TW200936003A - Surface treated copper foil and printed circuit board substrate - Google Patents

Abstract

The invention provides a surface-treated copper foil that satisfies the trends of downsizing and miniaturization of household electric appliances and portable electronic machines and also satisfies the requirement of formation of fine patternsg, especially referring to surface-treated copper foil that adheres well to an insulting substrate and has low contact resistance with conductive past containing metallic particles, and is applicable to IVH (interstitial via hole) circuit structure with low surface roughness. On the front and back surfaces of the insulting substrates in the laminated substrate, the above-mentioned surface-treated copper foils are configured to constitute the copper foil circuit. The filled metallic particles provided in the through holes of the above-mentioned surface-treated copper foils connect to the copper foil circuit. The surface treated copper foil contains surface treated layer that is arranged on at least one surface of the copper foil so that the contact area between the above-mentioned copper foil surface and the joining surface of the metallic particles in the joining portion is more than 30% of the copper foil surface area.

Description

200936003 ' IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a surface-treated copper foil, and more particularly to a circuit suitable for conducting a conductive composition (conductive paste) on the front and back sides ( A laminated circuit board (multilayer printed circuit board) of a line). Further, the present invention relates to a circuit board using the above surface-treated copper foil forming circuit. [Prior Art] A method of manufacturing a conventional laminated circuit substrate has a through-hole plating method in which a via hole is formed in an insulating layer after laminating a plurality of substrates for a multilayer circuit substrate, and by being in the via hole The mineral layer formed by coating on the circumference is used to conduct interlayer conduction. The laminated circuit substrate formed by the above-mentioned through-hole clock method has the advantage that the layers can be connected with a low and stable contact resistance, but the process is complicated, the steps are large, and the cost is high, which is the use of the laminated Q circuit substrate. An important factor of limitation. Further, in the laminated circuit board formed by the through hole plating method, there is a disadvantage that the components cannot be assembled directly above the through hole, and the degree of freedom in line layout is low. ''',, the above-mentioned disadvantages, in the laminated circuit board formed by the through-hole coating method, even using the extension t & π u main smear to make the shell perforation inclined with respect to the substrate surface, To avoid the configuration position of the assembled parts. In addition, in recent years, the interlayer bonding method which replaces the through-hole mineral film method is formed by a gap guiding technique (interstitial 2197-10192-PF; Dwwang 5 200936003 via h〇le; IVH) in which a conductive paste is filled in a through hole. The laminated circuit substrate has been put into practical use. As a result, the laminated circuit board using the conductive paste can be made simpler and lower in cost than the laminated lightning circuit board formed by the through-hole ore film method. A representative method for manufacturing a laminated circuit using the IVH method is ALIVH (please refer to the non-patent literature. In ALIVH, an aramid epoxy prepreg is used as an insulating substrate, and The laser hole is processed to form a through hole, and then a double-sided laminated copper box of the insulating substrate filled with the conductive paste with a conductive paste is adhered to the copper substrate and the insulating substrate by hot pressing. Thereafter, the pattern is formed. The copper is formed to form a predetermined circuit, and the above steps are repeated to form a laminated circuit substrate.

The copper box used for the IVH method such as ALIVH has been developed to have a double-sided thickness of 4 # m or more in order to adhere to the amine-impregnated epoxy prepreg and to the conductive paste. Treatment of copper foil or single-sided roughening of beryllium copper crucible. However, in recent years, home appliance products and portable electronic devices have been continuously thinned, miniaturized, and have a demand for fine graphics, but the surface-treated copper foil currently used cannot meet this demand. [Non-Patent Document 1] Please refer to CMC Publishing Co., Ltd. (CMC)

Publishing Co., Ltd.) "High Perf〇rmance MateHais for Electronics Package Substrate", published on January 31, 2005, page 18 [invention] 2197-10192-PF; Dwwang 6 200936003 [Problem to be Solved by the Invention] The present invention provides for the thinning and miniaturization of a home appliance, a portable device, and the like. The surface treatment of copper tears, especially the low surface roughness of the circuit structure suitable for m g, π lVH method and the adhesion to the insulating substrate from the cup, mtr good, contact resistance with the conductive paste metal particles In addition, the present invention provides a circuit board which is a circuit for forming a circuit by the above-described surface-treated copper foil, thereby forming a fine pattern. [Means for Solving the Problem] The surface-treated copper foil of the present invention, Early „ / 疋 疋 表面 一层 一层 一层 一层 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' a circuit, wherein the copper foil line is connected by a metal particle disposed in the via hole of the insulating substrate, and the surface-treated copper foil is characterized by: At least one surface treatment layer of the surface of the copper foil base, and the area of the joint surface of the joint portion of the copper box base with the metal particles and the metal particles is the surface area of the copper drop Above the road.

Preferably, the surface treatment 厗|A layer is a layer on which the roughened particles are attached to the surface of the copper foil-based foil, and the surface of the surface treatment layer of the surface layer has an RZ of U to 3.0" and a brightness value. It is 25 or less. Here, 'Rz is defined in JIS B 〇6〇b 1194 "Definition and Expression of Surface Roughness", which is r average roughness of ten points. In addition, according to Π SZ 81 0 5 (1 9 8 2 ), the white surface illuminated by the same condition is the relative brightness of the surface of the object based on the brightness of the object 2197-10192-PF/Dwwang 7 200936003 Sex, the brightness value is the value of this relative brightness and darkness. It is preferable that the surface of the surface treatment layer is the surface of the surface treatment layer #100"mx", and there are 25 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The surface treatment layer has a range in which the inner layer of the surface layer of the & p is taken in the surface of the surface treatment layer, and the surface is substantially evenly distributed with (four) protrusions composed of the coarse particles described above. Preferably, the maximum width between the protrusions in the surface treatment layer is 〇1" or more, 25, m divided by the number of the protrusions present in the range of the observation section 25" 2 times or less. The circuit board of the present invention is characterized in that it is made of a surface-treated surface foil. [Effect of the Invention] The present invention can provide a surface-treated copper foil that can meet the needs of miniaturization and miniaturization in response to the thinning of home appliances and portable electronic devices, and is particularly suitable for the low surface of the circuit structure of the IVH method. A surface-treated copper foil having a coarseness and good adhesion to an insulating substrate and a low contact resistance with conductive paste metal particles. Further, the present invention can provide a circuit board in which a surface-processed copper foil is formed into a circuit, whereby a circuit of a fine pattern can be formed. [Embodiment] [Best Mode for Carrying Out the Invention] 8 2197-10192-PF; Dwwang 200936003 The copper foil of this embodiment is a surface-treated copper box.

^ ω White is especially suitable for surface treatment copper boxes that use the IVH method to form circuits. A representative method of forming a laminated circuit by using the test is described by AUVH. Figs. 1(4) to 1(1) are cross-sectional views showing the steps of a method of manufacturing a laminated circuit substrate by ALIVH. First, as shown in Fig. 1U), a brewed amine epoxy resin prepreg is used as the insulating substrate 1; as shown in Fig. 1 (5), the through hole 2 is formed by laser drilling. Next, as shown in FIG. 1(C), the conductive paste 3 is filled in the through hole 2. Next, as shown in Fig. 1(c), the copper boxes 4 and 5 are laminated on both sides of the insulating substrate 1 in which the conductive paste 3 is filled in the through holes 2; as shown in the figure i(4), it is adhered by hot pressing. The copper foil 4 and the insulating substrate melt the conductive paste 3 by the heat of the hot pressing step, and the double-sided (four) core 5 is connected via the through hole 2 to be in an on state. - Next, as shown in Fig. 1(e), the steel box is patterned (etched) to form a predetermined circuit. The single layer substrate 10 is formed as described above. The above steps are repeated in order to multilayer the laminated substrate. For example, as shown in Fig. 1(f), the same substrate 11'12 as the one shown in Figs. 1(a) to 1(c) is formed, and is laminated on the upper surface and the lower surface of the substrate 1 respectively. Then, the copper foils 13, 14 are laminated on both sides of the laminate, and then the substrate 1 〇, 丨 ii 2 and the copper foil 丨 3, 〗 # are adhered by hot pressing as shown in the first figure. The heat of the hot pressing step melts the conductive paste and connects the double-sided steels a 4 and 5 to the conductive state via the through holes. Thereafter, as shown in the figure (h), the patterned (etched) copper foil is formed. And a predetermined circuit is formed. As described above, a laminated circuit substrate of three 'increased 2197-10192-PF/Dwwang 9 200936003 is formed. Ο ❹ In addition, the above process is repeated as needed. That is, in the above laminated circuit substrate The upper substrate and the lower surface respectively deposit the substrates 15 and 16, and the copper layers 17 and 18 are laminated on both sides of the laminate, and then the substrates and the copper foil are adhered by hot pressing, and the copper is patterned.帛 Formation of a predetermined circuit. Thus, a five-layer laminated laminated circuit substrate is formed as shown in Fig. 1 (& in this embodiment, before surface treatment) Copper H (hereinafter referred to as "mi-based:") is a copper foil or a copper alloy foil produced by electrolysis or rolling (referred to as copper 'Lo" in the case of no need for defects. The thickness of copper matte is relatively high. For the thickness of the copper box, if the thickness is less than (4), it is very difficult to roughen the surface of the copper enamel, so the thickness below is not good. The thickness of (4) used can be appropriately selected depending on the use. The surface roughness of the copper box (copper-based base box) is preferably Rz 〇·〇1//ιη~2/zm〇. The surface roughness of the steel knot on the hollow of the Ba Shi, Guan ^, 钔, and white base The copper-based base foil of RZ 0.01μm or less is difficult to manufacture in reality, and the manufacturing cost even if it can be manufactured does not meet the actual requirements; in addition, although steels of RZ 2. G # m or more can be used. Base, but considering the commercial frequency characteristics and micro-patterning, (4) the surface roughness Rz of the base box is preferably 2/zm or less. Here, the so-called agriculture and 4 Λ

The surface roughness Rz is defined by JIS B 060H 994 "Definition and Expression of Surface Roughness" and is a ten-point average roughness. In the present embodiment, at least one side of the steel box base is subjected to a surface 2197-l〇l 92-.pF; Dwwang 200936003: a wide surface roughening treatment is to make the roughened particles attached: two surfaces And become a rough surface. The surface roughening degree of the roughened surface is preferably the case of • u..., which is not satisfied by the surface treatment for the purpose of achieving the drawdown of 4|noise strong _ a a low and the so-called peel strength. More than 3. - then its high frequency - into micro: ❹ In the example: the surface treatment method of the steel box base, it is better to make the copper base or copper alloy attached to the copper The copper or copper is preferably 2 mg/dm 2 to 4 GG mg/dm 2 . When the amount of adhesion is not sufficient, the surface-treated copper foil for which the strength is low cannot be satisfied due to the low peel strength. If the amount of adhesion is greater than 400mg/dm2, |彳iw will pass the team, then the same frequency characteristics will decrease and the information will be reduced. The reason is that if the copper or copper alloy has a large amount of adhesion, then The coarsened particles are larger, and the surface roughness c is not large. In the case of a constant frequency, the current is higher at the conductor & the higher the frequency, the higher the current ❹ &, _, tends to flow on the surface portion (the increase in the concentration, the length of the surface where the current flows becomes longer and increases the resistance, because U However, the loss of current increases and the information is insufficient. Therefore, the adhesion amount of copper or 4ηπ 2 / secondary copper alloy is preferably 40 0 mg / (in) 2 or less, but the high-frequency characteristics can be ignored. In this case, the upper limit of the amount of adhesion can also be ignored. In this embodiment, the surface treatment of the copper foil base is a 丞/self surface treatment, so that the surface is bonded to a conductive paste, and the surface is contained in .v. The surface of the joint portion of the conductive paste in which the metal particles are bonded is equal to or larger than the surface area of the gold-plated copper box. The area of the joint surface of the particles is 2197-10192-PF; the area of the surface of the metal particles and the copper box of Dwwang 200936003. The surface area of the poorly-predetermined copper foil measured in the following section and the lengthwise direction of the longitudinal direction of the copper foil are long sounds in the width direction of the copper box, and the beryllium copper is the cross-sectional portion of the surface, and the degree of food is The same length is 1 / , will 1 ^ and 1 / know The length of the portion of the length direction of the sputum is measured by the result of using f as the surface area of _0. The image analysis of the BioArts, Co L software (Bi〇Arts Co., Ltd. 'seven d.) 敕俨m Q τ The length of the copper drop surface is measured along the periphery of the roughened particles. ^ 2〇〇6), the surface of the copper box; # τ & u _ The long-term production of ^, and the metal paste of the conductive paste The length of the part 'the length of s, the length of the steel surface, the metal particle of the electric paste, and the length of the J point of the ct 筏 mouth are all s, and S 舆 S' The multiplied value is the joint area. The joint area at this time is preferably 30% or more of the surface area of the copper box. If the area of the joint is more than 30% (inclusive) of the surface area of the copper foil, it can satisfy the stickiness. Force and reduce the contact resistance between the copper H (wiring circuit) and the metal particles, and the connection portion can be satisfied between the two. The contact area is insufficient in the following (4), and the contact resistance increases. The problem of heat and the like is not good. About the metal particles mixed with the conductive paste, Tungsten, lead, zinc, gold, silver, copper, nickel, cobalt, etc. are suitable for use. In addition, in the present embodiment, the roughened copper shoulder for surface roughening treatment has a brightness value of 30 or less, preferably. It is 25 or less. The brightness value in this embodiment is usually an index for observing the surface roughness, and the measurement method is 2197-10192-PF; Dwwang 12 200936003 ❹

A method in which light is irradiated on the surface of a measurement sample to measure the amount of reflection of light and is expressed as a brightness value. Here, according to JIS Z 81 05 (1982), the brightness value is a value which scales the attribute of the relative color of the relative brightness of the object, and is based on the white surface illuminated under the same condition. If the brightness of the treated surface of the surface-treated copper foil is measured by this method, the surface roughness Rz is large or the groove depth between the roughened particles is deep, and the lightness is low due to the small amount of light reflection. If the surface is smooth, the amount of light reflected is large, and the brightness tends to be biased. In order to increase the peeling strength of the surface-treated copper foil and the insulating substrate, the surface-treated copper foil has a lightness value of 3 Å or less, preferably 25 or less. Further, when the brightness exceeds 30, even if the RZ value of the roughened surface is large, the unevenness of the roughened surface makes the surface-treated copper foil and the insulating substrate poorly engaged, and the peel strength cannot be improved. The brightness is measured after the anti-rust treatment in the range of Ni · 0.01~0.5mg/dm2 Zn - 0. 〇1 -〇.5mg/dm2 Cr · 0.01-0. 3mg/dm2 of the copper foil to be tested. The measurement was carried out using a light meter (model name of SUGA TEST INSTRUMENTS C0·, LTD: S&M Col〇ur Computer model SM-4). The surface-treated copper box of the present embodiment having both the surface roughness (Rz) and the brightness value described above has excellent peel strength and fine pattern characteristics after lamination and compositing, whereby the surface-treated steel foil is used. The use of the circuit board can be manufactured. In the present embodiment, as described above, the surface of the copper box-based foil is roughened by 2197 to 10192 -pp; Dwwang 13 200936003, and the protrusion is formed by roughened particles for achieving an average peel strength in the surface. Preferably, it has an area of 100/^xmp and has 200 to 25,000 twisted private objects. If the number of large objects is less than 2, the inter-protrusion between the protrusions, the palace, and the pi', can not be cut into fine patterns; if the protrusions reach 2,500 or more, then It is not good for the twisting and twisting, the wind~, and the material that is too long to provide sufficient peeling strength. In addition, in order to obtain the right #工+, it has excellent peel strength and fine pattern characteristics without variation in the surface, and it is preferable that the protrusions formed by the roughened particles described later in the lamp are substantially evenly left. Eight, the child is in (knife cloth). That is, the height of the protrusions is preferably 1.0//Π1 to 5.0//m.形士+人/The height of the protrusion on the surface of the copper foil base foil is less than 1 · Ο β m ;'; w, mam Z because of the low height, the effect of improving the peel strength cannot be obtained; In the case of 5. 0 // m, the protrusions cannot be evenly distributed, and the surface roughness Rz of the surface of the copper v is increased in each range, and the peel strength of the stability is maintained. However, the Π»频特1· is not good enough to achieve micro-patterning. The height referred to here is the distance between the surface of the copper box base and the apex of the protrusion. In addition, the 'protrusion of the protrusions # # right ^, can not achieve the peel strength; and the right number is more, the surface of the copper foil 盥 - -, the dog's adhesion is also low, the effect is reduced Therefore, it is preferable to have 6 to 35 protrusions in the 25/m range of the observation section, and to select 1 to 20 protrusions. Here, the protrusions formed in the present embodiment are formed in the adjacent protrusions for a hard time of 4 months. The distance between the bottom of the groove portion and the apex of the protrusion (hereinafter referred to as the depth of the groove) is less than 0 _ 3 from m, and the adjacent protrusion is regarded as a large object; The depth of the protrusion is 2197-1Q192-PF; in the case of Dwwang. 200936003 or more, the adjacent protrusion is regarded as two protrusions. The height of the protrusion is the distance between the surface of the copper box base and the apex of the protrusion. 'This—the difference between the groove and the groove is that it is the distance between the bottom of the groove and the point of the protrusion after the surface treatment. The method of counting the number of objects is to treat the surface of the copper box. In the observation photograph obtained by observing the cross section of the grind electron microscope (SEM), the number of ten is in the range of T ^ number within the length of 25 # ra

测定 The method of measuring the number of the above-mentioned ambiguous projections is carried out. There are 6 to 35 dry circumferences of the number of protrusions having a height of 1.0 " m~5.〇", and a groove having a depth of 〇_3 "m or more exists between the protrusions and causes When the distribution is substantially uniform, it is possible to prevent the projections from being concentrated in a portion within 25, and to stabilize the peel strength in the width direction and the longitudinal direction of the copper foil. In the present embodiment, "substantially uniform distribution" means protrusions. The height between the apex and the copper surface is 1·1 to 5.0...the number of protrusions is η(number), and when the observation width when viewing the protrusions in section is 25 (#m), at (25/ In a region of the width of n) U m ), at least a part of one of the above-mentioned protrusions exists in this region. Further, in order to stabilize the peel strength, the width of the formed protrusions is preferably uniform, and the maximum width of each of the protrusions is preferably 5% or more, and 25#m divided by the protrusions existing in the range of 25 μm. The number of the objects is twice or less the length of the obtained number. The maximum width 此处 referred to herein means the maximum value of the distance in the direction perpendicular to the height direction of the projections in the SEM observation of the above cross section. 2197-10192-PP; Dwwang 15 200936003 In addition, in the groove depth between the protrusions, the average groove depth between the protrusions is more preferably 〇 _ 5 /z m or more. The average groove depth between the protrusions is determined by measuring the depth of the groove on both sides of each protrusion for the number of protrusions having a groove depth of 〇. 3 am or more, and the value at this time is Α1 ( When β m)Bl( μ m)...An( # m)Bn( # m), the value obtained by the following formula is the average groove depth between the protrusions. It is obtained by {[(A1+B1) +...+(An + Bn)]/2/n}. ❹ ❹ Fig. 2 is a view showing the observation surface of the surface-treated copper case in the embodiment of the present invention. - A protrusion P is formed on the surface of the untreated copper box SU. The number of the protrusions p is 6 or more in 25 (four), for example, there are (a) 5, and the 〇 and the degree 疋 are in the range of 5 (4). When the depth of the groove indicated by 卩a is not full, the projections are not counted, but the projections having a depth of '3:: or more in the groove indicated by b are included. The maximum width W of the projections P It is 2 times or less of the length obtained by dividing the number of the protrusions P which are present in the range of 25" or more. The figure is a diagram of the observation section of the surface treatment copper box which is not good. The surface of the large copper box is formed with protrusions p. The second of the protrusions p: in the range of "wide" and above, and having a width of more than 25" ', which exists in the range of 25 # m Makeup p from the gentleman 2 If If If # μ 大起物 P of the length of the different width of the protrusion P. Figure 4 is a poor surface in the untreated copper box face (10) wide Observe the cross-section of the figure. J / 曰 I face SU open" Consider the ancient space 1 w The object p is not evenly distributed p' which shows the convex surface in the brother 4, with C and 2197-10192-Pp Dwwang 16 200936003 There is no region of any part of the protrusion p, and this case cannot be regarded as a substantially uniform distribution. On the copper foil of the roughened surface of the above composition, chromium is formed. / or chromate (chr (10) ate) is coated with a film for rust-preventing treatment, or treated with a Si ane coupling agent or a rust-proof treatment plus a decane coupling agent as needed. Hereinafter, the present invention will be described in more detail based on the examples, but the present invention is not limited to the following description. 〈Examples The following copper foil base foils 1 to 4 were prepared.

Rz = 1·26 in m; shiny surface roughness ζ 1·52#πι; glossy surface raw sugar Thickness: 12#m; dark surface roughness Degree: Rz= 1. 82 # m electrolytic copper sway. Copper foil base foil two

Thickness: 12"m; dark surface roughness: Rz = l · electrolytic copper foil. Copper foil base foil three glossy surface roughness thickness: 12 a m; dark surface roughness: rz = 1. 86 . ΙΠ > degree. Rz = l. 20 / ζ πι electrolytic copper foil. Copper foil base foil four thickness: 12/ζιη; double-sided roughness foil.

Rolled copper with Rz=l.20 The copper-based base foils of the dry preparations are smeared with the following C, and the plating conditions are Λ, β, or surface treatment. In the table, the copper foil base box 10192-PF; the combination of Dwwang magic type and plating condition 〇 1 - _ 200936003 is shown. Further, each of the examples is a surface-treated copper case obtained by subjecting the copper foil-based foils to at least one plating in the order of plating bath 1 to plating bath 2 of plating conditions A, B, or C. The surface shapes of the finished surface-treated copper foil were shown in Table 1 as Examples 1 to 8. Further, in the roughened surface of some of the examples, nickel plating (0.3 mg/dm2), galvanization (0.1 g/dm2) was applied, and chromate treatment was applied thereto.

Plating conditions A forging bath 1 copper sulfate (copper metal source) sulfuric acid in the acid (key metal source) current density energization time plating bath temperature plating bath 2 copper sulfate (copper metal source) sulfuric acid current density energization time plating bath temperature plating conditions B plating bath 1 copper sulfate (copper metal source)

5~10g/dm3 30~120g/dra3 0. 1~5. Og/dm3 10~60A/dm2 1 second~2 minutes 20~60〇C

20~70g/dm3 30~120g/dm3 5~60A/dm2 1 second~2 minutes 20~65〇C 1~ 5 Og/dm2 2197-10192-PF; Dwwang 18 200936003 ' Nickel sulfate (nickel metal source) 2~ 25g/dm3 ammonium metavanadate; source of hunger metal 0. l~15g/dm3 pH 1.0-4.5 current density l~60A/dm2 power-on time 1 second~2 minutes plating bath temperature bath 2 20 ~60 °C Copper sulfate (source of copper metal) 10~70g/dm2 A Sulfuric acid 30~120g/dm2 Current density 5~60A/dm2 Power supply time 1 second~2 minutes Plating bath temperature Electric clock condition C Plating bath 1 20~65〇C Copper sulphate (source of copper metal) l~50g/dm2 ❾ sulphuric acid syllabus (drilling metal source) l~50g/dm3 in sulphate (key metal source) 0· 1 ～10g/dm3 pH value 0. 5~4. 0 Current density l~60A/dm2 Power-on time 1 second~2 minutes Plating bath temperature plating bath 2 20~60〇C Copper sulfate (source of copper metal) 10~70g/dm2 Sulfuric acid 30~120g/dm2 2197-10192-PF; Dwwang 19 200936003

5~60A/dm2 1 second~2 minutes 20-65〇C Current density energization time plating bath temperature gauge 1 copper foil type treatment surface plating----- copper foil base foil treatment surface roughness _ (//m) protrusion Average groove depth between objects (/ζπΟ maximum width among the protrusions (egg) 25/zm width of the height of l~5/zm number of protrusions decane coupling agent Example 1 Electrolysis Μ A 2 5 1.05 1.81 24 Benefit Example 2 Rolling - B 4 2 65 0.89 2.4 18 Example 3 Electrolytic Μ B 1. 2.85 1.37 1.52 28 Example 4 Rolling C — 4 2. 55 1.92 1.22 34 Summer Fox Example D % Solution B 2.8 1.18 1.14 26 Example 6 Electrolysis s A-一- _ 2.55 0.55 2. 63 13 Example 7 Electrolytic Μ A Γ~2.5 1.05 1.81 24 No Example 8 Electrolysis SA " 3.0 0.5 2.5 6 Example 1 Electrolysis r μ A1 1~~2Γ5 Less than 0.3 0.1 or less 0 There is a comparative example Z Electrolysis s B1 III 3. 65 Less than 0.3 0. 3 below 0 There is Comparative Example 3 Rolling — B' Four 2.65 Dissatisfied 0.3 0.1 The following 0 have Comparative Example 4 4# MA, — 2.5 Less than 0. 3 0.1 or less 0 There is Comparative Example 5 Electrolysis S B 2 3. 65 Less than 0. 3 0. 3 or less 0 Yes Comparative Example b 4 Solution M AJ — 1.7 Less than 0. 3 0.1 or less 0 Yes ❺

Ratio of joint area of metal particles to steel foil (%) Brightness projection distribution: Number of projections in 100x100/zm2 Increase in resistance value after heat treatment (%) Increase in resistance value after moisture resistance test (%) Peel strength (KN/m) Fine pattern characteristic minimum value L/S (Aim//zm) Appreciation Example 1 43 22.5 9200 45 77 0. 92 25/25 Example 2 35 23 5200 53 88 0. 96 25/25 Example 3 49 21 12500 40 72 1.02 30/30 Example 4 56 16 18600 35 66 1.10 25/25 Example 5 43 22 10800 42 74 0. 93 30/30 Example 6 30 25 2700 56 94 0. 86 25 /25 Example 7 43 22.5 9200 45 77 1.14 25/25 Example 8 r 37 24 6400 51 82 0.83 25/25 Comparative Example 1 21 38 0 151 186 0.47 30/30 Comparative Example 2 26 34 0 Bu 143 146 0. 54 55/55 Comparative Example d 22 39 0 154 182 0.42 30/30 Comparative Example 4 21 38 0 151 186 0.63 30/30 Comparative Example 5 26 34 0 143 146 0. 71 55/55 Comparative Example 6 17 38 0 166 220 0. 57 20/20 2197-10192-PF; Dwwang 20 200936003 <Comparative Example> Prepare the copper foil base foils one, three, and four with the following plating conditions A'

Or B' is subjected to a surface treatment. Table 1 also records the combination of the type of copper collar pig and the plating conditions. Each of the comparative examples is a surface-treated copper foil obtained by subjecting the copper foil-based foil to one or three plating baths 1 to B in the order of plating conditions A' or B'. On the surface of the surface of the surface-treated copper foil of the comparative example and the insulating substrate (roughened surface), wrought nickel (0.3 mg/dm2) and galvanized (0.1 mg/dm2) were applied. Then, chromate treatment was carried out thereon, and it became a test piece of a comparative example. The surface shape of the finished surface-treated copper foil was Comparative Example 1 to 6 and recorded in Table 1 for plating conditions A' plating bath 1 5~10g/dm3 30~120g/dm3 0.1-5. Og/dm3 10~ 60A/dm2 1 second~2 minutes 20~60〇C 20~70g/dm3 30~120g/dm3 3A/dm2 2 minutes or more (change time according to surface roughness) Copper sulfate (copper metal source) Molybdenum sulfate record (molybdenum Metal source) Current density energization time plating bath temperature plating bath 2 copper sulfate (copper metal source) sulfuric acid current density energization time 2197-10192-PF; Dwwang 21 200936003 plating bath temperature plating condition B' plating bath 1 copper sulfate (copper metal source Nickel sulphate (nickel metal source) ammonium bismuth citrate (synthesis metal source) pH current density energization time plating bath temperature plating bath 2 copper sulfate (copper metal source) sulfuric acid current density energization time plating bath temperature

15°C Reference l~50g/dm2 2~25g/dm3 0. l~15g/dm3 1.0-4.5 l~60A/dm2 1 second~2 minutes

20~60〇C 20~70g/dm2 30~120g/dm2 3A/dm2 2 minutes or more (change time according to surface roughness) 15. . [Measurement and Evaluation of Peeling Strength] After the surface-treated copper foil prepared in the examples and the comparative examples was cut into a length of 250 mm and a width of 250 Å, the surface subjected to the roughening treatment was placed after thermocompression bonding. The number of sheets of BT resin having a thickness of 1 mm (the trademark of Mitsubishi Gas Chemical Co., Ltd., which is a thermosetting resin composed of bismaleimide triazine resin) is placed on the whole The peeling strength of the attached 2197-10192-PF; Dwwang 22 200936003 was measured between two smooth stainless steel plates at a temperature of 19 ◦ ° C and a pressure of 50 kg/cm 2 for 90 minutes. The measurement of the peel strength was carried out in accordance with JIS C6471 in the direction of ι8 twist and peeled off. It is clear from Table 1 that each of the examples satisfies the peel strength of ΚΝ. 9ΚΝ/ιη or more, but the peel strength in Comparative Examples 1 to 6 is 〇·8 KN/m, and the peel strength is not satisfied. [Micro-pattern characteristic evaluation] Fig. 5 is a schematic cross-sectional view showing the surface-treated copper foil F produced as described above attached to the base SB of bt resin or the like, and processed as described below. As shown in Fig. 5, the copper vl F which has formed the resistance (4) R which determines the line width: L and the interval width: S is silver-engraved with a ferric chloride bath. The silver engraving time is determined by the same width of the top of the line width and the width of the resist. The conditions of each 〇 = 1 已 are formed to determine the width of each line and each of the 3 r r + U «, the valley interval is seen (in one piece The substrate of the resist R of the substrate was formed into 10 lines, and the rice was immersed in the ferric chloride at the time determined above. In each of the substrates, it was observed that there was no bridging between the wires, no residual roots, and the top width of the wires and the wires were the same as the resist. The value of the smallest L.S. in which no bridging and residual roots were observed in each of the substrates made under the condition of n = 1 示 is shown in Table 1. A K W n r can be made into a fine pattern of L/S--30/30 or less. Comparative examples other than Comparative Example 6 Although it is possible to make a 30/30 pattern, it is impossible to reduce it. Further, Comparative Example 6 was suitable for forming a fine pattern because the surface treatment roughness was small. [Measurement of increase rate of resistance after heating] The resin is opened to the core hole and filled with a conductive paste, and then pressed to make copper 2197-10192-PF; Dwwang 23 200936003 Particles are pressed and tested for resistance by bonding copper foil. value. The increase rate of the resistance value after heating the measurement result as shown in Table 1 is shown in Table 1. From the heat treatment of 1 to 6 after the subsequent resistance value, it is clearly shown in Table 1 that the increase rate of the heat in each of the examples is 60% or less, and the increase rate of the resistance value of the comparative example exceeds 14%. %. Further, the resistance value in the same place was measured after the wet test, and the increase rate of the resistance value before and after the moisture resistance test was calculated, and the merits and demerits were confirmed.

As is clear from Table i, the rate of increase in the resistance value after the (fourth) test in each of the examples was more than 14% by the increase rate of the resistance value after the fishery test of the comparative example 以下. [Measurement of Luminance] The measurement method of the brightness is the same as described above. In one embodiment, the brightness is 25 or less, and the comparative example 6 is 3 or more. As described above, in each of the examples, the bonding area of the metal particles and the copper flute is 30% or more, and the resistance values satisfying the peel strength, the brightness, the resistance value, the heating test, and the resistance test can be obtained. Increase the proportion of the copper box for the conditions of the micro-pattern. On the other hand, in the comparative example, the joint area of the metal particles and the copper box was 30% or less, and the result of satisfying the increase in the resistance value after the brightness test, the resistance value, the heating test, and the fish-resistant test was not obtained, and it was not satisfied. The conditions for the production of the peel strength and the fine pattern were not obtained, and the copper foil satisfying all the conditions was not obtained. The present invention is a surface-treated copper foil which is formed on the surface of a copper box, and the protrusions exhibit a specific shape and distribution formed by roughened particles, thereby ensuring strong adhesion even if the sugar content is small. And the surface area of the metal particles of the electric paste of the 2197-l〇l92-PF; Dwwang 24 200936003, and can provide a surface-treated copper foil which maintains stable electrical conductivity. [Simple description of the diagram] The Ua)~l(i) diagram is a step diagram illustrating the steps of the ΙνίΙ method. Fig. 2 is a schematic cross-sectional view showing an embodiment of the present invention. Figure 3 is a diagram showing the surface shape of a copper foil with a poor cross-sectional shape.

A schematic cross-sectional view of a cross section of a surface-treated copper foil. Fig. 4 is a schematic cross-sectional view showing a cross section of a surface-treated copper foil having a poor cross-sectional shape in a surface-treated steel. Figure 5 is a cross-sectional view showing the etching width in the formation of fine patterns [Description of main components] 1~insulating substrate; φ 2 ~through hole; 3 ~conductive paste; 4~copper foil; 5~copper foil; 11; substrate; 12~ substrate; 13~ copper foil; 14~ copper foil; 2197-10192-PF; Dwwang 200936003 15~ substrate; 1 6~ substrate; 1 7~ copper box; ~ The groove depth is less than 0.3. 3 # m; b~ groove depth is 0.3 / m (inclusive); c ~ there is no region of any part of the protrusion P;

P~protrusion; R~resist; S B~substrate; SU~untreated copper foil surface; W~max width. ❿ 2197-10192-PF; Dwwang 26

Claims (1)

200936003 X. Patent application scope: 1·- kinds of surface treatment steel box 'which is the table of the layer---in the laminated substrate, the front side of the board is provided with the above (4) line, and by the edge The via hole of the substrate is filled with A 岚 ▲ 7 and the metal particles are connected to the copper foil line, and the surface treated copper book comprises: a surface disposed on at least one surface of the copper ❹ to make the copper box base In the joint portion of the surface of the tank which is joined to the metal particles, the metal particles are joined to each other, and the area of the surface is 30% or more of the surface-treated steel product. 2. The surface-treated copper box according to claim 1, wherein the surface treatment layer is a layer to which roughened particles are attached to a surface of the steel base, and the surface of the surface treatment layer is Rz 4 U to 3.0. ...the brightness value is below 25 (inclusive). The surface treatment copper box of claim 1, wherein the surface treatment layer is 〇〇 〇〇 quot 该. . A surface-treated copper foil according to the above-mentioned roughened particle, wherein the surface is a surface-treated copper foil having a height of 25 Å and a height of 5 Å. In the range of the observation cross section of the surface treatment layer, the treatment layer has an average of 6 to 35 protrusions composed of the roughened particles having a height of 5#m. The surface treated copper foil, wherein the maximum width between the protrusions in the surface treatment layer is 2197-10192-pp. Dwwang 27 200936003 O.OUin or more, 250^ divided by the protrusions present in the observation truncation 6. The circuit board is characterized by the use of the surface-treated steel foil according to any one of items 1 to 5 in the range of 25/ζπι. to make. 2197-10192-PF; Dwwang 28