KR20210116968A - Polyimide-based alkali developable resin, method for manufacturing insulating film using the same and multilayered printed circuit board - Google Patents

Abstract

The present invention relates to a polyimide-based alkali-soluble resin, a method for manufacturing an insulating layer using the same, and a multilayer printed circuit board, and specifically, to a polyimide-based alkali-soluble resin that can improve dimensional stability at room temperature by controlling the type and content of an amine-based compound used in the polyimide-based alkali-soluble resin, a method for manufacturing an insulating layer using the same, and a multilayer printed circuit board.

Description

A polyimide-based alkali-soluble resin, an insulating layer manufacturing method using the same, and a multilayer printed circuit board

The present invention relates to a polyimide-based alkali-soluble resin, a method for manufacturing an insulating layer using the same, and a multilayer printed circuit board. Specifically, by controlling the type and content of an amine-based compound used in the polyimide-based alkali-soluble resin, the dimensions at room temperature are It relates to a polyimide-based alkali-soluble resin capable of improving stability, a method for manufacturing an insulating layer using the same, and a multilayer printed circuit board.

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

Multilayer printed circuit boards are capable of three-dimensional wiring from flat wiring. In particular, in the field of industrial electronics, integration of functional elements such as IC (integrated circuit) and LSI (large scale integration) has been improved, and electronic devices are miniaturized, lightweight, highly functional, and structurally structured. It is an advantageous product for electrical function integration, shortening of assembly time and cost reduction.

The build-up PCB used in this application area necessarily forms a via hole for connection between layers. The via hole corresponds to an electrical connection path between layers of a multi-layer printed circuit board. Drill), but as the diameter of the hole becomes smaller due to the miniaturization of the circuit, the processing method using a laser is shown as an alternative due to the increase in the processing cost due to the machining of the machine drilling and the limitation of the processing of the fine hole.

However, in the case of a laser processing method, a CO ₂ or YAG laser drill is used, but since the size of the via hole is determined by the laser drill, for example, in _{the case of a CO 2} laser drill, a diameter of 40 μm or less is used. There is a limitation in that it is difficult to manufacture a via hole having. In addition, when a plurality of via holes need to be formed, there is a limit in that the cost burden is large.

On the other hand, although the via hole is formed by patterning, there is a problem in that the size of the via hole is expanded when it is left at room temperature for 24 hours.

Accordingly, development of an insulating layer capable of maintaining the size of the hole even if left at room temperature for a long time is required.

The technical problem to be achieved by the present invention is to provide a polyimide-based alkali-soluble resin having improved dimensional stability at room temperature, a method for manufacturing an insulating layer using the same, and a multilayer printed circuit board.

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

An exemplary embodiment of the present invention is a polyimide-based alkali-soluble resin comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), wherein the polyimide-based alkali-soluble resin is represented by the following formula (3) It is a reaction product of a mixture containing a polymer containing a repeating unit, an aromatic diamine compound, and an amine compound containing an acidic functional group, and the content of the aromatic diamine compound is based on 100 parts by weight of a polymer containing a repeating unit represented by Formula 3 Provided is a polyimide-based alkali-soluble resin in an amount of 6 parts by weight or more and 15 parts by weight or less:

[Formula 1]

[Formula 2]

[Formula 3]

In Formula 1, R ₁ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or represented by Formula 4 below,

[Formula 4]

In Formula 2, n is an integer of 1 to 3,

In Formula 4, R ₂ is an alkylene group having 1 to 3 carbon atoms,

In Formulas 1 to 4, "*" means a bonding point.

Another embodiment of the present invention comprises the steps of providing a polymer resin layer including the polyimide-based alkali-soluble resin and a thermosetting binder on a conductor wiring; forming a laminate by providing a photosensitive resin layer on the polymer resin layer; patterning the laminate by exposure and alkali development; thermosetting the patterned polymer resin layer; and peeling off the patterned photosensitive resin layer.

According to another exemplary embodiment of the present invention, an insulating layer manufactured by the manufacturing method; And it provides a multilayer printed circuit board having a metal substrate provided with a pattern on the insulating layer.

An insulating layer having improved dimensional stability may be provided by using the polyimide-based alkali-soluble resin according to an exemplary embodiment of the present invention.

In the insulating layer manufacturing method according to another exemplary embodiment of the present invention, an insulating layer having improved dimensional stability at room temperature can be manufactured using the polyimide-based alkali-soluble resin.

The multilayer printed circuit board according to another exemplary embodiment of the present invention has improved dimensional stability at room temperature, thereby improving the reliability of semiconductor build-up.

Effects of the present invention are not limited to the above-described effects, and effects not mentioned will be clearly understood by those skilled in the art from the present specification and accompanying drawings.

1 schematically shows an insulating layer manufacturing process according to an embodiment of the present invention.
2 schematically shows a multilayer printed circuit board manufacturing process according to an embodiment of the present invention.
3 is a graph showing the glass transition temperature of the polymer resin layer prepared in Example 1 and Comparative Example 1 measured using a dynamic mechanical analyzer (DMA).
4 is an enlarged photograph of a pattern among the multilayer printed circuit boards of Example 1 and Comparative Example 1. FIG.

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

In this specification, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.

In the present specification, the unit “parts by weight” may mean a ratio of weight between each component.

In the present specification, the term “repeating unit” may refer to a form in which compounds capable of a polymerization reaction are reacted, and specifically, the compound undergoes a polymerization reaction to form a backbone of the polymer, for example, a main chain or a side chain, It can mean that there is a form.

In the present specification, the "glass transition temperature (Glass Temperature, Tg)" can be measured using a dynamic mechanical analyzer (DMA), specifically, using DMA (TA company, Q800), the sample The temperature is raised at a heating rate of 10 °C/min in a temperature range of -30 °C to 300 °C, and the glass transition temperature can be obtained as the maximum value of tan δ by performing an experiment twice (cycle) in the above section.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

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

An exemplary embodiment of the present invention is a polyimide-based alkali-soluble resin comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), wherein the polyimide-based alkali-soluble resin is represented by the following formula (3) It is a reaction product of a mixture containing a polymer containing a repeating unit, an aromatic diamine compound, and an amine compound containing an acidic functional group, and the content of the aromatic diamine compound is based on 100 parts by weight of a polymer containing a repeating unit represented by Formula 3 Provided is a polyimide-based alkali-soluble resin in an amount of 6 parts by weight or more and 15 parts by weight or less:

[Formula 1]

[Formula 2]

[Formula 3]

In Formula 1, R ₁ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or represented by Formula 4 below,

[Formula 4]

In Formula 2, n is an integer of 1 to 3,

In Formula 4, R ₂ is an alkylene group having 1 to 3 carbon atoms,

In Formulas 1 to 4, "*" means a bonding point.

An insulating layer having improved dimensional stability may be provided by using the polyimide-based alkali-soluble resin according to an exemplary embodiment of the present invention.

According to an exemplary embodiment of the present invention, the polyimide-based alkali-soluble resin includes a repeating unit represented by Formula 1 and a repeating unit represented by Formula 2 above. The polyimide-based alkali-soluble resin is a reaction product of a mixture including a polymer including the repeating unit represented by Chemical Formula 3, the aromatic diamine compound, and the acidic functional group-containing amine compound.

According to an exemplary embodiment of the present invention, the repeating unit represented by Formula 1 may be derived from the repeating unit represented by Formula 3 of the polymer and the acidic functional group-containing amine compound. Specifically, the repeating unit represented by Formula 1 may be formed through the reaction of the repeating unit represented by Formula 3 of the polymer with the acidic functional group-containing amine compound. In addition, the repeating unit represented by Formula 2 may be derived from the repeating unit represented by Formula 3 of the polymer and the aromatic diamine compound. Specifically, the repeating unit represented by Formula 2 may be formed through the reaction of the repeating unit represented by Formula 3 of the polymer with the aromatic diamine compound.

According to an exemplary embodiment of the present invention, a polyimide-based polyimide-based polymer having an elevated glass transition temperature using a mixture including the polymer including the repeating unit represented by Formula 3, the aromatic diamine compound, and the acidic functional group-containing amine compound Alkali-soluble resin can be manufactured.

According to an exemplary embodiment of the present invention, the polyimide-based alkali-soluble resin may include one or more repeating units represented by Formula 1, and may include one or more repeating units represented by Formula 2 above.

As the polyimide-based alkali-soluble resin contains one or more, or two or more, repeating units represented by Formula 2 derived from the aromatic diamine compound, the polyimide-based alkali-soluble resin contains active hydrogen contained in the aromatic diamine group. Since it has a plurality of structures, the reactivity with the thermosetting binder is improved during thermosetting, and the curing density can be increased to increase the heat resistance reliability and mechanical properties. In addition, as the cyclic imide functional group is present in the polyimide-based alkali-soluble resin, the polarity is increased by the carbonyl group and the tertiary amine group included in the cyclic imide-based alkali-soluble resin, so that the interfacial adhesive force of the polyimide-based alkali-soluble resin can increase

According to an exemplary embodiment of the present invention, the type of the polymer is not particularly limited as long as it includes the repeating unit represented by Formula 3 above.

According to an exemplary embodiment of the present invention, the content of the aromatic diamine compound included in the mixture may be 6 parts by weight or more and 15 parts by weight or less based on 100 parts by weight of the polymer including the repeating unit represented by Formula 3 above. Specifically, the content of the aromatic diamine compound included in the mixture is 7 parts by weight or more and 15 parts by weight or less, 7.5 parts by weight or more and 14 parts by weight or less, 7.5 parts by weight or more and 12.5 parts by weight or less, based on 100 parts by weight of the polymer; It may be 7.5 parts by weight or more and 10 parts by weight or less, 7.5 parts by weight or more and 9 parts by weight or less, 8 parts by weight or more and 10 parts by weight or less, or 12 parts by weight or more and 15 parts by weight or less. By adjusting the content of the aromatic diamine compound to the above range, the glass transition temperature of the polyimide-based alkali-soluble resin is improved, and the room temperature dimensional stability of the via hole coated by the polyimide-based alkali-soluble resin can be improved. .

According to an exemplary embodiment of the present invention, the aromatic diamine compound may be a compound represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5, n is an integer of 1 to 3. Specifically, in Formula 5, n may be an integer of 1 to 2, or 2.

By using the aromatic diamine compound represented by Formula 5, the glass transition temperature of the polyimide-based alkali-soluble resin can be improved, and the dimensional stability of the polymer resin layer (eg, insulating layer) to be described later can be improved.

According to an exemplary embodiment of the present invention, the aromatic diamine compound may include at least one of a compound represented by the following Chemical Formula 5-1 and a compound represented by the following Chemical Formula 5-2.

[Formula 5-1]

[Formula 5-2]

According to an exemplary embodiment of the present invention, the aromatic diamine compound represented by Formula 5-1 may include at least one of compounds represented by Formulas 5-1-a to 5-1-d below.

[Formula 5-1-a]

[Formula 5-1-b]

[Formula 5-1-c]

[Formula 5-1-d]

In addition, the aromatic diamine compound represented by Formula 5-2 may include at least one of compounds represented by Formulas 5-2-a to 5-2-d.

[Formula 5-2-a]

[Formula 5-2-b]

[Formula 5-2-c]

[Formula 5-2-d]

The polyimide-based alkali-soluble resin prepared by using the above-described aromatic diamine compound may implement an insulating layer with greatly improved dimensional stability at room temperature.

According to an exemplary embodiment of the present invention, the repeating unit represented by Chemical Formula 2 may include a repeating unit represented by the following Chemical Formula 2-1.

[Formula 2-1]

In Formula 2-1, "*" means a bonding point.

In the polyimide-based alkali-soluble resin including the repeating unit represented by Chemical Formula 2-1, the glass transition temperature may be effectively increased, and dimensional stability at room temperature may be greatly improved.

According to an exemplary embodiment of the present invention, the content of the acidic functional group-containing amine compound may be 60 parts by weight or more and 80 parts by weight or less based on 100 parts by weight of the polymer including the repeating unit represented by Formula 3 above. Specifically, the content of the acidic functional group-containing amine compound included in the mixture is 62.5 parts by weight or more and 77.5 parts by weight or less, 65 parts by weight or more and 75 parts by weight or less, 65 parts by weight or more and 70 parts by weight based on 100 parts by weight of the polymer. or less, 60 parts by weight or more and 70 parts by weight or less, 67.5 parts by weight or more and 72.5 parts by weight or less, or 70 parts by weight or more and 80 parts by weight or less. By adjusting the content of the acidic functional group-containing amine compound to the above range, alkali developability of the polymer resin layer including the polyimide-based alkali-soluble resin can be further improved, and the development speed of the polymer resin layer can be appropriately controlled. can do.

According to an exemplary embodiment of the present invention, the acidic functional group-containing amine compound may include a carboxyl group-containing amine compound and a hydroxyl group-containing amine compound. Specifically, the acidic functional group-containing amine compound may include at least a carboxyl group-containing amine compound. In this case, the amine compound may include a phenol group as a hydroxyl group. The amine compound may improve alkali developability of the polymer resin layer including the polyimide-based alkali-soluble resin by including a carboxyl group or a hydroxy group in the acidic functional group. In particular, by using a carboxy group as an acidic functional group, the numerical stability of the polyimide-based alkali-soluble resin can be improved.

According to an exemplary embodiment of the present invention, the acidic functional group-containing amine compound may include a compound represented by the following formula (6).

[Formula 6]

In Formula 6, R ₁ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or represented by Formula 4 below,

[Formula 4]

In Formula 4, R ₂ is an alkylene group having 1 to 3 carbon atoms, and "*" means a bonding point.

By using the acidic functional group-containing amine compound represented by Formula 6, alkali developability of the polymer resin layer including the polyimide-based alkali-soluble resin can be improved, and the dimensional stability of the polymer resin layer can be improved. .

According to an exemplary embodiment of the present invention, the alkylene group is a divalent functional group derived from an alkane, a straight-chain, branched or cyclic, methylene group, ethylene group, propylene group, isobutylene group, It may be a sec-butylene group, 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 the substituents 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 to 12 carbon atoms. of an aryl group, a heteroaryl group having 2 to 12 carbon atoms, an arylalkyl group having 6 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amide group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carbamate group , may be an alkoxy group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present invention, the term "substitution" means that another functional group is bonded instead 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, is not limited. , When two or more substituents are substituted, two or more substituents may be the same as or different from each other.

According to an exemplary embodiment of the present invention, the alkenyl group means containing one or more carbon-carbon double bonds in the middle or at the terminal of the above-described alkylene group, for example, ethylene, propylene, butylene, Hexylene, acetylene, etc. are mentioned. One or more hydrogen atoms in the alkenyl group may be substituted with the same substituents as in the case of the alkylene group.

According to an exemplary embodiment of the present invention, the arylene group is a divalent functional group derived from arene, and may be a cyclic group, such as a phenyl group or a naphthyl group. One or more hydrogen atoms included in the arylene group may be substituted with other substituents, and the substituents 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 to 12 carbon atoms. of an aryl group, a heteroaryl group having 2 to 12 carbon atoms, an arylalkyl group having 6 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amide group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carbamate group , may be an alkoxy group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present invention, the acidic functional group-containing amine compound may include a compound represented by the following Chemical Formula 6-1.

[Formula 6-1]

In Formula 6, R ₂ is an alkylene group having 1 to 3 carbon atoms.

Specifically, the acidic functional group-containing amine compound represented by Formula 6-1 may include a compound represented by Formula 6-1-a below.

[Formula 6-1-a]

The polyimide-based alkali-soluble resin prepared by using the above-mentioned type of acidic functional group-containing amine compound may improve alkali developability and development speed of the polymer resin layer. In addition, when the above-described type of the acid functional group-containing amine compound is used, a polymer resin layer having improved dimensional stability at room temperature can be implemented.

According to an exemplary embodiment of the present invention, the repeating unit represented by the formula (1) may include a repeating unit represented by the following formula (1-1).

[Formula 1-1]

In the polyimide-based alkali-soluble resin including the repeating unit represented by Formula 1-1, the glass transition temperature may be effectively increased, and dimensional stability at room temperature may be improved.

According to an exemplary embodiment of the present invention, the polyimide-based alkali-soluble resin may include a repeating unit represented by Formula 3 above. Specifically, the polymer included in the mixture includes a plurality of repeating units represented by Chemical Formula 3, some of the repeating units represented by Chemical Formula 3 react with the aromatic diamine compound, and another part contains the acidic functional group It may react with the amine compound, and another part may remain unreacted. That is, the unreacted repeating unit represented by Chemical Formula 3 in the polymer may be present in the polyimide-based alkali-soluble resin.

According to an exemplary embodiment of the present invention, the polyimide-based alkali-soluble resin may further include a vinyl-based repeating unit. The vinyl-based repeating unit is a repeating unit derived from a vinyl-based monomer containing at least one vinyl group in a molecule, and examples of the vinyl-based monomer are not particularly limited, for example, ethylene, propylene, isobutylene, butadiene, styrene, acrylic acid, methacrylic acid, maleic anhydride, or maleimide; and the like.

According to an exemplary embodiment of the present invention, the polyimide-based alkali-soluble resin may further include a repeating unit represented by the following formula (7).

[Formula 7]

In Formula 7, 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 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and "*" represents a bonding point it means. Specifically, in Formula 7, R ₃ may be phenylene, and R ₄ may be —OH.

According to an exemplary embodiment of the present invention, the mixture may further include an amine compound represented by the following Chemical Formula 8.

[Formula 8]

In Formula 8, R ₃ and R ₄ are the same as described above in Formula 7 above.

Through the reaction of the repeating unit represented by Formula 3 of the polymer included in the mixture with the amine compound represented by Formula 8 included in the mixture, the repeating unit represented by Formula 7 may be formed.

According to an exemplary embodiment of the present invention, the polyimide-based alkali-soluble resin has an acid value obtained by KOH titration of 50 mgKOH/g to 250 mgKOH/g, or 70 mgKOH/g to 200 mgKOH/g day can Examples of the method for measuring the acid value of the polyimide-based alkali-soluble resin are not particularly limited, but, for example, the following method may be used. Prepare a 0.1 N KOH solution (solvent: methanol) as a base solution, and prepare alpha-naphtholbenzein (pH: 0.8 ~ 8.2 yellow, 10.0 blue green) as an indicator did. Then, about 1 to 2 g of a polyimide-based alkali-soluble resin as a sample was taken, dissolved in 50 g of a dimethylformaldehyde (DMF) solvent, a marker was added, and then titrated with a base solvent. At the completion of the titration, the acid value was calculated as the amount of the base solvent used in units of mg KOH/g.

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

Another embodiment of the present invention comprises the steps of providing a polymer resin layer including the polyimide-based alkali-soluble resin and a thermosetting binder on a conductor wiring; forming a laminate by providing a photosensitive resin layer on the polymer resin layer; patterning the laminate by exposure and alkali development; thermosetting the patterned polymer resin layer; and peeling off the patterned photosensitive resin layer.

In the insulating layer manufacturing method according to another exemplary embodiment of the present invention, dimensional stability at room temperature can be improved by using the polyimide-based alkali-soluble resin.

An exemplary embodiment of the present invention includes providing a polymer resin layer including a polyimide-based alkali-soluble resin and a thermosetting binder on a conductor wiring. In this case, the polyimide-based alkali-soluble resin is a polyimide-based alkali-soluble resin according to the above-described embodiment.

According to an exemplary embodiment of the present invention, the polymer resin layer may be a film formed by drying a polymer resin composition including a polyimide-based alkali-soluble resin and a thermosetting binder.

According to an exemplary embodiment of the present invention, the polymer resin layer may exist alone or may exist in a state formed on a substrate including a semiconductor material such as a circuit board, a sheet, or a multilayer printed wiring board, and the polymer resin layer is disposed on the substrate. Examples of the forming method are not particularly limited, but for example, directly coating the polymer resin composition on a substrate, or in a state in which the polymer resin composition is applied on a carrier film, and then removing the carrier film method and the like can be used.

According to an exemplary embodiment of the present invention, the polymer resin layer includes a polyimide-based alkali-soluble resin and a thermosetting binder.

According to an exemplary embodiment of the present invention, the polymer resin layer contains 1 part by weight to 150 parts by weight of the thermosetting binder, or 10 parts by weight to 100 parts by weight, or 20 parts by weight to 100 parts by weight of the polyimide-based alkali-soluble resin. It may be included in 50 parts by weight. If the content of the thermosetting binder is too large, developability of the polymer resin layer may be deteriorated, and strength may be reduced. Conversely, when the content of the thermosetting binder is too low, the polymer resin layer may be developed excessively, and uniformity during coating may be deteriorated.

According to an exemplary embodiment of the present invention, the thermosetting binder is at least one 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. It may include a functional group and an epoxy group. That is, the thermosetting binder necessarily includes 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 It may include a mixture of two or more thereof. Such a thermosetting binder may form a cross-link with a polyimide-based alkali-soluble resin or the like by thermosetting to ensure heat resistance or mechanical properties of the insulating layer. More specifically, as the thermosetting binder, a polyfunctional resin compound including two or more of the above-described functional groups in a molecule may be used.

According to an exemplary embodiment of the present invention, 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. .

According to an exemplary embodiment of the present invention, the thermosetting binder including two or more cyclic (thio) ether groups in the molecule is any one or two types of 3, 4 or 5 membered cyclic ether groups or cyclic thioether groups in the molecule. It may include compounds having at least two or more groups.

According to an exemplary embodiment of the present invention, the compound having two or more cyclic thioether groups in the molecule may be bisphenol A episulfide resin YL7000 manufactured by Japan Epoxy Resins.

According to an exemplary embodiment of the present invention, the polyfunctional resin compound is a polyfunctional epoxy compound containing at least two or more epoxy groups in a molecule, a polyfunctional oxetane compound containing at least two or more oxetanyl groups in a molecule, or two in a molecule An episulfide resin containing at least two thioether groups, a polyfunctional cyanate ester compound containing at least two or more cyanide groups in a molecule, or a polyfunctional benzoxazine compound containing at least two or more benzoxazine groups in a molecule may be included. have.

According to an exemplary embodiment of the present invention, the polyfunctional epoxy compound is 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 Resin, glyoxal type epoxy resin, amino group-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoyl ethane resin, silicone It may be a modified epoxy resin or an ε-caprolactone modified epoxy resin. In addition, for imparting flame retardancy, one in which atoms such as phosphorus are introduced into the structure may be used. The said epoxy resin improves characteristics, such as adhesiveness of a cured film, solder heat resistance, and electroless-plating resistance, by thermosetting.

According to an exemplary embodiment of the present invention, the polyfunctional oxetane compound is bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl] Ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl -3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-ox In addition to polyfunctional oxetanes such as cetanyl)methyl methacrylate and their oligomers or copolymers, oxetane alcohol and novolak resins, poly(p-hydroxystyrene), cardo-type bisphenols, carixarenes, It may be an etherified product with a resin having a hydroxyl group such as carixresorcinarenes or silsesquioxane, and may be a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate.

According to an exemplary embodiment of the present invention, the polyfunctional cyanate ester compound is a bisphenol A-type cyanate ester resin, a bisphenol E-type cyanate ester resin, a bisphenol F-type cyanate ester resin, a bisphenol S-type cyanate ester resin, and a bisphenol M type cyanate ester resin, novolac type cyanate ester resin, phenol novolak type cyanate ester resin, cresol novolak type cyanate ester resin, novolak type cyanate ester resin of bisphenol A, biphenol type cyanate ester resins or oligomers or copolymers thereof.

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

According to an exemplary embodiment of the present invention, the polyfunctional benzoxazine compound is a bisphenol A-type benzoxazine resin, a bisphenol F-type benzoxazine resin, a phenolphthalein-type benzoxazine resin, a thiodiphenol-type benzoxazine resin, and a dicyclopentadiene-type benzoxine. Photo 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.

According to an exemplary embodiment of the present invention, the polyfunctional resin compound is YDCN-500-80P from Kukdo Chemical, phenol novolac-type cyanite Esner resin PT-30S from Lonza, and phenylmethane-type maleimide resin BMI- from Daiwa. 2300, may be a Pd-type benzoxazine resin from Shikoku.

According to an exemplary embodiment of the present invention, the polyimide-based alkali-soluble resin is as described above.

According to an exemplary embodiment of the present invention, the polymer resin layer 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.

According to an exemplary embodiment of the present invention, as the thermosetting catalyst, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4 -imidazole derivatives such as phenylimidazole, 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; It may be a phosphorus compound of triphenylphosphine. Specifically, Shikoku Chemical Co., Ltd. 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole-based compounds), U-CAT3503N, UCAT3502T (all are dimethylamine block isocyanate compounds by San Apro) trade names), DBU, DBN, U-CATS A102, and U-CAT5002 (all of which are bicyclic amidine compounds and salts thereof). It is not particularly limited thereto, and may be a thermosetting catalyst of an epoxy resin or an oxetane compound, or one that promotes 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-isosanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isosaanuric acid An S-triazine derivative such as an adduct may be used, and a compound that preferably functions also as an adhesive imparting agent may be used in combination with the thermosetting catalyst. By using the above-mentioned thermosetting catalyst, thermosetting of the thermosetting binder can be promoted.

According to an exemplary embodiment of the present invention, the inorganic filler may be silica, barium sulfate, barium titanate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica, or a mixture of two or more thereof.

According to an exemplary embodiment of the present invention, examples of the content of the inorganic filler are not particularly limited, but in order to achieve high rigidity of the polymer resin layer, with respect to 100 parts by weight of all resin components included in the polymer resin layer, the The inorganic filler may be added in an amount of 100 parts by weight or more, or 100 parts by weight to 600 parts by weight, or 150 parts by weight to 500 parts by weight, or 200 parts by weight to 500 parts by weight.

According to an exemplary embodiment of the present invention, the release agent may be low molecular weight polypropylene, low molecular weight polyethylene polyalkylene wax, ester wax, carnauba wax, or paraffin wax.

According to an exemplary embodiment of the present invention, the metal adhesion enhancer may be a material that does not cause a problem in the surface quality or transparency of the metal material. Specifically, a silane coupling agent or an organometallic coupling agent may be used.

According to an exemplary embodiment of the present invention, the leveling agent may be BYK-380N, BYK-307, BYK-378, BYK-350 of BYK-Chemie GmbH, and by using the leveling agent, popping the surface during film coating or craters can be removed.

According to an exemplary embodiment of the present invention, the polymer resin layer may further include a resin or elastomer having a weight average molecular weight of 5000 or more that may cause phase separation. Accordingly, roughening treatment of the cured product of the polymer resin layer may be possible. Examples of the method for measuring the molecular weight of the resin or elastomer having a weight average molecular weight of 5000 or more are not particularly limited, and for example, it means a weight average molecular weight in terms of polystyrene measured by GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a commonly known analyzer and a detector such as a differential refraction detector and a column for analysis may be used, and the temperature generally applied Conditions, solvents, and flow rates can be applied. Specific examples of the measurement conditions include a temperature of 30, a chloroform solvent (Chloroform), and a flow rate of 1 mL/min.

According to an exemplary embodiment of the present invention, the polymer resin layer may further include a photoinitiator in order to impart photocurable properties to the polymer resin layer. Specific examples of the photoinitiator are not particularly limited, and various compounds used in the art related to the photocurable resin composition may be used without limitation.

According to an exemplary embodiment of the present invention, the content of the photoinitiator contained in the polymer resin layer may be 0.01 wt% 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 relative to 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 that the photoinitiator is not included at all. . Accordingly, the interfacial detachability with the insulating layer or the conductive layer, which may be caused by the photoinitiator, may be reduced, and thus the adhesiveness and durability of the insulating layer may be improved.

According to an exemplary embodiment of the present invention, it comprises the step of forming a laminate by providing a photosensitive resin layer on the polymer resin layer.

The photosensitive resin layer includes a polymer whose molecular structure is changed by the action of light and changes in physical properties, and may be a photosensitive dry film resist (DFR) or a liquid resist.

According to an exemplary embodiment of the present invention, the photosensitive resin layer may exhibit photosensitivity and alkali solubility. Accordingly, the molecular structure may be deformed by the exposure process of irradiating light to the photosensitive resin layer, and the resin layer may be etched or removed by the developing process of contacting an alkaline developer.

According to an exemplary embodiment of the present invention, the example of the method of forming the photosensitive resin layer on the polymer resin layer is not particularly limited, but 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 method of coating the photosensitive resin composition on the polymer resin layer by spraying or dipping and pressing the photosensitive resin composition may be used.

According to an exemplary embodiment of the present invention, the thickness of the polymer resin layer is 1 μm to 500 μm, or 3 μm to 500 μm, or 3 μm to 200 μm, or 1 μm to 60 μm, or 5 μm to 30 μm. The thickness of the photosensitive resin layer formed on the polymer resin layer is 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. can When the thickness of the photosensitive resin layer is excessively increased, the resolution of the polymer resin layer may decrease.

According to an exemplary embodiment of the present invention, the method includes patterning a laminate provided with a photosensitive resin layer on the polymer resin layer by exposing and alkali development.

According to an exemplary embodiment of the present invention, the photosensitive resin layer may exhibit photosensitivity and alkali solubility. Accordingly, the molecular structure may be deformed by the exposure process of irradiating light to the photosensitive resin layer, and the resin layer may be etched or removed by the 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. As described above, the portion of the photosensitive resin layer that remains intact without being alkali-developed by exposure is referred to as a photosensitive resin pattern.

According to an exemplary embodiment of the present invention, in the method of exposing the photosensitive resin layer, a photomask formed in a predetermined pattern on the photosensitive resin layer is contacted and irradiated with ultraviolet rays, or a predetermined pattern included in the mask is projected with an objective lens. It is possible to selectively expose through a method such as irradiating ultraviolet light after imaging through a laser diode, or directly imaging using a laser diode as a light source and then irradiating ultraviolet light. At this time, examples of the ultraviolet irradiation condition include irradiation with a light amount of 5 mJ/cm 2 to 600 mJ/cm 2 .

According to an exemplary embodiment of the present invention, the method of alkali development after exposure to the photosensitive resin layer may be a method of treating an alkali developer. Examples of the alkali developer are not particularly limited, but may be used by adjusting 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, and amines. Also, alkali developer sold as a commercial product can be used. The specific amount of the alkali developer is not particularly limited, but it is necessary to adjust the concentration and temperature not to damage the photosensitive resin pattern. For example, 0.5 to 3% aqueous solution of sodium carbonate at 25 ° C. to 35 ° C. may be used.

According to an exemplary embodiment of the present invention, the ratio at which the photosensitive resin pattern is removed may be 0.01 wt% or less based on the total weight of the photosensitive resin pattern. When the ratio at which the photosensitive resin pattern is removed is 0.01 wt% or less based on the total weight of the photosensitive resin pattern, it may mean that the ratio at which the photosensitive resin pattern is removed is very insignificant or that the photosensitive resin pattern is not removed at all.

Accordingly, in the method of manufacturing the insulating layer, the photosensitive resin layer is exposed and alkali-developed to form a photosensitive resin pattern, and at the same time, the polymer resin layer exposed by the photosensitive resin pattern can be alkali-developed. As described above, in the photosensitive resin layer, a fine and uniform pattern can be formed using photosensitivity, and only a portion of the surface of the polymer resin layer exposed through the pattern formed on the photosensitive resin layer is selectively contacted with an alkali developer. Through this process, it is possible to secure the same level of precision or higher and higher process economics while replacing the conventional laser etching process.

That is, in the step of alkali-developing the polymer resin layer exposed by the photosensitive resin pattern, the photosensitive resin pattern is not removed by the alkaline developer, it remains as it is and is used as a resist mask, and alkali through the opening of the photosensitive resin pattern The developer may contact the polymer resin layer located below the photosensitive resin layer. In this case, since the polymer resin layer contains the polyimide-based alkali-soluble resin, it has alkali solubility that is dissolved by the alkali developer, and thus the portion of the polymer resin layer in contact with the alkali developer may be dissolved and removed.

Therefore, the polymer resin layer exposed by the photosensitive resin pattern means a portion of the polymer resin layer whose surface is not in contact with the photosensitive resin pattern, and alkali development of the polymer resin layer exposed by the photosensitive resin pattern is The method may include the step of allowing the alkali developer used to form the photosensitive resin pattern to pass through the photosensitive resin pattern and contact the lower polymer resin layer.

By alkali-developing the polymer resin layer exposed by the photosensitive resin pattern, a polymer resin pattern having the same shape as the photosensitive resin pattern may be formed on the polymer resin layer as shown in FIG. 1 below. 1 schematically shows an insulating layer manufacturing process according to an embodiment of the present invention. Like the photosensitive resin pattern, a portion of the polymer resin layer that remains as it is without alkali development may be referred to as a polymer resin pattern.

In this way, as pattern formation through the development of the photosensitive resin layer and pattern formation through the development of the polymer resin layer proceed simultaneously in one alkali developer, mass production is possible quickly, so the efficiency of the process can be improved. , it is possible to easily introduce a fine pattern having the same shape as the fine pattern formed on the photosensitive resin layer into the polymer resin layer by a chemical method.

According to an exemplary embodiment of the present invention, the photosensitive resin layer is exposed and alkali-developed to form a photosensitive resin pattern, and at the same time, after the step of alkali-developing the polymer resin layer exposed by the photosensitive resin pattern, the photosensitive resin pattern 0.1 wt% to 85 wt%, or 0.1 wt% to 50 wt%, or 0.1 wt% to 10 wt% based on the total weight of the polymer resin layer exposed by This seems to be because the polyimide-based alkali-soluble resin contained in the polymer resin layer was removed by the alkali developer, but the thermosetting binder or inorganic filler having little alkali developability was not removed and remained.

According to an exemplary embodiment of the present invention, in order to control the degree of remaining of the inorganic filler and the thermosetting binder, the weight ratio of the thermosetting binder and the inorganic filler to the polyimide-based alkali-soluble resin, the ratio of the acid functional groups on the surface of the inorganic filler, etc. Preferably, 20 to 100 parts by weight of the thermosetting binder and 100 to 600 parts by weight of the inorganic filler may be added relative to 100 parts by weight of the polyimide-based alkali-soluble resin, and the acid value of the inorganic filler surface ) may be 0 mgKOH/g to 5 mgKOH/g, or 0.01 mgKOH/g to 5 mgKOH/g. The content regarding the acid value is the same as the method for measuring the acid value of the polyimide-based alkali-soluble resin.

As such, in the process of alkali-developing the polymer resin layer exposed by the photosensitive resin pattern, as some polymer resin layers remain without being developed, the target polymer resin pattern is removed during the subsequent removal process of the photosensitive resin pattern. Instead, as the remaining polymer resin layer is removed, it is possible to prevent expansion of the via hole due to the removal of the polymer resin pattern.

According to an exemplary embodiment of the present invention, after the alkali development, it comprises the step of thermosetting the patterned polymer resin layer.

According to an exemplary embodiment of the present invention, the method for manufacturing the insulating layer may include thermosetting the polymer resin layer after the alkali development. By including the step of thermosetting the polymer resin layer, it is possible to minimize damage to the polymer resin layer during a subsequent photosensitive resin pattern peeling process.

At this time, the specific thermosetting conditions are not limited, and it can be carried out by adjusting the desired conditions according to the peeling method of the photosensitive resin pattern. For example, when the photoresist pattern is peeled off by treating the photoresist stripper, the thermosetting of the polymer resin layer may be performed at a temperature of 60 to 150° C. for 5 minutes to 2 hours. If the thermosetting temperature of the polymer resin layer is too low or the thermosetting time is short, the polymer resin pattern may be damaged by the stripper, and the thermosetting temperature of the polymer resin layer is high or the thermosetting time is long. In this case, it may be difficult to remove the photosensitive resin pattern by the stripper.

According to an exemplary embodiment of the present invention, when the resist mask is peeled through a desmear process, the step of thermosetting the polymer resin layer may be performed at a temperature of 150 to 230° C. for 1 hour to 4 hours. .

According to an exemplary embodiment of the present invention, it comprises the step of peeling the patterned photosensitive resin pattern.

According to an exemplary embodiment of the present invention, the method for manufacturing the insulating layer may include peeling the photosensitive resin pattern after the thermosetting. When removing the photosensitive resin pattern, it is preferable to use a method capable of removing only the photosensitive resin layer without removing the lower polymer resin layer as much as possible. In addition, a portion of the polymer resin layer may be removed to adjust the shape of the opening pattern or to remove residues of the polymer resin layer that may remain on the bottom surface of the opening pattern.

According to an exemplary embodiment of the present invention, the ratio at which the polymer resin layer is removed in the step of peeling the photosensitive resin pattern may be 10 wt% or less, or 1 wt% or less, or 0.01 wt% or less, based on the total weight of the polymer resin layer . When the ratio at which the polymer resin layer is removed is 0.01 wt % or less based on the total weight of the polymer resin layer, it may mean that the ratio at which the polymer resin layer is removed is very insignificant or that the polymer resin layer is not removed at all.

According to an exemplary embodiment of the present invention, as a specific example of the method for stripping the photosensitive resin pattern, a photoresist stripper may be treated, a desmear process or plasma etching may be performed, and the above methods may be mixed. You may.

According to an exemplary embodiment of the present invention, the peeling method using a photoresist stripper is not limited, but it can be used by adjusting the concentration and temperature of an aqueous alkali solution such as potassium hydroxide and sodium hydroxide, and Atotech's Resistrip product line, Oalchem's Commercially available products such as ORC-731, ORC-723K, ORC-740, and SLF-6000 can also be used. The specific amount of the photoresist stripper is not particularly limited, but it needs to be adjusted to a concentration and temperature that does not damage the lower polymer resin layer pattern, and a 1 to 5% aqueous solution of sodium hydroxide at 25°C to 60°C can be used. .

According to an exemplary embodiment of the present invention, the peeling method using the desmear process is not limited, and Atotech's desmear process chemicals include Securiganth E, Securiganth HP, Securiganth BLG, Securiganth MV SWELLER, Securiganth SAP SWELLER's sweater drugs, Securiganth P 500, Securiganth MV ETCH P, Securiganth SAP ETCH P's permanganic acid, Securiganth E Reduction Cleaner, Securiganth HP Reduction Cleaner, Securiganth BLG Reduction Cleaner, Securiganth MV Reduction Cleaner, Securiganth SAP Reduction Cleaner's reducing agent or Desmere's Oalchem As process chemicals, commercial products such as ORC-310A, ORC-315A, ORC-315H, ORC-312 sweller, ORC-340B, etc. can be used appropriately.

According to another exemplary embodiment of the present invention, an insulating layer manufactured by the manufacturing method; And it provides a multilayer printed circuit board having a metal substrate provided with a pattern on the insulating layer.

The multilayer printed circuit board according to another exemplary embodiment of the present invention has improved dimensional stability at room temperature, thereby improving the reliability of semiconductor build-up.

Specifically, the insulating layer manufactured by the insulating layer manufacturing method has improved physical properties by increasing the glass transition temperature, and since the metal substrate is provided on the insulating layer, dimensional stability is improved at room temperature, so that the via hole is left at room temperature for a long time. may not be expanded.

According to an exemplary embodiment of the present invention, the insulating layer may be used as an interlayer insulating material of a multilayer printed circuit board, and may include a thermosetting product of a polyimide-based alkali-soluble resin and a thermosetting binder. Details regarding the polyimide-based alkali-soluble resin and the thermosetting binder are the same as described above.

According to an exemplary embodiment of the present invention, the multilayer printed circuit board may be manufactured by performing the step of providing a metal substrate having a pattern on the insulating layer. The step of providing the metal substrate on which the pattern is formed on the insulating layer is a microcircuit pattern forming process known in the art as a Semi Additive Process (SAP), wherein the SAP process forms a microcircuit pattern with nothing on the insulating layer. It may mean the case of being equipped.

2 schematically shows a multilayer printed circuit board manufacturing process according to an exemplary embodiment of the present invention. According to an exemplary embodiment of the present invention, the step of providing a metal substrate having a pattern on the insulating layer as shown in FIG. 2 includes: providing a metal thin film on the insulating layer; providing a photosensitive resin layer having a pattern on the metal thin film; depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern; and removing the photosensitive resin layer and removing the exposed metal thin film.

According to an exemplary embodiment of the present invention, in the step of forming the metal thin film on the insulating layer, examples of the method for forming the metal thin film include a dry deposition process or a wet deposition process, and specifically, the dry deposition process is performed in a vacuum. vapor deposition, ion plating, sputtering, or the like.

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

According to an exemplary embodiment of the present invention, there are dry and wet methods depending on conditions in the roughening treatment process, and examples of the dry method include vacuum, atmospheric pressure, plasma treatment for each gas, Excimer UV treatment for each gas, etc. As an example of the wet method, a desmear treatment may be used. Through this roughening process, it is possible to increase the surface roughness of the metal thin film to improve adhesion to the metal deposited on the metal thin film.

According to an exemplary embodiment of the present invention, the step of providing the photosensitive resin layer with a pattern formed on the metal thin film may include exposing and developing the photosensitive resin layer formed on the metal thin film. The content of the photosensitive resin layer and exposure and development may include the content described above in the embodiment.

According to an exemplary embodiment of the present invention, in the step of depositing a metal on the metal thin film exposed by the photosensitive resin layer pattern, the metal thin film exposed by the photosensitive resin layer pattern is not in contact with the photosensitive resin layer on the surface It means the part of the metal thin film that is not. Copper may be used as the deposited metal, and the deposition method is not limited, and various known physical or chemical deposition methods may be used without limitation. Specifically, it is preferable to use an electrolytic copper plating method.

According to an exemplary embodiment of the present invention, in the step of removing the photosensitive resin layer and removing the exposed metal thin film, a photoresist stripper may be used as an example of a method for removing the photosensitive resin layer, and the photosensitive resin layer An etchant may be used as an example of a method of removing the metal thin film exposed due to the removal of the etchant.

According to an exemplary embodiment of the present invention, the multilayer printed circuit board manufactured by the method for manufacturing the multilayer printed circuit board can be used again as a build-up material, for example, on the multilayer printed circuit board of the exemplary embodiment. A first process of forming an insulating layer according to the insulating layer manufacturing method and a second process of forming a metal substrate on the insulating layer according to the method for manufacturing a multilayer printed circuit board of another embodiment may be repeated. Accordingly, the number of stacked layers included in the multilayer printed circuit board manufactured by the method for manufacturing the multilayer printed circuit board is also not significantly limited, and for example, one or more layers, or 1 to 20 layers, depending on the purpose and purpose of use. can have

Hereinafter, examples will be given to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present invention to those of ordinary skill in the art.

Example 1

<Production of polyimide alkali-soluble resin>

200 g of dimethyl acetamide (DMAc) as a solvent in a reaction vessel with a heating and cooling volume of 2 liters equipped with a manufacturing thermometer, a stirring device, a reflux cooling tube, and a moisture meter, including a repeating unit represented by the above formula (3) 100 g of Cray Valley's SMA1000 as a polymer to A mixture was prepared by mixing 70 g of 4-aminophenylacetic acid as the containing amine compound.

Thereafter, the mixture was stirred at 85° C. for 24 hours to prepare a polyimide-based alkali-soluble resin solution having a solid content of 50%.

<Manufacture of insulating layer>

Referring to the contents of FIG. 1 below, 16 g of the synthesized polyimide-based alkali-soluble resin, 5 g of MY-510 (manufactured by Huntsman) as a thermosetting binder, and 35 g of SC2050 MTO (70% solid content, manufactured by Adamatech) as an inorganic filler are mixed polymer The resin composition was applied to a PET film and dried to prepare a polymer resin layer (1) having a thickness of 15 µm. and. The polymer resin layer (1) was vacuum-laminated at 85°C on the circuit board on which the copper line (2) was formed on the copper clad laminate (3), and the PET film was removed. A 15 μm thick photosensitive dry film resist KL1015 (manufactured by Kolon Industries) (4) was laminated on the polymer resin layer (1) at 110°C.

A circular negative-type photomask having a diameter of 30 μm was brought into contact with the photosensitive dry film resist 4, irradiated with ultraviolet rays (amount of light of 25 mJ/cm 2 ), and then the dry film resist was passed through a 1% sodium carbonate developer at 30° C. (4) and the polymer resin layer (1) were developed sequentially.

At this time, the photosensitive dry film resist 4 on which the pattern is formed acts as a protective layer of the polymer resin layer 1, and the same pattern as the photosensitive dry film resist 4 is formed on the polymer resin layer 1 as well. A via hole 5 was formed. At this time, a white residue derived from the polymer resin layer 1 remained inside the via hole 5 .

Thereafter, after thermosetting at a temperature of 100 for 1 hour, the residue and the photosensitive dry film resist 4 were removed using a 3% sodium hydroxide resist stripper at a temperature of 50° C., and thermosetting at a temperature of 200° C. for 1 hour. The process of reconciliation was further carried out.

<Manufacturing of multilayer printed circuit boards>

2, copper (Cu) metal is reduced to 300 nm through sputtering while supplying a mixed gas of argon and oxygen to the upper surface of the prepared insulating layer 7 and the side of the via hole 5 to the deposition equipment. A seed layer 8 was formed by vapor deposition.

Thereafter, the photosensitive resin layer was exposed and developed on the seed layer 8 to form a photosensitive resin pattern 9 . Then, a metal substrate 10 made of copper was formed to a thickness of 20 μm on the seed layer 8 through electroplating. Next, the photosensitive resin pattern 9 was removed using a photosensitive resin stripper, and thus the exposed seed layer 8 was removed through etching to prepare a multilayer printed circuit board.

Comparative Example 1

To Example 1 a polyimide-based alkali-soluble resin in the manufacturing process in Example 1, the same multi-layer printed circuit board and, and except that the TPE-R 5g was prepared.

Experimental Example 1 (Glass Transition Temperature Measurement)

Using DMA (TA, Q800), the glass transition temperature of the polymer resin layer prepared in Example 1 and Comparative Example 1 was measured through the above-described method.

3 is a graph showing the glass transition temperature of the polymer resin layer prepared in Example 1 and Comparative Example 1 measured using a dynamic mechanical analyzer (DMA).

Referring to FIG. 3, using TPE-R as the aromatic diamine compound, the content of TPE-R was adjusted to 7.5 parts by weight based on 100 parts by weight of the polymer including the repeating unit represented by Formula 3, prepared in Example 1 It was confirmed that the glass transition temperature of the polymer resin layer was about 256 °C.

On the other hand, even when TPE-R is used, the glass transition of the polymer resin layer prepared in Comparative Example 1, wherein the content of TPE-R is 5 parts by weight based on 100 parts by weight of the polymer including the repeating unit represented by Chemical Formula 3 It was confirmed that the temperature was about 251 °C.

That is, it can be seen that the glass transition temperature of the polymer resin layer using the polyimide-based alkali-soluble resin according to an exemplary embodiment of the present invention is improved.

Experimental Example 2 (Dimensional stability evaluation)

Whether the pattern of the multilayer printed circuit board of Example 1 and Comparative Example 1 changed was confirmed with a microscope, and the size of the pattern was measured.

4 is an enlarged photograph of a pattern among the multilayer printed circuit boards of Example 1 and Comparative Example 1. FIG. Specifically, as shown in FIG. 4 , the pattern after peeling, the pattern before peeling immediately after the pattern was formed, and the pattern before peeling one day after the pattern was formed, were checked for size changes through a microscope, and the pattern before peeling immediately after the pattern was formed and the pattern was formed After 1 day, the size of the pattern before peeling was measured. The sizes of the measured patterns are summarized in Table 1 below.

division Example 1 Comparative Example 1 Pattern size immediately after pattern formation and before peeling (㎛) 13 13 Pattern size (μm) before peeling after 1 day of pattern formation 14 18

4 and Table 1, an example in which TPE-R is used as the aromatic diamine compound, and the content of TPE-R is adjusted to 7.5 parts by weight based on 100 parts by weight of the polymer including the repeating unit represented by Chemical Formula 3 1, it was confirmed that the size of the pattern was maintained almost the same, so that the dimensional stability at room temperature was improved.

In contrast, in Comparative Example 1, even when TPE-R is used, the content of TPE-R corresponds to 5 parts by weight with respect to 100 parts by weight of the polymer including the repeating unit represented by Formula 3, so the size of the pattern is expanded. It was confirmed that the dimensional stability at room temperature was low.

Therefore, it can be seen that an insulating layer having improved glass transition temperature and improved dimensional stability at room temperature can be implemented by using the polyimide-based alkali-soluble resin according to an exemplary embodiment of the present invention.

1: polymer resin layer
2: Copper line
3: Copper clad laminate
4: Photosensitive dry film resist (DFR)
5: Via Hall
6: metal layer
7: Insulation layer
8: seed layer
9: Photosensitive resin pattern
10: metal substrate
<1> to <6>: process sequence

Claims (10)

As a polyimide-based alkali-soluble resin comprising a repeating unit represented by the following formula (1), and a repeating unit represented by the following formula (2),
The polyimide-based alkali-soluble resin,
It is a reaction product of a mixture comprising a polymer including a repeating unit represented by the following Chemical Formula 3, an aromatic diamine compound, and an amine compound containing an acidic functional group,
The content of the aromatic diamine compound is 6 parts by weight or more and 15 parts by weight or less of the polyimide-based alkali-soluble resin based on 100 parts by weight of the polymer including the repeating unit represented by Formula 3:
[Formula 1]

[Formula 2]

[Formula 3]

In Formula 1, R ₁ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or represented by Formula 4 below,
[Formula 4]

In Formula 2, n is an integer of 1 to 3,
In Formula 4, R ₂ is an alkylene group having 1 to 3 carbon atoms,
In Formulas 1 to 4, "*" means a bonding point.
The method according to claim 1,
The aromatic diamine compound is a polyimide-based alkali-soluble resin, which is a compound represented by the following formula (5):
[Formula 5]

In Formula 5, n is an integer of 1 to 3.
3. The method according to claim 2,
The aromatic diamine compound is a polyimide-based alkali-soluble resin comprising at least one of a compound represented by the following Chemical Formula 5-1 and a compound represented by the following Chemical Formula 5-2:
[Formula 5-1]

[Formula 5-2]

The method according to claim 1,
The repeating unit represented by the formula (2) is a polyimide-based alkali-soluble resin comprising a repeating unit represented by the following formula (2-1):
[Formula 2-1]

In Formula 2-1, "*" means a bonding point.
The method according to claim 1,
The content of the acidic functional group-containing amine compound is 60 parts by weight or more and 80 parts by weight or less based on 100 parts by weight of the polymer including the repeating unit represented by Formula 3, polyimide-based alkali-soluble resin.
The method according to claim 1,
The acidic functional group-containing amine compound is a polyimide-based alkali-soluble resin comprising a compound represented by the following Chemical Formula 6:
[Formula 6]

In Formula 6, R ₁ is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or represented by Formula 4 below,
[Formula 4]

In Formula 4, R ₂ is an alkylene group having 1 to 3 carbon atoms, and "*" means a bonding point.
7. The method of claim 6,
The acidic functional group-containing amine compound is a polyimide-based alkali-soluble resin comprising a compound represented by the following Chemical Formula 6-1:
[Formula 6-1]

In Formula 6, R ₂ is an alkylene group having 1 to 3 carbon atoms.
providing a polymer resin layer including the polyimide-based alkali-soluble resin of claim 1 and a thermosetting binder on the conductor wiring;
forming a laminate by providing a photosensitive resin layer on the polymer resin layer;
patterning the laminate by exposure and alkali development;
thermosetting the patterned polymer resin layer; and
Insulating layer manufacturing method comprising; peeling off the patterned photosensitive resin layer.
9. The method of claim 8,
The polymer resin layer is an insulating layer manufacturing method comprising 1 part by weight to 150 parts by weight of a thermosetting binder based on 100 parts by weight of a polyimide-based alkali-soluble resin.
an insulating layer manufactured by the manufacturing method according to claim 8; and
A multilayer printed circuit board comprising a metal substrate having a pattern on the insulating layer.

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