TW201009119A - 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

Abstract

Provided is a surface-treated copper foil for a printed circuit board (PCB), including an antirust layer formed on a copper foil and a surface treatment film formed on the antirust layer, wherein the surface treatment film includes at least one compound selected from the group consisting of silane-based compounds represented by Formulae 1 through 4, or hydrolysates of the silane-based compounds: (Formula 1) (Formula 2) (Formula 3) (Formula 4) wherein R1, R2, and R3 are each independently a C1-C3 alkyl group and R4 and R5 are each independently hydrogen or a C1-C5 alkyl group.

Description

201009119 31972pif VI. Description of the Invention: [Related Application] The present application claims priority to Korean Patent Application No. 10-2008-0070081, filed on Jan. 18, 2008, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference. reference. BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a copper foil for a printed circuit board ('PCB), a method for preparing a copper foil, and a flexible copper clad laminate for a copper foil. And FCCL), and particularly a surface-treated copper foil for a PCB on which a surface-treated film comprising a hydrolysate comprising a silane-based compound or a hydroxyl compound is formed, and comprising the copper foil Fccl. [Prior Art] Flexible copper clad laminate (FCCL) is one of the forms of printed circuit boards (PCBs) and its current demand is increasing. The FCCL is a multilayer film formed of two or three layers in which a p〇lyimide is laminated on a copper foil.准确性 The accuracy of the wiring printed on the FCCL is increased, and the accuracy of the surname is also increased, 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 (e.g., 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 peel strength between the copper and the substrate. It is disclosed in Japanese Patent Application No. 1990-026097. 201009119 ό iy /zpit However, as the physical properties of the copper foil used in the PCB become tight, there is still a need for a copper enamel for a PCB formed by a surface-treated film having improved physical properties. 'Content of the invention】

The present invention provides a surface treated copper crucible for a printed circuit board (PCB) comprising a hydrolysate of a novel agglomerated compound or a calcined compound which provides excellent peel strength between the substrate and copper, 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 1>

<Formula 3> 201009119 31972pif

&lt;Formula 4&gt;

_ where R, R2 and R_3 are independent of each other. to. The alkyl groups, and the calipers 5 are each independently hydrogen or an alkyl group of (c to c5).

According to another aspect of the present invention, there is provided a red scale for a printed circuit board (PCBB): a method of preparing a treated tile. The method comprises: forming a layer on a copper crucible, a stomach washing and drying a rustproof layer formed thereon. Copper foil, as well as coating = Lu Li ^ anti-riding 'and dry coated rust-proof layer, to prepare the table and the object contains a group selected from the group of Shi Xi two "Μ" represented by Formula 1 to Formula 4 At least - a compound or the above-mentioned Weilkification &lt;Formula 1&gt;

<Formula 2> 8 201009119

Jl^/zpu &lt;Formula 3&gt;

<Formula 4>

Wherein Ri, R2 and r3 are each independently and R5 is independently a hydrogen or a thiol group of C1, and 4

According to the invention, one side is the other. (rccL) comprising the above-mentioned pc ' ^ flexible copper clad laminate formed on the copper surface treatment thin film; and in order to enable the above features and advantages of the present invention = only the following specific embodiments, and The drawings are described in detail below. f. Embodiments Hereinafter, a surface-treated copper foil for a printed circuit board (PCB), a copper foil for a PCB, and a method for preparing a copper foil for a PCB will be described in more detail according to an embodiment of the present invention. 9 201009119 31972pit and a flexible copper-clad layer Platen (FCCL). According to the embodiment, the surface-treated copper foil for a PCB comprises a rust-preventing layer formed on the copper foil and a surface-treated film formed on the rust-preventing layer, wherein the surface treatment _ comprises a method selected from the group consisting of Formulas 1 to 4 (four) At least a compound of the * group of the base compound, or a hydrolyzate of the compound. &lt;Formula 1>

&lt;Formula 3>

&lt;Formula 4&gt;

10 201009119

P

Cr wherein R!, R2 and R3 are each independently an alkyl group of Cl to Cs and R4 and R5 are each independently hydrogen or an alkyl group of (C to C5. The fluorenyl compound has a siloxane oxyalkyl group at one end thereof (siloxane gr0UP) Used to form a covalent bond with copper foil, and has an imidazole group and/or an amidino group (such as a coffee group) at the other end thereof, wherein the imidazolyl group and/or the amidoxime has a film with a polyimide film. A similar structure, 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, the alkoxy group contained in the fluorenyl compound ( Alkoxy group '-OR) reacts with a hydrazine Xy gr〇Up present in the metal surface to form a siloxane bond. The oxoalkyl group contained in the calcined compound can also be used. Forming a decane bond with the metal surface. According to another embodiment of the present invention, the core, r2 and R3 in the fluorenyl compound are each independently a acetophenone, and R4&R5 may be a nitrogen. (10)-step in the auxiliary and anti-rust layer from the zinc alloy to form the heat-resistant layer of metal or to a few hundred nanometers (four) In the case of the present invention, a nodules can be further inserted between the copper box and the heat-resistant layer 201009119 31972pif by making the current having a current density of 10 to 150 A/dm 2 at i 〇 ° C to 4 (The temperature of Tc flows through the electrolyte, wherein the electrolyte contains 1 to 40 g/L of copper metal and 30 to 250 g/L of sulfuric acid. The rustproof layer may contain chromium trioxide as a rust inhibitor , chromic acid, dichromic acid, sodium dichromate, and chromate. The anti-rust layer can be made to have a current density of 〇.〇! to 1 The current of 〇A/dm2 flows through the electrolyte at a temperature of 10 C to 50 c, and the concentration of the anti-mining agent is up to 10 g/L to form a thickness of several tens to several hundreds of nanometers. A zinc alloy, a nickel alloy or a cobalt alloy is formed and can be formed to have a thickness of several tens of lux to several hundreds of nanometers. Copper foil is usually 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 can be The method comprises: forming a rustproof layer on the copper foil; cleaning and drying the rustproof layer to form a copper ruthenium on the ruthenium, and coating the composition on the rustproof layer, and drying the coated rustproof layer to prepare the surface treated film The composition contains at least one compound selected from the group consisting of the shisha compound represented by Formulas 1 to 4 and a hydrolyzate of the dream alkyl compound. Ming &lt;Formula 1&gt;

&lt;Formula 2&gt; 12 201009119 jivv-ipu: &lt;Formula 3&gt;

&lt;Formula 4&gt;

〇 wherein R!, 112 and 113 are each independently an alkyl group of ^ to Q, and R4 and R5 are each independently hydrogen or an alkyl group of (C to C5).

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 sullphamic acid copper, and the alkali plating solution may contain copper cyanide or coke. Electrolyte solution of copper prophosphate. According to an embodiment of the present invention, the electrophotographic solution used in the preparation of the copper foil is not particularly limited, and any 13 2〇l〇〇9ii9 3l972pif plating solution used in the field to which the present invention pertains can 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, and chromate. The concentration of the chromium compound may range from 0.1 to 10 g/L, for example from 1.0 to 10 g/L. When a 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; Compounds such as phosphoric acid, polyphosphate pyrophosphate, phosphate or pyrophosphate; and organic compounds such as benzotriazole. The thickness of the rustproof layer may range from 01 to 1 nanometer. According to another embodiment of the present invention, the composition may comprise at least one compound selected from the group consisting of the compounds of the formulas j to 4, a hydrolyzate of the alkylene compound, and a solvent. The amount of the decyl compound may range from 1 to 5% by weight of the composition. When the amount of the fluorenyl compound is 〇 重量 1% by weight or less, the organic layer formed by the surface treatment agent cannot be sufficiently coated on the copper, so that the peel strength cannot be improved. When the amount of the mercaptoalkyl compound is 5% by weight or more, the thickness of the organic layer formed by the surface treatment agent increases and covers the bar on which the copper falls, 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, methyl 201009119 ^iy/zpn alcohol, ethanol, acetone, mercaptoethyl hydrazine 11^11丫11丫11^1; 〇116), fluorenyl group At least one of a group consisting of methylethylketone, ethylacetate, and benzene. 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 rust-preventing layer. The details of forming the heat-resistant layer are the same as those described for the copper foil for PCB, and therefore are not repeated. According to another embodiment of the present invention, 'in the above method, before the formation of the barrier layer, the layer can be further performed on the copper foil. Form a subsection. 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 collar for a PCB and a polyimide film formed on the surface treated film on the copper case. The flexible copper clad laminate may have a two-layer structure (2_φ 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'-diphenyl-tetracarboxylic acid (3, 3',4,4'-biphenonetetrahydrocarboxylic anhydride), 3,3',4,4'-biphenyltetrahydro acid dianhydride (3, 3,, 4, 4, - 15 201009119 31972pit biphenyltetracarboxylic dianhydride) and 3,3 ',4,4'-Oxo 3,4'-oxydiphthalic anhydride, and at least one diamine monomer may be selected from 4,4'·two Aminodiphenyl ether (4,4'-〇xydianiline), para-phenylene diamine, siloxanediamine (SD), 3,4-diaminodiphenyl (3,4) -oxydianiline) and a group of meta-phenylenediamine. The oxirane diamine (SD) may have the following structure: ch3 - SiO. fH3 - A I - CH ^ CH ^

In the structure of SD, n ranges from 2 to 12. After the monoanhydride monomer is reacted with the diamine monomer, the polyglycolic acid is a compound to which the bond is attached. For example, a poly-axis acid obtained from a pyromellitic acid bis-lactyl group has the following structure.

❹ S heat treatment polyamine warm day, imine. A polyfluorene having the following structure can be obtained 16 201009119 3iy/^pit

热处理 醢 Polyamide hydrazine The heat treatment of polylysine ends at about 6 ° C in a nitrogen atmosphere and finally 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/〇DA 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 synthesized compound in the following examples was confirmed using Brucker DRX_3()() MHz iH_NMR and Jasco 610 FT-IR. (Synthesis of Dreaming Compound (1)) Example 1: Synthesis of Compound 1 The compound represented by the formula [1] was synthesized according to the following Reaction Mechanism 1 &lt; Reaction Mechanism 1&gt; 17 1 ° 201009119 31972pil WWNH2 + 1-(3- Aminopropyl)

3. Glycidyloxypropyltrimethoxydecane N Qiao 3 Η 0 API·decane will be 162.68 g of tetrahydrofurane, 6.259 g (0.05 mol) of glycidyloxypropyltrimethoxysilane Glycidoxypropyltrimethoxysilane and 11.81 g (0.05 mol) of ® 1-(3-aminopropyl)-sigmoid (l-(3-aminopropyl)-imidazole) were charged into the reactor and reacted 6 The reactor was maintained at a temperature of 95 ° 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 to obtain 7 g (yield 98%) of Compound 1 represented by Formula 1. 4 NMR (300 MHz, CD3OD): δ 0.62~0.68 (m, 1H), 〇1.89~1.96 (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, SiOCH3), 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), 4.05~4.10(m, 9H), 6.95(s, 10H), 7.12~7.13(t, 11H), 7.65(s,12H) IR (neat, cm' 1) : 3650~3200(vOH), 3300~3200(vNH), 1120~1050(v~decyloxy)) 18 201009119 ^ivvzpit (Manufacture of surface treatment composition for copper foil) Example 2 by 1 : 9 by volume ratio of water and methanol to obtain a solvent mixture 'The solvent mixture was mixed with the compound 1 prepared in Example 1 to prepare a mixed solution of Compound 1 having ι % by weight. (Manufacture of two-layer FCCL) 实例 Example 3 The mixed solution prepared in Example 2 was allowed to stand alone for 60 minutes for hydrolysis, and then sprayed on the rolled, heat-resistant layer and rust-proof layer sequentially formed on the rolled (rolled) Copper foil (IL-2, manufactured by Iljin). Next, a copper foil was coated using an applicator (C.K Trading Company's model name: CKAF1〇〇3) 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), zinc alloy and chromium. The coated copper foil was dried at 120 ° C for 30 minutes. The box ginseng was sprayed with KRICT-PAA first (BPDA:PMDA:PDA:ODA=3:7:6:4) using copper foil treated with the table f, and using a doctor blade (d0Ct0r blade) in the paint group environment at 6 (TC was carried out for 30 minutes, 120X: 3 minutes, 1 ° = nitrogen for 30 minutes, and 4G0 °C for 10 minutes to harden the acid to prepare a polyimide film, thus preparing a polyamine-coated On the upper copper drop. The steel box amine film prepared in Example 3 was coated as "Riding as Sample 1. 201009119 31972pif Example 4 Preparation of copper coated with polyimide film in the same manner as in Example 3 The KRICT_PAA varnish was replaced with a varnish (product name: JY_001) manufactured by Jooyoung Industries Co., Ltd. The copper foil prepared in Example 4 is hereinafter referred to as Sample 2. Example 5 Preparation of polyfluorene in the same manner as in Example 3. The copper foil coated with an imide film 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 Substitious varnish made by UBE Co., Ltd. replaces ICRICT-PAA varnish ^ Copper foil prepared in Example 5 Hereinafter referred to as sample 3 〇Comparative Example 1 A copper foil coated with a polyimide film was prepared in the same manner as in Example 3 except that the surface treatment composition was omitted to treat the surface of the copper box. The copper foil prepared in Comparative Example 1 is hereinafter referred to as Comparative® Sample 1. Comparative Example 2 A steel crucible coated with a poly-imine film was prepared in the same manner as in Example 4 except that the surface treatment was omitted. The composition of the composition to treat the surface of the matte. The copper foil prepared in Comparative Example 2 is hereinafter referred to as comparison 20 201009119

Jl^/zpu sex 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 剥离: Peel Strength Test The peel strengths of Samples 1 to 3 and Comparative Samples 1 to 3 were measured using the method specified by ASTM D-638. Cross-pitch speed (cr〇ss_Hea (j Spee(j) was 25 mm/min and the width of the sample was 5 mm. Measurement was performed using Instnm 8516. The results of the measurement are shown in Table 1 below. &lt;Table 1&gt; Peel strength [kg/cm] I匕Comparative sand b fairness Example 0.73 0.32 0.76 0.38 0.58 0.28 As shown in Table 1, according to the embodiment of the present invention, compared with no use 21 201009119 31V/2pit surface treatment composition Comparative Samples 1 to 3 for the preparation of the materials, Samples 1 to 3 prepared using the surface treatment composition containing the bismuth-based compound showed a greatly increased peel strength between the polyimide and the copper foil. : Moisture resistance test at 50 C, relative humidity 8〇% in the thermo-hygrostat HIRAYANAPC-R7 stored samples] to 3 for 7 days, sample 1 to 3 discoloration (discoloration) is obvious. After 7 days , the color of samples 1 to 3 is not

There are changes. (Synthesis of the compound (2)) Example 6A: Synthesis of Compound 2A Compound 2A represented by Formula 2 was synthesized according to the following Reaction Mechanism 2. &lt;Reaction mechanism 2&gt; 〇

Wherein R is a methyl group. 125.712 g of tetrahydrofuran, 8 9645 g of 3-aminopropyltrimethoxysilane and 5.035 g of (0 05 mol) of succinic anhydri (ie) poured into the reactor and reacted for 6 hours, maintaining the reactor temperature at -5 C to 5 C under nitrogen, and the mechanical stirrer was rotated at 30 〇 rprn. After the completion of the reaction 22 201009119 jiy/zpu 'use The evaporator was rotated for 2 hours to remove the solvent from the product. Then, the product was dried in a vacuum oven for 24 hours to obtain 13.9 g (yield: 99%) of the compound 2A represented by the formula 2. ^NMR (300 MHz): δ 0.53~0.58(m, 1H)&gt; 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, SiOCH3), 8.00 (s, _NH_), 12.00 (s, -OH) IR (pure, cm-1): 3650~3200 (vOH), 3300~3200 (vNH), ❹ 1650 (vCONH), ii20 ~1050 (v Dream (from base)) Example 6B: Synthesis of Compound 2B The compound 2B represented by Formula 2 was synthesized according to the following Reaction Mechanism 2. <Reaction Mechanism 2>

Wherein R is an ethyl group. 125.712 grams of tetrahydrofuran, 11.08685 grams (0.05 moles) of 3-aminopropyltriethoxysilane and 5.035 grams (0.05 moles) of succinic anhydride were poured into the reactor and reacted for 6 hours. The reactor temperature was maintained at -5 ° C to 5 ° C under a nitrogen atmosphere, and the mechanical stirrer was rotated at 300 rpm. After the completion of the reaction, the solvent was removed from the product using a rotary evaporation 23 201009119 31972 pif 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. HNMR (300 ΜΗζ): δθ.58~0.60 (m, 1H), 1.22~1.25 (m, Si-CH2), 1.60~1.63 (m, 2H), 2.45~2.49 (m, 4Η), 2.51 ~2.54 (m, 5H), 3.20~3.25 (m, 3H), 3.83~3.87 (m, Si-CH3) IR (pure, cm·1): 3650~3200 (voh), 3300~3200 (vNH), 1650 (vCONH), 1120 to l〇5〇 (vq methoxy)) (Production of surface treatment composition for copper foil) Examples 7 to 11 By mixing water and methanol in a volume ratio of 1:9 to obtain a solvent The mixture was mixed with the compound 2A prepared in Example 6A to prepare a mixed solution of Compound 2A having 0.5% by weight, 1% by weight, 2% by weight, 3% by weight and 5% by weight, respectively. 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 wt%/〇, 1 wt%, respectively. A mixed solution of 2% by weight, 3% by weight, and 5% by weight of Compound 2B. (Manufacturing of two-layer FCCL) 24 201009119 Examples 17 to 26 f The mixed solutions prepared in Examples 7 to 16 were allowed to stand alone for 60 minutes to be solved by: i: then separately sprayed on &amp; coated rolled copper foil (several _2, P made). Next, the rolled copper foil was coated with an applicator to thereby coat the steel box. In the oven, dry and dry 30 * clock coated with Yuan Ben, Π, - Jooyoung Industry Co., Ltd. (product name: jy ~ 00 1) manufactured by squirting the silk paste at the surface of the paste composition (four), And use a scraper to cover it. Under a nitrogen atmosphere, the temperature was 60 ° C for 30 minutes, 12 (rc was carried out for 3 minutes, TC for 30 minutes, and prepared for a minute to harden the coated t-proline to prepare polyimine _, Thus, copper boxes to which the films were respectively applied were prepared. The copper treatments prepared in Examples 17 to 26 are hereinafter referred to as Samples 4 to 13. Comparative Example 4 Preparation of Polypyrene in the same manner as in Example 17 The copper film coated on the amine film was omitted except that the surface treatment composition was omitted to treat the surface of the copper box. 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 sample 25 201009119 31972 pif width was 5 mm. Measurements were performed using InStron 8516. The results of the measurement are shown in Table 2 below. <Table 2> Peel strength [kg/cm] Example Π (Sample 4) 0 78 Example 18 (Sample 5) 0.86 Example 19 (Sample 6) Example 20 (Sample 7 ) 0.93 1.05 Example 21 (Sample 8) 1 0.92 Example 22 (Sample 9) 0 82 Example 23 (Products) 1〇) 0.89 Example 24 (Sample 11) 1.02 Example 25 (Sample 12) 1.12 Example 26 (Sample 13) 0.94 Comparative Sample 4) 0.38 As shown in Table 2 'According to the embodiment of the present invention, compared to no surface used In Comparative Sample 4, which was prepared for the preparation of the composition, Samples 4 to 13 prepared using the surface treatment composition containing the Wei group of the compound showed a greatly increased peel strength between the polyimide film and the copper. Evaluation Example 2-2: Moisture Resistance Test Samples 4 to 13 were stored in a thermostat humidifier Hirayana 26 201009119 PC-R7 for 7 days at 50 C and a relative humidity of 8 ,, and the discoloration of the 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. &lt;Reaction mechanism 3&gt;

ΤΛ vn « Ό FOCA^TimS will be 125.712 grams of tetrahydrofuran, 8.9645 grams (0.05 moles) of 3-aminopropyltrimethoxy decane and 7.4550 grams (0.05 moles) of 2,3-pyridinium dianhydride (2, 3-pyridinedicarboxylic anhydride) was poured into the reactor and reacted for 5 hours, the temperature of the reactor was maintained under a nitrogen atmosphere, and the mechanical stirrer was rotated at 300 rpm. After the completion of the reaction, 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 4 g (yield 99%) of Compound 3 represented by Formula 3. !HNMR (300 MHz): δ〇.57-〇.59(ί, 1Η)' 1.62-1.80(m, 27 201009119 31972pit 2H), 3.62~3.67 (m, Si-CH3), 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, cnf1): 3650~3200(vOH), 3300~3200(vNH), 1650(Vc〇nh), .1120~1050(v hair (all oxygen)) (manufacture of copper surface treatment composition) 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 obtain a mixed solution of Compound 3 prepared in Example 27 to prepare a mixed solution of Compound 3 having 0.5% by weight and 1% by weight, respectively. . (Manufacture of two-layer FCCL) - Examples 30 to 31 The mixed solutions prepared in Examples 28 to 29 were separately allowed to stand for 6 minutes for hydrolysis, and then sprayed separately on a Cr-coated rolled copper foil (IL_2, 11 fine manufacturing). Next, the copper drop was coated using an applicator to prepare a coated copper. In the oven, on the 12 (rc dry 3G min coated copper ❹ τ τ 上 上 , , , , 制造 制造 Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up Up The coating was applied at 120 ° C for 30 minutes and minutes. Under a nitrogen atmosphere at 6 ° C for 3 〇 250 C for 3 〇 and 4 〇 (rc into 28 201009119 = amine acid to prepare (4) Comparative Example 5 The preparation of the imine film coated in the manner of the example % towel was repeated except that the surface treatment composition was omitted to treat the copper drop =. In Comparative Example 5 Prepared (4) hereinafter referred to as Comparative 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 in ASTM D-638. The cross-arm speed was 25 mm/min and the width of the sample was It is 5 mm. The measurement was performed using a DiStron 8516. The results of the measurement are shown in Table 3 below.

&lt;Table 3&gt;--&quot; Peel strength [kgf/cml Example 30 (Sample 14) 0 82 Example 31 (Sample 15) 0.78 Comparative Example 5 (Comparative Sample 5) ---- ------ __| — 0.32 As shown in Table 3, according to an embodiment of the present invention, a comparative sample 5 prepared without using a surface treating agent composition was prepared using a surface treating agent containing a decyl 29 201009119 319/^ρΐί compound. Samples 14 to 15 have a greatly increased peel strength between the polyimide film and copper fl. Evaluation Example 3-2: Moisture resistance test at 50. (:, relative humidity 80% was stored in the thermostat HIRAYANA PC_R7 for 14 days, and the discoloration of the samples 14 to 15 was remarkable. After 7 days, the color of the samples 14 to 15 did not change. (矽alkyl compound (4 Synthesis of Example 32A · Synthesis of Compound 4A Compound 4A represented by Formula 4 was synthesized according to the following Reaction Mechanism 4. <Reaction Mechanism 4>

Wherein R is a methyl group. 125.712 grams of tetrahydrofuran, 8.9645 grams of 3 -aminopropyltrimethoxydecane, and 9.6065 grams of (0.05 moles) of trimellitic anhydride (1,2,4-benzenetricarboxylic acid anhydride) (2,3 - «Bite 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 completion of the reaction, 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 to obtain 185 30 201009119 3iy / 2 psi (yield 99%) of Compound 4A represented by Formula 4. hNMR (300 MHz): δ θ.62~0.65 (t, 1H), 1.71 to 1.76 (m, 2H), 3.41 to 3.47 (m, Si-CH3), 3.56 to 3.60 (m, 3H), 7.45 (s, NH) IR (pure, cnT1): 3650~3200(voh), 3300~3200〇NH), 1650(Vc〇nh), 1120~1050(v 矽_(alkyl)) Example 32B: Synthesis of Compound 4B © Compound 4B represented by Formula 4 is synthesized according to the following Reaction Scheme 4 &lt; Reaction Mechanism 4&gt;

Wherein R is an ethyl group.

125J12g of tetrahydrofuran, 8.9645g (0.05m) of 3-aminopropyltriethoxydecane and 9.6065g (0.05m) of l,2,4-benzenetricarboxylic acid anhydride (2,3-Sebacic 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 completion of the reaction, 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 to obtain 2 〇 6 g (yield 99%) of Compound 4B represented by Formula 4. · 31 201009119 31972pit NMR (300 MHz, CD3〇D): δ〇.71 ~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-CH2) &gt; 8.55(s, NH) IR (pure, cm·1): 3650~3200(V〇H), 3300~3200(vNH), 1650( Vc_), 1120 to 1050 (v^(decyloxy)) (manufacture of surface treatment composition for copper foil) Examples 33 to 34 by mixing water and decyl alcohol in a volume ratio of 1:9 to obtain a solvent mixture' The solvent mixture was mixed with Compound 4A prepared in Example 32A to prepare a mixed solution of Compound 4A having 〇·5% by weight and 重量% by weight, respectively. Examples 35 to 36

And j, the mixture of water and decyl alcohol was mixed at a volume ratio of 1:9 to obtain a solvent mixture and the compound prepared in Example 32B was mixed with 5% by weight and 1% by weight, respectively. Mixing of Compound 4B (manufacture of two-layer FCCL) Examples 37 to 40 The mixed solution prepared by injecting 33 to 36 towels was separately allowed to stand for 60 minutes, and then separately sprayed on a Cr-coated rolled steel box (IL_2, manufactured). on. Next, copper was coated with an applicator to prepare 32 201009119 ^ly/zpn coated copper foil. In the oven in foil 0,

Uot: Drying 30 minutes coated copper (4) limited company made of varnish (product name: knife coated. Make silk treatment treatment _, and use scraping 25 〇. 〇 ^ Wei under the thief for 3G minutes, The preparation is carried out for 3 minutes, 聚 polyamine dosage for 3 〇t clock and 4 〇〇 ° C for 1 来 to harden the coated acid, to prepare poly-light amine _, thus preparing The amine/film blade was coated with copper. Examples 37 to 4 are referred to below as samples 16 to 19. Comparative Example 6 Copper prepared by coating a polyimide film in the same manner as in Example 37 was prepared. 'In addition to the step of omitting the surface treatment composition to treat the copper pig surface. The copper drop prepared in Comparative Example 6 is hereinafter referred to as Comparative Sample 6. Evaluation Example 4-1: Peel strength test specified using ASTM D-638 The method measures the peel strength of samples 16 to 19 and comparative sample 6. The cross-web speed was 25 mm/min and the width of the sample was 5 mm. The measurement was performed using an Instron 8516. The results of the measurement are shown in Table 4 below. &lt;Table 4&gt; 33 201009119 ^iy/2pu ----_ Peel strength [kgf/cm] —-37 (Sample 16) 1.6 0 —-Product 17) 1.35 —-Product 18) 1.98 ^Product 19) 1.57 Comparative sample 6) 1 0.38

As shown in Table 4, samples 16 to 19 prepared using a surface treatment composition comprising a ruthenium alkylation were compared to Comparative Sample 6 prepared without using a surface treatment composition, according to an embodiment of the present invention. There is a large enthalpy and entanglement strength between polyimine and _. Evaluation Example 4-2: Moisture Resistance Test Samples 16 to 19 were stored for 7 days at 50 t:, relative humidity of 80% in a thermostatic humidifier HIRAYANA P&lt;=^R7, and the samples 16 to 19 were significantly changed. The color of samples 16 to 19 did not change after 7 days.

(Comparison of peel strength according to the form of polyugly imine) (Production of 2-layer FCCL) Examples 41 to 44 Copper sheets coated with polyimide film were prepared in the same manner as in Example 37 except for use. PMDA/ODA varnish, BTDA/PDA varnish, BTDA/PMDA/ODA/PDA varnish and PMDA/ODA-SD varnish respectively replaced by 34 201009119

A varnish of the Upilex form. Here, the varnish described above using 〇5重田0 is a square PMDA/ODA varnish as described below. 255.000 g of N,N-dioxin 7 χτ, decyl acetamide (DMAc; Ν, Ν-dimethylacetamide), 21·538 g (0·1〇7563 Mo 4 4, ® diaminodiphenyl ether and 23·462 g (〇. 63 mol) of pyromellitic acid” While reacting 24+, the reactor temperature was maintained at -5 ° C to 5 ° C under a nitrogen atmosphere, and the mechanical stirrer was rotated at 35 rpm. Then, a 15% by weight poly-proline was prepared. Bright lacquer. BTDA/PDA varnish will have 255.000 grams of DMAc (N,N-dimercaptoamine), n.307 grams (0.104561 moles) of m-phenylenediamine and 33.693 grams (0.104561 moles) 3,3',4,4'-3,3,4,4-biphenontetracarboxylic acid anhydride was poured into the reactor and reacted for 24 hours to maintain the temperature of the reactor under nitrogen _5. 〇 to 5 °C ' and the mechanical scrambler is rotated at 350 rpm. Then, the instrument contains 15% by weight of phthalocyanine varnish. BTDA/PMDA/ODA/PDA varnish will be 255 g DMAc 6.334 g (0.031633 mol) of 4,4'- 35 201009119 31972pit diaminodiphenyl ether and 7.982 g (0.073811 mol) of m-diamine diamine were poured into the reactor and completely dissolved. Then, 23.784 g (0.073811) 3,3f,4,4'-dibenzophenonetetracarboxylic acid (3,3',4,4'-biphenontetracarboxylic anhydride) and 6.900 g (0.031633 mol) of pyromellitic dianhydride The reactor was placed in 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 polycondensate containing 15 parts by weight was prepared. Amino acid varnish. PMDA/ODA-SD varnish pours 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 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, and the temperature of the reactor was maintained at -5 under nitrogen atmosphere. °C to 5 ° C, and the mechanical stirrer was rotated at 350 rpm. Then, a varnish containing 15% by weight of polyamic acid was prepared. Comparative Examples 7 to 10 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 treating agent 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 36 201009119 ^iy/2Pu The peel strengths of the samples 2〇 to 23 and the comparative samples 7 to 1〇 were measured using the method specified in ASTM D-638. The cross roller 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 5 below. &lt;Table 5&gt; ———- Peel strength 丨kg/cml __ Example 41 (Sample 20) 1.02 _ Example 42 (Sample 21) 0.93 __Example 43 (Sample 22) _ Example 44 (Sample 23) _ 1.21 1.53 Sexual Example 7 (Comparative Sample 7) Sexual Example 8 (Comparative Sample 8) 0.52 0.39 _____^Comparative Example 9 (Comparative Sample 9) 0.61 Sexual Example 10 (Comparative Sample 1〇) ----- 0.72 As shown in Table 5, samples 2 to 23 prepared using a surface treatment composition containing a decyl compound were compared to Comparative Samples 7 to 1 prepared without using a surface treatment composition according to an embodiment of the present invention. It has a greatly increased peel strength between the polyimide film and the copper foil. As described above, the surface of the hydrolyzate containing a decyl group compound or a decyl group compound according to the present invention is compared with pCB formed on the surface of a PCB having no surface treatment film formed thereon or a surface treatment film containing a general decyl group compound. The processing of the above-mentioned pcB has an improved stripping. 37 201009119 31972pif Intensity The present invention has been disclosed in the above embodiments, but it is not intended to limit the spirit and scope of the present invention to the knowledge of the invention. Applicants' specializations and retouchings are attached to the original text [simplified in the drawing]. no. [Main component symbol description] None.

38

Claims (1)

201009119 VII. Patent application scope: 1. 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 The treatment film contains at least one compound selected from the group consisting of the fluorenyl compounds represented by Formulas 1 to 4, or a hydrolyzate of the decyl compound: &lt;Formula 1&gt; <Formula 2> &lt;Formula 3&gt; &lt;Formula 4&gt; 39 201009119 iiy/zpu Wherein Ri, Han 2 and r 3 are each independently an alkyl group of ci to Cs, and R·4 and Rs are each independently hydrogen or an alkyl group of 〇1 to 〇5. 2. The surface treated copper foil for a printed circuit board according to the invention of claim 2, wherein the 1 , the anaesthes 2 and the sizing 3 are each independently a methyl group or an ethyl group, and R 4 and R 5 are hydrogen. 3. The surface-treated copper foil for a printed circuit board according to claim 1, further comprising a heat-insulating layer interposed between the copper foil and the rust-preventing layer. 4. The surface treated copper foil for a printed circuit board according to claim 3, further comprising a small layer layer interposed between the copper foil and the barrier. And a method for manufacturing a surface-treated copper box for a printed circuit board, comprising: forming a rustproof layer on the copper foil; and cleaning and drying the copper foil on which the rustproof layer is formed Applying a composition on the anti-mine layer and drying the coated layer' to prepare a surface-treated film comprising: a compound to a group consisting of a dream compound represented by Formula 4 Or a hydrolyzate of the decyl compound: ^一201009119 j Ly /^.yu &lt;Formula 1&gt; &lt;Formula 2&gt;&lt;Formula3&gt;&lt;Formula4&gt; Wherein 仏, R 2 and R 3 are each independently an alkyl group of (C to C 3 ), and R 4 and R 5 are each independently hydrogen or an alkyl group of (C to C 5 ). 6. For printed circuit boards according to claim 5 The method for producing a surface-treated copper foil, wherein the amount of the oxime alkyl compound ranges from 0.001 to 5% by weight based on the total amount of the composition. 41 201009119 Chuan.Λφιι Surface treatment section 5 The printed circuit board is used for surface water, methanol, and a method for preparing the composition, wherein the composition comprises a solvent selected from the group consisting of methyl ethyl ketone, ethyl acetate and benzene. The printed circuit board according to the item is included in the copper red layer before the formation of the layer, and the surface of the printed circuit board according to item 8 of the patent application scope is included. Forming a small section on the copper. Further, a flexible copper clad laminate comprising a surface treated copper for use in a printed circuit board according to the scope of claims 1 to 4; A polyamine film on a surface treated film of copper matte. ❿ 11·If applied The flexible copper-clad laminate according to the item 19, wherein the polyiminoimide film comprises a hardened product of polyamic acid, and the poly-aracine is composed of at least one of two monomers and at least one a reaction product of a diamine monomer, wherein the at least one dianhydride monomer is selected from the group consisting of tetracarboxylic dianhydride, 3,3,4,4, benzophenone tetracarboxylic dianhydride, 3, 3, a group consisting of 4,4,. diphenyl benzoate and 3,3.,4,4'-oxydiphthalic anhydride, said at least: a diamine monomer selected from 4, 4, · 2 42 consisting of amino diphenyl scales, p-phenylene di-di-diamine, 3,4-diaminodiphenyl scales and m-phenylenediamines 2010 2010119119 IV. Designation of representative drawings: (1) Representative of the case: No. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 5 201009119 For the Chinese manual No. 98124127, there is no slash correction. The patent specification of the invention is %. "2006.01. (The format and order of this manual, please do not change it arbitrarily, please do not fill in the ※ part) ※Application number: ~7 ακ % ( 2〇〇6.〇1&gt; ※Application date: ※^(:Classification: C.^ % ^2006.01) % I. Invention name: (10)ο&οη w ^ ^ (2〇〇6.οι&gt; e for printed circuit boards Copper foil and preparation method thereof, and flexible copper clad laminate using polyacetic acid precursor and copper foil COPPER FOIL FOR PRINTED CIRCUIT BOARD, METHOD OF PREPARING THE SAME, AND FLEXIBLE COPPER CLAD LAMINATE USING POLYAMIC ACID PRECURSOR AND COPPER FOIL II. Abstract of Chinese invention: A surface-treated copper foil for a printed circuit board comprising a rust-preventing layer formed on a copper foil and a surface-treated film formed on the rust-preventing 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 sulfonyl compound _: &lt;Formula 1&gt; <Formula 2> 201009119 3ΐν/^ριπ VI. Description of the Invention: [Related application] This application claims priority to Korean Patent Application No. 10-2008-0070081, filed on Jan. 18, 2008, in the Korean Intellectual Property Office. The disclosure is incorporated herein by reference. [Technical Field] The present invention relates to a copper foil for printed circuit board (PCB), a method for preparing a copper foil, and a flexible copper clad laminate comprising a copper foil. ; FCCL), 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 compound is formed And the fccl containing this copper foil. [Prior Art] Flexible copper clad laminate (FCCL) is one form of printed circuit board (PCB), and its demand today is increasing. The FCCL is a multilayer film formed of two or three layers in which a p〇lyimide 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 (e.g., the polyimide film) is lowered. At this point, it is necessary to propose a means of peeling 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. Hei 90-026097. 201009119 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. [Summary of the Invention] 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 _ for a printed circuit board (PCB) comprising: a layer formed of copper red and a surface treated film formed on the anti-mine layer, wherein the surface-treated film comprises selected from the group consisting of At least one compound of the group consisting of a decyl group compound represented by Formula 1 to Formula 4 or a hydrolyzate of the methacrylic compound, &lt;Formula 1&gt; <Formula 2> HO h &lt;Formula 3&gt; 7 201009119 <Formula 4> Wherein RrR2*% are each independently an alkyl group, and R and each of the cores are independently hydrogen or (^ to (5) alkyl. According to another aspect of the present invention, there is provided a method for preparing a printed circuit board (PCB), the method comprising: a copper foil formed on a woven upper group and a dry rustproof layer, and coated Coating the rust-preventing layer and drying the coated rust-preventing layer to prepare a smear-type smear-type table 1. at least one compound of the constituent group or the one &lt;Formula 1&gt; &lt;Formula 2&gt; 8 2〇l〇〇9ii9 &lt;Formula 3&gt;&lt;Formula4&gt; And R Ί ώ 1 2 and 厌 3 are each independently C! to C3 and R And I each have independent money or C1W5 base. And &amp; (FCcd) provides a flexible steel-clad laminate/polyimine film formed on a surface treated film of steel reed. The above features and advantages of the present invention are more obvious. The following specific embodiments are described in detail with reference to the following description. [Embodiment] Hereinafter, a surface-treated steel collar for a printed circuit board (PCB) will be described in more detail according to an embodiment of the present invention. The preparation method of (4) for pCB is 20109119 ^iy/ζριιι method and flexible copper clad laminate (FCCL). According to the embodiment, the surface-treated copper foil for PCB comprises a rustproof layer formed on the copper foil. And a surface-treated film formed on the rust-preventing layer, wherein the surface-treated film contains at least one compound selected from the group consisting of fluorenyl compounds represented by Formulas 1 to 4, or a hydrolyzate of the decyl-based compound. Equation 1&gt; &lt;Formula 2&gt;&lt;Formula3&gt;&lt;Formula4&gt; D 卜 ❿ ❹ 201009119 wherein Ri, R2 and R3 are each independently an alkyl group of C! to C3, and each of r4 and I is independently hydrogen or an alkyl group of &lt;^ to C5. The sulphur-based compound has a siloxane group at one end for forming a covalent bond with the copper foil and an imidazole grouP and/or an imide group at the other end. Among them, the menthol group and/or the decylene have a structure similar to that of the polyimide film, thereby improving the bonding strength with the polyimide film. Therefore, the bonding strength between the copper foil and the polyimide film can be improved. Specifically, the alkoxy grc UP 〇 〇 R contained in the fluorenyl compound reacts with a hydroxy group present in the surface of the metal to form a siloxane bond. The decyloxy group contained in the sulphur-based compound may also form a decane bond with the metal surface. According to another embodiment of the present invention, R!, R2 and each of the fluorenyl compounds are each independently a methyl group or an ethyl group, and R4 and R5 may be hydrogen. According to another embodiment of the present invention, a heat resistance layer (heafbioeking iayer) may be further interposed between the copper foil and the rustproof layer. The heat resistant layer may be formed, for example, of zinc σ gold and may have a thickness of several tens to several hundreds of m). The metal or alloy forming the heat resistant layer is not made, and any metal or alloy used as the heat resistant layer in the field of the present invention can be used. According to another embodiment of the present invention, a nodules can be inserted between the copper yoke and the thermal barrier layer 11 201009119 Jiy/^ριπ. Flowing through the electrolyte at 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 flow through the electrolyte at a temperature of 10C to 50C by a current having a current density of 〇·〇1 to 10 A/dm2, and the concentration of the rust inhibitor is 〇1. Up to 10 g/L to form a thickness of several tens to several 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.羯 The copper bismuth is usually formed on the ridge and 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 copper foil for a PCB is formed by: forming a rustproof layer on copper red; cleaning and drying the copper foil on the rust proof; and coating the composition on the rustproof layer, a Forming party An anti-pain layer to prepare a surface-treated film, coated with 4! The #-based compound represented by Formula 4 contains a hydrolyzate selected from the compound or the above-described alkylene compound. , at least one 4 &lt;Formula 1&gt;&lt;Formula2&gt; 12 201009119 Ilit HO h &lt;式3&gt; R R R / <Formula 4> wherein R!, R2 and R3 are each independently a C1 to C3 alkyl group and R4 and R5 are each independently hydrogen or (^ to c5 alkyl group). Copper foil can be honored by performing a copper clock on the material or substrate to be electroplated. In copper ore, an acid ore solution or a electroplating solution can be used. The acid plating solution may comprise a copper bell solution, a copper fluoroborate or a sulfamic acid copper electric clock solution, and the alkali plating solution may comprise copper cyanide (copper cyanide). Or a plating solution of copper prophosphate. The electroplating solution used in the preparation of the copper foil according to an embodiment of the present invention is not particularly limited, and any of the 13 201009119 〇 / dipux plating solutions used in the field to which the present invention pertains can 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, for example from 1.0 to 10 g/L. When an anti-recording 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: a zinc compound such as zinc acetate, zinc chloride, zinc cyanide, zinc nitrate or zinc sulfate; phosphorus compound For example, acid filling, polyphosphate pyrophosphate, phosphate or pyrophosphate; and organic compounds such as benzotriazole. The thickness of the rustproof layer may range from 〇.丨 to 1〇N. According to another embodiment of the present invention, the composition may comprise at least one compound selected from the group consisting of the fluorenyl compounds represented by Formulas 1 to 4, a hydrolyzate of the cyclamate compound, and a solvent. The amount of the calcined base compound may range from 〇〇 to 5% by weight of the composition. When the amount of the compound of the shixi compound is 5% by weight or less, the organic layer formed by the surface treatment agent may not be sufficient. Is applied to the copper foil, so the peel strength cannot be improved. When the amount of the fluorenyl compound is 5% by weight or more, the thickness of the organic layer formed by the treatment of the surface φ increases, and covers the bars on the copper foil, thus 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, 曱201009119^iy/ζριπ alcohol, ethanol, acetone, methyl ethyl ketone (111 her coffee%11 such as 〇116), methyl At least one of a group consisting of methylethylketone, ethylacetate, and benzene. According to another embodiment of the present invention, in the above method, before the formation of the rustproof layer, further A heat resistant layer is formed on the copper foil. The details of forming the heat resistant layer are the same as those described for the copper foil for the PCB, and thus will not be repeated. According to another embodiment of the present invention, in the above method, Before the formation of the barrier layer, a further formation can be formed on the copper foil. In the formation of the section, a small section is formed on the copper crucible by using a cupric oxide product, so that the copper foil and the additional coating layer The contact area between the two increases, thereby increasing the peel strength between the copper foil and the additional coating layer. According to another embodiment of the present invention, the flexible copper clad laminate may comprise 'a copper foil for PCB and formed on the copper foil The polyimide film on the surface treated film. The flexible copper clad laminate may have a two-layer structure (2_parameter layer) or a three-layer structure (3 layer) according to 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 a reaction product of at least one dianhydride monomer and at least one diamine monomer. At least one of the dianhydride monomers may be selected from the group consisting of pyromellitic dianhydride, 3,3,4,4,-benzophenone tetraphthalic acid dianhydride (3,3,4,4-benzophenone tetracarboxylic acid) Dianhydride), 3,3',4,4 -biphenyltetrahydropyrubic acid (3, 3,, 4, 4, _ 15 201009119 ^iy/zpui biphenyltetracarboxylic dianhydride) and 3,3',4,4'-oxybisphthalic anhydride (3,3 ',4,4,_oxydiphthalic anhydride' and the at least one diamine monomer may be selected from 4,4'-oxydianiline, para-phenylene diamine ), a group of siloxane diamine (SD), 3,4-oxydianiline, and meta-phenylenediamine. The oxane diamine (SD) may have the following structure. ·έ_ι In the structure of SD, η ranges from 2 to 12. After the monoanhydride monomer is reacted with the diamine monomer, the polyglycolic acid is a compound which is bonded to the bond. For example, the arginine obtained by the reaction of stupidinoic acid di-needle and gas-pure diphenyl ether has the following structure. 〇 0 HO-CT -II 0 Poly-proline δ Η η Imine when heat-treated poly-transacids can be called a brew with the following structure 201009119 The heat treatment of polylysine is about 6 Torr under a nitrogen atmosphere. The 〇 begins and ends at a high temperature of about 400 °C. In polyamic acid and polyamidiamine, the range of ^ is from 40 to 200. The varnish may be, for example, a pmda/〇dΑ 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 synthesized compound in the following examples was confirmed using Brucker DRX-3 〇〇MHz i-NMR and Jasco 610 FT-IR. (Synthesis of a mercaptoalkyl compound (1)) Example 1: Synthesis of Compound 1 The compound represented by Formula 1 was synthesized according to the following Reaction Mechanism 1 &lt; Reaction Mechanism 1&gt; 17 201009119 jiy//piiA N^\ CNs/ *N/NH2 + 3-glycidyl 6|氡propyltrimethoxy fever 1-(3-aminopropyl) oxazole Hd CH, 'N^N^, Si-«〇«a^3 API-decane ch3 162.68 g of tetrahydrofurane, 6 259 g (0.05 mol) of 3-glycidyloxypropyl 3-glycidoxypropyltrimethoxysilane and 11.87 g of H3-aminopropyl-imidazole are charged to the reactor. After reacting for 6 hours, the temperature of the reactor was maintained at 95 ° 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 to obtain 7 g (yield: 98%) of Compound 1 represented by Formula 1. H NMR (300 MHz, CD3OD): δ 0.62~0.68(m, 1Η) &gt; ❿ 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, SiOCH3), 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 (neat), Cm·1) : 3650 to 3200 (vOH) ' 3300 to 3200 (Vnh), 1120 to 1050 (v 矽 _ (alkoxy)) 18 201009119 Diy/jipin (Manufacture of surface treatment composition for copper foil) Example 2 A solvent mixture was mixed with the compound 1 prepared in Example 1 by mixing water and decyl alcohol in a volume ratio of k 9 to prepare a mixed solution having 1.0% by weight of Compound 1. (Manufacturing of two-layer FCCL) 10 Example 3 The mixed solution prepared in Example 2 was allowed to stand alone for 6 minutes for hydrolysis, and then sprayed on the small section, the heat-resistant layer, and the rust-proof layer sequentially formed thereon ( Rolled copper foil (IL-2, manufactured by Iljin). Next, a copper foil was coated with a smear (a. pp., CKAF1 〇〇 3) 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), zinc alloy and chromium. The coated copper was dried in a baking &amp; at 30 ° C for 30 minutes. The phase φ was sprayed with KRICT-PAA bright #, (BPDAzPMDAiPDAiODAi: 7:6:4) using a surface treated metal foil' and applied in a container with a doctor blade at 6 (TC for 30 minutes, 120 (; 3 minutes, 3 minutes in nitrogen line and 10 minutes in 400 ° C to harden the coated C acid to prepare a polyimide film, thus preparing copper coated with poly=branched amine The copper box prepared in Example 3 is hereinafter referred to as 3 film coating 19 201009119 ^iv/zpui Example 4 A copper foil coated with a polyimide film was prepared in the same manner as in Example 3 except The varnish (product name: JY-001) manufactured by J〇〇y〇ung Industries Co., Ltd. replaced the KRICT_PAA varnish. The copper foil prepared in Example 4 is hereinafter referred to as sample 2. Example 5 In the same manner as in Example 3. Preparation of a polyimide film coated with a polyimide film. Instead of using a roll made of NikkG material (four) (product τTM^Υ_22Β·Τ) instead of rolled copper iridium (IL_2 'made by Iljin), and by KRICT - The varnish of the UpUeX form made by PA^t replaced the vat paint. In Example 5, Lai fl was prepared. The procedure for preparing a surface coated with a polyimide film is described below in the manner of the sample comparative example j. The surface treatment composition was used to treat the copper foil sample 1. The copper prepared in Example 1 The foil is hereinafter referred to as Comparative Comparative Example 2 1. 丨JL. . . t_ The preparation of the surface coated with the poly-light amine film in the above manner. The surface treatment composition is used to treat the copper box at +(4) The copper prepared in Comparative Example 2 is hereinafter referred to as Comparative 20 201009119 Sex Sample 2. Comparative Example 3 The copper 4 was coated with the (IV) imine film on the side of the Example 5, except that the surface treatment agent was omitted. The composition was used to treat the copper surface. The sample prepared in Comparative Example 3 is hereinafter referred to as Comparative Sample 3. Reference Evaluation Example 1-1: Peel Strength Test Sample 1 was measured using the method specified in ASTM D-638. 3 and the peel strength of comparative samples 1 to 3. The cross-speed (cr0Ss-Head 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 measurement are shown in the following table. 1 is shown. &lt;Table 1&gt; Degree [kg/cm] Example 3 (Sample 1) 0.73 Comparative Example 1 (Comparative Sample 1) 0.32 Example 4 (Sample 2) 0.76 Comparative Example 2 (Comparative Sample 2) 0.38 Example 5 (Sample 3) 0.58 Comparison Sexual Example 3 (Comparative Sample 3) 0.28 As shown in Table 1, according to the examples of the present invention, comparative samples i to 3 prepared without using 21 201009119 J iy/ζριη table were used. The sample containing the composition of the composition of the composition of the composition of the composition of the composition of the composition of the composition of the composition of the composition of the composition of the composition of the composition of the composition of the composition of the composition of the composition of Evaluation Example 1-2: Moisture resistance test At 50 C, the degree of dependence (10)% was stored in the thermostat (thennG_hygr〇staf HIRAYANAPC-R7 for 7 days, sample i to The discoloration of 3 (d1SC0l0rati0n) is obvious. After 7 days, the colors of samples i to 3 did not change. (Synthesis of Dream Alkyl Compound (2)) Example 6A: Synthesis of Compound 2A Compound 2A represented by Formula 2 was synthesized according to the following Reaction Mechanism 2. &lt;Reaction mechanism 2&gt; 〇 Where R is methyl^ 125.712 grams of tetra-argonic ablation, 8.% 45 grams (〇〇5 moles) of 3-aminopropyltrimeth〇xysilane, and 5.035 grams (0.05 moles) of succinic acid The needle (succinic her coffee (10) was poured into the reactor and reacted for 6 hours. 'The temperature of the reverse yarn in the money environment was 5 ° C to 5 ° C ' and the mechanical scrambler was rotated at 3 rpm. 201009119 j 17 /ζ,μιιι, using a rotary evaporator for 2 hours to remove the solvent from the product. Then, the product was dried in a vacuum oven for 24 hours' to obtain 13.9 g (yield 99%) represented by Formula 2. Compound 2Α hNMR (300 ΜΗζ): δ 0.53~0.58 (m, 1Η), 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, SiOCH3), 8.00 (s, -NH-), 12.00 (s, -OH) IR (pure, cm 1): 3650~3200 (v〇h), 3300~3200 (Vnh), • 1650 (Vc〇nh), 1120 to 1050 (v $_(system)) Example 6B: Synthesis of Compound 2B The compound 2B represented by Formula 2 was synthesized according to the following Reaction Mechanism 2. Mechanism 2&gt; Wherein R is an ethyl group. 125.712 grams of tetrahydrofuran, 11.085 grams (0.05 moles) of 3-aminopropyl triethoxy saminopropyitriethoxysiiane and 5.035 grams (0.05 moles) of succinic anhydride were poured into the reactor and reacted for 6 hours. The reactor temperature was maintained at -5 Torr to 5 in 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 evaporation 23 201009119 ^ly/zpm for 2 hours. Then, the product was dried in a vacuum oven for 24 hours, thereby 16 g (yield 99%) of the compound 2B represented by the formula 2 is obtained. lK NMR (300 MHz): 60.58 to 0.60 (m, lH) '1.22 to 1.25 (m, Si-CH2), 1.60 to 1.63 (m, 2Η), 2·45~2.49(m, 4H), 2.51~2.54(m, 5H), 3.20~3.25(m, 3H), 3.83~3.87(m, Si-CH3) IR (pure, cm·1) : 3650 to 3200 (vOH), 3300 to 3200 (vNH), 1650 (Vc〇nh), 1120 to 1050 (v 矽 _ (alkoxy j Φ (manufacture of surface treatment composition for copper foil) Example 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, respectively. % by weight and 5% by weight of a mixed solution of Compound 2A. Q Examples 12 to 16 by mixing water and decyl alcohol in a volume ratio of 1:9 to obtain a solvent mixture 'In a case of Example 6B The prepared Compound 2B was mixed to prepare a mixed solution of Compound 2B each having 0.5% by weight, 1% by weight, 2% by weight, 3% by weight, and 5% by weight. (Manufacture of a two-layer FCCL) 24 e ❹ 201009119 Example 17 to 26 The mixed solutions prepared in Examples 7 to 16 t were separately hydrolyzed = after the WE coating by the Q coating, respectively, to obtain: Γ coating, followed by coating the rolled steel foil with an applicator And thus _ _. In the oven at 12 (r dry for 30 minutes, coated with bright light 2:7 (4) knife = copper box treated with surface treatment composition, and scraped under nitrogen at 6 Gt for 3G minutes, U = 1 row 3 ° minutes and wc for 10 minutes:: two-coated amino acid to prepare a polyimide film, so that the S film is separately applied to the upper layer. The sample copper foil is hereinafter referred to as sample 4 to 13 Comparative Example 4 prepared in the above: =:====, ί::Γ. The copper drop prepared in Comparative Example 4 is hereinafter referred to as Evaluation Example 2-1: Peel Strength Test ^ Using ASTM D- The method specified in 638 measures sample 4 and comparative sample 4 _ off-strength. The leak rate is 25 mm/min and the sample = 25 201009119 has a width of 5 mm. The measurement is performed using an Instron 8516. The results of the measurement are shown in Table 2 below. &lt;Table 2&gt; - Peel Strength [kg/cm] Example 17 (Sample 4) 0.78 Example 18 (Sample 5) 0.86 Example 19 (Sample 6) 0.93 Example 20 (Sample 7) 1.05 Example 21 (Sample 8) __ 0.92 Example 22 (Sample 9) L 0.82 Example 23 (Sample 1〇) 0.89 Example 24 (Sample 11) 1.02 Example 25 (Sample 12) 1.12 Example 2 6 (Sample 13) 0.94 Comparative Example 4 (Comparative Sample 4) 0.38 As shown in Table 2, according to the embodiment of the present invention, decane was used as compared with Comparative Sample 4 prepared without using the surface treating agent composition. Samples 4 to 13 prepared from the surface treatment composition of the base compound showed a greatly increased peel strength between the polyimide film and the copper drop. Evaluation Example 2-2: moisture resistance test at 50 ° C, relative humidity 80% Samples 4 to 13 were stored in a thermostat humidifier HIRAYANA 26 201009119 PC-R7 for 7 days, and the discoloration of samples 4 to 13 was remarkable. After 7 days, the color 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 Reaction Mechanism 3 below. &lt;Reaction mechanism 3&gt; PDCA-TMOS will have 125.712 grams of tetrahydrofuran, 8.9645 grams (0.05 moles) of 3-aminopropyltridecyldecane and 7.4550 grams (0.05 moles) of 2,3-acridine phthalic anhydride (2,3-pyridinedicarboxylic). The anhydride was poured into the reactor and reacted for 5 hours. The temperature of the reactor was maintained to 5 ° C under a nitrogen atmosphere, and the mechanical stirrer was rotated at 300 rpm. After the completion of the reaction, 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. bNMR (300 MHz): δ0·57~0.59(t,1H), 1.62~1.8〇(m, 27 201009119 2H), 3.62~3.67(m,Si-CH3), 3.85~3.87(t,3H), 7.93 ~7 95(t, 4H), 8.56(s, NH), δ·64~8.67(d,5H), 9.09~9.11(d,6H), 13.80(s, OH) IR (pure, cm-1) : 3650 to 3200 (vOH), 3300 to 3200 (vNH), 1650 (vCONH), 1120 to 1050 (v 矽 _ (decyloxy)) (manufacture of a surface treatment composition for copper foil) Example 28 to 29 A solvent mixture was obtained by mixing water and methanol in a volume ratio of 1:9 to prepare a solvent mixture and a compound 3 prepared in Example 27 to prepare a mixed solution of compound 3 having 0.5% by weight and 丨% by weight, respectively. . (Manufacturing of two-layer 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 separately on a Cr-coated rolled copper foil (IL_2, manufactured by Hjin). )on. Next, the copper drop was coated using an applicator to prepare a coated copper foil. The coated copper foil was dried in an oven at 12 ° C for 3 minutes.喷洒 A copper box 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. It was carried out at 6 ° C for 30 minutes and 120 in a nitrogen atmosphere. (: 30 minutes, 201009119 J 1.7 f ^, yiL t 10 minutes to harden the coated thus prepared 'prepared copper foil prepared in polyimine 30 to 31 2: c:: 3 〇 minutes and wc To prepare a polyimide film, 1. The copper foil coated on the knife. It is hereinafter referred to as Samples 14 to 15. Throughout Comparative Example 5, the polyimine was prepared in the same manner as in Example 3 G. Film coating © 】, 5 'Prepared the step of treating the copper ruthenium using the surface treatment composition. The copper pig prepared in Comparative Example 5 is hereinafter referred to as Comparative Evaluation Example 3-1: Peel Strength Test Using ASTM D· The method specified in 638 measures the sample and the comparative sample 5 off the drum. The paving speed is 25 mm/min and the width of the sample is 5 mm. The InStr (10) (4) is measured. The results of the measurement are shown in Table 3 below. Table 3 &gt; ~---Intensity [kgf/cm] Example 30 (Sample 14), 0 82 Example 31 (Sample 15) ~ 0.78 Comparative Example 5 (Comparative Sample 5) ~ 0.32 As shown in Table 3 according to the present invention Example, compared to no use of 29 201009119 surface treatment composition (4) Sample 5, Samples 14 to 15 prepared using the surface treatment composition containing the sulphur-based compound had a greatly increased peel strength between the polyimide film and the copper foil. Evaluation Example 3-2: moisture resistance test Samples 14 to 15 were stored in a thermostat humidifier HIRAYANA PC-R7 for 7 days at 5 ° C and a relative humidity of 80 %, and the discoloration of the samples 14 to 15 was remarkable. After 7 days, the colors of the samples 14 to 15 did not change. Synthesis of Compound Shi (4) Example 32A: Synthesis of Compound 4A Compound 4A represented by Formula 4 was synthesized according to the following Reaction Scheme 4. <Reaction Mechanism 4> Wherein R is a thiol group. 125.712 grams of tetrahydrofuran, 8.9645 grams (0.05 moles) of 3-aminopropyltrimethoxynonane and 9.6065 grams (0.05 moles) of Sf(1,2,4-benzenetricarboxylic anhydride) (2,3 The mixture 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. The product was dried in a vacuum oven for 48 hours after 201009119, whereby 18.5 g (yield 99%) of Compound 4A represented by Formula 4 was obtained. !H NMR (300 MHz): 50.62~0.65(t, 1H)' 1.71~1.76(m, 2H), 3.41~3.47(m,Si-CH3), 3.56~3.60(m,3H), 7.45(s, NH) IR (pure, cm·1): 3650~3200(vOH), 3300~3200(vNH), 1650(vCONH), 1120~1050(v dream-(hyun-based)) Example 32B: Compound 4B Synthesis Compound 4B represented by Formula 4 was synthesized according to the following reaction mechanism 4. &lt;Reaction mechanism 4&gt; 125.712 grams of tetrahydrofuran, 8.9645 grams of 3-aminopropyltriethoxydecane, and 9.6065 grams of trimellitic anhydride (1,2,4-benzenetricarboxylic anhydride) (2,3-pyridine dianhydride) was poured into the reactor and reacted for 6 hours, maintaining the reactor temperature at -5 ° C to 5 ° C in a nitrogen atmosphere and the mechanical stirrer was rotated at 250 rpm. &amp;Complete $ should be followed by using a rotary evaporator for 1 hour to remove solvent from the product. Then, the resultant was dried in a vacuum oven for 48 hours to obtain a compound of 4 in terms of 2 〇·6 g rate of 99%. 31 201009119 4 NMR (300 MHz, CD3OD) : δθ.71 ~0.73(t, 1H), 1.14~1.23(m,Si-CH3), 1.71~1.74(m,2H), 3.58~3.60(t, 3H) &gt; 3.79-3.86(m, Si-CH2) &gt; 8.55(s, NH) IR (pure, cm.1): 3650~3200(vOH), 3300~3200〇NH), 1650(vCONH), 1120~ 1050 (v decyloxy)) (manufacture of a surface treatment composition for copper foil) Examples 33 to 34 A solvent mixture was obtained by mixing water and methanol in a volume ratio of 1:9 with the solvent mixture in Example 32A. The prepared Compound 4A was mixed to prepare a weight of 〇·5, respectively. / Mixture of 1% by weight of Compound 4a. Examples 35 to 36 were mixed with water and decyl alcohol in a volume ratio of 1:9 to obtain a solvent mixture r, and the solvent mixture was mixed with the compound 43 prepared in Example 32B to have a weight of 5% by weight and a weight, respectively. Mixing of % of compound 4B (manufacture of two-layer FCCL) Examples 37 to 40 The mixed solutions prepared in/from the examples 33 to 36 were separately allowed to stand for 60 minutes to be hydrolyzed by the lyophilized m. (IL_2, ginseng 201009119 manufactured by Hjin) coated steel, coated with an applicator to prepare a foil. Dry in UNC for 30 minutes in UNC. Coated copper JY-0〇l^t knife coated 2耽^〇4 4 at 6〇t for 30 minutes' boots for 30 minutes, thin medium separately prepared for polymerization The brewed imine is hereinafter referred to as the addition of 7 to (4). Comparative Example 6 was prepared in the same manner as in μ a/S Example 37. The coated polyimide film was coated except that the surface treatment composition was omitted to treat the copper pig. Tit. The copper box prepared in Comparative Example 6 is hereinafter referred to as Comparative 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 roller 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 4 below. 33 201009119 <Table 4> Peel strength [kgf/cm] Π) Width Example 19) Specific rotation lj_X^ sample 6) 1.60 1.35 1.98 1.57 0.38 As shown in Table 4, according to the examples of the present invention, samples 16 to 19 of the surface treatment #1 composition (IV) containing a decyl compound were used in comparison to the comparative sample 6 which was not used for the surface treatment composition. There is a greatly increased peel strength between the quinone imine film and the copper enamel. Evaluation Example 4-2: Moisture Resistance Test Samples 16 to 19 were stored in a thermostatic humidifier HIRAYANA PC_R7 at 50 ° C and a relative humidity of 80% for 7 days, and the samples 16 to 19 were significantly changed. After 7 days, the colors of samples 16 to 19 did not change. (Comparison of peel strength according to the form of polyimine) (Production of 2-layer FCCL) Examples 41 to 44 Copper foil coated with a polyimide film was prepared in the same manner as in Example 37 except PMDA/ODA varnish, BTDA/PDA varnish, BTDA/PMDA/ODA/PDA varnish and 34 201009119 The varnish is replaced by Jooyoung Co., Ltd.::: lacquer (product name: JY Gu). Here, 5% by weight of Chemicals &amp; 4B is used as a surface treatment agent. Examples 41 to hereinafter are referred to as samples 2G to 23. The varnish described above is manufactured by the method described by Machi to produce PMDA/ODA varnish with 255.000 g of N,N-dimethylacetamide (DMAc; ❹N'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 for 24 hours, maintaining the reactor temperature at -5 ° C under nitrogen atmosphere. To 5. (:, and the mechanical stirrer is rotated at 350 rpm. Then, a varnish containing 15% by weight of polyglycolic acid is prepared. BTDA/PDA varnish will be 255.000 grams of DMAc (N,N-dimercaptoacetamide) ), 11.307 g (0.104561 mol) of m-phenylenediamine and 33.693 g (0.104561 mol) of 3,3f,4,4'-benzophenonetetracarboxylic acid diif (3,3',4,4'- The benzophenone tetracarboxylic dianhydride was poured into the reactor and reacted for 24 hours, the reactor temperature was maintained at -5 ° C to 5 ° C under nitrogen, and the mechanical stirrer was rotated at 350 rpm. Then, the preparation from rain contained 15 weights. 5% melamine varnish lacquer BTDA/PMDA/ODA/PDA varnish 35 201009119 255 g of DMAc, 6.334 g (0.031633 mol) of 4,4,_ diaminodiphenyl ether and 7.982 g (0.073811) The m-phenylenediamine was poured into the reactor and completely dissolved. Then '23.784 g (0.073811 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (3,3') , 4,4'-benzophenone tetracarboxylic dianhydride) and 6.900 g (0.031633 mol) of pyromellitic dianhydride were 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 polyglycolic acid was prepared. PMDA/ODA-SD The varnish pours 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 into the reactor and completely dissolves. 11.267 g (0.0.051653 mol) of pyromellitic dianhydride was poured into the reactor and reacted for 24 hours. The temperature of the reactor was maintained at -5 Torr to 5 ° C under a nitrogen atmosphere, and the mechanical stirrer was 350 rpm rotation. Then, a varnish containing 15% by weight of polyglycolic acid was prepared. Comparative Examples 7 to 10 Copper foil coated with a polyimide film was prepared in the same manner as in Examples 41 to 44. The step of treating the copper box surface was omitted except that 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 1 〇. Evaluation Example 5 - Peel Strength Test 36 201009119 The peel strengths of samples 20 to 23 and comparative samples of 7 to 1 Torr were measured using the method specified by ASTM D-638. The cross roller 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 5 below. &lt;Table 5&gt; Peel strength [kg/cm] _ Example 41 (Sample 20) 1.02 Example 42 (Post product 21) 0.93 _-Example 43 (Sample 22) 1.21 - Example 44 (Sample 23) 1.53 - Raw oysters Raw Example 7 (Comparative Sample 7) 0.52 _ (Comparative Sample 8) 0.39 - Comparative Example 9 (Comparative Sample % 0.61 - Example 10 (Comparative Sample 1 〇) 0.72 ❹ As shown in Table 5, according to the present invention In the embodiment, samples 20 to 23 prepared using a surface-treated contact comprising a ceramide compound were used between the polyimide film and the domain, compared to the comparative sample 7 to which no surface treatment composition was used. It has a large increase in the off-strength strength. As described above, the surface-treated film containing the above-mentioned Wei-based compound formed on the upper surface is formed by the Wei-based compound or the Wei-based compound according to the present invention. The PCB on which the surface treatment film is formed has an improved peeling strength of 37 201009119. Although the invention has been disclosed above by way of example, it is not intended to limit the invention, and any one of ordinary skill in the art does not The invention Within the scope of God and the scope, the scope of protection of the invention is subject to the definition of the scope of the patent application. [Simplified description of the diagram] None. [Description of main components] None. 10 38 201009119 For the Chinese manual No. 98124127, there is no slash correction. The patent specification for the invention is %. "2006.01. (The format and order of this manual should not be changed at any time. Please do not fill in the ※ part) ※Application number: ~7 ακ % ( 2〇〇6.〇1&gt; ※Application date: ※^(:Classification: C.^ % ^2006.01) % I. Invention name: (10)ο&οη w ^ ^ (2〇〇6.οι&gt; e for printed circuit boards Copper foil and preparation method thereof, and flexible copper clad laminate using polyacetic acid precursor and copper foil COPPER FOIL FOR PRINTED CIRCUIT BOARD, METHOD OF PREPARING THE SAME, AND FLEXIBLE COPPER CLAD LAMINATE USING POLYAMIC ACID PRECURSOR AND COPPER FOIL II. Abstract of Chinese invention: A surface-treated copper foil for a printed circuit board comprising a rust-preventing layer formed on a copper foil and a surface-treated film formed on the rust-preventing 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 sulfonyl compound _: &lt;Formula 1&gt; <式2> 201009119 31972ρίΠ &lt;Formula 3&gt; &lt;Formula 4&gt; Wherein R!, R2 and R3 are each independently an alkyl group of q to C3, and R4 and R5 are each independently hydrogen or (^ to (: 5 alkyl groups. s 201009119 31^72ρΐί1 III. English Abstract: Provided is a surface-treated copper foil for a printed circuit board (PCB), including an antirust layer formed on a copper foil and a surface treatment film formed on the antirust layer, the surface treatment film includes at least one compound selected from the Group consisting of silane-based compounds represented by Formulae 1 through 4, or hydrolysates of the silane-based compounds: <Formula 1&gt; <Formula 4> 201009119 31972piti R1? R2, and R3 are each independently a C1-C3 alkyl group and R4 and R5 are each independently hydrogen or a C1-C5 alkyl group. 201009119 VII. Patent application scope: 1. Surface treatment for printed circuit boards a copper foil 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 cerium alkyl compound selected from the group consisting of Formulas 1 to 4. At least one compound of the group, or a hydrolyzate of the decyl compound: &lt;Formula 1&gt; &lt;Formula 2&gt;&lt;Formula3&gt; &lt;Formula 4&gt; 39 201009119 «&gt;17/ ^.UXl A Wherein R!, R2 and r3 are each independently a C to C3 alkyl group, and R4 and Rs are each independently hydrogen or (^ to 〇5 alkyl group. 2. The printed circuit board of claim 1 The surface-treated steel foil, wherein Ri, R2, and R3 are each independently a methyl group or an ethyl group, and R4 and R5 are hydrogen. 3. The surface of the printed circuit board according to claim 1 of the patent application. The treated copper foil further comprises a heat-resistant layer interposed between the copper foil and the rust-proof layer. 4. The surface-treated copper foil for a printed circuit board according to claim 3, Further comprising a small layer layer interposed between the copper foil and the heat resistant layer. 5. A method for preparing a surface treated copper foil for a printed circuit board, comprising: forming a rustproof layer on the copper foil; And cleaning and drying the steel falling layer formed on the rustproof layer, and coating the composition on the rustproof layer, and drying the coated anti-correcting layer to prepare a surface treated film. The composition comprises at least one compound selected from the group consisting of fluorenyl compounds represented by formulas i to 4 Alkyl or a hydrolyzate of the silicon compound: 201009119 &lt; Formula ι &gt; &lt; Formula 2 &gt; &lt;Formula 3&gt;&lt;Formula4&gt; Wherein R 4 , R 2 and R 3 are each independently an alkyl group of (C to C 3 ), and R 4 and R 5 are each independently hydrogen or an alkyl group of (C to C 5 ). 6. For printed circuit boards according to claim 5 of claim 5 The method for producing a surface-treated copper foil, wherein the amount of the oxime alkyl compound ranges from 0.001 to 5% by weight based on the total amount of the composition. 41 201009119 〇 / ^pui 7. The invention relates to a method for preparing a surface-treated copper foil for a printed circuit board, wherein the composition comprises a component selected from the group consisting of water, methanol, ethanol, acetone, methyl ethyl ketone, ethyl acetate and benzene. At least one solvent of the group. The method for preparing a surface-treated copper foil for a printed circuit board according to claim 5, further comprising the copper box before forming the rustproof layer A heat resistant layer is formed on the upper surface. 9. The method of preparing a surface-treated copper foil for a printed circuit board according to the invention of claim 8, further comprising forming a measure 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 the surface treatment formed on the steel foil Polyimine film on the film. U. The flexible copper clad laminate of claim 1 , wherein the (iv) imine film comprises a hardening product of (iv) an amine acid, and the polystyrene comprises at least H monomer and at least one Diamine 2 calving, forming, wherein the at least one dianhydride is selected from the group consisting of benzene: acid two needles, 3,3,4,4, dibenzoic acid dianhydride, 3,3,,4,4, _ biphenyltetracarboxylic acid monoanhydride and 3,3',4,4,-oxydiphthalic acid liver composition of the family of at least one diamine monomer selected from 4,4,-diamino 2, jin : group of diamine, 3,4-diamino di-bung and stupid diamine 42 201009119 Fourth, the designated representative map: (a) the designated representative of the case: no. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 5