KR20210052075A - Method for manufacturing insulating film and method for manufacturing multilayered printed circuit board - Google Patents

Abstract

The present invention provides an insulating layer with excellent adhesion to a metal pattern layer, a method for manufacturing the insulating layer with high roughness, and a method for manufacturing a multilayered printed circuit board using the same. The method for manufacturing the insulating layer can manufacture the insulating layer having uniform and high surface roughness by roughening a polymer resin layer containing a surface-treated inorganic filler with an alkaline solution, and the insulating layer of the present invention is manufactured by the method of the present invention to have the uniform and high surface roughness, thereby having excellent adhesion to the metal pattern layer. The method for manufacturing the multilayered printed circuit board can manufacture the multilayered printed circuit board in which the metal pattern layer is stably adhered to the insulating layer having the high surface roughness.

Description

Insulation layer manufacturing method and multilayer printed circuit board manufacturing method {METHOD FOR MANUFACTURING INSULATING FILM AND METHOD FOR MANUFACTURING MULTILAYERED PRINTED CIRCUIT BOARD}

The present invention relates to a method for manufacturing an insulating layer and a method for manufacturing a multilayer printed circuit board. Specifically, it relates to a method of manufacturing an insulating layer having high illuminance and a method of manufacturing a multilayer printed circuit board using the same.

Recently, electronic devices are becoming more compact, lighter, and highly functional. In order to meet the demands of such a recent electronic device field, it is necessary to mount a semiconductor device inside the electronic device, and it is a trend that is realized as the miniaturization and integration level of semiconductor devices are recently improved.

In order for a semiconductor device to receive an electrical signal inside an electronic device, electrical wiring is essential, and in this case, insulation for the semiconductor device and electrical wiring is required for stable electrical signal transmission.

In this way, to connect the electrical wiring of semiconductor devices as well as to form an insulating layer therebetween, a build-up semiconductor packaging process is used, and this semiconductor packaging process improves the integration of functional devices and reduces the size, weight, and high functionality of electronic devices. It has advantages such as structural electrical function integration, assembly time reduction and cost reduction.

In the build-up semiconductor packaging process, in order to form a fine circuit on the insulating layer, adhesion between the build-up insulating layer and the conductive layer, that is, the layer on which the circuit is formed is important. Therefore, generally, a roughening treatment such as a desmear process was accompanied after the formation of the insulating layer.

However, recently, the specific gravity of spherical silica, which is an inorganic filler, is increasing, and the substrate is becoming lighter and thinner.When the roughening treatment is performed with the existing desmear process, it becomes difficult to form a uniform roughness, and a conductive layer formed on the insulating layer. , There has been a problem that the adhesion between the metal pattern layer such as the circuit layer and the insulating layer decreases.

Accordingly, in order to improve the adhesion between the insulating layer and the metal pattern layer, it is necessary to develop a roughening treatment process capable of forming a uniform roughness.

The technical problem to be achieved by the present invention is to provide a method of manufacturing an insulating layer having excellent adhesion with a metal pattern layer and having high roughness, and to provide a method of manufacturing a multilayer printed circuit board using the same.

According to an aspect of the present invention, forming a polymer resin layer comprising an alkali-soluble resin, a thermosetting binder, and a surface-treated inorganic filler on a substrate; Forming a pattern layer on the polymer resin layer; Developing and curing the polymer resin layer on which the pattern layer is formed; Forming a patterned polymer resin layer by removing the pattern layer from the cured polymer resin layer; And roughening the surface of the patterned polymer resin layer with an alkaline solution.

According to another aspect of the present invention, there is provided a method of manufacturing a multilayer printed circuit board comprising; forming a metal pattern layer on the insulating layer manufactured according to an embodiment of the present invention.

Through the method of manufacturing the insulating layer according to an embodiment of the present invention, by forming the surface roughness by detaching the inorganic filler from the surface, the surface roughness is high and uniform, thereby producing an insulating layer having excellent adhesion when a metal pattern layer is formed. It can be done, and the durability of the insulating layer can be excellent by using the surface-treated inorganic filler.

A method of manufacturing a multilayer printed circuit board according to another embodiment of the present invention comprises the step of forming a metal pattern layer on the insulating layer according to an embodiment of the present invention, thereby forming a metal pattern on the insulating layer having a high surface roughness. The layer can be firmly adhered.

1 is a schematic diagram of a method of manufacturing an insulating layer according to an embodiment of the present invention.
2 is a SEM photograph of the surface of the insulating layer of Example 1 or Comparative Example 1. FIG.
3 is an image of an upper surface roughness of an insulating layer of Example 1 or Comparative Example 1. FIG.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

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

The insulating layer manufacturing method according to an embodiment of the present invention comprises the steps of forming a polymer resin layer including an alkali-soluble resin, a thermosetting binder, and a surface-treated inorganic filler on a substrate; Forming a pattern layer on the polymer resin layer; Developing and curing the polymer resin layer on which the pattern layer is formed; Forming a patterned polymer resin layer by removing the pattern layer from the cured polymer resin layer; And roughening the surface of the patterned polymer resin layer with an alkaline solution.

1 shows a schematic diagram of a method of manufacturing an insulating layer according to an embodiment of the present invention. 1, a method of manufacturing an insulating layer according to an embodiment of the present invention. Forming a polymer resin layer 200 on the substrate 100 (1); Forming a pattern layer 300 on the polymer resin layer 200 (2); Developing (3-1) and curing (3-2) the polymer resin layer 200; Removing the pattern layer 300 (4); And a step of performing a harmonic process (5).

Hereinafter, each step will be described in detail.

(1) forming a polymer resin layer including an alkali-soluble resin, a thermosetting binder, and a releasable coated inorganic filler on a substrate

According to one embodiment of the present invention, first, a polymer resin layer, which is the basis of the insulating layer, is formed on a substrate.

The substrate may be a circuit board such as a copper clad laminate, a sheet, a multilayer printed wiring board, a semiconductor material such as a silicon wafer, and the thickness of the polymer resin layer is 1 µm to 500 µm, or 3 µm to 500 µm, or 3 µm to It may be 200 μm, or 1 μm to 60 μm, or 5 μm to 30 μm.

The polymer resin layer may include an alkali-soluble resin, a thermosetting binder, and a releasable coated inorganic filler, and specifically, an alkali-soluble resin, a thermosetting binder, and a polymer resin composition including a releasable coated inorganic filler are prepared and used. Thus, a polymer resin layer can be formed.

The method of forming the polymer resin layer is not limited, but for example, a polymer resin composition is directly applied on a substrate and dried or cured, or a polymer resin composition is applied on a separate carrier film and dried or cured. The polymer resin layer can be formed by laminating on the top and then removing the carrier film. Preferably, after forming an adhesive layer on the substrate, a polymer resin composition is directly coated on the adhesive layer, or a polymer resin layer is formed by coating the polymer resin composition on a carrier film, and then the adhesive layer and the polymer resin layer on the substrate are laminated. A method of forming a polymer resin layer by coating a polymer resin composition on a carrier film, and then forming an adhesive layer on the polymer resin layer and laminating a substrate and an adhesive layer, or the like may be used.

The example of the adhesive layer is not limited to a large extent, and various adhesive layers widely known in the field of semiconductor devices and electrical and electronic materials can be used without limitation, for example, a debondable temporary adhesive or a die bonding film. Attach Film, DAF) can be used.

Alkali soluble resin

According to one embodiment of the present invention, the alkali-soluble resin is an acidic functional group; And at least one or two or more cyclic imide functional groups substituted with an amino group, respectively. Examples of the acidic functional group are not largely limited, but may include, for example, a carboxyl group or a phenol group. The alkali-soluble resin includes at least two or more acidic functional groups, so that the polymer resin layer exhibits higher alkali developability, and the developing speed of the polymer resin layer can be controlled.

The cyclic imide functional group substituted with the amino group includes an amino group and a cyclic imide group in the functional group structure, and may be included in at least two or more. As the alkali-soluble resin contains at least two or more cyclic imide functional groups substituted with the amino group, the alkali-soluble resin has a structure in which a large number of active hydrogens contained in the amino group are present, and thus, it is combined with a thermosetting binder during thermal curing. As the reactivity is improved, the curing density can be increased to increase heat resistance reliability and mechanical properties.

In addition, as a plurality of cyclic imide functional groups are present in the alkali-soluble resin, the polarity is increased by the carbonyl group and tertiary amine group included in the cyclic imide functional group, thereby increasing the interfacial adhesion of the alkali-soluble resin. Accordingly, the polymer resin layer containing the alkali-soluble resin may increase the interfacial adhesion with the metal layer laminated thereon, and specifically, may have higher adhesion than the interfacial adhesion between the carrier film and the metal layer laminated on the metal layer. Thus, as described later, physical peeling between the carrier film and the metal layer may be possible.

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

[Formula 1]

In Formula 1, R1 is an alkylene group or alkenyl group having 1 to 10 carbon atoms, or 1 to 5, or 1 to 3, and "*" means a bonding point. The alkylene group is a divalent functional group derived from alkane, for example, as a straight chain, branched or cyclic, methylene group, ethylene group, propylene group, isobutylene group, sec-butylene group, It may be a tert-butylene group, a pentylene group, a hexylene group, and the like. One or more hydrogen atoms included in the alkylene group may be substituted with other substituents, 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, and 6 Aryl group of to 12, heteroaryl group of 2 to 12 carbon atoms, arylalkyl group of 6 to 12 carbon atoms, halogen atom, cyano group, amino group, amidino group, nitro group, amide group, carbonyl group, hydroxy group, sulfonyl group, carba A mate group, a C1-C10 alkoxy group, etc. are mentioned.

The term "substituted" means that other functional groups are bonded in place of a hydrogen atom in the compound, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent can be substituted, and when two or more are substituted, two or more The substituents may be the same or different from each other.

The alkenyl group means containing one or more carbon-carbon double bonds in the middle or terminal of the above-described alkylene group, and examples thereof include ethylene, propylene, butylene, hexylene, and acetylene. . At least one hydrogen atom in the alkenyl group may be substituted with the same substituent as in the case of the alkylene group.

Preferably, the cyclic imide functional group substituted with the amino group may be a functional group represented by the following formula (2).

[Formula 2]

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

As described above, the alkali-soluble resin includes a cyclic imide functional group substituted with an amino group together with an acidic functional group, and specifically, an acidic functional group is bonded to at least one end of the cyclic imide functional group substituted with the amino group can do. At this time, the cyclic imide functional group substituted with the amino group and the acidic functional group may be bonded via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, for example, a cyclic type substituted with the amino group An acidic functional group may be bonded to the terminal of the amino group included in the imide functional group via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and already included in the cyclic imide functional group substituted with the amino group. The acidic functional group may be bonded to the terminal of the de functional group via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group.

More specifically, the terminal of the amino group included in the cyclic imide functional group substituted with the amino group means a nitrogen atom included in the amino group in Formula 1, and already included in the cyclic imide functional group substituted with the amino group. The terminal of the de functional group may mean a nitrogen atom included in the cyclic imide functional group in Formula 1 above.

The alkylene group is a divalent functional group derived from alkane, for example, as a straight chain, branched or cyclic, methylene group, ethylene group, propylene group, isobutylene group, sec-butylene group, It may be a tert-butylene group, a pentylene group, a hexylene group, and the like. One or more hydrogen atoms included in the alkylene group may be substituted with other substituents, 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, and 6 Aryl group of to 12, heteroaryl group of 2 to 12 carbon atoms, arylalkyl group of 6 to 12 carbon atoms, halogen atom, cyano group, amino group, amidino group, nitro group, amide group, carbonyl group, hydroxy group, sulfonyl group, carba A mate group, a C1-C10 alkoxy group, etc. are mentioned.

The arylene group is a divalent functional group derived from arene, for example, a cyclic type, and may be a phenyl group, a naphthyl group, or the like. One or more hydrogen atoms included in the arylene group may be substituted with other substituents, 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, and 6 carbon atoms. Aryl group of to 12, heteroaryl group of 2 to 12 carbon atoms, arylalkyl group of 6 to 12 carbon atoms, halogen atom, cyano group, amino group, amidino group, nitro group, amide group, carbonyl group, hydroxy group, sulfonyl group, carba A mate group, a C1-C10 alkoxy group, etc. are mentioned.

Examples of the method for producing the alkali-soluble resin are not limited to a large extent, for example, a cyclic unsaturated imide compound; And it may be prepared through the reaction of an amine compound. At this time, the cyclic unsaturated imide compound; And at least one or more of the amine compound may include an acidic functional group substituted at the terminal. That is, an acidic functional group may be substituted at the terminal of the cyclic unsaturated imide compound, the amine compound, or both of these compounds. The contents of the acidic functional group are as described above.

The cyclic imide compound is a compound containing the aforementioned cyclic imide functional group, and the cyclic unsaturated imide compound refers to a compound containing at least one or more unsaturated bonds, that is, double bonds or triple bonds in the cyclic imide compound. do.

The alkali-soluble resin may be prepared through a reaction of an amino group included in the amine compound and a double bond or a triple bond included in the cyclic unsaturated imide compound.

Examples of the weight ratio for reacting the cyclic unsaturated imide compound and the amine compound are not largely limited, for example, 10 to 80 parts by weight of the amine compound based on 100 parts by weight of the cyclic unsaturated imide compound, Alternatively, it may be reacted by mixing in 30 to 60 parts by weight.

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

The monofunctional N-substituted maleimide compound is a compound in which a functional group is substituted with a nitrogen atom included in one maleimide compound, and the polyfunctional N-substituted maleimide compound has a nitrogen atom contained in each of two or more maleimide compounds. It is a compound bonded by means of.

In the monofunctional N-substituted maleimide compound, the functional group substituted with the nitrogen atom included in the maleimide compound may include, without limitation, various known aliphatic, alicyclic or aromatic functional groups, and the functional group substituted with the nitrogen atom May include a functional group in which an acidic functional group is substituted with an aliphatic, alicyclic or aromatic functional group. The contents of the acidic functional group are as described above.

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

In the polyfunctional N-substituted maleimide compound, the functional group that mediates the bond between nitrogen atoms included in each of the two or more maleimide compounds may include, without limitation, various known aliphatic, alicyclic or aromatic functional groups, and specific examples , 4,4'-diphenylmethane functional groups, etc. may be used. The functional group substituted with the nitrogen atom may include a functional group in which an acidic functional group is substituted with an aliphatic, alicyclic or aromatic functional group. The contents of the acidic functional group are as described above.

Specific examples of the polyfunctional N-substituted maleimide compound include 4,4'-diphenylmethane bismaleimide (Daiwakasei's BMI-1000, BMI-1100, etc.), phenylmethane bismaleimide, m-phenylenemethane bismalei Mid, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide Mid, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, etc. are mentioned.

The amine compound may be a primary amine compound containing at least one amino group (-NH2) in the molecular structure, more preferably a carboxylic acid compound substituted with an amino group, a polyfunctional amine compound containing two or more amino groups, or these Mixtures of can be used.

In the carboxylic acid compound substituted with the amino group, the carboxylic acid compound is a compound containing a carboxylic acid (-COOH) functional group in the molecule, and may include all aliphatic, alicyclic, or aromatic carboxylic acids depending on the type of hydrocarbon bonded to the carboxylic acid functional group. . Through the carboxylic acid compound substituted with the amino group, a plurality of carboxylic acid functional groups, which are acidic functional groups, are included in the alkali-soluble resin, so that the developability of the alkali-soluble resin may be improved.

The term "substituted" means that other functional groups are bonded instead of hydrogen atoms in the compound, and the position at which the amino group is substituted in the carboxylic acid compound is not limited as long as the position where the hydrogen atom is substituted, and the number of amino groups to be substituted is 1 or more. I can.

Specific examples of the amino group-substituted carboxylic acid compounds include 20 kinds of α-amino acids, 4-aminobutanoic acids, 5-aminopentanoic acids, 6-aminohexanoic acids, 7-aminoheptanoic acids, and 8 known as raw materials for proteins. -Aminooctanoic acid, 4-aminobenzoic acid, 4-aminophenylacetic acid, 4-amino cyclohexane carboxylic acid, etc. are mentioned.

In addition, the polyfunctional amine compound containing two or more amino groups is a compound containing two or more amino groups (-NH2) in a molecule, and may include all aliphatic, alicyclic, or aromatic polyfunctional amines depending on the type of hydrocarbon bonded to the amino group. . Flexibility, toughness, copper foil adhesion, and the like of the alkali-soluble resin may be improved through the polyfunctional amine compound including two or more amino groups.

Specific examples of the polyfunctional amine compound containing two or more amino groups, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis(aminomethyl)-cyclohexane, 1,4-bis (Aminomethyl)-cyclohexane, bis(aminomethyl)-norbornene, octahydro-4,7-methanoindene-1(2), 5(6)-dimethanamine, 4,4'-methylenebis( Cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), isophoronediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,5-dimethyl-1,4 -Phenylenediamine, 2,3,5,6,-tetramethyl-1,4-phenylenediamine, 2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2,3,5 ,6-tetrafluoro-1,4-phenylenediamine, 4,6-diaminoresorcinol, 2,5-diamino-1,4-benzenedithiol, 3-aminobenzylamine, 4-aminobenzyl Amine, 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-diisopropylbenzene, 1,3-bis[2-(4- Aminofe Nyl)-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) Si)-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-aminobenzoxazole, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5 -Amine, 4,6-diaminoresorcinol, 2,3,5,6-pyridine tetraamine, a polyfunctional amine containing a siloxane structure of Shin-Etsu silicone (PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, X-22-9409), polyfunctional amines including Dow Corning's siloxane structure (Dow Corning 3055), including polyether structures Polyfunctional amines (Huntsman company, BASF company), etc. are mentioned.

In addition, the alkali-soluble resin is a repeating unit represented by the following formula (3); And at least one or more repeating units represented by the following Chemical Formula 4, respectively.

[Formula 3]

In Formula 3, 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 "*" means a bonding point,

[Formula 4]

In Formula 4, 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, and R4 is -H, -OH, -NR5R6, halogen, or An alkyl group having 1 to 20 carbon atoms, and R5 and R6 may each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and "*" means a bonding point.

Preferably, in Formula 3, R2 is phenylene, in Formula 4, R3 is phenylene, and R4 may be -OH.

On the other hand, the alkali-soluble resin is a repeating unit represented by the formula (3); And it may further include a vinyl-based repeating unit in addition to the repeating unit represented by the 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 limited, for example, ethylene, propylene, isobutylene. , Butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, or maleimide.

A repeating unit represented by Formula 3 above; And the alkali-soluble resin each containing at least one or more repeating units represented by Formula 3 is a reaction of a polymer including a repeating unit represented by Formula 5, an amine represented by Formula 6, and an amine represented by Formula 7 below. Can be manufactured.

[Formula 5]

[Formula 6]

[Formula 7]

In Formulas 5 to 7, R2 to R4 are the same as those described above in Formulas 3 and 4, and "*" means a bonding point.

Specific examples of the polymer including the repeating unit represented by Chemical Formula 5 are not largely limited, for example, SMA of Cray valley, Xiran of Polyscope, Scripset of Solenis, Isobam of Kuraray, Polyanhydride resin of Chevron Phillips Chemical, Lindau Chemicals. Maldene of the company, etc. are mentioned.

In addition, the repeating unit represented by the above-described formula (3); And the alkali-soluble resin each including at least one or more repeating units represented by Formula 3 may be prepared by a reaction of a compound represented by Formula 8 below and a compound represented by Formula 9.

[Formula 8]

[Formula 9]

In Formulas 8 to 9, R2 to R4 are the same as those described above in Formulas 3 and 4.

In addition, as the alkali-soluble resin, a conventionally known 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 phenol group-containing resin may be mixed with the carboxy group-containing resin or the carboxy group-containing resin.

The carboxy group-containing resin may be any one of the resins (1) to (7) listed below.

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

(2) a carboxy group-containing resin obtained by reacting a bifunctional epoxy resin with a bifunctional phenol and/or a dicarboxyl group and then reacting a polybasic acid anhydride,

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

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

(5) A polyamic acid resin obtained by reacting diamine and dianhydride or a copolymer resin of a polyamic acid resin

(6) Polyacrylic acid resin reacted with acrylic acid or copolymer of polyacrylic acid resin

(7) Polymaleic anhydride resin reacted with maleic anhydride and a resin prepared by ring-opening the anhydride of the polymaleic anhydride resin copolymer with weak acid, diamine, imidazole, dimethyl sulfoxide, etc. Although it can be mentioned, it is not limited to these.

More specific examples of the carboxy group-containing resin include CCR-1291H from Nippon Explosives, SHA-1216CA60 from Shin-A T&C, Noverite K-700 from Lubrizol, or a mixture of two or more thereof.

Examples of the phenol group-containing resin are not largely limited, for example, novolac resins such as phenol novolac resin, cresol novolac resin, bisphenol F (BPF) novolac resin, or 4,4'-(1-(4) -(2-(4-hydroxyphenyl)propan-2-yl)phenyl)ethane-1,1-diyl)diphenol [4,4'-(1-(4-(2-(4-Hydroxyphenyl)) Bisphenol A resins such as propan-2-yl)phenyl)ethane-1,1-diyl)diphenol] 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 by KOH titration. Although an example of a method of measuring the acid value of the alkali-soluble resin is not largely limited, for example, the following method may be used. A 0.1 N KOH solution (solvent: methanol) was prepared as a base solution, and alpha-naphtholbenzein (pH: 0.8 ~ 8.2 yellow, 10.0 blue green) was prepared as an indicator. I did. Then, about 1 to 2 g of an alkali-soluble resin as a sample was taken and dissolved in 50 g of a dimethylformaldehyde (DMF) solvent, and then a marker was added, followed by titration with a base solvent. The acid value was calculated in units of mg KOH/g as the amount of the base solvent used at the time of completion of the titration.

When the acid value of the alkali-soluble resin is excessively reduced to less than 50 mgKOH/g, the developability of the alkali-soluble resin is lowered, and it may be difficult to proceed with the developing process. In addition, when the acid value of the alkali-soluble resin is excessively increased to more than 250 mgKOH/g, phase separation with other resins may occur due to increased polarity.

Thermosetting binder

The thermosetting binder may include at least one functional group selected from the group consisting of a thermosetting functional group, an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyanide group, a maleimide group, and a benzoxazine group, and an epoxy group. That is, the thermosetting binder necessarily contains an epoxy group, and in addition to the epoxy group, an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyanide group, a maleimide group, a benzoxazine group, or their It may contain a mixture of two or more. Such a thermosetting binder can secure heat resistance or mechanical properties of the insulating layer by forming a crosslinking bond with an alkali-soluble resin or the like through heat curing.

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

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 a molecule.

The thermosetting binder containing two or more cyclic (thio) ether groups in the molecule includes a compound having at least two or more of one or two groups of 3, 4 or 5 membered cyclic ether groups, or cyclic thioether groups in the molecule. can do.

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 Co., Ltd. and the like.

In addition, the polyfunctional resin compound is a polyfunctional epoxy compound containing at least two or more epoxy groups in the molecule, a polyfunctional oxetane compound containing at least two or more oxetanyl groups in the molecule, or episulfation containing two or more thioether groups in the molecule. A feed resin, a polyfunctional cyanate ester compound containing at least two or more cyanide groups in the molecule, or a polyfunctional benzoxazine compound containing at least two or more benzoxazine groups in the molecule may be included.

Specific examples of the polyfunctional epoxy compound include, for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin. , Phenol novolak type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, gly Oxal type epoxy resin, amino group-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, diglycidylphthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoylethane resin, silicone modified epoxy resin and ε-caprolactone-modified epoxy resins. Further, in order to impart flame retardancy, one in which an atom such as phosphorus is introduced into the structure may be used. By thermosetting these epoxy resins, properties such as adhesion of the cured film, solder heat resistance, and electroless plating resistance are improved.

Examples of the polyfunctional oxetane compound include 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)methylacrylic Rate, (3-ethyl-3-oxetanyl)methylacrylate, (3-methyl-3-oxetanyl)methylmethacrylate, (3-ethyl-3-oxetanyl)methylmethacrylate or these In addition to polyfunctional oxetanes such as oligomers or copolymers, oxetane alcohol and novolac resins, poly(p-hydroxystyrene), cardo-type bisphenols, carixarenes, carixresolecin arenes, or silses And ether products with resins having a hydroxy group such as quioxane. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate may be mentioned.

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, novolac-type cyanate ester resin of bisphenol A, biphenol-type cyanate ester resin or oligomers or copolymers thereof Coalescence, etc. are mentioned.

Examples of the multifunctional maleimide compound include 4,4'-diphenylmethane bismaleimide, phenylmethane bismaleimide, and 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-phenylene bismaleimide, 1,6'- bismaleimide Mid-(2,2,4-trimethyl)hexane (1,6'-bismaleimide-(2,2,4-trimethyl)hexane) and the like.

Examples of the polyfunctional benzoxazine compound include bisphenol A-type benzoxazine resin, bisphenol F-type benzoxazine resin, phenolphthalein-type benzoxazine resin, thiodiphenol-type benzoxazine resin, dicyclo pentadiene-type benzoxazine resin, 3,3' -(Methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine (3,3'-(methylene-1,4-diphenylene)bis(3,4- dihydro-2H-1,3-benzoxazine) resin, etc. are mentioned.

More specific examples of the polyfunctional resin compound include Kukdo Chemical's YDCN-500-80P, Ronza's phenol novolak-type cyanate Ethner resin PT-30S, Daiwa's phenylmethane-type maleimide resin BMI-2300, and Shikoku's Pd Type benzoxazine resin, etc. are mentioned.

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

Releasable coated inorganic filler

According to an embodiment of the present invention, the surface-treated inorganic filler comprises: silane-modifying the surface of the inorganic filler by mixing an inorganic filler and an epoxy silane-based compound; And releasing the surface of the silane-modified inorganic filler by mixing the silane-modified inorganic filler with an oxidizing agent.

By mixing the inorganic filler and the epoxy silane compound by stirring for 10 to 60 minutes, the surface of the inorganic filler may be modified with silane. Specifically, the surface of the inorganic filler may be silane-modified by bonding the epoxy silane-based compound to the surface of the inorganic filler by chemical reaction.

By mixing the silane-coated inorganic filler with an oxidizing agent by stirring for 10 to 60 minutes, the oxidizing agent may perform a release treatment on the surface of the silane-modified inorganic filler. Specifically, the oxidizing agent may react with the silane of the silane-modified inorganic filler to perform a release treatment on the surface, and a surface-treated inorganic filler may be obtained to have a release property.

The surface-treated inorganic filler has a high releasability on a part of the surface and a high bonding strength with the alkali-soluble resin contained in the insulating layer, so that the durability of the insulating layer is excellent, while being easily used on the upper surface of the insulating layer. Desorption can form high illuminance.

The surface-treated inorganic filler can be detached from the upper surface of the polymer resin layer in the process of roughening the polymer resin layer with a basic solution, and the depth of the surface roughness of the polymer resin layer is proportional to the diameter of the releasable coated inorganic filler. Therefore, it is possible to uniformly form the roughness, and by using inorganic fillers of various diameters according to the purpose, it is possible to achieve a required degree of roughness.

The inorganic filler may be one or more of silica, barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica, and preferably silica.

The epoxy silane-based compound may be mixed with the inorganic filler in an amount of 0.3 to 3 parts by weight based on 100 parts by weight of the inorganic filler. When the epoxy silane-based compound is mixed with the inorganic filler within the above content range, there may be an effect of improving mechanical properties through crosslinking of the alkali-soluble resin and the filler.

The epoxy silane compound is 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-[2,3-epoxypropoxypropyl]methyldimethoxysilane, 3-[2, It may be one or more of 3-epoxypropoxypropylmethyldiethoxysilane, 2-[3,4-epoxycyclohexyl]ethylmethyldimethoxysilane, and 2-[3,4-epoxycyclohexyl]ethyltrimethoxysilane. .

According to one embodiment of the present invention, the oxidizing agent may be mixed in an amount of 0.1 to 1.5 parts by weight based on 100 parts by weight of the inorganic filler. When the oxidizing agent is mixed with the silane-coated inorganic filler within the above content range, not only the release treatment, but also the remaining epoxy silane-based compound not combined with the oxidizing agent may react with the resin, thereby improving mechanical properties.

According to an embodiment of the present invention, the oxidizing agent may include at least one of a fluorine-based organic acid and an anhydride of the fluorine-based organic acid, and specifically, the fluorine-based organic acid is trifluoroacetic acid, 3,3,3-trifluoro Ropeanoic acid, 4,4,4-trifluorobutyric acid, 2,2,3,3-tetrafluoro-3-(trifluoroethoxy)propionic acid, 3-(trifluoromethyl)benzoic acid, 4 -(Trifluoromethyl)benzoic acid, (3,3,3-trifluoro-2-methoxy-2-phenylpropanoyl)3,3,3-trifluoro-2-methoxy-2- Phenylpropanoic acid, benzoic trifluoroacetic acid, aspirin trifluoroacetic acid, 2-cyanoacetic trifluoroacetic acid, phenylacetic trifluoroacetic acid, buta-2,3-dienoic trifluoroacetic acid and acrylic- One or more of fluorine-based organic acids such as trifluoroacetic acid may be included, and the oxidizing agent may include one or more of these fluorine-based organic acids and anhydrides of each of the fluorine-based organic acids.

Other additives

The polymer resin layer may further include one or more additives selected from the group consisting of a thermosetting catalyst, a leveling agent, a dispersant, a release agent, and a metal adhesion promoter.

The thermosetting catalyst serves to accelerate the thermosetting of the thermosetting binder. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine compound; Hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. In addition, as commercially available ones, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ manufactured by Shikoku Kasei Kogyo (all are brand names of imidazole compounds), U-CAT3503N, UCAT3502T manufactured by San Apro (All are trade names of dimethylamine block isocyanate compounds), DBU, DBN, U-CAT A102, U-CAT5002 (all bicyclic amidine compounds and salts thereof), and the like. It is not particularly limited to these, and may be a thermosetting catalyst of an epoxy resin or an oxetane compound, or a reaction between an epoxy group and/or an oxetanyl group and a carboxyl group, and may be used alone or in combination of two or more . In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine-isosaanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isosaanuric acid S-triazine derivatives such as adducts can also be used, and preferably, compounds that also function as adhesion-imparting agents can be used in combination with the thermosetting catalyst.

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

The metal adhesion promoter may be a material that does not cause a problem in the surface deterioration or transparency of the metal material, for example, a silane coupling agent or an organometallic coupling agent.

The leveling agent serves to remove popping or craters on the surface during film coating, and for example, BYK-380N, BYK-307, BYK-378, BYK-350, etc. of BYK-Chemie GmbH may be used.

In addition, the polymer resin layer may further include a resin or elastomer having a molecular weight of 5000 g/mol or more capable of causing phase separation. Accordingly, a roughening treatment of the cured product of the polymer resin layer may be possible. An example of a method for measuring the molecular weight of the resin or elastomer having a molecular weight of 5000 g/mol or more is not limited, for example, it means a weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analysis device, a detector such as a Refractive Index Detector, and a column for analysis may be used. Conditions, solvents, and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 30, a chloroform solvent, and a flow rate of 1 mL/min.

In addition, the polymer resin layer may further include a thermosetting binder including a photoreactive unsaturated group or an alkali-soluble resin including a photoreactive unsaturated group and a photoinitiator in order to impart photocurable properties to the polymer resin layer. Specific examples of the thermosetting binder including the photoreactive unsaturated group, the alkali-soluble resin including the photoreactive unsaturated group, and the photoinitiator are not limited thereto, and various compounds used in the technical field related to the photocurable resin composition may be used without limitation.

The content of the photoinitiator contained in the polymer resin layer may be 0.01% by weight or less based on the total weight of the polymer resin layer. When the content of the photoinitiator contained in the polymer resin layer is 0.01% by weight or less based on the total weight of the polymer resin layer, it may mean that the content of the photoinitiator contained in the polymer resin layer is very insignificant or no photoinitiator is included. . Accordingly, the interfacial desorption property with the insulating layer or the conductive layer that may be generated by the photoinitiator may be reduced, and thus the adhesion and durability of the insulating layer may be improved.

(2) forming a pattern layer on the polymer resin layer

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

The term “pattern layer” means that a pattern can be formed on the polymer resin layer by developing the exposed area by exposing some areas of the polymer resin layer as they are and not exposing some areas of the polymer resin layer. do. That is, the pattern layer functions as a resist mask capable of transferring a pattern of the pattern layer onto the polymer resin layer by exposing some areas of the polymer resin layer to be developed and protecting some areas from development.

The method of forming the pattern layer is not particularly limited, and as an example, the pattern layer may be formed using a photosensitive resin layer.

The forming of the pattern layer on the polymer resin layer may include forming a photosensitive resin layer on the polymer resin layer; And forming a pattern layer by exposing the photosensitive resin layer to light and alkali developing the photosensitive resin layer in an unexposed region.

An example of a method of forming the photosensitive resin layer on the polymer resin layer is not limited, for example, a method of laminating a photosensitive resin in the form of a film such as a photosensitive dry film resist on the polymer resin layer, or a spray or dipping method As a result, a photosensitive resin composition may be coated on the polymer resin layer and then pressed.

The photosensitive resin layer includes a polymer in which a molecular structure is changed and physical properties are changed by an action of light, and a photosensitive dry film resist (DFR) or a liquid resist may be used. The photosensitive resin layer may exhibit photosensitivity and alkali solubility. Accordingly, the molecular structure may be modified by an exposure process of irradiating light onto the photosensitive resin layer, and the resin layer may be etched or removed by a developing process of contacting an alkaline developer.

Accordingly, when a portion of the photosensitive resin layer is selectively exposed and then alkali developed, the exposed portion is not developed, and only the unexposed portion may be selectively etched and removed. In this way, a part of the photosensitive resin layer that is not alkali developed by exposure and remains as it may be the pattern layer.

That is, as an example of a method of exposing the photosensitive resin layer, a photomask having a predetermined pattern formed on the photosensitive resin layer is contacted and irradiated with ultraviolet rays, or a predetermined pattern included in the mask is imaged through a projection objective lens. Then, the photosensitive resin layer may be selectively exposed through a method such as irradiating ultraviolet rays or performing direct imaging using a laser diode as a light source and then irradiating ultraviolet rays. In this case, the ultraviolet rays may be irradiated under a light quantity condition of 5mJ/cm2 to 600mJ/cm2.

In addition, an example of a method of developing alkali after exposure to the photosensitive resin layer includes a method of treating an alkali developer. Examples of the alkali developer are not largely limited, but, for example, the concentration and temperature of an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, amines, etc. It can be used by adjusting and an alkali developer sold as a product can also be used. A specific amount of the alkali developer is not limited, but it needs to be adjusted to a concentration and temperature that does not damage the pattern layer. For example, an aqueous solution of 0.5 to 3% sodium carbonate of 25 to 35 may be used.

The thickness of the pattern layer formed on the polymer resin layer may be 1 µm to 500 µm, or 3 µm to 500 µm, or 3 µm to 200 µm, or 1 µm to 60 µm, or 5 µm to 30 µm. When the thickness of the pattern layer is excessively increased, the resolution of the polymer resin layer may decrease.

(3) developing and curing the polymer resin layer

According to an embodiment of the present invention, the polymer resin layer on which the pattern layer is formed is developed and cured. Specifically, after developing the polymer resin layer in which a partial region is exposed by the pattern layer to form a pattern on the polymer resin layer, the polymer resin layer is thermally cured or photocured.

That is, in the step of developing the polymer resin layer exposed by the pattern layer, the pattern layer remains as it is used as a resist mask due to the characteristic that it is not removed by a developer, and an alkali developer is used as a photosensitive resin layer through the opening of the pattern layer. It can contact the polymer resin layer located at the bottom. In this case, since the polymer resin layer contains an alkali-soluble resin, it has alkali solubility that is dissolved by an alkali developer, and thus a portion of the polymer resin layer in contact with the developer may be dissolved and removed.

Accordingly, the polymer resin layer exposed by the pattern layer refers to a portion of the polymer resin layer whose surface does not contact the pattern layer, and the step of alkali developing the polymer resin layer exposed by the pattern layer includes an alkali developer. It may include the step of passing through and contacting the lower polymer resin layer.

By the developing step, the polymer resin layer may be patterned in the same form as the pattern of the pattern layer on the polymer resin layer.

After developing the polymer resin layer as described above, it may be cured, specifically, thermal curing or photocuring. By including the step of curing the polymer resin layer, it is possible to minimize damage to the polymer resin layer during subsequent removal of the pattern layer.

Through the curing step of the polymer resin layer, a main chain including an ester bond may be formed in the polymer resin block. Examples of the ester bond include a method of photocuring through an acrylic resin in which acrylic acid is ester bonded, or thermosetting so that an ester bond is formed by a reaction of a carboxylic acid and an epoxy.

At this time, the specific thermal curing conditions are not limited, and preferable conditions may be adjusted according to the method of removing the pattern layer. For example, when removing the pattern layer by treating the photoresist stripper, the step of thermally curing the polymer resin layer may be performed at a temperature of 60 to 150° C. for 5 minutes to 2 hours. If the heat curing temperature of the polymer resin layer is too low or the heat curing time is short, the polymer resin layer may be damaged by the stripper, and the heat curing temperature of the polymer resin layer is high, or the heat curing time is prolonged. If so, it may be difficult to remove the pattern layer by the stripper, and excessive warpage may occur in the polymer resin layer.

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

(4) Step of removing the pattern layer

According to one embodiment of the present invention, a patterned polymer resin layer is formed by removing the pattern layer from the cured polymer resin layer.

When removing the pattern layer, it is preferable to use a method capable of removing only the pattern layer while not removing the lower polymer resin layer as much as possible.

The removal of the pattern layer may be performed by any one of a photoresist stripper treatment, a desmear process, and a plasma etching method, or the above methods may be used in combination.

Although the example of the treatment method using the photoresist stripper is not limited, for example, it can be used by controlling the concentration and temperature of an alkaline aqueous solution such as potassium hydroxide and sodium hydroxide, and Atotech's Resistrip product line, Oalchem's ORC-731 , ORC-723K, ORC-740, SLF-6000, and other commercially available products can also be used. The specific amount of the photoresist stripper is not limited, but it needs to be adjusted to a concentration and temperature that does not damage the lower polymer resin layer pattern.For example, 1 to 5% sodium hydroxide aqueous solution of 25 to 60 is used. I can.

An example of a peeling method using the desmear process is not limited, for example, Securiganth E, Securiganth HP, Securiganth BLG, Securiganth MV SWELLER, Securiganth SAP SWELLER, Securiganth P Permanganate chemicals such as 500, Securiganth MV ETCH P, Securiganth SAP ETCH P, Securiganth E Reduction Cleaner, Securiganth HP Reduction Cleaner, Securiganth BLG Reduction Cleaner, Securiganth MV Reduction Cleaner, Securiganth SAP Reduction Cleaner, etc. As process chemicals, commercially available products such as sweller drugs such as ORC-310A, ORC-315A, ORC-315H, ORC-312, permanganate drugs such as ORC-340B, and reducing agent drugs such as ORC-370 and ORC-372 are used for each process. It can be used according to the conditions.

In addition, according to an embodiment of the present invention, after the step of removing the pattern 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, as described above, secondary curing may be performed on the patterned polymer resin layer after the removing step of the pattern layer as described above. Through this, the chemical resistance of the finally manufactured insulating layer may be improved.

Specific examples of the curing method are not largely limited, and both thermal curing or photocuring methods may be used without limitation, and may be cured at a temperature of 150° C. to 250° C. for 0.1 to 10 hours.

(5) Harmonization processing step

According to one embodiment of the present invention, the patterned surface of the polymer resin layer is roughened with an alkaline solution.

Conventionally, surface roughness was formed by roughening treatment by desmear treatment, vacuum plasma treatment, etc., but the relative specific gravity of spherical silica, which is an inorganic filler, is increased due to the recent light and thinner reduction of the substrate, so even if the roughening treatment is performed, the roughness is not formed. Even if is formed, it was not uniform, and the adhesion to the metal pattern layer and the like was remarkably reduced afterwards.

According to one embodiment of the present invention, in the case of roughening treatment with the alkaline solution, the releasable coated inorganic filler may be detached from the upper surface of the patterned polymer resin layer. Accordingly, irregularities may be formed on the surface of the patterned polymer resin layer, and since the depth of the surface roughness of the polymer resin layer is proportional to the diameter of the releasable coated inorganic filler, uniform roughness can be obtained.

Since the releasable coating is formed on the surface of the inorganic filler, the releasable-coated inorganic filler can be easily removed from the patterned polymer resin layer by being treated with an alkaline solution.

According to one embodiment of the present invention, the alkaline solution may have a pH of 9 to pH 13 or a pH of 10 to pH 13.

The alkaline solution can be used by adjusting the concentration and temperature of aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, tetramethylammonium hydroxide, and amines. Solutions can be applied. Commercial products include ORC-730, ORC-725, SLF-6000, SLF-7000 from ORcam, DR-56, DR-78, DR-79, DR-11, DR-10, DR-50, QDR from YMT. -20, DR-12, Hwabaek Engineering's ST-201, etc. can be used, but are not limited to the products listed above. For example, the alkaline solution may be a 3% to 5% sodium hydroxide aqueous solution.

When uniform roughness is formed on the surface of the patterned polymer resin layer by roughening treatment with an alkaline solution, adhesion with the metal layer may be improved when it is subsequently applied to a multilayer printed circuit board or the like.

Insulating layer

The insulating layer according to another embodiment of the present invention is positioned on a substrate and may be manufactured by a method according to an embodiment of the present invention.

The insulating layer according to an embodiment of the present invention is roughened with an alkaline solution to form a uniform roughness by desorption of the releasable coated inorganic filler from the surface, and since it is applied to a multilayer printed circuit board, adhesion to the metal layer is improved. It can be excellent.

The insulating layer may be used as an interlayer insulating material such as a multilayer printed circuit board, and may include a cured product of a polymer resin composition including an alkali-soluble resin, a thermosetting binder, and a release-treated inorganic filler, and the alkali-soluble resin, Details of the thermosetting binder and the release-treated inorganic filler are as described above.

Multilayer printed circuit board manufacturing method

A method of manufacturing a multilayer printed circuit board according to another embodiment of the present invention includes forming a metal pattern layer on the insulating layer manufactured by the method according to an embodiment of the present invention.

The “metal pattern layer” may mean a patterned metal layer. The forming of the metal pattern layer may include forming a metal thin film on the insulating layer; Forming a pattern layer on the metal thin film; Depositing a metal on the metal thin film exposed by the pattern layer; And removing the pattern layer and removing the metal thin film exposed by removing the pattern layer.

As the insulating layer manufactured by the method according to the embodiment of the present invention includes a certain opening pattern, in the process of newly laminating a metal pattern layer on the insulating layer, the inside of the opening pattern is filled with metal, so that insulation Based on the layer, it was confirmed that metal substrates located at the upper and lower portions were connected to each other to manufacture a multilayer printed circuit board, and the invention was completed.

It may further include forming a surface treatment layer on the insulating layer before the step of forming the metal thin film. Through this, adhesion between the metal pattern layer and the insulating layer may be further improved.

Specifically, as an example of a method of forming a surface treatment layer on the insulating layer, at least one of an ion assist reaction method, an ion beam treatment method, and a plasma treatment method may 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 including a reactive functional group may be formed on the surface of the insulating layer. Another example of a method of forming a surface treatment layer on the insulating layer may be a method of depositing a chromium (Cr) or titanium (Ti) metal having a thickness of 50 nm to 300 nm on the surface of the insulating layer.

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

On the other hand, specific examples of the wet deposition process include electroless plating of various metals, and electroless copper plating is common.

In the step of forming the pattern layer on the metal thin film, the information on the formation of the pattern layer may include the details described above in the exemplary embodiment.

In the step of depositing a metal on the metal thin film exposed by the pattern layer, the metal thin film exposed by the pattern layer refers to a portion of the metal thin film on the surface that is not in contact with the pattern layer. Copper may be used as the deposited metal, and examples of the deposition method are not largely limited, and various known physical or chemical vapor deposition methods may be used without limitation, and an electrolytic copper plating method may be used as a general-purpose example. .

In the step of removing the pattern layer and removing the metal thin film exposed by removing the pattern layer, the metal thin film exposed by removing the pattern layer refers to a portion of the metal thin film that has been in contact with the pattern layer on the surface. The content of the pattern layer removal may include the content described above in the embodiment.

The multilayer printed circuit board manufactured by the multilayer printed circuit board manufacturing method may be used again as a build-up material, and for example, an insulating layer is formed on the multilayer printed circuit board according to the insulating layer manufacturing method of the embodiment. A first process of forming a metal substrate on the insulating layer and a second process of forming a metal substrate on the insulating layer according to the method of manufacturing a multilayer printed circuit board according to the other embodiment may be repeated.

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

Hereinafter, in order to describe the present invention in detail, it will be described in detail with reference to embodiments. However, embodiments according to the present invention may be modified in various forms, and the scope of the present invention is not construed as being limited to the embodiments described below. Embodiments of the present specification are provided to more completely describe the present invention to those of ordinary skill in the art.

Preparation Example 1_ Preparation of alkali-soluble resin

543 g of dimethylacetamide (DMAc) as a solvent was added to a reaction vessel with a volume of 2 liters capable of heating and cooling equipped with a thermometer, agitating device, a reflux cooling tube, and a moisture meter, and 350 g of SMA1000 from Cray Valley, 4-aminobenzo. Ik acid (4-aminobenzoic acid, PABA) 144g, 4-aminophenol (4-aminophenol, PAP) 49g was added and mixed. In a nitrogen atmosphere, the temperature of the reactor was set to 80° C., and the acid anhydride and the aniline derivative reacted to form amic acid for 24 hours. Then, the temperature of the reactor was set to 150° C. and the imidation reaction was continued for 24 hours. , To prepare an alkali-soluble resin solution of 50% solid content.

Preparation Example 2 Manufacture of surface-treated inorganic filler

70 g of SFP-120MC silica without Denka's surface treatment as an inorganic silica filler, 40 g of methyl ethyl ketone and 0.7 g of KBM-403 (3-glycidoxypropyl trimethoxysilane, >99%) as a solvent. The mixture was stirred for a period of time, and the surface of the inorganic silica filler was silane-modified.

To the silane-modified inorganic silica filler, 0.3 g of trifluoroacetic anhydride was added as an oxidizing agent, stirred for 30 minutes with a paste mixer, and mixed to prepare a surface-treated silica inorganic filler.

Example 1

A copper substrate of 5 cm * 5 cm standard was prepared as a substrate. 100 parts by weight of the alkali-soluble resin of Preparation Example 1 as an alkali-soluble resin, 30 parts by weight of MY-510 (manufactured by Huntsman) as a thermosetting binder, 200 parts by weight of the surface-treated silica inorganic filler of Preparation Example 2, and DMAC 20 as a solvent A mixture containing parts by weight was prepared. The mixture was applied on a PET film and dried to prepare a 15 μm thick polymer resin layer.

The polymer resin layer was vacuum-laminated at 85° C. on a circuit board in which a copper line was formed on a copper clad laminate, and the PET film was removed. A 15 μm-thick photosensitive dry film resist KL1015 (manufactured by Kolon Industries) was laminated at 110°C on the polymer resin layer.

A circular negative photomask having a diameter of 30 µm is contacted on the photosensitive dry film resist, irradiated with ultraviolet rays (amount of light of 25 mJ/cm 2 ), and then the dry film resist and the polymer are numbered through a 1% sodium carbonate developer at 30°C. The strata were developed one after the other. At this time, the photosensitive dry film resist on which the pattern was formed acts as a protective layer of the polymer resin layer, so that the same pattern as the photosensitive dry film resist was formed in the polymer resin layer. Thereafter, after heat curing at a temperature of 115° C. for 1 hour, the residue and the photosensitive dry film resist were removed and roughened using a 3% sodium hydroxide resist stripper at a temperature of 50° C. to complete the process. Finally, after heat curing at a temperature of 200° C. for 1 hour, an insulating layer was prepared.

Comparative Example 1

In place of the surface-treated silica inorganic filler of Preparation Example 2, an insulating layer was prepared under the same conditions as in Example 1, except that SFP-120MC silica, which was not surface-treated by Denka, was used after silane modification.

SEM analysis

The upper surface of the insulating layer prepared in Example 1 and Comparative Example 1 was photographed with a scanning electron microscope (SEM, Hitachi, S-4800) at 5000 magnification to observe the surface.

2A is a SEM photograph of the surface of the insulating layer of Example 1, and FIG. 2B is a SEM photograph of the surface of the insulating layer of Comparative Example 1.

2A and 2B, in the case of the insulating layer prepared in Example 1, it can be seen that the releasable coated inorganic filler is detached. On the other hand, in the case of the insulating layer of Comparative Example 1 using an inorganic filler that is not separately coated on the surface, it can be confirmed that the inorganic filler is attached to the surface as it is.

That is, even if it is roughened with an alkaline solution, it can be confirmed that the surface roughness is hardly improved in the case of the insulating layer manufactured according to the prior art. It can be seen that the roughness of the surface of the insulating layer is remarkably improved by desorption of a large amount of the releasable coated inorganic filler when the solution is roughened.

Illuminance analysis

Surface roughness images were photographed on the upper surface of the insulating layer prepared in Example 1 and Comparative Example 1 with an NVM-4151 device of Nanosystems, which is a non-contact surface shape measuring device.

3A and 3B are top surface roughness images of insulating layers prepared in Example 1 and Comparative Example 1. FIG.

3A and 3B, it can be seen that the upper surface of the insulating layer prepared in Example 1 has a higher roughness than the upper surface of the insulating layer prepared in Comparative Example 1. That is, a high roughness can be formed by using the surface-treated inorganic filler and removing the surface-treated inorganic filler from the surface of the insulating layer with an alkaline solution. In addition, since the roughness formed on the upper surface of the insulating layer is proportional to the diameter of the inorganic filler, it is possible to easily adjust the surface roughness of the insulating layer by using inorganic fillers of various diameters as desired.

100: substrate
200, 201, 202, 203: polymer resin layer
300: pattern layer

Claims (14)

Forming a polymer resin layer including an alkali-soluble resin, a thermosetting binder, and a surface-treated inorganic filler on a substrate;
Forming a pattern layer on the polymer resin layer;
Developing and curing the polymer resin layer on which the pattern layer is formed;
Forming a patterned polymer resin layer by removing the pattern layer from the cured polymer resin layer; And
Insulating layer manufacturing method comprising; roughening the surface of the patterned polymer resin layer with an alkaline solution.
The method of claim 1,
The surface-treated inorganic filler,
Silane-modifying the surface of the inorganic filler by mixing the inorganic filler and the epoxy silane compound; And releasing the surface of the silane-modified inorganic filler by mixing the silane-modified inorganic filler with an oxidizing agent.
The method of claim 2,
The inorganic filler is one or more of silica, barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.
The method of claim 2,
The method of manufacturing an insulating layer, wherein the epoxy silane-based compound is mixed with the inorganic filler in an amount of 0.3 to 3 parts by weight based on 100 parts by weight of the inorganic filler.
The method of claim 2,
The epoxy silane compound is 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-[2,3-epoxypropoxypropyl]methyldimethoxysilane, 3-[2, Insulation layer comprising at least one of 3-epoxypropoxypropylmethyldiethoxysilane, 2-[3,4-epoxycyclohexyl]ethylmethyldimethoxysilane, and 2-[3,4-epoxycyclohexyl]ethyltrimethoxysilane Manufacturing method.
The method of claim 2,
The oxidizing agent is a method of manufacturing an insulating layer comprising at least one of a fluorine-based organic acid and an anhydride of the fluorine-based organic acid.
The method of claim 6,
The fluorine-based organic acid is trifluoroacetic acid, 3,3,3-trifluoropropanoic acid, 4,4,4-trifluorobutyric acid, 2,2,3,3-tetrafluoro-3- (trifluoro Fethoxy) propionic acid, 3-(trifluoromethyl)benzoic acid, 4-(trifluoromethyl)benzoic acid, (3,3,3-trifluoro-2-methoxy-2-phenylpropanoyl) 3,3,3-trifluoro-2-methoxy-2-phenylpropanoic acid, benzoic trifluoroacetic acid, aspirin trifluoroacetic acid, 2-cyanoacetic trifluoroacetic acid, phenylacetic trifluoro A method for producing an insulating layer comprising at least one of acetic acid, buta-2,3-dienoic trifluoroacetic acid and acrylic-trifluoroacetic acid.
The method of claim 2,
The method of manufacturing an insulating layer in which the oxidizing agent is mixed in an amount of 0.1 to 1.5 parts by weight based on 100 parts by weight of the inorganic filler.
The method of claim 1,
The alkali-soluble resin may include at least one acidic functional group; And a cyclic imide functional group substituted with one or more amino groups.
The method of claim 1,
The thermosetting binder includes at least one functional group selected from the group consisting of an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyanide group, a maleimide group, and a benzoxazine group; And an epoxy group; containing, the insulating layer manufacturing method.
The method of claim 1,
Forming the pattern layer on the polymer resin layer,
Forming a photosensitive resin layer on the polymer resin layer; And
And forming a pattern layer by exposing the photosensitive resin layer to light and alkali developing the photosensitive resin layer in an unexposed region.
The method of claim 1,
The removal is performed by any one of a photoresist stripper treatment, a desmear process, and plasma etching.
The method of claim 1,
The alkaline solution is pH 9 to pH 13, the insulating layer manufacturing method.
Forming a metal pattern layer on the insulating layer manufactured by the method according to any one of claims 1 to 13; Containing, a method for manufacturing a multilayer printed circuit board.

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