KR20230052472A - Method for manufacturing cupper clad laminate - Google Patents

Abstract

The present invention relates to a method for manufacturing a copper clad laminate of a multi-layer structure. More specifically, the present invention relates to the method for manufacturing the copper clad laminate of the multi-layer structure by forming a copper thin film on a surface of a surface-processed polymer substrate after surface processing the polymer substrate with a surface processing composition for a substrate adhesion comprising a triazine compound having an alkoxysilane through an ethylene glycol residue and a triazine backbone substituted with amino through an alkylene residue. Therefore, the present invention is capable of solving for a problem such as a decrease of durability and the like.

Description

Manufacturing method of copper clad laminate with multi-layer structure {METHOD FOR MANUFACTURING CUPPER CLAD LAMINATE}

The present invention relates to a method for manufacturing a copper clad laminate having a multi-layer structure, and more particularly, to adhesion to a substrate including a triazine compound having a triazine backbone substituted with an alkoxysilane through an ethylene glycol residue and an amino-substituted triazine backbone through an alkylene residue It relates to a method for manufacturing a copper-clad laminate having a multilayer structure by surface-treating a polymer substrate with a surface treatment composition and then forming a copper thin film (copper foil) on the surface of the surface-treated polymer substrate.

Flexible Cupper Clad Laminate (FCCL), a core material of FPCB (Flexible Printed Circuit Board) used in mobile phones and LCDs, is a multi-layered two- or three-layer structure in which polyimide is laminated on copper foil. It is a film.

The three-layer FCCL consists of an insulating layer, an adhesive layer, and a copper foil layer, and an adhesive layer exists in the middle of the two layers to combine the insulating layer, PI (polyimide) film or MPI (modified PI) film and the copper foil layer. . However, the FCCL having a three-layer structure has problems in that the thickness of the FCCL becomes thick due to the existence of the adhesive layer, it is disadvantageous to miniaturization of the copper pattern, and the dielectric constant increases due to the adhesive. In addition, due to lack of transparency of the adhesive or deterioration of the adhesive, a problem in durability may occur.

The two-layer structure FCCL is composed of only an insulating layer and a copper foil layer without using the above adhesive, and has an advantage in that it is thinner and realizes a narrower pitch.

As the precision of the wiring printed on the FCCL improves, the surface roughness of the copper foil is required to be lowered in order to cope with the improvement in etching precision. However, when the roughness of the surface of the copper foil is lowered, the adhesive strength between the copper foil layer and the insulating layer (eg, polyimide film) is lowered, so a means for supplementing this is required.

The copper clad laminate (CCL, Cupper Clad Laminate) used in conventional flexible printed circuit boards is a three-layer copper clad laminate using an epoxy adhesive. has the disadvantage of being unsuitable.

Recently, as the reduction in roughness and thickness of copper foil is required due to microcircuits, the adhesive strength between the copper foil and the insulating substrate is required to be higher. That is, in the case of the existing copper foil with adhesive used in the manufacture of copper clad laminates and printed circuit boards, since the roughness of the copper foil is high, when the adhesive used here is used as it is, when the copper foil roughness is lowered, the adhesive strength is reduced.

Conventionally, a method of using a silane coupling agent as a surface treatment agent for tin foil has been known to enhance the adhesion between the copper foil layer and the substrate, but using the silane coupling agent alone causes problems with the stability of the coating solution, resulting in product degradation over manufacturing time. There is a problem in reproducibility, and there is a disadvantage in that the adhesion between the copper foil having no surface roughness (Rz less than 0.80 μm), that is, the copper foil without roughening treatment and the polyimide is low.

That is, the known techniques are still insufficient in improving the adhesiveness, and there is a problem that they can be applied only to a specific foil.

Therefore, in order to manufacture a flexible copper clad laminate having excellent adhesion, a surface treatment agent applicable to various insulating layers as well as copper foil is required.

KR 10-1298998 B1 KR 10-0282065 B1

An object of the present invention is to provide a method for manufacturing a copper clad laminate having a multilayer structure having a strong bonding force between a copper thin film and an insulating substrate.

The present invention provides a method for manufacturing a copper clad laminate having a multilayer structure using a surface treatment composition for substrate adhesion comprising a triazine-based compound having a triazine backbone in which alkoxysilane through an ethylene glycol residue and amino through an alkylene residue are substituted. intended to provide

In order to achieve the above object, the present invention is a surface treatment composition for substrate adhesion comprising a triazine-based compound having a triazine backbone in which an alkoxysilane through an ethylene glycol residue and an amino through an alkylene residue are substituted. Surface treatment of a polymer substrate After the surface treatment, a copper thin film is formed on the surface of the polymer substrate to provide a method for manufacturing a copper clad laminate having a multi-layer structure.

Specifically, the present invention comprises the steps of treating the surface of a polymer substrate with a surface treatment composition for substrate adhesion comprising a compound represented by Formula 1; and forming a copper thin film by plating copper on the surface of the surface-treated polymer substrate.

[Formula 1]

In Formulas 1 and 2,

이고;R ¹ is hydrogen or

ego;

이고;R ² is hydrogen or

ego;

또는

이고;R ^A is

or

ego;

또는

이고;R ^B is hydrogen,

or

ego;

R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 and R ^d2 to R ^f2 are each independently C1-C10 alkyl;

m1, n1, m2, n2, m3, n3, m4 and n4 are each independently an integer of 1 to 10.

In the manufacturing method according to an embodiment, the compound of Formula 1 may be represented by Formula 2 or Formula 3 below.

[Formula 2]

[Formula 3]

In Formulas 2 and 3,

이고;R ¹ is hydrogen or

ego;

이고;R ² is hydrogen or

ego;

이고;R ^B1 is hydrogen or

ego;

이고;R ^B2 is hydrogen or

ego;

R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 and R ^d2 to R ^f2 are each independently C1-C10 alkyl;

m1, n1, m2, n2, m3, n3, m4 and n4 are each independently an integer of 1 to 10.

In Chemical Formulas 2 and 3 according to an embodiment, R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 , and R ^d2 to R ^f2 are each independently C1-C3 alkyl; m1, n1, m2, n2, m3, n3, m4, and n4 may each independently be an integer of 1 to 5.

이고; R^B1는

이고; n1, n2, n3 및 n4은 각각 독립적으로 1 내지 5의 정수일 수 있다.In Formula 2 according to an embodiment, R ² is

ego; R ^B1 is

ego; n1, n2, n3, and n4 may each independently be an integer of 1 to 5.

이고; R^B2는

이고; R^a1 내지 R^c1, R^a2 내지 R^c2, R^d1 내지 R^f1 및 R^d2 내지 R^f2는 각각 독립적으로 C1-C3알킬이고; m1, m2, m3 및 m4은 각각 독립적으로 1 내지 5의 정수일 수 있다.In Formula 3 according to an embodiment, R ¹ is

ego; R ^B2 is

ego; R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 and R ^d2 to R ^f2 are each independently C1-C3 alkyl; m1, m2, m3 and m4 may each independently be an integer of 1 to 5.

이고; n1 및 n2은 각각 독립적으로 1 내지 5의 정수일 수 있다.In Formula 3 according to an embodiment, R ² is

ego; n1 and n2 may each independently be an integer of 1 to 5.

In one embodiment, the surface treatment composition for substrate adhesion may further include a solvent, wherein the solvent is one or two or more selected from the group consisting of water, alcohol, ketone, aromatic hydrocarbon, aliphatic hydrocarbon, ester, and ether. It may be a mixture, but is not limited thereto.

In one embodiment, the surface treatment composition for substrate adhesion may include the compound of Formula 1 in an amount of 0.001 to 10% by weight based on the total weight of the composition, but is not limited thereto.

In one embodiment, the surface treatment of the polymer substrate may be performed by immersing the polymer substrate in the surface treatment composition for substrate adhesion.

According to one embodiment, the plating may be electroless plating.

According to one embodiment, the polymer substrate may include polyimide (　PI), modified polyimide (MPI), polyetherether ketone (PEEK), syndiotactic polystyrene (SPS), and It may be one or more selected from polytetrafluoroethylene (PTFE), but is not limited thereto.

According to one embodiment, the multi-layered laminate may be a 2-layer flexible copper clad laminate (2-FCCL).

A method for manufacturing a copper clad laminate having a multi-layer structure according to the present invention uses a surface treatment composition for substrate adhesion that includes a triazine-based compound having a triazine backbone in which an alkoxysilane through an ethylene glycol residue and an amino through an alkylene residue are substituted. After the surface treatment of the polymer substrate, a copper thin film is formed on the surface of the surface-treated polymer substrate to manufacture a flexible copper-clad laminate having a multilayer structure with a significantly reduced thickness and significantly improved adhesive strength without using a separate adhesive.

In addition, according to the present invention, since a separate adhesive is not used, it is possible to manufacture a flexible copper clad laminate having a multi-layer structure with a smaller thickness, and problems such as an increase in dielectric constant due to the adhesive and a decrease in durability due to deterioration of the adhesive can be solved. can be resolved

That is, according to the present invention, a low dielectric constant low loss copper clad laminate (CCL), specifically a flexible copper clad laminate (FCCL), more specifically a two-layer structure flexible copper clad laminate ( 2-FCCL) can be efficiently produced.

Hereinafter, the present invention will be described in more detail. If there is no other definition in the technical terms and scientific terms used at this time, they have meanings commonly understood by those of ordinary skill in the art to which this invention belongs, and will unnecessarily obscure the gist of the present invention in the following description. Descriptions of possible known functions and configurations are omitted.

In this specification, the term “alkyl” is a monovalent substituent, and includes both linear and branched forms.

In this specification, the term “comprising” is an open-ended description having an equivalent meaning to expressions such as “includes”, “includes”, “has” or “characterized by”, and is not further listed. It does not exclude any element, material or process that is not

In this specification, the singular form used may be intended to include the plural form as well, unless the context specifically dictates otherwise.

In this specification, units used without particular notice are based on weight, and for example, % or a unit of ratio means weight% or weight ratio.

In the present specification, a metal clad laminate means a plate including an insulating layer and a metal layer laminated on one or both surfaces of the insulating layer, and is an original plate for manufacturing a printed circuit board, that is, It is used as a concept including Copper Clad Laminate (CCL), etc., which is used to manufacture a PCB (Printed Circuit Board) original plate.

The present invention is a surface treatment agent composition for substrate adhesion comprising a triazine-based compound having a triazine backbone in which an alkoxysilane through an ethylene glycol residue and an amino through an alkylene residue are substituted, specifically a compound represented by the following formula (1), which is a polymer substrate treating the surface of; And forming a copper thin film by plating copper on the surface of the surface-treated polymer substrate; provides a method for manufacturing a copper clad laminate having a multi-layer structure including:

[Formula 1]

In Formula 1,

이고;R ¹ is hydrogen or

ego;

이고;R ² is hydrogen or

ego;

또는

이고;R ^A is

or

ego;

또는

이고;R ^B is hydrogen,

or

ego;

R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 and R ^d2 to R ^f2 are each independently C1-C10 alkyl;

m1, n1, m2, n2, m3, n3, m4 and n4 are each independently an integer of 1 to 10.

In the method for manufacturing a copper clad laminate having a multi-layer structure according to the present invention, the surface of a polymer substrate is treated with a surface treatment composition containing the compound of Formula 1, and copper is plated on the surface of the surface-treated polymer substrate to form a copper foil, The copper foil and the polymer substrate can be strongly bonded while substantially maintaining the flexibility derived from the polymer substrate.

In one embodiment, the compound of Formula 1 may be represented by Formula 2 or Formula 3 below.

[Formula 2]

[Formula 3]

In Formulas 2 and 3,

이고;R ¹ is hydrogen or

ego;

이고;R ² is hydrogen or

ego;

이고;R ^B1 is hydrogen or

ego;

이고;R ^B2 is hydrogen or

ego;

R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 and R ^d2 to R ^f2 are each independently C1-C10 alkyl;

m1, n1, m2, n2, m3, n3, m4 and n4 are each independently an integer of 1 to 10.

Specifically, in the compounds of Formulas 2 and 3, three nitrogen atoms are bonded to the triazine backbone, one of the three nitrogen atoms bonded to the triazine backbone is bonded to alkoxysilane through an ethylene glycol residue, and the remaining nitrogen One of the atoms includes a structure bonded to an aminoalkyl in common, and the compounds of Formulas 2 and 3 differ only in the structure of the moiety bonded to the last nitrogen atom bonded to the triazine backbone in addition to the common portion described above.

As described above, the compounds of Formulas 2 and 3 having a triazine backbone in which an alkoxysilane through an ethylene glycol residue and an amino through an alkylene residue are substituted alone or in combination are applied as surface treatment agents for various polymer substrates, and thus, the polymer substrate and Formula 2 And / or the compound of formulas 2 and / or 3 is more strongly bound / adsorbed to the surface of the polymer substrate by chemical bonding or strong adsorption generated by the reaction between the compounds of 3, so that the copper foil formed by subsequent plating It can be integrated to realize maximized adhesive strength.

In one embodiment, the surface treatment composition for substrate adhesion may include the compound of Chemical Formula 2.

In one embodiment, the surface treatment composition for substrate adhesion may include the compound of Chemical Formula 3.

In one embodiment, the surface treatment composition for substrate adhesion may include a mixture of the compound of Formula 2 and the compound of Formula 3.

In Chemical Formulas 2 and 3 according to an embodiment, R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 , and R ^d2 to R ^f2 are each independently C1-C3 alkyl; m1, n1, m2, n2, m3, n3, m4, and n4 may each independently be an integer of 1 to 5.

이고; R^B1는

이고; n1, n2, n3 및 n4은 각각 독립적으로 1 내지 5의 정수일 수 있다.In Formula 2 according to an embodiment, R ² is

ego; R ^B1 is

ego; n1, n2, n3, and n4 may each independently be an integer of 1 to 5.

Preferably, Chemical Formula 2 according to an embodiment may be represented by Chemical Formula 2-1 or Chemical Formula 2-2.

[Formula 2-1]

[Formula 2-2]

In Chemical Formulas 1-1 and 1-2,

이고; R ² is hydrogen or

ego;

이고; R ^B1 is hydrogen or

ego;

R ^a to R ^c are each independently C1-C3 alkyl;

m, n, n1, n2, n3 and n4 are each independently an integer of 1 to 5;

In one embodiment, R ^a to R ^c are the same as each other and may be methyl or ethyl.

이고; R^B2는

이고; R^a1 내지 R^c1, R^a2 내지 R^c2, R^d1 내지 R^f1 및 R^d2 내지 R^f2는 각각 독립적으로 각각 독립적으로 C1-C3알킬이고; m1, m2, m3 및 m4은 각각 독립적으로 1 내지 5의 정수일 수 있다.In Formula 3 according to an embodiment, R ¹¹ is

ego; R ^B2 is

ego; R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 and R ^d2 to R ^f2 are each independently C1-C3 alkyl; m1, m2, m3 and m4 may each independently be an integer of 1 to 5.

이고; n1 및 n2은 각각 독립적으로 1 내지 5의 정수일 수 있다.In Formula 3 according to an embodiment, R ² is

ego; n1 and n2 may each independently be an integer of 1 to 5.

Preferably, Chemical Formula 3 according to an embodiment may be represented by Chemical Formula 3-1 or Chemical Formula 3-2.

[Formula 3-1]

[Formula 3-2]

In Chemical Formulas 3-1 and 3-2,

이고; R ¹ is hydrogen or

ego;

이고;R ² is hydrogen or

ego;

이고;R ^B2 is hydrogen or

ego;

R ^a to R ^f , R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 and R ^d2 to R ^f2 are each independently C1-C3 alkyl;

m, n, n1, n2, m1, m2, m3 and m4 are each independently an integer of 1 to 5;

In one embodiment, R ^a to R ^f are the same as each other and may be methyl or ethyl.

In one embodiment, R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 , and R ^d2 to R ^f2 are the same as each other, and may be methyl or ethyl.

In one embodiment, the compound of Formula 2 may be selected from the following structure, but is not limited thereto.

The above m and n are each independently an integer of 2 or 3.

In one embodiment, the compound of Formula 3 may be selected from the following structures, but is not limited thereto.

The above p and q are each independently an integer of 2 or 3.

In one embodiment, a solvent may be further included to further improve the dispersibility of the surface treatment composition, and the solvent is selected from the group consisting of water, alcohol, ketone, aromatic hydrocarbon, aliphatic hydrocarbon, ester and ether It may be one or a mixture of two or more, but is not limited thereto.

Specifically, the solvent may be a single solvent selected from the group consisting of water, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methoxyethanol, ethoxyethanol, isopropoxyethanol, and ethyl acetate, or a mixed solvent of two or more there is.

In one embodiment, the solvent may be water or a mixed solvent of water and alcohol, specifically water or a mixed solvent of water and ethanol.

The compound of Formula 1, specifically the compound of Formula 2 and the compound of Formula 3 may react with water to form a hydrolyzate containing hydroxyl.

That is, the surface of the polymer substrate treated with the surface treatment composition for substrate adhesion has an alkoxysilyl group or a hydroxysilyl group through an ethylene glycol residue and an amino group through an alkylene residue, thereby greatly improving the properties of the polymer substrate It can be.

In one embodiment, the composition of the surface treatment agent for substrate adhesion may include the compound of Formula 1 in an amount of 0.001 to 10% by weight based on the total weight of the composition, and a residual amount of a solvent. That is, it may be dissolved in the solvent at 0.001 to 10% by weight based on the solid content.

In one embodiment, the content of the compound of Formula 1 may be 0.001 to 10% by weight, specifically 0.01 to 5% by weight, more specifically 0.05 to 3% by weight based on the total weight of the composition, Within the above content range, the dispersibility of the compound of Formula 1 in the surface treatment agent composition is improved, so that it can be uniformly applied on the polymer substrate. Due to the uniform coating property, it is possible to form a copper clad laminate having a multilayer structure with maximized adhesive strength by improving the adhesion between the surface-treated polymer substrate and the copper foil formed by subsequent plating.

As described above, due to the compound of Formula 1 having a triazine backbone in which an alkoxysilane through an ethylene glycol residue and an amino through an alkylene residue are substituted, a reaction between various polymer substrates and the compound of Formula 1 produces Since the compound of Formula 1 is strongly bound/adsorbed to the surface of the substrate by chemical bonding or strong adsorption, the surface of various polymer substrates can be modified. That is, the surface-treated polymer substrate may have an alkoxysilyl group and/or a hydroxysilyl group through an ethylene glycol residue, and an amino group through an alkylene residue.

Before the surface treatment of the polymer substrate, one or two or more treatments selected from cleaning treatment, corona discharge treatment, plasma discharge treatment, ultraviolet irradiation, acid treatment, alkali treatment, steam treatment, and chemical treatment may be performed on the polymer substrate. there is.

For example, the conversion treatment is a hydroxide of a group I element, a salt of a group I element, a hydroxide of a group II element, a salt of a group II element, ammonia, ammonium salt, hydrazine, hydrazine derivative, amines, phosphoric acid, phosphate, carbonate, carboxylic acid, Carboxylate, silicic acid, silicate, fluoride, etc. may be used, and a film or the like may be formed on the surface of the polymer substrate by the chemical conversion treatment.

After the surface treatment step of the substrate, heat treatment may be performed, if necessary.

In one embodiment, the method of treating the polymer substrate with the surface treatment composition for substrate adhesion is a known method such as impregnation, soaking, coating, doping, spraying, and the like. It may include, but is not limited to.

According to one embodiment, the step of treating the surface of the polymer substrate may be performed by immersing the polymer substrate in a solution containing the compound of Formula 1.

The immersion time of the polymer substrate may be 1 second to 3 hours, specifically 1 second to 1 hour, more specifically 1 second to 30 minutes, and more specifically 10 seconds to 15 minutes.

The immersion temperature of the polymer substrate may be 0 to 80 °C, specifically 10 to 60 °C, and more specifically 20 to 40 °C.

In one embodiment, the surface-treated polymer substrate may be maintained at 0 to 200 ° C., specifically, 20 to 50 ° C., more specifically than 10 to 60 ° C., under a vacuum atmosphere, atmospheric pressure, or pressure, wherein the holding time may be 10 minutes or more, specifically 1 hour or more, and more specifically 1 to 24 hours, but is not limited thereto.

According to one embodiment, one or both sides of the polymer substrate may be surface treated.

According to one embodiment, the polymer substrate may include polyimide (　PI), modified polyimide (MPI), polyetherether ketone (PEEK), syndiotactic polystyrene (SPS), and It may be one or more selected from polytetrafluoroethylene (PTFE), but is not limited thereto.

According to an embodiment, a copper thin film may be formed on the surface of the surface-treated polymer substrate by plating, and a thin copper thin film (copper foil) having a uniform thickness and a smooth surface may be formed by plating. there is.

In one embodiment, the plating may be electroless plating. Electroless plating is plating of copper by a reduction reaction, and electroless plating is advantageous for producing a flat copper thin film on the surface of the polymer substrate subjected to surface treatment, and manufacturing a thin and uniform copper thin film having a flat surface. advantageous to do

Electroless plating may be performed by immersing the surface-treated polymer substrate in a copper plating solution. The copper plating solution may contain a copper precursor, a reducing agent and a complexing agent. Copper precursors include copper sulfate, hydroxides, oxides, and carbonates, and reducing agents include organic aldehydes such as formalin or glyoxylic acid, sugars, hydroquinone, hypophosphorous acid, borohydride, and reduced phenols such as diamine borane. Examples of the complexing agent include hydantoin, organic carboxylic acid, organic carboxylic acid salt, and organic amino carboxylic acid. The content of the copper precursor in the copper plating solution may be 3 to 8 g/L, the content of the reducing agent may be 10 to 50 g/L, and the content of the complexing agent may be 100 to 300 g/L. It is not limited, and it is sufficient to have materials and compositions commonly used in conventional electroless copper plating solutions. The copper plating solution may further contain conventionally known additives such as a surface charge control agent, a plating catalyst, and a stabilizer in addition to a copper precursor, a reducing agent, and a complexing agent. As a practical example, the copper plating solution may further contain an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., and the content of the alkali metal hydroxide in the plating solution may be 20 to 50 g/L, but these additives must be present. And it is not limited to the content. During electroless plating, the temperature of the plating solution may be at a level of 20 to 70° C., substantially room temperature, and the electroless plating time may be appropriately adjusted in consideration of the desired thickness of the copper thin film. As a practical example considering the use of an electronic component, particularly a flexible printed circuit board (FPBC) for a portable terminal, the thickness of the copper thin film is 2 to 200 μm, 2 to 100 μm, 2 to 35 μm, 3 to 20 μm, or 3 to 10 μm. μm.

According to one embodiment, the multi-layered copper clad laminate may be a flexible copper clad laminate (FCCL), more specifically, a two-layer flexible copper clad laminate (2-FCCL).

The multi-layered laminate manufactured by the above method may satisfy physical properties of an adhesive strength of 11.0 N/cm or more, specifically 11.0 to 20.0 N/cm, and more specifically 11.0 to 14.0 N/cm according to the measurement method JISC-5016.

According to the present invention, after surface treatment of a polymer substrate with a surface treatment composition for substrate adhesion containing the compound of Formula 1 having a triazine backbone in which an alkoxysilane through an ethylene glycol residue and an amino through an alkylene residue are substituted, the surface By forming a copper thin film on the surface of the treated polymer substrate, it is possible to manufacture a flexible copper clad laminate having a multi-layer structure with significantly improved adhesion even though the thickness is considerably thin without a separate adhesive. As a result, according to the present invention, in the adhesion of copper foil and polymer substrates having different properties, the surface of the polymer substrate is treated with a surface treatment composition having a specific structure without using a separate adhesive, and then copper is plated to achieve adhesive strength even though the thickness is considerably thin. A flexible copper clad laminate having a remarkably improved multi-layer structure can be manufactured.

In addition, according to the present invention, since a separate adhesive is not used, a laminate having a thinner multi-layer structure, specifically, a flexible copper clad laminate can be manufactured, and the adhesive increases the dielectric constant and decreases durability due to deterioration of the adhesive. etc. can be solved.

That is, according to the present invention, a low dielectric constant low loss copper clad laminate (CCL), specifically a flexible copper clad laminate (FCCL), more specifically a two-layer structure flexible copper clad laminate ( 2-FCCL) can be efficiently produced.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

* Adhesion test

For each of the specimens prepared in the above Examples and Comparative Examples, the peel strength was measured using a peel tester (Autograph P-100 manufactured by Shimadzu Corporation) according to the method specified in JISC-5016. . The peeling speed at the time of measurement was the condition of 5 mm/min.

[Preparation Example 1] Preparation of Compound 1

After adding cyanuric chloride (100mmol) to THF (200mL) under an argon atmosphere and cooling to -30 ° C, a mixed solution of compound 1-a (120mmol) and THF (20mL) was added to the cyanide over 50 minutes. It was slowly added dropwise to the nuric chloride solution. After completion of the dropwise addition, a mixed solution of triethylamine (120mmol) and THF (20mL) was slowly added dropwise to the reaction mixture over 50 minutes. After completion of the dropwise addition, the mixture was stirred at -30°C for 2 hours, and the filtrate obtained by filtration was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate/n-hexane) to obtain compound 1-b.

¹ H NMR (400 MHz, CDCl ₃ ): δ 3.2-3.3 (t, 2H), 3.55-3.61 (m, 17H), 3.94-3.97 (m, 2H), 3.98-4.01 (m, 1H)

A mixed solution of compound 1-b (20mmol) and THF (50mL) was added dropwise to compound 1-c (140mmol) under an argon atmosphere, then slowly heated to 90°C and stirred for 17 hours. Upon completion of stirring, the mixture was cooled to room temperature, the reaction mixture was filtered through celite, and the filtrate was concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate/n-hexane) to obtain Compound 1.

¹ H NMR (400 MHz, CDCl ₃ ): δ 2.0 (br s, 4H), 2.78-2.91 (m, 4H), 3.21-3.35 (m, 6H), 3.51-3.61 (m, 17H), 3.94-3.97 (m, 2H), 4.01 (br s, 3H)

[Preparation Example 2] Preparation of Compound 2

Compound 2-a (120 mmol) was used instead of Compound 1-a, Compound 2-b (20 mmol) was used instead of Compound 1-b, and Compound 2-c (140 mmol) was used instead of Compound 1-c. Compound 2 was prepared in the same manner as in Preparation Example 1 except for the above.

¹ H NMR (400 MHz, CDCl ₃ ): δ 1.19-1.25 (m, 18H), 2.0 (br s, 8H), 2.81-8.91 (m, 8H), 3.21-3.25 (m, 4H), 3.31-3.33 (m, 8H), 3.54-3.61 (m, 16H), 3.81-3.87 (m, 12H), 3.94-3.97 (m, 4H)

[Preparation Example 3] Preparation of Compound 3

Compound 2-a (240 mmol) was used instead of Compound 1-a, Compound 3-b (20 mmol) was used instead of Compound 1-b, and Compound 2-c (70 mmol) was used instead of Compound 1-c. Compound 3 was prepared in the same manner as in Preparation Example 1 except for the above.

¹ H NMR (400 MHz, CDCl ₃ ): δ 1.18-1.23 (m, 36H), 2.0 (br s, 2H), 2.86-2.89 (m, 2H), 3.21-3.25 (m, 8H), 3.30-3.33 (m, 2H), 3.51-3.62 (m, 32H), 3.81-3.86 (m, 24H), 3.94-3.97 (m, 8H), 4.0 (br s, 1H)

[Preparation Example 4] Preparation of Compound 4

Except for using compound 1-a (240 mmol), using compound 4-b (20 mmol) instead of compound 1-b, and using compound 2-c (70 mmol) instead of compound 1-c, the above preparation Compound 4 was prepared in the same manner as in Example 1.

¹ H NMR (400 MHz, CDCl ₃ ): δ 2.0 (br s, 4H), 2.86-2.89 (m, 4H), 3.21-3.25 (m, 4H), 3.31-3.33 (m, 4H), 3.52-3.61 (m, 34H), 3.94-3.97 (m, 4H), 4.0 (br s, 2H)

[Examples 1 to 8]

A polymer substrate (10 mm × 20 mm × 0.1 mm) described in Table 1 below was prepared. The polymer substrate was ultrasonically degreased in ethanol at 40° C. for 15 minutes, and then washed with ethanol. As a result, the surface of the polymer substrate was cleaned. After purification, drying was performed in a vacuum desiccator.

The polymer substrate was immersed in an aqueous solution containing the compound of Formula 1 (0.1% by weight) shown in Table 1 below for 20 seconds, and then the polymer substrate was taken out and thoroughly washed with distilled water. Thereafter, it was maintained for 24 hours under vacuum (0.1 mmHg or less) in a dry desiccator at 20° C. to obtain a surface-treated polymer substrate.

Electroless plating was performed by immersing the surface-treated polymer substrate in a copper plating solution (6.7 g/L copper sulfate pentahydrate, 40 g/L sodium hydroxide (NaOH), 140 g/L sodium potassium tartrate, 20 ml formalin) for 20 minutes Thus, a flexible copper clad laminate (2-FCCL) having a two-layer structure was manufactured. At this time, the thickness of the copper thin film formed by plating was 2 μm.

[Comparative Examples 1 to 8]

A polymer substrate (10 mm × 20 mm × 0.1 mm) described in Table 1 below was prepared. The polymer substrate was ultrasonically degreased in ethanol at 40° C. for 15 minutes, and then washed with ethanol. As a result, the surfaces of the Cu substrate and the polymer substrate were cleaned. After purification, drying was performed in a vacuum desiccator.

After immersing the polymer substrate in an aqueous solution containing the following compounds A to H (0.1% by weight) for 20 seconds, the polymer substrate was taken out and thoroughly washed with distilled water. Thereafter, it was maintained for 24 hours under vacuum (0.1 mmHg or less) in a dry desiccator at 20° C. to obtain a surface-treated polymer substrate.

Copper was plated on the surface-treated polymer substrate in the same manner as in the above example to obtain a two-layer flexible copper clad laminate (2-FCCL).

Table 1 below shows the results of measuring the adhesion of 2-FCCL prepared in each Example and Comparative Example.

metal substrate polymer substrate Polymer Substrate Surface Treatment adhesive strength
(N/cm) Example One Cu (plating) PI compound 1 11.9 2 Cu (plating) PEEK compound 1 12.5 3 Cu (plating) SPS compound 1 12.4 4 Cu (plating) PTFE compound 1 11.8 5 Cu (plating) PI compound 2 12.2 6 Cu (plating) PEEK compound 2 12.6 7 Cu (plating) SPS compound 2 12.9 8 Cu (plating) PTFE compound 2 12.0 9 Cu (plating) PI compound 3 12.5 10 Cu (plating) PEEK compound 3 13.0 11 Cu (plating) SPS compound 3 12.8 12 Cu (plating) PTFE compound 3 12.7 13 Cu (plating) PI compound 4 13.7 14 Cu (plating) PEEK compound 4 13.9 15 Cu (plating) SPS compound 4 13.4 16 Cu (plating) PTFE compound 4 13.2 comparative example One Cu (plating) PI compound A 5.5 2 Cu (plating) PEEK compound B 5.3 3 Cu (plating) SPS compound C 5.1 4 Cu (plating) PTFE compound D 5.9 5 Cu (plating) PI compound E 6.1 6 Cu (plating) PEEK compound F 5.7 7 Cu (plating) SPS compound G 6.0 8 Cu (plating) PTFE compound H 5.6

As shown in Table 1, the 2-FCCL of Examples 1 to 16 using the surface treatment composition according to the present invention has higher adhesive strength between various polymer substrates and the copper thin film than the 2-FCCL of Comparative Examples 1 to 8. Significantly improved.

That is, after surface treatment of a polymer substrate with a surface treatment composition for substrate adhesion comprising the compound of Formula 1 having a triazine backbone in which an alkoxysilane through an ethylene glycol residue and an amino through an alkylene residue are substituted according to the present invention, copper By plating, it was confirmed that the adhesive strength between the copper thin film and the polymer substrate, that is, the copper thin film and the insulating substrate, can be maximized without a separate adhesive.

As described above, the embodiments of the present invention have been described in detail, but those of ordinary skill in the art to which the present invention pertains, without departing from the spirit and scope of the present invention defined in the appended claims. It will be possible to implement the invention by modifying it in various ways. Therefore, changes in future embodiments of the present invention will not deviate from the technology of the present invention.

Claims (13)

Treating the surface of a polymer substrate with a surface treatment composition for substrate adhesion comprising a compound represented by Formula 1 below; and
forming a copper thin film by plating copper on the surface of the surface-treated polymer substrate;
Method for manufacturing a copper clad laminate having a multi-layer structure comprising a.
[Formula 1]

In Formula 1,
R ¹ is hydrogen or

ego;
R ² is hydrogen or

ego;
R ^A is

or

ego;
R ^B is hydrogen,

or

ego;
R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 and R ^d2 to R ^f2 are each independently C1-C10 alkyl;
m1, n1, m2, n2, m3, n3, m4 and n4 are each independently an integer of 1 to 10. According to claim 1,
The compound of Chemical Formula 1 is represented by the following Chemical Formula 2 or Chemical Formula 3, a method for manufacturing a copper clad laminate having a multi-layer structure.
[Formula 2]

[Formula 3]

In Formulas 2 and 3,
R ¹ is hydrogen or

ego;
R ² is hydrogen or

ego;
R ^B1 is hydrogen or

ego;
R ^B2 is hydrogen or

ego;
R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 and R ^d2 to R ^f2 are each independently C1-C10 alkyl;
m1, n1, m2, n2, m3, n3, m4 and n4 are each independently an integer of 1 to 10. According to claim 2,
In Formulas 2 and 3, R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 and R ^d2 to R ^f2 are each independently C1-C3 alkyl; m1, n1, m2, n2, m3, n3, m4, and n4 are each independently an integer of 1 to 5, a method for manufacturing a copper clad laminated board having a multilayer structure. According to claim 2,
In Formula 2, R ² is

ego; R ^B1 is

ego; n1, n2, n3 and n4 are each independently an integer of 1 to 5, a method of manufacturing a copper clad laminated board having a multilayer structure. According to claim 2,
In Formula 3, R ¹ is

ego; R ^B2 is

ego; R ^a1 to R ^c1 , R ^a2 to R ^c2 , R ^d1 to R ^f1 and R ^d2 to R ^f2 are each independently C1-C3 alkyl; m1, m2, m3 and m4 are each independently an integer of 1 to 5, a method for manufacturing a copper clad laminated board having a multilayer structure. According to claim 2,
In Formula 3, R ² is

ego; n1 and n2 are each independently an integer of 1 to 5, a method for manufacturing a copper clad laminate having a multilayer structure. According to claim 1,
The method of manufacturing a copper clad laminated board having a multi-layer structure, wherein the surface treatment composition for substrate adhesion further comprises a solvent. According to claim 7,
Wherein the solvent is one or a mixture of two or more selected from the group consisting of water, alcohol, ketone, aromatic hydrocarbon, aliphatic hydrocarbon, ester and ether. According to claim 1,
The method of manufacturing a copper clad laminated board having a multilayer structure, wherein the surface treatment composition for substrate adhesion includes the compound of Formula 1 in an amount of 0.001 to 10% by weight based on the total weight of the composition. According to claim 1,
The step of surface treatment of the polymer substrate is performed by immersing the polymer substrate in the surface treatment composition for substrate adhesion, a method for manufacturing a multi-layered copper clad laminate. According to claim 1,
The plating is electroless plating, a method of manufacturing a copper clad laminated board of a multi-layer structure. According to claim 1,
The polymer substrate includes polyimide (PI), modified polyimide (MPI), polyetherether ketone (PEEK), syndiotactic polystyrene (SPS) and polytetrafluoroethylene ( A method of manufacturing a copper clad laminate having a multi-layer structure, which is at least one selected from polytetrafluoroethylene; PTFE). According to claim 1,
The multi-layered laminate is a two-layer flexible copper-clad laminate (2-FCCL), a method for manufacturing a multi-layered copper-clad laminate.