′-bis (4-amino-3-fluorophenyl) fluorene, 9,9′-bis (4-amino-3-methylphenyl) fluorene, 3,4′-diaminodiphenylether, 4,4′-diaminodiphenylether, 1,3-bis (3-aminophenoxy) -benzene, 1,3-bis (4-aminophenoxy) -benzene, 1,4- 2- (4-aminophenoxy) -benzene, 1,4-bis (4-amino-2-trifluoromethylphenoxy) -benzene, 4,4'-bis (4-aminophenoxy) -biphenyl, 2,2'- Bis [4- (4-aminophenoxy) -phenyl] propane, 2,2'-bis [4- (4-aminophenoxy) -phenyl] hexafluoropropane, bis (2-aminophenyl) sulfide, bis (4- Aminophenyl) sulfide, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, bis (3-amino-4-hydroxy) sulfone, bis [4- (3-aminophenoxy) -phenyl] sulfone, Bis [4- (4-aminophenoxy) -phenyl] sulfone, o-tolidinesulfone, 3,6-diaminocarbazole, 1,3,5- Tris (4-aminophenyl) -benzene, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, 4,4′-diaminobenzanilide, 2- (3-aminophenyl) -5-aminobenzimidazole , 2- (4-aminophenyl) -5-aminobenzoxazole, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 4,6 -Diaminoresorcinol, 2,3,5,6-pyridinetetraamine, a polyfunctional amine having a siloxane structure of Shin-Etsu Silicone (PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012) , KF-8008, X-22-1660B-3, X-22-9409), a polyfunctional amine containing a siloxane structure of Dow Corning Dow Corning3055), polyfunctional amine containing polyether structure (Huntsman Corporation, BASF Corporation).

  In addition, the alkali-soluble resin may include at least one repeating unit represented by Formula 3 below; and at least one repeating unit represented by Formula 4 below.

In Formula 3, R ₂ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and “ ^* ” means a bonding point. ,

In Formula 4, R ₃ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and R ₄ is —H, —OH, —NR ₅ R ₆ , halogen, or an alkyl group having 1 to 20 carbon atoms, wherein R ₅ and R ₆ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. It may be an aryl group, and " ^* " means the point of attachment.

Preferably, in Formula 3, R ₂ is phenylene, and in Formula 4, R ₃ is phenylene and R ₄ may be —OH.

  Meanwhile, the alkali-soluble resin may further include a vinyl repeating unit in addition to the repeating unit represented by Formula 3; and the repeating unit represented by Formula 4. The vinyl-based repeating unit is a repeating unit contained in a homopolymer of a vinyl-based monomer containing at least one vinyl group in a molecule, and examples of the vinyl-based monomer are particularly limited. Instead, examples thereof include ethylene, propylene, isobutylene, butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, and maleimide.

  The alkali-soluble resin containing at least one repeating unit represented by the above formula 3; and the repeating unit represented by the formula 3 is a polymer containing the repeating unit represented by the following chemical formula 5, It can be prepared by reacting an amine represented by Formula 6 and an amine represented by Formula 7 below.

In Chemical Formulas 5 to 7, R _{2 to} R ₄ are the same as those described in Chemical Formulas 3 and 4, and “ ^* ” means a bonding point.

  Specific examples of the polymer containing the repeating unit represented by Formula 5 are not particularly limited, and include, for example, SMA of Cray Valley, Xiran of Polyscope, Scripset of Solenis, Isobam of Kuraray, and Chevron Phillips Chemical. And Polydane resin, Maldene of Lindau Chemicals, and the like.

  In addition, the alkali-soluble resin containing at least one repeating unit represented by the above-described chemical formula 3; and the repeating unit represented by the chemical formula 3 is a compound represented by the following chemical formula 8 and a compound represented by the following chemical formula 9: It can be prepared by the reaction of the compounds represented.

In Chemical Formulas 8 and 9, R _{2 to} R ₄ are the same as those described in Chemical Formulas 3 and 4.

  Further, as the alkali-soluble resin, a known and commonly used carboxy group-containing resin or phenol group-containing resin having a carboxy group or a phenol group in a molecule can be used. Preferably, the carboxy group-containing resin or a mixture of the carboxy group-containing resin and a phenol group-containing resin can be used.

  Examples of the carboxy group-containing resin include the resins (1) to (7) listed below.

(1) a carboxy group-containing resin obtained by reacting a polyfunctional epoxy resin with a saturated or unsaturated monocarboxy group and then reacting with a polybasic acid anhydride;
(2) a carboxy group-containing resin obtained by reacting a bifunctional epoxy resin with a bifunctional phenol and / or a dicarboxy group and then reacting with a polybasic acid anhydride;
(3) a carboxy group-containing resin obtained by reacting a compound having one epoxy group in a molecule with a polyfunctional phenol resin and then reacting with a polybasic acid anhydride;
(4) a carboxy group-containing resin obtained by reacting a compound having two or more alcoholic hydroxyl groups in a molecule with a polybasic acid anhydride;
(5) a polyamic acid resin obtained by reacting diamine and dianhydride, or a copolymer resin of polyamic acid resin;
(6) polyacrylic acid resin reacted with acrylic acid or a copolymer of polyacrylic acid resin,
(7) Manufacture by subjecting maleic anhydride-reacted polymaleic anhydride resin and polymaleic anhydride resin copolymer anhydride to ring opening with weak acid, diamine, imidazole, and dimethyl sulfoxide. However, the present invention is not limited to these.

  As more specific examples of the carboxy group-containing resin, CCR-1291H manufactured by Nippon Kayaku Co., Ltd., SHA-1216CA60 manufactured by SHIN-AT & C, Noverite K-700 manufactured by Lubrizol, or two kinds of these. Examples thereof include the above mixtures.

  Examples of the phenol group-containing resin are not particularly limited. For example, a phenol novolak resin, a cresol novolak resin, a novolak resin such as a bisphenol F (BPF) novolak resin, or 4,4 ′-(1- (4- (2- ( (4-hydroxyphenyl) propan-2-yl) phenyl) ethane-1,1-diyl) diphenol [4,4 '-(1- (4- (2- (4-hydroxyphenyl) propan-2-yl)) bisphenol A-based resins such as phenyl) ethane-1 and 1-diyl) diphenol] can be used alone or in combination.

  The polymer resin layer may further include at least one additive selected from the group consisting of a thermosetting catalyst, an inorganic filler, a leveling agent, a dispersant, a release agent, and a metal adhesion promoter.

  The thermosetting catalyst plays a role in accelerating the thermosetting of the thermosetting binder. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, Imidazole derivatives such as-(2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethyl Amine compounds such as benzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic dihydrazide and sebacic dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U-CAT3503N manufactured by San Apro. , UCAT3502T (all trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATS A102, and U-CAT5002 (all bicyclic amidine compounds and salts thereof). The present invention is not particularly limited thereto, and may be a thermosetting catalyst for an epoxy resin or an oxetane compound, or may be one that promotes a reaction between an epoxy group and / or an oxetanyl group and a carboxy group. They can be used in combination. Also, guanamine, acetoguanamine, penzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2-vinyl-4,6 S-triazine derivatives such as -diamino-S-triazine-isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct can also be used. A compound that also functions as an imparting agent can be used in combination with the thermosetting catalyst.

  Examples of the inorganic filler include silica, barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, and a mixture of two or more of these.

  Examples of the content of the inorganic filler are not particularly limited, in order to achieve high rigidity of the polymer resin layer, based on 100 parts by weight of all resin components contained in the polymer resin layer, The inorganic filler can be added in an amount of 100 parts by weight or more, or 100 to 600 parts by weight, or 100 to 500 parts by weight.

  Examples of the release agent include polyalkylene wax such as low molecular weight polypropylene and low molecular weight polyethylene, ester wax, carnauba wax, and paraffin wax.

  As the metal adhesion promoter, a substance that does not cause a problem in surface deterioration or transparency of the metal material, for example, a silane coupling agent or an organic metal coupling agent can be used.

  The leveling agent plays a role in removing surface popping and craters during film coating, and for example, BYK-Chemie GmbH's BYK-380N, BYK-307, BYK-378, and BYK-350 can be used.

  Further, the polymer resin layer may further include a resin or an elastomer having a molecular weight of 5,000 g / mol or more capable of inducing phase separation. This enables a roughening treatment of the cured product of the polymer resin layer. The method for measuring the molecular weight of the resin or elastomer having a molecular weight of 5,000 g / mol or more is not particularly limited, and means, for example, a polystyrene-equivalent weight average molecular weight measured by a GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a generally known analyzer and a detector such as a differential refractive index detector (Refractive Index Detector) and an analytical column can be used. Temperature conditions, solvents and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 30 ° C., a chloroform solvent (Chloroform), and a flow rate of 1 mL / min (flow rate).

  Further, the polymer resin layer, in order to impart photocurable properties to the polymer resin layer, a thermosetting binder containing a photoreactive unsaturated group or an alkali-soluble resin containing a photoreactive unsaturated group. A photoinitiator may be further included. Specific examples of the thermosetting binder containing the photoreactive unsaturated group, the alkali-soluble resin containing the photoreactive unsaturated group, and the photoinitiator are not particularly limited, and the related technical field of the photocurable resin composition The various compounds used in can be used without limitation.

  The content of the photoinitiator contained in the polymer resin layer may be 0.01% by weight or less based on the weight of the entire polymer resin layer. That the content of the photoinitiator contained in the polymer resin layer is 0.01% by weight or less based on the weight of the entire polymer resin layer means that the content of the photoinitiator contained in the polymer resin layer is not more than 0.01% by weight. It means that the content is very small or contains no photoinitiator. Therefore, the desorption at the interface between the insulating layer and the conductive layer, which can be generated by the photoinitiator, is reduced, so that the adhesiveness and durability of the insulating layer can be improved.

  In one embodiment, the method of manufacturing an insulating layer may include forming a pattern on a polymer resin layer while maintaining a sealed state of the semiconductor device having the metal protrusions formed on the surface. .

  The method for manufacturing an insulating layer according to the embodiment includes forming a pattern on the polymer resin layer while maintaining a sealed state of the semiconductor element having the metal protrusions formed on the surface thereof. A high-resolution fine opening (via hole) can be formed in the polymer resin layer without physical damage without affecting. In the method for manufacturing a multilayer printed circuit board to be described later, by filling the fine opening (via hole) with metal, it can serve as an electrical path between the lower substrate and the upper substrate with respect to the insulating layer. In addition, the degree of integration on a circuit board having a multilayer structure can be improved.

  The pattern formed in the polymer resin layer means a state in which an opening (Opening) is partially formed in the polymer resin layer, and specifically, the pattern is formed in the polymer resin layer. Thereby, a part of the surface of the base material layer below the polymer resin layer can be exposed through the opening. That is, the step of forming a pattern on the polymer resin layer while maintaining the state in which the semiconductor element having the metal protrusions formed on the surface is sealed is performed in a state in which the semiconductor element having the metal protrusions formed on the surface is sealed. And forming a via hole in the polymer resin layer.

  In the step of forming a pattern on the polymer resin layer, the semiconductor device having the metal protrusions formed on the surface may be maintained in a sealed state. That is, in the process of partially forming the opening in the polymer resin layer, the opening is not formed near the portion where the semiconductor element is located. Therefore, even when a pattern is formed on the polymer resin layer, the semiconductor elements and the metal protrusions on the surface are maintained without physical and chemical influences, and the polymer resin layer maintains a sealed state in which all surfaces are in contact. Will be.

  On the other hand, as an example of a method of forming a pattern on the polymer resin layer, a chemical layer is formed by forming a pattern layer on the polymer resin layer and using the pattern layer as an etching mask pattern to etch the polymer resin layer. An etching method can be used. That is, forming the pattern on the polymer resin layer may include forming a pattern layer on the polymer resin layer; and performing alkali development on the polymer resin layer exposed by the pattern layer. . At this time, a photosensitive resin pattern layer or a metal pattern layer can be used as an example of the pattern layer.

  Meanwhile, after the step of alkali developing the polymer resin layer exposed by the pattern layer, 0.1% to 85% by weight or 0.1% by weight based on the total weight of the polymer resin layer exposed by the pattern layer. 1% to 50% by weight, or 0.1% to 10% by weight, can remain. This is thought to be because the alkali-soluble resin contained in the polymer resin layer was removed by the alkali developer, but the thermosetting binder or inorganic filler having little alkali developability remained without being removed. Can be

  In particular, in order to adjust the degree to which the inorganic filler and the thermosetting binder remain, the weight ratio of the alkali-soluble resin to the thermosetting binder and the inorganic filler, the acid functional group ratio on the surface of the inorganic filler, and the like can be adjusted. Preferably, 20 to 100 parts by weight of the thermosetting binder and 100 to 600 parts by weight of the inorganic filler can be added to 100 parts by weight of the alkali-soluble resin, and the acid value (acid value) of the surface of the inorganic filler can be added. ) Can be from 0 mg KOH / g to 5 mg KOH / g, or from 0.01 mg KOH / g to 5 mg KOH / g. The content regarding the acid value is the same as the method for measuring the acid value of the alkali-soluble resin.

  As described above, in the step of alkali developing the polymer resin layer exposed by the pattern layer, a portion of the polymer resin layer is left undeveloped and remains, so that the target polymer resin is removed in the subsequent pattern layer removing step. Instead of removing the pattern, the expansion of the via hole due to the removal of the polymer resin pattern can be prevented while the remaining polymer resin layer is removed.

  When a photosensitive resin pattern layer is used as a mask pattern of the polymer resin layer, the step of forming a pattern on the polymer resin layer includes forming a photosensitive resin layer on the polymer resin layer; The method may further include forming the photosensitive resin pattern by exposing the photosensitive resin layer and developing with an alkali, and also developing the polymer resin layer exposed by the photosensitive resin pattern with the alkali.

  The photosensitive resin layer can exhibit photosensitivity and alkali solubility. For this reason, the molecular structure is deformed by the exposure step of irradiating the photosensitive resin layer with light, and the resin layer can be etched or removed by the development step of contacting with an alkaline developer.

  Therefore, when the photosensitive resin layer is selectively exposed to a portion and then subjected to alkali development, the exposed portion is not developed, and only the unexposed portion is selectively etched and removed. Can be In this way, a part of the photosensitive resin layer which is not alkali-developed by exposure and remains as it is is called a photosensitive resin pattern.

That is, the method of exposing the photosensitive resin layer is, for example, by contacting a photomask having a predetermined pattern formed on the photosensitive resin layer and irradiating ultraviolet rays, or applying a predetermined pattern included in the mask. After imaging through a projection objective lens, ultraviolet light can be irradiated. Alternatively, direct imaging can be performed using a laser diode (Laser Diode) as a light source, and then selectively exposed through a method of irradiating ultraviolet light. At this time, as an example of the ultraviolet irradiation condition, irradiation with a light amount of 5 mJ / cm ^{2 to} 600 mJ / cm ² may be mentioned.

  Examples of the method of performing alkali development after exposure of the photosensitive resin layer include a method of treating an alkali developer. Examples of the alkali developer include, but are not particularly limited to, for example, an alkali aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, and amines. Can be used by adjusting the concentration and temperature thereof, and an alkaline developer sold as a commercial product can also be used. The specific amount of the alkali developer used is not particularly limited, but it is necessary to adjust the concentration and the temperature so as not to damage the photosensitive resin pattern. For example, sodium carbonate 0.5 to 3% at 25 to 35 ° C. Aqueous solutions can be used.

  The ratio at which the photosensitive resin pattern is removed may be 0.01% by weight or less based on the weight of the entire photosensitive resin pattern. The fact that the ratio at which the photosensitive resin pattern is removed is 0.01% by weight or less based on the weight of the entire photosensitive resin pattern means that the ratio at which the photosensitive resin pattern is removed is extremely small, It means that the resin pattern is not removed at all.

  Thereby, the photosensitive resin layer can be exposed and alkali-developed to form a photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern can be alkali-developed. As described above, the photosensitive resin layer can form a fine and uniform pattern using photosensitivity, and a portion of the polymer resin exposed through the pattern formed on the photosensitive resin layer. Through the process of selectively contacting only the surface of the layer with the alkali developing solution, it is possible to secure the same level of precision or higher and higher process economy while replacing the conventional etching process using a laser.

  That is, at the stage of developing the polymer resin layer exposed by the photosensitive resin pattern with an alkali, the photosensitive resin pattern is left as it is and is used as a resist mask because it is not removed by an alkali developer. The alkali developing solution can come into contact with the polymer resin layer located below the photosensitive resin layer through the opening. At this time, since the polymer resin layer contains an alkali-soluble resin and has alkali solubility that is dissolved by an alkali developer, a portion of the polymer resin layer contacted with the alkali developer is dissolved, Can be removed.

  Therefore, the polymer resin layer exposed by the photosensitive resin pattern means a portion of the polymer resin layer whose surface does not contact the photosensitive resin pattern, and the polymer resin layer exposed by the photosensitive resin pattern is alkali-developed. The step of performing may include a step in which the alkaline developer used in forming the photosensitive resin pattern passes through the photosensitive resin pattern and contacts the lower polymer resin layer.

  The polymer resin layer having the same shape as the photosensitive resin pattern may be formed on the polymer resin layer by performing the alkali development on the polymer resin layer exposed by the photosensitive resin pattern. Like the photosensitive resin pattern, a part of the polymer resin layer which is not subjected to alkali development and remains as it is can be said to be a polymer resin pattern.

  As described above, since the pattern formation through the development of the photosensitive resin layer and the pattern formation through the development of the polymer resin layer are performed simultaneously with one alkali developer, rapid mass production is possible. The efficiency of the process can be improved, and a fine pattern having the same shape as the fine pattern formed on the photosensitive resin layer can be easily introduced into the polymer resin layer by a chemical method.

  Further, when a metal pattern layer is used as a mask pattern of the polymer resin layer, the step of forming a pattern on the polymer resin layer may include the steps of: Adhering to the carrier film; forming a patterned photosensitive resin layer on the carrier film; removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer. Forming; removing the carrier film from the patterned metal layer; and performing alkali development on the polymer resin layer exposed by the patterned metal layer.

  At the step of adhering the opposite side of the metal layer to which the carrier film is adhered on one side onto the polymer resin layer, the method of adhering the opposite side of the metal layer to which the carrier film is adhered on one side onto the polymer resin layer For example, a method in which a polymer resin composition is applied to the opposite surface of the metal layer having the carrier film adhered to the one surface and dried may be used.

  The step of forming a patterned photosensitive resin layer on the carrier film may include forming a photosensitive resin layer on the carrier film, exposing the photosensitive resin layer and developing with an alkali. The contents relating to the photosensitive resin layer and the exposure and development thereof include the contents described above for the photosensitive resin pattern layer used for the mask pattern of the polymer resin layer.

  The step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer forms the photosensitive resin pattern on the carrier film and the metal layer. Used as a resist for Therefore, the carrier film and the metal layer exposed by the photosensitive resin layer pattern mean a portion of the carrier film and the metal layer that does not contact the photosensitive resin layer on the surface.

  Specifically, the step of removing the carrier film and the metal layer exposed by the photosensitive resin layer pattern may include the step of contacting the etchant with the carrier film and the metal layer through the patterned photosensitive resin layer. Can be included.

  The etchant can be selected according to the types of the carrier film and the metal layer, and it is preferable to use a substance which has as little influence as possible on the lower copper line and does not affect the photosensitive resin layer.

  Preferably, the same material as that of the metal layer is used as the material of the carrier film, so that the carrier film and the metal layer are simultaneously or sequentially removed by the same etchant, so that a pattern can be easily formed.

  On the other hand, in the step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form the patterned metal layer, the ratio at which the polymer resin layer is removed is equal to the entire polymer resin layer. 0.01% by weight or less based on the weight of The removal rate of the polymer resin layer of 0.01% by weight or less based on the weight of the entire polymer resin layer means that the degree of removal of the polymer resin layer is extremely small, Is not removed.

  That is, the etchant used in the step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form the patterned metal layer is physically different from the polymer resin layer. It has no chemical effect at all, so the polymer resin layer is stably maintained until the fine metal pattern layer is formed, and the aspect ratio is lowered by using the fine metal pattern layer as a resist mask, The resolution of the via hole can be increased.

  After passing through the step of removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer, the metal layer patterned on the polymer resin layer, the pattern The patterned carrier film and the patterned photosensitive resin layer can be sequentially laminated.

  At this time, in order to form the insulating layer, all layers except for the polymer resin layer and the patterned metal layer formed on the polymer resin layer must be removed. To this end, conventionally, an alkali developer is used to remove the photosensitive resin layer used for pattern formation, and at this time, the alkali developer develops the polymer resin layer simultaneously or sequentially. There was a problem. Further, when the metal layer used for forming the pattern is used, since an etching solution is used to remove the metal layer, problems such as corrosion of the lower copper line can be caused.

  On the other hand, in the case of the first embodiment, the polymer resin layer and the patterned metal layer formed on the polymer resin layer are removed through a simple method of separating and removing the carrier film and the metal layer. Layer can be easily removed.

  Since the adhesive force between the carrier film and the metal layer is smaller than the adhesive force between the polymer resin layer and the metal layer, peeling of the polymer resin layer and the metal layer during physical separation of the carrier film and the metal layer is prevented. can do.

  In addition, in the process of separating the carrier film and the metal layer, the carrier film and the photosensitive resin layer formed on the carrier film are removed together in a bonded or peeled state. The resolution of the via hole can be increased by leaving the fine metal pattern mask alone on the polymer resin layer without using it and lowering the aspect ratio through the patterning process.

  In the step of alkali developing the polymer resin layer exposed by the metal layer pattern, the metal layer pattern is used as a resist for forming a pattern on the polymer resin layer. Therefore, the polymer resin layer exposed by the metal layer pattern means a portion of the polymer resin layer whose surface does not contact the metal layer.

  Specifically, the step of alkali developing the polymer resin layer exposed by the metal layer pattern may include a step of contacting the polymer resin layer with an alkali developer passing through the metal layer on which the pattern is formed. it can.

  Since the polymer resin layer contains an alkali-soluble resin and has alkali solubility that is dissolved by an alkali developer, a portion of the polymer resin layer that contacts the alkali developer may be dissolved and removed. it can.

  Examples of the alkali developer include, but are not particularly limited to, for example, an alkali aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, and amines. And preferably a 30 ° C., 1% sodium carbonate developing solution. The specific amount of the alkali developer used is not particularly limited.

  At this time, the portion of the polymer resin layer that is dissolved and removed by contact with the alkali developer can form a via hole, and the average of the via holes included in the polymer resin layer on which the pattern is formed can be formed. The diameter can be 1 μm to 500 μm, or 100 μm to 300 μm.

  In one embodiment, the method of manufacturing an insulating layer may include a step of first curing the polymer resin layer on which the pattern is formed. In the step of curing the polymer resin layer, a specific example of a curing method is not particularly limited, and any of a thermosetting method and a photocuring method can be used without any limitation.

  Through the primary curing step, a main chain including an ester bond may be formed in the polymer resin layer. Examples of the ester bond include a method of photo-curing through an acrylic resin in which acrylic acid is ester-bonded, and a method of heat-curing such that an ester bond is formed by a reaction between carboxylic acid and epoxy.

  At this time, specific thermosetting conditions are not limited, and the process can be performed by adjusting desired conditions by an etching method of a polymer resin layer described later. For example, when treating a photoresist stripper to etch a polymer resin layer, the primary curing of the polymer resin layer may proceed at a temperature of 50C to 150C for 0.1 hour to 2 hours. it can. If the thermosetting temperature of the polymer resin layer is too low or the thermosetting time is short, the polymer resin layer is excessively damaged by the release liquid, and the thermosetting temperature of the polymer resin layer is high or the thermosetting time is shortened. When the length is longer, the etching of the polymer resin layer by the stripping liquid may not easily proceed.

  The method of manufacturing an insulating layer according to the embodiment may include a step of exposing metal protrusions by etching the surface of the cured polymer resin layer with an alkaline aqueous solution. Exposing the metal protrusions by etching the surface of the cured polymer resin layer with an alkaline aqueous solution, thereby connecting an electrical signal to the conductor wiring sealed inside the cured polymer resin layer through the exposed metal protrusions. Can be.

  The above-described exposure of the metal protrusions can proceed through etching with an alkaline aqueous solution. The alkaline aqueous solution may have a temperature of 10 ° C to 100 ° C, or 25 ° C to 60 ° C and a concentration of 1% to 10%, or 1% to 5%, and more specifically, use a photoresist stripper. can do. The alkaline aqueous solution can etch away the polymer resin layer by cutting out the ester bond in the polymer resin layer in which the main chain including the ester bond is formed through the primary curing. At this time, by adjusting the concentration and temperature of the alkaline aqueous solution, it is possible to control the etching rate of the polymer resin layer by the alkaline aqueous solution, and to maintain an appropriate level of etching rate within the above-described range to improve the process efficiency. , The thickness of the polymer resin layer can be easily adjusted.

  As the alkaline aqueous solution, an aqueous solution of a metal hydroxide such as potassium hydroxide or sodium hydroxide can be used. Atotech's Resistrip product group, Orchem's ORC-731, ORC-723K, Commercially available products such as ORC-740 and SLF-6000 can also be used.

  The etching with the alkaline aqueous solution can proceed from the cured polymer resin layer surface. The surface of the cured polymer resin layer means an area where the polymer resin layer sealing the conductor wiring having the metal protrusions formed on the surface is in contact with air, from the surface of the cured polymer resin layer to the surface. The metal projections can be exposed by the progress of the etching inside the polymer resin layer that seals the conductor wiring on which the metal projections are formed.

  Since the etching with the alkaline aqueous solution proceeds from the surface of the cured polymer resin layer, the aqueous alkaline solution can contact the surface of the cured polymer resin layer. At this time, the alkaline aqueous solution is brought into contact with the surface of the polymer resin layer through a method such as spraying through a spray in order to ensure uniformity of the thickness by uniform removal without physical damage of the polymer resin layer. be able to.

  Before the step of exposing the metal protrusions by etching the cured polymer resin layer surface with an alkaline aqueous solution, a step of removing the pattern layer remaining on the polymer resin layer may be performed, if necessary. Examples of the method of removing the photosensitive resin pattern layer or the metal pattern layer used for the pattern layer are not particularly limited, and may include treating a photoresist stripping solution, or proceeding with a desmear process or plasma etching. The thickness of the copper foil of the metal layer is extremely thin to 3 μm or less, and the metal layer is removed while partially removing the lower copper circuit, or the metal layer is removed, but the lower copper circuit is affected. Can be used. However, it is preferable to use a method of selectively removing only the pattern layer and not affecting the lower polymer resin layer.

  In one embodiment, the method of manufacturing an insulating layer may include a step of secondary curing the polymer resin layer with the metal protrusions exposed. Through the secondary curing step, the chemical resistance of the finally manufactured insulating layer can be improved.

  At this time, specific curing conditions are not limited. For example, the secondary curing step of the polymer resin layer may proceed at a temperature of 150 ° C. to 250 ° C. for 0.1 hour to 2 hours. .

  Meanwhile, according to another embodiment of the present invention, there can be provided a method of manufacturing a multilayer printed circuit board including a step of forming a metal pattern layer on the insulating layer manufactured according to the one embodiment.

  The present inventors have found that the insulating layer manufactured in one embodiment includes a semiconductor element having a metal protrusion formed on an inner surface thereof, and the metal protrusion is exposed outside the insulating layer, and is formed on the insulating layer. The present invention was completed when it was confirmed that when the metal pattern layer was further laminated, the metal pattern layer could exchange electrical signals with the semiconductor device inside the insulating layer through the metal protrusions.

  The insulating layer may be used as an interlayer insulating material of a multilayer printed circuit board, and may include a cured product of an alkali-soluble resin and a thermosetting binder, specifically, a thermosetting product or a photo-curing product. The contents regarding the alkali-soluble resin and the thermosetting binder include the contents described above in the one embodiment.

  More specifically, the step of forming a metal pattern layer on the insulating layer includes, for example, forming a metal thin film on the insulating layer; and forming a photosensitive resin layer having a pattern formed on the metal thin film. Depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern; and removing the photosensitive resin layer and removing the exposed metal thin film.

  In the step of forming the metal thin film on the insulating layer, examples of the method of forming the metal thin film include a dry deposition process or a wet deposition process, and specific examples of the dry deposition process include vacuum deposition and ion deposition. Examples include plating and sputtering.

  On the other hand, specific examples of the wet vapor deposition process include electroless plating of various metals, and electroless copper plating is generally used, and a roughening process before or after vapor deposition is further performed. Can be included.

  The roughening process also includes a dry process and a wet process depending on conditions. Examples of the dry process include vacuum, normal pressure, plasma treatment by gas, and excimer UV treatment by gas. As an example of the method, desmearing can be used. Through such a roughening process, the surface roughness of the metal thin film can be increased, and the adhesion to the metal deposited on the metal thin film can be improved.

  In addition, forming the metal thin film on the insulating layer may further include forming a surface treatment layer on the insulating layer before depositing the metal thin film. Thereby, the adhesive force between the metal thin film and the insulating layer can be improved.

  Specifically, as an example of a method for forming a surface treatment layer on the insulating layer, at least one of an ion assisted reaction method, an ion beam treatment method, and a plasma treatment method can be used. The plasma processing method may include any one of a normal pressure plasma processing method, a DC plasma processing method, and an RF plasma processing method. As a result of the surface treatment step, a surface treatment layer containing a reactive functional group can be formed on the surface of the insulating layer. As another example of a method of forming a surface treatment layer on the insulating layer, a method of depositing chromium (Cr) or titanium (Ti) metal with a thickness of 50 nm to 300 nm on the surface of the insulating layer may be mentioned.

  Meanwhile, forming the photosensitive resin layer having the pattern formed on the metal thin film may include exposing and developing the photosensitive resin layer formed on the metal thin film. The photosensitive resin layer and the contents for exposure and development may include the contents described above in the one embodiment.

  In particular, it is preferable that the pattern formed on the metal thin film is formed such that an opening included in the pattern can be in contact with a metal projection exposed outside the insulating layer. The opening included in the pattern means a portion that is removed through exposure and development of the photosensitive resin layer, and corresponds to a portion where a metal is deposited through metal deposition described below to form the metal pattern layer. . Therefore, if the opening included in the pattern is not formed so as to be able to contact with the metal protrusion exposed outside the insulating layer, the metal pattern layer contacts the metal protrusion and the semiconductor device inside the insulating layer. And can not exchange electrical signals.

  In the step of depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern, the metal thin film exposed by the photosensitive resin layer pattern means a metal thin film portion that does not contact the photosensitive resin layer on the surface. The metal to be deposited may be copper, examples of the deposition method are not particularly limited, and various known physical or chemical deposition methods can be used without limitation. A plating method can be used.

  At this time, a metal deposited on the metal thin film exposed by the photosensitive resin layer pattern may form the metal pattern layer described above, and more specifically, the metal pattern layer may be a semiconductor device through a metal protrusion. It can be formed to be connected to. Accordingly, the metal pattern layer can exchange electrical signals with a semiconductor element included in the insulating layer. More specifically, one end of the metal protrusion contacts the semiconductor device, and the other end of the metal protrusion contacts the metal pattern layer to electrically connect the conductor wiring and the metal pattern layer.

  In the step of removing the photosensitive resin layer and removing the exposed metal thin film, as an example of the method of removing the photosensitive resin layer, a photoresist stripper can be used, and by removing the photosensitive resin layer, As an example of the method of removing the exposed metal thin film, an etching solution can be used.

  The multilayer printed circuit board manufactured by the method for manufacturing a multilayer printed circuit board can be used again as a build-up material, for example, an insulating layer formed on the multilayer printed circuit board by the method for manufacturing an insulating layer according to the one embodiment. And a second step of forming a metal substrate on the insulating layer by the method for manufacturing a multilayer printed circuit board according to the other embodiment can be repeatedly performed.

  Therefore, the number of laminated layers included in the multilayer printed circuit board manufactured by the method for manufacturing a multilayer printed circuit board is not particularly limited, either. For example, one or more layers or 1 to 20 depending on the purpose of use and application. Can have layers.

  Forming the metal pattern layer on the insulating layer may include filling a via hole included in the insulating layer internal pattern with a metal. As described above, the insulating layer manufactured in the embodiment includes a pattern including a via hole (opening) therein, and the insulating layer is formed in a process of forming a metal pattern layer on the insulating layer. Internal via holes (openings) can be filled with metal. Specifically, in the step of forming the metal thin film on the insulating layer, the metal thin film may be formed on the surface of the insulating layer surrounding the via hole (opening) included in the insulating layer and also on the surface of the lower substrate. Through the step of depositing metal on the metal thin film, the via hole (opening) may be filled with metal while the metal is deposited inside the via hole (opening).

  By filling the fine opening (via hole) with a metal as described above, it can function as an electrical path between the lower substrate and the upper substrate with respect to the insulating layer, and thus has a multilayered circuit board. , The degree of integration can be improved.

  Meanwhile, after the step of forming the metal pattern layer on the insulating layer, the method may further include removing a base material formed below the semiconductor device, if necessary. As described above, the semiconductor element may exist in a state formed on a base material including a semiconductor material such as a circuit board, a sheet, and a multilayer printed wiring board underneath. For the formation of a multilayer circuit board having a finer structure, the lower substrate of the semiconductor element can be removed, if necessary, and the substrate exists in a state of being bonded or adhered to the polymer resin layer. And can be physically peeled and removed.

  ADVANTAGE OF THE INVENTION According to this invention, it can manufacture by a quicker and simpler method, can improve process efficiency, can easily adjust the thickness of an insulating layer, and can form a high-resolution via hole without physical damage. A method for manufacturing an insulating layer that can be formed and a method for manufacturing a multilayer printed circuit board using the insulating layer obtained by the method for manufacturing an insulating layer can be provided.

FIG. 4 is a diagram schematically illustrating a manufacturing process of the insulating layer of the first embodiment. FIG. 4 is a diagram schematically illustrating a manufacturing process of the multilayer printed circuit board according to the first embodiment. FIG. 9 is a diagram schematically illustrating a manufacturing process of an insulating layer of Example 2. FIG. 9 is a diagram schematically illustrating a manufacturing process of the multilayer printed circuit board according to the second embodiment.

  The invention is described in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by these examples.

<Production Example: Production of alkali-soluble resin>
Production Example 1
In a 2-liter heatable and coolable reaction vessel equipped with a production thermometer, a stirrer, a reflux condenser, and a moisture meter, 632 g of dimethylformamide (Dimethylformamide, DMF) as a solvent and BMI as an N-substituted maleimide compound 358 g of -1100 (manufactured by Daiwa Chemical Industry Co., Ltd.) and 151 g of 4-aminophenylacetic acid as an amine compound were mixed and stirred at 85 ° C. for 24 hours to produce an alkali-soluble resin solution having a solid content of 50%. .

Production Example 2
In a reaction vessel having a capacity of 2 liters capable of heating and cooling equipped with a production thermometer, a stirrer, a reflux condenser, and a water content meter, 632 g of dimethylformamide (Dimethylformamide, DMF) as a solvent and p as an N-substituted maleimide compound 434 g of -carboxyphenylmaleimide and 198 g of 4,4'-diaminodiphenylmethane as an amine compound were mixed and stirred at 85 ° C for 24 hours to produce an alkali-soluble resin solution having a solid content of 50%.

Production Example 3
543 g of dimethylacetamide (Dimethylacetamide, DMAc) was placed as a solvent in a reaction vessel having a capacity of 2 liters capable of heating and cooling equipped with a production thermometer, a stirrer, a reflux condenser, and a water content meter. 350 g of SMA 1000, 144 g of 4-aminobenzoic acid (4-aminobenzoic acid, PABA) and 49 g of 4-aminophenol (4-aminophenol, PAP) were added and mixed. After the reaction of the acid anhydride with the aniline derivative to form an amic acid for 24 hours under a nitrogen atmosphere at a reactor temperature of 80 ° C., the reactor temperature is maintained at 150 ° C. for 24 hours, and The oxidation reaction was allowed to proceed to produce an alkali-soluble resin solution having a solid content of 50%.

Production Example 4
In a 2 liter reaction vessel equipped with a production thermometer, a stirrer, a reflux condenser, and a moisture meter that can be heated and cooled, 516 g of methyl ethyl ketone (MEK) is added as a solvent, and p-carboxyphenylmaleimide ( After 228 g of p-carboxyphenylmaleimide, 85 g of p-hydroxyphenylmaleimide (p-hydroxyphenylmaleimide), 203 g of styrene, and 0.12 g of azobisisobutyronitrile (AIBN) were added and mixed. After gradually raising the temperature of the reactor to 70 ° C. under a nitrogen atmosphere, an alkali-soluble resin solution having a solid content of 50% was produced for 24 hours.

<Examples 1 and 2: Production of insulating layer and multilayer printed circuit board>
Example 1
(1) Production of Insulating Layer An insulating layer was produced in the order of the steps <1> to <10> as follows.

  <1> A debondable temporary fixing adhesive (Debondable Temporary Adhesive) 2 was formed on a silicon wafer 1.

  <2> A pattern is formed by spin-coating a photoresist on a semiconductor chip 3 having a thickness of 80 μm, and a copper bump 4 having a height of 15 μm and a diameter of 20 μm is formed by electroplating. The bonded semiconductor chip 3 is laminated on a debondable temporary adhesive (Debondable Temporary Adhesive) 2 on the silicon wafer 1, and the silicon wafer 1-a debondable temporary adhesive (Debondable Temporary Adhesive) 2-a semiconductor chip A structure laminated in the order of 3-copper bumps 4 was formed.

  <3> An alkali synthesized in Production Example 1 on the opposite surface of a 3 μm-thick ultra-thin copper foil 6 (trade name: MT18SD-H, manufactured by Mitsui Mining & Smelting Co., Ltd.) having a carrier copper foil 7 adhered to one surface. A polymer resin composition obtained by mixing 16 g of a soluble resin, 5 g of a thermosetting binder (trade name: MY-510, manufactured by Huntsman), and 35 g of an inorganic filler (trade name: SC2050 MTO, manufactured by Adamatech) to a thickness of 100 μm. After applying and drying to produce a structure in which the carrier copper foil 7-the ultrathin copper foil 6-the polymer resin layer 5 is laminated in this order, the debonding type temporary fixing adhesive (Debondable) on the silicon wafer 1 is formed. (Temporary Adhesive) 2 and the polymer resin layer 5 are vacuum-laminated at 85 ° C. to form a silicon wafer 1-bonding type temporary fixed connection. Adhesive (Debondable Temporary Adhesive) 2-semiconductor chip 3-copper bump 4-polymer resin layer 5-ultra-thin copper foil 6-carrier copper foil 7 The copper bump 4 was sealed.

<4> A photosensitive dry film resist 8 (trade name: KL1015, manufactured by Kolon Industry Co., Ltd.) having a thickness of 15 μm is laminated on the carrier copper foil 7 at 110 ° C., and a diameter is formed on the photosensitive dry film resist 8. After contacting a 150 μm circular negative type photomask and irradiating ultraviolet rays (light quantity of 25 mJ / cm ² ), the photosensitive dry film resist 8 was developed by passing through a 1% sodium carbonate developing solution at 30 ° C. Was formed. Then, the carrier copper foil 7 and the ultra-thin copper foil 6 were etched by treating the etchant. At this time, the photosensitive dry film resist 8 on which the pattern is formed acts as a protective layer for the carrier copper foil 7 and the ultra-thin copper foil 6, and the photosensitive dry film resist 8 also acts on the carrier copper foil 7 and the ultra-thin copper foil 6. The same pattern as that of the resist 8 was formed.

  <5> The ultra-thin copper foil 6 and the carrier copper foil 7 were separated, and the carrier copper foil 7 and the photosensitive dry film resist 8 laminated on the carrier copper foil 7 were removed.

  <6> The polymer resin layer 5 was developed at 30 ° C. through a 1% sodium carbonate developer. At this time, the ultra-thin copper foil 6 on which the pattern is formed acts as a protective layer for the polymer resin layer 5, and the same pattern as that of the ultra-thin copper foil 6 is formed on the polymer resin layer 5 as well. A 200 μm via hole 9 was formed.

  <7> The polymer resin layer 5 on which the pattern was formed was thermally cured at a temperature of 100 ° C. for 1 hour.

  <8> The ultra-thin copper foil 6 remaining on the polymer resin layer 5 was removed by treating the etchant.

  <9> A 3% sodium hydroxide resist stripping solution at a temperature of 50 ° C. is sprayed onto the surface of the polymer resin layer 5 to remove the copper bump 4 from the surface of the polymer resin layer 5 to a depth of about 3 μm, thereby leaving the copper bump 4 on the surface. And washed with water and dried. At this time, the process of exposing the copper bump 4 was performed in a continuous process for 10 to 60 seconds per panel.

  <10> The polymer resin layer 5 having the copper bumps 4 exposed on the surface was thermally cured at a temperature of 200 ° C. for 1 hour to produce an insulating layer.

(2) Production of Multilayer Printed Circuit Board A multilayer printed circuit board was produced in the order of the steps <11> to <13> as follows.

  <11> A titanium-copper thin film is deposited on the manufactured insulating layer by using a sputter and heated at a temperature of 100 ° C. for 30 minutes to improve the adhesion to the sputtered layer. (Trade name: RY-5319, manufactured by Hitachi Chemical Co., Ltd.) was laminated to form a pattern, and a metal-patterned circuit was formed by electroplating, and the via hole 9 was filled with metal.

<12> A 15 μm-thick photosensitive dry film resist (trade name: KL1015, manufactured by Kolon Industry Co., Ltd.) is laminated on the circuit at 110 ° C., and a 30 μm-diameter circular shape is formed on the photosensitive dry film resist. After contacting a negative photomask and irradiating ultraviolet rays (light amount of 25 mJ / cm ² ), the photosensitive dry film resist is developed through a 1% sodium carbonate developing solution at 30 ° C. to form a solder resist having a predetermined pattern. 10 was formed.

  <13> The silicon wafer 1 and the debondable temporary adhesive (Debondable Adhesive) 2 were separated and removed from the insulating layer to complete a multilayer printed circuit board.

Example 2
An insulating layer was manufactured in the order of the steps <1> to <10> as follows.

  <1> An ultra-thin copper foil 6 was formed on a copper-clad laminate (trade name: LG-500GA VB / VB, LG Chemical Co., Ltd.) 1, and a carrier copper foil 7 was formed on the ultra-thin copper foil 6. .

  <2> A pattern is formed by spin-coating a photoresist on the semiconductor chip 3, electroplating is performed to form a copper bump 4 having a height of 15 μm and a diameter of 20 μm, and then the semiconductor chip on which the copper bump 4 is formed. 3 is laminated on the carrier copper foil 7 on the copper-clad laminate 1 by the die bonding film 2, and the copper-clad laminate 1-the ultra-thin copper foil 6-the carrier copper foil 7-the die bonding film 2-the semiconductor chip 3- A structure laminated in the order of the copper bumps 4 was formed.

  <3> An alkali synthesized in Production Example 1 on the opposite surface of a 3 μm-thick ultra-thin copper foil 6 (trade name: MT18SD-H, manufactured by Mitsui Mining & Smelting Co., Ltd.) having a carrier copper foil 7 adhered to one surface. A polymer resin composition obtained by mixing 16 g of a soluble resin, 5 g of a thermosetting binder (trade name: MY-510, manufactured by Huntsman), and 35 g of an inorganic filler (trade name: SC2050 MTO, manufactured by Adamatech) to a thickness of 100 μm. After coating and drying to produce a structure in which the carrier copper foil 7-the ultra-thin copper foil 6-the polymer resin layer 5 is laminated in this order, the carrier copper foil 7 on the copper clad laminate 1 and the high The molecular resin layer 5 is vacuum-laminated at 85 ° C. to form a copper-clad laminate 1-ultra-thin copper foil 6-carrier copper foil 7-die bonding film 2-semiconductor chip 3-copper bump 4-polymer resin layer 5-pole Thin copper foil 6-cap To form a sequentially with laminated structure of Adohaku 7 was sealed semiconductor chip 3 and the copper bumps 4.

<4> A photosensitive dry film resist 8 (trade name: KL1015, manufactured by Kolon Industry Co., Ltd.) having a thickness of 15 μm is laminated on the carrier copper foil 7 at 110 ° C., and a diameter is formed on the photosensitive dry film resist 8. After contacting a 150 μm circular negative type photomask and irradiating ultraviolet rays (light quantity of 25 mJ / cm ² ), the photosensitive dry film resist 8 was developed by passing through a 1% sodium carbonate developing solution at 30 ° C. Was formed. Then, the carrier copper foil 7 and the ultra-thin copper foil 6 were etched by treating the etchant. At this time, the photosensitive dry film resist 8 on which the pattern is formed acts as a protective layer for the carrier copper foil 7 and the ultra-thin copper foil 6, and the photosensitive dry film resist 8 also acts on the carrier copper foil 7 and the ultra-thin copper foil 6. The same pattern as that of the resist 8 was formed.

  <5> The ultra-thin copper foil 6 and the carrier copper foil 7 were separated, and the carrier copper foil 7 and the photosensitive dry film resist 8 laminated on the carrier copper foil 7 were removed.

  <6> The polymer resin layer 5 was developed at 30 ° C. through a 1% sodium carbonate developer. At this time, the ultra-thin copper foil 6 on which the pattern is formed acts as a protective layer for the polymer resin layer 5, and the same pattern as that of the ultra-thin copper foil 6 is formed on the polymer resin layer 5 as well. A 200 μm via hole 9 was formed.

  <7> The polymer resin layer 5 on which the pattern was formed was thermally cured at a temperature of 100 ° C. for 1 hour.

  <8> The ultra-thin copper foil 6 remaining on the polymer resin layer 5 was removed by treating the etchant.

  <9> A 3% sodium hydroxide resist stripping solution at a temperature of 50 ° C. is sprayed onto the surface of the polymer resin layer 5 to remove the copper bump 4 from the surface of the polymer resin layer 5 to a depth of about 3 μm, thereby leaving the copper bump 4 on the surface. And washed with water and dried. At this time, the process of exposing the copper bump 4 was performed in a continuous process for 10 to 60 seconds per panel.

  <10> The polymer resin layer 5 having the copper bumps 4 exposed on the surface was thermally cured at a temperature of 200 ° C. for 1 hour to produce an insulating layer.

(2) Production of Multilayer Printed Circuit Board A multilayer printed circuit board was produced in the order of the steps <11> to <14> as follows.

  <11> A copper thin film is deposited on the manufactured insulating layer using electroless copper plating, and heated at a temperature of 100 ° C. for 30 minutes to improve adhesion to the electroless copper plating, and then dried. (Trade name: RY-5319, manufactured by Hitachi Chemical Co., Ltd.) was laminated to form a pattern, and a metal-patterned circuit was formed by electroplating, and the via hole 9 was filled with metal.

<12> A 15 μm-thick photosensitive dry film resist (trade name: KL1015, manufactured by Kolon Industry Co., Ltd.) is laminated on the circuit at 110 ° C., and a 30 μm-diameter circular shape is formed on the photosensitive dry film resist. After contacting a negative photomask and irradiating ultraviolet rays (light amount of 25 mJ / cm ² ), the photosensitive dry film resist is developed through a 1% sodium carbonate developing solution at 30 ° C. to form a solder resist having a predetermined pattern. 10 was formed.

  <13> The ultra-thin copper foil 6 and the carrier copper foil 7 were separated, and the ultra-thin copper foil 6 and the copper-clad laminate 1 laminated below the ultra-thin copper foil 6 were removed.

  <14> The carrier copper foil 7 remaining under the insulating layer was removed by etching to complete a multilayer printed circuit board.

Example 3
The same as in Example 1 except that the alkali-soluble resin synthesized in Manufacturing Example 2 was used instead of the alkali-soluble resin synthesized in Manufacturing Example 1 in the manufacturing step of the insulating layer of Example 1. An insulating layer and a multilayer printed circuit board were manufactured by the method.

Example 4
In the same manner as in Example 1 except that the alkali-soluble resin synthesized in Production Example 3 was used instead of the alkali-soluble resin synthesized in Production Example 1 in the step of manufacturing the insulating layer of Example 1. An insulating layer and a multilayer printed circuit board were manufactured by the method.

Example 5
The same as in Example 1 except that the alkali-soluble resin synthesized in Production Example 4 was used instead of the alkali-soluble resin synthesized in Production Example 1 in the step of manufacturing the insulating layer of Example 1. An insulating layer and a multilayer printed circuit board were manufactured by the method.

Example 6
During the production of the polymer resin layer, 16 g of the alkali-soluble resin synthesized in Production Example 1, 5 g of a thermosetting binder (trade name: MY-510, manufactured by Huntsman), inorganic filler (trade name: SC2050 MTO, solid content 70) %, Manufactured by Adamatech Co., Ltd.) An insulating layer and a multilayer printed circuit board were manufactured in the same manner as in Example 1, except that a polymer resin composition mixed with 43 g was used.

Example 7
An insulating layer and a multilayer printed circuit board were manufactured in the same manner as in Example 6 except that the alkali-soluble resin synthesized in Manufacturing Example 2 was used instead of the alkali-soluble resin synthesized in Manufacturing Example 1. did.

Example 8
An insulating layer and a multilayer printed circuit board were manufactured in the same manner as in Example 6 except that the alkali-soluble resin synthesized in Manufacturing Example 3 was used instead of the alkali-soluble resin synthesized in Manufacturing Example 1. did.

Example 9
An insulating layer and a multilayer printed circuit board were manufactured in the same manner as in Example 6 except that the alkali-soluble resin synthesized in Manufacturing Example 4 was used instead of the alkali-soluble resin synthesized in Manufacturing Example 1. did.

<Comparative Examples 1 to 3: Production of insulating layer and multilayer printed circuit board>
Comparative Example 1
In step <3>, a 100 μm-thick molding sheet (trade name: LE-T17B, Ajinomoto Co., Inc.) was used to perform vacuum lamination at 120 ° C. instead of the polymer resin layer of the production example. In step 7>, after heat-curing at a temperature of 170 ° C. for 1 hour, in step <9>, the surface of the heat-cured polymer resin layer is ground with a grinding machine to expose the copper bumps. An insulating layer was manufactured in the same manner as in Example 1 except for the above.

  At this time, since the step of exposing the copper bump is performed for 10 to 20 minutes per panel in the arrangement step, it can be confirmed that it takes longer time than in the example.

Comparative Example 2
In the step <9>, instead of spraying a 3% sodium hydroxide resist stripping solution at a temperature of 50 ° C. onto the surface of the polymer resin layer, Sweller (Atotech, Sweller-p, 40%) is used in a usual manner. , Etching (KMnO ₄ 9%, NaOH, 6%) and neutralization (H ₂ SO ₄ , 9%) in this order, and desmearing, removing about 3 μm depth from the surface of the polymer resin layer to remove the copper bumps from the surface. An insulating layer and a multilayer printed circuit board were manufactured in the same manner as in Example 1 except that the insulating layer was exposed above.

  At this time, since the desmearing process of exposing the copper bumps is performed in a continuous arrangement process only for the etching stage for 5 to 10 minutes per panel, it takes a longer time than in the embodiment, It was confirmed that not only must such harmful chemical substances be introduced, but also that there is a limit that it is difficult to control the thickness of the polymer resin layer.

Comparative Example 3
An insulating layer was manufactured in the same manner as in Example 1 except that the step of primary thermosetting of the polymer resin layer in the step <7> at a temperature of 100 ° C. for 1 hour was omitted.

  At this time, in the case of Comparative Example 3, there is a technical limit that the polymer resin layer is completely removed within 10 seconds after spraying the sodium hydroxide resist stripping solution, and the copper bump and the lower circuit are exposed. confirmed.

  That is, when the curing step for the polymer resin layer does not proceed before the release liquid is sprayed as in Comparative Example 3, it is difficult to control the degree to which the polymer resin layer is removed. Was not suitable for exposing to the surface of the polymer resin layer.

DESCRIPTION OF SYMBOLS 1 Silicon wafer or copper clad laminated board 2 Debonding type temporary fixing adhesive or die bonding film 3 Semiconductor chip 4 Copper bump 5 Polymer resin layer 6 Ultra-thin copper foil 7 Carrier copper foil 8 Photosensitive dry film resist 9 Via hole 10 Solder resist <1> to <14> Process progress order

Claims (19)

Sealing the semiconductor element having the metal protrusions formed on its surface with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder;
Forming a pattern on the polymer resin layer while maintaining the semiconductor device having the metal protrusions formed on the surface in a sealed state;
First curing the polymer resin layer on which the pattern is formed;
Step is etched to expose the metal projection surface of the cured polymer resin layer with an alkaline aqueous solution; in a state and said metal projection is exposed, see contains a step of curing the polymeric resin layer secondary,
The step of forming a pattern layer on the polymer resin layer,
Adhering the opposite side of the metal layer having the carrier film adhered on one side to the polymer resin layer;
Forming a patterned photosensitive resin layer on the carrier film;
Removing the carrier film and the metal layer exposed by the patterned photosensitive resin layer to form a patterned metal layer; and
The patterned including the step of separating and removing the carrier film from the metal layer, the production method of the insulating layer. The step of forming a pattern on the polymer resin layer,
The method of claim 1, further comprising: forming a pattern layer on the polymer resin layer; and performing alkali development on the polymer resin layer exposed by the pattern layer. At the step of adhering the opposite surface of the metal layer to which the carrier film is adhered to the one surface on a polymer resin layer containing an alkali-soluble resin and a thermosetting binder,
The method of claim 1 , wherein an adhesive force between the carrier film and the metal layer is smaller than an adhesive force between the polymer resin layer and the metal layer.   The method for producing an insulating layer according to claim 1, wherein the alkali-soluble resin includes at least two or more acidic functional groups; and at least two cyclic imide functional groups substituted with amino groups. The method for producing an insulating layer according to claim 4 , wherein the cyclic imide functional group substituted with an amino group includes a functional group represented by the following Chemical Formula 1.

In Formula 1, R ₁ is an alkylene group or an alkenyl group having 1 to 10 carbon atoms, and “ ^* ” means a bonding point.   The alkali-soluble resin is produced through a reaction of a cyclic unsaturated imide compound; and an amine compound, and at least one of the cyclic unsaturated imide compound and the amine compound contains a terminally substituted acidic functional group. Item 2. The method for producing an insulating layer according to Item 1. The insulating layer according to claim 6 , wherein the amine compound includes at least one selected from the group consisting of a carboxylic acid compound substituted with an amino group, and a polyfunctional amine compound containing two or more amino groups. Production method. 2. The method of claim 1, wherein the alkali-soluble resin comprises at least one repeating unit represented by Formula 3 below; and at least one repeating unit represented by Formula 4 below: 3.

In Formula 3, R ₂ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and “ ^* ” means a bonding point. ,

In Formula 4, R ₃ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms;
R ₄ is —H, —OH, —NR ₅ R ₆ , halogen, or an alkyl group having 1 to 20 carbon atoms;
R ₅ and R ₆ may each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;
“ ^* ” Means a connection point. The said alkali-soluble resin is manufactured by the reaction of the polymer containing the repeating unit represented by following Chemical Formula 5, the amine represented by following Chemical Formula 6, and the amine represented by following Chemical Formula 7. The method for producing an insulating layer according to Item 8 :

In Chemical Formulas 5 to 7, R _{2 to} R ₄ are as defined in claim 8 , and “ ^* ” means a bonding point. The alkali-soluble resin, the chemical compound represented by 8 below, and is produced by the reaction of the compound represented by Formula 9 below, the manufacturing method of the insulating layer according to claim 8:

In Chemical Formulas 8 and 9, R _{2 to} R ₄ are as defined in claim 8 .   2. The method of claim 1, wherein the polymer resin layer includes 1 to 150 parts by weight of a thermosetting binder with respect to 100 parts by weight of the alkali-soluble resin. After the step of alkali developing the polymer resin layer exposed by the pattern layer,
The method of claim 2, wherein 0.1% to 85% by weight of the polymer resin layer exposed by the pattern layer remains.   The method for producing an insulating layer according to claim 1, wherein the polymer resin layer contains at least 100 parts by weight of an inorganic filler based on 100 parts by weight of the total weight of the alkali-soluble resin and the thermosetting binder.   The method according to claim 1, wherein the primary curing proceeds at a temperature of 50 ° C. to 150 ° C. for 0.1 hour to 2 hours.   The method according to claim 1, wherein the secondary curing proceeds at a temperature of 150 ° C. to 250 ° C. for 0.1 hour to 10 hours.   A method for manufacturing a multilayer printed circuit board, comprising forming a metal pattern layer on an insulating layer manufactured according to claims 1 to 15. 17. The method of claim 16 , wherein the insulating layer includes a cured product of an alkali-soluble resin and a thermosetting binder. Forming a metal pattern layer on the insulating layer,
Forming a metal thin film on the insulating layer;
Forming a photosensitive resin layer having a pattern formed on the metal thin film; and depositing metal on the metal thin film exposed by the photosensitive resin layer pattern; and removing the photosensitive resin layer to expose the metal. The method of claim 16 , further comprising removing the thin metal film. The method of claim 16 , wherein the metal pattern layer is connected to the semiconductor device through a metal protrusion.

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