KR20200101751A - Dielectric resin composition for semiconductor device build up - Google Patents

Abstract

The present invention relates to an insulating resin composition for a semiconductor device build up, having excellent adhesion at an interface with a metal thin film without any separate treatment, and a method for the semiconductor device build up using the same. The insulating resin composition for the semiconductor device build up includes an alkali-soluble resin and a compound represented by chemical formula 1.

Description

Insulating resin composition for semiconductor device build-up {DIELECTRIC RESIN COMPOSITION FOR SEMICONDUCTOR DEVICE BUILD UP}

The present invention relates to an insulating resin composition for build-up of a semiconductor device, and more particularly, to an insulating resin composition for build-up of a semiconductor device having excellent adhesion at an interface with a metal thin film without a separate treatment.

Electronic devices in recent years are becoming more compact, lightweight, and high-performance. To this end, as the application field of a build-up printed circuit board (build-up PCB) is rapidly expanding centering on small devices, the use of multilayer printed circuit boards is rapidly increasing.

Multi-layer printed circuit boards are capable of three-dimensional wiring from flat wiring. In particular, in the industrial electronics field, the integration of functional elements such as IC (integrated circuit) and LSI (large scale integration) is improved, as well as miniaturization, weight reduction, high performance, and structural This product is advantageous for integrating electrical functions, shortening assembly time and reducing cost.

However, as the width of the circuit wiring used for the printed circuit board or semiconductor packaging material becomes thinner, the roughness of the insulating material decreases, and thus the specific surface area of contact with the wiring decreases, requiring higher adhesion to the insulating material. Has become.

Conventionally, there is a method of increasing the adhesion between resin and copper foil by forming surface irregularities to increase the surface area.However, as the precision of circuit wiring increases, the surface roughness is limited, and surface treatment such as plasma treatment is limited in the process. Due to the addition of additional steps, there was a limit to a large cost burden.

Accordingly, there is a need for development of an insulating resin composition for building up a new semiconductor device that can have excellent adhesion between the insulating layer and the metal thin film layer at low cost.

The present invention is to provide an insulating resin composition for build-up of a semiconductor device having excellent adhesion at an interface with a metal thin film without any additional treatment.

Further, the present invention is to provide a method for building up a semiconductor device using the insulating resin composition for building up a semiconductor device.

In the present specification, there is provided an insulating resin composition for building up a semiconductor device, including an alkali-soluble resin and a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

L ₁ is an alkylene group having 1 to 10 carbon atoms,

Ar ₁ and Ar ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having an epoxy functional group bonded to the terminal.

In addition, in this specification, alkali-soluble resin; And forming a curable resin insulating layer using an insulating resin composition including the compound represented by Formula 1 above. A method for building up a semiconductor device is provided.

Hereinafter, an insulating resin composition for building up a semiconductor device and a method for building up a semiconductor device according to a specific embodiment of the present invention will be described in more detail.

The terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise", "include" or "have" are intended to designate the presence of implemented features, numbers, steps, components, or a combination thereof, and one or more other features or It is to be understood that the possibility of the presence or addition of numbers, steps, elements, or combinations thereof is not preliminarily excluded.

The present invention will be described in detail below and exemplify specific embodiments, as various changes can be made and various forms can be obtained. However, this is not intended to limit the present invention to a specific form disclosed, it is to be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

According to one embodiment of the invention, an alkali-soluble resin; And an insulating resin composition for build-up of a semiconductor device, including a compound represented by the following Formula 1 may be provided:

[Formula 1]

In Formula 1,

L ₁ is an alkylene group having 1 to 10 carbon atoms,

Ar ₁ and Ar ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having an epoxy functional group bonded to the terminal.

The present inventors conducted research on components that can be used in the build-up of semiconductor devices, and by the introduction of a compound represented by Formula 1 in which an alkali-soluble resin and a resin composition including the compound represented by Formula 1 are highly polar. Therefore, it was confirmed through an experiment that the adhesion between the resin and the metal thin film was improved by increasing the chemical bond between the molecules and the invention was completed.

Specifically, the compound of Formula 1 includes one or more functional groups in which an epoxy group is bonded to the terminal in the molecule, and can react with other resin moieties in the insulating resin composition, and the composition becomes polar due to the triazine structure, It may have an effect of improving adhesion at the interface with the metal thin film.

The alkyl group is a monovalent functional group derived from alkane, for example, as a straight chain, branched or cyclic, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, Hexyl may be used, and the description of the alkyl group described above may be applied except that the alkylene group is a divalent group.

As described above, in Formula 1, Ar ₁ and Ar ₂ may each independently be hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which an epoxy functional group is bonded to the terminal, specifically Ar ₁ And Ar ₂ may each independently represent the following Formula 2:

[Formula 2]

In Chemical Formula 2,

L ₂ is a single bond; Or an alkylene group having 1 to 5 carbon atoms,

n and m are each independently an integer of 0 to 3,

n + m= 3,

* Is the point of attachment.

More specifically, in Formula 2, m may be 0 or 1, for example, Formula 1 may be represented by Formula 1-2 below:

[Formula 1-2]

On the other hand, the compound represented by Formula 1 may be included in 3 to 10 parts by weight, or 4 to 6 parts by weight, or 4 to 5 parts by weight based on 100 parts by weight of the alkali-soluble resin, the compound represented by the formula 1 When included in the insulating resin composition for build-up of a semiconductor device in the same amount as, the resin composition has sufficient polarity, and thus metal adhesion can be increased.

When the compound represented by Formula 1 is less than 3 parts by weight based on 100 parts by weight of the alkali-soluble resin, the polarity is insufficient in the resin composition, and there is a risk that the adhesion between the resin and the metal thin film may decrease, and when it exceeds 10 parts by weight , Viscosity increases, and there is a concern that the reaction may proceed due to activation of some functional groups at room temperature, and reliability may be degraded.

On the other hand, 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 one or 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 one or two or more. As the alkali-soluble resin contains at least one or 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. As the reactivity with the thermosetting binder is improved, the curing density can be increased, thereby increasing 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 will be 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 the following formula (3).

[Formula 3]

In Formula 3, R ₁ is an alkylene group or alkenyl group having 1 to 10 carbon atoms, and * is 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 the 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 3-2.

[Chemical Formula 3-2]

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 and the acidic functional group substituted with the amino group may be bonded via a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, for example, a cyclic group substituted with the amino group An acidic functional group may be bonded to the terminal of the amino group included in the imide functional group through 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 3, and already included in the cyclic imide functional group substituted with the amino group. The terminus of the de functional group may mean a nitrogen atom included in the cyclic imide functional group in Chemical Formula 3.

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 cyclic imide functional group described above, 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 the maleimide compound, and the N-substituted maleimide compound is a monofunctional N-substituted maleimide depending on the number of N-substituted maleimide compounds. It can be classified into compounds and polyfunctional N-substituted maleimide compounds.

The monofunctional N-substituted maleimide compound is a compound in which a functional group is substituted with a nitrogen atom contained 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 through

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 contained 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 diphenylether 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 (-NH ₂ ) in the molecular structure, and more preferably a carboxylic acid compound substituted with an amino group, a polyfunctional amine compound containing two or more amino groups, or Mixtures of these 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. . The acidic action in the alkali-soluble resin through the carboxylic acid compound substituted with the amino group

As the container contains a large number of carboxylic acid functional groups, 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 carboxylic acid compound substituted with the amino group 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 (-NH ₂ ) in the molecule, and may contain all aliphatic, alicyclic or aromatic polyfunctional amines depending on the type of hydrocarbon bonded to the amino group. have. 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- Aminophenyl )-2-propyl]benzene, 1,1'-bis(4-aminophenyl)-cyclohexane, 9,9'-bis(4-aminophenyl)-fluorene, 9,9'-bis(4-amino -3-chlorophenyl)fluorene, 9,9'-bis(4-amino-3-fluorophenyl)fluorene, 9,9'-bis(4-amino-3-methylphenyl)fluorene,3,4 '-Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)-benzene, 1,3-bis(4-aminophenoxy)-benzene , 1,4-bis(4-aminophenoxy)-benzene, 1,4-bis(4-amino-2-trifluoromethylphenoxy)-benzene, 4,4'-bis(4-aminophenoxy) )-Biphenyl, 2,2'-bis[4-(4-aminophenoxy)-phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)-phenyl]hexafluoropropane, Bis(2-aminophenyl)sulfide, bis(4-aminophenyl)sulfide, bis(3-aminophenyl)sulfone, bis(4-aminophenyl)sulfone, bis(3-amino-4-hydroxy)sulfone, bis [4-(3-aminophenoxy)-phenyl]sulfone, bis[4-(4-aminophenoxy)-phenyl]sulfone, o-tolidine sulfone, 3,6-diaminocarbazole, 1,3, 5-tris(4-aminophenyl)-benzene, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, 4,4'-diaminobenzanilide, 2-(3-aminophenyl)-5- Aminobenzimidazole, 2-(4-aminophenyl)-5-aminobenzoxazole, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5- Amine, 4,6-diaminoresorcinol, 2,3,5,6-pyridine tetraamine, polyfunctional amines including the 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), and polyether structures. Functional amines (Huntsman, BASF), etc. are mentioned.

In addition, the alkali-soluble resin is a repeating unit represented by the following formula (4); And at least one or more repeating units represented by the following formula (5).

[Formula 4]

In Formula 4, R ₂ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, * denotes a bonding point,

[Formula 5]

In Formula 5, R ₃ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and R ₄ is -H, -OH, -NR ₅ R ₆ , halogen, or an alkyl group having 1 to 20 carbon atoms, wherein R ₅ and R ₆ 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 4, R ₂ may be phenylene, in Formula 5, R ₃ may be phenylene, and R ₄ may be -OH.

On the other hand, the alkali-soluble resin is a repeating unit represented by the formula (4); And, in addition to the repeating unit represented by Chemical Formula 5, a vinyl repeating unit may be further included. 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, and examples of the vinyl-based monomer are not limited, for example, ethylene, propylene, isobutylene. , Butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, maleimide, and the like.

A repeating unit represented by Formula 4 above; And the alkali-soluble resin each comprising at least one or more repeating units represented by Formula 5 is prepared by reaction of a polymer including a repeating unit represented by Formula 6, an amine represented by Formula 7 below, and an amine represented by Formula 8 below. Can be.

[Formula 6]

[Formula 7]

[Formula 8]

In Formulas 6 to 8, R ₂ to R ₄ are the same as those described above in Formulas 4 and 5, and * denotes a bonding point.

Specific examples of the polymer including the repeating unit represented by Formula 6 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 is mentioned.

In addition, a repeating unit represented by Chemical Formula 4 described above; And the alkali-soluble resin each including at least one or more repeating units represented by Formula 4 may be prepared by a reaction of a compound represented by Formula 9 below and a compound represented by Formula 10 below.

[Formula 9]

[Formula 10]

In Formulas 9 to 10, R ₂ to R ₄ are the same as those described in Formulas 4 and 5.

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.

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

(1) a carboxy group-containing resin obtained by reacting a polyfunctional epoxy resin with a saturated or unsaturated monocarboxy group and then reacting 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 carboxy 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) Polyamic acid resin obtained by reacting diamine and dianhydride or copolymer resin of 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 an anhydride of a 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.

Meanwhile, the insulating resin composition for build-up of the semiconductor device may further include a 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 these 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 by 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 contain 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 either or two groups of a 3, 4 or 5 membered cyclic ether group or a cyclic thioether group 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 novolak type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, chelate type epoxy resin, 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, those 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, carix arenes, 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 polyfunctional maleimide compound include 4,4'-diphenylmethane bismaleimide, phenylmethane bismaleimide, m-phenylmethane bismaleimide, and m-phenylmethane bismaleimide. 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-(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 multifunctional resin compound include Kukdo Chemical's YDCN-500-80P, Ronza's phenol novolak-type cyanite Ethner resin PT-30S, Daiwa's phenylmethane-type maleimide resin BMI-2300, and Shikoku's Pd-type benzoxazine resin, etc. are mentioned.

Meanwhile, the insulating resin composition for build-up of the semiconductor device may further include one or more additives selected from the group consisting of a thermosetting catalyst, an inorganic filler, a leveling agent, a dispersant, a release agent, and a metal adhesion promoter.

The thermosetting catalyst 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 of them are trade names of dimethylamine block isocyanate compounds), DBU, DBN, U-CATS A102, and U-CAT5002 (all of them 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 inorganic filler include silica, barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, or a mixture of two or more thereof.

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 insulating resin composition for build-up of the semiconductor device 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. Specific examples of the thermosetting binder containing the photoreactive unsaturated group, the alkali-soluble resin containing the photoreactive unsaturated group, and the photoinitiator are not limited thereto, and various compounds used in the technical field related to the photocurable resin composition may be used without limitation.

The content of another type of adhesion promoter or photoinitiator contained in the insulating resin composition for build-up of the semiconductor device may be 5% by weight or less based on the total weight of the insulating resin composition. That the content of other types of adhesion promoters or photoinitiators contained in the insulating resin composition is 5% by weight or less based on the total weight of the insulating resin composition, the content of other types of adhesion promoters or photoinitiators contained in the insulating resin composition is very insignificant or , This may mean that no other types of adhesion promoters or photoinitiators are included. Accordingly, the interfacial desorption property with the insulating layer or the conductive layer, which may be generated by other types of adhesion promoters or photoinitiators, may be reduced, and thus adhesion and durability of the insulating layer may be improved.

On the other hand, according to another embodiment of the invention, an alkali-soluble resin; And forming a curable resin insulating layer by using an insulating resin composition including the compound represented by Formula 1 above. A method of building up a semiconductor device may be provided.

Specific contents of Formula 1 include the contents described above in the insulating resin composition for build-up of the semiconductor device of the embodiment.

When a semiconductor device is stacked, that is, build-up, in general, for electrical disconnection of the base layer and the upper layer, or the lower and upper layers, an insulating layer using an insulating material is formed, and for electrical connection between the layers. After the via hole is formed, a metal thin film layer, that is, a conductive layer, which can provide an electrical path between each layer through the via hole, is formed on the insulating layer.

However, a polymerization inhibitor or a photoinitiator used together with the insulating material may lower the adhesion between the insulating layer and the metal thin film layer, that is, the conductive layer, and eventually, may cause interfacial dropping at the boundary between the insulating layer and the metal thin film layer.

The insulating resin composition of the above-described embodiment may be used as a composition for building up a semiconductor device through the following process.

First, after the insulating resin composition is applied on a substrate on which a circuit is formed, exposure is selectively performed on the insulating resin composition in the portion where the pattern is to be formed. When such exposure is performed, the unsaturated functional groups contained in the insulating resin composition may cause photocuring to form crosslinks with each other, and as a result, a crosslinked structure may be formed by photocuring in the exposed portion.

Thereafter, when development is performed using an alkali developer, the insulating resin composition of the exposed portion in which the crosslinked structure is formed remains on the substrate on which the circuit is formed, and the insulating resin composition of the remaining non-exposed portion may be dissolved in the developer and removed.

Then, when thermally curing the insulating resin composition remaining on the substrate on which the circuit is formed, the functional groups contained in the insulating resin composition react with the thermally curable functional groups of the thermosetting binder to form crosslinks, As a result, a crosslinked structure by thermosetting is formed, and a desired portion on the substrate on which the circuit is formed, that is, a patterned curable resin insulating layer may be formed.

By using this, it is possible to form a finer pattern in a uniform shape compared to the laser processing method such as the ABF process, and it is possible to implement excellent adhesion between the conductive layer and the insulating layer in the manufactured semiconductor device.

In addition, the process of forming a pattern by photo-curing only a part of the insulating layer, developing, and then forming a conductive layer (Photoimageable dielectric process, PID process) is faster and at a relatively low cost compared to the conventional laser processing method. Since mass production is possible, the efficiency of the process can be improved.

According to the present invention, an insulating resin composition for build-up of a semiconductor device having excellent adhesion at an interface with a metal thin film can be provided without a separate treatment.

In addition, according to the present invention, a method for building up a semiconductor device using the insulating resin composition for building up the semiconductor device may be provided.

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

<Example>

[Example 1]

Manufacturing of insulating resin composition for semiconductor device build-up

As an acid-modified oligomer, ZFR-1122 of Nippon Explosives was used in 27% by weight, polyfunctional epoxy acrylate (DPEA-12 of Nippon Explosives) was used as a polyfunctional acrylate monomer, 10% by weight, and Darocur TPO (Chiba Specialty Chemical) was used as a photoinitiator. 3% by weight, YDCN-500-80P (Kukdo Chemical) 16% by weight as a thermosetting binder, 2MUSIZ (Shikoku Chemical) 2% by weight as a silane-based coupling agent, 1% by weight of 2-phenylimidazole as a thermosetting catalyst, 30% by weight of UFP-40 (Denka Silica) as a filler, 1% by weight of BYK's BYK-UV3570 as an additive, and 10% by weight of DMF as a solvent. After mixing and stirring each component, a three-roll mill equipment filler Was dispersed to prepare an insulating resin composition for build-up of a semiconductor device.

After applying the prepared resin composition to PET used as a carrier film using a comma coater, it is dried by passing through an oven at 95°C for 8 minutes, and then PE is laminated as a release film. A dry film for forming a curable resin insulating layer composed of a photocurable and thermosetting binder resin layer and a release film was prepared.

[Comparative Example 1]

As the acid-modified oligomer, it was carried out in the same manner as in Example 1, except that 29% by weight of ZAR-2000 of Nippon Explosives was used and no silane-based coupling agent was used.

Semiconductor device build-up

After peeling off the release film of the prepared dry film, a binder resin layer was vacuum-laminated on the substrate on which the circuit was formed with a vacuum laminator (MV LP-500 manufactured by Meiki Seisakusho Co., Ltd.), and then UV in the 365 nm wavelength band under the application of a pattern mask. After exposing to 150mJ/cm ² , the carrier film was removed. The resulting product was immersed in an alkaline solution of 1w% Na ₂ CO ₃ at 31° C. being stirred for 60 seconds, developed, and heated and cured at 105° C. for 1 hour to form a pattern.

Meanwhile, the substrate on which the circuit is formed is a copper clad laminate LG-T-500GA of LG Chem with a thickness of 0.1 mm and a copper foil thickness of 12 μm, cut into a substrate of 5 cm in width and 5 cm in length, and fine roughness is formed on the copper foil surface by chemical etching. One was used.

The prepared printed circuit board was subjected to a desmear process under the conditions shown in Table 1 below to remove smear.

fair Chemicals used Temperature
(℃) time
(min) Swelling Securiganth MV SWELLER 65 5 NaOH (50w/w%) Permanganation Securiganth MV ETCH P 80 10 NaOH (50w/w%) Neutralization Securiganth MV Reduction Conditioner 50 4 H ₂ SO4 (60w/w%)

Thereafter, chemical copper plating was performed under the conditions shown in Table 2 below to form a metal thin film layer on the curable resin insulating layer to build up a semiconductor device. All reagents used are from Atotech.

fair Chemicals used Temperature
(℃) time
(min) Conditioning Neoganth MV Conditioner 60 5 Acid dipping H ₂ SO ₄ (60w/w%) RT One Pre dipping Neoganth MV Pre Dip RT One Activating Neoganth MV Activator 40 5 NaOH (50w/w%) Reduction Neoganth MV Reducer 3 3 Electroless Copper plating Printoganth MV BASIC 14 14 Printoganth MV COPPER Printoganth MV Plus STABILIZER Printoganth MV STARTER Reduction Solution Copper

After completion of the chemical copper plating, in order to measure the plating adhesion, electro-copper plating was performed using the plating solution shown in Table 3 below to increase the thickness of the metal thin film layer.

Chemicals used volume
(liter) weight
(kg) DI water 85 85 CuSO ₄ (5H ₂ O) 20 H ₂ SO ₄ (49w%, density=1.4g/cm ³ ) 8.57 12 HCl (37w%, density = 1.19g/cm ³ ) 0.012 0.014 Cupracid MV Brightener 0.15 EXPT Cupracid MV2 Leveller 2 EXPT Cupracid MV2 Correction 1.8

All of the reagents used were manufactured by Atotech, and plating was performed for 60 minutes under a current condition of 1A.

<Experimental Example>

Adhesion evaluation

After the electrolytic copper plating, the adhesion between the plated copper foil and the interface of the curable resin insulating layer was measured as follows.

The specimen plated in the examples was cut into a width of 1 cm and a length of 10 cm to obtain a specimen. 180 degree peel strength was measured using the Texture Analyzer XT Plus of Stable micro system. After measuring 560mm at a speed of 5mm/s in tension mode, the average values of all sections are summarized in Table 4 below.

Peel strength (kgf/cm) Example 1 0.13 Comparative Example 1 0.09

As a result of the experiment, when the compound of Formula 1 of Example 1 of the present invention was used as an insulating resin composition for build-up of a semiconductor device, the peel strength was about 0.13 kgf/cm, compared to 0.09 kgf/cm of the comparative example. It could be confirmed that it was improved by %.

Accordingly, it was found that the insulating resin composition for build-up of a semiconductor device of the present invention has excellent adhesive strength at the interface with the metal thin film without a separate treatment.

Claims (10)

Alkali-soluble resin; And an insulating resin composition for build-up of a semiconductor device comprising a compound represented by the following Formula 1:
[Formula 1]

In Formula 1,
L ₁ is an alkylene group having 1 to 10 carbon atoms,
Ar ₁ and Ar ₂ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having an epoxy functional group bonded to the terminal.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently of the following formula (2), an insulating resin composition for the build-up of a semiconductor device:
[Formula 2]

In Chemical Formula 2,
L ₂ is a single bond; Or an alkylene group having 1 to 5 carbon atoms,
n and m are each independently an integer of 0 to 3,
n + m= 3,
* Is the point of attachment.
The method of claim 1,
Formula 1 is an insulating resin composition for build-up of a semiconductor device represented by Formula 1-2 below:
[Formula 1-2]

.
The method of claim 1,
The compound represented by Formula 1 contains 3 to 10 parts by weight based on 100 parts by weight of an alkali-soluble resin, an insulating resin composition for a build-up of a semiconductor device.
The method of claim 1,
The alkali-soluble resin is an acidic functional group; And at least one or more cyclic imide functional groups each substituted with an amino group.
The method of claim 5,
The cyclic imide functional group substituted with the amino group comprises a functional group represented by the following formula (3), an insulating resin composition for building up a semiconductor device:
[Formula 3]

In Chemical Formula 3,
R ₁ is an alkylene group or alkenyl group having 1 to 10 carbon atoms,
* Is the point of attachment.
The method of claim 1,
An insulating resin composition for build-up of a semiconductor device, further comprising a thermosetting binder.
The method of claim 1,
An insulating resin composition for build-up of a semiconductor device further comprising at least one selected from the group consisting of a thermosetting catalyst, an inorganic filler, a leveling agent, a dispersant, a release agent, and a metal adhesion promoter.
The method of claim 1,
The insulating resin composition is used for forming a curable resin insulating layer, an insulating resin composition for building up a semiconductor device.
Alkali-soluble resin; And forming a curable resin insulating layer using an insulating resin composition comprising the compound represented by Chemical Formula 1; including, a method for building up a semiconductor device.