Insulating layer for multilayer printed circuit board, multilayer printed circuit board including the same, and method for manufacturing the same

Abstract

The present disclosure provides an insulating layer for a multilayer printed circuit board, a multilayer printed circuit board including the same, and a method for manufacturing the same. The insulating layer of the present disclosure includes a polymer resin layer including a melamine derivative, and thus can have excellent adhesion to a patterned metal layer.

Description

Technical Field

[0001] This application claims the benefit of the filing date of Korean Patent Application No. 10-2019-0132823 filed in the Korean Intellectual Property Office on October 24, 2019, the contents of which are incorporated herein in their entirety.

[0002] The present disclosure relates to an insulating layer for a multilayer printed circuit board, a multilayer printed circuit board including the same, and a method for manufacturing the same. Specifically, the present disclosure relates to an insulating layer for a multilayer printed circuit board having excellent adhesion to a patterned metal layer, a multilayer printed circuit board including the same, and a method for manufacturing the same. Background Art

[0003] Recent electronic devices have gradually become smaller, lighter, and more highly functional. In order to meet such recent demands in the field of electronic devices, it is necessary to install semiconductor elements inside electronic devices. In recent years, as semiconductor elements have become smaller in size and their integration density has increased, such a trend has been achieved.

[0004] In order for a semiconductor element to receive an electric signal in an electronic device, electric wiring is indispensable, and in this case, insulation of the semiconductor element and the electric wiring is required for stable electric signal transmission.

[0005] In this way, the build-up semiconductor packaging process is used not only for electrical wiring connections between semiconductor elements but also for forming an insulating layer between these elements. Such a semiconductor packaging process has the advantages that it can improve the integration density of functional elements, make electronic devices smaller, lighter and highly functional, realize structural integration of electrical functions, and reduce assembly time and cost.

[0006] In the build-up semiconductor packaging process, in order to form a microcircuit on the insulating layer, it is important to ensure the adhesion between the build-up insulating layer and the conductive layer on which the circuit is formed. In recent years, due to the limitation of the insulating layer pattern that can be formed by laser drilling, a method of forming a fine pattern by developing with a weak alkaline solution has been used.

[0007] Therefore, the structure of melamine is known to be effective for improving adhesion and is widely used. However, melamine is insoluble in most solvents due to its highly stable structure, so it cannot be well dispersed or dissolved and is not easily developed with a weak alkaline solution. Therefore, melamine is difficult to use for making fine patterns. Summary of the invention

[0008] Technical issues

[0009] An object of the present disclosure is to provide an insulating layer for a multilayer printed circuit board having excellent adhesion to a patterned metal layer, a multilayer printed circuit board including the same, and a method for manufacturing the same.

[0010] Technical Solution

[0011] According to one aspect of the present disclosure, there is provided an insulating layer for a multilayer printed circuit board, the insulating layer comprising a patterned polymer resin layer, the patterned polymer resin layer comprising an alkali-soluble resin, a thermosetting binder, and a melamine derivative, wherein the melamine derivative has a structure of the following Chemical Formula 1:

[0012] [Chemical formula 1]

[0013]

[0014] Wherein A is an alkyl group containing 1 to 6 carboxyl groups, or an amine group containing 1 to 6 carboxyl groups.

[0015] According to another aspect of the present disclosure, a multilayer printed circuit board is provided, the multilayer printed circuit board including: the insulating layer; and a patterned metal layer disposed on the insulating layer.

[0016] According to yet another aspect of the present disclosure, there is provided a method for manufacturing the insulating layer, the method comprising the steps of: forming a polymer resin layer including an alkali-soluble resin, a thermosetting binder, and a melamine derivative on a substrate; forming a patterned layer on the polymer resin layer; developing and curing the polymer resin layer on which the patterned layer is formed; and forming a patterned polymer resin layer by removing the patterned layer from the cured polymer resin layer, wherein the melamine derivative has a structure of the following Chemical Formula 1:

[0017] [Chemical formula 1]

[0018]

[0019] Wherein A is an alkyl group containing 1 to 6 carboxyl groups, or an amine group containing 1 to 6 carboxyl groups.

[0020] Beneficial Effects

[0021] An insulating layer for a multilayer printed circuit board according to one embodiment of the present disclosure has excellent adhesion to a patterned metal layer by including a melamine derivative.

[0022] A multilayer printed circuit board according to another embodiment of the present disclosure has excellent adhesion between an insulating layer including a melamine derivative and a patterned metal layer.

[0023] The insulating layer manufactured according to the method for manufacturing an insulating layer according to still another embodiment of the present disclosure has excellent adhesion to a patterned metal layer by including a melamine derivative. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is a schematic diagram illustrating a method for manufacturing an insulating layer according to an embodiment of the present disclosure. DETAILED DESCRIPTION

[0025] Throughout the present specification, it should be understood that when any part is referred to as “comprising” any component, it does not exclude other components but may further include other components unless otherwise specified.

[0026] Throughout this specification, when any member is referred to as being 'on' another member, it not only refers to a case where any member is in contact with another member but also refers to a case where a third member exists between the two members.

[0027] Hereinafter, the present disclosure will be described in more detail.

[0028] An insulating layer for a multilayer printed circuit board according to one embodiment of the present disclosure includes a patterned polymer resin layer including an alkali-soluble resin, a thermosetting binder, and a melamine derivative, wherein the melamine derivative has a structure of the following Chemical Formula 1:

[0029] [Chemical formula 1]

[0030]

[0031] Wherein A is an alkyl group containing 1 to 6 carboxyl groups, or an amine group containing 1 to 6 carboxyl groups.

[0032] Hereinafter, each component will be described in detail.

[0033] Alkali soluble resin

[0034] According to one embodiment of the present disclosure, the patterned polymer resin layer includes an alkali-soluble resin.

[0035] According to one embodiment of the present disclosure, the alkali-soluble resin may include: one or more acidic functional groups; and one or more cyclic imide functional groups substituted with one or more amino groups. Examples of the acidic functional groups are not particularly limited, but may include a carboxyl group or a phenolic group. The alkali-soluble resin may include at least two acidic functional groups, so that the polymer resin layer may exhibit higher alkaline developability, and the development rate of the polymer resin layer may be controlled.

[0036] The amino-substituted cyclic imide functional group may contain at least two amino groups and a cyclic imide group in the structure of the functional group. When the alkali-soluble resin contains at least two cyclic imide functional groups substituted by amino groups, the alkali-soluble resin may have a structure in which a large number of active hydrogen atoms are present in the amino groups present, and thus its reactivity with a thermosetting binder during thermal curing may be improved, and at the same time, the curing density may be increased, thereby increasing heat-resistant reliability and mechanical properties.

[0037] In addition, since there are multiple cyclic imide functional groups in the alkali-soluble resin, its polarity can be increased by the carbonyl and tertiary amine groups contained in the cyclic imide functional groups, thereby increasing the interfacial adhesion of the alkali-soluble resin. Therefore, the polymer resin layer containing the alkali-soluble resin can have an increased interfacial adhesion with the metal layer laminated thereon. Specifically, the polymer resin layer can have an adhesion higher than the interfacial adhesion between the carrier film laminated on the metal layer and the metal layer, and therefore, as will be described later, physical separation between the carrier film and the metal layer may be possible.

[0038] More specifically, the amino-substituted cyclic imide functional group may include a functional group represented by the following Formula 1:

[0039] [Formula 1]

[0040]

[0041] Wherein R1 is an alkylene or alkenyl group having 1 to 10 carbon atoms, or 1 to 5 carbon atoms, or 1 to 3 carbon atoms, and "*" represents a bonding point. Alkylene is a divalent functional group derived from an alkane, and examples thereof include linear, branched or cyclic groups such as methylene, ethylene, propylene, isobutylene, sec-butylene, tert-butylene, pentylene, hexylene, and the like. One or more hydrogen atoms contained in the alkylene group may be substituted with another substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 12 carbon atoms, an arylalkyl group having 6 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amide group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carbamate group, an alkoxy group having 1 to 10 carbon atoms, and the like.

[0042] The term "substituted" as used herein means that another functional group is bonded in the compound instead of the hydrogen atom, and the position to be substituted is not limited as long as it is a position where the hydrogen atom is substituted (i.e., a position where the hydrogen atom can be substituted by a substituent). When two or more hydrogen atoms are substituted, the two or more substituents may be the same or different from each other.

[0043] The alkenyl group means that the above-mentioned alkylene group contains at least one carbon-carbon double bond in the middle or at a terminal thereof, and examples thereof include ethylene, propylene, butene, hexene, acetylene, etc. One or more hydrogen atoms in the alkenyl group may be substituted with a substituent in the same manner as in the alkylene group.

[0044] Preferably, the amino-substituted cyclic imide functional group may be a functional group represented by the following Formula 2:

[0045] [Formula 2]

[0046]

[0047] Wherein, “*” indicates the bonding point.

[0048] As mentioned above, the alkali soluble resin includes an amino-substituted cyclic imide functional group and an acidic functional group. Specifically, the acidic functional group can be bonded to at least one end of the amino-substituted cyclic imide functional group. In this case, the amino-substituted cyclic imide functional group and the acidic functional group can be bonded to each other via substituted or unsubstituted alkylene or substituted or unsubstituted arylene. For example, the acidic functional group can be bonded to the end of the amino group contained in the amino-substituted cyclic imide functional group via substituted or unsubstituted alkylene or substituted or unsubstituted arylene. The acidic functional group can be bonded to the end of the imide functional group contained in the amino-substituted cyclic imide functional group via substituted or unsubstituted alkylene or substituted or unsubstituted arylene.

[0049] More specifically, the end of the amino group included in the amino-substituted cyclic imide functional group may refer to the nitrogen atom included in the amino group in Formula 1, and the end of the imide functional group included in the amino-substituted cyclic imide functional group may refer to the nitrogen atom included in the cyclic imide functional group in Formula 1.

[0050] The alkylene group is a divalent functional group derived from an alkane, and examples thereof include linear, branched or cyclic groups such as methylene, ethylene, propylene, isobutylene, sec-butylene, tert-butylene, pentylene, hexylene, etc. One or more hydrogen atoms contained in the alkylene group may be substituted with another substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 12 carbon atoms, an arylalkyl group having 6 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amide group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carbamate group, an alkoxy group having 1 to 10 carbon atoms, and the like.

[0051] The arylene group means a divalent functional group derived from aromatic hydrocarbons, and examples thereof include cyclic groups such as phenyl, naphthyl, etc. One or more hydrogen atoms contained in the arylene group may be substituted with another substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 12 carbon atoms, an arylalkyl group having 6 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amide group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carbamate group, an alkoxy group having 1 to 10 carbon atoms, and the like.

[0052] Examples of methods for preparing alkali-soluble resins are not particularly limited, but alkali-soluble resins can be prepared, for example, by a reaction between a cyclic unsaturated imide compound and an amine compound. In this case, at least one of the cyclic unsaturated imide compound and the amine compound may contain an acidic functional group substituted at its end. That is, the end of the cyclic unsaturated imide compound or the amine compound, or the ends of both compounds may be substituted with an acidic functional group. The details of the acidic functional group are as described above.

[0053] The cyclic imide compound is a compound including the above-mentioned cyclic imide functional group, and the cyclic unsaturated imide compound refers to a compound including at least one unsaturated bond, that is, a double bond or a triple bond in the cyclic imide compound.

[0054] The alkali-soluble resin may be prepared by a reaction between an amino group included in an amine compound and a double bond or a triple bond included in a cyclic unsaturated imide compound.

[0055] Examples of the weight ratio for reacting the cyclic unsaturated imide compound with the amine compound are not particularly limited, but for example, based on 100 parts by weight of the cyclic unsaturated imide compound, the amine compound can be mixed and used for the reaction in an amount of 10 parts by weight to 80 parts by weight, or 30 parts by weight to 60 parts by weight.

[0056] Examples of cyclic unsaturated imide compounds include N-substituted maleimide compounds. The term "N-substituted" means that a functional group is bonded to a nitrogen atom contained in the maleimide compound instead of a hydrogen atom. Depending on the number of N-substituted maleimide compounds, the N-substituted maleimide compounds can be divided into monofunctional N-substituted maleimide compounds and polyfunctional N-substituted maleimide compounds.

[0057] The monofunctional N-substituted maleimide compound is a compound in which a nitrogen atom contained in one maleimide compound is substituted with a functional group, and the polyfunctional N-substituted maleimide compound is a compound in which nitrogen atoms contained in each of two or more maleimide compounds are bonded via a functional group.

[0058] In the monofunctional N-substituted maleimide compound, the functional group replacing the nitrogen atom contained in the maleimide compound may include, but is not limited to, various known aliphatic, alicyclic or aromatic functional groups, and the functional group replacing the nitrogen atom may also include a functional group in which the aliphatic, alicyclic or aromatic functional group is replaced by an acidic functional group. The details of the acidic functional group are as described above.

[0059] Specific examples of the monofunctional N-substituted maleimide compound include o-methylphenylmaleimide, p-hydroxyphenylmaleimide, p-carboxyphenylmaleimide, dodecylmaleimide and the like.

[0060] In the multifunctional N-substituted maleimide compound, the functional group mediating the bond between the nitrogen atoms contained in each of the two or more maleimide compounds may include, but is not limited to, various known aliphatic, alicyclic or aromatic functional groups. In a specific example, 4,4'-diphenylmethane functional groups and the like may be used. The functional group replacing the nitrogen atom may include a functional group in which an aliphatic, alicyclic or aromatic functional group is substituted by an acidic functional group. The details of the acidic functional group are as described above.

[0061] Specific examples of the polyfunctional N-substituted maleimide compounds include 4,4′-diphenylmethane bismaleimide (BMI-1000, BMI-1100, etc. commercially available from Daiwakasei Industry Co., Ltd.), phenylmethane bismaleimide, meta-phenylenemethane bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6′-bismaleimide-(2,2,4-trimethyl)hexane, and the like.

[0062] As the amine compound, a primary amine compound containing at least one amino group (-NH2) in the molecular structure can be used. More preferably, an amino-substituted carboxylic acid compound, a polyfunctional amine compound containing two or more amino groups, or a mixture thereof can be used.

[0063] In the amino-substituted carboxylic acid compound, the carboxylic acid compound may be a compound containing a carboxylic acid (-COOH) functional group in the molecule, and according to the type of hydrocarbon bonded to the carboxylic acid functional group, the carboxylic acid compound may include all aliphatic, alicyclic or aromatic carboxylic acids. When a large amount of carboxylic acid functional groups (which are acid functional groups) are contained in the alkali-soluble resin via the amino-substituted carboxylic acid compound, the developing characteristics of the alkali-soluble resin may be improved.

[0064] The term "substituted" means that another functional group is bonded in the compound instead of the hydrogen atom, and the position of the carboxylic acid compound substituted with the amino group is not limited as long as it is a position where the hydrogen atom can be substituted. The number of the amino group as a substituent may be 1 or more.

[0065] Specific examples of the amino-substituted carboxylic acid compound include 20 α-amino acids called protein amino acids, 4-aminobutyric acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 4-aminobenzoic acid, 4-aminophenylacetic acid, 4-aminocyclohexanecarboxylic acid, and the like.

[0066] In addition, the polyfunctional amine compound containing two or more amino groups can be a compound containing two or more amino groups (-NH2) in the molecule, and according to the type of hydrocarbon bonded to the amino group, it can include all aliphatic, alicyclic or aromatic polyfunctional amines. The flexibility, toughness, copper foil adhesion, etc. of the alkali-soluble resin can be improved via the polyfunctional amine compound containing two or more amino groups.

[0067] 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-methyleneindene-1(2),5(6)-dimethylamine, 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-phenylenediamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 4 ,6-diaminoresorcinol, 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'-diaminodiphenylmethane, 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-difluoropropane Isopropylbenzene, 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'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)-benzene, 1,3-bis(4-aminophenoxy)-benzene, 1,4-bis(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-tolidine sulfone, 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-aminobenzoic acid, azole, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 4,6-diaminoresorcinol, 2,3,5,6-pyridinetetramine, a polyfunctional amine containing a siloxane structure (products PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3 and X-22-9409 of Shin-Etsu Silicone Co., Ltd.), a polyfunctional amine containing a siloxane structure (Dow Corning's product Dow Corning 3055), a polyfunctional amine containing a polyether structure (Huntsman and BASF), and the like.

[0068] In addition, the alkali-soluble resin may include at least one repeating unit represented by the following Formula 3 and at least one repeating unit represented by the following Formula 4:

[0069] [Formula 3]

[0070]

[0071] wherein R2 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 "*" represents a bonding point,

[0072] [Formula 4]

[0073]

[0074] Wherein R3 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, R4 is -H, -OH, -NR5R6, a halogen, or an alkyl group having 1 to 20 carbon atoms, R5 and R6 can each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and "*" indicates a bonding point.

[0075] Preferably, in Formula 3, R2 may be a phenylene group, and in Formula 4, R3 may be a phenylene group, and R4 may be -OH.

[0076] Meanwhile, the alkali-soluble resin may further include a vinyl-based 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 not particularly limited and include ethylene, propylene, isobutylene, butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, maleimide, and the like.

[0077] The alkali-soluble resin including at least one repeating unit represented by Formula 3 and at least one repeating unit represented by Formula 4 may be prepared by a reaction between a polymer including a repeating unit represented by Formula 5 below, an amine represented by Formula 6 below, and an amine represented by Formula 7 below.

[0078] [Formula 5]

[0079]

[0080] [Formula 6]

[0081]

[0082] [Formula 7]

[0083]

[0084] In Formulae 5 to 7, R2 to R4 are as defined above with respect to Formulae 3 and 4, and “*” represents a bonding point.

[0085] Specific examples of the polymer including the repeating unit represented by Formula 5 are not particularly limited, and include SMA (Cray Valley), Xiran (Polyscope), Scripset (Solenis), Isobam (Kuraray), polyanhydride resin (Chevron Phillips Chemical Company), Maldene (Lindau Chemicals), and the like.

[0086] In addition, an alkali-soluble resin including at least one repeating unit represented by Formula 3 and at least one repeating unit represented by Formula 4 may be prepared by a reaction between a compound represented by the following Formula 8 and a compound represented by the following Formula 9:

[0087] [Formula 8]

[0088]

[0089] [Formula 9]

[0090]

[0091] In Formula 8 and Formula 9, R2 to R4 are as defined above with respect to Formula 3 and Formula 4.

[0092] In addition, as the alkali-soluble resin, a known and commonly used carboxyl-containing resin or phenol-containing resin containing a carboxyl group or a phenol-containing resin in its molecule can be used. Preferably, a carboxyl-containing resin or a mixture of a carboxyl-containing resin and a phenol-containing resin can be used.

[0093] The carboxyl group-containing resin may be any one of the resins listed in (1) to (7) below, but is not limited thereto:

[0094] (1) a carboxyl-containing resin obtained by reacting a multifunctional epoxy resin with a saturated or unsaturated monocarboxylic acid and then with a polyacid anhydride,

[0095] (2) a carboxyl-containing resin obtained by reacting a bifunctional epoxy resin with a bifunctional phenol and / or a dicarboxylic acid and then reacting with a polyacid anhydride,

[0096] (3) a carboxyl-containing resin obtained by reacting a polyfunctional phenolic resin with a compound having an epoxy group in its molecule and then reacting it with a polyacid anhydride,

[0097] (4) a carboxyl group-containing resin obtained by reacting a compound having two or more alcoholic hydroxyl groups in its molecule with a polyacid anhydride,

[0098] (5) a polyamic acid resin obtained by reacting a diamine with a dianhydride, or a copolymer resin of a polyamic acid resin,

[0099] (6) a polyacrylic acid resin obtained by reacting acrylic acid, or a copolymer of a polyacrylic acid resin, and

[0100] (7) Resins prepared by ring-opening anhydrides of polymaleic anhydride resins (obtained by reacting maleic anhydride) and copolymers of polymaleic anhydride resins with weak acids, diamines, imidazoles or dimethyl sulfoxide.

[0101] More specific examples of the carboxyl group-containing resin include CCR-1291H (Nippon Kayaku), SHA-1216CA60 (Shin-A T&C), Noverite K-700 (Lubrizol), or a mixture of two or more thereof.

[0102] Examples of the phenol group-containing resin are not particularly limited, but include novolac resins (e.g., phenol novolac resins, cresol novolac resins, bisphenol F (BPF) novolac resins) or bisphenol A-based resins (e.g., 4,4'-(1-(4-(2-(4-hydroxyphenyl)propane-2-yl)phenyl)ethane-1,1-diyl)biphenol), which may be used alone or in combination.

[0103] The acid value of the alkali-soluble resin determined by KOH titration can be 50 mgKOH / g to 250 mgKOH / g, or 70 mgKOH / g to 200 mgKOH / g. The example of the method for measuring the acid value of the alkali-soluble resin is not particularly limited, but for example, the following method can be used. A KOH solution (solvent: methanol) with a concentration of 0.1N is prepared as an alkaline solution, and α-naphtholbenzene (pH: 0.8 to 8.2 yellow, or 10.0 blue-green) is prepared as an indicator. Subsequently, about 1 g to 2 g of the alkali-soluble resin sample is taken and dissolved in 50 g of dimethylformaldehyde (DMF) solvent, and then the indicator is added thereto, followed by titration with the alkaline solution. When the titration is completed, the acid value is determined in units of mgKOH / g based on the amount of the alkaline solution used.

[0104] If the acid value of the alkali-soluble resin is excessively reduced to less than 50 mgKOH / g, the developing characteristics of the alkali-soluble resin may be reduced, thereby making it difficult to perform the developing process. In addition, if the acid value of the alkali-soluble resin is excessively increased to more than 250 mgKOH / g, phase separation from other resins may occur due to increased polarity.

[0105] Thermosetting adhesive

[0106] According to one embodiment of the present disclosure, the patterned polymer resin layer includes a thermosetting binder.

[0107] The thermosetting binder may contain an epoxy group and an oxetane group, a cyclic ether group, a cyclic thioether group, a cyanide group, a maleimide group and a benzophenone group as a heat-curable functional group. That is, the thermosetting binder necessarily contains epoxy groups, and in addition to epoxy groups, may also contain oxetane groups, cyclic ether groups, cyclic thioether groups, cyanide groups, maleimide groups, benzophenone groups, etc. The thermosetting binder can ensure heat resistance or mechanical properties of the insulating layer by forming crosslinks with an alkali-soluble resin or the like through thermal curing.

[0108] More specifically, as the thermosetting binder, a polyfunctional resin compound containing the above-mentioned two or more functional groups in its molecule may be used.

[0109] The polyfunctional resin compound may include a resin including two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio)ether groups) in its molecule.

[0110] The thermosetting binder including two or more cyclic (thio)ether groups in its molecule may include a compound having at least two 3-membered, 4-membered or 5-membered cyclic ether groups and / or at least two cyclic thioether groups in its molecule.

[0111] Examples of the compound having two or more cyclic thioether groups in the molecule include bisphenol A episulfide resin YL7000 manufactured by Japan Epoxy Resin, and the like.

[0112] In addition, the polyfunctional resin compound may include a polyfunctional epoxy compound including at least two epoxy groups in its molecule, a polyfunctional oxetane compound including at least two oxetane groups in its molecule, an episulfide resin including two or more thioether groups in its molecule, a polyfunctional cyanate compound including at least two cyanide groups in its molecule, or a polyfunctional benzoate compound including at least two benzophenone groups in its molecule. Multifunctional benzophenones with oxazine groups Oxazine compounds.

[0113] Specific examples of the polyfunctional epoxy compound include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolac type epoxy resin, bisxylenol type epoxy resin, bisphenol type epoxy resin, chelate type epoxy resin, glyoxal type epoxy resin, amino-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenol type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenol ethane resin, silicone-modified epoxy resin, ε-caprolactone-modified epoxy resin, etc. In addition, in order to impart flame retardancy, those in which atoms such as phosphorus are introduced into the structure can be used. When these epoxy resins are heat cured, they improve the properties of the cured coating such as adhesion, solder heat resistance, and electroless plating resistance.

[0114] Examples of the polyfunctional oxetane compound include polyfunctional oxetanes such as 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-oxetanyl)methyl methacrylate, or oligomers or copolymers thereof; and copolymers of oxetane alcohol and hydroxyl-containing resins (e.g., novolac resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarene, calixresorcinarene, and the like. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth)acrylates.

[0115] 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, novolac type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac type cyanate ester resin, bisphenol A novolac type cyanate ester resin, bisphenol type cyanate ester resin, or oligomers or copolymers thereof.

[0116] Examples of the polyfunctional maleimide compound include 4,4′-diphenylmethanebismaleimide, phenylmethanebismaleimide, metaphenylmethanebismaleimide, bisphenol A diphenyl ether 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.

[0117] Multifunctional benzo Examples of oxazine compounds include bisphenol A type benzophenone Azine resin, bisphenol F type benzo Azine resin, phenolphthalein type benzo Azine resin, thiodiphenol type benzo Azine resin, dicyclopentadiene type benzo Oxazine resin, 3,3'-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzo Oxazine) resin, etc.

[0118] More specific examples of the multifunctional resin compound include YDCN-500-80P (Kukdo Chemical Co., Ltd.), phenol novolac type cyanate resin PT-30S (LONZA Ltd.), phenylmethane type maleimide resin BMI-2300 (Daiwa Kasei Kogyo Co., Ltd.), Pd type benzophenone Oxazine resin (Shikoku Chemicals Corporation), etc.

[0119] Based on 100 parts by weight of the alkali-soluble resin, the polymer resin layer may contain a thermosetting binder in an amount of 1 to 150 parts by weight, or 10 to 100 parts by weight, or 20 to 50 parts by weight. If the content of the thermosetting binder is too high, the developing characteristics of the polymer resin layer may be reduced and the strength of the polymer resin layer may decrease. On the other hand, if the content of the thermosetting binder is too low, not only may the polymer resin layer be overdeveloped, but also the uniformity during coating may be deteriorated.

[0120] Melamine derivatives

[0121] According to one embodiment of the present disclosure, the patterned polymer resin layer includes a melamine derivative. The melamine derivative has excellent compatibility while improving the adhesion between the insulating layer and the patterned metal layer to be formed on the insulating layer later. Therefore, the melamine derivative makes it easy to prepare the polymer resin composition.

[0122] According to one embodiment of the present disclosure, the melamine derivative has a structure of the following Chemical Formula 1. Therefore, the melamine derivative contains 1 to 6 carboxyl groups, which are acidic functional groups with relatively high reactivity, in its molecule, and thus can actively react with a thermosetting binder. Therefore, the melamine derivative can further increase the adhesion between the insulating layer and the patterned metal layer. In addition, the melamine derivative can be easily developed even with a weakly alkaline solution, and thus can be useful for the formation of the insulating layer.

[0123] [Chemical formula 1]

[0124]

[0125] In the above Chemical Formula 1, A is an alkyl group containing 1 to 6, 1 to 5, 2 to 6, 1 to 4, 2 to 5, 3 to 6, 1 to 3, 2 to 4, 3 to 5, or 4 to 6 carboxyl groups, or an amine group containing 1 to 6, 1 to 5, 2 to 6, 1 to 4, 2 to 5, 3 to 6, 1 to 3, 2 to 4, 3 to 5, or 4 to 6 carboxyl groups. The melamine derivative may be prepared by various methods, and the method for preparing the melamine derivative is not limited as long as the melamine derivative has the structure of Chemical Formula 1.

[0126] In Chemical Formula 1, A may include 1 to 4 or 1 to 2 sulfur atoms.

[0127] According to one embodiment of the present disclosure, the polymer resin layer may include the melamine derivative in an amount of 3 to 30 parts by weight or 10 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the melamine derivative is included in an amount within the above range, the insulating layer may have excellent adhesion to the patterned metal layer.

[0128] According to one embodiment of the present disclosure, the solubility of the melamine derivative in the aprotic solvent at 25° C. may be 5 to 20. The aprotic solvent may be one or more of dimethyl sulfoxide, N-methylpyrrolidone, dimethylacetamide, and dimethylformamide. “Solubility” may mean the mass (g) of the melamine derivative that can be dissolved in 100 g of the solvent at most. That is, for example, 10 to 20 g of the melamine derivative may be dissolved in 100 g of dimethyl sulfoxide.

[0129] Multilayer printed circuit board

[0130] A multilayer printed circuit board according to another embodiment of the present disclosure includes: the insulating layer; and a patterned metal layer disposed on the insulating layer.

[0131] In a multilayer printed circuit board according to an embodiment of the present disclosure, after the multilayer printed circuit board is left to stand at a temperature of 135° C. and a humidity of 85% for 48 hours, the peel strength of the patterned metal layer measured according to the IPC-TM-650 standard may be 0.4 to 1.2 kgf / cm, 0.5 to 1.0 kgf / cm, 0.5 to 0.7 kgf / cm, or 0.51 to 0.54 kgf / cm. When the patterned metal layer has a peel strength within the above range, the insulating layer may have excellent metal adhesion.

[0132] Since the insulating layer manufactured by the method according to one embodiment of the present disclosure includes the melamine derivative having the structure of Chemical Formula 1, the insulating layer may have excellent adhesion to a patterned metal layer formed on the insulating layer.

[0133] Method for producing an insulating layer

[0134] The present disclosure also provides a method for manufacturing an insulating layer, the method comprising the following steps: forming a polymer resin layer comprising an alkali-soluble resin, a thermosetting binder and a melamine derivative on a substrate; forming a patterned layer on the polymer resin layer; developing and curing the polymer resin layer on which the patterned layer is formed; and forming a patterned polymer resin layer by removing the patterned layer from the cured polymer resin layer, wherein the melamine derivative has a structure of Chemical Formula 1.

[0135] Figure 1 is a schematic diagram showing a method for manufacturing an insulating layer according to an embodiment of the present disclosure. Figure 1 According to one embodiment of the present disclosure, a method for manufacturing an insulating layer includes the following steps: (1) forming a polymer resin layer 200 on a substrate 100; (2) forming a patterned layer 300 on the polymer resin layer 200; (3-1) developing the polymer resin layer 200, and (3-2) curing the developed polymer resin layer; and (4) removing the patterned layer 300.

[0136] Hereinafter, each step will be described in detail.

[0137] (1) forming a polymer resin comprising an alkali-soluble resin, a thermosetting binder and a melamine derivative on a substrate; Steps of lipid layer

[0138] According to one embodiment of the present disclosure, a polymer resin layer serving as a base for an insulating layer is first formed on a substrate.

[0139] The substrate may be a circuit board, such as a copper-clad laminate, a sheet, a multilayer printed circuit board, or a semiconductor material, such as a silicon wafer. 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 or 30 μm.

[0140] The polymer resin layer may include an alkali-soluble resin, a thermosetting binder, and a melamine derivative. Specifically, after preparing a polymer resin composition including an alkali-soluble resin, a thermosetting binder, and a melamine derivative having a structure of Chemical Formula 1, the polymer resin layer may be formed using the composition.

[0141] The details of the polymer resin composition including the alkali-soluble resin, the thermosetting binder and the melamine derivative having the structure of Chemical Formula 1 are as described above.

[0142] The method for forming the polymer resin layer is not limited. However, for example, the following method may be used to form the polymer resin layer: a method of directly applying a polymer resin composition on a substrate and drying or curing; or a method of applying a polymer resin composition on a separate carrier film and drying or curing, and laminating the carrier film on which the polymer resin composition is applied on the substrate, and then removing the carrier film. Preferably, a method of forming an adhesive layer on a substrate and then directly coating the adhesive layer with a polymer resin composition may be used; or a method of applying a polymer resin composition on a carrier film to form a polymer resin layer, and then laminating the polymer resin layer with the adhesive layer on the substrate; or a method of applying a polymer resin composition on a carrier film to form a polymer resin layer, and then forming an adhesive layer on the polymer resin layer, and laminating the substrate with the adhesive layer.

[0143] Examples of the adhesive layer are not particularly limited, and various adhesive layers widely known in the field of semiconductor elements and electric and electronic materials can be used without limitation. For example, a removable temporary adhesive or a die attach film (DAF) can be used.

[0144] (2) Step of forming a patterned layer on the polymer resin layer

[0145] According to one embodiment of the present disclosure, a patterned layer is formed on a polymer resin layer formed on a substrate.

[0146] As used herein, the term "patterned layer" refers to a layer disposed on a polymer resin layer so that a portion of the polymer resin layer is exposed and other portions of the polymer resin layer are not exposed, whereby a pattern can be formed on the polymer resin layer by developing the exposed portion. That is, the patterned layer serves as a resist mask that exposes a portion of the polymer resin layer so that the portion can be developed, and protects other portions of the polymer resin layer from being developed so that the pattern of the patterned layer can be completely transferred to the polymer resin layer.

[0147] The method of forming the patterned layer is not particularly limited. For example, the patterned layer may be formed using a photosensitive resin layer.

[0148] The step of forming the patterned layer on the polymer resin layer may include the steps of: forming a photosensitive resin layer on the polymer resin layer; and exposing the photosensitive resin layer to light and performing alkaline development on unexposed portions of the photosensitive resin layer to form the patterned layer.

[0149] Examples of the method of forming the photosensitive resin layer on the polymer resin layer are not particularly limited. However, for example, a method of laminating a film-type photosensitive resin such as a photosensitive dry film resist on the polymer resin layer; or a method of coating the polymer resin layer with a photosensitive resin composition by a spraying method or a dipping method and pressing the coated composition may be used.

[0150] The photosensitive resin layer contains a polymer whose molecular structure and physical properties are changed by the action of light. As the photosensitive resin layer, a photosensitive dry film resist (DFR) or a photosensitive liquid resist can be used. The photosensitive resin layer can show photosensitivity and alkali solubility. Therefore, the molecular structure of the photosensitive resin layer can be changed by an exposure process of irradiating the photosensitive resin layer with light, and the photosensitive resin layer can be etched or removed by a development process of contacting an alkaline developer with it.

[0151] Therefore, when a portion of the photosensitive resin layer is selectively exposed and then subjected to alkaline development, the exposed portion is not developed and only the unexposed portion can be selectively etched and removed. Therefore, a portion of the photosensitive resin layer that remains intact without alkaline development after exposure can be a patterned layer.

[0152] That is, examples of the method of selectively exposing the photosensitive resin layer include a method of bringing a photomask formed with a predetermined pattern into contact with the photosensitive resin layer and irradiating the photosensitive resin layer with UV light; or a method of imaging a predetermined pattern contained in the mask on the photosensitive resin layer through a projection objective lens and then irradiating with UV light; or a method of directly imaging the photosensitive resin layer using a laser diode as a light source and then irradiating with UV light. In this case, UV light at 5 mJ / cm 2 Up to 600mJ / cm 2 The photosensitive resin layer is irradiated with an amount of.

[0153] In addition, examples of methods for alkaline development of the photosensitive resin layer after exposure include methods for treating the photosensitive resin layer with an alkaline developer. Examples of alkaline developers are not particularly limited. However, for example, an aqueous solution of an alkali such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide or amine can be used at an adjusted concentration and temperature. In addition, commercially available alkaline developers can be used. Although the specific amount of the alkaline developer used is not particularly limited, it is necessary to adjust the concentration and temperature of the alkaline developer so as not to damage the patterned layer. For example, a 0.5% to 3% sodium carbonate aqueous solution at a temperature of 25°C to 35°C can be used.

[0154] The thickness of the patterned layer formed on the polymer resin layer may be 1 to 500 μm, 3 to 500 μm, 3 to 200 μm, 1 to 60 μm, or 5 to 30 μm. If the thickness of the patterned layer is excessively increased, the resolution of the polymer resin layer may be reduced.

[0155] (3) Step of developing and curing the polymer resin layer

[0156] According to one embodiment of the present disclosure, the polymer resin layer having the patterned layer formed thereon is developed and cured. Specifically, a portion of the polymer resin layer exposed by the patterned layer is developed to form a pattern on the polymer resin layer, and then the polymer resin layer is thermally cured or photocured.

[0157] That is, in the step of developing the polymer resin layer exposed by the patterned layer, since the patterned layer is not removed by the developer, the patterned layer remains intact and serves as a resist mask. In addition, the alkaline developer can contact the patterned layer and the underlying polymer resin layer through the opening of the patterned layer. At this time, the portion of the polymer resin layer in contact with the developer can be dissolved and removed because the polymer resin layer has alkali solubility due to the inclusion of an alkali-soluble resin (which means that the polymer resin layer is dissolved by the alkaline developer).

[0158] Therefore, the polymer resin layer exposed through the patterned layer means a portion of the polymer resin layer whose surface does not contact the patterned layer. The step of alkaline developing the polymer resin layer exposed through the patterned layer may include the step of passing an alkaline developer through the patterned layer and contacting the underlying polymer resin layer.

[0159] Through the step of developing the polymer resin layer, the polymer resin layer may be patterned to have the same shape as the pattern of the patterning layer.

[0160] After the polymer resin layer is developed as described above, it can be cured. Specifically, the polymer resin layer can be thermally cured or photocured. Due to the inclusion of the step of curing the polymer resin layer, damage to the polymer resin layer during subsequent removal of the patterned layer can be minimized.

[0161] By the step of curing the polymer resin layer, a main chain containing an ester bond can be formed in the polymer resin block. Examples of the method of forming the ester bond include a method of photocuring the polymer resin layer through an acrylic resin in which an acrylate is bonded; or a method of thermally curing the polymer resin layer so that an ester bond is formed by a reaction between a carboxylic acid and an epoxy group.

[0162] In this case, the specific conditions for thermal curing are not limited and can be adjusted to preferred conditions according to the method for removing the patterned layer. For example, when the patterned layer is removed by treating with a photoresist stripper solution, the step of thermally curing the polymer resin layer can be performed at a temperature of 60°C to 150°C for 5 minutes to 2 hours. If the thermal curing temperature of the polymer resin layer is too low or its thermal curing time becomes shorter, the polymer resin layer may be damaged by the stripper solution. On the other hand, if the thermal curing temperature of the polymer resin layer is high or its thermal curing time becomes longer, it may be difficult to remove the patterned layer by the stripper solution, and excessive warping may occur in the polymer layer.

[0163] As another example, when the patterned layer is removed by a desmear process, the step of thermally curing the polymer resin layer may be performed at a temperature of 150° C. to 230° C. for 1 to 4 hours.

[0164] (4) Step of removing the patterned layer

[0165] According to one embodiment of the present disclosure, the patterned polymer resin layer is formed by removing the patterned layer from the cured polymer resin layer.

[0166] For removing the patterned layer, it is preferred to use a method capable of removing only the patterned layer as much as possible without removing the underlying polymer resin layer.

[0167] Removal of the patterned layer may be performed by treatment with a photoresist stripper solution.

[0168] The example of the method for treating the patterned layer with a photoresist stripper solution is not particularly limited. However, for example, as a photoresist stripper solution, an aqueous solution of an alkali (e.g., potassium hydroxide and sodium hydroxide) can be used at an adjusted concentration and temperature. In addition, commercially available products such as the Resistrip product group (commercially available from Atotech), or ORC-731, ORC-723K, ORC-740 or SLF-6000 (commercially available from Orchem Corporation) can also be used. The specific amount of the photoresist stripper solution used is not particularly limited, but the concentration and temperature of the photoresist stripper solution must be adjusted so as not to damage the pattern of the polymer resin layer below. For example, a 1% to 5% sodium hydroxide aqueous solution at 25°C to 60°C can be used.

[0169] Examples of the method of stripping the patterned layer using the desmear process are not particularly limited. For example, for stripping the patterned layer, commercially available products such as desmear process chemicals commercially available from Atotech, i.e., Sweller chemicals such as Securiganth E, Securiganth HP, Securiganth BLG, Securiganth MVSWELLER, or Securiganth SAP SWELLER, permanganate chemicals such as Securiganth P 500, Securiganth MV ETCH P, or Securiganth SAP ETCH P, or reducing agent chemicals such as Securiganth E Reduction Cleaner, Securiganth HP Reduction Cleaner, Securiganth BLG Reduction Cleaner, Securiganth MV Reduction Cleaner, or Securiganth SAP Reduction Cleaner, or commercially available from Orchem may be used according to the respective process conditions. The desmear process chemicals are commercially available from ORC Corporation, namely, Sweller chemicals such as ORC-310A, ORC-315A, ORC-315H or ORC-312, permanganate chemicals such as ORC-340B, or reducing agent chemicals such as ORC-370 and ORC-372.

[0170] According to one embodiment of the present disclosure, after the step of removing the patterned layer, a step of curing the patterned polymer resin layer may be further included.

[0171] If the polymer resin layer is cured as a primary cure, the patterned polymer resin layer may be subjected to secondary curing after the step of removing the patterned layer as described above, thereby improving the chemical resistance of the insulating layer finally manufactured.

[0172] Examples of the method for secondary curing are not particularly limited, and a thermal curing method or a photocuring method may be used without limitation. The secondary curing may be performed at a temperature of 150° C. to 250° C. for 0.1 to 10 hours.

[0173] According to one embodiment of the present disclosure, after forming the patterned polymer resin layer, a step of subjecting the patterned polymer resin layer to a roughening treatment to improve adhesion to a patterned metal layer to be formed later may be further included.

[0174] The roughening treatment can be performed by a dry method or a wet method according to the conditions. Examples of dry methods include vacuum treatment, atmospheric pressure treatment or gas plasma treatment, gas excimer UV treatment, etc., and examples of wet methods include desmear treatment. Through the roughening treatment, the surface roughness of the patterned polymer resin layer can be increased, thereby increasing its adhesion to the metal deposited on the patterned polymer resin layer.

[0175] Method for manufacturing a multilayer printed circuit board

[0176] A method of manufacturing a multilayer printed circuit board according to another embodiment of the present disclosure includes the steps of: manufacturing an insulating layer by the method according to one embodiment of the present disclosure; and forming a patterned metal layer on the insulating layer.

[0177] The term "patterned metal layer" may refer to a metal pattern layer. The step of forming the patterned metal layer may include the following steps: forming a metal film on an insulating layer; forming a patterned layer on the metal film; depositing metal on the metal film exposed by the patterned layer; and removing the patterned layer and removing the metal film exposed by removing the patterned layer.

[0178] It was found that since the insulating layer manufactured by the method according to one embodiment of the present disclosure includes a predetermined opening pattern, the inside of the opening pattern can be filled with metal in the process of newly laminating a patterned metal layer on the insulating layer, whereby the metal substrates disposed above and below the insulating layer can be connected together, thereby manufacturing a multilayer printed circuit board. Based on this discovery, the present disclosure was completed.

[0179] Before the step of forming the metal thin film, a step of forming a surface treatment layer on the insulating layer may be further included, so that the adhesion between the patterned metal layer and the insulating layer can be further improved.

[0180] Specifically, as an example of a method for forming a surface treatment layer on an insulating layer, at least any one of an ion-assisted reaction method, an ion beam treatment method, and a plasma treatment method can be used. The plasma treatment method may include any one of an atmospheric pressure plasma treatment method, a DC plasma treatment method, and an RF plasma treatment method. As a result of the surface treatment process, a surface treatment layer containing reactive functional groups can be formed on the surface of the insulating layer. Another example of a method for forming a surface treatment layer on an insulating layer can include a method for depositing chromium (Cr) or titanium (Ti) metal to a thickness of 50nm to 300nm on the surface of the insulating layer.

[0181] In the step of forming the metal thin film on the insulating layer, examples of the method of forming the metal thin film include dry deposition or wet deposition. Specific examples of the dry deposition method include vacuum deposition, ion plating, sputtering, and the like.

[0182] Meanwhile, specific examples of the wet deposition method include electroless plating of various metals, and electroless copper plating is generally used.

[0183] In the step of forming a patterned layer on the metal thin film, details related to forming the patterned layer may include the details described above with respect to the embodiment.

[0184] In the step of depositing metal on the metal film exposed by the patterned layer, the metal film exposed by the patterned layer means a portion of the metal film whose surface is not in contact with the patterned layer. As the metal to be deposited, copper can be used. Examples of methods for depositing metal are not particularly limited, and various known physical or chemical vapor deposition methods can be used without limitation. As a general example, an electrolytic copper plating method can be used.

[0185] In the step of removing the patterned layer and removing the metal film exposed by removing the patterned layer, the metal film exposed by removing the patterned layer refers to the portion of the metal film whose surface contacts the patterned layer. The details related to removing the patterned layer may include the details described above with respect to the embodiment.

[0186] The multilayer printed circuit board manufactured by the method for manufacturing a multilayer printed circuit board can be used as a build-up material again. For example, the first process of forming an insulating layer on a multilayer printed circuit board according to the insulating layer manufacturing method of the embodiment and the second process of forming a metal base on the insulating layer according to the multilayer printed circuit board manufacturing method of another embodiment can be repeated.

[0187] Therefore, the number of stacked layers included in the multilayer printed circuit board manufactured by the multilayer printed circuit board manufacturing method is also not particularly limited, and the multilayer printed circuit board may have, for example, one or more layers or 1 to 20 layers according to its intended use or purpose.

[0188] Embodiments of the invention

[0189] Hereinafter, the present disclosure will be described in detail with reference to embodiments. However, embodiments according to the present disclosure may be modified into various forms, and the scope of the present disclosure should not be construed as being limited to the embodiments described below. The embodiments of the present disclosure are provided to more fully illustrate the present disclosure to those skilled in the art.

[0190] Preparation Example 1

[0191] 242 g of dimethyl sulfoxide as an aprotic solvent, 105 g of thiomalic acid, 137 g of 2-vinyl-4,6-diamino-1,3,5-triazine and 16 g of azobisisobutyronitrile were placed in a 1 L reactor, heated to 80° C. while stirring, and then maintained for 24 hours to obtain a transparent solution. The obtained solution was precipitated in methanol, and the formed solid was dried to prepare the melamine derivative of the following Chemical Formula 2:

[0192] [Chemical formula 2]

[0193]

[0194] Preparation Example 2

[0195] 205 g of dimethyl sulfoxide as an aprotic solvent, 105 g of thiomalic acid, 100 g of diallylmelamine and 16 g of azobisisobutyronitrile were placed in a 1 L reactor, heated to 80° C. while stirring, and then maintained for 24 hours to obtain a transparent solution. The obtained solution was precipitated in methanol, and the formed solid was dried to prepare the melamine derivative of the following Chemical Formula 3:

[0196] [Chemical formula 3]

[0197]

[0198] Preparation Example 3

[0199] 221 g of 10 wt% sodium hydroxide solution, 75 g of glycine and 146 g of 2-chloro-4,6-diamino-1,3,5-triazine were placed in a 1L reactor, heated to 80°C while stirring, and then maintained for 24 hours to obtain a transparent solution. The obtained solution was precipitated in methanol, and the formed solid was dried to prepare the melamine derivative of the following Chemical Formula 4:

[0200] [Chemical formula 4]

[0201]

[0202] Preparation Example 4: Alkali-soluble resin

[0203] In a 2-liter coolable and heatable reactor equipped with a thermometer, a stirrer, a reflux condenser and a quantitative moisture analyzer, 543 g of dimethylacetamide (DMAc) as a solvent, 350 g of SMA1000 (manufactured by Cray Valley), 144 g of 4-aminobenzoic acid (PABA) and 49 g of 4-aminophenol (PAP) were placed and mixed together. After the temperature of the reactor was set to 80° C. under a nitrogen atmosphere, the anhydride and the aniline derivative were continuously reacted for 24 hours to form an amic acid. Then, the temperature of the reactor was set to 150° C., and the imidization reaction was continuously carried out for 24 hours to prepare an alkali-soluble resin solution having a solid content of 50%.

[0204] Insulation layer manufacturing

[0205] Example 1

[0206] As a substrate, a copper substrate having a size of 5 cm*5 cm was prepared. A mixture containing 100 parts by weight of the resin synthesized in Preparation Example 4 as an alkali-soluble resin, 30 parts by weight of MY-510 (manufactured by Huntsman) as a thermosetting binder, 180 parts by weight of SC2050MB as an inorganic filler, 4 parts by weight of the melamine derivative prepared in Preparation Example 1, and 20 parts by weight of DMSO as a solvent was prepared. The mixture was applied on a PET film and dried to produce a polymer resin layer having a thickness of 15 μm.

[0207] The manufactured polymer resin layer was vacuum laminated on a circuit board in which copper wires were formed on a copper clad laminate at 85° C. Then, the PET film was removed. A photosensitive dry film resist KL1015 (manufactured by KOLON Industries) having a thickness of 15 μm was laminated on the polymer resin layer at 110° C.

[0208] A circular negative photomask with a diameter of 30 μm was placed in contact with the surface of the photosensitive dry film resist and exposed to UV light (dose of 25 mJ / cm 2 ) was irradiated to the photosensitive dry film resist, and then the dry film resist and the polymer resin layer were sequentially developed with a 1% sodium carbonate developer solution at 30°C. At this time, the photosensitive dry film resist having a pattern formed therein served as a protective layer for the polymer resin layer, and thus a pattern identical to that of the photosensitive dry film resist was also formed in the polymer resin layer. Subsequently, the polymer resin layer was thermally cured at a temperature of 100°C for 1 hour, and then, the residue and the photosensitive dry film resist were removed using a 3% sodium hydroxide resist stripper solution at a temperature of 50°C. Then, the polymer resin layer was thermally cured at a temperature of 200°C for 1 hour, thereby manufacturing an insulating layer.

[0209] Example 2

[0210] An insulating layer was manufactured in the same manner as in Example 1, except that 4 parts by weight of the melamine derivative prepared in Preparation Example 2 was used instead of the melamine derivative prepared in Preparation Example 1.

[0211] Example 3

[0212] An insulating layer was manufactured in the same manner as in Example 1, except that 4 parts by weight of the melamine derivative prepared in Preparation Example 3 was used instead of the melamine derivative prepared in Preparation Example 1.

[0213] Comparative Example 1

[0214] An insulating layer was manufactured in the same manner as in Example 1, except that the melamine derivative prepared in Preparation Example 1 was not added.

[0215] Comparative Example 2

[0216] An insulating layer was manufactured in the same manner as in Example 1, except that 4 parts by weight of melamine (Sigma Aldrich) was used instead of the melamine derivative prepared in Preparation Example 1. As a result, melamine was not dissolved and the coating was not uniform, and thus evaluation could not be performed.

[0217] Manufacturing of multilayer printed circuit boards

[0218] Example 4

[0219] On the upper surface of the insulating layer manufactured in Example 1, a metal thin film was formed by depositing titanium (Ti) metal and copper (Cu) metal to thicknesses of 50 nm and 0.5 μm, respectively, by a sputtering method while supplying a mixed gas of argon and oxygen through a deposition system.

[0220] Thereafter, a photosensitive resin layer is formed on the metal film, exposed and developed to form a patterned photosensitive resin layer. In addition, a metal substrate made of copper is formed on the metal film by electroplating. Next, the patterned photosensitive resin layer is removed using a photosensitive resin stripper solution, and the seed layer exposed by removing the patterned photosensitive resin layer is etched away to form a patterned metal layer on the insulating layer, thereby manufacturing a multilayer printed circuit board.

[0221] Example 5 and Example 6 and Comparative Example 3

[0222] A multilayer printed circuit board of Example 5 was manufactured in the same manner as in Example 4, except that the insulating layer manufactured in Example 2 was used instead of the insulating layer manufactured in Example 1.

[0223] Furthermore, a multilayer printed circuit board of Example 6 was manufactured in the same manner as in Example 4 except that the insulating layer manufactured in Example 3 was used.

[0224] Furthermore, a multilayer printed circuit board of Comparative Example 3 was manufactured in the same manner as in Example 4, except that the insulating layer manufactured in Comparative Example 1 was used.

[0225] Measurement of metal adhesion

[0226] The multilayer printed circuit boards manufactured in Examples 4 to 6 and Comparative Example 3 were left standing at 135° C. and 85% humidity for 48 hours, and then the peel strength of the patterned metal layer in each multilayer printed circuit board was measured according to IPC-TM-650 standard and recorded as metal adhesion.

[0227] Table 1 below shows the results of measuring the metal adhesion between the insulating layer and the patterned metal layer in each of the multilayer printed circuit boards manufactured in Examples 4 to 6 and Comparative Example 3.

[0228] [Table 1]

[0229] Metal adhesion (kgf / cm) Example 4 0.51 Example 5 0.54 Example 6 0.52 Comparative Example 3 0.22

[0230] Referring to Table 1 above, it can be determined that the metal adhesion of the multilayer printed circuit boards of Examples 4, 5 and 6, which were respectively manufactured using the insulating layers of Examples 1, 2 and 3 containing the melamine derivative, was excellent, being 0.51 kgf / cm, 0.54 kgf / cm and 0.52 kgf / cm, respectively. However, it can be determined that the multilayer printed circuit board of Comparative Example 3, which was manufactured using the insulating layer of Comparative Example 1 not containing the melamine derivative, had very low metal adhesion. That is, it can be determined that the multilayer printed circuit board according to one embodiment of the present disclosure has excellent adhesion between the insulating layer and the patterned metal layer, indicating that the melamine derivative has an effect of improving adhesion.

[0231] [Explanation of Reference Numerals]

[0232] 100: Base

[0233] 200, 201, 202: polymer resin layer

[0234] 300: Patterned layer

Claims

1. An insulating layer for a multilayer printed circuit board, the insulating layer comprising a patterned polymer resin layer, the patterned polymer resin layer comprising an alkali-soluble resin, a thermosetting binder and a melamine derivative, wherein the patterned polymer resin layer comprises the melamine derivative in an amount of 3 parts by weight to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin, wherein the patterned polymer resin layer comprises the thermosetting binder in an amount of 1 part by weight to 150 parts by weight based on 100 parts by weight of the alkali-soluble resin, wherein the alkali-soluble resin comprises: one or more acidic functional groups; and a cyclic imide functional group substituted with one or more amino groups, and The melamine derivative has the following chemical formula 1: [Chemical formula 1] wherein A is a C1 to C10 alkyl group substituted with 2 to 6 carboxyl groups, or a C1 to C10 alkylamino group substituted with 1 to 6 carboxyl groups, wherein the alkyl group and the alkyl chain of the alkylamino group optionally include a thioether group. 2 . The insulating layer according to claim 1 , wherein the solubility of the melamine derivative in an aprotic solvent at 25° C. is 5 to 20.

3. The insulating layer according to claim 1, wherein the thermosetting binder comprises an epoxy group and a group selected from an oxetane group, a cyclic ether group, a cyclic thioether group, a cyanide group, a maleimide group and a benzophenone group. One or more functional groups in the oxazine group.

4. A multilayer printed circuit board comprising: The insulating layer according to claim 1; and a patterned metal layer disposed on the insulating layer.

5. The multilayer printed circuit board according to claim 4, wherein the peel strength of the patterned metal layer measured according to IPC-TM-650 standard is 0.4 to 1.2 kgf / cm after the multilayer printed circuit board is left to stand at a temperature of 135° C. and a humidity of 85% for 48 hours.

6. A method for manufacturing the insulating layer according to claim 1, the method comprising the following steps: forming a polymer resin layer comprising an alkali-soluble resin, a thermosetting binder, and a melamine derivative on a substrate; forming a patterned layer on the polymer resin layer; developing and curing the polymer resin layer on which the patterned layer is formed; as well as forming a patterned polymer resin layer by removing the patterned layer from the cured polymer resin layer, The melamine derivative has the following chemical formula 1: [Chemical formula 1] wherein A is a C1 to C10 alkyl group substituted with 2 to 6 carboxyl groups, or a C1 to C10 alkylamino group substituted with 1 to 6 carboxyl groups, wherein the alkyl group and the alkyl chain of the alkylamino group optionally include a thioether group.

7. The method according to claim 6, wherein the step of forming the patterned layer on the polymer resin layer comprises the following steps: forming a photosensitive resin layer on the polymer resin layer; as well as The patterned layer is formed by exposing the photosensitive resin layer to light and performing alkali development on unexposed portions of the photosensitive resin layer.

8. The method of claim 6, wherein removing the patterned layer is performed by treating with a photoresist stripper solution.

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