KR20230172229A - Insulating layer for multilayered printed circuit board - Google Patents

Abstract

The present invention relates to an insulating layer for a multilayer printed circuit board, and specifically to an insulating layer for a multilayer printed circuit board in which metal adhesion is improved by selecting the type of compound included to produce an alkali-soluble resin.

Description

Insulating layer for multilayer printed circuit board {INSULATING LAYER FOR MULTILAYERED PRINTED CIRCUIT BOARD}

The present invention relates to an insulating layer for a multilayer printed circuit board, and specifically to an insulating layer for a multilayer printed circuit board in which metal adhesion is improved by selecting the type of compound included to produce an alkali-soluble resin.

Recently, electronic devices are becoming increasingly smaller, lighter, and more highly functional. To this end, as the application field of build-up printed circuit boards (PCBs) is rapidly expanding, focusing on small devices, the use of multilayer printed circuit boards is rapidly increasing.

Multilayer printed circuit boards allow for two-dimensional to three-dimensional wiring. Especially in the industrial electronics field, the integration of functional elements such as IC (integrated circuit) and LSI (large scale integration) is improved, and electronic devices are miniaturized, lightweight, highly functional, and structural. This product is advantageous for integrating electrical functions, shortening assembly time, and reducing costs.

The build-up PCB used in these application areas must form a via hole to connect each layer. A via hole corresponds to an electrical connection passage between the layers of a multilayer printed circuit board, and was previously used with a mechanical drill. Drill), but as the diameter of the hole became smaller due to the miniaturization of the circuit, the processing cost using a machine drill increased and the limitations of fine hole processing led to the emergence of a processing method using a laser as an alternative.

However, in the case of processing using a laser, a CO ₂ or YAG laser drill is used, but since the size of the via hole is determined by the laser drill, for example, in the case of a CO 2 laser drill, the via hole has a diameter of 50 ㎛ or less. There are limitations that make it difficult to manufacture via holes. In addition, when multiple via holes must be formed, there is a limitation in that the cost burden is large.

Accordingly, instead of the above-described laser processing technology, a method of forming a via hole with a fine diameter at low cost using a photosensitive insulating material was proposed. Specifically, the photosensitive insulating material includes a photosensitive insulating film called solder resist that can form a fine opening pattern using photosensitivity.

These photosensitive insulating materials or solder resists can be divided into those that use sodium carbonate developer to form patterns and those that use other developers. When using other developers, photosensitive insulating materials or solder resists have limitations that make them difficult to apply in actual processes due to environmental and cost reasons.

On the other hand, using a sodium carbonate developer has the advantage of being environmentally friendly. In this case, an acid-modified acrylate resin containing multiple carboxylic acids and acrylate groups is used to provide photosensitivity. Since most of the acrylate groups and carboxy groups are connected by ester bonds, polymerization inhibitors, etc. are used to polymerize into the desired shape. It includes a photoinitiator, etc. to cause a radical reaction by ultraviolet irradiation.

However, the polymerization inhibitor or photoinitiator may diffuse out of the resin under high temperature conditions and cause interfacial detachment from the insulating layer or conductive layer during or after the semiconductor package process. In addition, the ester bond in the resin causes a hydrolysis reaction at high humidity and reduces the cross-linking density of the resin, causing an increase in the moisture absorption rate of the resin. When the moisture absorption rate is high, polymerization inhibitors or photoinitiators are used under high temperature conditions. It is converted out of the resin and may cause interfacial detachment from the insulating layer or conductive layer during or after the semiconductor package process is completed, and HAST characteristics also deteriorate.

Meanwhile, with the miniaturization of electronic devices, printed circuit boards are also becoming smaller and thinner, and in order to work with thinner boards, the insulating materials used in the boards are also required to have high rigidity.

In order to improve the rigidity of a photosensitive insulating material or solder resist, the ratio of inorganic filler in the resin must be increased. However, in the case of opaque inorganic filler, there is a problem of not allowing light to pass through, and even in the case of transparent inorganic filler, light is scattered, making it photosensitive. There were limitations that made it difficult to form an opening pattern using .

Accordingly, there is a need for the development of a method for manufacturing an insulating layer that has excellent rigidity and can implement uniform and fine patterns at low cost while preventing interfacial detachment from the insulating layer or conductive layer.

The technical problem to be achieved by the present invention is to provide an insulating layer for a multilayer printed circuit board that can easily form fine patterns and has excellent metal adhesion.

However, the problem to be solved by the present invention is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

An exemplary embodiment of the present invention includes an alkali-soluble resin comprising a resin containing repeating units represented by the following formulas (1) and (2); and an insulating layer for a multilayer printed circuit board comprising a polymer resin layer containing a thermosetting binder.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, each of R ₁ and R ₂ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted group having 6 to 15 carbon atoms. is an aryl group, and R ₃ is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, and * is a connection Indicates a point.

The insulating layer for a multilayer printed circuit board according to an embodiment of the present invention contains a polymer resin with excellent alkali solubility, and can implement a circuit in a fine pattern.

The insulating layer for a multilayer printed circuit board according to an embodiment of the present invention may have excellent mechanical properties such as tensile strength and Young's modulus.

The insulating layer for a multilayer printed circuit board according to an exemplary embodiment of the present invention can have an excellent appearance even when exposed to extreme conditions.

The insulating layer for a multilayer printed circuit board according to an exemplary embodiment of the present invention may have excellent metal adhesion to copper.

The effect of the present invention is not limited to the above-mentioned effect, and effects not mentioned will be clearly understood by those skilled in the art from the present specification and the attached drawings.

Throughout the specification of the present application, when a part is said to “include” a certain element, this means that it may further include other elements rather than excluding other elements, unless specifically stated to the contrary.

Throughout this specification, when a member is said to be located “on” another member, this includes not only the case where the member is in contact with the other member, but also the case where another member exists between the two members.

Throughout the specification herein, the unit “part by weight” may refer to the ratio of weight between each component.

Throughout the specification herein, the unit “molar part” may refer to the molar ratio between each component.

Throughout this specification, “(meth)acrylate” is used to collectively refer to acrylates and methacrylates.

Throughout this specification, “A and/or B” means “A and B, or A or B.”

Throughout the specification herein, the term "repeat unit" may refer to a form in which monomers are reacted in a polymer, and specifically, the monomer undergoes a polymerization reaction to form the backbone of the polymer, for example, the main chain or side chain. It can mean the form being formed.

Throughout this specification, the “weight average molecular weight” and “number average molecular weight” of a compound can be calculated using the molecular weight and molecular weight distribution of the compound. Specifically, tetrahydrofuran (THF) and a compound were placed in a 1 ml glass bottle to prepare a sample sample with a compound concentration of 1 wt%, and the standard sample (polystyrene) and the sample sample were filtered (pore size). After filtering through 0.45㎛, it is injected into a GPC injector, and the molecular weight and molecular weight distribution of the compound can be obtained by comparing the elution time of the sample with the calibration curve of the standard sample. At this time, Infinity II 1260 (Agilient) can be used as a measuring device, the flow rate can be set to 1.00 mL/min, and the column temperature can be set to 40.0 ℃.

Throughout the specification herein, “glass transition temperature (Tg)” can be measured using differential scanning calorimetry (DSC), specifically DSC (Differential Scanning Calorimeter, DSC-STAR3, METTLER TOLEDO Using the company, the sample was heated at a heating rate of 5 ℃/min in the temperature range of -60 ℃ to 150 ℃, and the experiment was conducted 2 times (cycle) in the above section, and a DSC curve was created at the point where there is a thermal change. The glass transition temperature can be obtained by measuring the midpoint of .

Hereinafter, the present invention will be described in more detail.

An exemplary embodiment of the present invention includes an alkali-soluble resin comprising a resin containing repeating units represented by the following formulas (1) and (2); and a polymer resin layer containing a thermosetting binder.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2, each of R ₁ and R ₂ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted group having 6 to 15 carbon atoms. is an aryl group, and R ₃ is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, and * is a connection Indicates a point.

The “alkylene group” may refer to a group containing a saturated hydrocarbon group bonded to the remainder of the molecule by two different bonds, and the “alkenylene group” may refer to a group containing a saturated hydrocarbon group bonded to the remainder of the molecule by two different bonds. An unsaturated hydrocarbon group may refer to a group containing a carbon-carbon double bond, and the “arylene group” may refer to a group containing an aromatic ring bonded to the remainder of the molecule by two other bonds.

The “alkyl group” may refer to a group containing a saturated hydrocarbon group bonded to the remainder of the molecule by one bond, and the “alkenyl group” may refer to an unsaturated hydrocarbon group bonded to the remainder of the molecule by one bond. It may refer to a group containing a carbon-carbon double bond.

The insulating layer for a multilayer printed circuit board according to an embodiment of the present invention contains a polymer resin with excellent alkali solubility, can implement a circuit in a fine pattern, can have excellent mechanical properties such as tensile strength and Young's modulus, and can be used under extreme conditions. Even when exposed to , the appearance can be excellent and the metal adhesion to copper can be excellent.

According to one embodiment of the present invention, the insulating layer for a multilayer printed circuit board includes a polymer resin layer, and the polymer resin layer refers to a film formed through drying a polymer resin composition containing an alkali-soluble resin and a thermosetting binder. You can.

According to one embodiment of the present invention, the polymer resin layer is an alkali-soluble resin containing a resin containing repeating units represented by Formula 1 and Formula 2; and a thermosetting binder. Specifically, the polymer resin composition includes an alkali-soluble resin containing a resin containing repeating units represented by Formula 1 and Formula 2; and a thermosetting binder.

According to one embodiment of the present invention, the alkali-soluble resin includes a resin containing repeating units represented by Formula 1 and Formula 2. Metal adhesion can be improved by including repeating units represented by Formula 1 and Formula 2 containing a thioacetyl group at the terminal.

According to one embodiment of the present invention, the molar ratio of the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 contained in the resin may be 9:1 to 1:9. Specifically, the molar ratio of the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 may be 8:2 to 2:8, 7:3 to 3:7, or 6:4 to 4:6. By adjusting the molar ratio of the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 included in the resin within the above-mentioned range, alkali developability can be excellent, thereby forming a pattern with a finer structure. and can improve metal adhesion.

According to one embodiment of the present invention, the repeating unit represented by Formula 1 may be included in an amount of 10 mole parts or more and 90 mole parts or less with respect to 100 mole parts of the repeating unit of the resin. By adjusting the molar ratio of the repeating unit represented by Formula 1 within the above-mentioned range, alkali developability can be excellent, and thus a pattern with a finer structure can be formed.

According to one embodiment of the present invention, the repeating unit represented by Formula 2 may be included in an amount of 10 mole parts or more and 90 mole parts or less with respect to 100 mole parts of the repeating unit of the resin. By adjusting the molar ratio of the repeating unit represented by Formula 2 within the above-described range, alkali developability can be excellent, and thus a pattern with a finer structure can be formed.

According to one embodiment of the present invention, the resin is a basic resin containing a repeating unit represented by the following formula (3); A compound represented by the following formula (4); and a compound represented by the following formula (5).

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5, each of R ₁ and R ₂ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 15 carbon atoms. and R ₃ is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, and * represents the connection point. indicates.

According to one embodiment of the present invention, the base resin may be a novolak epoxy resin. Specifically, the base resin may be a cresol novolak epoxy resin. When the base resin is a novolac epoxy resin, the mechanical properties of the insulating layer may be excellent, and the adhesion to metal may be excellent, so that the interfacial adhesion with the metal layer may be excellent when a multilayer printed circuit board is manufactured later.

According to one embodiment of the present invention, the base resin may have an epoxy group equivalent weight of 100 g/eq to 300 g/eq.

According to one embodiment of the present invention, the resin may include a thiol group derived from the compound represented by Formula 4 above.

According to one embodiment of the present invention, the compound represented by Formula 4 may be one selected from thiolacetic acid, thiolbenzoic acid, and combinations thereof.

According to one embodiment of the present invention, the resin may include an acid anhydride group derived from the compound represented by Formula 5 above.

According to an exemplary embodiment of the present invention, the compound represented by Formula 5 may include one or more of phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, succinic anhydride, and glutaric anhydride.

According to one embodiment of the present invention, the resin may be manufactured by reacting the compound represented by Formula 5 with the hydroxy group generated by the reaction of the base resin and the compound represented by Formula 4. Specifically, the compound represented by Formula 5 may form two carboxyl groups by ring-opening the cyclic anhydride group contained in the compound, and the hydroxy group produced by the reaction of the base resin and the compound represented by Formula 4 and the compound. One of the carboxyl groups contained in reacts to form an ester group, and the remaining carboxyl group contained in the compound may become the carboxyl group of the resin.

According to one embodiment of the present invention, the resin may be manufactured by reacting 0.5 mole to 1.5 mole of the compound represented by Formula 4 with respect to 1 mole of the epoxy group of the base resin.

According to one embodiment of the present invention, the resin may be manufactured by reacting 0.1 mole to 1.0 mole of the compound represented by Formula 5 with respect to 1 mole of the epoxy group of the base resin. That is, the base resin and the compound represented by Formula 4 react to form a hydroxy group, the hydroxy group reacts with the compound represented by Formula 5, and the base resin and the compound represented by Formula 4 react to form a hydroxy group. The number of moles of hydroxy groups may mean the same as the number of moles of epoxy groups of the base resin. Therefore, the resin may be manufactured by reacting 0.1 mole to 1.0 mole of the compound represented by Formula 5 with respect to 1 mole of hydroxyl group produced by the reaction of the base resin and the compound represented by Formula 4. Specifically, it may be produced by the reaction of 0.2 mole to 0.9 mole, 0.3 mole to 0.8 mole, 0.4 mole to 0.7 mole, or 0.5 mole to 0.6 mole of the compound represented by Formula 5 with respect to 1 mole of the epoxy group of the base resin. . By adjusting the molar ratio of the reaction between the base resin and the compound represented by Formula 5 within the above-mentioned range, it is possible to provide a resin containing a large amount of carboxyl groups and having excellent alkali solubility.

According to one embodiment of the present invention, the resin may have an acid value determined by KOH titration of 50 mgKOH/g to 250 mgKOH/g, or 70 mgKOH/g to 200 mgKOH/g. By adjusting the acid value of the second resin within the above-mentioned range, the development process performed on the polymer resin layer later can proceed smoothly.

According to an exemplary embodiment of the present invention, examples of methods for measuring the acid value of the alkali-soluble resin are not greatly limited, but for example, the following method can be used. Prepare a KOH solution (solvent: methanol) with a concentration of 0.1 N as a base solution, and alpha-naphtholbenzein (pH: 0.8 ~ 8.2 yellow, 10.0 blue green) as an indicator. prepared. Next, about 1 to 2 g of alkali-soluble resin as a sample was collected and dissolved in 50 g of dimethylformaldehyde (DMF) solvent, and then a marker was added and titrated with the base solvent. The acid value was determined in mg KOH/g based on the amount of base solvent used at the time of completion of titration.

According to one embodiment of the present invention, the thermosetting binder may include 1 to 150 parts by weight, 10 to 100 parts by weight, and 20 to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin. If the content of the thermosetting binder is too high, the developability of the polymer resin layer may decrease and the strength may decrease. Conversely, if the content of the thermosetting binder is too low, not only may the polymer resin layer be developed excessively, but uniformity during coating may also be reduced.

According to one embodiment of the present invention, the thermosetting binder includes an epoxy group and at least one functional group selected from the group consisting of an oxetanyl group, a cyclic ether group, a cyclic thio ether group, a cyanide group, a maleimide group, and a benzoxazine group. It may be. 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 thio ether group, a cyanide group, a maleimide group, a benzoxazine group, or these. It may contain a mixture of two or more types. These thermosetting binders can secure the heat resistance or mechanical properties of the insulating layer by forming crosslinks with alkali-soluble resins, etc. through thermal curing.

According to one embodiment of the present invention, as the thermosetting binder, a multifunctional resin compound containing two or more of the above-mentioned functional groups in the molecule can be used.

According to one embodiment of the present invention, the multifunctional resin compound may contain a resin containing two or more cyclic ether groups and/or cyclic thioether groups (hereinafter referred to as cyclic (thio)ether groups) in the molecule. .

According to one embodiment of the present invention, the thermosetting binder containing two or more cyclic (thio)ether groups in the molecule contains one or two of a 3-, 4-, or 5-membered ring cyclic ether group, or a cyclic thioether group in the molecule. It may include compounds having at least two groups.

According to one embodiment of the present invention, 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.

According to one embodiment of the present invention, the multifunctional resin compound is a multifunctional epoxy compound containing at least two or more epoxy groups in the molecule, a polyfunctional oxetane compound containing at least two or more oxetanyl groups in the molecule, or two in the molecule. It may include an episulfide resin containing the above thioether group, a polyfunctional cyanate ester compound containing at least two or more cyanide groups in the molecule, or a polyfunctional benzoxazine compound containing at least two or more benzoxazine groups in the molecule.

According to one embodiment of the present invention, specific examples of the multifunctional epoxy compound include, for example, bisphenol A-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, brominated bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S. type epoxy resin, novolac type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, bixylenol type epoxy resin, biphenol type Epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidylc. Silenoylethane resin, silicone modified epoxy resin, ε-caprolactone modified epoxy resin, etc. can be mentioned. Additionally, in order to impart flame retardancy, those in which atoms such as phosphorus are introduced into the structure can also be used. These epoxy resins are heat cured to improve properties such as adhesion of the cured film, solder heat resistance, and electroless plating resistance.

According to an exemplary embodiment of the present invention, the polyfunctional oxetane compound includes bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl] Ether, 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)methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxe) In addition to polyfunctional oxetanes such as cetanyl) methyl methacrylate and their oligomers or copolymers, oxetane alcohol, novolac resin, poly(p-hydroxystyrene), cardo-type bisphenols, carixarenes, and etherified products with resins having hydroxy groups such as carixresorcinarenes or silsesquioxane. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate.

According to an exemplary embodiment of the present invention, examples of the multifunctional cyanate ester compound include bisphenol A-type cyanate ester resin, bisphenol E-type cyanate ester resin, bisphenol F-type cyanate ester resin, and bisphenol S-type cyanate ester resin. , bisphenol M type cyanate ester resin, novolak type cyanate ester resin, phenol novolak type cyanate ester resin, cresol novolak type cyanate ester resin, novolak type cyanate ester resin of bisphenol A, biphenol type cyanate ester resin. Nate ester resins, oligomers or copolymers thereof, etc. may be mentioned.

According to an exemplary embodiment of the present invention, examples of the multifunctional maleimide compound include 4,4'-diphenylmethane bismaleimide, phenylmethane bismaleimide, m -phenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenyl Methane bismaleimide (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide), 4-methyl-1,3-phenylene bismaleimide (4-methyl-1,3- phenylene bismaleimide), 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, etc.

According to an exemplary embodiment of the present invention, examples of the multifunctional benzoxazine compound include bisphenol A-type benzoxazine resin, bisphenol F-type benzoxazine resin, phenolphthalein-type benzoxazine resin, thiodiphenol-type benzoxazine resin, and dicyclo pentadiene. Type benzoxazine resin, 3,3'-(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, etc. can be mentioned.

According to an embodiment of the present invention, more specific examples of the multifunctional resin compound include YDCN-500-80P from Kukdo Chemical, phenol novolak-type cyanate ester resin PT-30S from Lonza, and phenyl methane-type maleimide from Daiwa. Resin BMI-2300, Shikoku's P-d type benzoxazine resin, etc. are mentioned.

According to one embodiment of the present invention, the polymer resin layer may further include one or more selected from the group consisting of a thermosetting catalyst, an inorganic filler, a leveling agent, a dispersant, a mold release agent, and a metal adhesion enhancer.

According to one embodiment of the present invention, the thermosetting catalyst serves to promote thermal curing of the thermosetting binder. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine. compound; Hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as triphenylphosphine, etc. are mentioned. Additionally, commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all brand names of imidazole-based compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT3503N and UCAT3502T manufactured by San-Apro. (all are brand names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATS A102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), etc. It is not particularly limited to these, and may be a thermal curing catalyst of an epoxy resin or an oxetane compound, or a catalyst that promotes the reaction between an epoxy group and/or an oxetanyl group and a carboxyl group, and may be used alone or in a mixture of two or more types. . Additionally, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine Azine, 2-vinyl-4,6-diamino-S-triazine-isosanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isosanuric acid S-triazine derivatives such as adducts may be used, and preferably, compounds that also function as adhesion imparting agents may be used in combination with the thermosetting catalyst.

According to one embodiment of the present invention, examples of the inorganic filler include silica, barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, or mixtures of two or more types thereof. there is.

According to one embodiment of the present invention, the example of the content of the inorganic filler is not greatly limited, but in order to achieve high rigidity of the polymer resin layer, for 100 parts by weight of all resin components contained in the polymer resin layer, The inorganic filler may 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.

According to one embodiment of the present invention, examples of the release agent include polyalkylene wax such as low molecular weight polypropylene and low molecular weight polyethylene, ester wax, carnauba wax, paraffin wax, etc.

According to one embodiment of the present invention, the metal adhesion enhancer may be a material that does not cause problems with surface deterioration or transparency of the metal material, for example, a silane coupling agent or an organic metal coupling agent.

According to one embodiment of the present invention, the leveling agent serves to remove surface popping or craters during film coating, for example, BYK-380N, BYK-307, BYK-378, BYK-Chemie GmbH. 350 etc. can be used.

According to one embodiment of the present invention, the polymer resin layer may further include a resin or elastomer with a molecular weight of 5000 g/mol or more, which can cause phase separation. Accordingly, roughening treatment of the cured product of the polymer resin layer may be possible. Examples of methods for measuring the molecular weight of a resin or elastomer with a molecular weight of 5000 g/mol or more are not greatly limited, and for example, it refers to the weight average molecular weight in terms of polystyrene measured by GPC method. In the process of measuring the weight average molecular weight of polystyrene equivalent measured by the GPC method, commonly known analysis devices, detectors such as differential refractive index detectors, and analytical columns can be used, and the commonly applied temperature Conditions, solvent, and flow rate can be applied. Specific examples of the measurement conditions include a temperature of 30, chloroform solvent, and a flow rate of 1 mL/min.

According to one embodiment of the present invention, the polymer resin layer further includes a thermosetting binder containing a photoreactive unsaturated group or an alkali-soluble resin containing a photoreactive unsaturated group and a photoinitiator in order to impart photocurable properties to the polymer resin layer. can do. 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 greatly limited, and various compounds used in the technical field related to photocurable resin compositions can be used without limitation.

According to one embodiment of the present invention, the content of the photoinitiator contained in the polymer resin layer may be 0.01% by weight or less based on the total weight of the polymer resin layer. The fact that the content of the photoinitiator contained in the polymer resin layer is 0.01% by weight or less relative to the total weight of the polymer resin layer may mean that the content of the photoinitiator contained in the polymer resin layer is very small or that the photoinitiator is not included at all. . Accordingly, the interfacial detachment between the insulating layer and the conductive layer that can be caused by the photoinitiator can be reduced, and the adhesion and durability of the insulating layer can be improved.

According to an exemplary embodiment of the present invention, a method for manufacturing the insulating layer for the multilayer printed circuit board can be provided. Specifically, sealing the conductor wiring on which metal protrusions are formed on the surface with a polymer resin layer including an alkali-soluble resin and a thermosetting binder; Primary curing the polymer resin layer; etching the surface of the cured polymer resin layer with an aqueous alkaline solution to expose metal protrusions; And a method of manufacturing an insulating layer can be provided, including the step of secondary curing the polymer resin layer in a state where the metal protrusion is exposed.

First, in the step of sealing the conductor wire with metal protrusions formed on the surface with a polymer resin layer containing an alkali-soluble resin and a thermosetting binder, metal protrusions may be formed on the surface of the conductor wire. Examples of methods for forming metal protrusions on the surface of the conductor wiring are not greatly limited, and for example, a plating process for the opening of the photosensitive resin layer pattern or an adhesion process using an adhesive may be used.

Specific examples of the plating process for the openings of the photosensitive resin layer pattern include laminating a photosensitive resin layer on a conductor wiring; forming a pattern on the photosensitive resin layer; and a method of forming metal protrusions including electroplating.

Alternatively, a wet deposition process may be used, and specific examples of the dry deposition process include vacuum deposition, ion plating, and sputtering methods.

Meanwhile, specific examples of wet deposition processes include electroless plating of various metals, electroless copper plating is common, and a roughening process may be further included before or after deposition.

The conditioning process also includes dry and wet methods depending on conditions. Examples of the dry method include vacuum, normal pressure, plasma treatment for each gas, Excimer UV treatment for each gas, and examples of the wet method include desmear. Processing can be used. Through this roughening process, the surface roughness of the metal thin film can be increased to improve adhesion with the metal deposited on the metal thin film.

Additionally, in order to leave only metal protrusions, a step of removing the photosensitive resin layer may be further included after the electroplating step. When removing the photosensitive resin pattern, it is preferable to use a method that can remove only the photosensitive resin layer while avoiding removing the underlying conductor wiring and metal protrusions as much as possible.

For specific examples of the method of peeling off the photosensitive resin pattern, treatment with a photoresist stripping solution, a desmear process, or plasma etching may be performed, and the above methods may be used in combination.

According to one embodiment of the present invention, a specific example of the adhesion process using the adhesive is to form a metal protrusion on the surface of a passive device such as a micc or an active device such as a semiconductor chip, and then attach the opposite side of the formed metal protrusion with an insulating adhesive. A method of adhering to the surface of the conductor wiring using a method such as a method may be used. At this time, the method of forming metal protrusions on the surface of the passive device or active device can be done by using the plating process for the opening of the photosensitive resin layer pattern described above. For example, a method of forming a photosensitive resin layer pattern on the surface of a passive device or an active device and then plating metal in the openings of the pattern can be used.

According to one embodiment of the present invention, the thickness of the polymer resin layer is 1 ㎛ to 500 ㎛, or 3 ㎛ to 500 ㎛, or 3 ㎛ to 200 ㎛, or 1 ㎛ to 60 ㎛, or 5 ㎛ to 30 ㎛. The metal protrusions may have a height of 1 ㎛ to 20 ㎛ and a cross-sectional diameter of 5 ㎛ to 30 ㎛. The cross-sectional diameter may mean the diameter of a cross-section cut from the metal protrusion in a direction perpendicular to the height direction of the metal protrusion, or the maximum diameter. For example, the shape of the metal protrusion may include a cylinder, truncated cone, polygonal prism, polygonal pyramid, inverted truncated cone, or inverted polygonal pyramid. Examples of metal components included in the metal protrusions are also not greatly limited, and for example, conductive metals such as copper and aluminum may be used.

According to one embodiment of the present invention, the conductor wiring on which metal protrusions are formed on the surface may be sealed with a polymer resin layer. More specifically, the conductor wiring may be formed on a substrate including a semiconductor material such as a circuit board, sheet, or multilayer printed wiring board. In this way, with the conductor wiring present on the substrate, the conductor wiring can be sealed through a method of forming a polymer resin layer on the substrate.

According to an exemplary embodiment of the present invention, examples of methods for forming a polymer resin layer on a substrate are not greatly limited, but for example, the polymer resin composition for forming the polymer resin layer is directly coated on the substrate, A method of applying a polymer resin composition on a carrier film to form a polymer resin layer and then laminating the substrate and the polymer resin layer can be used.

According to one embodiment of the present invention, as the conductor wiring having metal protrusions formed on the surface is sealed with a polymer resin layer, all surfaces of the conductor wiring except the portion in contact with the substrate formed below and the portion in contact with the metal protrusion are It may come into contact with the polymer resin layer. Additionally, all surfaces of the metal protrusions formed on the surface of the conductor wiring are also sealed by the polymer resin layer and can be in contact with the polymer resin layer.

Next, the polymer resin layer can be primary cured. In the step of curing the polymer resin layer, examples of specific curing methods are not greatly limited, and both thermal curing and photocuring methods can be used without limitation.

According to one embodiment of the present invention, through the first curing step, a main chain containing an ester bond can be formed in the polymer resin layer. Examples of the ester bond include photocuring through an acrylic resin in which acrylic acid is ester bonded, or heat curing to form an ester bond through a reaction between carboxylic acid and epoxy.

At this time, specific thermal curing conditions are not limited, and the process can be carried out by adjusting the desired conditions according to the etching method of the polymer resin layer, which will be described later. For example, when etching a polymer resin layer by treating it with a photoresist stripper, the first curing step of the polymer resin layer may be performed at a temperature of 50°C to 150°C for 0.1 to 2 hours. If the thermal curing temperature of the polymer resin layer is too low or the thermal curing time is short, the polymer resin layer may be excessively damaged by the stripper. If the thermal curing temperature of the polymer resin layer is high or the thermal curing time is short, the polymer resin layer may be excessively damaged by the stripper. If it becomes longer, it may be difficult for the polymer resin layer to be etched by the stripper.

According to one embodiment of the present invention, the method of manufacturing the insulating layer may include the step of exposing the metal protrusions by etching the surface of the primary cured polymer resin layer with an aqueous alkaline solution. As the surface of the cured polymer resin layer is etched with an aqueous alkaline solution to expose metal protrusions, an electrical signal can be connected to a conductor wire sealed inside the cured polymer resin layer through the exposed metal protrusions.

According to an exemplary embodiment of the present invention, the metal protrusions may be exposed through etching using an aqueous alkaline 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%. More specifically, a photoresist stripper may be used. The aqueous alkaline solution can etch and remove the polymer resin layer by breaking the ester bonds in the polymer resin layer in which the main chain including the ester bonds is formed through the primary curing.

At this time, by adjusting the concentration and temperature of the aqueous alkaline solution, the etching rate of the polymer resin layer by the aqueous alkaline solution can be controlled, and the etching rate is maintained at an appropriate level within the above-mentioned range to ensure process efficiency and facilitate polymer etching. The thickness of the resin layer can be adjusted.

According to one embodiment of the present invention, the aqueous alkaline solution may be an aqueous solution of metal hydroxides such as potassium hydroxide and sodium hydroxide, including Atotech's Resistrip product line, ORChem's ORC-731, ORC-723K, ORC-740, SLF- Commercially sold products such as 6000 can also be used.

According to one embodiment of the present invention, etching by the alkaline aqueous solution may proceed from the surface of the cured polymer resin layer. The surface of the cured polymer resin layer refers to the area where the polymer resin layer sealing the conductor wiring with metal protrusions formed on the surface is in contact with the air, and from the surface of the cured polymer resin layer to the conductor wiring with metal protrusions formed on the surface. As etching progresses inside the polymer resin layer that seals, metal protrusions may be exposed.

According to one embodiment of the present invention, in order for etching by the aqueous alkaline solution to proceed from the surface of the cured polymer resin layer, the aqueous alkaline solution may be in contact with the surface of the cured polymer resin layer. At this time, in order to ensure thickness uniformity through uniform removal without physical damage to the polymer resin layer, the aqueous alkaline solution can be brought into contact with the surface of the polymer resin layer through a method such as spraying.

According to one embodiment of the present invention, the method of manufacturing the insulating layer may include the step of secondary curing the polymer resin layer in a state where the metal protrusions are exposed. Through the secondary curing step, the chemical resistance of the insulating layer finally manufactured through the secondary curing step can be improved.

At this time, specific curing conditions are not limited, and for example, the secondary curing step of the polymer resin layer may be performed at a temperature of 150 ℃ to 250 ℃ for 0.1 to 2 hours.

According to one embodiment of the present invention, after the step of secondary curing the polymer resin layer in a state in which the metal protrusion is exposed, the step of removing the substrate formed below the conductor wiring may be further included, if necessary. . As described above, the conductor wiring may be formed on a substrate including a semiconductor material such as a circuit board, sheet, or multilayer printed wiring board. To form a multilayer circuit board with a finer structure, the substrate underneath the conductor wiring can be removed, if necessary, and the substrate exists in a state of adhesion or adhesion to the polymer resin layer and can be removed by physically peeling off. .

According to one embodiment of the present invention, a method for manufacturing a multilayer printed circuit board can be provided, including forming a metal pattern layer with a pattern on the insulating layer manufactured in the above embodiment.

The insulating layer manufactured by the multilayer printed circuit board manufacturing method according to an embodiment of the present invention includes a conductor wire with metal protrusions formed on the surface thereof, and the metal protrusions are exposed to the outside of the insulating layer, forming a layer on the insulating layer. When a new metal pattern layer is laminated, the metal pattern layer can exchange electrical signals with the conductor wiring inside the insulating layer through the metal protrusion.

According to one embodiment of the present invention, 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 thermoset or photocure. Details regarding the alkali-soluble resin and thermosetting binder include the above-described content.

According to one embodiment of the present invention, forming a metal pattern layer on the insulating layer includes forming a metal thin film on the insulating layer; Forming a photosensitive resin layer with a pattern formed on the metal thin film; Depositing metal on the metal thin film exposed by the photosensitive resin layer pattern; And it may include removing the photosensitive resin layer and removing the exposed metal thin film.

According to one embodiment of the present invention, in the step of forming a 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 Examples include vacuum deposition, ion plating, and sputtering methods.

According to one embodiment of the present invention, examples of the wet deposition process include electroless plating of various metals, electroless copper plating is common, and a roughening process may be further included before or after deposition.

According to an embodiment of the present invention, the roughening treatment process includes dry and wet methods depending on conditions, and examples of the dry method include vacuum, normal pressure, plasma treatment for each gas, Excimer UV treatment for each gas, etc., As an example of the wet method, desmear treatment can be used. Through this roughening process, the surface roughness of the metal thin film can be increased to improve adhesion with the metal deposited on the metal thin film.

According to one embodiment of the present invention, forming a 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. Through this, the adhesion between the metal thin film and the insulating layer can be improved.

According to an exemplary embodiment of the present invention, a method of forming a surface treatment layer on the insulating layer may use at least one of an ion-assisted reaction method, an ion beam treatment method, and a plasma treatment method. The plasma processing method may include any one of an atmospheric pressure plasma processing method, a DC plasma processing method, and an RF plasma processing method. As a result of the surface treatment process, a surface treatment layer containing a reactive functional group may be formed on the surface of the insulating layer. Another example of a method of forming a surface treatment layer on the insulating layer is 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.

According to one embodiment of the present invention, forming a photosensitive resin layer with a pattern formed on the metal thin film may include exposing and developing the photosensitive resin layer formed on the metal thin film. Details about the photosensitive resin layer, exposure, and development may include the contents described above.

According to one embodiment of the present invention, the pattern formed on the metal thin film is preferably formed so that the openings included in the pattern can contact the metal protrusions exposed to the outside of the insulating layer. The opening included in the pattern refers to a portion removed through exposure and development of the photosensitive resin layer, and corresponds to a portion where metal is deposited through metal deposition to be described later to form the metal pattern layer. Therefore, the openings included in the pattern must be formed to contact the metal protrusions exposed to the outside of the insulating layer, so that the metal pattern layer can contact the metal protrusions and exchange electrical signals with the conductor wiring inside the insulating layer.

According to one embodiment of the present invention, 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 is not in contact with the photosensitive resin layer at the surface. It refers to the part of the metal thin film that is not present. The metal to be deposited may be copper, examples of the deposition method are not greatly limited, and various known physical or chemical deposition methods may be used without limitation, and an electrolytic copper plating method may be used as a general example. .

At this time, the metal deposited on the metal thin film exposed by the photosensitive resin layer pattern can form the metal pattern layer described above. More specifically, the metal pattern layer is connected to the conductor wiring through the metal protrusion. can be formed.

Through this, the metal pattern layer can exchange electrical signals with the conductor wiring included within the insulating layer. More specifically, one end of the metal protrusion may contact the conductor wiring, and the other end of the metal protrusion may contact the metal pattern layer to electrically connect the conductor wiring and the metal pattern layer.

According to one embodiment of the present invention, in the step of removing the photosensitive resin layer and removing the exposed metal thin film, a photoresist stripper may be used as an example of a method of removing the photosensitive resin layer, and the photosensitive resin layer As an example of a method of removing the metal thin film exposed due to the removal, an etching solution can be used.

According to one embodiment of the present invention, the multilayer printed circuit board manufactured by the multilayer printed circuit board manufacturing method can be used again as a build-up material, for example, the insulation of the embodiment on the multilayer printed circuit board. The first process of forming an insulating layer according to the layer manufacturing method and the second process of forming a metal substrate on the insulating layer according to the multilayer printed circuit board manufacturing method of the other embodiment may be repeatedly performed.

Accordingly, the number of laminated layers included in the multilayer printed circuit board manufactured by the above multilayer printed circuit board manufacturing method is also not greatly limited, and depending on the purpose and use, for example, 1 or more layers, or 1 to 20 layers. You can have

Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of this specification are provided to more completely explain the present invention to those skilled in the art.

Manufacturing Example 1

Manufacturing: 125 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent and cresol novolac epoxy resin (YDCN- 500-90P, Kukdo Chemical Co., Ltd., number of moles of epoxy group: 0.37 mol), 75 g, and 26 g of thioacetic acid (ratio of 1 mole to 1 mole of epoxy group of the cresol novolak epoxy resin) were mixed and reacted to produce a reactant. was manufactured. Afterwards, the reactant and 26 g (0.18 mol) of tetrahydrophthalic anhydride were mixed and stirred at 100° C. for 24 hours to prepare a resin solution with a solid content of 50% (the acid value of the resin was 88.59 mgKOH/g). Here, tetrahydrophthalic anhydride was mixed at a ratio of 0.5 mol per 1 mol of hydroxyl group of the basic resin.

Production example 2

Manufacturing: 75 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent and cresol novolac epoxy resin (YDCN- 500-90P, Kukdo Chemical Co., number of moles of epoxy group: 0.37 mol) and 75 g of thiobenzoic acid (ratio of 1 mole to 1 mole of epoxy group of the cresol novolak epoxy resin) were mixed and reacted to form a reactant. was manufactured. Afterwards, the above reactant was mixed with 26 g (0.18 mol) of tetrahydrophthalic anhydride and stirred at 100°C for 24 hours to prepare a resin solution with a solid content of 50% (the acid value of the resin was 76 mgKOH/g). Here, tetrahydrophthalic anhydride was mixed at a ratio of 0.4 mol per 1 mol of hydroxyl group of the basic resin.

Comparative Manufacturing Example 1

Add 205 g of cresol novolac epoxy resin (Kukdo Chemical YDCN-500-90P), 72 g of acrylic acid (1 equivalent to cresol novolac epoxy resin), 2.6 g of triphenylphosphine, and 225 g of PGMEA solvent, blow in nitrogen, and stir to 98 degrees Celsius. It was reacted at ℃ for 4 hours. Afterwards, 61 g of tetrahydrophthalic anhydride (0.4 equivalent of cresol novolak epoxy resin) was added to the obtained compound, and the reaction was carried out at 85°C for 8 hours to prepare a (meth)acrylate-based resin with a solid content of 60%.

Example 1

Manufacturing of insulating layer

20 g of the resin solution of Preparation Example 1 as an alkali-soluble resin, 7 g of MY-510 (Huntsman) as a thermosetting binder, and 30 g of SC2050MTO (70% solid content, manufactured by Admatechs) as an inorganic filler were mixed to form a PET film with a thickness of 25 μm. and dried to prepare a polymer resin layer with a thickness of 18 μm.

A dry film (RY-5319, Hitachi Chemical) was laminated on a copper clad laminate (LG-500GA VB/VB, LG Chemical) to which ultra-thin copper foil was adhered to form a pattern, followed by electroplating to form a circuit using the MSAP method. . Afterwards, the dry film was laminated on the circuit to form a pattern, and electroplating was performed to form copper bumps with a height of 15 μm and a diameter of 20 μm.

A polymer resin layer was vacuum laminated on the copper clad laminate at 85° C. to seal the circuit and copper bumps, and the PET film was removed from the polymer resin layer. The laminated polymer resin layer was first thermally cured at a temperature of 100°C for 1 hour, and then a 3% sodium hydroxide resist stripper at a temperature of 50°C was sprayed on the surface of the polymer resin layer to a depth of about 3μm from the surface. was removed to expose the copper bumps to the surface, then washed and dried. At this time, the spraying process of the stripper to expose the copper bumps was performed for 10 to 60 seconds per panel.

Next, the polymer resin layer with exposed copper bumps was heat-cured at 200°C for 1 hour to prepare an insulating layer.

Manufacturing of multilayer printed circuit boards

A copper thin film was deposited on the insulating layer using electroless copper plating, heated at 100°C for 30 minutes to improve adhesion to the electroless copper plating, and then laminated with a dry film (RY-5319, Hitachi Chemical). A pattern was formed, electroplated, and a circuit was formed using the SAP method. Then, the copper clad laminate and the ultra-thin copper foil were removed from the insulating layer to prepare a multilayer printed circuit board.

Example 2

In Example 1, an insulating layer and a multilayer printed circuit board were manufactured in the same manner as Example 1, except that 20 g of the resin solution of Preparation Example 2 was used as the alkali-soluble resin.

Comparative Example 1

In Example 1, an insulating layer and a multilayer printed circuit board were manufactured in the same manner as Example 1, except that 20 g of the resin solution of Comparative Preparation Example 1 was used as the alkali-soluble resin.

Experimental Example 1: Alkali developability evaluation

When the polymer resin layers of Example 1, Example 2, and Comparative Example 1 were cut to 10 cm in length and 0.5 cm in width and immersed in an aqueous solution of sodium carbonate (containing 1 part by weight of sodium carbonate per 100 parts by weight of water), the development occurred within 2 minutes. Check whether progress is being made. If the development did not proceed or there were residues, it was evaluated as 'NG', and if development occurred without these symptoms, it was evaluated as 'OK'.

Experimental Example 2: Tensile strength and Young's modulus

The polymer resin layers of Example 1, Example 2, and Comparative Example 1 were cut to a length of 10 cm and a width of 0.5 cm, and the tensile strength and Young's modulus were measured using a universal testing machine.

Experimental Example 3: Metal adhesion due to moisture absorption

The multilayer printed circuit boards of Example 1, Example 2, and Comparative Example 1 were left at a temperature of 135° C. and a humidity of 85% for 48 hours, and then the peel strength of the metal was measured according to the IPC-TM-650 standard.

Experimental Example 4: HAST resistance

HAST resistance was confirmed for the multilayer printed circuit boards of Example 1, Example 2, and Comparative Example 1 according to JESD22-A101 standards. Specifically, after applying a voltage of 3 V to a specimen circuit board with a width of 50 μm, a spacing of 50 μm, and a thickness of 12 μm and leaving it for 168 hours, the presence or absence of any abnormalities in the appearance of the specimen circuit board was checked under the following criteria. If no abnormalities were observed in the appearance of the film, it was evaluated as OK, and if blisters occurred on the film or the film peeled off, it was evaluated as NG.

Alkali developability tensile strength
(MPa) Young's modulus
(Gpa) metal adhesion
(kgf/cm) HAST attribute Comparative Example 1 OK 54.6 6.1 0.03 OK Example 1 OK 63.6 6.6 0.32 OK Example 2 OK 68.7 7.0 0.30 OK

Referring to Table 1, when the insulating layer of Examples 1 and 2 is included, the adhesion between the insulating layer and the metal layer of the multilayer printed circuit board is excellent, and as a polymer resin layer, alkali developability is excellent, forming a fine pattern. It was confirmed that it was easy to use, had high tensile strength and Young's modulus, and had excellent mechanical properties.

Meanwhile, in the case of Comparative Example 1, it was confirmed that the metal adhesion of Experimental Example 3 was rapidly reduced.

In the above, although the present invention has been described in terms of limited embodiments, the present invention is not limited thereto, and the technical idea of the present invention and the patent claims described below will be understood by those skilled in the art in the technical field to which the present invention pertains. Of course, various modifications and variations are possible within the scope of equality.

Claims (11)

An alkali-soluble resin comprising a resin containing repeating units represented by the following formulas (1) and (2); and
Insulating layer for a multilayer printed circuit board comprising a polymer resin layer containing a thermosetting binder:
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
Each of R ₁ and R ₂ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 15 carbon atoms,
R ₃ is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms,
* indicates connection point.
In claim 1,
The resin includes a base resin containing a repeating unit represented by the following formula (3); A compound represented by the following formula (4); and a compound represented by the following formula (5): An insulating layer for a multilayer printed circuit board manufactured by the reaction of:
[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5,
Each of R ₁ and R ₂ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 15 carbon atoms,
R ₃ is independently a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms,
* indicates connection point.
In claim 2,
The resin is an insulating layer for a multilayer printed circuit board that is manufactured by reacting a compound represented by Formula 5 with a hydroxy group generated by the reaction of the base resin and the compound represented by Formula 4.
In claim 3,
The resin is an insulating layer for a multilayer printed circuit board that is manufactured by reacting 0.5 mole to 1.5 mole of the compound represented by Formula 4 with respect to 1 mole of the epoxy group of the base resin.
In claim 3,
The resin is an insulating layer for a multilayer printed circuit board that is manufactured by reacting 0.1 mole to 1.0 mole of the compound represented by Formula 5 with respect to 1 mole of the epoxy group of the base resin.
In claim 2,
An insulating layer for a multilayer printed circuit board, wherein the compound represented by Formula 4 is one selected from thioacetic acid, thiobenzoic acid, and combinations thereof.
In claim 2,
An insulating layer for a multilayer printed circuit board, wherein the compound represented by Formula 5 includes one or more of phthalic anhydride, tetrahydrophthalic anhydride, maleic anhydride, succinic anhydride, and glutaric anhydride.
In claim 1,
An insulating layer for a multilayer printed circuit board wherein the acid value of the resin is 50 mgKOH/g or more and 250 mgKOH/g or less.
In claim 1,
The thermosetting binder is an insulating layer for a multilayer printed circuit board, wherein the thermosetting binder is included in an amount of 1 to 150 parts by weight based on 100 parts by weight of the alkali-soluble resin.
In claim 1,
The thermosetting binder is an insulating layer for a multilayer printed circuit board comprising an epoxy group and at least one functional group selected from the group consisting of oxetanyl group, cyclic ether group, cyclic thio ether group, cyanide group, maleimide group, and benzoxazine group. .
In claim 1,
The polymer resin layer is an insulating layer for a multilayer printed circuit board, wherein the polymer resin layer further includes one or more selected from the group consisting of a thermosetting catalyst, an inorganic filler, a leveling agent, a dispersant, a mold release agent, and a metal adhesion enhancer.