TWI344804B - Flexible laminate board and process - Google Patents

Description

1344804 IX. Description of the Invention: [Technical Field to Which the Invention Is Applicable] The present invention relates to the susceptibility of a metal $ and a poly S! imine insulating resin layer in the field of electronic materials, particularly for forming a circuit. Product. Laminate. [Prior Art] Polyimine 4 film is superior in thermal properties, insulation properties, solvent resistance, etc. It has been widely used as a material for electrical/electronic machine parts such as mobile phones. In recent years, with the development of thinner and more functional mobile phones, the substrate on which the pot machine parts are mounted has been converted from a rigid substrate to a disposable printed circuit board. Such a flexible printed circuit board is widely used as a permittable laminate, and a part of the flexible laminate is in the insulating resin layer adjacent to the metal, using a resin such as epoxy resin, and the substrate The insulating resin layer of the part is made of a polyamidide resin. However, in response to the error-free fresh tin in recent years, as the time for mounting semiconductor components is shortened and the efficiency is increased, it is predicted that the temperature and pressure of the ampere will rise. This is the case when using a flexible laminate of epoxy resin because The heat resistance and the like of the epoxy resin are low, and it is pointed out that it is difficult to handle the high temperature. Therefore, it is known that, as in the patent document, it is known to use a flexible laminate of a heat-resistant high-density iodized tree wax adjacent to a metal foil adjacent to a metal foil, but even such a metal is used. A two-layer flexible laminate composed of a foil and a polyimide resin layer, since it is still required to laminate a metal drop on the insulating wax layer so that the metal polyimide adjacent to the polyimide layer '曰' is used all over, thermoplastic polystyrene tree. However, even if the flexible laminate of the thermoplastic polyimine resin known from 317J92 5 1344804 is used, it is practically incapable of withstanding the superior thermal characteristics of the semiconductor element mounting in response to high temperature/high pressure conditions, and is not provided. The characteristics of the flexible laminate. [Patent Document 1] WO 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 专利 另 另 另 另 另 另 另 另 另 另 另 另 另 另 另In order to miniaturize an electronic device, there has been developed a technique of mounting a semiconductor element on a wiring board on which a circuit has been formed. For example, Patent Document 2 discloses a semiconductor device and a method of manufacturing the same, and in a technique similar to the technique described in the Japanese Patent Application, in order to center the semiconductor when the resin is mounted on the wiring substrate, The resin component is hardened or softened, and the semiconductor component and the package jig are twisted to a high temperature. In this heating temperature, Patent Document 2 describes heating to 28 〇: 30 (TC or more, but this temperature will be heated to 25 (TC or more). In addition, the resin is not centered, but adjacent bismuth metal A method of forming a eutectic with each other, in which case it is heated to a higher temperature household. As in Patent Field 2, the mounting of the conductor element to the substrate is performed by applying a bump to the conductor layer of the wiring substrate. The semiconductor element bump projections adjacent to the conductor circuit of the laminated board are pressed against the substrate in a high temperature state and pressed, so that the heat resistance of the resin layer adjacent to the wiring substrate is biased. When the material is low, the pressure is concentrated with the temperature at the joint portion: the circuit on the resin layer of the human wiring substrate or a part of the semiconductor element is in the insulating resin layer of the substrate, and the stable mounting cannot be performed. 317J92 1344804 - Situation. • The above problem may be solved by filling the wiring board with inorganic materials. However, in this case, the wiring substrate cannot be bent. In the field of the use of a flexible laminate, which is different from the industrial use, a heat resistant resin composition focusing on the elastic modulus of the heat resistant resin at a high temperature (3 Å), and The technique of using the #35 wiring board is described in Patent Document 3. However, the resin composition described in Patent Document 3 can be used as a surface protective film for a semiconductor wafer or an interlayer insulating film for a semiconductor package. In the case of a substrate interlayer insulating film for mounting a semiconductor element, in actuality, it is not sufficient to be suitable for semiconductor mounting applications while maintaining flexibility characteristics, and is similar to a conventional flexible laminate. 'The design is not considered for the purpose of installation. f Inventive content】 (Problems to be solved by the invention) Provide a kind of glass transition temperature (four), virtual temperature region that does not damage the (four) nature of the metal (4) (3 thieves) The material elasticity is difficult, and it is possible to obtain a flexible laminate which can withstand the conditions of the women's clothing (4). (The means for solving the problem) The inventors discovered that the insulating resin ▲ ^ of the flexible laminated board can be upgraded and characterized by a (four) riding structure 换 a sentence H & laminated board '遂 to complete the present invention. The flexible single-sided or double-sided surface of the present invention has a full genus~... knowing that there is a flexible laminated board with metal mooring 317192 1344804 i. The edge resin layer is composed of a plurality of layers of polyimide resin. The polyimine resin which is composed of at least one layer adjacent to the metal stream has a storage elastic modulus of ΙχΙΟ8 to 2M09Pa and a glass transition temperature of 3〇〇 to 4〇〇〇c. The resin layer formed of the elastic layer is formed of at least one layer, and the resin layer other than the high elastic resin layer has at least one layer of a low thermal expansion resin layer having a coefficient of expansion of 2 〇χ 1 〇·6/Κ or less, and an insulating resin. The layer has a high elastic resin layer thickness ratio in the range of 3 to 45%. Among them, by satisfying any one or more of the following requirements, a more favorable flexible laminate can be formed: a) a low elastic expansion resin layer on both sides of the high elastic resin layer; 2) a structure adjacent to the metal foil The polyaniline resin of the high elastic resin layer is obtained by using pyromellitic dianhydride and a diamine, and the diamine is used in an amount of 5 to 80 mol% selected from 2, bismuth [4_( 4_Aminophenoxy)j-yl]propane, 1,4-bis(4-aminophenoxy)benzene, hydrazine bis-aminophenoxy) benzene, 4,4··bis (4 The surface roughness of the surface of the metal foil adjacent to the polyimine resin layer of the at least one of the biphenyl groups in the biphenyl group, or 3) is in the range of 0.6 to 10,000. Furthermore, the method for producing a flexible laminate according to the present invention comprises at least one metal foil and at least two layers of a polyimide resin; and the following Y-steps are included in the surface roughness (Rz). On the surface of the metal flame in the range of 0 to 〇, the storage elastic modulus of the composition at 3 5 〇 ° C is 1 X 1 2 ] 〇Pa, and the glass transition temperature is 300 to 400. (: a high elastic resin layer, a step silver of a polyanilin precursor resin; 2) a low thermal expansion property of a linear expansion coefficient of 20×10. VK or less coated on the resin layer of the polyimide precursor precursor a step of a polyimine precursor resin of a resin layer; and 3) 3) 7) 92 8 1344804 A step of performing a heat hardening treatment in a state in which a plurality of layers of a polyimide intermediate resin layer are provided on a metal foil. Hereinafter, the flexible laminate of the present invention will be described in detail. The removable laminate of the present invention is composed of an insulating resin layer and a metal composite, and has a metal foil on one or both sides of the insulating resin layer. Wherein, the insulating resin layer is composed of a plurality of layers of polyimide resin, and at least one layer of the polyimide resin layer adjacent to the metal junction is at 35 (the storage elastic modulus of the rc is JxlO8 to 2xl09Pa, and the glass transition temperature is at 3〇〇 to 4〇〇. A highly elastic resin layer is formed in the range of 匸. Further, in the insulating resin layer, the thickness ratio of the high elastic resin layer must be in the range of 3 to 45%. In addition, the high elastic resin layer Preferably, it is disposed adjacent to both sides of the low heat-expandable resin layer. The polyimine resin used in the present invention is suitably selected from a known diamine compound, a tetracarboxylic acid or a dehydrated product thereof, and the like. When the reaction is carried out in an organic solvent, it is possible to obtain the characteristics of each layer of the insulating resin layer. In the present invention, when it is referred to as "polyimine resin", it means a polyazide having a quinone-amine bond in the molecule. The amine resin or the polyamidoximine resin as a main component may not necessarily be a single polyimine resin, and may be a mixture thereof with a fat. When it is mixed with other resins, the other resin is Contains less than 30%, the best 2% or less. In addition, if a small amount of ^ can be blended into the inorganic filler, these formulations may impair the folding resistance and circuit processability of the flexible laminate of the present invention. In essence, the insulating resin layer is preferably composed of an amine resin layer. & In the present invention, the composition 35 (TC storage elastic modulus) x 〇 s to 317192 9 1344804 2Xl 〇 9] Pa, A polyimide resin having a high elastic resin layer (hereinafter referred to as "high elastic resin layer j") having a glass transition temperature of 300 to 400 ° C (hereinafter referred to as "South Elastic Polyimide Resin") satisfies its characteristics. There is no particular limitation on the premise, but it is preferably a polyimine resin having the structural unit represented by the following general formula (I).

In the general formula (1), Arl, A. a divalent aromatic residue having 12 or more carbon atoms; 4 μl of the Ar 2 carbon number of 6 or more, and a kine group residue; k, ??? The constituent unit Moerby Hui is more than the sheep 'k is 20 to 95, and the 丨 is 80 to 5 numerical value.

Arl is preferably a divalent group represented by the formula (a).

Furthermore, Ar2 is preferably as shown in formula (b). [Chemical 3] 4-valent group 〇

(10) in the ten: in the upper:: 317192 10 1344804 [chemical 4] ω

"'"OK0~|Qpa~OH' ω (ί) The storage modulus of the highly elastic polyimide resin at 350 ° C must be in the range of lxlO8 to 2xl09Pa, especially in the range of lxlO8 to ixioka. If the value is lower than 1 X 1 〇 8 Pa, for example, when the semiconductor element is mounted at a high temperature, the insulating resin layer adjacent to the metal foil will flow in this mounting temperature, resulting in occurrence of metal wiring sinking. On the other hand, the high elastic resin has a storage elastic modulus of more than 2 x 1 〇 9 Pa, which is preferable from the viewpoint of the high-temperature heat characteristics of the object of the present invention, but the flexibility is exhibited, and the flexibility of the bending property of the laminated sheet is likely to be reduce. Further, the glass transition temperature (Tg) of the highly elastic resin layer must be in the range of 3 Torr to 4 Torr, particularly in the target range of 380 C. If the glass transition temperature is lower than the above, the metal wiring sinks easily, and the flexible laminate (4) tin heat resistance will also deteriorate. On the other hand, the degree exceeds 4 〇 (the TC's lord, take the Λ 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾 圾The structure of the complex layer has a line expansion coefficient of 317)92

(D 1344804 20χ) 0·6/Κ· The following is the best calculation. X10 7/K to 2〇x〗 〇-6/k low thermal expansion resin layer. Poly s! Amine resin (hereinafter also referred to as "low thermal expansion poly yam face and #, -# ^ imine tree"), there is no special restriction on the premise of satisfying its characteristics, but the most important thing is the female g, D + It is preferably a polyimine resin having a structural unit represented by the following general formula (Η).

q, d do not 〇 to the value of 4. A very different low-grade base; the above four-valent base. Further, in the formula (1)r; it is preferred that the following formula (h) is directly bonded to the one shown in (1). X means S02, CO, 〇 or [6]

(b) ω The unit 妗m丄 structural unit shown in the above general formula (II). ° ' is preferably as shown in the following formula (III) [Chem. 7]

317192 12 1344804 The structural unit represented by the general formula (Π) or (III) may contain 50 mol% or more of the total polyamidene structural unit of the low thermal expansion polyimide resin. The metal foil used in the present invention includes copper foil, stainless steel foil, alloy foil, and the like. • The term “alloy alloy” refers to a metal foil that contains a copper box and contains at least a metal box of at least the weight of the elements such as lanthanum, lanthanum, lanthanum, and the like, and has a copper content of 90% or more. When a metal foil is used, surface treatment may be performed by galvanizing, nickel plating, orthopedic coupling agent or the like. As the metal wiring is ultra-fine pitched, it is preferable to use a thinner metal. From this point of view, it is preferable that the metal junction has a thickness of 5 to 35 μm, particularly preferably 8 to 8 "m. Further, it is preferable that the metal falling layer used has a surface roughness (Rz) of 〇 6 to 〇 ( #(7) in the adjoining surface with the polyimide resin. When the surface roughness (Rz) is lower than 〇.6//m, the adhesion between the metal falling layer and the polyimide layer of the polyimide resin layer cannot be maintained, and conversely, when the above case, the transparency of the polyimide film is lowered. It will hinder the semiconductor component and mount it. Further, by setting the surface roughness (Rz) of the metal junction: the above range Θ ', the metal component which occurs during the circuit processing can be reduced in the case of the polyimine resin layer. As described above, the metal foil having the surface roughness (10) in the above range 颇 is quite suitable for the ultrafine pitch of the metal wiring. The flexible laminate of the present invention is a multilayer structure composed of an insulating resin layer formed of a plurality of layers of polyimide resin, and is set to at least one layer of the polyimide resin layer adjacent to the metal drop. The above-mentioned high elastic resin layer of a specific thickness range can form a laminate which can withstand high temperature and high dust installation conditions. Among them, by setting the thickness of the metal junction and the surface roughness (4) to the above range, it is particularly suitable for high-density mounting applications. Sigh 3) 7192 i3448°4. The flexible laminated board of the present invention is a multilayer structure composed of an insulating resin layer formed of a plurality of layers of polyimide resin, and the best layer structure can be exemplified as follows. ) to the layer structure shown in 5). Among them, lanthanide metal foil, η-based high-elastic "genic yoke imine resin, L-based low thermal expansion poly aniline resin, ρ system meets the storage elastic modulus or linear expansion coefficient of Η or L Wake up the imine resin. 1) M/H/L, 2) M/H/L/H/M, 3) M/H/L/H, 4) M/H/L/P/M, 5) M/H/L/ P, # Moreover, the ratio of the thickness of H in the insulating resin layer is from 3 to 45%, preferably from 5 to 20%. When the other polyimide resin p is provided for controlling warpage after etching of the metal foil, it is preferable to use a resin having a physical property similar to that of yttrium, in particular, a difference in linear expansion coefficient with H is 1 〇χ 10 Those who are within /K are better. In order to form a removable laminate having metal mooring on both sides of the insulating resin layer, it is advantageous to apply a method of heating and crimping the metal foil, so in this case, adjacent to L and concatenated _ The layer of the polyimide resin P' is preferably a thermoplastic resin having a linear expansion coefficient of 3〇χ1 (Γ6/κ or more. ^ Next, although the method for producing the flexible laminate of the present invention is described, The same contents in the flexible laminated board have been described and succinctly explained. ^ The replaceable laminated board of the present invention is applied on a metal jurisdiction, and the coated polyimide II squirrel Vi 曰 经The thermal cracking treatment can form a laminate in which a layer of a polyimide resin layer is laminated on a gold plate. On the metal junction (the coated polyimide precursor resin is preferably in a solution state, It is usually coated in the state of 'Solution' in the 'Apparel Cold'. The polyurethane-precursor resin; 14 317192 8! 1344804 . The metal surface of the cloth is 'surface roughness (RZ) is best in 〇ι .6 to 】. 〇 _ _ _ 巳 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Polyurethane precursor resin coated directly on the shoulder sill, after hardening at 35 〇. The storage and storage modulus is H08 to 2xl〇9Pa, and the glass transition temperature is 3〇〇 to 4〇〇• 2 The south elastic resin layer is obtained by directly coating the precursor resin 3 constituting the high elastic resin layer on the metal mesh to obtain the adhesive strength of the metal/polyimine resin. The coating method is not particularly limited. As a limitation, a well-known method such as a bar coating method, a gravure coating method, a light coating method, a die coating method, etc. may be appropriately selected. The polyimine precursor resin layer coated by the main metal foil is When the solvent is contained, it is dried to an appropriate range. The drying temperature at this time is preferably carried out at a temperature at which the polyimide phase of the polyimide precursor resin layer is not subjected to the hydrazine imidization reaction, preferably at 15 〇c. In the following, especially from 11 〇 to 14 〇. The range of 匸 is preferred. The amount of cleavage in the resin layer of the dried yttrium imide precursor is preferably used to form a resin corresponding to the polyimide precursor. 50 parts by weight or less of the weight part φ. The flexible laminate of the present invention In addition to the (IV) imide resin layer of the above-mentioned highly elastic resin layer, it has a low expansion coefficient of 2〇xHT6/K or less...the expanded i-resin layer of the expanded resin layer I. The low #expandable resin layer is the most The polyimine precursor resin layer constituting the highly elastic resin layer formed as described above is formed by coating in a precursor state. The precursor resin of the low-expansion resin is preferably also a solution. In the case of coating in a state where it is applied in a state containing a solvent, it is preferable to carry out drying as described above. 317192 15 1344804 Applying a layer of a highly elastically expandable resin layer successively to each other in the genus > Carrying the day /, low heat shot, 丨 心 ' ' ' After drying, in order to control the distortion of the metal poetry after the engraving, 丨杳: Xiong Ye Shao... pot t or better set up a layer of polyimine precursor Resin layer. Wherein, the layer of the ##,, Ώ layer is preferably similar to the above-mentioned high elastic resin layer, in particular, the difference between the high elastic resin layer and the linear expansion coefficient is I 〇 X 1 〇 -6 / κ LV is free of soil * The inside is made of yt. In order to form a flexible laminate which has a metal-based technique on both sides of the insulating resin layer and a rabbit edge, the method of heating and crimping the metal is performed. It will be advantageous, so in this case: The (iv) imine layer laminated on the low heat-expandable resin layer is preferably a thermoplastic (tetra) imine (4) having a linear expansion coefficient of 3 〇χ 1 ()·6/Κ or more. The polyimine resin layer arbitrarily provided in the flexible laminate of the present invention can also be formed by coating and drying the same as the method for forming the two polyimide layers. As described above, if it is on a metal foil 2 or more of the polyimine precursor resin layer is subjected to coating 'drying, and then the plurality of layers of the polyimine precursor resin layer on the metal foil are heat-treated and heat-hardened. Hardened room to implement, in this case, from 〖5 (near rc) The stage temperature rises, and finally heats up to 25 〇 or more, preferably up to 3 〇〇 ° C and yttrium. If the maximum heating / JDL of the heat applied for hydrazine imidization exceeds two, 'resin fear It will decompose, so it is best not to heat it to a temperature 20 ° C lower than the decomposition start temperature. In addition, this heat treatment may be followed by the same apparatus after the above drying step. By this step, the polyimine precursor The resin can be substantially imidized. On the finished imidized resin layer, 'the necessary metal layer is laminated. The layering method is to heat the predetermined metal foil under stamping or roller, and add 317192 1344804. The method of applying is relatively simple, and the heating temperature is preferably above the glass transition temperature of the polyamidide resin layer adjacent to the accumulated metal layer. Further, the metal layer deposited here may be as described above. In the case where the metal layer is deposited by heating or pressure treatment, in order to maintain the adhesion with the polyimide, it is advantageous that Rz is greater than 1. 〇 # m. (Effect of the invention) The metal layer of the present invention adjacent Polyimine resin, because of the high Tg that can not be achieved by the adhesive polyimide resin up to now, and the high storage elastic modulus at 350 ° C, will maintain high dot-to-metal Therefore, since the flexible laminated board of the present invention is excellent in heat resistance characteristics of the insulating resin layer, it is suitable for use in high-temperature mounting of semiconductor elements, and COF (film over-filming) (Chip 0n F )) used is flexible. Further, the flexible laminate sheet of the present invention is composed of a plurality of layers of an insulating resin layer. Not only the polyimide resin of the insulating resin layer has high thermal characteristics, but also has a curved portion of a mobile phone or the like. Because of its high flexibility, it can be used in small electronic devices such as mobile phones, and it is an invention with industrial price. [Embodiment] Hereinafter, an embodiment of the present invention will be described. Further, each of the film properties was measured by the following method. 1) Glass transition temperature (Tg), high temperature region (350. Storage elastic modulus of ') is obtained by using polypyridinium precursor resin of each synthesis example> Polycrystalline film made by Pheonietric Scientific Co., Ltd. The dynamic viscoelasticity measuring device measures the dynamic viscoelasticity at a temperature rise of 5 (: /mi, and obtains the Tg (maximum tail of tail 17 317192 8) and the storage elastic modulus of 350T:) The number system knows that the TMA (10) type thermomechanical analysis made by Seiko Industrial Co., Ltd. 'slows the temperature at 20 ΐ /min' 51 / _ cooling rate, - the dimensional change from 100 ΐ to 24 未 when no cooling is taken. ' 3) The adhesion between the steel knots was determined by using a Toograph made by Toyo Seiki under the ΐ / dish, with a weight of 2 kg and a chuck speed of 5 〇 mm/min, and stretching the copper collar in the direction of (10) degrees. The evaluation criteria are based on adhesions as assessed below. 〇: adhesion force 0.8kN/m or more △. adhesion force 0'5kN/m or more, lower than 〇8kN/m X: adhesion less than 0.5kN/m 4) surface roughness (rz) of metal tungsten is based on JIS B 〇 65 I was measured using a high-sensitivity surface spreader (p_15, manufactured by KLA_Tencor Co., Ltd.) under the conditions of a measurement speed of 0.02 mm/sec and a radius of curvature of 2 μm. 5) The soldering heat of the flexible laminate is immersed in a solder bath of a predetermined temperature for 10 seconds, and the highest temperature is regarded as the solder heat-resistant temperature at a temperature at which metal box peeling or resin expansion does not occur. Description of the code in the embodiment. DMAc : Ν,:Ν'-dimethylacetamide PMDA: pyromellitic acid two-needle BPDA: 3,3',4,4,biphenyltetracarboxylic dianhydride DSDA: diphenylsulfonyl-3, 4,3·,4'-tetracarboxylic acid dianhydride BTDA: benzophenone-3,4,3,,4'·tetracarboxylic dianhydride ΒΑΡΡ : 2,2-bis[4-(4-amino group Phenoxy)phenyl]propane 3)7)92 1344804 BAPB: 4,4'-bis(4-aminophenoxy)biphenylbutene PE-Q: 1,4-bis(4-amino phenyl) Base) stupid TPE_H'· 1,3_bis(4.aminophenoxy) stupid-m-TB: 2,2'-dimercapto-4,4'-diaminobiphenyl synthesis example to 3 BAPP and BAPB were supplied to DMAc and dissolved, and then PMDA was supplied, and at room temperature (d) for about 3 hours, a polyimine precursor resin solution composed of the components of the composition was prepared. Further, in all the synthesis examples, the ratio of the tetracarboxylic dianhydride component to the diamine component was set to be about 100 mol% stoichiometric. Further, the number of columns of the resin raw material composition in Table i means the molar ratio. The obtained polyimine precursor resin solution is coated on a copper foil, and the surface of the ruthenium resin layer is dried to a point of no suffocation at /jnL of 14 0 C or less, and then at 50 to 360 In the temperature range of °C, the temperature is heated in several stages, and the polyimide is imidized to form a polytheneimine film of thickness 25#m. The film is deposited at 35〇〇c. Elastic modulus, glass transition temperature (Tg), and coefficient of linear expansion. The results are shown in Table 1. Synthesis Examples 4 and 5 BAPP and ΤΡΕ-Q were supplied to DMAc and dissolved, and then PMDA was supplied, and stirred at room temperature for about 3 hours to prepare a polyimine precursor composed of the components shown in the table. Resin solution. This polyimide precursor resin solution was treated in the same manner as in Synthesis Example 1 to form a polyimide film, and its physical properties were evaluated. The results are shown in the table. 317) 92 19 1344804 Synthesis Example 6, 7 BAPP and TPE-R were supplied to DMAc and dissolved, and then PMDA was stirred for about 3 hours at room temperature to prepare a composition of the composition. Imine precursor resin solution. This polyamidene precursor resin solution was treated in the same manner as in the synthesis example, and a polyimide film was evaluated and its physical properties were evaluated. The results are shown in the table. ^ Synthesis Example 8

BAPP was supplied to the DMAc towel and dissolved, and then PMDA and DSDA were sequentially supplied, and stirred at room temperature for about 3 hours to prepare a polyimine precursor resin solution composed of the components shown in the table. The rhodium imine precursor resin solution was subjected to the same method as in the synthesis example to form a polyimide II film, and its physical properties were evaluated. The results are shown in Synthesis Example 9' shown in Table 1, BAPF was supplied to DMAc and dissolved, and then PMDA and BTDA were sequentially supplied, and the mixture was stirred at room temperature for about 3 hours to prepare the composition shown in ##. A polyimine precursor resin solution is formed. This polyimine precursor resin solution was treated in the same manner as in the synthesis example to form a polyimide film, and its physical properties were evaluated. The results are shown in Table 1. Synthesis Example 10 ''

The BAPF is supplied to the DMAc and dissolved, and then the supply of the A is stirred at room temperature for about 3 hours to prepare the polyamine which is composed of the components shown in the table. This (iv) imine precursor resin solution is based on synthesis! The same method was carried out to form a polyimide film, and the physical properties were evaluated. The results are shown in the table. 317192 20 1344804 Liquid. This polyimine precursor resin solution was treated in the same manner as in Synthesis Example 1 to form a polyimide film having a linear expansion coefficient of 2.5 ppm. (Example 1) On a copper junction having a thickness of 12 " m and a surface roughness RZ of 0.7 #m, the polyimine precursor resin solution prepared in Synthesis Example 1 was cured to a thickness of 6 m from m. The method is applied and is below 4 〇. Dry at 5 minutes in the temperature of the crucible. Herein, the poly-imine precursor resin solution prepared in Synthesis Example 12 was subjected to a thickness of 29 m after hardening, and dried at a temperature lower than norne for 15 minutes. Further, the small sub-private/resin resin solution adjusted in Synthesis Example 1 was coated on the polyimine precursor resin layer of the second layer, and the thickness after hardening was 6 #(1), and Drying at a temperature lower than 14 〇t: for 5 minutes, in a temperature range of 150 to 36 (the temperature range of rc is separated, and the temperature is heated for 15 minutes in a stepwise manner to obtain a steel strength on one side of the insulating resin layer. ;= > Slabs. ^ The copper foil of the obtained flexible laminate is etched to process the specified circuit. For this flexible laminate, the adhesion to copper (4) is evaluated, and the solder heat resistance is evaluated. The results show that the adhesion between the copper and the copper is 8 kN/m or more, and the evaluation results of the solder heat resistance temperature of 4 〇〇ΐ or more are shown in Table 2. In the example I, The type of the polyimine precursor resin layer forming the high elastic tree layer of the first layer and the third layer was changed to 曰317192 22 1344804 in Synthesis Examples 2 to 7. For the adhesion between the flexible foils Sex, welding

The obtained resin layer' was made into a highly elastic resin layer of a pliable laminated ply, and evaluated for heat resistance to steel tin. The evaluation results are shown in Table 2. Comparative Examples 1 to 4 In Example 1, the polyimine precursor resin forming the first layer and the layer was layered and changed to: ? The resin layer obtained in the early blush was made flexible to: 1 The laminated layer was used as the evaluation surface of the resin, and the soldering heat resistance was improved. The evaluation results are as shown in Table 2 (Table 2) τ The first and third layers of polyimine precursor resin layer type ^------ Adhesive bright tin between copper foil and hot temperature (0) Example I Synthesis Example I '---〇$400 Example 2 Synthesis Example 2^-____ 〇$400 Example 3 Synthesis Example 3 —--- 〇^400 Example 4 Synthesis Example 4 ~__ 〇$400 Implementation Example 5 Synthesis Example 5 -~~~~-_ 〇2400 Example 6 Synthesis Example 6 --- 〇 ^ 400 Example 7 Synthesis Example 7 ---~~~- 〇^400 Comparative Example 1 Synthesis Example 8 '-______ 〇 370 Comparative Example 2 Synthesis Example 9 - H △ 360 Comparative Example 3 Synthesis Example 0 to ~~~ 〇390 Comparative Example <4 Synthesis Example Π ^400 317192 23

Claims (1)

Patent Application No. 094,122,032, March 19, 2011, Amendment and Replacement Page 10, Patent Application Range: -- L A flexible laminated board having a metal crucible on one or both sides of an insulating resin layer a flexible laminate; characterized in that the 'insulating resin layer is composed of a plurality of layers of polyimide resin, wherein at least one layer of the polyimide resin adjacent to the metal foil is stored at 35 〇t The resin layer having a modulus of IxlO8 to 2xl09Pa and a glass transition temperature of 325 to 38 Å<t is formed; and at least one layer of the resin layer other than the high elastic resin layer has a coefficient of linear expansion of 2 〇χ 1 〇 A low thermal expansion resin layer of 6/κ or less, and a high elastic resin layer thickness ratio of the insulating resin layer is in the range of 3 to 45%. 2. The flexible laminate according to the first aspect of the invention, wherein the polyimine resin constituting the elastic resin layer adjacent to the metal foil is made of succinic acid dianhydride and diamine. Derived, and the diamine is used in an amount of 5 to 80 mol% selected from 2,2·bis[4-(4-aminophenoxy)phenyl]propane, 1,4-bis(4-amino group) A quinone-based benzene, a bis-aminophenoxy)benzene, and at least a quinone diamine of 4,4'-bis(4-aminophenoxy)biphenyl. 3. The flexible laminate according to claim 2 or 2, wherein the surface roughness (Rz') of the surface of the metal tantalum adjacent to the polyimide layer is in the range of 0.6 to 1.0 μm. The method for producing a flexible laminate is composed of at least one gold foil at least two layers of polyimide resin, and is characterized by the following steps: 1) on the surface roughness (called 〇.6 to i The surface of the metal box in the center of the core is coated to form a highly elastic resin layer. (IV) The yttrium imide precursor tree 317192 (Revised) 24 Ϊ 144804 A March, March, 2013 曰 Correction of the step of replacing the I grease The elastic resin layer has a range of lxlO8 to 2xl〇9pa, a glass transition temperature of 325 to 3 ribs; /2) on the polyimine precursor resin layer, the coating has a linear expansion coefficient of 2〇χ1〇-6 /Κ a low heat-expandable resin layer under the step of argon-polyimide precursor resin; 3) A step of performing a heat hardening treatment in a state in which a plurality of layers of the polyimide intermediate resin layer are provided on the metal. 317192 (amendment) 25