TWI376174B - - Google Patents

Description

丄: WOi /4 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a surface-treated copper foil, and more particularly to a substrate which can be used as a laminated circuit substrate with a polyimine. A surface-treated copper foil forming a correct circuit, a surface treatment method thereof, and a laminated circuit substrate using the copper drop. [Prior Art] 3 The copper box for the T-brush circuit board is to bond the copper drop to the resin substrate, but it must increase the strength of the squeezing and meet the electrical characteristics required for the printed circuit board. • Qianfu 11, heat resistance, and drug resistance Sex. Therefore, the joint surface of the copper ruthenium (hereinafter sometimes referred to as untreated (four)) and the resin substrate is mixed, and the surface of the roughened surface is further subjected to soldering (10). And the like, and the chromic acid is applied to the surface on which the Zn or wrought iron has been applied, and the like, and various treatment methods are performed. φ In recent years, the density of IC package substrates used to drive liquid crystal displays, which are display units for personal computers, mobile phones, or pdas, has been required to be processed at a temperature to form a correct circuit. In the laminated circuit board manufactured by the printed circuit board, the requirements for constructing the circuit for the correct processing at a high temperature 'the electrolytic copper forming the conductive copper drop and the polyimine which is the resin substrate which can be used at a high temperature are both Then, _ hundreds of degrees of foxes go hot. For example, as shown in the specific example of Fig. 2, heat treatment is carried out at 33 (TC, 12 MP. The φ of the two temperatures is followed by φ; column 曰 慝 慝 梃幵 诒 诒 诒 诒 诒 诒 诒 诒 诒 诒 诒 诒

The bonding strength of 2197-9984-PF 5 1376174 is the technique disclosed in Patent Document 1, and is a means for solving the problem, for example, a technique of roughening a copper foil surface with a Zn-containing alloy and 'as a steel drop and The laminated circuit substrate used by the squash, the surface of the slab, and the surface of the untreated copper box, which contains the key, the iron, Drilling, recording, and crane; at least one type of electrolyte is subjected to surface treatment, and a layer of Μn or a layer of N1 or a layer of Zn or ruthenium is provided on the layer (refer to Patent Document 2). [Patent Document 1] Japanese Laid-Open Patent Publication No. H-256389 (Patent Document 2) [Problems to be Solved by the Invention] The Zn-containing layer-containing raw sugar described in the patent document The treatment layer has an effect of improving the adhesion strength between the copper foil and the resin substrate at a high temperature. However, after the copper foil and the resin substrate are followed by etching treatment with an acid solution to form a circuit, at this time, since the acid is easily dissolved in the acid, the Zn layer which is next between the copper foil and the resin substrate is eluted, so that the copper after the circuit formation is formed. The extreme decrease in the bonding strength between the foil and the resin substrate has a fear that the copper foil is peeled off from the resin substrate during use of the circuit board. In order to prevent this accident, it is necessary to shorten the time required to minimize the dissolution and discharge of the Zn layer, which makes the etching process require a high degree of technology and management system, thereby reducing the productivity of the laminated circuit substrate and increasing the cost. There is no benefit caused. According to the above-mentioned patent document, the crude saccharification treatment, like the above-mentioned 2197-9984-PF 6 1376174, cannot fully satisfy the adhesion strength, acid resistance, and surname of the styrene, and cannot provide a surface satisfying such characteristics. Handle copper foil. The purpose of this month is to provide a surface treatment steel which can satisfy all of the adhesive strength and acid resistance of the brewed imine, a treatment method for the surface treatment of copper falling, and a steel lamination circuit using the surface treatment. board. [Means for Solving the Problem] The surface treatment of the invention is performed by applying a surface treatment layer composed of a Ni_p_Zn alloy on at least one side of the untreated steel. In the surface treatment method of copper 0 of the present invention, at least the side surface of the S untreated copper foil contains Ni:g/L, p: 〇 〇i~5〇 g/L,

Zn: 0.01 to 1. An electrolytic bath of 〇 g/L forms a surface treatment layer composed of a Ni_p_zn alloy. The laminated circuit board of the present invention is formed by laminating a surface of the f layer on the surface of the surface-treated copper crucible with a resin substrate, wherein the surface treatment copper is provided on at least one side of the untreated copper foil. It is composed of a surface treatment layer composed of Alloy I. According to the present invention, it is possible to provide a surface-treated copper foil which satisfies the adhesion strength, acid resistance and etching property with polyimine. Further, the surface treatment method of the copper foil according to the present invention provides a surface treatment method which satisfies the copper drop of the adhesion strength, acid resistance and etching property of the polyimide. Further, according to the laminated circuit board of the present invention, it is possible to provide a laminated circuit board in which the resin substrate, particularly the polyimide and the copper foil, has high adhesion strength, has acid resistance when forming a circuit, and satisfies etching properties. 2197-9984-PF 7 1376174 [Embodiment] The surface-treated copper foil (untreated copper foil) of the present invention may be one of an electrolytic copper flute or a rolled copper box... and, without special distinction, there is It is also simply expressed as copper matte or untreated (four). The thickness of the untreated copper is preferably 5 // π ϋ ”. If the thickness of the copper foil is thinner than 5 (four), for example, an enemy fold is generated at the time of manufacture, and the cost of the thin copper box does not exist in reality. When the foil thickness of the copper foil is thicker than 12 "m, it is thinner and smaller than the K: package substrate for driving the display unit of a personal computer, a mobile phone, or m. Poor,: 厚 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有 具有) - Surface treatment of bis (Zn) binary alloy layer. As a surface treatment layer placed on the surface of copper foil, it is enough to prevent copper from falling from copper to surface treatment layer, 3 1 energy 9 .... 75·content;; is / "t% ~ acidity is poor, ... is (4) poor. In the case of 5 〇 (4) or less, it is resistant to the surface treatment layer provided on the surface of the copper box, and since it contains the effect of homogenizing the Ni-Zii alloy layer and suppressing (4) or less, the effect of adding p is not included, and the content of 5% by weight is 〇· ! The surface treatment layer set on the steel surface has a reduced strength. Improve the adhesion of the resin substrate (especially the poly-imine) to Zn, capable of / π bond strength, and prevent the connection

2197-9984-PF 8 1376174 The strength of the bond is deteriorated by heat, and the content thereof is from 5 wt% to 60 wt%, preferably from 10 wt% to 35 wt%. When the content is 5 wt% or less, there is no effect of adding Zn. When the content is 60 wt% or more, the acid resistance is poor. Fig. 2 is a graph showing the relationship between the Zn content and the peel strength (kN/m) in the Ni-P-Zn alloy layer, and Fig. 2 (1) is not the initial stage after the surface treatment of the copper foil with the polyimide. The measurement result of the relationship between the peeling strength and the Zn content, FIG. 2 (丨丨) shows the measurement result of the relationship between the peel strength and the Zn content after heat treatment after the polyimide-attached surface-treated copper foil. 2 ( Π I ) shows the measurement result of the relationship between the peeling strength and the Zn content after the copper foil was applied to the surface of the polyimide. The initial peel strength of the laminated plate of the copper foil and the polyimide and the peeling strength after the acid treatment is 〇 6 kN/m or more, and it is industrially practical, and the peeling strength after the heat treatment is before the heat treatment (initial When the peeling strength is 80% or more and the minimum is 〇5 kN/m or more, it can be put into practical use in the industry. Therefore, if the criterion is 0. 6 kN/m or more, or 8〇% or more of the initial peel strength, The initial peel strength is not affected by the peeling strength as shown in Fig. 2 (work) φ. If the peel strength after heat treatment is reduced as shown in the figure, the peel strength is lowered. However, if the content is 50/〇 or more, the peel strength is not affected. Practicality, the peeling strength after the acid treatment is as shown in Fig. 2 (ΠΙ). When the content exceeds 6% by weight, the peel strength is extremely lowered, and the Ζη content is preferably 5 wt% to 60 wt. %. In the present invention, the surface roughness of the surface-treated copper foil is preferably 依.2(4)~U n . The formation of the Nl_b Zn alloy layer from the surface of the sub-steel V is by electrolytic treatment.

2197-9984-pF 9 1376174 The composition of Ni, p, and Zn in the electrolytic treatment bath is as follows.

Ni composition. As the Ni metal, 〇i g/L 〜 200 g/L is contained, preferably 25 g/L to 55 g/L. P component. As P metal, it contains 001 g/L~5〇 g/L, preferably contains 〇. 2 g/L~1. 〇 g/L.

Zn component: as Zn metal containing 〇 g 1 g / L ~ 1 〇〇 g / L, preferably containing 0. 5 g / L ~ 1. 〇 g / L.

The temperature of the electrolytic bath is 3 (TC~7 (rc, preferably 4 〇&lt;t~6〇. It is still after the formation of the Ni-p-Zn alloy layer on the surface of the copper foil, preferably in the alloy layer The surface is provided with a chromic acid treatment layer and a coupling treatment layer. The present invention will be more specifically described by way of examples. <Examples 1 and 2> Copper poise (untreated steel foil): Furukawa foil of Furukawa Circuit F〇u (stock) Rz: 1_ 〇 is added as a Νι metal component to 4 〇g/L. 6H2 添加 is added as a P metal component to be NaH (4) of 〇6 g/L. "As a Zn metal component, zns(1) is added as 〇5 § Add H 〇g/L to other ingredients as H3B〇3 45〇C 3. 5 0.5 A/dm2 10 second bath temperature

pH current density treatment time Z-long surface treatment was carried out on the above-mentioned untreated copper helium Π μ, +., W ▲ electrolytic bath and conditions. Start with the first rabbit sound, human beings. Example 1, second time is Example 2, right

2197-9984-PF 10 r4 The surface-treated copper foil was subjected to the following measurement, and the measurement results are shown in Table 1 as Examples 2 and 2. (1) Alloy composition of the surface treated layer deposited on the surface of the copper foil: analysis by fluorescent X-ray. (2) Initial peel strength: The surface-treated copper foils of Examples 1 and 2 were then laminated with polyimine (25 VT manufactured by Ube). Then the condition is as shown in Figure ι. The peel strength after the measurement was measured. Since the initial peel strength is required to be 〇 6 or more, 0.6 kN/m or more is acceptable, and the judgment criteria are as shown in Table i. (3) Peel strength after heat treatment: After the polyimine, the peel strength after heat treatment at 168 hours was measured. The criterion for determining the peel strength after the heat treatment was 8 % or more of the initial peel strength. Moreover, the criterion (calculation method) is shown in Table 1. (4) Peel strength after acid treatment: Surface-treated copper foil and polyimide were then immersed in a dilute hydrochloric acid solution for 1 hour in a ffr-shirt, and then the peel strength was measured. (5) Etchability: After the surface-treated copper foil and the polyimide were bonded, the circuit of the width i was cut with vaporized copper/liquid to measure the bottom width and the top width by SEM, and the difference was obtained. The judgment criteria are shown in Table i. <Examples 3 and 4> WZ copper foil and Rz: 1·0, which are added as N1 metal components, and added as 40 mass/L of NiS〇4·H2〇 as P metal component 〇·6 g/L (4) 孤·6H2〇 is added as Zn component 1. 〇g/L ZnSCh. 7H2 〇 is added as 1.0 g/L for other components.

: 45»C 2197-9984-pp PH : 3.5 Current density: (K 5 A/dm2 treatment time: 15 seconds in the above untreated copper box with the above-mentioned electrolytic bath and conditions for 2 person surface treatment. The treated copper foil was the same as that of Example 疋, and the first time was Example 3 and the second time was Example 4, and the results are shown in Table 1 as Examples 3 and 4.

<Examples 5 and 6> Copper foil: wz copper foil of Furukawa Circuit Foil (R): Rz: 1〇 NiSi〇4 which is added as a Ni metal component to be 4〇g/L. 6Ih〇 is added as a p metal component. 6 g/L of NaH2p〇2. h2〇 is added as a Zn metal component to become 〇.丨g/L of ZnS〇4. 7H2〇 is added as other ingredients 1. 〇g/L of h3B〇3 bath temperature

pH

45 It 3. 5 0.5 A/dm2 ά *1' Interval Current-tight treatment The surface treatment was carried out twice with the untreated copper 4 and the above-mentioned electrolytic bath and conditions. The surface-treated copper foil was subjected to the same measurement as in Example ,, and the first time was Example 5 and the second time was Example 6, and the results are shown in Table 1 as Examples 5 and 6. <Examples 7, 8>

Copper foil: wz copper foil of Rukoi Circuit Foil (R): Rz: L 〇 is added as Ni metal component to make Ni〇4. 4H2O 2197-9984-PF 12 g/L of NaH2P〇2 H2〇7H2〇 is added as a P metal component so that it is added as a Ζπ metal component to lose 9 η τ

The ruler becomes 2.0 g/L of ZnSO as the other component to add 1.0 g/L of H3B〇3 bath temperature pH current density processing time: 45 〇C: 3. 5:0. 5 A/dffi2: 20 seconds ^ The above untreated copper crucible was subjected to a two-person surface treatment under the above-described electrolytic bath and conditions. The surface-treated copper foil was subjected to the same measurement as in the case of the first embodiment, and the first time was the seventh embodiment and the second time was the eighth embodiment. The results are shown in Table 1 as Examples 7 and 8. <Comparative Example 1, 2 &gt; Copper foil: Furukawa Circuit Foil (copper) copper foil, Εζ: ι 〇 is added as Ni metal component to be 4 〇g / L of Nis 〇 4 . 6H2 〇 is added as a P metal component 6 g/L of NaH2p〇2 · h2〇 is added as a Zn metal component to become 5 g/L of zns〇4 · 7 Hz 〇 as other components, adding 1 〇g/L of h3B 〇 3 bath temperature pH current Density treatment time 45 〇 C 3. 5 0.5 A/dm 2 16 seconds The surface treatment was carried out twice on the above untreated copper foil in an electrolytic bath having the above composition and conditions. The surface-treated copper foil was subjected to the same measurement as in Example 1 with the first comparative example and the second comparative example 2'. The result was 2197-9984-PF 13 weight 174 was Comparative Example 1. 2, together with the table lc <Comparative Example 3, 4> 45〇C 3. 5

Copper 'metallurgy: WZ copper foil of Fukui Foil (share), Rz: 1. 0 NiSi〇4 which is added as a Ni metal component to be 4〇g/L. 6H2〇 is added as a p metal component to become 〇. 6 g /L of NaH2P〇2 . HzO is added as a Zn metal component to make i〇g/L zns〇4 · 7H2〇 as other components to add 1.0 g/L of H3B〇3 bath temperature

pH 0. 5 A/dm2 15 sec. Current density Treatment time The surface treatment was carried out twice in the above-mentioned untreated steel foil under the above-described electrolytic bath and conditions. The surface-treated copper foil was subjected to the same measurement as in Example 1 in the first comparative example 3 and the second time in the comparative example 4. The results are shown in Table 1 as Comparative Examples 3 and 4. <Comparative Examples 5 and 6> Copper foil: WZ copper foil of Furukawa Circuit Foil (R): Rz: 1. Ni was added as Ni metal component to be 4 〇g/L of NiSCh. 6H2 〇 was added as a P metal component. g. 6 g / L of NaH2P 〇 2 . HzO as other components added 1 · 〇g / L HsBCh bath temperature pH current density processing time 45 〇 C 3. 5 0.5 A / dm 3. · 5 seconds 14

2197-9984-PF 1376174 Two surface treatments were carried out on the above untreated copper foil in the same manner as in the electrolytic bath of the above composition. The surface-treated copper foil was subjected to the same measurement as in Example 2, with the first comparative example 5 and the second comparative example 6, and the results are shown in Table i as Comparative Examples 5 and 6. <Comparative Example 7, 8 &gt; 45 C 3. 5 1.0 A/dm2 1 G Winter I·, Copper Foil: WZ Copper Foil of Ryogo Circuit Foil (R): RZ: 1. 〇 is added as a Zn metal component to become 1 . 5 g/L of ZnSCh · 7H2〇 is added as other ingredients! · 〇 g / L HAL bath temperature

pH Current Density Treatment time The surface treatment was carried out twice in the above-mentioned untreated steel flute with the above-described electrolytic bath and conditions. The first time was Comparative Example 7, and the second time was Comparative Example 8, and the surface treated (4) was subjected to the same enthalpy as in Example i, and the results were shown in Tables as Comparative Examples 7 and 8. 2197-9984-PF 15 1376174 Table 1

The alloy composition of the surface of the Zn amount of copper foil in the No_ electrolytic bath is determined by the upper part of the peel strength (mg/dm2) (g/L). The lower part (wt?〇 after the initial heat treatment after the acid treatment, the shoe-etched Ni P Zn Example 1 0.5 0.35 0.03 0.11 ◎ ◎ ◎ ◎ ◎ 71.7 6.6 21.8 Example 2 0.5 0. 35 0.03 0.10 ◎ ◎ ◎ ◎ ◎ 72.6 6.6 20.7 Example 3 1 0.36 0.03 0.19 ◎ ◎ ◎ ◎ ◎ 61.9 5.5 32.6 Example 4 1 0.35 0.03 0,19 ◎ ◎ ◎ ◎ ◎ 61.1 5.2 33.7 Example 5 0.1 0. 34 0.03 0. 03 〇〇〇〇〇 84.0 7.9 8.1 Example 6 0.1 0.33 0.03 0.03 〇〇〇〇〇 84.2 8.2 7.7 Example 7 2 0 38 0.03 0.30 ◎ ◎ 〇〇〇 53.8 4.2 42.0 Example 8 2 0. 35 0. 03 0.29 ◎ ◎ 〇〇〇 52.0 4.4 43.6 Comparative Example 1 5 0.35 0.01 0. 95 ◎ ◎ XXX 26.6 0.5 73.0 Comparative Example 2 5 0.33 0.01 0.90 ◎ ◎ XXX 26.8 0.5 72.7 Comparative Example 3 10 0.31 0. 01 1.07 ◎ ◎ XXX 22.0 0.7 77.3 Comparative Example 4 10 0.31 0.01 1.10 ◎ ◎ XXX 22.0 0.7 77.3 Comparative Example 5 0 0.32 0. 02 0.00 〇X 〇〇 X 95.0 5.0 0.0 Compare 6 0 0.32 0.02 0.00 〇X 〇〇X 95.5 4.5 0.0 Comparative Example 7 Zn 0.00 0.00 0.31 ◎ 〇 XXX 0.0 0.0 100.0 Comparative Example 8 Only Zn 0.00 0. 00 0. 31 ◎ 〇 XXX 0.0 0.0 100.0 Initial judgment base Peel strength (unit: kN/m) -0. 6x 0.6-0.80 0. 8-® Peel strength after heat resistance test (unit: kN/m)* ~0. 48x 0.48-0. 640 0. 64-© Acid resistance test After peeling strength (unit: kN/m) -0. 6x 0. 6-0. 80 0. 8&quot;·© Etching (by width 1 color reduction width unit / / m) -4. 0® 4. 0- 6. 0〇6. 0~x * Heat-resistant peel strength (%) = [1 - (initial peel strength - peel strength after heat treatment) / initial peel strength] X100 2197-9984-PF 16 1376174 As shown in Table 1, Examples 1 to 4 were 6 〇 wt% to 75 5%, P was 5 Wt% to 7 wt%, and ^ was 20 wt% to 35 wt%, and the satisfaction value of each measurement was passed (total evaluation ◎). In Examples 5 to 6, Ni is 80 wt% or more, and is not more than 1 〇 (4). Since the content of bismuth is small, the peel strength at the initial stage and after the heat treatment is slightly lower than the satisfying value, and the (four) etchability is slightly due to the high content of Ni. Poor, on the whole, can meet the requirements (summary evaluation). Ni of Examples 7 to 8 was 50 wt%, and Zn was 45 wt%.

_ -- w L/u, ttf &gt;7; 'the content of Zili is large', so the peel strength after the initial stage and after the heat treatment is passed, but the peel strength after the acid treatment is slightly lower than the satisfying value H, and the The content of Zn is somewhat poor and is generally satisfactory (total evaluation 〇).

In the case of the above-mentioned 以及 的 J 的 ζ 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In Comparative Examples 5 and 6, since Ζη was not contained, the peel strength was inferior, and Comparative Examples 7 and 8 were not suitable for the circuit board because of the acidity η' and thus the acid treatment property and the (4) property. The copper foil can satisfy the industrially excellent surface area for the polyfluorene. As described above, the surface treatment amine of the present invention has the adhesive strength, acid resistance, and etching property, and the copper box is treated. Further, the surface treatment method of the copper foil according to the present invention is industrially satisfactory for the adhesion strength of the polyimide and the surface treatment of the acid-resistant copper foil. 17

2197-9984-PF/〇丄74 Further, according to the laminated circuit substrate of the present invention, it is possible to provide a laminated circuit substrate in which the resin substrate, in particular, the polyimide and the steel foil have high bonding strength and have a circuit formation. It is acid-resistant and meets etchability, and has an explanatory diagram of excellent [schematic description]. Zn in the alloy layer Figure 1 is not a pressure condition for measuring the peel strength.

Fig. 2 is a graph showing the relationship between the Ni-P-Zn content of the copper foil surface treatment layer and the peel strength. [Main component symbol description]

2197-9984-PF 18

Claims (1)

1376174 No. 097134379, December 12, 2003 X. The scope of application for patents: Shangyu: The surface treatment of the copper surface is added to the surface of the untreated copper II-- side with a surface treatment layer composed of "Bu Bu Zn alloy, .n, confuse. Ni is 50 to 90% by weight, P is 0.1 to 15 wu, and ytterbium is 5 to 43 6 wt%, and u. The surface of the second surface treatment layer is contained. '. 3~ - The surface treatment method of the copper box, on the surface of at least the untreated copper pig, with the electrolysis containing Nl: 25~55g / L, p: 〇 2~i 〇g / L, Zn (a) ~ ^ A surface-treated layer composed of a Ni-P-Zn alloy having a content of z·5 to 43.6 wt% and a content of zn of n·SOmg/dm 2 was formed. 3.-Laminating a circuit substrate 'The surface of the surface-treated layer of the surface-treated copper mat is formed in tandem with the tree board, wherein the surface treatment (4) is that φ Ni_p_zn is provided on at least one side of the untreated steel fl a surface treatment layer formed of an alloy, wherein a surface of the surface treatment layer of the surface-treated copper box is further connected to the resin substrate, and a composition of the surface treatment layer is 5 〇 9 9 、 1%, 1 gt; 〇i~ and Zn are 5~43. 6wt%, and the aforementioned &amp; 3 of the surface treatment layer is set to 〇〇3~〇. 3〇mg/dni2. The laminated circuit board according to the third aspect of the invention, wherein the initial peeling strength of the surface of the surface-treated copper foil and the resin substrate is 〇6 kN/ra or more, and after the air heating test The peel strength maintains the strength of 80% or more of the initial peel strength. 2197'9984-ppi 19