TWI328623B - - Google Patents

Description

[Technical Field] The present invention relates to an electrolytic copper foil of an electrolytic copper foil, which is used in the electrolytic copper foil or on the surface, in particular, a method for producing the deposition surface side. The manufacturing method, the surface-treated copper foil obtained by the foil produced by the method, and the copper-clad laminate obtained by the steel flute. Electrolytic steel box characterized by low profile [Prior Art] Electrolytic copper is widely used as a base material for printed wiring boards. (4) For the electronic machine writing machine that uses a printed wiring board, it is required to be lightweight, short, and so on. In the past, in order to realize the lightness and thinness of such electronic equipment and electrical equipment, the signal circuit of the printed wiring board to be used needs to be as fine as possible. Therefore, when manufacturing a printed wiring board, shortening the formation by the material (4) The set time of the remaining time is increased by the use of a thinner copper foil in order to improve the etching factor of the formed < ° I ~ wind. s Then, at the same time, for miniaturized 'lightweight electronic and electrical machines Therefore, it is required to be highly functional. Therefore, in the area of the limited printed wiring board, in order to ensure the mounting area of the part as much as possible, the etching parameters at the time of circuit formation are also good. Directly mounted on a π-belt automated bonding structure (ΤΑΒ) substrate or a w Λ f f-type 溥 film flip-chip (COF) substrate, in order to make the etch factor better, the ash is too low, and the printed wiring board is low. The outline of the electrolytic copper drop. Also, low to the virtual, #low profile is used to refer to the copper drop with 2213-8439-PF; Ahddub 5 1328623 substrate resin has a very low bump at the joint interface. In the patent document i (Japanese Patent Application Laid-Open No. 2004-3591-8), it is shown that in the method of manufacturing electrolytic copper by electrolysis of an acid copper plating solution, A method for producing an electrolytic copper box characterized by a sulfuric acid acidic copper plating solution of a copolymer of allyl dialkyl ammonium salt and sulfur dioxide. The sulfuric acid copper plating solution contains polyethylene glycol and gas and 3_锍Preferably, the surface roughness (precipitation surface roughness) of the bonding surface of the electrolytic copper foil obtained by the manufacturing method and the insulating substrate is small, and the thickness is 1 〇" In the case of the copper foil, it is a low profile (thickness) of the degree of Rz = 1.00 ± 0. 5# m. In the patent document 2 (Japanese Patent Application Laid-Open No. Hei 2 4-1 62144) In the method of manufacturing an electrolytic copper foil which is electrically decomposed by a sulfuric acid acidic copper plating solution, it is possible to produce an electrolytic copper foil having a small surface roughness and a high expansion ratio without using gelatin or glue. Characterized by the use of benzylidene alcohol and gas and 3-sulfenyl-1-supply acid Acidic acid copper electroplating liquid. Then, the surface roughness (precipitation surface roughness) of the bonding surface of the electrolytic copper foil obtained by the manufacturing method and the insulating substrate is small, and the electrolytic copper crucible is 1 μm thick. In the case of Rz = 1.5±5. 5/zm, the low profile (thickness). In the patent document 3 (Japanese Patent Application Laid-Open No. 2004-1 07786), the disclosure is made by making 1 A method in which an amine compound having a specific bone path and a copper electrolyte containing an organic sulfur compound as an additive obtained by additionally reacting a compound having one or more epoxy groups in a molecule with an amine compound is used for the production of an electrolytic copper foil. The electrolytic copper foil obtained by the manufacturing method has a surface roughness of from 0.90 to 1.20/ΖΠ1 of 2213-8439-PF and Ahddub 6 1328623 range of normal temperature expansion ratio of 6.62 to 8. 9 by the description of the embodiment. 〇%, normal temperature tensile resistance is 3〇·5~37.9kgf/mm2, high temperature expansion ratio is 12.b 18 2%, high temperature tensile resistance is 20·b 22. 3kgf/mm2.

In the patent document 4 (Japanese Laid-Open Patent Publication No. 2004437588), it is shown that by reacting a compound containing i or more epoxy groups in the i molecule with an amine compound, the nitrogen is 4-staged. A method of obtaining a copper-based electrolyte having a specific bone path and a copper electrolyte containing an organic sulfur compound as an additive for producing an electrolytic copper foil. Then, the electrolytic copper crucible obtained by the production method has a surface roughness of 0.94 to 1.23/zm in the range of 0.94 to 1.23/zm, a room temperature expansion ratio of 6 72 to 9 2 %, and a normal temperature tensile strength of 30.5. 37.21^Caf 2, the high temperature expansion ratio is 11.9~18.2%, and the high temperature tensile resistance is 199~23.41^[/1111112. On the other hand, in the patent document 5 (Japanese Laid-Open Patent Publication No. Hei 9-143785), the surface roughness Rz of the untreated electrolytic copper surface is revealed, and the gloss of the untreated electrolytic copper is smeared. The surface roughness Rz of the surface is the same, or a roughening treatment is applied to the deposition surface of the smaller foil to provide a surface-treated electrolytic copper foil characterized by a bonding surface. Then, the above-mentioned electrolytic copper box is manufactured by (4) a compound having a sulfhydryl group, 2 = a vaporized ion, a low molecular weight gel having a molecular weight of 1,000,000 or less, and an electrolyte of an ancient octahole. Specifically, the compound having a thiol group is a ketone group, and the molecular weight of the low molecular weight gum is 3 Å or less, and the polymer polysaccharide is hydroxyethyl cellulose. It is indeed inconspicuous. Then, using these manufacturing methods, an electrolytic steel foil is produced into an excellent low-profile precipitation surface as a low-profile electrolytic steel falling 7 2213-8439-PF; Ahddub 1328623 is an excellent property. However, the number of generation frequencies of electronic equipment or electrical equipment has also risen sharply, and the calculation speed has leaped. The clock of the personal computer has become faster and faster. Then, not only is the simple data of the original role in the computer, but the computer itself also has the same function as the AV machine. , j卩 In addition to the music player ... attached to the MD video player, n by the video recorder, TV phone functions and other functions.

Along with this, the screen of the personal computer is not a simple data screen, and it is required that the image of the movie can be tolerated for a long time. Moreover, it is required to supply such a quality screen at a low cost and in a large amount. Then, nowadays, the screen uses a liquid crystal screen. The driver of the liquid crystal panel generally uses the above-mentioned strip-shaped automatic bonding structure (10) substrate or a tape-type film flip-chip ((10)) substrate. Therefore, in order for the screen to correspond to a high-quality image, the aforementioned driver is also required to form a finer circuit. Further, the copper foil used as the current collector for a lithium ion battery is preferably smoothed with #surface. That is, when the active material is coated on the copper foil, it is advantageous to apply the suspension containing the active material to the copper foil with a uniform coating film thickness to use a copper foil having a smooth surface as a current collector. Then, since the negative electrode active material reversibly expands and contracts during charge and discharge, the dimensional variation of the copper foil which follows the expansion and contraction as the current collector is also large, and there is a phenomenon in which it is impossible to follow and break. Therefore, the mechanical properties of the copper foil of the current collector are required to have a good tensile strength and expansion ratio for the expansion and contraction behavior. Further, when a dielectric layer for a capacitor is formed by a sol-gel method on a copper foil, it is also advantageous to use a smooth copper foil. 2213-8439-PF; Ahddub is lower than the conventionally supplied 'low-profile with good mechanical strength. From the above, in the market, electrolytic steel, the ancient + β is in the lower profile of copper foil Claim. In order to solve the above problems, the present inventors have intensively studied to obtain an electrolytic copper foil by electrolysis using a sulfuric acid-based copper core obtained by adding a tetra-ammonium salt polymer having a cyclic structure. As a result, it is thought that the production of the low profile copper (4) which is superior to the conventional low profile copper (4) can be stably carried out by privately using the manufacturing conditions shown below, and the obtained profile quality of the electrolytic copper crucible is also small. . The present invention is as follows. Method for producing low-profile electrolytic copper drop: The method for producing electrolytic copper drop is to produce a method for producing an electrolytic copper collar by electrolyzing a copper sulfate electrolyte having a cyclic structure of a 4-stage ammonium salt polymer and gas. In the t 4 -type ammonium salt polymer contained in the sulfuric acid-based copper electrolytic solution, a method for producing an electrolytic copper foil of a dimer dimethyl dimethyl vaporized ammonium polymer having a volume of 2 or more is used. In the method for producing an electrolytic copper according to the present invention, the fourth-order ammonium salt polymer contained in the sulfuric acid-based copper electrolyte uses a number average molecular weight of 30 (M〇〇〇〇 of diallyldimethyl gas). In the method for producing an electrolytic copper foil according to the present invention, the acid-based copper electrolyte contains bis(3-sulfopropyl)disulfide or has a woven group. The compound 3-mercapto-propane sulfonic acid is selected from the above solution. The concentration thereof is preferably 0.5 ppm to 200 ppni. 2213-8439-PF; Ahddub 9 1328623 and 'Manufacture of electrolytic copper foil related to the present invention. In the method, the concentration of the 4-stage bond salt polymer in the melon & L-based copper electrolyte is preferably 1 ppm to 15 〇 ppm. Further, in the method for producing an electrolytic copper foil according to the present invention, the foregoing The gas concentration in the copper sulfate-based electrolyte is preferably 5 _. qing. Then, in the method for producing an electrolytic copper foil according to the present invention, the above-mentioned claw-stained steel electrolyte has a liquid temperature of 20 to 600 °. C, current density 15A/dm2~9GA/dra2 for electrolysis, for low profile electrolysis (4) = The electricity obtained by the method for producing an electrolytic copper foil according to the present invention is obtained by the method for producing an electrolytic steel foil according to the present invention: copper mooring, by electrolysis of the above-mentioned copper sulfate electrolyte The electrolytic copper obtained by the treatment is characterized in that the surface roughness (Rzjis) of the surface of the electrolysis_# copper V white is i.〇em below the low profile' and the gloss of the precipitation surface (Gs( 60)) is 4 〇〇 or more. The surface treatment of the present invention is related to the surface of the copper (2); since: the surface related to the present invention is roughened, prevented, and organically deposited on the surface of the electrolytic copper box. Any two or more types of the mixture treatment, and then the surface roughness (1?2^3) of the bonding surface of the insulating resin substrate with the above-mentioned person and the main treatment steel is 2 孖4 stations. The lower profile is characterized by a copper cladding layer a ^ 9 * _ .

> White or tantalum surface treated copper foil, and the J 夕 古 σ is particularly suitable for the quality of copper clad laminates for printed circuit board manufacturing.攸教故2213-8439-PF; Ahddub 10 1328623 [Effect of the Invention] According to the electrolytic copper box of the present invention, the low-profile electrolytic steel supplied to the market, β 从 from the mouth The composition of the electrolytic steel box related to the present invention is small and has a small difference in the production of a low profile and high-strength mechanical characteristics, and is different from the conventional low-profile electrolytic copper enamel. The manufactured product 'is excellent in solution stability' and can be safely used for long-term electrolysis, and it does not cause cost increase even if it is treated with waste liquid. Further, the low-profile electrolytic copper box obtained by the above-described production method is subjected to surface treatment on the deposition surface as a surface-treated copper foil, and also maintains low roundness and excellent mechanical properties. Therefore, the requirements for the low rim of (4) are strong, and it is suitable for the formation of a fine pitch circuit of a strip-shaped automated bonding (TAB) substrate or a tape-type film-coated (COF) substrate. Further, it is also suitable for use in the field of electric materials such as the anode of the ion secondary battery. [Embodiment] The manufacturing method of the electrolytic copper box according to the present invention: the method for manufacturing the low profile electrolytic copper box according to the present invention is to use a sulfuric acid based copper containing a 4-stage ammonium salt polymer and a gas having a ring structure. In the method for producing an electrolytic solution, a method of producing a dimer dimethyl dimethyl vaporized ammonium (hereinafter referred to as "DDAC") polymer having a volume of two or more is used in the above-described fourth-order ammonium salt polymer. That is, the above-described form is a concept in which a DDAC single body (monomer) is excluded, and a DDAC polymer of 2 or more bodies is selectively used. Further, as a 4th grade salt, it is composed of 2213-8439-PF; Ahddub 11 1328623, 2 = c, when it is a polymer structure, it has a ring structure, a ring structure 2; and a nitrogen atom of a wide-range salt. Then, the c-polymer is made up of a ring structure of 4 贞 ring ~7 ::: Therefore, the compound in this polymer is a 5-membered ring structure::::::: or less. This polymer is clearly expressed as a polymer structure of 2 or more linings. That is, ώ2 Λρ, Λ* * ^ 贱 贱, does not contribute to the low profile of the electrolytic copper " surface. (4) The main chain of this DDAC polymer is composed of only carbon and hydrogen.

Then, by using a sulfuric acid-based copper electrolytic solution containing the above-mentioned polymer of the above-mentioned two-component or more, it is possible to stably manufacture the electrolytic copper crucible having a lower profile electric low profile surface. Set low 丄 < (10) The team's permanent compound, if the right molecular weight is too large, the manufacturing of the low-profile electrolytic copper foil and the raw At ^ smelting are low. In many cases, it is a body of 2 to 150, a body of & U θ 偁k, and a body of 4 to 14 is preferred. In the case of a single case and in the case of more than 150 parts of the body, there is no contribution to the low-round templeization of the surface of the electrolytic copper box, and the contour of the rim is different. Then, if it is used in a more extensive range, then the county - J has the most determined and no difference to achieve the electrolysis 2213-8439-PF; the surface of the Ahddub steel foil is low profiled. Further, from the viewpoint of the number average molecular weight, it is preferable that the polymer suitable for the upper part is in the range of the above.眶 Rate: The number average molecular weight is 300 or less. The existence ratio of the single body is as shown in the comparative example described later, and the low profile is difficult to change. However, the low profile of the electrolysis (4) relating to the present invention is not intended to mean that the turret is good when measured by a stylus type roughness meter. Rather, the gloss of the precipitated surface is significantly different compared to the low profile copper foil obtained by the electrolytic method of bismuth, and the flatness of the flat surface is also greatly improved:: after 'if _c polymer If the number average molecular weight exceeds, even if the concentration of other additives coexisting is adjusted, it cannot contribute to the formation of the temple, and the wheel 2 of the deposition surface of the obtained electrolysis (4) becomes large. In addition, even if the number average molecular weight is 1,000,000 or more, if it exceeds 7 "〇〇〇, for example, the concentration of the coexisting double (3_propyl) disulfide (hereinafter referred to as "sps") is not 100 ppm or more. Then, the difference in the profile of the deposited surface of the obtained electrolytic copper junction is remarkably large. Therefore, if the difference in conditions such as the liquid temperature and concentration during the electrolysis operation in the general management degree is considered, the number average molecular weight is 3 〇〇, and the polymer of the 〇〇 is better, and the average molecular weight is 600 to 2500. The DDAC polymer is better. However, even if a DDAC polymer is to be produced, there is an unavoidable residual amount of a single body. In this case, since the residual single-body DMC is a trace amount, it is not necessary to explicitly exclude it here. Further, the above number average molecular weight is determined by the following measurement method. Namely, the sample was dissolved in a solvent and measured by a colloidal color layer analyzer (GPC) under the conditions of 2213-8439-PF and Ahddub 13 1328623 shown below. The detector uses a multi-angle laser light scattered luminometer (MALS). Further, the value of "the second dimensional coefficient X concentration" is assumed to be Omol/g, and for the standard sample for calculating the inflection rate concentration change (dn/dc), polyethylene oxide (SRM1924); NIST is used. [GPC measurement conditions] Column: TKKgel α -4000 ' a -2500 ( 0 7. 8mm x 30cm); manufactured by Tosoh Co., Ltd. Solvent: water system: methanol = 50: 50 (volume ratio)

Flow rate: 0. 504mL/min Temperature: 23°C ±2°C

Detector: MALS (DAWN-EOS type); Wyatt Technology Wavelength: 690 nm Temperature: 23 ° C ± 2 ° C Further, as a sulfuric acid-based copper electrolyte used in the method for producing an electrolytic copper foil according to the present invention The concentration of the DDAC polymer of the fourth-order ammonium salt polymer is determined in consideration of the relationship between the concentration of SPS or 3-sulfo-1-propionic acid (hereinafter referred to as "MPS"). The concentration of the DDAC polymer is preferably from 1 ppm to 150 ppm, more preferably from 2 ppm to 100 ppm, more preferably from 3 ppm to 80 ppm. Here, in the case where the concentration of the DDAC polymer in the sulfuric acid-based copper electrolytic solution is less than 1 ppm, even if the concentration of SPS or MPS is increased anyway, the precipitation surface of the electrolytic copper crucible becomes thick, and it becomes difficult to obtain low profile. Electrolytic copper foil. When the concentration of the DDAC polymer in the sulfuric acid-based copper electrolytic solution exceeds 15 〇ρριη, the steel precipitation state is also unstable, and it is difficult to obtain a low-profile electrolytic copper foil. Then, the sulfur copper 2213-8439-PF used in the manufacturing method of the electrolytic copper flute relating to the present invention; the Ahddub 14 1328623 acid copper electrolytic solution, the miscellaneous-missing MPS containing the compound selected from SPS or having a mercapto group Choose at least! More than one type of cat and cockroach, and a low profile electrolytic copper drop can be obtained with higher precision, and the slabs w Λ , ^ υ · 5 ppm 〜 2 〇〇 ppm are preferable, and 4 ppm 〜 150 ρρπι is preferable, and 4 pPm 〜 50 ppm is preferable. . If the concentration of sps or mps is less than 0.5 ppm, the precipitation surface of the electrolytic copper foil becomes thick, and it becomes difficult to obtain a low rim electrolytic copper foil. On the other hand, ο ^ ’ right SPS or MPS concentration exceeds 200ppm, and the obtained electrolytic copper knot #山I L > I can not improve the smoothing effect, but the electrolysis state is not stable. In addition, in the present invention, SPS or MPS means that the salt is also contained in the meaning of the salt. The concentration is described as the sodium 3-mercapto-1-propanesulfonate (hereinafter referred to as "Mps_Na") as the steel salt. Conversion value. Then, the MPS is formed into an sm structure by being subjected to two-dimensionalization in a sulfuric acid-based copper electrolytic solution. Therefore, the concentration of 'SPS or MPS' is included as a substance added by sps and as an MPS monomer of other MPS or MPS-Natang_.., the wind-seeking type is added to the electrolyte and then mass-produced into SPS. Transgender private | &

The concentration of the corrugated material ^ The structural formula of the MPS is shown in the following 2, and the structural formula of the SPS is shown in γ '3. From the comparison of these structural formulas, it is known that the SPS structure is the 9 θ of the MPS 2. The Xia body.

2213-8439-PF; Ahddub 15 1328623 3.

Further, the umbrella of the above-mentioned sulfuric acid-based copper electrolyte is increased, and the agricultural degree is 5 ppm to 120, and more preferably 10 ppm to 50 ppm. This chlorine thick sound ~ and the right is less than 5ppm. The precipitation surface of the electrolytic copper foil becomes thicker and cannot be maintained below the gallery.

On the other hand, if the chlorine concentration exceeds 12 Oppm, the precipitation surface of the electrolytic steel crucible is coarse and the electrolysis state cannot be stabilized, and the low-profile deposition surface cannot be formed. As described above, in the above-mentioned sulfuric acid-based copper electrolytic solution, the balance of sps or scent 5 and ddac polymer and gas is the most important. If the balance of these amounts exceeds the above range, the precipitation surface of the electrolytic copper foil becomes thick. It is impossible to maintain a low rim. Further, in the sulfuric acid-based copper electrolytic solution of the present invention, a solution having a copper concentration of 5 〇g/l to 120 g/l and a free sulfuric acid concentration of 6 〇g/b 25 〇g/1 is considered. Then, when using the above-mentioned sulfuric acid-based copper electrolyte to produce an electrolytic copper box, it is preferable to use a liquid temperature of 2 〇 ° C to 6 (TC, current density of 15 A/dm 2 to 90 A/dm 2 for electrolysis. The liquid temperature is less than 2 ( In the case of TC, the precipitation speed is low, and the difference in mechanical properties such as the expansion ratio and the tensile strength becomes large. On the other hand, if the liquid temperature exceeds 6 〇C, the amount of evaporated water increases, and the fluctuation of the liquid concentration becomes fast, and the obtained electrolytic copper is obtained. The precipitation surface of 4 cannot maintain good smoothness. Then, the liquid temperature is better in the range of 40. (: ~55T:. Moreover, if the current density is less than 15 A/dm2, the precipitation rate of copper is small. On the other hand, if the current density is 2213-8439-PF and the Ahddub 16 1328623 exceeds 90 A/dm2, the surface roughness of the obtained electrolytic copper treatment surface becomes large, and the low corridor cannot be maintained. More preferably, the current density is in the range of 40 A/dm to 70 A/dm 2 . <Electrolysis steel column obtained by the manufacturing method according to the present invention, the electrolytic copper crucible obtained by the manufacturing method according to the present invention, characterized The surface roughness of the deposition surface side, wjis) is as follows : contour, and the glossiness (Gs (6 〇.)) of the precipitation surface is 4 〇〇 or more. In a strict sense, the surface roughness of the cup of the electrolytic copper foil _ + white is as follows The concept of the thickness of the electrolytic copper crucible varies. However, according to the manufacturing method of the electrolytic copper crucible according to the present invention, the surface roughness and gloss of the obtained electrolytic copper drop are 45 可 which can be produced as an electrolytic copper box. "The thickness of the entire thickness of the electrolytic copper below the thickness 羯' The surface roughness (Rzjis) on the side of the precipitated surface is a low profile of 1. 0 β m or less, and the gloss of the precipitated surface (Gs (6〇) .)) In order to satisfy the conditions of 400 or more, the "electrolytic copper box" referred to in the present invention is sometimes referred to as "untreated copper foil" and "dissociated" because it does not have any surface treatment.羯", etc. In this specification, it is simply referred to as "electrolytic copper drop." In the manufacture of the electrolytic steel foil, a continuous production method, a rotary cathode in the shape of a roller, and a shape along the rotary cathode are generally used. Oppositely configured tantalum anode or dimensionally stable anode (DSA) Between the two, the copper sulfate-based solution was used to precipitate copper on the surface of the roller of the rotary cathode by electrolytic reaction. The precipitated steel was in the form of a foil, and the electrolytic copper foil was produced by continuous stripping from the rotary cathode. In the stage, there is no surface treatment such as rust-preventing treatment. The state of copper after activation is electrolyzed, and it is in a state of being easily oxidized by oxygen in the air of 2213^8439-PF; Ahddub 17 1328623. The surface shape of the contact side of the electrolytic copper crucible with the rotary cathode has the shape of the shape of the surface of the rotary cathode which is subjected to the mirror processing, and since it is a smooth surface having a gloss, this surface is referred to as a glossy surface. On the other hand, the surface shape of the precipitation side is generally different because the crystal growth rate of the precipitated copper differs depending on the crystal surface, and as a result, the surface of the mountain shape is displayed as a rough surface or It is the precipitation surface. Usually, the deposition surface is a laminate surface of the insulating layer when the copper frost screen is used. However, the smaller the surface roughness of this precipitation surface, the better the low-voltage temple electrolysis copper and mooring. Furthermore, in the electrolytic copper crucible according to the present invention, the surface roughness of the precipitation surface is smoother than that of the copper crucible which is generally produced by using an electrolytic roller, so that the use of the rough surface is not used. It is the "precipitation surface". Then, in the electrolysis (4), in the surface treatment process, the precipitation surface is usually subjected to roughening treatment and rust prevention treatment. The roughening treatment of the precipitation surface is performed by electrolyzing a copper sulfate solution in a so-called pyroelectric condition, depositing fine copper particles on the deposition surface, and immediately applying electrolysis by smoothing electricity. The electric clock is covered to prevent the disposal of fine steel particles from falling off and the like. Therefore, the deposition surface on which the fine copper particles are deposited and adhered is referred to as a "roughening surface". Then, in the surface treatment process, 'in the surface of the electrolytic copper falling surface: in the surface, the 'iron-proofing, alloying, electric clock, etc.' is used for the anti-iron treatment: the operation of ordering the winding, etc. The electrolytic copper falls. The product so paid for. Generally referred to as "surface treatment foil." Electrolysis (4) related to this issue/(4) has 2213-84 39-PF whose surface roughness ((1)) is not full and gloss [Gs(60.)] is 4〇〇 or more; Ahddub 18 1328623

characteristic. Then 'better' is the surface roughness ((5)(4) not (five) 〇m, and the gloss [Gs(6G.)] is above 6Q〇. First, the gloss is explained. Here the gloss of '[Gs(10).)] The measurement light is irradiated on the surface of the electrolysis (4) at an incident angle of 6 (Γ, at a reflection angle of 6 〇. The intensity of the rebound light is measured. The incident angle here is a direction perpendicular to the illumination surface of the light 〇 β. Then, according to JIS 874 8741-1 997, the five specular gloss measurement methods describing the difference in incident angles should be selected according to the gloss of the test, and the angle of incidence should be selected. The angle of 6 〇 β is a wide range of samples which can be measured from a low gloss sample to a high gloss. Therefore, the glossiness of an electrolytic copper foil or the like according to the present invention is mainly measured by 6 Å. In general, for electrolysis The smoothness of the precipitation surface of the matte is evaluated by using the surface roughness Rzjis as a parameter. However, only Rzjis can obtain the information of the height direction and the information of the unevenness or the vortex. The degree reflects the parameters of the two Therefore, by using Rzjis in combination, it is possible to judge various parameters such as the surface roughness cycle, the fullness, and the uniformity in their faces. In the case of the electrolytic copper flute relating to the present invention, the surface roughness of the precipitated surface side. (Rzjis) satisfies less than 1.0", and the gloss of the precipitate (Gs(6().)) is 400 or more. That is, in this range, the quality can be supplied to the market.纟 纟 纟 纟 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后 然后The electrolytic copper of the deposition surface of 7 〇〇 or more is not limited here, but it is judged from experience that [Gs(60.)] is about 8 为 as the upper limit.本发2213-8439-PF;Ahddub 19 16

The glossiness in the Ming Dynasty is estimated to be g φ A. The type 'measured according to the JISZ 8741_ = method for measuring the glossiness. Then, regarding the electrolytic steel falling here, the thickness is not limited. This is because, as the thickness is thicker, the smaller the thickness of the precipitated surface, the better the glossiness is also increased. If it is hard to set the upper limit, the industrial electrolytic copper fl will not be the extent of the copper foil of the thickness t 45 () "m". Further, the surface roughness of the precipitation side is not set here. The lower limit of (Rzjis). Although it varies according to the sensitivity of the measuring device, empirically, the lower limit of the surface roughness is about 4. However, in the actual measurement, the difference is seen, so it is guaranteed The lower limit of the measured value is 〇2ym. On such a smooth deposition surface, even if it is subjected to roughening treatment or anti-mine treatment, it is of course possible to obtain a lower rim surface treatment than before. The copper box is also treated with a copper surface on the surface of the roughened surface of the low profile. Then, if the surface treated copper pig is attached to the insulating resin substrate, a moderate physical fixing effect can be obtained, and the unevenness of the interface is also changed. When the chemical solution such as the etching solution on the interface is small, the chemical penetration of the chemical liquid is small, and the mechanical properties of the electrolytic copper foil according to the present invention are 33 kgf/mm 2 or more in the normal state. The rate is 5% or more. After heating (18 (TC x 60 minutes, atmospheric atmosphere) tensile strength is above 3〇kgf/mm2, and the expansion ratio is preferably 8% or more. 20 2213*8439-PF; Ahddub then 'in the present invention, by The production conditions are optimized so that the normal tensile strength is 38 kgf/mm 2 or more, and after heating (18 (rC x 6 ,, atmospheric atmosphere) tensile strength is 33 kgf/mm 2 or more, a more excellent mechanical characteristic can be obtained. This good mechanical property can not only fully withstand the bending of the flexible circuit board, but also is suitable for the use of the current collector of the negative electrode of a lithium-human battery or the like which is subjected to expansion and contraction behavior. </, the surface treatment of the present invention Copper box〉

The surface-treated copper foil according to the present invention is one or more selected from the group consisting of a roughening treatment, a rust-preventing treatment, and a decane coupling agent treatment on the deposition surface of the electrolytic copper foil. That is, the electrolytic copper foil used herein has a low profile of a surface roughness (referred to as 18) of 1 〇"m or less, and a glossiness (Gs(10).) of the deposition surface is _ The above-mentioned "electrolytic copper box obtained by using a sulfuric acid-based copper electrolytic solution obtained by adding a 4-stage ammonium salt polymer having a cyclic structure". Di && treatment system makes the attachment of fine metal/particles to electrolytic copper

And a method of forming a roughened surface by a shoe engraving method, and forming a fine metal particle to be adhered thereto, and exemplifying the adhesion of copper fine particles in the form of φ & The method of doing things in the face of precipitation. This roughening process is based on the electrolysis of copper, the batch of sputum, and the smashing of the copper slag (the precipitation of the copper fine particles deposited on the precipitation surface, and to prevent this micro+:, Luo's broken electric ore process is to make the deposition of fine copper particles by the electrolysis method on the precipitation surface of the electrolytic steel, and (4) the conditions of the electroplating are used as the electrolysis conditions. Therefore, in general, the fine copper is made. The solution group 21 2213-8439-PF used in the process of particle precipitation and attachment; Ahddub is set to be a setting for low concentration of copper ions in order to make it easy to make a burning condition. The condition for burning electricity is not particularly limited. Instead, consider the characteristics of the production line -3'. If you use copper sulphate, you can concentrate copper 5 20g / l, sulfuric acid 5 〇 2 〇〇 g / i, other additives according to the necessary α _ naphthylquinone dextrin, win, sulfur gland, etc.), liquid temperature b~4 (TC, current density 10~50A/dm2 conditions. Then, Ά. Horse prevents the peeling of fine copper particles from the plating process, In order to prevent the precipitation of the adhered fine copper particles, the coating is smoothed to make the coating The method of making a copper-to-precipitation as a fine steel grain. Therefore, the same solution used in the process of forming a groove of the bulk copper described above is used as a supply source of copper ions. There is no: the appointment, but the characteristics of the production line are set. For example, if the sulfur = system solution is used, the concentration can be copper 5Q~8()g/b sulfuric acid.bo, liquid temperature 4〇~5 〇t: The condition of the current density of 〇~50A/dm2. Next, the method of forming the rust-preventing layer will be described. In the manufacturing process of the steel-clad laminate and the manufacturing of the printed wiring board, the use of the printed wiring board is not hindered. ...to prevent the oxidation of the surface of the electrolytic copper box layer or the method used for the treatment of the rot (4), (4) use the clumsy oik 〇4t ^ . r 7T - rust, machine rust, or use zinc, chrome, alloy, etc. | - Do not ask for the purpose of electrolysis (4);:: = agent, spray coating, electric button method, etc. -: Yi can apply the method of electrolysis to prevent the anti-clock element from falling out of the electrolytic copper layer. Or use other so-called displacement precipitation methods, etc. For example, at 22l3-8439-PF; Ahddub 22 ~ Xin In the case of treatment, a zinc pyrophosphate plating bath, a cyanide octane plating/combination, a zinc sulfate plating bath, etc. may be used. For example, if the zinc pyrophosphate is combined, the zinc concentration may be 5 to 30 g/l 'focal The concentration of potassium phosphate is 5〇〇g/bu liquid temperature 20~50°C, pH 9~12, current density 〇. 3~l〇A/dm2. After j decane coupling agent treatment, it is roughened and treated. The rust treatment is used to improve the chemical adhesion between the yoke and the insulating layer. The decane coupling agent used for the treatment of the decane coupling agent is not particularly limited. It can be selected from the epoxy-based cyclane coupling agent, the 16-based decane coupling agent, the fluorene-based decane coupling agent, etc., in consideration of the properties of the m-edge layer constituent material or the printed wiring board used in the manufacture of the printed wiring board. More specifically, it is preferably selected from the same coupler as the glass fiber woven fabric for prepreg used for the printed wiring board, and for example, diethylenetrimethoxymethane or divinylphenyltrimethoxy can be used. Base money, r-mercaptopropyl propyl propyl trimethoxy money, plant glycidoxypropyl trioxane基石夕烧, 4-3⁄4 oxypropylbutyl dimethyl sulphate 丞 虱 虱 虱 矽 、 、 r r r r 、 、 、 、 、 r r r r 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺(4-luamine propoxy)butoxy)propyl_3_aminopropyltrimethylhydrazine, imidazolium, diazinoxane, 7*-mercaptopropyltrimethoxydecane, and the like. Then, using the electrolytic copper drop according to the present invention, the surface treatment steel having the desired surface treatment described above is applied to the surface, and the surface roughness (Rzjis) of the insulating layer constituent material and the bonding surface is less than or equal to 4 The characteristics of the low wheel gallery. When the roughened surface having such a low rim is attached to the 23 2213-8439-PF; Ahddub 1328623 insulating layer constituting material, it is possible to ensure the practically unobstructed adhesion. • After the second, it is possible to obtain a heat-resistant property that is not impeded as a substrate, and it is resistant to chemicals and peeling strength. In the form of a copper-clad laminate according to the present invention, the electrolytic steel foil is not subjected to roughening treatment or rust-preventing treatment, and the electrolytic steel foil and the glass-epoxy base material and the glass-poly are laminated. A material for forming an insulating layer of a soft base material such as a film of a phenol-based phenol resin-based prepreg or a polyimide film such as an imino substrate, which can be bonded by hot pressing or the like by a predetermined method. A copper clad laminate was obtained. Further, in the case of producing a soft copper clad laminate, a polyurethane resin base material layer may be formed by a casting method. However, in order to ensure the adhesion between the electrodeposited copper foil and the insulating layer constituting material, a roughening treatment, a rustproofing treatment, and a shovel smear can be appropriately applied to the contiguous surface of the electrolytic copper foil. The mixture treatment or the like is used to bond the surface to the insulating layer constituent material. In the case of the selection of the low profile follower at this time, in the case of the electrolytic copper ruthenium according to the present invention, since the deposition surface is more glossy than the glossy surface, any one of the faces can be selected as the bonding surface. Then, the copper clad laminate as used herein includes a so-called rigid copper clad laminate, a soft copper clad laminate such as a COF tape, and the like. Then, as for the manufacturing method thereof, it is expressly possible to use any of the known methods. The following is a description of embodiments of the invention. [Examples] Production of Electrolytic Copper Complex: In this example, a sulfuric acid-based copper electrolytic solution was prepared by preparing a copper concentration of 80 g/l, a free sulfuric acid concentration of i4〇g/1, and an SPS or MPS described in Table i. A solution of DDAC polymer concentration and gas concentration at a concentration, a predetermined number average molecular weight (3〇9, 2213-8439-PF; Ahddub 24 1328623 1120, 2170, 7250). Further, the DDAC polymer having a number average molecular weight of 309 is described as a quantity of DDAC. Further, SPS and MPS are added as a sodium salt. Table 1 SPS or MPS concentration (ppm) Grade 4 ammonium salt polymer (DDAC polymer) Gas concentration (I) pn 〇 MPS SPS concentration (ppm) Number average molecular weight Example 1, 2 7 . — 5 309 (2 amount 10) Example 3, 4 1220 Example 5, 6 2170 Example 7 - 120· 7250 Example 8 - 200 71 40 Comparative Example 1 7 · 150 SPS or MPS 1 degree: 3-Weiyl-1- - Sodium citrate sodium salt conversion value DMC polymer: diallyl dimethyl ammonium chloride polymer _ Then, for the use of the cathode surface with #2000 of abrasive paper for the grinding surface roughness Ra is adjusted to 0. 2 ym of titanium plate electrode, anode using DSA, liquid temperature of 50 ° C, in the example of Example 6 at a current density of 60 A / dm 2 , in Example 7 and Example 8 at a current density of 52 A / dm2 . Thus, five kinds of electrolytic copper foils having a thickness of 12/m thick in Examples 1, 3, 5, 7, and 8 were produced, and then, 210 " m thick electrolytic copper foils of Examples 2, 4, and 6 were produced. 3 types. A total of 8 kinds of electrolytic copper foils were obtained. Further, the crystal structure of these electrolytic copper foils is substantially randomly aligned in the entire thickness direction. The measurement of the surface roughness and gloss of the electrodeposited copper foil was carried out as follows. The evaluation results of the precipitation surface are shown in Table 2. Further, the surface of the titanium plate and the surface roughness (Ra of 0.20 // m) were evaluated by evaluating the shiny side of the obtained electrolytic copper foil. · Surface roughness: Surface roughness meter 25 2213-8439-PF, Ahddub 1328623 SE-3500, manufactured by Otaru Research Institute Co., Ltd., measured according to jiS b 〇6 (Π-1 994, the obtained Rz is taken as The value of Rz jis. Gloss: It is measured by JIS ζ 8741-1 997, which is based on the method for measuring glossiness, using the gloss meter VG-2Ο00 type manufactured by 电本电色工业股份有限公司. Table 2 Thickness of the surface of the electrolytic copper foil ( Um) Gloss Tensile Strength Scaling Surface Treatment Thickness of Copper Sample Rzjis Ra Gs (60°) (kgf/mrn2) (%) Foil Surface Thickness (jt/ra) Ave. S, D. Ave. SD Ave. Rzjis (/im) after normal heating of SD after normal heating Example 1 12 0.41 0.02 0.09 0.01 721 7.1 38.5 35.6 7.8 11.1 幺2 Example 2 210 0.48 0.03 0.11 0.01 715 7.2 I—幺2 霣Example 3 12 ϋ. 53 0.01 0.15 0.01 710 7.5 37. 7| 33. 2 7.0| 9.5 < 2 Example 4 210 0.68 0.03 0.17 0.02 677 6.3 . < 2 Example 5 12 0.49 0.02 0.11 0.01 689 7.0 40.0 36.0 8.2 12.5 < 2 Poor Example 6 210 U.61 0.04 0.16 0. 02 680 7.2 I - <2 Example 7 12 ϋ. 54 0.03 0.17 0.04 683 8. 1 34.9 31.1 5.5 8.8 <2 Summer Her Case 8 12 ϋ. 50 0.04 0.19 0.05 686 12.5 34.3 30.6 R.2 8.2 <9 Comparative Example 1 12 1.01 0.05 0.24 0. 02 293 7.8 37.2 35.5 5.3 6.8 3 Z1U -- - 1. Ιϋ Μ7 0.31 0. 03 233 8. 1 3 Comparative Example 2 12 ΟΙ η 0.85 0.16 0.18 F〇3 ~283 TT 36^ 32.4 To] 5.6 ώΐϋ U. Ιΰ 0. 11 0.14 0. 04 221 2.8 3 Compare Example 3 12 0.83 0.12 "〇. 17 0.04 丽Τβ" 3ΐΤ4ί 26.8 3.5l 5.8 210 1. 22 0.38 0.31 0.05 386 3.1 ...- 3 Table 2 The average value and standard of the surface roughness of the deposited surface Poor, the measured value of the 30 points is only 1 θ @, 佐 α α 十 mean and private standard deviation. Then, the gloss and the average value and standard deviation of the measured values of 30 points are also shown. j, the surface roughness of the surface-treated copper matte' indicates the average value of the measured values of 30 points on the surface after the roughening treatment. Production of surface-treated copper foil: surface treatment of the subsequent treatment of the fine copper particles, and rust-preventing treatment. The surface of the electrodeposited copper foil is pickled, and then cleaned before the formation of the roughened surface as the above-mentioned various kinds of electrolytic copper adhered to the deposition surface. This pickling strip 26 2213-8439-PF; Ahddub

For the L piece, the concentration is 100g/bu liquid temperature 3 (diluted sulfuric acid solution of rc, the dipping time is 30 seconds. After the pickling process is finished, 'as a fine standing on the deposition surface of the electrolytic copper foil, ^ she thinks that The coating process for depositing fine copper particles on the deposition surface and the coating plating process for preventing the fine copper particles from falling off. In the case of the electroplating process in which fine copper particles are deposited and adhered, the use of copper farmers is 15/ g. A copper sulfate-based solution having a free sulfuric acid concentration of 14 〇g/i, using electrolytic copper 4 as a cathode, and an anode using DsA, and electrolyzing for 5 seconds under the conditions of a liquid temperature of 25 and a current exceeding degree of 25 A/dm 2 . After the fine copper particles are deposited on the deposition surface, the fine copper particles are detached from the coated electric ore, and the copper is uniformly precipitated by coating the micro and copper particles I under a smooth electric clock condition. For the smoothing of the key conditions, a copper sulfate solution having a copper concentration of 70 g/1 and a free sulfuric acid concentration is used, and the electrolytic copper is used as a cathode, and the anode is used as a liquid, and the liquid temperature is 45. The conditions of the liquid temperature are 45. 〇, electric sensation, degree 25A/dm2, electrolysis 1 〇 second. • After the end of the roughening process, An anti-rust treatment is applied to both sides of the copper drop, and an inorganic anti-clock is used here. The sulfuric acid has a sulfuric acid concentration of 7〇g/b zinc concentration of 2〇g/1 to electrolyze the copper crucible. A zinc plate was used for the cathode 'anode, and electrolysis was performed at a liquid temperature of 4 (TC, current density of 15 A/dm 2 ' for 5 seconds, and zinc rust treatment was applied. Further, in the case of the present embodiment, on the aforementioned iron layer The electrolysis is used to form the bell layer. The electrolysis conditions at this time are: using a cold solution of 5 〇g/i of complex acid and pH 1-5, using the electrolytic copper foil as the cathode, and using the anode for another $, at a liquid temperature of 35 C. Current density 8A/dm2, electrolysis for 5 seconds. 2213-8439-PF; Ahddub 27 1328623 After the above rust-preventing treatment is completed, it is washed with water and immediately in the decane coupling agent treatment tank 'on the rust-preventing treatment layer of the roughened surface The decane coupling agent is sorbed. The composition of the solution used at this time is added by using ion-exchanged water as a solvent, and γ-glycidoxypropyltrimethoxy decane is added at a concentration of 5 g/1. The solution is sorbed by blowing it in a spray bath. After the treatment of the decane coupling agent, it is made by an electric heater. The foil temperature is 14 〇. (:, in 4 seconds, the furnace is heated to adjust the temperature of the atmosphere to vaporize the water to promote the condensation reaction of the decane coupling agent, and finally obtain a thickness of 丨2 in m of 5 and a thickness of There are three kinds of surface-treated copper foils of 21〇#m. The surface roughness of the roughened surface after this surface treatment is divided into 12ym thick foil and 21〇μm foil and is shown in Table 2. [Comparative Example 1] In this comparative example, an electrolytic copper foil was obtained using the same conditions as in Examples 1 to 6 except that a single-draw DDAC was used instead of the DDAC polymer in the copper electrolytic solution used in the examples. The measurement results of the surface roughness and gloss of the φ precipitation surface of the electrolytic copper foil are shown in Table 2 together with the examples. Thereafter, a surface-treated copper foil was obtained in the same manner as in the example, and the surface roughness of the roughened surface was shown in Table 2 together with the examples. [Comparative Example 2] This comparative example is a tracking experiment of Example 1 shown in Patent Document 1. Copper sulfate (test drug) and sulfuric acid (test drug) were dissolved in pure water to prepare an aqueous solution of copper sulfate (5 hydrate conversion) of 280 g/l and free sulfuric acid concentration of 9 〇g/1. Here, 'addition of a copolymer of diallyl dialkyl sulphate and sulphur dioxide (manufactured by Mindong Textile Co., Ltd.) under the trade name PAS-A-5, weight average molecular weight 4 〇〇〇: 28 2213-8439-PF; Ahddub 1328623 4ppm) and polyethylene glycol (average molecular weight 1〇〇〇: ι〇卯心, with MPS (lppm), use gasification sodium to adjust the gas concentration to 2〇ppm, prepare sulfuric acid acid copper plating solution. Then 'The surface roughness Ra of the surface of the cathode using the #2000 abrasive paper is adjusted to 〇. 2〇&quot; m of the titanium plate electrode, the anode uses the lead plate 'the above electrolyte is the liquid temperature 4 〇〇 c The current density is 5 〇A/dm2 for electrolysis, and an electrolytic copper foil having a thickness of 12 #m and a thickness of 210 ym is obtained. The measurement results of the surface roughness and gloss of the precipitation surface of the electrolytic copper box are together with the example The results are shown in Table 2. Thereafter, the electrolytic copper foil was treated in the same manner as in Example 1 to obtain a surface-treated copper pig. The surface roughness of the roughened surface was shown in Table 2 with the example [Comparative Example 3] Copper concentration 90g / l 'free sulfuric acid concentration ii 〇 g / i of sulfuric acid copper electrolyte, through activated carbon The filter was cleaned, and then, in the electrolytic φ liquid, the gas concentration was 30 ppm, and MPS-Na (1 ppm), ethyl cellulose (5 ppm) as a ruthenium molecular polysaccharide, and low molecular weight were added. Glue (quantitative average molecular weight: 1560: 4 ppm) to prepare an electrolyte. This electrolyte was used. For the cathode, the surface roughness Ra of the surface was polished with #2000 of abrasive paper to 〇. 2 m of titanium plate electrode, anode Electrolysis was carried out using a DSA at a liquid temperature of 58 ° C and a current density of 50 A/dm 2 to obtain an electrolytic copper foil having a thickness of 12/ζηι and a thickness of 210 °m. The surface roughness and gloss of the precipitated surface of the electrolytic copper foil were The measurement results are shown in Table 2 together with the examples. Then, this electrolytic copper foil was treated in the same manner as in Example 1 to obtain a surface 2213-8439-PF; Ahddub 29 1328623 treated copper foil. The roughened surface was rough. The degree is shown in Table 1 together with the examples. <Examples 1, 3, 5 and Examples 7 and 8. Comparison> Here, the case of using MPS having a mercapto compound and the case of using SPS are compared. 2 It can be clearly seen that the surface roughness of the deposited surface of the obtained electrolytic copper foil After the normal state of gloss, tensile strength, and heating, the normal state of the expansion ratio and the surface roughness of the surface-treated copper foil are almost the same. Therefore, the sps or Mps used for preparing the copper electrolyte is added even if MPS is added. It is also confirmed that other SPSs such as a monomer or an MPS-Na salt can obtain the same effect. <Comparison of Examples and Comparative Examples> Surface roughness of the precipitation surface: In the case of comparing the surface roughness with Ra, EXAMPLES The difference between the precipitation surface of the electrolytic copper drop obtained in Example 8 and the deposition surface of the electrolytic copper foil obtained in Comparative Example 1 to Comparative Example 3 was small, and the average value and standard deviation were not large. . However, if Rzjis is used to compare the surface roughness, the electrolytic copper flute obtained in the electrolytic copper box example obtained in the comparative example has a lower profile of the two sides as compared with the average value. However, after the 'from the comparative example! Compared with the examples, the single-phase II, right-hand side of the DDAC polymer, the obvious smoothing effect is poor, and the comparison from the standard deviation (and (four) coefficient), the electrolysis obtained in the example The copper fl is "expressed, and it shows that the difference is small and the stability is excellent. Then, this is the same as the thickness of the falling layer: the same direction: the table", that is, the precipitation surface measured only by the stylus type roughness meter The wheel corridor (RZjiS) to judge 'the comparative example of the electrolytic method 2213-8439-PF obtained in Comparative Example 3; Ahddub 30 1328623 copper enamel is also in the range of the low-profile electrolytic copper foil of the electrolytic copper box, but with the implementation The electrolytic copper foils of Examples 1 to 8 achieved a uniform and excellent 2 profile. Further, from the comparison of W 2 and the examples, even if the polymer is a salt, the main chain is a DDAC polymer composed only of carbon and hydrogen, and a uniform and excellent low profile can be obtained.

Then, even if compared with a surface treated copper box, the same result can be obtained by comparing the surface roughness (Rzjis) of the electrolytic copper pavilion. That is, the electrolytic copper obtained in Example 8 was used with respect to the surface roughness (Rzjis) of the surface of the electrolytically roughened copper surface obtained by the comparative example. The surface of the crucible is treated with a roughened surface of the crucible, and the surface roughness (Rzjis) is 2" or less, and a more excellent low-rotation material can be obtained. Gloss: Each of the electrolytic copper foils obtained in comparison with the comparative examples The average glossiness, the gloss of the electrolytic copper flute obtained in Examples 1 to 8 was a relatively high value, showing a completely different range. From this point of view, compared with Comparative Example 3 Each of the electrolytic copper crucibles obtained in Example 8 is closer to a flat mirror surface, and can be said to have a uniform deposition surface. Tensile strength and expansion ratio: obtained by using preferred manufacturing conditions In each of the electrolytic copper foils of the examples, the tensile strength was almost the same as that of the electrolytic copper cases obtained in Comparative Example and Comparative Example 2, compared with the electrolytic copper foil obtained in the comparative example, and compared with W 3 The electrolysis obtained (IV), regarding the tensile strength The difference is that it has a characteristic that the tensile strength in the normal state is small and is lowered due to heating. Then, regarding the tensile strength, it has excellent characteristics in comparison with each of Comparative Examples 2231-84 39-PF; Ahddub 31 1328623. Turtle base with special difference _ by contrast heating, it is used. Therefore, it is suitable for the use of the invention in the form of a pile into a plate and an electrolytic copper foil, which can be suitably used for the purpose of the heat history. Industrial Applicability] The use of the electro-electrolysis (4) related to the present invention can be efficiently supplied to the second: = manufacturing 蚣廒 姑 姑 妒 妒 、 、 、 、 、 、 、 、 、 给 给 给 给 给 给 给The low rim is electrolyzed by copper, and the electrolysis (4) of (4) has a surface that is farther than the previous supply of low profile electrolysis (4). The reason is that the surface is treated on the precipitation surface, even if roughening is applied. The case of processing i± W ^ -tr J makes it easy to pay for the low-profile surface treatment copper box that has never been graded. Because of t, *人^^ ϋ,. ώ ., Α Therefore 'suitable as a belt Automated Adhesive (TAB) substrate or 揲 | The film-coated (COF) earth plate is specially formed for the fine pitch circuit. Further, the tantalum-electrolytic steel foil has a surface roughness of the surface of the precipitate, and both surfaces are glossy smooth surfaces. It is also suitable for use as a negative electrode of a lithium secondary battery because it has excellent tensile strength _, *human AU Α and z, and the evaluation rate is the same as the conventional low-profile electrolytic steel crucible. , why use t. [Simple description of the diagram] No 0 [Description of main components] Description 0 2213-8439-PF; Ahddub 32

Claims (1)

i;52^b25 &quot; No. 9514〇188 Application for revision of patent scope. X. Patent application scope: Revision date: 99.5.4 Lions &lt;Monthly amendments 1. A method for manufacturing electrolytic copper foil, electrolysis Contains a ring makeup! The 4th grade ammonium salt polymer 盥 之 傅 Fu Fu ^ 咏 之 糸 糸 糸 糸 得到 得到 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' Ammonium phosphate polymer In the above-described sulfuric acid-based copper electrolytic solution, a method for producing a two-electrolytic copper foil having a volume of two or more is used, wherein the concentration of the fourth-order salt-salt polymer in the sulfuric acid-based copper electrolytic solution is from 1 to 15. The gas concentration in the copper sulfate-based electrolyte is 5 ppm to 120 Å, and the sulfuric acid-based copper electrolyte contains a compound selected from the group consisting of bis(3-sulfopropyl)disulfide and the compound having (4) One or more types of acid are burned, and the concentration thereof is from 0.5 ppm to 200 ppm. 2. The method for producing an electrolytic copper foil according to the scope of the patent application, wherein the fourth-order ammonium salt polymer contained in the sulfuric acid-based copper electrolyte is recited 3: a method for producing an electrolytic copper foil having an average molecular weight of 30 (M 〇〇〇 0). 3. The method for producing an electrolytic copper foil according to the above application, wherein 'the sulfuric acid copper will be described The electrolyte is obtained at a liquid temperature of 2 〇 〇 〇 〇 〇 〇 电流 电流 电流 电流 电流 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. 4. The surface roughness (Rz jis) of the deposition surface side is 1. 低// m lower wheel 33 2213-8439-PF; Ahddub profile, and the precipitation and the date of the correction of the precipitation surface (Gs(10).)) is positive for 4^_ steel coating, which is characterized by • • • • • • • • • • . Month Patent No. 4 6. Surface-treated copper foil, Item 4 of the right-hand side is characterized by · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · One or two or more types of processing. .... For surface treated steel according to item 6 of the patent application [(1), the surface roughness of the surface of the surface treated copper octabase substrate (RzJis) is a low profile of 2#m or less. The copper clad laminate ' is characterized by the use of the surface treated copper foil of the scope of claim b. 2213-84 39-pp;Ahciciub 34