TWI391531B - Copper foil for printed circuit board, method of preparing the same, and flexible copper clad laminate using polyamic acid precursor and copper foil - Google Patents

Description

Copper foil for printed circuit board, preparation method thereof and use of polyamic acid Flexible copper clad laminate with precursor and copper foil [related application]

The present application claims priority to Korean Patent Application No. 10-2008-0070081, filed on Jan.

The present invention relates to a copper foil for a printed circuit board (PCB), a method for preparing the copper foil, and a flexible copper clad laminate (FCCL) including a copper foil, and in particular A surface-treated copper foil for a PCB on which a surface-treated film comprising a silane-based compound or a hydrolysate of a mercapto compound is formed, and an FCCL comprising the copper foil.

Flexible copper clad laminates (FCCL) are a form of printed circuit board (PCB) and their demand today is increasing. The FCCL is a multilayer film formed of two or three layers in which a polyimide film is laminated on a copper foil. As the accuracy of the wiring printed on the FCCL increases, the accuracy of etching also increases, so it is necessary to reduce the surface roughness of the copper foil. However, when the surface roughness of the copper foil is lowered, the peel strength between the copper foil and the substrate (for example, a polyimide film) may decrease. At this point, there is a need to improve the peel strength.

The copper foil for PCB is usually used as a surface treatment agent for copper foil using a decane coupling agent for strengthening the peeling strength between the copper foil and the substrate, which is disclosed in Japanese Patent Application Laid-Open No. 1990-026097.

However, as the requirements for the physical properties of the copper foil used in the PCB become tight, there is still a need for a copper foil for a PCB on which a surface-treated film having improved physical properties is formed.

The present invention provides a surface treated copper foil for a printed circuit board (PCB) comprising a hydrolyzate of a novel germanium alkyl compound or a novel germanium alkyl compound which provides excellent peel strength between the substrate and the copper foil, and the present invention also provides A method for preparing a copper foil for PCB, and a flexible copper clad laminate (FCCL) comprising a polyimide layer stacked on a copper foil for PCB.

According to an aspect of the invention, there is provided a surface-treated copper foil for a printed circuit board (PCB) comprising a rustproof layer formed on a copper foil and a surface treated film formed on the rustproof layer, wherein the surface treated film At least one compound comprising a group selected from the group consisting of a fluorenyl compound represented by Formulas 1 to 4, or a hydrolyzate of the decyl compound:

<Formula 3>

Wherein R ₁ , R ₂ and R ₃ are each independently a C ₁ to C ₃ alkyl group, and R ₄ and R ₅ are each independently hydrogen or a C ₁ to C ₅ alkyl group.

According to another aspect of the present invention, there is provided a method of preparing a surface-treated copper foil for a printed circuit board (PCB), the method comprising: forming a rustproof layer on a copper foil; and cleaning and drying the rustproof layer formed thereon a copper foil, and a coating composition on the rustproof layer, and drying the coated rustproof layer to prepare a surface treated film, the composition comprising a decyl group compound selected from the group consisting of Formulas 1 to 4. At least one compound of the population or a hydrolyzate of the decyl compound:

<Formula 2>

Wherein R ₁ , R ₂ and R ₃ are each independently a C ₁ to C ₃ alkyl group, and R ₄ and R ₅ are each independently hydrogen or a C ₁ to C ₅ alkyl group.

According to still another aspect of the present invention, there is provided a flexible copper clad laminate (FCCL) comprising the surface treated copper foil for the above PCB; and a polyimide film formed on the surface treated film of the copper foil.

The above described features and advantages of the present invention will be more apparent from the following description.

Hereinafter, a method of preparing a surface-treated copper foil for a printed circuit board (PCB), a copper foil for a PCB, and a method for manufacturing a PCB according to an embodiment of the present invention will be described in more detail. Flexible copper clad laminate (FCCL).

According to the embodiment, the surface-treated copper foil for PCB includes a rustproof layer formed on the copper foil and a surface-treated film formed on the rust-preventing layer, wherein the surface-treated film comprises a film selected from the group consisting of Formulas 1 to 4. At least one compound of the group consisting of a decyl compound, or a hydrolyzate of the decyl compound.

<Formula 4>

Wherein R ₁ , R ₂ and R ₃ are each independently a C ₁ to C ₃ alkyl group, and R ₄ and R ₅ are each independently hydrogen or a C ₁ to C ₅ alkyl group.

The oxime compound has a siloxane group at one end thereof to form a covalent bond with the copper foil, and an imidazole group and/or an imide group at the other end, wherein the imidazole group The base and/or linoleamide has a structure similar to that of the polyimide film, thereby increasing the bonding strength with the polyimide film. Therefore, the bonding strength between the copper foil and the polyimide film can be improved.

In particular, an alkoxy group (-OR) contained in a decyl group compound reacts with a hydroxy group present in a metal surface to form a siloxane bond. The decyloxy group contained in the decyl group compound may also form a decane bond with the metal surface.

According to another embodiment of the present invention, R ₁ , R ₂ and R ₃ in the fluorenyl compound are each independently a methyl group or an ethyl group, and R ₄ and R ₅ may be hydrogen.

According to another embodiment of the present invention, a heat-blocking layer may be further interposed between the copper foil and the rustproof layer. The heat resistant layer may be formed, for example, of a zinc alloy and may have a thickness of several tens to several hundreds of nanometers (nm). The metal or alloy forming the heat-resistant layer is not particularly limited, and any metal or alloy used as a heat-resistant layer in the field to which the present invention pertains can be used.

According to another embodiment of the present invention, nodules may be further inserted between the copper foil and the heat resistant layer. By flowing a current having a current density of 10 to 150 A/dm ² at a temperature of 10 ° C to 40 ° C, wherein the electrolyte contains 1 to 40 g/L of copper metal and 30 to 250 g/L sulfuric acid.

The rustproof layer may contain chromium trioxide, chromic acid, dichromic acid, sodium dichromate or chroma as a rust inhibitor. The rustproof layer can be formed by causing a current having a current density of 0.01 to 10 A/dm ² to flow through the electrolyte at a temperature of 10 ° C to 50 ° C, and the concentration of the rust inhibitor is 0.1 to 10 g/L. A thickness of tens to hundreds of nanometers. The heat resistant layer may be formed of a zinc alloy, a nickel alloy, or a cobalt alloy, and may be formed to have a thickness of several tens to several hundreds of nanometers.

Copper foil is typically formed on a substrate as is well known in the art of the present invention. Although an additional description of the substrate is omitted, the use of the substrate is not excluded.

According to another embodiment of the present invention, a method for preparing a copper foil for a PCB may include: forming a rustproof layer on the copper foil; cleaning and drying the copper foil on which the rustproof layer is formed, and coating the composition on the rustproof layer And coating the rust-preventing layer to prepare a surface-treated film comprising at least one compound selected from the group consisting of the fluorenyl compounds represented by Formulas 1 to 4 or the decyl compound Hydrolyzate.

<Formula 2>

Wherein R ₁ , R ₂ and R ₃ are each independently a C ₁ to C ₃ alkyl group, and R ₄ and R ₅ are each independently hydrogen or a C ₁ to C ₅ alkyl group.

The copper foil can be prepared by copper plating on a material or substrate to be electroplated. In copper plating, an acid plating solution or an alkali plating solution can be used. The acid plating solution may comprise a plating solution of copper sulfate, copper fluoroborate or sulfamic acid copper, and the alkali plating solution may contain copper cyanide or coke. Electroplating solution of copper phosphate (copper prophosphate). According to an embodiment of the present invention, the plating solution used in the preparation of the copper foil is not particularly limited, and any plating solution used in the field to which the present invention pertains may be used.

The rustproof layer can be formed by electro-depositing chromium on the surface of the copper foil. The chromium compound used may contain, for example, chromium trioxide, chromic acid, dichromic acid, sodium dichromate or chromate. The concentration of the chromium compound may range from 0.1 to 10 g/L, such as from 1.0 to 10 g/L. When the rustproof layer is formed, a synergist may be further added to increase the efficiency of electrolytic deposition of the chromium compound. Examples of the synergist may include: zinc compounds such as zinc acetate, zinc chloride, zinc cyanide, zinc nitrate or zinc sulfate; phosphorus compounds For example, phosphoric acid, polyphosphate pyrophosphate, phosphate or pyrophosphate; and organic compounds such as benzotriazole. The thickness of the rustproof layer may range from 0.1 to 10 nm.

According to another embodiment of the present invention, the composition may contain at least one compound selected from the group consisting of the fluorenyl compounds represented by Formulas 1 to 4, a hydrolyzate of the decyl compound, and a solvent.

The amount of the decyl compound may range from 0.001 to 5% by weight of the composition. When the amount of the decyl group compound is 0.001% by weight or less, the organic layer formed by the surface treatment agent cannot be sufficiently coated on the copper foil, so that the peel strength cannot be improved. When the amount of the decyl group compound is 5% by weight or more, the thickness of the organic layer formed by the surface treatment agent is increased, and the measure on the copper foil is covered, so that the peel strength cannot be improved.

According to another embodiment of the present invention, the solvent may comprise a solvent selected from the group consisting of water, methanol, ethanol, acetone, methylethylketone, methylethylketone, ethylacetate, and benzene. At least one of the ethnic groups formed.

According to another embodiment of the present invention, in the above method, the heat resistant layer may be further formed on the copper foil before the formation of the rustproof layer. The details of forming the heat-resistant layer are the same as those described for the copper foil for the PCB, and therefore will not be repeated.

According to another embodiment of the present invention, in the above method, the formation of the measure on the copper foil may be further performed before the formation of the heat resistant layer. In forming the section, by using a cupric oxide product to form a measure on the copper foil, the contact area between the copper foil and the additional coating layer is increased, thereby increasing the copper foil and the additional coating layer. Peel strength.

According to another embodiment of the present invention, the flexible copper clad laminate may comprise a copper foil for a PCB and a polyimide film formed on the surface treated film on the copper foil.

The flexible copper clad laminate may have a two-layer structure (2-layer) or a three-layer structure (3-layer) depending on its use.

According to another embodiment of the present invention, the polyimide film may be a hardened product of a polyamic acid solution, and the polyphthalic acid may be at least one dianhydride monomer and at least one diamine ( Diamine) a reaction product of a monomer, wherein at least one dianhydride monomer may be selected from the group consisting of pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (3,3) ',4,4'-benzophenone tetracarboxylic dianhydride), 3,3',4,4'-biphenyltetracarboxylic dianhydride (3,3',4,4'-biphenyltetracarboxylic dianhydride) and 3,3',4 a group consisting of 4', 3', 4'-oxydiphthalic anhydride, and at least one diamine monomer may be selected from 4,4'-diaminodiphenyl ether (4,4'-oxydianiline), para-phenylene diamine, siloxane diamine (SD), 3,4-diaminodiphenyl ether (3,4- A group of oxydianiline) and meta-phenylenediamine.

The oxane diamine (SD) may have the following structure.

In the structure of SD, n ranges from 2 to 12.

After the dianhydride monomer is reacted with the diamine monomer, the polyglycolic acid is a compound linked by a -C(=O)-NH- bond. For example, polylysine obtained by reacting pyromellitic dianhydride and diaminodiphenyl ether has the following structure.

When the polyamic acid is heat-treated, a polyimine having the following structure can be obtained.

The heat treatment of polylysine begins and ends at about 60 ° C in a nitrogen atmosphere. It ends at a high temperature of about 400 °C. In polylysine and polyimine, n ranges from 40 to 200.

The varnish may be, for example, a PMDA/ODA mixture, a BTDA/PDA mixture, a BTDA/PMDA/ODA/PDA mixture or a PMDA/ODA-SD mixture. The appropriate mixing ratio can be selected according to its use.

Hereinafter, the present invention will be described in more detail with reference to the following examples; however, the invention is not limited thereto. The structure of the compound synthesized in the following examples was confirmed using Brucker DRX-300 MHz ¹ H-NMR and Jasco 610 FT-IR.

(Synthesis of fluorenyl compound (1)) Example 1: Synthesis of Compound 1

Compound 1 represented by Formula 1 was synthesized according to Reaction Mechanism 1 below.

162.68 grams of tetrahydrofurane, 6.259 grams (0.05 moles) of 3-glycidyloxypropyltrimethoxydecane (3-glycidoxypropyltrimethoxysilane) and 11.81 g (0.05 mol) of 1-(3-aminopropyl)-imidazole were charged into the reactor and reacted for 6 hours in nitrogen. The reactor temperature was maintained at 95 ° C and the mechanical stirrer was rotated at 300 rpm. After the reaction was completed, a rotary evaporator was used for 2 hours to remove the solvent from the product. Then, the resultant was dried in a vacuum oven for 24 hours, whereby 7 g (yield 98%) of Compound 1 represented by Formula 1 was obtained.

¹ H NMR (300 MHz, CD ₃ OD): δ 0.62~0.68 (m, 1H), 1.89~1.96 (m, 8H), 1.64~1.67 (t, 2H), 2.54~2.56 (t, 7H), 2.58 ~2.61(m,6H), 3.28~3.31(m,SiOCH ₃ ), 3.38~3.40(d,3H), 3.42~3.44(d,4H), 3.50~3.58(m,5H), 3.64(s,- NH-), 3.80 (s, OH), 4.05 to 4.10 (m, 9H), 6.95 (s, 10H), 7.12 to 7.13 (t, 11H), 7.65 (s, 12H)

IR (neat, cm ^-1 ): 3650~3200(ν _OH ), 3300~3200(ν _NH ), 1120~1050(ν _矽-(alkoxy) )

(Manufacture of surface treatment composition for copper foil) Example 2

A solvent mixture was mixed with Compound 1 prepared in Example 1 by mixing water and methanol in a volume ratio of 1:9 to prepare a mixed solution having 1.0% by weight of Compound 1.

(Manufacture of two-layer FCCL) Example 3

The mixed solution prepared in Example 2 was allowed to stand alone for 60 minutes to carry out hydrolysis, and then sprayed on a rolled copper foil (IL-2, manufactured by Iljin) which was sequentially formed on the measure, the heat-resistant layer and the rust-preventing layer. )on. Next, a rolled copper foil was coated using an applicator (C.K Trading Co., model name: CKAF1003) to prepare a coated copper foil. The bars, the heat-resistant layer and the rust-proof layer on the rolled copper foil are respectively formed of copper (Cu), a zinc alloy and chromium. The coated copper foil was dried in an oven at 120 ° C for 30 minutes.

The copper foil treated with the surface treatment composition was sprayed with a KRICT-PAA varnish (BPDA: PMDA: PDA: ODA = 3:7:6:4) and coated with a doctor blade. The coated polylysine is cured by performing 30 minutes at 60 ° C, 30 minutes at 120 ° C, 30 minutes at 250 ° C, and 10 minutes at 400 ° C in a nitrogen atmosphere to prepare a polyimide film, thereby preparing A copper foil coated with a polyimide film. The copper foil prepared in Example 3 is hereinafter referred to as Sample 1.

Example 4

A copper foil coated with a polyimide film was prepared in the same manner as in Example 3 except that a varnish (product name: JY-001) manufactured by Jooyoung Industries Co., Ltd. was used in place of the KRICT-PAA varnish. The copper foil prepared in Example 4 is hereinafter referred to as Sample 2.

Example 5

Preparation of a polyimide film coated in the same manner as in Example 3. The copper foil on the top was replaced with a rolled copper foil (product name: BHY-22B-T) made of Nikko material instead of a rolled copper foil (IL-2, manufactured by Iljin), and Upilex manufactured by UBE Co., Ltd. The form of varnish replaces the KRICT-PAA varnish. The copper foil prepared in Example 5 is hereinafter referred to as Sample 3.

Comparative example 1

A copper foil coated with a polyimide film was prepared in the same manner as in Example 3 except that the step of treating the surface of the copper foil using the surface treatment composition was omitted. The copper foil prepared in Comparative Example 1 is hereinafter referred to as Comparative Sample 1.

Comparative example 2

A copper foil coated with a polyimide film was prepared in the same manner as in Example 4 except that the step of treating the surface of the copper foil using the surface treatment composition was omitted. The copper foil prepared in Comparative Example 2 is hereinafter referred to as Comparative Sample 2.

Comparative example 3

A copper foil coated with a polyimide film was prepared in the same manner as in Example 5 except that the step of treating the surface of the copper foil using the surface treatment composition was omitted. The copper foil prepared in Comparative Example 3 is hereinafter referred to as Comparative Sample 3.

Evaluation Example 1-1: Peel Strength Test

The peel strengths of Samples 1 to 3 and Comparative Samples 1 to 3 were measured using the method specified in ASTM D-638. The cross-head speed is 25 mm/min and the width of the sample is 5 mm. Measurements were performed using an Instron 8516. The results of the measurements are shown in Table 1 below.

As shown in Table 1, according to the examples of the present invention, Samples 1 to 3 prepared using the surface treatment composition containing a decyl compound were compared to Comparative Samples 1 to 3 prepared without using the surface treatment composition. A large increase in peel strength is exhibited between the polyimide film and the copper foil.

Evaluation Example 1-2: Moisture resistance test

Samples 1 to 3 were stored in a thermo-hygrostat HIRAYANA PC-R7 at 50 ° C and a relative humidity of 80% for 7 days, and discoloration of samples 1 to 3 was remarkable. After 7 days, the colors of samples 1 to 3 were not There are changes.

(Synthesis of fluorenyl compound (2)) Example 6A: Synthesis of Compound 2A

The compound 2A represented by Formula 2 was synthesized according to the following Reaction Mechanism 2.

Wherein R is a methyl group.

125.712 grams of tetrahydrofuran, 8.9645 grams (0.05 moles) of 3-aminopropyltrimethoxysilane and 5.035 grams (0.05 moles) of succinic anhydride were poured into the reactor and reacted. The reactor temperature was maintained at -5 ° C to 5 ° C under nitrogen for 6 hours and the mechanical stirrer was rotated at 300 rpm. After the reaction was completed, a rotary evaporator was used for 2 hours to remove the solvent from the product. Then, the resultant was dried in a vacuum oven for 24 hours to obtain 13.9 g (yield: 99%) of Compound 2A represented by Formula 2.

¹ H NMR (300 MHz): δ 0.53~0.58 (m, 1H), 1.42~1.45 (m, 2H), 2.29~2.31 (d, 4H), 2.38~2.43 (m, 5H), 2.98~3.00 (m) , 3H), 3.40~3.46 (m, SiOCH ₃ ), 8.00 (s, -NH-), 12.00 (s, -OH)

IR (pure, cm ^-1 ): 3650~3200(ν _OH ), 3300~3200(ν _NH ), 1650(ν _CONH ), 1120~1050(ν _矽-(alkoxy) )

Example 6B: Synthesis of Compound 2B

The compound 2B represented by Formula 2 was synthesized according to the following Reaction Mechanism 2.

Wherein R is an ethyl group.

125.712 g of tetrahydrofuran, 11.08685 g (0.05 mol) of 3-aminopropyltriethoxysilane and 5.035 g (0.05 mol) of succinic anhydride were poured into the reactor and reacted for 6 hours. The temperature of the reactor was maintained at -5 ° C to 5 ° C under a nitrogen atmosphere, and the mechanical stirrer was rotated at 300 rpm. After the reaction was completed, the solvent was removed from the product using a rotary evaporator for 2 hours. Then, the resultant was dried in a vacuum oven for 24 hours, thereby obtaining 16 g (yield 99%) of Compound 2B represented by Formula 2.

¹ H NMR (300 MHz): δ 0.58~0.60 (m, 1H), 1.22~1.25 (m, Si-CH ₂ ), 1.60~1.63 (m, 2H), 2.45~2.49 (m, 4H), 2.51 ~2.54(m,5H), 3.20~3.25(m,3H),3.83~3.87(m,Si-CH ₃ )

IR (pure, cm ^-1 ): 3650~3200(ν _OH ), 3300~3200(ν _NH ), 1650(ν _CONH ), 1120~1050(ν _矽-(alkoxy) )

(Manufacture of surface treatment composition for copper foil) Examples 7 to 11

The solvent mixture was mixed with the compound 2A prepared in Example 6A by mixing water and methanol in a volume ratio of 1:9 to prepare 0.5% by weight, 1% by weight, 2% by weight, and 3 parts by weight, respectively. A mixed solution of % and 5% by weight of Compound 2A.

Examples 12 to 16

The solvent mixture was mixed with the compound 2B prepared in Example 6B by mixing water and methanol in a volume ratio of 1:9 to prepare 0.5% by weight, 1% by weight, 2% by weight, and 3 parts by weight, respectively. A mixed solution of % and 5% by weight of Compound 2B.

(Manufacture of second-tier FCCL) Examples 17 to 26

The mixed solutions prepared in Examples 7 to 16 were allowed to stand alone for 60 minutes for hydrolysis, and then sprayed on a Cr-coated rolled copper foil (IL-2, manufactured by Iljin), respectively. Next, the rolled copper foil was coated with an applicator to obtain a coated copper foil. The coated copper foil was dried in an oven at 120 ° C for 30 minutes.

Spray copper foil treated with a surface treatment agent composition with a varnish manufactured by Jooyoung Industries Co., Ltd. (product name: JY-001), and use a scraping Knife coated.

The coated polylysine is cured by performing 30 minutes at 60 ° C, 30 minutes at 120 ° C, 30 minutes at 250 ° C, and 10 minutes at 400 ° C in a nitrogen atmosphere to prepare a polyimide film, thereby preparing The polyimide film is applied to the upper copper foil by a polyimide film. The copper foils prepared in Examples 17 to 26 are hereinafter referred to as Samples 4 to 13.

Comparative example 4

A copper foil coated with a polyimide film was prepared in the same manner as in Example 17, except that the step of treating the surface of the copper foil using the surface treatment composition was omitted. The copper foil prepared in Comparative Example 4 is hereinafter referred to as Comparative Sample 4.

Evaluation Example 2-1: Peel Strength Test

The peel strengths of Samples 4 to 13 and Comparative Sample 4 were measured using the method specified in ASTM D-638. The cross-arm speed was 25 mm/min and the width of the sample was 5 mm. Measurements were performed using an Instron 8516. The results of the measurements are shown in Table 2 below.

As shown in Table 2, samples 4 to 13 prepared using a surface treatment composition containing a decyl compound were compared to Comparative Sample 4 prepared without using a surface treatment composition according to an embodiment of the present invention. The imide film and the copper foil showed a greatly increased peel strength.

Evaluation Example 2-2: Moisture Resistance Test

Samples 4 to 13 were stored in a thermostat humidifier HIRAYANA PC-R7 at 50 ° C and a relative humidity of 80% for 7 days, and the discoloration of samples 4 to 13 was remarkable. After 7 days, the colors of samples 4 to 13 did not change.

(Synthesis of fluorenyl compound (3)) Example 27: Synthesis of Compound 3

Compound 3 represented by Formula 3 was synthesized according to the following Reaction Mechanism 3.

<Reaction mechanism 3>

125.712 grams of tetrahydrofuran, 8.9645 grams (0.05 moles) of 3-aminopropyltrimethoxynonane and 7.4550 grams (0.05 moles) of 2,3-pyridinedicarboxylic anhydride were poured into the reaction. The reaction was carried out for 5 hours, the temperature of the reactor was maintained at -5 ° C to 5 ° C under a nitrogen atmosphere, and the mechanical stirrer was rotated at 300 rpm. After the reaction was completed, a rotary evaporator was used for 2 hours to remove the solvent from the product. Then, the resultant was dried in a vacuum oven for 24 hours, whereby 16.4 g (yield 99%) of Compound 3 represented by Formula 3 was obtained.

¹ H NMR (300 MHz): δ 0.57~0.59 (t, 1H), 1.62~1.80 (m, 2H), 3.62~3.67 (m, Si-CH ₃ ), 3.85~3.87 (t, 3H), 7.93 ~7.95(t,4H), 8.56(s,NH), 8.64~8.67(d,5H), 9.09~9.11(d,6H), 13.80(s,OH)

IR (pure, cm ^-1 ): 3650~3200(ν _OH ), 3300~3200(ν _NH ), 1650(ν _CONH ), 1120~1050(ν _矽-(alkoxy) )

(Manufacture of surface treatment composition for copper foil) Examples 28 to 29

The solvent mixture was mixed with the compound 3 prepared in Example 27 by mixing water and methanol in a volume ratio of 1:9 to prepare a mixed solution of Compound 3 having 0.5% by weight and 1% by weight, respectively.

(Manufacture of second-tier FCCL) Examples 30 to 31

The mixed solutions prepared in Examples 28 to 29 were separately allowed to stand for 60 minutes for hydrolysis, and then sprayed on a Cr-coated rolled copper foil (IL-2, manufactured by Iljin), respectively. Next, the copper foil was coated with an applicator to prepare a coated copper foil. The coated copper foil was dried in an oven at 120 ° C for 30 minutes.

A copper foil treated with a surface treatment composition was sprayed with a varnish of the Upilex form manufactured by UBE Co., Ltd. (product name: U-varnish-S), and coated with a doctor blade.

The coated polylysine is cured by performing 30 minutes at 60 ° C, 30 minutes at 120 ° C, 30 minutes at 250 ° C, and 10 minutes at 400 ° C in a nitrogen atmosphere to prepare a polyimide film, thereby preparing The polyimide film is applied to the upper copper foil by a polyimide film. The copper foils prepared in Examples 30 to 31 are hereinafter referred to as Samples 14 to 15.

Comparative example 5

A copper foil coated with a polyimide film was prepared in the same manner as in Example 30 except that the surface treatment composition was omitted to treat the copper foil. Surface steps. The copper foil prepared in Comparative Example 5 is hereinafter referred to as Comparative Sample 5.

Evaluation Example 3-1: Peel Strength Test

The peel strengths of samples 14 to 15 and comparative sample 5 were measured using the method specified by ASTM D-638. The cross-arm speed was 25 mm/min and the width of the sample was 5 mm. Measurements were performed using an Instron 8516. The results of the measurements are shown in Table 3 below.

As shown in Table 3, samples 14 to 15 prepared using a surface treatment composition containing a decyl compound were compared to Comparative Sample 5 prepared without using a surface treatment composition, according to an embodiment of the present invention. The imide film and the copper foil have a greatly increased peel strength.

Evaluation Example 3-2: Moisture Resistance Test

Samples 14 to 15 were stored in a thermostat humidifier HIRAYANA PC-R7 at 50 ° C and a relative humidity of 80% for 7 days, and the discoloration of the samples 14 to 15 was remarkable. After 7 days, the colors of samples 14 to 15 did not change.

(Synthesis of fluorenyl compound (4)) Example 32A: Synthesis of Compound 4A

Compound 4A represented by Formula 4 was synthesized according to the following reaction mechanism 4.

Wherein R is a methyl group.

125.712 grams of tetrahydrofuran, 8.9645 grams (0.05 moles) of 3-aminopropyltrimethoxynonane and 9.6065 grams (0.05 moles) of trimellitic anhydride (1,2,4-benzenetricarboxylic anhydride) (2,3-pyridine II) The anhydride was poured into the reactor and reacted for 6 hours, the temperature of the reactor was maintained at -5 ° C to 5 ° C under a nitrogen atmosphere, and the mechanical stirrer was rotated at 250 rpm. After the reaction was completed, a rotary evaporator was used for 1 hour to remove the solvent from the product. Then, the resultant was dried in a vacuum oven for 48 hours, whereby 18.5 g (yield 99%) of Compound 4A represented by Formula 4 was obtained.

¹ H NMR (300 MHz): δ 0.62~0.65 (t, 1H), 1.71~1.76 (m, 2H), 3.41~3.47 (m, Si-CH ₃ ), 3.56~3.60 (m, 3H), 7.45 (s, NH)

IR (pure, cm ^-1 ): 3650~3200(ν _OH ), 3300~3200(ν _NH ), 1650(ν _CONH ), 1120~1050(ν _矽-(alkoxy) )

Example 32B: Synthesis of Compound 4B

The compound 4B represented by Formula 4 was synthesized according to the following reaction mechanism 4.

Wherein R is an ethyl group.

125.712 grams of tetrahydrofuran, 8.9645 grams (0.05 moles) of 3-aminopropyltriethoxynonane and 9.6065 grams (0.05 moles) of trimellitic anhydride (1,2,4-benzenetricarboxylic anhydride) (2,3-pyridine) The dianhydride was poured into the reactor and reacted for 6 hours, the temperature of the reactor was maintained at -5 ° C to 5 ° C under a nitrogen atmosphere, and the mechanical stirrer was rotated at 250 rpm. After the reaction was completed, a rotary evaporator was used for 1 hour to remove the solvent from the product. Then, the resultant was dried in a vacuum oven for 48 hours, whereby 20.6 g (yield 99%) of Compound 4B represented by Formula 4 was obtained.

¹ H NMR (300 MHz, CD ₃ OD): δ 0.71~0.73 (t, 1H), 1.14~1.23 (m, Si-CH3), 1.71~1.74 (m, 2H), 3.58~3.60 (t, 3H) ), 3.79~3.86 (m, Si-CH ₂ ), 8.55 (s, NH)

IR (pure, cm ^-1 ): 3650~3200(ν _OH ), 3300~3200(ν _NH ), 1650(ν _CONH ), 1120~1050(ν _矽-(alkoxy) )

(Manufacture of surface treatment composition for copper foil) Examples 33 to 34

The solvent mixture was mixed with the compound 4A prepared in Example 32A by mixing water and methanol in a volume ratio of 1:9 to prepare a mixed solution of Compound 4A having 0.5% by weight and 1% by weight, respectively.

Examples 35 to 36

The solvent mixture was mixed with the compound 4B prepared in Example 32B by mixing water and methanol in a volume ratio of 1:9 to prepare a mixed solution of compound 4B each having 0.5% by weight and 1% by weight.

(Manufacture of two-layer FCCL) Examples 37 to 40

The mixed solutions prepared in Examples 33 to 36 were separately allowed to stand for 60 minutes for hydrolysis, and then sprayed on a Cr-coated rolled copper foil (IL-2, manufactured by Iljin), respectively. Next, the copper foil was coated with an applicator to prepare a coated copper foil. The coated copper foil was dried in an oven at 120 ° C for 30 minutes.

A copper foil treated with a surface treatment composition was sprayed with a varnish (product name: JY-001) manufactured by Jooyoung Co., Ltd., and coated with a doctor blade.

Hardening was carried out in a nitrogen atmosphere at 60 ° C for 30 minutes, at 120 ° C for 30 minutes, at 250 ° C for 30 minutes, and at 400 ° C for 10 minutes. The polyaminic acid was coated to prepare a polyimide film, and thus, a copper foil coated with a polyimide film separately was prepared. The copper foils prepared in Examples 37 to 40 are hereinafter referred to as Samples 16 to 19.

Comparative example 6

A copper foil coated with a polyimide film was prepared in the same manner as in Example 37 except that the step of treating the surface of the copper foil using the surface treatment composition was omitted. The copper foil prepared in Comparative Example 6 is hereinafter referred to as Comparative Sample 6.

Evaluation Example 4-1: Peel Strength Test

The peel strengths of samples 16 to 19 and comparative sample 6 were measured using the method specified by ASTM D-638. The cross-arm speed was 25 mm/min and the width of the sample was 5 mm. Measurements were performed using an Instron 8516. The results of the measurements are shown in Table 4 below.

As shown in Table 4, samples 16 to 19 prepared using the surface treatment composition containing a decyl compound were compared to the comparative sample 6 prepared without using the surface treatment composition, according to the embodiment of the present invention. The imide film and the copper foil have a greatly increased peel strength.

Evaluation Example 4-2: Moisture Resistance Test

Samples 16 to 19 were stored in a thermostat humidifier HIRAYANA PC-R7 at 50 ° C and a relative humidity of 80% for 7 days, and the discoloration of the samples 16 to 19 was remarkable. After 7 days, the colors of samples 16 to 19 did not change.

(Comparison of peel strength according to the form of polyimine) (Manufacture of 2-layer FCCL) Examples 41 to 44

A copper foil coated with a polyimide film was prepared in the same manner as in Example 37 except that PMDA/ODA varnish, BTDA/PDA varnish, BTDA/PMDA/ODA/PDA varnish, and PMDA/ODA were used. -SD varnish replaces the varnish (product name: JY-001) manufactured by Jooyoung Co., Ltd., respectively. Here, 0.5% by weight of the compound 4B was used as a surface treatment agent. The copper foils prepared in Examples 41 to 44 are hereinafter referred to as Samples 20 to 23.

The varnish described above is manufactured by the method described below

PMDA/ODA varnish

255.000 grams of N,N-dimethylacetamide (DMAc; N,N-dimethylacetamide), 21.538 g (0.107563 mol) of 4,4'-diaminodiphenyl ether and 23.462 g (0.107563 mol) of pyromellitic dianhydride were sequentially poured into the reactor and reacted 24 The reactor was maintained at a temperature of -5 ° C to 5 ° C under a nitrogen atmosphere and the mechanical stirrer was rotated at 350 rpm. Then, a varnish containing 15% by weight of polyamic acid was prepared.

BTDA/PDA varnish

255.000 grams of DMAc (N,N-dimethylacetamide), 11.307 grams (0.104561 moles) of m-phenylenediamine and 33.693 grams (0.104561 moles) of 3,3',4,4'-two Phenolone tetracarboxylic dianhydride (3,3',4,4'-benzophenone tetracarboxylic dianhydride) was poured into the reactor and reacted for 24 hours, maintaining the temperature of the reactor under a nitrogen atmosphere of -5 ° C to 5 ° C, and mechanical The agitator was rotated at 350 rpm. Then, a varnish containing 15% by weight of polyamic acid was prepared.

BTDA/PMDA/ODA/PDA varnish

255 grams of DMAc, 6.334 grams (0.031633 moles) of 4,4'-diaminodiphenyl ether, and 7.982 grams (0.073811 moles) of m-phenylenediamine were poured into the reactor and completely dissolved. Then, 23.784 g (0.073811 mol) of 3,3',4,4'-benzophenone tetracarboxylic dianhydride and 6.900 g (0.031633 mol) The pyromellitic dianhydride was poured into the reactor and reacted for 24 hours, the temperature of the reactor was maintained at -5 ° C to 5 ° C under a nitrogen atmosphere, and the mechanical stirrer was rotated at 350 rpm. Then, a varnish containing 15% by weight of polyamic acid was prepared.

PMDA/ODA-SD varnish

127.5 grams of DMAc, 9.826 grams (0.04907 moles) of 4,4'-diaminodiphenyl ether, and 1.408 grams (0.002583 moles) of SD-545 were poured into the reactor and completely dissolved. Then, 11.267 g (0.0.051653 mol) of pyromellitic dianhydride was poured into the reactor and reacted for 24 hours, maintaining the temperature of the reactor under a nitrogen atmosphere of -5 ° C to 5 ° C, and a mechanical stirrer Rotate at 350 rpm. Then, a varnish containing 15% by weight of polyamic acid was prepared.

Comparative Examples 7 to 10

A copper foil coated with a polyimide film was prepared in the same manner as in Examples 41 to 44 except that the step of treating the surface of the copper foil using the surface treatment composition was omitted. The copper foils prepared in Comparative Examples 7 to 10 are hereinafter referred to as Comparative Samples 7 to 10.

Evaluation Example 5 - Peel Strength Test

The peel strengths of samples 20 to 23 and comparative samples 7 to 10 were measured using the method specified by ASTM D-638. The cross-arm speed was 25 mm/min and the width of the sample was 5 mm. Measurements were performed using an Instron 8516. The results of the measurements are shown in Table 5 below.

As shown in Table 5, samples 20 to 23 prepared using the surface treatment composition containing a decyl compound were compared to Comparative Samples 7 to 10 prepared without using the surface treatment composition, according to an embodiment of the present invention. There is a greatly increased peel strength between the polyimide film and the copper foil.

As described above, the surface of the hydrolyzate containing the mercaptoalkyl compound or the mercapto compound according to the present invention is compared to the PCB on which the surface treatment film is not formed or the PCB on which the surface treatment film containing the general mercapto compound is formed. The PCB on which the treatment film is formed has an improved peel strength.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

Claims (11)

A surface-treated copper foil for a printed circuit board comprising a rustproof layer formed on a copper foil and a surface treated film formed on the rustproof layer, wherein the surface treated film comprises a formula selected from the formula 1 to At least one compound of the group consisting of a fluorenyl compound represented by 4, or a hydrolyzate of the decyl compound: <Formula 4> Wherein R1, R2 and R3 are each independently a C1 to C3 alkyl group, and R4 and R5 are each independently hydrogen or a C1 to C5 alkyl group. The surface-treated copper foil for a printed circuit board according to claim 1, wherein R ₁ , R ₂ and R ₃ are each independently a methyl group or an ethyl group, and R ₄ and R ₅ are hydrogen. The surface-treated copper foil for a printed circuit board according to claim 1, further comprising a heat-resistant layer interposed between the copper foil and the rust-preventing layer. The surface-treated copper foil for a printed circuit board according to claim 3, further comprising a layer layer interposed between the copper foil and the heat-resistant layer. A method for preparing a surface-treated copper foil for a printed circuit board, comprising: forming a rustproof layer on a copper foil; and cleaning and drying the copper foil on which the rustproof layer is formed, and a coating composition And coating the rustproof layer on the rustproof layer to prepare a surface treated film, the composition comprising at least one selected from the group consisting of decyl compounds represented by Formulas 1 to 4. a compound or a hydrolyzate of the decyl compound: Wherein R1, R2 and R3 are each independently a C1 to C3 alkyl group, and R4 and R5 are each independently hydrogen or a C1 to C5 alkyl group. The method for producing a surface-treated copper foil for a printed circuit board according to claim 5, wherein the amount of the decyl group compound is in the range of 0.001 to 5% by weight based on the total amount of the composition. . The method for producing a surface-treated copper foil for a printed circuit board according to claim 5, wherein the composition comprises a solvent selected from the group consisting of water, methanol, ethanol, acetone, methyl ethyl ketone, and ethyl acetate. And at least one solvent of the group consisting of benzene. The method for preparing a surface-treated copper foil for a printed circuit board according to claim 5, further comprising forming a heat-resistant layer on the copper foil before forming the rust-preventing layer. The method for preparing a surface-treated copper foil for a printed circuit board according to claim 8 is further comprising forming a small bump on the copper foil before forming the heat-resistant layer. A flexible copper-clad laminate comprising the surface-treated copper foil for a printed circuit board according to any one of claims 1 to 4; and a surface-treated film formed on the copper foil Polyimine film. The flexible copper clad laminate according to claim 10, wherein the polyimine film comprises a hardened product of polylysine, and the polyamic acid is composed of at least one dianhydride monomer and a reaction product of at least one diamine monomer, wherein the at least one dianhydride monomer is selected from the group consisting of pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3, a group consisting of 3',4,4'-biphenyltetracarboxylic dianhydride and 3,3',4,4'-oxydiphthalic anhydride, and the at least one diamine monomer is selected from 4 a group consisting of 4'-diaminodiphenyl ether, p-phenylenediamine, decylamine diamine, 3,4-diaminodiphenyl ether and m-phenylenediamine.