TW202130508A - Insulating layer for multilayer printed circuit board, multilayer printed circuit board including the same, and method for fabricating the same - Google Patents

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 fabricating the same. The insulating layer of the present disclosure includes a polymer resin layer containing a melamine derivative, and thus may have excellent adhesion to a patterned metal layer.

Description

Insulation layer for multilayer printed circuit board, multilayer printed circuit board containing it, and manufacturing method thereof

This application claims the rights and interests of the filing date of Korean Patent Application No. 10-2019-0132823, which was filed with the Korean Intellectual Property Office on October 24, 2019, the entire content of which is incorporated herein.

This disclosure relates to insulating layers for multilayer printed circuit boards, multilayer printed circuit boards containing them, and manufacturing methods thereof. Specifically, the present disclosure relates to an insulating layer for a multilayer printed circuit board with excellent adhesion to a patterned metal layer, a multilayer printed circuit board containing it, and a manufacturing method thereof.

Recent electronic devices have gradually become smaller, lighter, and highly functional. In order to meet these recent demands in the field of electronic devices, semiconductor components need to be installed inside the electronic devices. In recent years, this trend has been realized as the size of semiconductor components has become smaller and their integrated density has increased.

In order for the semiconductor element to receive electrical signals in the electronic device, electrical wiring is necessary. In this case, in order to achieve stable electrical signal transmission, insulation between the semiconductor element and the electrical wiring is required.

Here, the build-up semiconductor packaging process is not only used for electrical wiring connections between semiconductor components, but also used for forming an insulating layer between these components. The advantage of this semiconductor packaging process is that it can improve the integrated density of functional components, make electronic devices smaller, lighter, and highly functional, achieve structural integration of electrical functions, and reduce assembly time and cost.

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 insulating layer patterns that can be formed by laser drilling, a method of developing fine patterns with weak alkaline solutions has been used.

Therefore, it is known that the structure of melamine can effectively improve adhesion and is widely used. However, the highly stable structure of melamine makes it insoluble in most solvents, so it cannot be well dispersed or dissolved, and it is not easy to develop with weak alkaline solutions. Based on this factor, it is difficult to use melamine to make fine patterns.

One purpose of the present disclosure is to provide an insulating layer for a multilayer printed circuit board with excellent adhesion to a patterned metal layer, a multilayer printed circuit board containing it, and a manufacturing method thereof.

According to one aspect of the present disclosure, an insulating layer for a multilayer printed circuit board is provided. The insulating layer includes an alkali-soluble resin, a thermosetting binder, and a melamine derivative. The patterned polymer resin layer, wherein the melamine derivative has the structure of the following chemical formula 1:

[Chemical formula 1]

Wherein, A is an alkyl group containing 1 to 6 carboxyl groups, or an amino group containing 1 to 6 carboxyl groups.

According to another aspect of the present disclosure, a multilayer printed circuit board is provided, which includes an insulating layer and a patterned metal layer on the insulating layer.

According to another aspect of the present disclosure, there is provided a method of manufacturing the insulating layer. The method includes the following steps: forming a polymer resin layer containing an alkali-soluble resin, a thermosetting adhesive, and a melamine derivative on a substrate; A patterned layer is formed on the resin layer; the polymer resin layer on which the patterned layer is formed is developed and cured; and the patterned polymer resin is formed by removing the patterned layer from the cured polymer resin layer Layer, wherein the melamine derivative has the structure of the following chemical formula 1:

[Chemical formula 1]

Wherein, A is an alkyl group containing 1 to 6 carboxyl groups, or an amino group containing 1 to 6 carboxyl groups.

Throughout this specification, it should be understood that unless otherwise specified, when any part is referred to as "comprising" any component, it does not exclude other components, but may further include other components.

Throughout this specification, when any component is referred to as being "on" another component, it not only refers to the situation where any component is in contact with another component, but also refers to the situation where a third component exists between the two components.

Hereinafter, the present disclosure will be explained in more detail.

The insulating layer for a multilayer printed circuit board according to one embodiment of the present disclosure includes a patterned polymer resin layer containing an alkali-soluble resin, a thermosetting adhesive, and a melamine derivative, wherein the melamine derivative has the following chemical formula 1 The structure:

[Chemical formula 1]

Wherein, A is an alkyl group containing 1 to 6 carboxyl groups, or an amino group containing 1 to 6 carboxyl groups.

Hereinafter, each component is described in detail.

Alkali-soluble resin

According to one embodiment of the present disclosure, the patterned polymer resin layer contains alkali-soluble resin.

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 amide functional groups substituted with one or more amine groups (cyclic imide functional group). Examples of the acidic functional group are not particularly limited, but may include a carboxyl group or a phenol group. The alkali-soluble resin may include at least two acidic functional groups, so the polymer resin layer can exhibit higher alkali developability and the developing rate of the polymer resin layer can be controlled.

The cyclic amide functional group substituted with an amine group may contain at least two amine groups and a cyclic amide group in the structure of the functional group. When the alkali-soluble resin contains at least two cyclic amide functional groups substituted with amine groups, the alkali-soluble resin may have a structure in which a large number of active hydrogen atoms are in the existing amine groups, thereby improving the thermal curing period Its reactivity with thermosetting adhesives, and at the same time, the curing density can be increased, thereby improving the reliability of heat resistance and mechanical properties.

In addition, when multiple cyclic amide functional groups are present in the alkali-soluble resin, their polarity will be increased due to the carbonyl group and tertiary amine group contained in the cyclic amide functional group, thereby increasing the alkali-soluble resin The interface adhesion. Therefore, the polymer resin layer containing alkali-soluble resin can improve the interfacial adhesion with the metal layer laminated on it. Specifically, the polymer resin layer may have higher adhesiveness than the interfacial adhesiveness between the carrier film laminated on the metal layer and the metal layer. Therefore, as described later, the carrier film and the metal layer May be physically separated.

More specifically, the cyclic imine functional group substituted by an amino group may include a functional group represented by the following formula 1:

[Formula 1]

Wherein, R ₁ is an alkylene group or alkenyl group having 1 to 10 carbon atoms, or 1 to 5 carbon atoms, or 1 to 3 carbon atoms, and "*" means a bonding point. Alkylene is a divalent functional group derived from alkane, examples of which include linear, branched or cyclic groups, such as methylene, ethylene, propylene, isobutyl, dibutylene, Tertiary butyl, pentylene, hexylene, etc. One or more hydrogen atoms contained in the alkylene group may be substituted by another substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, Alkynyl groups of 2 to 10 carbon atoms, aryl groups of 6 to 12 carbon atoms, heteroaryl groups of 2 to 12 carbon atoms, arylalkyl groups of 6 to 12 carbon atoms, halogen atoms, cyano Group, amine group, amidino group, nitro group, amide group, carbonyl group, hydroxyl group, sulfonyl group, carbamate group, alkoxy group having 1 to 10 carbon atoms, etc.

The term "substituted" as used herein means to bond another functional group to replace the hydrogen atom in the compound, and the position to be substituted is not limited, as long as it is the position where the hydrogen atom is substituted (ie, the hydrogen atom can be replaced by The position where the substituent is substituted). When two or more hydrogen atoms are substituted, the two or more substituents may be the same or different from each other.

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

Preferably, the cyclic imine functional group substituted by an amino group may be a functional group represented by the following formula:

[Equation 2]

Among them, "*" represents the bond point.

As mentioned above, the alkali-soluble resin includes a cyclic amide functional group substituted with an amine group and an acidic functional group. Specifically, the acidic functional group can be bonded to at least one end of the cyclic imine functional group substituted with an amino group. In this case, the cyclic imine functional group and the acidic functional group substituted by the amino group can be bonded to each other through a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group Knot. For example, the acidic functional group can be bonded to the amine contained in the amino-substituted cyclic imine functional group through a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group The end of the base. The acidic functional group can be bonded to the amide contained in the cyclic amide functional group substituted by the amino group through the substituted or unsubstituted alkylene group or the substituted or unsubstituted arylene group The end of the functional group.

More specifically, the end of the amine group contained in the cyclic amide group substituted by the amino group may refer to the nitrogen atom contained in the amine group in Formula 1, and the cyclic amide group substituted by the amino group The end of the amide functional group contained in the amine functional group may refer to the nitrogen atom contained in the cyclic amide functional group in Formula 1.

Alkylene is a divalent functional group derived from alkane, and examples thereof include linear, branched or cyclic groups such as methylene, ethylene, propylene, isobutyl, dibutylene, Tertiary butyl, pentylene, hexylene, etc. One or more hydrogen atoms contained in the alkylene group may be substituted by another substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, Alkynyl groups of 2 to 10 carbon atoms, aryl groups of 6 to 12 carbon atoms, heteroaryl groups of 2 to 12 carbon atoms, arylalkyl groups of 6 to 12 carbon atoms, halogen atoms, cyano Group, amino group, formamidino group, nitro group, amide group, carbonyl group, hydroxyl group, sulfonyl group, carbamate group, alkoxy group having 1 to 10 carbon atoms, etc.

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

The example of the method of producing the alkali-soluble resin is not particularly limited, but the alkali-soluble resin can be produced, for example, by a reaction between a cyclic unsaturated imidine compound and an amine compound. In this case, at least one of the cyclic unsaturated amide compound and the amine compound may contain an acidic functional group substituted at its terminal. That is, the terminal of the cyclic unsaturated amide compound or the amine compound, or the terminal of these two compounds may be substituted with an acidic functional group. The details of the acid functional group are as described above.

The cyclic imide compound is a compound containing the above-mentioned cyclic imide functional group, and the cyclic unsaturated imide compound means that the cyclic imide compound contains at least A compound with an unsaturated bond (ie, a double bond or a triple bond).

The alkali-soluble resin can be produced by the reaction between the amine group contained in the amine compound and the double bond or triple bond contained in the cyclic unsaturated amide compound.

Examples of the weight ratio used in the reaction between the cyclic unsaturated amide compound and the amine compound are not particularly limited, but for example, based on 100 parts by weight of the cyclic unsaturated amide compound, the amine compound may be 10 To 80 parts by weight, or 30 to 60 parts by weight, are mixed and used for reaction.

Examples of the cyclic unsaturated amide compound include N-substituted maleimide compound (N-substituted maleimide compound). The term "N substitution" means that the functional group replacing the hydrogen atom is bonded to the nitrogen atom contained in the maleimide compound. According to the number of N-substituted maleimide compounds, N-substituted maleimide compounds can be classified into monofunctional N-substituted maleimide compounds and polyfunctional N-substituted maleimide compounds Maleic imine compound.

The monofunctional N-substituted maleimide compound (monofunctional N-substituted maleimide compound) is a compound in which the nitrogen atom contained in a maleimide compound is substituted by a functional group, and the polyfunctional N-substituted maleimide compound The polyfunctional N-substituted maleimide compound is a compound in which the nitrogen atoms contained in each of two or more maleimide compounds are bonded through a functional group.

In the monofunctional N-substituted maleimide compound, the functional group that replaces the nitrogen atom contained in the maleimide compound may include, but is not limited to, various known aliphatic, cycloaliphatic, or The aromatic functional group, and the functional group substituted for the nitrogen atom may include a functional group in which an aliphatic, alicyclic, or aromatic functional group is substituted with an acidic functional group. The details of the acid functional group are as described above.

Specific examples of monofunctional N-substituted maleimide compounds include o-methylphenyl maleimide (o-methylphenyl maleimide), p-hydroxyphenyl maleimide (p- hydroxyphenyl maleimide, p-carboxyphenyl maleimide, dodecyl maleimide, etc.

In the polyfunctional N-substituted maleimide compound, the functional group that mediates the bond between the nitrogen atoms contained in each of the two or more maleimide compounds may include but It is not limited to various known aliphatic, cycloaliphatic, or aromatic functional groups. In a specific example, 4,4'-diphenylmethane functional group (4,4'-diphenylmethane functional group) and the like can be used. The functional group substituted for the nitrogen atom may include a functional group in which an aliphatic, alicyclic, or aromatic functional group is substituted with an acidic functional group. The details of the acidic functional group are as described above.

Specific examples of multifunctional N-substituted maleimide compounds include 4,4'-diphenylmethane bismaleimide (4,4'-diphenylmethane bismaleimide) (BMI-1000, BMI-1100) Etc., available from Daiwakasei Industry Co., Ltd.), toluene bismaleimide (phenylmethane bismaleimide), m-phenylene methane bismaleimide (m-phenylene methane bismaleimide), double Phenol A diphenyl ether bismaleimide (bisphenol A diphenyl ether bismaleimide), 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bis-cis 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylmethane bismaleimide (4-methyl-1,3-phenylene bismaleimide), 1,6'-bismaleimide-(2,2,4-trimethyl)hexane (1,6'-bismaleimide-(2 ,2,4-trimethyl)hexane) and so on.

As the amine compound, a primary amine compound containing at least one amine group (-NH _{2) in the molecular structure can be used.} More preferably, a carboxylic acid compound substituted with an amine group, a multifunctional amine compound containing two or more amine groups, or a mixture thereof can be used.

Among the carboxylic acid compounds substituted with an amine group, the carboxylic acid compound may be a compound containing a carboxylic acid (-COOH) functional group in the molecule, and depends on the type of hydrocarbon bonded to the carboxylic acid functional group, which may include All aliphatic, cycloaliphatic, or aromatic carboxylic acids. Since a large amount of carboxylic acid functional groups which are acid functional groups are contained in the alkali-soluble resin through the carboxylic acid compound substituted with amine groups, the development properties of the alkali-soluble resin can be improved.

The term "substituted" means to bond with another functional group to replace the hydrogen atom in the compound, and the position where the carboxylic acid compound is substituted by the amino group is not limited, as long as it is a position where the hydrogen atom can be substituted. The number of amine groups as substituents may be 1 or more.

Specific examples of amino-substituted carboxylic acid compounds include 20 kinds of α-amino acids known as proteinogenic amino acids, 4-aminobutanoic acid, and 5-aminobutanoic acid. 5-aminopentanoic acid, 6-aminohexanoic acid, 7-amino heptanoic acid, 8-aminooctanoic acid, 4- 4-aminobenzoic acid, 4-aminophenylacetic acid, 4-aminocyclohexane carboxylic acid, etc.

In addition, the polyfunctional amine compound containing two or more amine groups may be a compound containing two or more amine groups (-NH ₂ ) in the molecule, and depends on the type of hydrocarbon bonded to the amine group, which may include All aliphatic, cycloaliphatic, or aromatic polyfunctional amines. The flexibility, toughness and copper foil adhesion of alkali-soluble resins can be improved through multifunctional amine compounds containing two or more amine groups.

Specific examples of polyfunctional amine compounds containing two or more amine groups include 1,3-cyclohexanediamine (1,3-cyclohexanediamine), 1,4-cyclohexanediamine (1,4-cyclohexanediamine), 1, 3-bis(aminomethyl)-cyclohexane (1,3-bis(aminomethyl)-cyclohexane), 1,4-bis(aminomethyl)-cyclohexane (1,4-bis(aminomethyl) -cyclohexane), bis(aminomethyl)-norbornene, octahydro-4,7-methylene indene-1(2)(octahydro-4,7-methanoindene-1 (2)), 5(6)-dimethanamine (5(6)-dimethanamine), 4,4'-methylenebis(cyclohexylamine)(4,4'-methylenebis(cyclohexylamine)), 4, 4'-methylenebis(2-methylcyclohexylamine) (4,4'-methylenebis(2-methylcyclohexylamine)), isophoronediamine (isophoronediamine), 1,3-phenylenediamine (1,3 -phenylenediamine), 1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine (2,5-dimethyl-1,4-phenylenediamine), 2,3,5,6-tetra Methyl-1,4-phenylenediamine (2,3,5,6-tetramethyl-1,4-phenylenediamine), 2,4,5,6-tetrafluoro-1,3-phenylenediamine (2,4 ,5,6-tetrafluoro-1,3-phenylenediamine), 2,3,5,6-tetrafluoro-1,4-phenylenediamine, 4,6-diaminoresorcinol (4,6-diaminoresorcinol ), 2,5-diamino-1,4-benzenedithiol, 3-aminobenzylamine, 4-aminobenzylamine , M-xylenediamine, p-xylenediamine, 1,5-diaminonaphthalene, 2,7-diaminonaphthalene (2,7- diaminofluorene), 2,6-diaminoanthraquinone, m-tolidine, o-tolidine, 3,3',5,5'- Tetramethylbenzidine (3,3',5 ,5'-tetramethylbenzidine) (TMB), o-dianisidine (o-dianisidine), 4,4'-methylenebis(2-chloroaniline) (4,4'-methylenebis(2-chloroaniline)), 3,3'-diaminobenzidine (3,3'-diaminobenzidine), 2,2'-bis(trifluoromethyl)-benzidine (2,2'-bis(trifluoromethyl)-benzidine), 4, 4'-diaminooctafluorobiphenyl (4,4'-diaminooctafluorobiphenyl), 4,4'-diamino-p-terphenyl (4,4'-diamino-p-terphenyl), 3,3'-di Aminodiphenylmethane (3,3'-diaminodiphenylmethane), 3,4'-diaminodiphenylmethane (3,4'-diaminodiphenylmethane), 4,4'-diaminodiphenylmethane, 4,4' -Diamino-3,3'-dimethyldiphenylmethane (4,4'-diamino-3,3'-dimethyldiphenylmethane), 4,4'-methylene bis(2-ethyl-6-methyl) Phenylamine) (4,4'-methylenebis(2-ethyl-6-methylaniline)), 4,4'-methylenebis(2,6-diethylaniline) (4,4'-methylenebis(2, 6-diethylaniline)), 3,3'-diaminobenzophenone (3,3'-diaminobenzophenone), 4,4'-diaminobenzophenone (4,4'-diaminobenzophenone), 4, 4'-ethylenedianiline (4,4'-ethylenedianiline), 4,4'-diamino-2,2'-dimethylbibenzyl (4,4'-diamino-2,2'-dimethylbibenzyl), 2,2'-bis(3-amino-4-hydroxyphenyl)propane (2,2'-bis(3-amino-4-hydroxyphenyl)propane), 2,2'-bis(3-aminobenzene) Yl)-hexafluoropropane (2,2'-bis(3-aminophenyl)-hexafluoropropane), 2,2'-bis(4-aminophenyl)-hexafluoropropane (2,2'-bis(4- aminophenyl)-hexafluoropropane), 2,2'-bis(3-amino-4-methylphenyl)-hexafluoropropane (2,2'-bis(3-amino-4-methylphenyl)-hexafluoroprop ane), 2,2'-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (2,2'-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane), α,α'- Bis(4-aminophenyl)-1,4-diisopropylbenzene (α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene), 1,3-bis-[2-(4- Aminophenyl)-2-propyl]benzene (1,3-bis-[2-(4-aminophenyl)-2-propyl]benzene), 1,1'-bis(4-aminophenyl)- Cyclohexane (1,1'-bis(4-aminophenyl)-cyclohexane), 9,9'-bis(4-aminophenyl)-fluorene (9,9'-bis(4-aminophenyl)-fluorene) , 9,9'-bis(4-amino-3-chlorophenyl) fluorene (9,9'-bis(4-amino-3-chlorophenyl) fluorene), 9,9'-bis(4-amino -3-fluorophenyl) fluorene (9,9'-bis(4-amino-3-fluorophenyl)fluorene), 9,9'-bis(4-amino-3-methylphenyl)fluorene (9, 9'-bis(4-amino-3-methylphenyl)fluorene), 3,4'-diaminodiphenyl ether (3,4'-diaminodiphenyl ether), 4,4'-diaminodiphenyl ether , 1,3-bis(3-aminophenoxy)-benzene (1,3-bis(3-aminophenoxy)-benzene), 1,3-bis(4-aminophenoxy)-benzene (1 ,3-bis(4-aminophenoxy)-benzene), 1,4-bis(4-aminophenoxy)-benzene (1,4-bis(4-aminophenoxy)-benzene), 1,4-bis( 4-amino-2-trifluoromethylphenoxy)-benzene (1,4-bis(4-amino-2-trifluoromethylphenoxy)-benzene), 4,4'-bis(4-aminophenoxy) )-Biphenyl (4,4'-bis(4-aminophenoxy)-biphenyl), 2,2'-bis-[4-(4-aminophenoxy)-phenyl]propane(2,2'- bis-[4-(4-aminophenoxy)-phenyl]propane), 2,2'-bis-[4-(4-aminophenoxy)-phenyl]hexafluoropropane(2,2'-bis- [4-(4-aminophenoxy)-phenyl]hexafluoro propane), bis(2-aminophenyl)sulfide, bis(4-aminophenyl) sulfide, bis(3-amine) Bis(3-aminophenyl)sulfone, bis(4-aminophenyl)sulfone, bis(3-aminophenyl)sulfone, bis(3-aminophenyl)sulfone 3-amino-4-hydroxy)sulfone), bis[4-(3-aminophenoxy)-phenyl]sulfone (bis[4-(3-aminophenoxy)-phenyl]sulfone), bis-[4- (4-aminophenoxy)-phenyl]sulfone (bis-[4-(4-aminophenoxy)-phenyl]sulfone), o-tolidine sulfone, 3,6-diamino Carbazole (3,6-diaminocarbazole), 1,3,5-ginseng (4-aminophenyl)-benzene (1,3,5-tris(4-aminophenyl)-benzene), 1,3-bis( 3-aminopropyl)-tetramethyldisiloxane (1,3-bis(3-aminopropyl)-tetramethyldisiloxane), 4,4'-diaminobenzanilide (4,4'-diaminobenzanilide) ), 2-(3-aminophenyl)-5-aminobenzimidazole (2-(3-aminophenyl)-5-aminobenzimidazole), 2-(4-aminophenyl)-5-aminobenzene 2-(4-aminophenyl)-5-aminobenzoxazole, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5 -Amine (1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine), 4,6-diaminoresorcinol (4,6- diaminoresorcinol), 2,3,5,6-pyridine tetraamine (2,3,5,6-pyridine tetraamine), polyfunctional amine (PAM-E, KF-8010, X -22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3 and X-22-9409, which are products of Shin-Etsu Silicone Co., Ltd.), containing Polyfunctional amine with siloxane structure (D ow Corning 3055, which is a product of Dow Corning), polyether structure-containing polyfunctional amines (Huntsman and BASF), etc.

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:

[Equation 3]

Wherein, R ₂ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and "*" represents the bond point,

[Equation 4]

Wherein, R ₃ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R ₄ is -H, -OH, -NR ₅ R ₆ , halogen, or an alkyl group having 1 to 20 carbon atoms; R ₅ and R ₆ may each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, or having 6 to An aryl group with 20 carbon atoms, and "*" indicates the point of bonding.

Preferably, in Formula 3, R ₂ can be phenylene, and in Formula 4, R ₃ can be phenylene and R ₄ can be -OH.

In addition, 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 the molecule. Examples of the vinyl-based monomer are not particularly limited and include ethylene, propylene, isobutylene, Butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, maleimide, etc.

The alkali-soluble resin containing at least one repeating unit represented by formula 3 and at least one repeating unit represented by formula 4 can be obtained by a polymer containing a repeating unit represented by the following formula 5, an amine represented by the following formula 6 and the following formula 7. Manufactured by the reaction between the amines:

[Equation 5]

[Equation 6]

[Equation 7]

In formulas 5 to 7, R ₂ to R ₄ are as defined above for formulas 3 and 4, and "*" represents a bonding point.

Specific examples of the polymer containing 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), etc.

In addition, the alkali-soluble resin containing at least one repeating unit represented by formula 3 and at least one repeating unit represented by formula 4 can be produced by the reaction between the compound represented by the following formula 8 and the compound represented by the following formula 9:

[Equation 8]

[Equation 9]

In formulas 8 and 9, R ₂ to R ₄ are as defined above for formulas 3 and 4.

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

The carboxyl group-containing resin can be any one of the following resins listed in (1) to (7), but is not limited thereto:

(1) A carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin with a saturated or unsaturated monocarboxylic acid and then reacting with a polybasic acid anhydride,

(2) A carboxyl group-containing resin obtained by reacting bifunctional epoxy resin with bifunctional phenol and/or dicarboxylic acid and then reacting with polybasic acid anhydride,

(3) A carboxyl group-containing resin obtained by reacting a polyfunctional phenolic resin with a compound having an epoxy group in the molecule, and then reacting with a polybasic acid anhydride,

(4) A carboxyl group-containing resin obtained by reacting a compound having two or more alcoholic hydroxyl groups in the molecule with a polybasic acid anhydride,

(5) Polyamic acid resin or copolymer resin of the polyamic acid resin obtained by reacting diamine and dianhydride,

(6) A polyacrylic acid resin or a copolymer of the polyacrylic acid resin obtained by the reaction of acrylic acid, and

(7) A polymaleic anhydride resin (obtained by reacting maleic anhydride) with a weak acid, diamine, imidazole, or dimethylene oxide, and the polymaleic anhydride resin A resin prepared by ring-opening the anhydride of a copolymer of dianhydrides.

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.

Examples of phenolic group-containing resins are not particularly limited, but include novolac resins, such as phenol novolac resins, cresol novolac resins, and bisphenol resins. F (bisphenol F) (BPF) phenolic resin, or bisphenol A based resin such as 4,4'-(1-(4-(2-(4-hydroxyphenyl)prop-2-yl )Phenyl)ethane-1,1-diyl)diphenol (4,4'-(1-(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl)ethane-1,1-diyl )diphenol), they can be used alone or in combination.

The alkali-soluble resin may have an acid value of 50 mgKOH/g to 250 mgKOH/g, or 70 mgKOH/g to 200 mgKOH/g as determined by KOH titration. Examples of the method for measuring the acid value of the alkali-soluble resin are not particularly limited, but, for example, the following method can be used. Prepare a KOH solution (solvent: methanol) with a concentration of 0.1 N as an alkali solution, and prepare (α-naphthol) benzyl alcohol (alpha-naphtholbenzein) (pH: 0.8 to 8.2 for yellow, or 10.0 for blue-green) as an indicator (indicator). Subsequently, about 1 g to 2 g of alkali-soluble resin was sampled and dissolved in 50 g of dimethylformamide (DMF) solvent, and then an indicator was added thereto, followed by titration with the alkali solution. When the titration is completed, the acid value is determined according to the amount of alkali solution used, and the unit is mg KOH/g.

If the acid value of the alkali-soluble resin is excessively reduced below 50 mgKOH/g, the development properties of the alkali-soluble resin will be reduced, thus making it difficult to perform the development 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 will occur due to the increased polarity.

Thermosetting adhesive

According to one embodiment of the present disclosure, the patterned polymer resin layer contains a thermosetting binder.

The thermosetting adhesive may include an epoxy group and at least one functional group selected from the group consisting of: oxetanyl group, cyclic ether group, and cyclic thioether group. group), cyano group, maleimide group and benzoxazine group, which are heat-curable functional groups. That is, the thermosetting adhesive must contain an epoxy group, and in addition to the epoxy group, it may also contain an oxo group, a cyclic ether group, a cyclic thioether group, a cyano group, a maleimide group, and a benzo 𠯤 base, or a mixture of two or more of them.

The thermosetting adhesive can ensure the heat resistance or mechanical properties of the insulating layer by forming crosslinks with alkali-soluble resins and the like through thermal curing.

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

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

Thermosetting adhesives containing two or more cyclic (thio) ether groups in the molecule may include those having at least two 3-membered, 4-membered, or 5-membered cyclic ether groups and/or at least two cyclic thioether groups in the molecule. Compound.

Examples of the compound having two or more cyclic sulfide groups in the molecule include bisphenol A episulfide resin YL 7000 (manufactured by Japan Epoxy Resin) and the like.

In addition, the polyfunctional resin compound may include a polyfunctional epoxy compound containing at least two epoxy groups in the molecule, a polyfunctional epoxy compound containing at least two oxygen groups in the molecule, and a polyfunctional epoxy compound containing two or more in the molecule. Sulfide-based episulfide resins, polyfunctional cyanate compounds containing at least two cyano groups in the molecule, or polyfunctional benzophenone compounds containing at least two benzothio groups in the molecule.

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, and bisphenol F type epoxy resin. Oxygen resin, bisphenol S type epoxy resin, novolac-type epoxy resin, phenol novolac-type epoxy resin, cresol novolac epoxy resin -type epoxy resin), N-glycidyl-type epoxy resin, bisphenol A novolac-type epoxy resin, joint phenolic epoxy Resin (bixylenol-type epoxy resin), biphenol-type epoxy resin, chelate-type epoxy resin, glyoxal-type epoxy resin resin), amine-containing epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic-type epoxy resin, phthalic acid epoxy resin Diglycidylphthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoylethane resin, silicone-modified epoxy resin resin), ε-caprolactone-modified epoxy resin, etc. In addition, in order to impart flame retardancy, a structure having atoms such as phosphorus introduced into the structure can be used. When the epoxy resins are thermally cured, they improve the properties of the cured coating, such as adhesion, solder heat resistance, and electroless plating resistance.

Examples of polyfunctional oxetane compounds include polyfunctional oxetane compounds such as bis[(3-methyl-3-oxetanemethoxy)methyl]ether (bis[(3-methyl-3-methyl-3- oxetanylmethoxy)methyl]ether), bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether), bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether), 1,4-bis [(3-methyl-3-oxetanylmethoxy)methyl]benzene (1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene), 1,4-bis[(3- Ethyl-3-oxetanylmethoxy)methyl]benzene (1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene), (3-methyl-3-oxetanylmethoxy)methyl]benzene 3-methyl-3-oxetanyl methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl- 3-oxetanyl) methylmethacrylate (3-methyl-3-oxetanyl) methylmethacrylate), (3-ethyl-3-oxetanyl) methylmethacrylate ((3-ethyl-3- oxetanyl methylmethacrylate), or its oligomer or copolymer, as well as oxetane alcohol and hydroxyl-containing resins such as phenolic resin, poly(p-hydroxystyrene), cardo bisphenol , Calixarene, calixresorcin arene, or etherification product of silsesquioxane, etc. Other examples include copolymers of unsaturated monomers having an oxygen ring and alkyl (meth)acrylates.

Examples of polyfunctional cyanate ester compounds include bisphenol A type cyanate ester resins, bisphenol E type cyanate ester resins, bisphenol F type cyanate ester resins, bisphenol S type cyanate ester resins, and bisphenol M type cyanate ester resins. Acid ester resin, novolak type cyanate ester resin, phenol novolak type cyanate ester resin, cresol novolak type cyanate ester resin, bisphenol A novolak type cyanate ester resin, biphenol type cyanate ester resin, or its oligomer Polymer or copolymer.

Examples of polyfunctional maleimide compounds include 4,4'-diphenylmethane bismaleimide (4,4'-diphenylmethanebismaleimide), toluene bismaleimide (phenylmethane bismaleimide) ), m-phenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl -5,5'-diethyl-4,4'-diphenylmethane bismaleimide (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide), 4-methyl-1,3-phenylenebismaleimide (4-methyl-1,3-phenylenebismaleimide), 1,6'-bismaleimide-(2,2 ,4-Trimethyl)hexane (1,6'-bismaleimide-(2,2,4-trimethyl)hexane) and so on.

Examples of polyfunctional benzoxazine compounds include bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, phenolphthalein-type benzoxazine resin, Thiodiphenol-type benzoxazine resin, dicyclopentadiene-type benzoxazine resin, 3,3'-(methylene-1,4- Biphenyl) bis(3,4-dihydro-2H-1,3-benzodihydro-2H) resin (3,3'-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H -1,3-benzoxazine) resin) etc.

More specific examples of the polyfunctional resin compound include YDCN-500-80P (Kukdo Chemical Co., Ltd.), phenolic phenolic cyanate resin PT-30S (LONZA Ltd.), toluene maleimide Resin BMI-2300 (Daiwa Kasei Kogyo Co., Ltd.), Pd-type benzo 㗁𠯤 resin (Shikoku Chemicals Corporation), etc.

The polymer resin layer may include a thermosetting adhesive in an amount of 1 to 150 parts by weight, 10 to 100 parts by weight, or 20 to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin. If the content of the thermosetting adhesive is too high, the developing properties of the polymer resin layer will decrease, and the strength of the polymer resin layer will decrease. On the other hand, if the content of the thermosetting adhesive is too low, not only the polymer resin layer will be overdeveloped, but the uniformity during coating will also deteriorate.

Melamine derivatives

According to one embodiment of the present disclosure, the patterned polymer resin layer contains a melamine derivative. Melamine derivatives have excellent compatibility and at the same time improve the adhesion between the insulating layer and the patterned metal layer formed on the insulating layer later. Therefore, the melamine derivative makes it easy to prepare the polymer resin composition.

According to one embodiment of the present disclosure, the melamine derivative has the structure of Chemical Formula 1 below. Therefore, the melamine derivative contains 1 to 6 carboxyl groups (which are acidic functional groups with relatively high reactivity) in the molecule, and thus can actively react with the thermosetting adhesive. Therefore, the melamine derivative can further improve the adhesion between the insulating layer and the patterned metal layer. In addition, even if a weak alkaline solution is used, the melamine derivative can be easily developed and thus can be used to form an insulating layer.

[Chemical formula 1]

In the above chemical formula 1, A contains 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 Alkyl groups, or amines 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 base. The melamine derivative can be manufactured 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.

In Chemical Formula 1, A may contain 1 to 4 or 1 to 2 sulfur atoms.

According to an embodiment of the present disclosure, the polymer resin layer may contain 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 content of the melamine derivative is within the above range, the insulating layer can have excellent adhesion to the patterned metal layer.

According to one aspect of the present disclosure, the melamine derivative can have a solubility of 5 to 20 in an aprotic solvent at 25°C. The aprotic solvent can be dimethyl sulfide, N-methyl pyrrolidone, dimethylacetamide, and dimethylformamide One or more. "Solubility" can mean the mass (g) of the melamine derivative that can be dissolved in 100 g of solvent at the maximum. That is, for example, 10 to 20 g of a melamine derivative can be dissolved in 100 g of dimethyl sulfoxide.

Multilayer printed circuit board

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

In the multilayer printed circuit board according to one embodiment of the present disclosure, the patterned metal layer may be allowed to stand for 48 hours on the multilayer printed circuit board at a temperature of 135°C and a humidity of 85% according to the IPC-TM-650 standard. Then, the peel strength was measured at 0.4 kgf/cm to 1.2 kgf/cm, 0.5 kgf/cm to 1.0 kgf/cm, 0.5 kgf/cm to 0.7 kgf/cm, or 0.51 kgf/cm 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.

Since the insulating layer manufactured by the method according to one embodiment of the present disclosure contains the melamine derivative having the structure of Chemical Formula 1, the insulating layer can have excellent adhesion to the patterned metal layer formed on the insulating layer sex.

Method of manufacturing insulating layer

The present disclosure also provides a method for manufacturing an insulating layer. The method includes the following steps: forming a polymer resin layer containing an alkali-soluble resin, a thermosetting adhesive, and a melamine derivative on a substrate; and forming a pattern on the polymer resin layer 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 The derivative has the structure of Chemical Formula 1.

FIG. 1 is a schematic diagram showing a method of manufacturing an insulating layer according to an embodiment of the present disclosure. Referring to FIG. 1, the method of manufacturing an insulating layer according to one embodiment of the present disclosure includes the following steps: (1) forming a polymer resin layer 200 on a substrate 100; (2) forming a pattern on the polymer resin layer 200 (3-1) develop the polymer resin layer 200, and (3-2) cure the developed polymer resin layer; and (4) remove the patterned layer 300.

The steps are described in detail below.

(1) Step of forming a polymer resin layer containing alkali-soluble resin, thermosetting adhesive and melamine derivative on a substrate

According to one embodiment of the present disclosure, the polymer resin layer used as the base of the insulating layer is first formed on the substrate.

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 can be 1 µm to 500 µm, or 3 µm to 500 µm, or 3 µm to 200 µm, or 1 µm to 60 µm, or 5 µm to 30 µm.

The polymer resin layer may contain an alkali-soluble resin, a thermosetting adhesive, and a melamine derivative. Specifically, after preparing a polymer resin composition containing an alkali-soluble resin, a thermosetting adhesive, and a melamine derivative having the structure of Chemical Formula 1, they can be used to form a polymer resin layer.

The details of the polymer resin composition containing the alkali-soluble resin, the thermosetting adhesive, and the melamine derivative having the structure of Chemical Formula 1 are as described above.

The method of forming the polymer resin layer is not limited. However, for example, the formation of the polymer resin layer may use a method of directly applying the polymer resin composition to the substrate and drying or curing, or applying the polymer resin composition to another carrier film and A method of drying or curing, laminating the carrier film applied with the polymer resin composition to the substrate and then removing it. Preferably, a method of forming an adhesive layer on a substrate and then directly coating the adhesive layer with a polymer resin composition can be used; or applying the polymer resin composition to the carrier film to form the polymer resin layer , Then the polymer resin layer and the adhesive layer on the substrate are laminated together; or the polymer resin composition is applied to the carrier film to form the polymer resin layer, and then the adhesive layer is formed on the A method of laminating the base material and the adhesive layer on the polymer resin layer.

Examples of the adhesive layer are not particularly limited, and various adhesive layers that are widely known in the fields of semiconductor devices and electrical and electronic materials can be used without limitation. For example, a debondable temporary adhesive or die attach film (DAF) can be used.

(2) Steps of forming a patterned layer on the polymer resin layer

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

As used herein, the term "patterned layer" refers to a layer located on the polymer resin layer so that a part of the polymer resin layer is exposed and the other part of the polymer resin layer is not exposed. The exposed part is developed to form a pattern on the polymer resin layer. That is, the patterned layer is used as a resist mask to expose a part of the polymer resin layer to make the part developable, and to protect other parts of the polymer resin layer from developing, so that the pattern of the patterned layer Can be completely transferred to the polymer resin layer.

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

The step of forming a patterned layer on the polymer resin layer may include the following steps: forming a photosensitive resin layer on the polymer resin layer; and exposing the photosensitive resin layer, and making the unexposed part of the photosensitive resin layer alkaline Alkali-developing to form a patterned layer.

The example of the method of forming the photosensitive resin layer on the polymer resin layer is not particularly limited. However, for example, a method of laminating a film-type photosensitive resin (such as photosensitive dry film resist) on a polymer resin layer; or a photosensitive resin composition by spraying ( spray) or dipping (dipping) method to coat the polymer resin layer and pressurize the coated composition.

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 (photosensitive liquid resist) can be used. The photosensitive resin layer can exhibit photosensitivity and alkali solubility. Therefore, the molecular structure of the photosensitive resin layer can be changed by the exposure process of irradiating the photosensitive resin layer with light, and the photosensitive resin layer can be etched or removed by the development process of bringing the alkaline developer into contact with it.

Therefore, when a part of the photosensitive resin layer is selectively exposed and then subjected to alkali development, the exposed part is not developed, and only the unexposed part is selectively etched and removed. Therefore, the portion of the photosensitive resin layer that remains intact and not developed by alkali after exposure can be a patterned layer.

That is, examples of the method of selectively exposing the photosensitive resin layer include a method of bringing a formed photomask having a predetermined pattern into contact with the photosensitive resin layer and irradiating the photosensitive resin layer with UV light; or a method contained in the mask The predetermined pattern is imaged on the photosensitive resin layer through a projection objective lens and then irradiated with UV light; or the photosensitive resin layer is directly imaged by using a laser diode as the light source, Then irradiate with UV light. In this case, the photosensitive resin layer may be irradiated with UV light at a ^{dose of 5 mJ/cm 2} to 600 mJ/cm ^2.

In addition, examples of the method of alkali-developing the photosensitive resin layer after exposure include a method of treating the photosensitive resin layer with an alkali developer. Examples of the alkali developer (alkali developer) are not particularly limited. However, for example, an aqueous solution of alkali such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, or amine (at adjusted concentration and temperature ). In addition, a commercially available alkali developer can be used. Although the specific amount of the alkali developer used is not particularly limited, the concentration and temperature of the alkali developer need to be adjusted to avoid damage to the patterned layer. For example, a 0.5 to 3% aqueous solution of sodium carbonate at a temperature of 25 to 35°C can be used.

The thickness of the patterned layer formed on the polymer resin layer can be 1 µm to 500 µm, or 3 µm to 500 µm, or 3 µm to 200 µm, or 1 µm to 60 µm, or 5 µm to 30 µm. If the thickness of the patterned layer is excessively increased, the resolution of the polymer resin layer will decrease.

(3) Steps of developing and curing polymer resin layer

According to one embodiment of the present disclosure, the polymer resin layer on which the patterned layer is formed is developed and cured. Specifically, a part of the polymer resin layer exposed through 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.

That is, in the step of developing the polymer resin layer exposed through the patterned layer, since the patterned layer is not removed by the developer, the patterned layer remains intact and serves as a photoresist mask. In addition, the alkali developer can contact the patterned layer and the polymer resin layer underneath through the openings of the patterned layer. At this time, since the polymer resin layer has alkali solubility by containing alkali-soluble resin (which means that the polymer resin layer is dissolved by the alkali developer), the part of the polymer resin layer in contact with the developer can be dissolved and removed .

Therefore, the polymer resin layer exposed through the patterned layer means the portion of the polymer resin layer whose surface is not in contact with the patterned layer. The step of alkali-developing the polymer resin layer exposed through the patterned layer may include the step of passing an alkali developer through the patterned layer and contacting the polymer resin layer underneath.

Through the step of developing the polymer resin layer, the polymer resin layer can be patterned to have the same shape as the pattern of the patterned layer.

After the polymer resin layer is developed as described above, it can be cured. Specifically, the polymer resin layer may be cured by heat or light. When the step of curing the polymer resin layer is included, damage to the polymer resin layer during subsequent removal of the patterned layer can be minimized.

Through the step of curing the polymer resin layer, the main chain containing the ester bond can be formed in the polymer resin block. Examples of the method of forming ester bonds include a method of photocuring the polymer resin layer through an acrylic resin (among which, acrylic ester-bonded), or a method of thermally curing the polymer resin layer by carboxylic acid The reaction with epoxy groups to form ester bonds.

In this case, the specific conditions of thermal curing are not limited, and can be adjusted to better conditions depending on the method of removing the patterned layer. For example, when the patterned layer is removed by treatment with a photoresist stripper solution, the step of thermally curing the polymer resin layer can be performed at a temperature of 60 to 150° C. for 5 minutes to 2 hours. If the thermal curing temperature of the polymer resin layer is too low or the thermal curing time becomes shorter, the polymer resin layer will be damaged by the removal solution. On the other hand, if the thermal curing temperature of the polymer resin layer is high or the thermal curing time becomes longer, it will be difficult to remove the patterned layer by the removing solution, and the polymer resin layer will be excessively warpaged.

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

(4) Steps to remove the patterned layer

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.

In order to remove the patterned layer, it is preferable to use a method capable of removing only the patterned layer without removing the underlying polymer resin layer as much as possible.

The removal of the patterned layer can be performed by processing with a photoresist removal solution.

The example of the method of treating the patterned layer with the photoresist removal solution is not particularly limited. However, for example, as the photoresist removal solution, an aqueous alkali solution (at adjusted concentration and temperature) such as potassium hydroxide and sodium hydroxide can be used. In addition, commercially available products, such as the Resistrip product group (available from Atotech), or ORC-731, ORC-723K, ORC-740, or SLF-6000 (available from Orchem Corporation), can also be used. The specific amount of the photoresist removal solution used is not particularly limited, but the concentration and temperature of the photoresist removal solution need to be adjusted to avoid damage to 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.

Examples of the method of removing the patterned layer using the desmear program are not particularly limited. For example, to remove the patterned layer, commercially available products such as Sweller chemicals such as Securiganth E, Securiganth HP, Securiganth BLG, Securiganth MV SWELLER, or Securiganth SAP SWELLER, and permanganate chemicals such as Securiganth P can be used depending on the process conditions. 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. Desmear process chemicals purchased by Atotech; or 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 or ORC-372, which are desmear process chemicals available from Orchem Corporation.

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

If the curing of the polymer resin layer is the first curing, the patterned polymer resin layer can be cured for the second time after the step of removing the patterned layer as described above. Thereby, the chemical resistance of the finally manufactured insulating layer can be improved.

Examples of the method of secondary curing are not particularly limited, and thermal curing or light curing methods can be used without limitation. The secondary curing can be performed at a temperature of 150°C to 250°C for 0.1 hour to 10 hours.

According to one embodiment of the present disclosure, after the patterned polymer resin layer is formed, it may further include roughening treatment on the patterned polymer resin layer to improve the performance of the patterned metal layer to be formed later. Adhesion.

The roughening treatment may be performed by a dry method or a wet method depending on the conditions. Examples of the dry method include vacuum, atmospheric pressure or gas plasma treatment, gas excimer UV treatment, etc.; and examples of the wet method include desmearing treatment.

Through the roughening treatment, the surface roughness of the patterned polymer resin layer can be increased, thereby improving its adhesion to the metal deposited on the patterned polymer resin layer.

Method for manufacturing multilayer printed circuit board

A method for manufacturing a multilayer printed circuit board according to another embodiment of the present disclosure includes the following steps: 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.

The term "patterned metal layer" can refer to a metal pattern layer. The step of forming a patterned metal layer may include the following steps: forming a metal film on the insulating layer; forming a patterned layer on the metal film; depositing metal on the metal film exposed through the patterned layer; and removing the patterning Layer, and remove the metal film exposed by removing the patterned layer.

It has been found that since the insulating layer manufactured by the method according to one embodiment of the present disclosure includes a predetermined opening pattern, in the process of newly laminating the patterned metal layer on the insulating layer, the inside of the opening pattern can be filled with metal Therefore, the metal substrates located above and below the insulating layer can be connected together to produce a multilayer printed circuit board. Based on this finding, the present disclosure has been completed.

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. Thereby, the adhesion between the patterned metal layer and the insulating layer can be further improved.

Specifically, as an example of a method of forming a surface treatment layer on an insulating layer, an ion-assisted reaction method, an ion beam treatment method, and a plasma treatment method can be used. treatment method) at least any one of them. 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. Due to 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 of forming a surface treatment layer on the insulating layer may include a method of depositing chromium (Cr) or titanium (Ti) metal on the surface of the insulating layer to a thickness of 50 nm to 300 nm.

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

In addition, specific examples of the wet deposition method include electroless plating of various metals, and electroless copper plating is generally used.

In the step of forming the patterned layer on the metal thin film, the details related to the formation of the patterned layer may include the above-mentioned details about the embodiment.

In the step of depositing metal on the metal thin film exposed through the patterned layer, the metal thin film exposed through the patterned layer refers to the part of the metal thin 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 metals are not particularly limited, and various known physical or chemical vapor deposition methods can be used without limitation. As an example of general use, an electrolytic copper plating method can be used.

In the steps of removing the patterned layer and removing the metal thin film exposed by removing the patterned layer, the metal thin film exposed by removing the patterned layer refers to the part of the metal thin film whose surface is in contact with the patterned layer . The related details of the removal of the patterned layer may include the above-mentioned details about this embodiment.

The multilayer printed circuit board manufactured by the method of manufacturing the multilayer printed circuit board can be used again as a build-up material. For example, the first process of forming an insulating layer on a multilayer printed circuit board according to the method of manufacturing an insulating layer of this embodiment, and the method of forming a metal substrate on the insulating layer according to another embodiment of the method of manufacturing a multilayer printed circuit board The second procedure is repeatable.

Therefore, the number of stacked layers included in the multilayer printed circuit board manufactured by the multilayer printed circuit board manufacturing method is not particularly limited, and the multilayer printed circuit board may have, for example, one or more layers or one layer depending on its intended use or purpose. Up to the 20th floor.

Hereinafter, the present disclosure will be described in detail with reference to examples. However, the examples according to the present disclosure can be modified into various different forms, and the scope of the present disclosure is not construed as being limited to the following examples. Examples of the present disclosure are provided to explain the present disclosure more completely to those familiar with the field.

Manufacturing example 1

As an aprotic solvent, 242 g of dimethyl sulfoxide, 105 g of thiomalic acid, 137 g of 2-vinyl-4,6-diamino-1,3,5-tri 𠯤 (2-vinyl-4,6-diamino-1,3,5-triazine) and 16 g of azobisisobutyronitrile (azobisisobutyronitrile) are placed in a 1-L reactor, heated to 80°C under stirring, Then keep for 24 hours to obtain a clear solution. The obtained solution is precipitated in methanol, and the formed solid is dried to produce a melamine derivative having the following chemical formula 2:

[Chemical formula 2]

Manufacturing example 2

Put 205 g of dimethylsulfoxide, 105 g of thiomalic acid, 100 g of diallylmelamine, and 16 g of azobisisobutyronitrile as an aprotic solvent into 1-L The reactor was heated to 80°C with stirring, and then kept for 24 hours to obtain a transparent solution. The obtained solution is precipitated in methanol, and the formed solid is dried, thereby producing a melamine derivative having the following chemical formula 3:

[Chemical formula 3]

Manufacturing example 3

Combine 221 g of 10 wt% sodium hydroxide solution, 75 g of glycine, and 146 g of 2-chloro-4,6-diamino-1,3,5-tris (2-chloro -4,6-diamino-1,3,5-triazine) was placed in a 1-L reactor, heated to 80°C under stirring, and then kept for 24 hours to obtain a transparent solution. The obtained solution was precipitated in methanol, and the formed solid was dried, thereby producing a melamine derivative having the following chemical formula 4:

[Chemical formula 4]

Manufacturing example 4 ：Alkali-soluble resin

As a solvent, 543 g of dimethylacetamide (DMAc), 350 g of SMA1000 (manufactured by Cray Valley), 144 g of 4-aminobenzoic acid (PABA), And 49 g of 4-aminophenol (PAP) are placed in 2 liters equipped with thermometer, stirrer, reflux condenser and quantitative moisture analyzer, which can be cooled and can be cooled. Heat the reactor and mix together. After the temperature of the reactor is set to 80°C under a nitrogen atmosphere, the acid anhydride and the aniline derivative are allowed to react continuously for 24 hours to form amic acid. Then, the reactor temperature was set to 150° C., and the imidization reaction was continued for 24 hours to produce an alkali-soluble resin solution with a solid content of 50%.

Manufacturing of insulating layer

Example 1

Prepare a copper substrate with a size of 5 cm * 5 cm as the substrate. A mixture was prepared, which included 100 parts by weight of the resin (synthesized in Manufacturing Example 4) as an alkali-soluble resin, 30 parts by weight of MY-510 (manufactured by Huntsman) as a thermosetting adhesive, and 180 parts by weight as an inorganic filler SC2050MB, 4 parts by weight of the melamine derivative produced in Production Example 1, and 20 parts by weight of DMSO as a solvent. The mixture was applied on a PET film and dried to produce a polymer resin layer with a thickness of 15 μm.

The manufactured polymer resin layer was vacuum-laminated at 85°C until the copper wire was formed on the circuit board on the copper clad laminate. Then remove the PET film. A photosensitive dry film resist KL1015 (manufactured by Kolon Industries) with a thickness of 15 µm was laminated on the polymer resin layer at 110°C.

Place a circular negative photomask with a diameter of 30 µm in contact with the surface of the photosensitive dry film resist, and irradiate the photosensitive dry film resist ^{with UV light (dose of 25 mJ/cm 2 ), and then} Sequentially develop the dry film photoresist and the polymer resin layer with a 1% sodium carbonate developer solution at 30°C. At this time, the photosensitive dry film photoresist with the pattern formed therein serves as the protective layer of the polymer resin layer, so that the same pattern as the photosensitive dry film photoresist is 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 a 3% sodium hydroxide photoresist stripper solution (resist stripper solution) at a temperature of 50°C was used to remove the residue and the photosensitive dry film. Hinder. Then, the polymer resin layer was thermally cured at a temperature of 200° C. for 1 hour to produce an insulating layer.

Example 2

The insulating layer was manufactured in the same manner as in Example 1, except that 4 parts by weight of the melamine derivative manufactured in Manufacturing Example 2 was used instead of the melamine derivative manufactured in Manufacturing Example 1.

Example 3

The insulating layer was manufactured in the same manner as in Example 1, except that 4 parts by weight of the melamine derivative manufactured in Manufacturing Example 3 was used instead of the melamine derivative manufactured in Manufacturing Example 1.

Comparative example 1

The insulating layer was manufactured in the same manner as in Example 1, except that the melamine derivative manufactured in Manufacturing Example 1 was not added.

Comparative example 2

The insulating layer was manufactured in the same manner as in Example 1, but using 4 parts by weight of melamine (Sigma Aldrich) instead of the melamine derivative manufactured in Manufacturing Example 1. As a result, melamine did not dissolve, and the coating was uneven, so evaluation could not be performed.

Manufacturing of multilayer printed circuit boards

Example 4

On the upper surface of the insulating layer manufactured in Example 1, with a mixed gas of argon and oxygen supplied by the deposition system, titanium (Ti) metal and copper (Cu) metal were deposited by sputtering to a thickness of 50 nm and 0.5 µm to form a metal thin film.

Afterwards, 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 through electroplating. Then, using a photosensitive resin removing solution to remove the patterned photosensitive resin layer, and etch away the seed layer exposed by removing the patterned photosensitive resin layer to form a patterned metal layer on the insulating layer, Thus, a multilayer printed circuit board is manufactured.

Example 5 and 6 And a comparative example 3

The multilayer printed circuit board of Example 5 was manufactured in the same manner as Example 4, but the insulating layer manufactured in Example 2 was used instead of the insulating layer manufactured in Example 1.

In addition, the multilayer printed circuit board of Example 6 was manufactured in the same manner as Example 4, but the insulating layer manufactured in Example 3 was used.

In addition, the multilayer printed circuit board of Comparative Example 3 was manufactured in the same manner as in Example 4, but the insulating layer manufactured in Comparative Example 1 was used.

Metal adhesion measurement

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

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

[Table 1] Metal adhesion (kgf/cm) Example 4 0.51 Example 5 0.54 Example 6 0.52 Comparative example 3 0.22

Referring to Table 1 above, it can be confirmed that the multilayer printed circuit boards of Examples 4, 5, and 6 manufactured using the insulating layers of Examples 1, 2, and 3 containing melamine derivatives, respectively, have extremely excellent metal adhesion properties, each being 0.51 kgf /cm, 0.54 kgf/cm and 0.52 kgf/cm. However, it can be confirmed that the multilayer printed circuit board of Comparative Example 3 manufactured using the insulating layer of Comparative Example 1 that does not contain a melamine derivative has extremely low metal adhesion. That is, it can be confirmed that the multilayer printed circuit board according to an embodiment of the present disclosure has excellent adhesion between the insulating layer and the patterned metal layer, which means that the melamine derivative has the effect of improving adhesion.

As described above, the insulating layer for the multilayer printed circuit board according to one embodiment of the present disclosure has excellent adhesion to the patterned metal layer because it contains a melamine derivative.

The multilayer printed circuit board according to another embodiment of the present disclosure has excellent adhesion between the insulating layer containing the melamine derivative and the patterned metal layer.

The insulating layer manufactured by the insulating layer manufacturing method according to yet another embodiment of the present disclosure contains melamine derivatives and has excellent adhesion to the patterned metal layer.

100: Substrate 200, 201, 202: polymer resin layer 300: patterned layer

[Fig. 1] is a schematic diagram showing a method of manufacturing an insulating layer according to an embodiment of the present disclosure.

100: Substrate

200, 201, 202: polymer resin layer

300: patterned layer

Claims (10)

An insulating layer for a multilayer printed circuit board, the insulating layer comprising a patterned polymer resin layer containing an alkali-soluble resin, a thermosetting adhesive, and a melamine derivative, wherein the melamine derivative has the structure of the following chemical formula 1: [Chemical formula 1]

Wherein, A is an alkyl group containing 1 to 6 carboxyl groups, or an amino group containing 1 to 6 carboxyl groups. The insulating layer of claim 1, wherein the polymer resin layer contains a melamine derivative in an amount of 3 to 30 parts by weight based on 100 parts by weight of the alkali-soluble resin. The insulating layer of claim 1, wherein the solubility of the melamine derivative in an aprotic solvent at 25° C. is 5 to 20. The insulating layer of claim 1, wherein the alkali-soluble resin contains: one or more acidic functional groups; and a cyclic amide functional group substituted with one or more amine groups. The insulating layer of claim 1, wherein the thermosetting adhesive contains an epoxy group and one or more functional groups selected from the group consisting of: oxetanyl group, cyclic ether group, ring Shape thioether group, cyano group, maleimide group, and benzoxazine group. A multilayer printed circuit board comprising: an insulating layer as claimed in claim 1; and a patterned metal layer on the insulating layer. Such as the multilayer printed circuit board of claim 6, wherein the patterned metal layer has a value of 0.4 kgf as measured after the multilayer printed circuit board is allowed to stand for 48 hours at a temperature of 135°C and a humidity of 85% according to the IPC-TM-650 standard /cm to 1.2 kgf/cm peel strength. A method of manufacturing the insulating layer according to claim 1, the method comprising the following steps: forming a polymer resin layer containing alkali-soluble resin, thermosetting adhesive and melamine derivative on a substrate; forming a pattern 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 The melamine derivative has the structure of the following chemical formula 1: [Chemical formula 1]

Wherein, A is an alkyl group containing 1 to 6 carboxyl groups, or an amino group containing 1 to 6 carboxyl groups. The method of claim 8, wherein the step of forming the patterned layer on the polymer resin layer includes the following steps: Forming a photosensitive resin layer on the polymer resin layer; and The patterned layer is formed by exposing the photosensitive resin layer and developing an unexposed portion of the photosensitive resin layer with alkali. The method of claim 8, wherein the removal of the patterned layer is performed by processing with a photoresist stripper solution.

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