TW200806100A - Double side conductor laminates and its manufacture - Google Patents

Abstract

Disclosed are a flexible double-sided conductor laminate in which a conductor is provided on both surfaces of a polyimide layer without being connected to a thermoplastic polyimide layer, and a method of manufacturing the same.

Description

200806100 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a flexible double-sided conductor laminate and a method of manufacturing the same, wherein a conductor on a double surface of a polyamic acid layer has a conductor Not attached to the thermoplastic polyimide layer. [Prior Art]

Recently, the related industries have continuously developed mobile phones, PDAs, and the like, as well as the latest electronic devices such as video recording. The demand for electronic circuits such as Wei Wei, thin and t = compliant is also increasing. In order to cope with such a situation, electronic parts of double-sided/single-sided circuit boards or multi-layer circuit boards which are difficult to self-flexible circuit boards have also been developed in the market. "The previous flexible circuit board is a flexible substrate that adheres the copper case to the surface of the heat-resistant film using an epoxy adhesive, but it has low heat resistance and is volatile due to the use of the adhesive. The problem is that it is difficult to form a fine circuit and it is difficult to reduce the thickness of the integrated circuit caused by the components. In order to solve the problem of the three-layer flexible circuit board, a double-layer type without using an adhesive has been developed and used. Flexible circuit board, which uses a deposition process to deposit copper on a polytheneamine film, laminates a copper box onto a thermoplastic polyimide film, or uses a process (casting) The poly-mineral amine precursor is washed on the copper tank layer and then produced by aramidization, etc. The first technique requires high cost, especially for the high-priced equipment. However, the press-bonding process requires an additional expensive plasticized polyamic acid amine film, so the manufacturing cost is higher than that of the casting method. Therefore, even though the 5 200806100 casting method has the disadvantages of complicated process, the production cost is relatively low. So In the past, a double-layer flexible circuit board is mainly used for the production of a two-layer flexible circuit board. Specifically, a flexible circuit board coated with a double-sided copper foil can be manufactured by the method described in U.S. Patent No. 5,112,694. The method comprises: washing and casting a single layer of thermoplastic polyiminamide on one side of the first steel layer, drying it, and then performing an iminelation reaction, and then using the single side of the second copper layer with the poly-bristamine The layer is pressed at a high temperature/high pressure; or it is produced by a method as described in WO2004-085146, which comprises: sequentially casting a first layer of heat-sensitive polyamic acid layer (3), low thermal expansion a polyimide layer (2,) and a second thermoplastic polyimide layer (3) are dried on one side of the first copper layer (1), followed by a mercaptoamination reaction, and The surface of the second thermoplastic polyimide layer (3,) is pressed against the second copper layer (1,) at a high temperature/high pressure to achieve the structure as shown in the fourth figure. However, the above method must allow the thermoplasticity. The polyimide layer (3, 3,) 15 is attached to the surface of the conductor, so it has a low coefficient of thermal expansion (about 18 ppmA:). The interface between the surface of the body and the thermoplastic polyimide layer having a relatively high coefficient of thermal expansion causes interfacial stress, which inevitably reduces dimensional stability. In addition, the thermoplastic resin exhibits relatively high moisture absorption. Sexuality will eventually lead to the adverse effects of electronic components on the signal and the gradual decrease in adhesion between the two components. If there is a combination of thermoplasticity, low thermal expansion, and low hygroscopicity. The methylene chloride resin can easily solve the above problems, but in fact it is difficult to overcome. In addition, in the above method, the first copper layer and the second copper layer are connected to the polyaluminum by using a casting process and a pressing process, respectively. The amine resin layer will have different physical properties due to the different methods used in 6 200806100. Generally, when the temperature of each metal exceeds its intrinsic recrystallization temperature, small crystals of glutinous rice size will recrystallize, while the treatment temperature is Time is the key factor in determining the ultimate physicality. However, the casting process needs to be processed at a temperature of 5 degrees higher than the recrystallization temperature for several tens of minutes, and the pressing process requires only a few minutes or less of processing time, so that the double-sided copper layer cannot have the same physical properties. . Therefore, the use of a flexible double-sided conductor laminate is problematic because the user needs to carefully distinguish the surface having high peel strength and low peel strength, and to manufacture a fine circuit having a circuit width of 100 μm or less. A series of process conditions, that is, one or more conditions that alternate between dry film photoresist (DFR) press, exposure, development, etching, and stripping processes; or in dry film photoresist, UV One or more materials between the light source, the developer, the etching solution, and the stripping solution require problems for different applications. Further, when a fine circuit is formed under the same conditions, the possibility of causing a defect such as circuit delamination is also increased, and the formation of a high integrated circuit is limited due to a change in realizing a small-sized circuit width. . SUMMARY OF THE INVENTION To this end, an embodiment of the present invention provides a flexible double-sided 20-conductor laminate having a conductor on both sides of a polyimide layer, and the guide is not high-suction Moisture and high thermal expansion of thermoplastic polytheneamine linkages, thus preventing interfacial stress and electrons between the conductor and the thermoplastic polyamidoamine, adverse effects of the signal transmission, and adhesion to the conductor $ Reduce the problem and achieve improved dimensional stability. 7 200806100 Meanwhile, another embodiment of the present invention provides a method of manufacturing a double-sided conductor laminate. Another embodiment of the present invention provides a flexible double-sided conductor laminate having a conductor on both sides of a polyimide layer, thus between a surface of a resin and a conductor, and a resin The difference in peel strength between a surface and a conductor is adjusted to a predetermined standard, thereby effectively simplifying the process and improving productivity and integration. Another embodiment of the present invention provides a press process that allows the conductors to have the same physical properties. According to an embodiment of the present invention, a detachable double-sided conductor laminate provided by the present invention comprises a first conductor; a polyimide layer connected to the first conductor; at least one layer An adhesive resin-containing layer; a second polyamidamine resin layer connected to the second conductor; and a second conductor, wherein the first conductor and the second conductor may be identical to each other or different from each other;醢, the resin and the second polyamidamine resin may be identical to each other or the same; the coefficient of thermal expansion of the first polyimide layer and the thermal expansion coefficient of the first conductor may be the same or different from each other; The coefficient of thermal expansion of the second poly-Asia = and the contact expansion of the second conductor may be different from each other. According to another embodiment of the present invention, the extractable tapered conductor layer plate provided by the present invention comprises a first conductor; and is connected to the first: -1 = amidoxime tree m - a heterogeneous hard-to-comprise layer: a second polyamidole resin layer of the conductor; and a second conductor, wherein: the conductor and the first conductor may be identical to each other or different from each other; the first poly-branched 8 200806100 々村月曰弟弟-laic acid The amine resins may be identical to each other or different from each other; the thermal expansion coefficient of the first polyamide resin layer and the thermal expansion f of the first conductor may be the same or different from each other; the thermal expansion of the second polyimide resin layer The coefficients and the thermal expansion coefficients of the first conductor may be the same as each other or the same as each other; the peeling strength between the first conductor and the first polyamido resin layer is between the interlayer of the second polyimide and the second polyimide The peel strength is doubled to 1.6 times. According to the flexible double-sided conductor laminate according to the embodiment of the present invention, the first conductive rainbow may comprise a first polyimide resin layer and is connected to the first poly 10 melamine resin layer by casting. The adhesive resin comprises a layer; the second conductor may comprise a second poly-gi gi amine resin layer, and is attached to the second poly-styliamine resin layer by an elution method; the adhesive resin-containing layer; and the adhesion of the first conductor The resin-containing layer and the adhesive resin-containing layer of the first conductor are connected to each other through a press-bonding process. The flexible double-sided conductor laminate according to the embodiment of the invention, wherein the first conductor and the second conductor are connectable under the heat treatment condition of (4). The flexible double-sided conductor laminate according to the embodiment of the present invention, wherein the polyamidamide resin is a resin having a melamine ring structure, and is selected from the group consisting of polyetherimide and polyamidamine. Amine (4) Jiafu-Qing and Poly 20 poly 醯 醯 胺 amine (polyesterimide). - a flexible double-sided conductor laminate according to an embodiment of the present invention, wherein the first conductor and the poly-polyimino acid resin layer, or the second conductor and the second polyamic acid amine resin layer Poor, may be 1 Gppm / (> c or less. According to the embodiment of the invention, the detachable double-sided conductor layer board, wherein, 9 200806100 first polyamine resin layer or second take-up is contained in Between the aromatic rings, there is a layer of ~-most amide amine resin, which may contain a kind of _S02-, -C〇_〇_, _CJJ2,: 0-C0...-NHCO-, -S-, a monomer, and a ring in the aromatic ring. <CH3) 2-chain dianhydride and diamine soft 5 -s-, -scv, -c〇-〇...CH does not have ... C0 ... Li CO-, hard monomer, in its Mobi ratio 2 _C (CH3) 2 _ chain of dianhydride and diamine combined polyimide resin. For example, the ratio of the ratio of 10 to 8 to 2, the polydiamine-waking amine resin layer may comprise a layer of a sulfonamide resin or a first substance. Mixing of three or more kinds of polyamidamine resins 0 According to the embodiment of the present invention, the composition and thickness of the first phthalic acid amine resin layer and the second double-sided conductor layer plate. The 1 melamine resin layer may have the flexible double-sided conductor laminate of the same embodiment, wherein the first polyimide resin layer 哎篦 _ , 15

It is 1% or lower. The second-polyimine resin layer, the hygroscopicity of which can be described in the flexible double-sided conductor laminate according to the embodiment, wherein the layer may comprise a layer or a plurality of layers. The adhesive resin is composed of a thermoplastic resin polyacetal resin, an oxygen resin, and a phenol resin having a temperature of 12 G ° C to 35 G C after the sub-chemical reaction. Further, the thermoplastic polyamidamide resin may be used in combination with -0-, (:0-, -NHCO-, each, -SOy, C〇_〇_, _ch2-, -c between the aromatic rings. (ch3) Thermoplastic polyimide obtained by polymerization of 2-chain dianhydride and diamine soft monomer. Further, the thermoplastic polyimide resin may have a glass transition temperature of 120 QC to 350. Thermoplasticity 20 200806100 Mixture of polyimine resin. Meanwhile, thermoplastic polytheneamine may contain a kind of 〇_, _C〇_, ΝΗα)·, S_, _s〇2_, _c〇 between the aromatic rings.软, -C(CH3)2·chain dianhydride and diamine soft monomer, and in the aromatic ring = 5 does not have -〇-, -CO-, -NHCO-, 1, -S02-, a CO Poly-anthracene obtained by polymerizing a -0-, CH-C(CH3)2-chain dianhydride and a diamine hard monomer under the conditions of a molar ratio range of 2 to 10 to 2 to 8. Amine resin. The flexible double-sided conductor laminate according to the embodiment of the invention, wherein the thickness of the first polyimide layer and the second polyimide resin layer is sufficient to satisfy Equation 1 below. . Equation 1 [〇.8 X (Ε2 X Τ2)] <[Ε1 X Τ1] <[ι·2 X (Ε2 X Τ2)] wherein, El means the coefficient of thermal expansion of the first polyamidene resin layer (ppm/°C); 15 E2 means the enthalpy of the bismuth dimerization resin layer Silk (4) (5) ~); T1 means the thickness of the first polyamidene resin layer to melon; T2 means the thickness of the second polyamidamine resin layer. According to the flexible double-sided conductor laminate according to the embodiment of the invention, the thickness of the adhesive resin-containing layer, the first-polyamine-based resin layer and the first-water-imide resin layer can satisfy the following. Equation 2 ^ (ΤΙ + Τ 2)] <Τ3 <[3·〇 x(丁! + 丁2)], and 〇 5 <T3 m ^ means the thickness of the first-polyamine resin layer ((iv); 糸 refers to the thickness of the second polyamidene resin layer (μηι); 20 200806100 butyl 3 refers to the thickness of the layer containing the transition ((4) The flexible double-sided conductor laminate according to the first embodiment, wherein: two: two and two, steel, gold, silver, nickel, zinc, iron, alloy of the genus (10) i, or the foregoing metal Oxide. Another Example of Conductor II J3 - The present invention provides a method for producing a flexible double-sided surface, including: in the first-poly-film--the first resin-containing layer, and at a high temperature / The high-pressure atmosphere will be used to form a layer of a double-sided conductor layer according to the embodiment of the present invention. The conductor is deposited on the other side of the first polyimide film and the second polyimide film. 15 20. According to a preferred embodiment of the present invention, the present invention provides a flexible double-sided, bulk layer manufacturing The method comprises the steps of: coating the first-polyimine i-amine or its precursor on the surface of the first conductor, and then sticking the money Applying a resin thereon, and then performing a mercaptochemical reaction under a high temperature atmosphere to prepare a first layer comprising a first conductor, a first polysorbent resin layer and an adhesive layer; Further, a second polyamidamine resin or a precursor thereof is coated on one surface of the second conductor, followed by drying, and then an adhesive resin is applied thereon, followed by drying, and imidization in a high temperature atmosphere. Reacting to separately prepare a second layer comprising a second conductor, a second polyimide resin layer and an adhesive resin-containing layer; and pressing the first layer and the second layer at a high temperature and a high pressure The adhesive resin-containing layer of the first layer is bonded to the adhesive resin-containing layer of the second layer. A flexible double-sided 12 200806100 conductor laminate provided by the above preferred embodiment of the present invention In the manufacturing method, a layer of the resin may be added to the layer, and then the layer is dried, to prepare a third resin layer, and the first layer and the second layer are plated so that the pressure layer and the high pressure layer can be pressed against each other. Facing the joint step = brother #脂层和转性树脂包雔In another preferred embodiment, the present invention provides a method for producing a flexible and slab-like laminate comprising: coating a poly-poly resin or a precursor thereof: after: two bodies = cloth thereon And then drying, and preparing a first layer comprising a first conductor, a poly-myramine tree layer and a third resin layer in a high temperature atmosphere; in addition, one of the second conductors 15 20 = coating The dimeric amine listens or rides on the fabric, the money is dried, and then the four-component resin is coated thereon, and then dried, and subjected to a sub-aminated reaction under a high temperature atmosphere to separately prepare the second conductor. a second polyacrylic resin layer and an adhesive resin comprising a second layer of the layer; and pressing the first layer and the second layer at a high temperature and a high pressure to make the third layer of the first layer The layers of the adhesive resin layer of the layer and the other layer are joined to each other. A method of manufacturing a flexible double-sided conductor laminate according to an embodiment of the present invention, wherein the high temperature is equal to or higher than a glass transition temperature of the adhesive resin-containing layer, and the pressure range of the high pressure is i to 200 kgf/cm 2 Or for work up to 200 kgf/cm 〇 In the prior art, since the thermoplastic polytheneamine must be connected to the conductor, the advantages of the thermosetting polyamidamide cannot be fully utilized, and the disadvantages of the thermoplastic polytheneamine such as hygroscopicity High, low heat resistance and high thermal expansion are all obvious. 200806100 is very obvious. However, the flexible double-sided conductor laminate 2 provided by the present invention can avoid the above problems and improve the reliability, heat resistance and moisture absorption of electronic components. v In addition, in the case where the peeling strength between the conductor on both sides of the laminate and the resin is equal to each other, when the flexible double-sided conductor laminate is applied, the laminate can be solved in the same two processes. The problem caused by the difference in peel strength between the conductor and the resin, that is, the process conditions for fabricating a fine circuit board, such as dry film photoresist bonding, exposure 'development, etching, and stripping processes One or more conditions that alternate between them; or one or more materials between dry film photoresist, ίο UV source, developer, etchant, stripper, etc., for different applications, and under the same conditions When a fine circuit is formed, the possibility of causing a defect such as circuit delamination is also increased, and the formation of a high integrated circuit is limited due to a change in the width of a small-sized circuit. 15 [Simple description of the drawings] The figure is a cross-sectional view of the consistent embodiment of the present invention, showing a releasable double-sided conductor laminate. 2 is a cross-sectional view showing a second embodiment of the present invention, showing a double-sided conductor laminate. The second drawing is a cross-sectional view showing a flexible double-sided conductor laminate according to a third embodiment of the present invention. ' ^ The fourth figure is a scraped view of a flexible double-sided conductor laminate. The fifth drawing is an enlarged photograph of a circuit board made of the flexible composite double-sided conductor laminate of Example 1 made of 200806100. The sixth drawing is an enlarged photograph of a circuit board obtained by using the flexible double-sided conductor laminate of Comparative Example 3. ' 5 [main component symbol f tiger description] '1 first copper layer 1, second copper layer 2' low thermal expansion polyimine layer • 3 first thermoplastic polyimide layer 3' second thermoplastic poly The melamine layer 10 Η the first conductor 11, the second conductor 12, the first polyimide resin layer 12, the second polyimide resin layer 13, 13, the thermoplastic polyimide resin layer (adhesive resin) (20) The third resin layer 曰 15 [Embodiment] φ The detailed description of the present invention is as follows: The structure of the flexible double-sided conductor laminate of the present invention is as shown in the first to third figures. In the structure of the first figure, the first conductor (11), the first polyimide resin layer (12), the thermoplastic polyimide resin layer (13, 13,), and the second 20 polythene are laminated. The amine resin layer (12,) and the second conductor (11,); in the structure of the second figure, the first conductor (11), the first polyimide resin layer (12), and the third resin layer ( 20) a thermoplastic polyiminamide resin layer (13,), a second polyamidamine resin layer (12') and a second conductor (1); and in the structure of the third figure, the first conductor is laminated (11), first polyamidamine resin layer (12), thermoplastic polyimide 15 200806100 resin layer (13), third resin layer (20), thermoplastic polyimide resin layer (13') a second polyamidamine resin layer (12,) and a second conductor (11,). The structures shown in the first to third drawings are for showing the flexible double-sided conductor laminate of the present invention, but the present invention is not limited thereto. 5 In the first to third figures, in addition to the first conductor, the second conductor, the first polyamidosin resin layer and the second polyamidamide resin layer, the thermoplastic polyacrylamide resin layer is separately provided, Or a combination of a thermoplastic polyacrylamide resin layer and a third resin layer is defined as "a thermoplastic polyimide-containing resin-containing layer comprising at least one layer of a thermoplastic polyimide resin layer". Specifically, in the present invention, the thermoplastic polyimide resin layer may be replaced by a layer of an adhesive resin, that is, an epoxy resin or a phenol resin, and the definition is "at least one layer of an adhesive resin-containing layer". The flexible double-sided conductor laminate of the present invention, wherein the polyamidene resin is a general resin having a sulfonium ring structure, comprising: a polyether sulfonamide, a 15 polyamidimide, and a polyester amide. Amidoxime and the like. In the present invention, conventional or novel polyamidamide resins can be used as long as the technical framework of the present invention can be achieved. For example, in U.S. Patent Nos. 6,184,333, 5,773,509, 4,847,349, and 3,847,867, and Japan’s unexamined public notices Showa 63.84, ΐ88 and 2nd Korea, Republic of Korea, No. 5 Polyalkylamine resin disclosed in -2004_0084029. Road = first conductor (11) and the second conductor (11,), and the first polyimide resin layer (12) and the second polyimide resin layer (12) adjacent thereto ) 'The coefficients of thermal expansion are the same or different from each other. Specifically, it is preferable that 16 200806100 has a difference in thermal expansion coefficient of 10 ppm/QC or less. For example, if the copper and smelting layer having a thermal expansion coefficient of 18 ppm/C is a conductor, the thermal acceptance coefficient of the polyimide layer adjacent to the copper platy layer preferably ranges from $ to 28 PPm. /°C. If the difference in thermal expansion coefficient between the conductor and the adjacent polyimide resin layer is greater than 10 ppm/t, the laminate may be severely bent, and it is difficult to avoid the interfacial tension between the conductor and the resin layer, thereby causing dimensional stability. Reduced problems. The above polyamidamide resin may be a thermosetting resin, and its glass transition temperature cannot be measured after the hardening reaction. The above-mentioned thermosetting resin 10 can be obtained by a polymerization reaction from a monomer (hereinafter referred to as "hard monomer") containing a dianhydride and a diamine which are present in a molecular chain without a flexible chain. "Specifically, the so-called rigid single system can be obtained by the presence of -〇_, -CO·, -NHCO, -S-, -S02-, -C0-0- between the aromatic rings in the monomer structure, a chain of 15-CH2·, or -C(CH3)2·, that is, a chain having no flexible chain. For example, the dianhydride includes: 3, 3, 4, 4, _ biphenyl tetra Carboxylic acid dianhydride (3,3'4,4'-biphenyltetracarboxylic acid dianhydride, BPDA), pyromellitic acid dianhydride (PMDA), etc.; and diamines including p-phenylenediamine (p-phenylenediamine, PPDA), m-phenylenediamine (MPDA), etc. In addition, the polyamidene resin may include a monomer capable of achieving a low thermal expansion coefficient and having a flexible chain in its molecular structure (hereinafter referred to as It is a "soft monomer"). Preferably, the molar ratio of the soft monomer to the rigid monomer is from 1 to 8 to 2, more preferably from 5 to 9.5 to 5 to 5. 17 200806100 § When the molar ratio of the monomer to the hard monomer exceeds 8 to 2, the polytheneamine resin containing an excessive amount of soft monomer will lower the glass transition temperature and increase the coefficient of thermal expansion. < Further, the first polyamidamine resin layer and the second polyamidamide resin may be one or more polyamidene resin mixtures. In the example of the polyamidene resin mixture, if the thermal expansion coefficient of the polyimide resin mixture satisfies the above preferred conditions, the thermal expansion coefficient or the glass transition temperature of the respective constituent components is not limited at all. For example, BpDA_ppDA polyamidoamine resin with a coefficient of thermal expansion of 8 ppm/〇c can be used, and BpDA_4,4,-diamine^diphenyl ether with a coefficient of thermal expansion of 32 ppm/QC (4,4) '-diamin〇diphenylether, DDE) Polyamidamine tree 曰 曰 以 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 The melamine resin layer may or may not have the same composition. In addition, the polyamidamide resin contained in the first polyimino acid resin layer and the second polyamidamine resin layer is preferably 1% lower and more hygroscopic. Sex is superior to most common thermoplastic polyalkylene amine resins. In the case of the 兮Ϊ f 明 ' 在 在 在 层叠 层叠 层叠 层叠 层叠 层叠 层叠 层叠 层叠 层叠 层叠 层叠 层叠 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在The tree T/l and the sub-layer are used as an adhesive in the adhesive adhesive layer. I can be used as an alternative heat to form a sticky resin reed of the Wei-Lion layer, which can be used as an adhesive ring.曰18 200806100 In the case where the adhesive resin layer contains a thermoplastic polyimide resin layer, in order to achieve the aforementioned function, the thermoplastic plastic polyimide resin has the best glass transition temperature after the hydralization reaction. It is 35 〇 Qc or lower. In the preferred embodiment, when the glass transition temperature ranges from 120 〇 c to 35 〇〇 c, 5 can prevent the heat resistance of the product from being lowered, and the manufacturing process of the product can also be avoided. Or deformation during the post-treatment process due to heat generated by mechanical friction. Therefore, it is possible to avoid a decrease in production efficiency or an unnecessary increase in manufacturing cost. The thermoplastic polyamido amide resin can be passed through a dianhydride and a diamine. The polymerization is reversed to 10; as for the soft monomer, It contains _〇_, -NHCO-, each, -S02-, -CO-0-, -CH2-, or -C(CH3)2-chain between its aromatic rings. For example, dianhydride includes There are: 4,4,-oxydiphthalic acid dianhydride (ODPA), 3,3,,4,4,-diphenylpyrene and tetrabasic acid (3,3, 4,4'-benzophenonetetracarboxylic acid 15 dianhydride, BTDA), bisphenol A dianhydride (BPADA), 3,3',4,4'·diphenyl sulfone tetracarboxylic dianhydride (3,3' , 4,4,-diphenylsulfbnetetracarboxylic acid dianhydride, DPSDA), ethyleneglycol bis (anhydrous-trimellitate (TMEG), etc.; and diamine including 4,4'· 2〇 Diamine diphenyl ether (DDE), 4,4'-diaminobenzoic acid aniline (4,4'-(^111^1(^6112&11 also (^, 0 into 6 VIII), 1,3-bis(3-aminophenoxy)benzene (1,3-bis(3-aminophenoxy) benzene, APB), 4,4, (1,3-phenylene) Isopropyl)diphenylamine (4,4'-(l,3-phenylenediisopropylidene)dianiline,PDPDA), 2,2- 200806100 bis[-4_(4-amine Phenoxy)phenyl]propane (2,2-bis[_4_(4-aminophenoxy)phenyl] propane, BAPP), bis[4-(3-aminophenoxy)phenyl] hard (bis[4_( 3-aminophenoxy)phenyl]sulfone, BAPSM), 3,3,-diamine 5 diphenyl hard (3,3'-(^11^11〇(^1^11>^111£〇1^,008), etc. In addition, the thermoplastic polytheneamine resin is a technical object capable of achieving a thermoplastic polyamic acid amine resin, and may include a hard monomer having a molecular structure, and a soft monomer and a hard monomer. The ear ratio range is 1 to 2 to 8. In particular, in the preferred embodiment of the invention, a molar ratio of 10 to 0 to 5 to 5 is preferred to achieve the glass transition temperature and purpose of the present invention. Further, the thermoplastic polyamidamide resin may be a mixture of one or more polyamidamide resins. In the case where the thermoplastic polyimide resin layer is a thermoplastic polytheneamine resin mixture, it comprises one or more kinds of trees, and the glass transition temperature thereof satisfies the above after the imidization reaction. Preferably, there is no limitation on the glass transition temperature of the added polyamido resin. For example, a mixture comprising BpDA_pDA poly(decylamine) cannot be measured for its glass transition temperature after amidoximation reaction. Degree, and after the subsynthesis reaction, BPADA/BTDA-DDE polyamidamine resin having a glass transition temperature of 2 〇 232 ° C, the above two resins are mixed at a molar ratio of 5 to 5, It can be used as a thermoplastic polyacrylamide resin. A flexible double-sided conductor laminate of the present invention having a configuration as shown in the first to third embodiments, wherein the thickness of the first polyimide layer (T1) and the second polymer of the second layer The thickness (T2) of the amine resin layer may be the same. If the thickness is different, it needs to be adjusted to satisfy the following Equation 1 to prevent bending of the product. Equation 1 [〇·δ X (Ε2 X Τ2)] <[Ε1 X Τ1] <[1·2 X (Ε2 X Τ2)] 5 wherein E1 is the coefficient of expansion of the first polyamidamine resin layer (ppm/°C); “, E2 is the second polyamidene resin The coefficient of thermal expansion of the layer (ppm/〇c); T1 is the thickness (_) of the first polyimide layer; and T2 is the thickness (μιη) of the second polyimide layer. A layer of adhesive resin consists of the thickness of the layer (Τ3), which satisfies the following Equation 2, and can be 〇.5 μπι 〇 Equation 2 [0.01 X (ΤΙ +Τ2)] <Τ3 <[3·0 x(Tl + D2)], and 〇.5 <Τ3 wherein Τ1 is the thickness (μιη) of the first polyamidamine resin layer; 15 Τ2 is the thickness (μιη) of the second polyamidamine resin layer; and butyl 3 is the adhesive resin-containing layer Thickness (_). Here, 'Τ3 can be converted to the thickness of the thermoplastic poly-mineral resin layer (13, 13') in the first figure; and in the second figure, Τ3 can be interpreted as the third resin layer (20) and the The thermoplastic polyimide layer (13) and in the third figure, Τ3 can be interpreted as the thickness of the thermoplastic polysulfide layer (13, 13,) and the third resin layer (20). sum. At least one layer of the adhesive resin contains the layer Τ3, and if it is within the above range, it has sufficient adhesion when the pressure-bonding process is performed under high temperature/high pressure, and the quality and dimensional stability can be effectively improved. 21 200806100 In addition, the flexible double-sided conductor laminate of the present invention, the at least one adhesive resin-containing layer shown in the second or third embodiment is a multilayer structure comprising a single layer or a double layer of thermoplastic polymer. a melamine resin layer, and the third resin layer. Specifically, the two-layer structure shown in the second figure is a single layer of a 5 thermoplastic polyimide resin layer (13), and the third resin layer (20). The three-layer structure shown in Fig. 3 is such that the third resin layer (2〇) is interposed between the thermoplastic polyimide resin layers (13, 13'). As shown in the third figure, in the example of r at least one layer of the adhesive resin containing layer, it has a symmetrical structure which can be formed by the following order: thermoplastic polyimide resin ίο layer-third resin The layer is a thermoplastic polyimide resin layer, and the thickness of the two layers of the thermoplastic polyimide resin layer described above may be the same. If the adhesive resin comprises a three-layer structure, but an asymmetric structure (meaning that the thicknesses of the layers are different from each other), first calculate the average thermal expansion coefficient of the thermoplastic polyimide layer, and then The coefficient of thermal expansion is adjusted to 15 degrees thick by each layer to prevent bending. Further, as shown in the second figure, in the example in which the "at least one adhesive resin-containing layer" has a two-layer structure, the first polyimide resin layer (12) and the heat are averaged based on the third resin layer. After the thermal expansion coefficient of the plasticized polyimide resin layer (13,), the thickness of each layer is adjusted according to the calculated value to prevent the occurrence of bending. Here, the third resin may be the same as or different from the first polyamidamine resin layer and the second polyamidamine resin layer, and may or may not be a thermoplastic resin. Examples of the third resin include polysulfone (psF), epoxy resin, phenol resin, and the like. In the present invention, the resin layers connected to the conductors on the right side are each a polyimide resin layer, and 22 200806100 can attain the object of the present invention, and thus the third resin is not limited. The flexible double-sided conductor laminate of the present invention, wherein the polyimide layer has a total thickness of 35 μm or less. In addition, in order to improve product quality, the polyimide resin layer may contain 5 known additives such as a hardener, a silane coupling agent, an epoxy (ep0xy) compound, and a property-imparting agent. Pool agent), antioxidants, anti-aging agents, etc. In addition, a non-conducting inorganic material may be added to control the thermal expansion coefficient, strength, ductility, and adhesion of the resin layer, wherein the inorganic material may be: silica, montmorillonite, Alumina, clay (ciay), carbon nanofibers. In the present invention, the conductor is not limited to copper (c〇pper) or aluminum', and may also include metals which are well known as conductors, including: gold, silver, nickel ( Nickel), zinc, iron, cobalt, lead, tantalum, titanium, zirconium, and alloys of the foregoing, or oxides of the foregoing metals , such as Indium tin oxide (ITO). According to the embodiment relating to the method of manufacturing the flexible double-sided conductor laminate of the present invention, a conventional press-forming process and a deposition process can be utilized. Since the conductor needs to be connected to the thermoplastic poly] polyamide resin layer due to the press-bonding process, the press-bonding process is not separately used in the present invention. A polyacrylamide film composed of the above polyimide resin layer is first prepared by a deposition process. That is, the above-mentioned thermoplastic polyiminamide resin layer is laminated on one side of a general polyimide film, and then a general polyamidamine film is pressed thereon to prepare a polyimide. 200806100 film, then in the ship (four) _ double hoarding The washing process can include the following steps: ▲ its precursor is coated on one of the first conductor, ami amide resin or 5 15 20 resin coated on it Upper, then dry, ;^,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, One of the second conductors is coated with a bismuth amide resin, and then dried and then subjected to an acid amination reaction to separately prepare a second dimerized resin layer. And the first sound squid — — 及 及 及 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏 黏The layer_adhesive resin layer 13 of the second layer is joined to each other. The flexible double-sided conductor laminate obtained by the above method may have a structure as shown in the first drawing. For example, one of the first layer or the second layer may further comprise a third resin layer by applying a so-called fat precursor to the adhesive resin-containing layer, followed by drying. In this example, the pressing of the first layer and the second layer is performed under high temperature/high pressure conditions, so that the second resin layer and the adhesive resin containing layer are bonded to each other to obtain a Flexible double-sided conductor laminate. The flexible double-sided conductor laminate obtained by the above method may have a structure as shown in the third drawing. Another example of the flexible double-sided conductor laminate produced by the casting method in the present invention may include the steps of: coating the first polyimide resin or its precursor on one side of the first conductor, and then Drying, applying a third resin or its 24 200806100 precursor thereon, followed by drying, and under a high temperature atmosphere, amidoximation reaction to prepare the first conductor, the first poly resin and the first a first-layer plate of a three-resin layer; coating a second poly-branched amine tree = its river flooding on the surface of the second conductor, followed by drying, and applying a 5-adhesive resin or its precursor to it And then drying, and under a temperature atmosphere, performing a mercaptochemical reaction to separately prepare the third conductor comprising the second conductor, the second polyimide resin, and the adhesive resin layer: And pressing the first layer sheet and the second layer sheet under high temperature/high pressure conditions to make the third resin layer of the first layer sheet and the second layer sheet adhere to the resin-containing resin layer Engage each other. The flexible double-sided conductor laminate obtained by the above method may have a structure as shown in the second drawing. Further, in the method for manufacturing the flexible double-sided conductor layer according to the present invention, in the +, the adhesion by the high temperature/high pressure bonding can be performed by using the surface of the press or by using a crimping process (roll to roll) ) The line is glued. The process temperature is 15 or higher than the glass transition temperature (Tg) of the adhesive resin, specifically, the temperature is in the range of 180 ° C to 400 ° C, more preferably 280 ° C to 36 Torr. Hey. Further, in order to uniformly achieve the adhesion of the adhesive resin by using heat, the pressure ranges from 1 kgf/cm2 to 200 kgf/cm2, and in particular, a pressure range of from 3 〇kgf/cm2 to 80 kgf/cm2 is available. In Example 20 in which the crimping process was used for press-fitting, the line adhesion permeable pressure range was 〇·1 to 20 〇 kgf/cm 2 and the rate range was 0.1 to 30 m/min. Recently, in order to increase the production volume, various types of pressurization using the crimping process have been developed, and the Japanese Unexamined Patent Publication No. 2005-199615 can be referred to. If the above conditions of high temperature and high pressure are not met, it is impossible to obtain a layer with sufficient adhesion and appearance. According to a preferred embodiment of the present invention, the flexible double-sided conductor laminate, wherein the peel strength between the first conductor and the first polyimide resin layer is the second conductor and the second polyimide The peel strength between the resin layers is from 0.565 to h6 times. If the peel strength between the conductor and the resin on both sides of the laminate exceeds the above range, the conditions for the optimum post-process of the double-sided may vary, and the minimum circuit width that can be formed may also be reported. Although there is no limitation in the method for satisfying the range of the peeling tension difference, the control of the pressing method still has the best example. Specifically, in the foregoing process, the first conductive system is coupled to the first polyamidosin resin layer and the adhesive resin containing layer by a casting method, and the second conductive system is coupled to the second polymerization (4) The linoleic layer and the adhesive resin-containing layer, and the adhesive resin-containing layer of the first conductor and the adhesive resin-containing layer of the first conductor are connected to each other by a press-bonding process. Thus, when the layers are connected, the two conductors can be joined by the same heat treatment process, and they can have the same physical properties. Therefore, the peel strength between the conductor and the resin on both sides of the laminate is 20 degrees. y The flexible double-sided conductor laminate is exemplified by the following examples, but the invention is not limited thereto: "analytical method" Thermal expansion coefficient · Thermomechanical analyzer (Model 〇働祖, D, 26 200806100 The heating rate is l〇°C per second, and the average thermal expansion coefficient is measured from 1〇〇 to 200oC. Glass transfer temperature: differential thermal scanning analyzer (Model Exstar6〇〇〇DSC6100, Seiko), heating rate is per minute Iq〇c. 5 Moisture absorption rate: Immerse the double-sided conductor layer of 1〇X 10 cm2 in a 13% nitric acid solution to thoroughly etch the conductor and measure the weight of the resin layer after etching. The layer of Μ月曰 is fully impregnated in pure water. After standing for 24 hours, it is removed from the water and dried, and then the weight is measured, and the hygroscopicity is defined by calculating the added weight. Film bending · 10 X 10 cm2 on the flat surface. Edge of the sample. A peeling strength 1: Using a universal testing machine (Model Instron 3300 series) 1 Measure the peel strength between the conductor and the resin layer 180 degrees. Here, First conductor and first poly The peel strength between the amine resin layers was named as peel strength of 15 degrees 1β1; and the peel strength between the second conductor and the second polyimide resin layer was named peel strength 1-2. Peel strength 2: use universal test Machine (Model Instr〇n 3300 Series) 1 Measure the peel strength between the adhesive layer and the adhesive surface at 18 degrees. Dimensional change after etching · Measurement 1〇x 10cm2 double-sided conductor layer coating 20 cloth direction Dimensions and dimensions in the direction of 9 degrees to the direction of coating; the double-sided conductor laminate to be 10 X 10 cm2 is immersed in a 13% nitric acid solution, so that the conductor is completely etched, as before etching At the measurement points, the size of the coating direction of the remaining resin layer after etching and the dimension in the direction of the coating direction of 90 degrees were measured, and the change of the size 27 200806100 before and after the etching was measured and averaged. (Using the instrument: EG3020M, Fiat Precision Measuring Instrument Co., Ltd.). The surface resistance of the mountain is not wetted: the 5 x 5em2 double-sided conductor laminate is immersed in a 13% acid solution, resulting in complete conductor On the ground side, the instrument will be engraved The remaining 5 resin layer was dried at 100 ° C for 30 minutes, and the surface resistance of the double-sided conductor layer was measured, and then the laminate was placed at a humidity of 1%, a temperature of 121 C, and an atmospheric pressure of 2 atm. In the atmosphere for 2 hours (using the instrument: PC-422R8D 'Japan Hirayama), and then drying, the surface resistance of both sides of the laminate was measured, and the stability of the electronic signal due to hygroscopicity was evaluated by 10 degrees. The higher the resistance, the greater the stability and reliability of electronic components. (Instruments for measuring surface resistance: high current source measurement unit, model M〇dd 238, Keithley Instruments). "Synthesis of Polyimine Resin" 15 Synthesis Example 1 In order to obtain a polytheneamine resin having low thermal expansion, 28.1 g of p-phenylenediamine was placed at a temperature of 4 ° C and 2 L of nitrogen was present. In the reactor, 800 g of dimercaptoacetamide (DMAc) solvent was added, and the mixture was stirred for 30 minutes to completely dissolve it, when 76·5 g of 3,3,4,4,4-biphenyltetracarboxylate The acid 2 phthalic anhydride (BPDA) was added in 1 aliquots and then subjected to a polymerization reaction for 5 hours to obtain a polyamic acid. The polyamic acid obtained by the polymerization was applied onto a glass substrate, and dried at 300 Å. The azide was dried in a vacuum oven at €:, after which the heat % factor was measured. The results are shown in Table 1. 28 200806100 Synthesis Examples 2 to 9 Polyamic acid was prepared in the same manner as in Synthesis Example 1, except that the composition and amount of the dianhydride and the diamine were changed in accordance with the equivalent ratio shown in Table 1, and the poly-aracine was carried out. After the amidoximation reaction, the coefficient of thermal expansion and the glass transition temperature were measured. The results are shown in Table 1, in which the glass transition temperatures of Synthesis Examples 1 and 3 were difficult to define, and the glass transition temperature of Synthesis Example 2 was estimated with low accuracy. [Table 1] —-—A composition of 5 parts (equivalent) Softness: Hard monomer Mohs ratio hygroscopicity (%) Thermal expansion coefficient (ppm/°C) Tg Diamine dianhydride 1 PPDA (50) BPDA ( 50) 0 : 10 0.7 8 vw 2 PPDA(35)? DDE(15) BPDA(50) 1.5 : 8.5 0·7 13 360* 3 PPDA(40) DDE(10) BPDA(IO) BTDA(40) 5: 5 0.8 18 - 4 PPDA(20) DDS(30) BTDA(30) PMDA(20) 6:4 1.0 32 288 5 PPDA(IO) DDE(40) BTDA(50) 9:1 2.2 35 255 6 DDE(50 ) BTDA(50) 10 : 〇2.1 36 291 7 BAPS(50) BTDA(50) 10 : 〇2.7 40 215 8 BAPP(50) BTDA(40) BPDA(IO) 9:1 2.6 61 192 9 — BAPSM(50 ) BTDA (25) DPSDA (25) 10 ·· 0 2.9 57 172 "Manufacture of flexible double-sided conductor laminate" Example 1 The precursors of Examples 1 and 4 were mixed at a weight ratio of 5 ··5, and Hot expansion 29 200806100 eoati^^T! C poly-awakening amine resin precursor to a coating rod (bar on a rough surface with a thermal expansion coefficient of 17 8 ppm / 〇c and a thickness of Μ哗, followed by heating air drying Machine, in the 15th generation minutes. The average thickness of the 'dry rider' is 12.4 _. Applying 5% of the 6th heat-polymerizable polyamine-sphincamine precursor to the dry-collecting surface The table of Fortune (4), after the drying of the city 'is! It is dried for 3 minutes. Thus, the flat layer of the dried resin layer = thickness 16,7μηη. The single-sided conductor laminate obtained in the nitrogen drying phase of 3 (10). , the imidization and hardening were carried out for 2 hours to obtain a single-sided conductor laminate (a). - The thickness of the resin layer was made thinner due to the reduction of residual solvent and moisture, and the cross section was observed by an electron microscope. The thickness of the melamine resin layer is 10·2 μm, and the thickness of the thermoplastic polyimide resin layer is 2.6 μm. The two single-sided conductor laminates (8) are treated with a high temperature/high pressure laminator. Adhesive at 350 〇C and 50 kgf/cm2 for 10 minutes, and the thermoplastic polyimide layer of the two-conductor laminate is bonded to each other to obtain a flexible double-sided conductor laminate (please refer to the first figure) EMBODIMENT 2 A single-sided conductor laminate was produced in the same manner as in Example 1, except that the poly-branched amine resin of Synthesis Example 2 was used. Two single-sided conductor laminates (9) are pressed together to produce a flexible double-sided conductor laminate. Example 3 A single-sided conductor laminate (c) was produced by the same method as in Example 1, except that the polyimide resin of Synthesis Example 3 was used. Two single-sided conductor layers were pressed together to produce a flexible double-sided conductor laminate. (9) Comparative Example 1 A flexible double-sided conductor substrate was produced by the same method as in Example 1, except that the polyamic acid of Synthesis Example 2 was applied instead of the thermoplastic poly-feline compound of Synthesis Example 6. . However, after pressing, the adhesion is low. ° Li Ming

Example 4 The polyiminamide of Synthesis Example 4 was coated on a thermal expansion coefficient of $

Ppm/°C and a thickness of 35 μm on the surface of the box layer, using a hot air oven at 15 〇. 0: Dry for 30 minutes. At this time, the average factory density of the dried resin layer was 12.2 μm. The thermoplastic polybenzamine resin precursor of Synthesis Example 8 was applied to the surface of the dried polyamido resin precursor by means of a crepe bar, and the crucible 15 was dried at 15 ° C with a hot air dryer. Dry for 30 minutes. At this time, the dry tree 浐 has an average thickness of 16·2 μιη. The obtained single-sided conductor laminate was subjected to amidization and hardening for 2 hours in a nitrogen oven to obtain a single-sided = bulk layer (d). At this time, the thickness of the layer of the moon is thinner due to the decrease in residual solvent and moisture. The cut surface was observed by an electron microscope, and the thickness of the low-twist 20 resin layer was 1 (U (four), and the degree of the thermoplastic resin layer was 2.3 μm. Also... The two single-sided conductor laminates (d) were subjected to high temperature. / High-pressure glue machine, adhered at 50 ° C and 50 kgf / cm 2 T for 10 minutes, the surface of the thermoplastic resin of the two-conductor laminate was joined to each other to obtain a flexible double-sided conductive layer 31 200806100 board. Example 5 In the same manner as in Example 2, the thickness of the polyamidoquinone lipid layer was prepared. The early-face layer (b) was used. This single-sided conductor laminate (b) and Example 1 were used. The single-sided limb guide layer (8) is adhered at 350 〇c and 50 kgf/c 荽 the two-conductor laminate # G4, and the surfaces of the double-sided conductor layer i are joined to each other to obtain an interchangeable embodiment 6 2. The high-pressure glue machine's the single-sided conductor laminate (4) of Example 1 and the early conductor laminate (8) of column 2 of 2, were adhered at 37 ° C and 4 〇 kg fW for 10 minutes to make the two-conductor laminate The surfaces of the thermoplastic resin are bonded to each other to produce a flexible double-sided conductor laminate. Example 7 15 20 Using the same method as the case 1 A flexible double-sided conductor laminate was prepared by using the thermoplastic polyisanamide resin precursor of Synthesis Example 9 as a thermoplastic polyimide resin precursor. Examples 8 to 10 were carried out by compression. The single-sided conductor laminate (a) of Example 1 and the single-sided conductor laminate 0 gt of the second embodiment are such that the thermoplastic polyimide layer of the two conductor laminates are joined to each other to obtain a flexible double a surface conductor laminate, except for the thickness of the polyimide layer (first polyimide layer) of the single-sided conductor laminate (a), and the polyimide layer of the single-sided conductor laminate (0) The thickness of the second polyamidamine layer is changed as shown in Table 2 below. 32 200806100 Example 11 The polyimide precursor of Synthesis Example 3 was coated on a rough surface of a first copper layer having a thermal expansion coefficient of 17.8 ppm/° C. and a thickness of 18 μm by a coating bar. Then, using a hot air dryer, it was dried at 15 ° C for 30 minutes. Further, the thermoplastic poly] resin of Synthesis Example 7 was applied onto the surface of the dried polyweiramine resin precursor by a coating bar, and then dried at 150 ° C for 3 minutes using a hot air dryer. . Further, the polyimide precursor of Synthesis Example 2 was coated on a dry poly-Asian precursor (4) surface by a coating bar: it was dried for 30 minutes under air. The obtained single-sided conductor laminate was subjected to a berylation and hardening for 2 hours in a xenon oven to face conductor laminate (f). Early and additionally, 3% of the polyacrylamide resin precursor of Example 3 was coated with 15 rods on a rough surface of a second copper layer having a thermal expansion coefficient of Π·8 ppm/QC and a thickness of Μ. Thereafter, it was dried for 30 minutes in 15 passages using a hot air dryer. Further, 'the thermoplastic polyacrylamide resin precursor of Synthesis Example 5 was coated on the surface of the dried polyamido resin precursor with a k-bar, and then dried at 150 ° C using a hot air dryer. minute. The -= body layer plate was subjected to sub-ization and hardening in a nitrogen gas supply tank of 300 ° C for 2 hours to obtain a single-sided conductor laminate (g). Using a high temperature/high pressure glue machine, the single-sided conductor laminate (f) and the single-sided conductor laminate (=)' are adhered at 380 ° C and 50 kgf / cm 2 for 20 minutes, so that the heat of the two conductor laminate The plastic resin surfaces are joined to each other to produce a flexible 33 200806100 double-sided conductor laminate. The thickness of the resin layer such as the first copper foil layer is 10 2 μm. (Please use an electron microscope to observe the resin layer of the cut surface of the product to the resin layer of the second copper layer, the order is 9.8 μηη, 3.5 μηι, Q μηι, μηι > 5 refer to the third figure) Example 12 The polyamidite tree of Synthesis Example 3 was coated with a thermal expansion coefficient of π.8ρρη^, and the _ rod was coated with μ ^ l μ to a thickness of β μιη, which was made into a copper foil layer, and then made for 30 minutes. In addition, the gland people, m He Shi DU L under the drying of the 泠 泠 (10) poly-liminamide resin precursor, coated with cloth before the remaining polyamine resin, the dryer 'dry under the armpit for 30 minutes. In the obtained single = frif nitrogen oven, the amination and hardening were carried out for 2 hours to obtain a single-sided conductor laminate (h). 15 20 / ί, / high pressure gluing machine, single turn tree 曰 layer, and the single-sided guide plate of Example 9 (_ thermoplastic resin layer ' made at 3800c and 50 kgf /cm2 under 20 minutes ^ Adhere 'make it's mutually joined to make a flexible double-sided conductor laminate. Observe the cut surface of the product using an electron microscope. From the first copper layer to the fourth layer to the fourth - The resin layer of the copper rhyme, the thickness of the resin layers is 16.2 jum, 7 8 uni, 4 s iim, the second figure is 4.5, and 25.4 μm. (See Example 13 for example 2) | An acid amine resin precursor, coated with a coating bar 34 200806100 on a rough surface with a thermal expansion coefficient of 17.8 PpmrC and a thickness of 18, called a steel layer, followed by a hot air dryer at 150 ° C Dry for 2 μ〇 minutes. The average thickness of the 'dry resin layer is 12.5 哗. The early surface conductor layer is made at 3GG ° C with air oven towel for 2 hours of amination and hardening to make a single Face conductor laminate (1). Thus, the thickness of the resin layer is thinner due to the reduction of residual agent and moisture, _ electron microscopy Observe the cut surface. The thickness of the obtained resin layer is 1〇1 μηη. Several 10 15 20 will contain 1 part by weight of epoxy resin (YD (m, National Chemical Co., Ltd.), 5 parts of 5 parts, 4'-diaminodiphenyl hydrazine (DDS), and fine parts by weight, T_(MEK) epoxy-remanent resin mixture, poly-manganese resin coated on the single-sided conductor layer plate (i) The layer is then dried using a thief dryer at 1G °C for 1G minutes to produce a single-sided conductor laminate ω. Thus, the dry oxygen-heating tree is thick and thick, and the titt is slightly sticky. Hardened state, and its glass transfer temperature.f to, 15G ° C. Using a high temperature / high pressure glue machine, single-sided two-sided (1) and early-face conductor laminates ' at 25 ° ° C and 10 kgf / 20 cm under the cm2 adhesive layer so that the resin layers are bonded to each other to produce a flexible double-sided bulk layer. Example 14 = Fabrication of a flexible double-sided conductor layer 2' with: := replacing the epoxy resin mixture with an adhesive resin mixture containing 100 parts by weight of epoxy resin, 20 parts by weight of phenol (DDS^ 51 } ' 5 * ^ and 200 parts by weight of methyl ethyl ketone (MEK) 35 200806100 Comparative Example 2 = Example 2 is a single-sided conductor laminate (a) obtained in Example 1. Comparative Example 3 contains a first conductor, a thermoplastic polymer resin layer, and a configuration (please refer to the fourth figure) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) ) 17.8ppm / 〇c, and the thickness of the copper is 18 落 thick, on the surface, then use a hot air dryer, dry under i5 〇〇 c) 3 mourn 0 points! in. The average thickness of the dried resin layer was 4 3 division. The == 1 T region of Synthesis Example 2 was applied to the dried polyacrylamide by a coating bar and dried for 3 minutes. So, dry it at 1 and let I wind dry the city at 150〇c τ_ 3() with an average thickness of 27·7 μιη. In the oven of the celestial celestial layer, the θ is also in the oven of the tree, and the early conductor layer is immersed in a nitrogen gas of 3oo°c in a small amount of sulfonamide to form a single side. Guide layer (4). Scale, due to _ dissolve water 20 body layer connected to the thermoplastic poly Asia _ layer 2 = 庠 A 3 2 _, 1 〇 (He Li 曰 repeatedly thickness according to the single-sided conductor shoulder price 以及, and 3.0 μηι. Use high temperature / High-duty glue machine, 17.8 ppm/X^H plastic surface, _ expansion coefficient is eight; the roughness of the copper foil layer of 18 μηι is adhered at 36 200806100 350QC and 50 kgf/cm2 for 10 minutes' They were joined to each other to obtain a flexible double-sided conductor laminate. Reference Example 1 Production of the single-sided conductor laminate (8) of Example 1 'The conditions of 'sub-amination 5 and hardening were changed to 250. And 3 hours 'to produce a single-sided conductor laminate (1); then using a high temperature / high pressure glue machine, the single-sided conductor laminate (1) and the single-sided conductor laminate (a) resin layer, and examples 1 Adhesive under the same conditions to obtain a flexible double-sided conductor laminate. The thickness of the layer 10 of the double-sided conductor laminate obtained in the examples and the comparative examples was measured, peel strength, film bending, and etching. Dimensional stability. The results are shown in Table 2 below. [Table 2] The second layer of the first pi layer

Peel strength peel strength 2

Distinguish between thermoplastic η layer or adhesive resin layer Thermal expansion coefficient (ppm/°C) Thermal expansion coefficient (ppm/°C) (kgfi^cm) Film Bending (mm) Dimensional change after etching (%)

37 200806100 Example 13 10.1 13 5.0 Average 132 10.1 13 1.2 1.2 0.9 0 0.044 Example 14 10.1 13 5.2 Average 145 10.1 13 1.2 1.2 1.1 0 0.039 Comparative Example 1 10.3 20 Polyiminide layer 10.3 20 1.2 L2 <0.1 Swallow / Preparation of the product Comparative Example 2 9.2 13 2.7 291 Single-sided conductor laminate 1.2 - - 42 0.118 Comparative Example 3 Refer to the above description 0.8 1.5 1.0 0 0.052 Reference Example 1 10.2 20 5.2 291 10.2 20 0.6 1.2 1.0 21 0.186 Measurement by The double-sided conductor laminates obtained in the examples and the comparative examples showed a change in surface resistance after moisture absorption. The results are shown in Table 3 below.

[Table 3: Distinguishing the average surface resistance before moisture absorption (8) (1012 ohms) Average surface resistance after moisture absorption (B) (1012 ohms) A/B Example 1 0.97 0.43 2.26 Example 2 2.05 1.32 1.55 Example 3 1.86 0.92 2.02 Example 4 1.92 1.11 1.73 Example 5 1.24 0.85 1.46 Example 6 1.42 0.92 1.54 Example 7 0.95 0.32 2.97 Example 8 1.32 0.72 1.83 Example 9 1.57 0.95 1.49 Example 10 1.22 0.88 1.39 Example 11 1.93 0.99 1.95 Implementation Example 12 3.37 1.86 1.81 Example 13 0.95 0.45 2.11 Example 14 1.02 0.48 2.13 Comparative Example 1 Sample could not be obtained Comparative Example 2 0.91 0.23 3.96 Comparative Example 3 0.82 0.08 10.25 Reference Example 1 1.01 0.26 3.88 5 *Average before moisture absorption The lower the surface resistance (A) / the average surface resistance (B) after moisture absorption, the better the electron stability against moisture absorption. 38 200806100 As shown in the results of Table 3, the flexible double-turn plate board obtained by the examples 丨 to 14 and the reference example i has the electronic stability of the simpleness of the simpler than the conventional one. The result of the revival case 3 is even more hurt. 5 More New Zealand's in the actual customs 1 to 14, the first conductor (four)

The peeling strength between the polyamidamide resins is equal to or less than the peeling strength between the first conductor and the second polyamine resin, and the range is 〇.65 to 1.6 times, and the hygroscopic electrons thereof The stability is even better. In addition, the flexible double-sided conductor laminates of Example 1 and Comparative Example 3 are treated separately (dry film photoresist technology service center, which has a high peel strength - surface or a part == 2, and On the other surface, under the same conditions, a circuit with a circuit degree of 60 μm is formed. 15 20 The enlarged photo of the above-mentioned circuit board is shown in the fifth and sixth figures as shown in the fifth figure. As shown in the sixth figure, the circuit board produced in Comparative Example 3 was delaminated from the circuit board prepared in Comparative Example 3 as compared with the circuit board manufactured in Example 1. The circuit line was delaminated. The phenomenon is considered to be that the etching solution penetrates between the surface of the copper foil layer with a low peel strength and the polyimide layer. This phenomenon can seriously damage the circuit and greatly reduce the performance of electronic parts. 39 200806100 [Simplified description of the drawings] The first figure is a cross-sectional view showing a first embodiment of the present invention, showing a flexible double-sided conductor laminate. The second diagram is a cross-sectional view of a second embodiment of the present invention. , showing flexible 5 double-sided conductor laminate. · 'The third picture is A cross-sectional view of a third embodiment of the invention showing a flexible double-sided conductor laminate. The fourth diagram is a cross-sectional view of a conventional flexible double-sided conductor laminate. The fifth diagram is flexible using the embodiment 1. A magnified photograph of a circuit board made of a double-sided conductor laminate. The sixth diagram is an enlarged photograph of a circuit board obtained by using the flexible double-sided conductor laminate of Comparative Example 3. [Main component symbol description 】 15 1 first copper layer Γ second copper layer 2 ′ low thermal expansion polyimide layer 3 first thermoplastic poly melamine layer 3 ′ second thermoplastic polyimide layer 11 first conductor 11 , Two-conductor 2〇I2 first polythinamide resin layer 12' second polyamidamine resin layer 13, 13' thermoplastic polyimide resin layer (adhesive resin-containing layer) 20 brothers resin layer

Claims (2)

200806100 X. Patent application scope: 1. A flexible double-sided conductor laminate comprising: a first conductor; a first layer of an imide resin layer connected to the first conductor; at least one layer of an adhesive resin comprising a layer; a first polyaminin resin layer connected to the second conductor; and the second conductor; wherein the first conductor and the second conductor are the same or different from each other, the first polyamido resin and The second polyamidamide resins are the same or different from each other, and the thermal expansion coefficient of the di-anthracene amine resin and the thermal expansion coefficient of the first conductor are the same or different from each other, and the second polyarylene The coefficient of thermal expansion of the amine resin and the coefficient of thermal expansion of the second conductor are the same or different from each other. 2) a flexible double-sided conductor laminate comprising: a first conductor; I5 a first polyamidene resin layer attached to the first conductor; at least one layer of an adhesive resin comprising a layer; An amine resin layer connected to the second conductor; and the second conductor; wherein the first conductor and the second conductor are the same or different from each other, 2〇 the first polyamido resin and the second poly The guanamine resins are the same or different from each other, the thermal expansion coefficient of the first polyamidene resin and the thermal expansion coefficient of the first conductor are the same or different from each other, and the thermal expansion coefficient of the second polyamidene resin and the second The coefficient of thermal expansion of the conductors is the same or different from each other, and the peeling strength between the first conductor and the first polyimide resin is 200,806,100. The peel strength between the second conductor and the second polyimide resin is 0. 65 to 1.6 times. 3. The conductor laminate according to claim 1 or 2, wherein the first conductor comprises the first polyimide resin layer and is connected to the first polymer by a casting process The adhesive resin of the melamine resin layer comprises a layer, the second conductor comprising the second polyimide resin layer, and the adhesive resin-containing layer connected to the second polyimide resin layer by a casting process And the adhesive resin-containing layer of the first conductor and the adhesive resin-containing layer of the second conductor are joined by a press-bonding process to be joined to each other. 4. The conductor laminate of claim 1 or 2, wherein the first conductor and the second conductor are joined under the same heat treatment conditions. 5. The conductor laminate according to claim 1 or 2, wherein the polyamido resin is a resin having a melamine ring structure and is selected from the group consisting of polyether amides and polyfluorenes. Between the amine imine and the polyester amide. 6. The conductor laminate according to claim 1 or 2, wherein the conductor and the first polyimide resin layer or the second conductor and the second polyimide resin The layer has a difference in thermal expansion coefficient of 20 10 ppm/°C or less. The conductor laminate according to claim 6, wherein the first polyimide resin layer or the second polyimide resin layer comprises a polyamidene resin, the polyamine The resin is composed of -〇-, -co-, -NHCO-, -s-, -so2-, -co-ο-, -ch2-, or ·〇(εΗ3)2-42 between the aromatic rings thereof. a soft monomer of a chain dianhydride and a diamine, and having no -0-, -CO-, -NHCO-, -S-, -S〇2-, -CO-O-, -CH2 between its aromatic rings A hard monomer of -, or -C(CH3)2-chain dianhydride and diamine is polymerized in a molar ratio ranging from 0 to 10 to 8 to 2. The conductor laminate according to claim 7, wherein the first polyimide resin layer or the second polyimide resin layer comprises one or more polyimide resin mixtures. The conductive laminate according to claim 1 or 2, wherein the first polyamido resin layer and the second polyimide resin layer 10 have the same composition and thickness. The conductor laminate according to claim 1 or 2, wherein the first polyimide resin layer or the second polyimide resin layer has a hygroscopicity of 1% or more. low. 11. The conductor laminate according to claim 1 or 2, wherein the adhesive resin-containing layer comprises one or more adhesive resins, and φ is selected from the group consisting of glass transfer after the hydrazide reaction. The temperature is between 120QC and 350 °C ^ between the thermoplastic poly] amide resin, epoxy resin and phenol resin. 12. The conductor laminate according to claim 11, wherein the thermoplastic polyamidamide resin comprises a mixture between the aromatic rings... Thermoplasticity of polymerization of soft monomers such as 20-CO-, -NHCO-, -S-, -S02-, _c〇-〇-, d, or -C(CH3)2- bond and one amine The conductive laminate according to claim 11, wherein the thermoplastic polyamidamide resin is a thermoplastic polymer comprising a glass transition temperature of 43 200806100 120 c to 350 ° C. A mixture of melamine resins. The conductor laminate according to claim 4, wherein the thermoplastic polyamine contains a polyamidene resin, and the polyamidene resin is contained between the aromatic rings thereof. 〇-, _c〇__NHC〇_, _s_, =2, _C〇_〇-, or _C(CH3)2-bond dianhydride and diamine soft oxime monomer, and not between its aromatic rings a hard monomer having _〇_, _c〇_, _NHC〇_, _s_, s〇厂, _C0-0-, -CHr, or -C(CH3)2_ chain dianhydride and diamine The molar ratio ranges from 1 to 聚合 to 2 to 8 and is polymerized as 0. 15. The conductor laminate according to item 1 or 2 of the patent application, 该中该一聚亚胺胺树脂The thickness of the layer and the second polyimine resin layer 'stains to satisfy the following Equation 1: Equation 1 [0.8 χ(Ε2 X Τ2)]<[Ε1 χ Τ1]<[1.2 χ(Ε2 χ Τ2)] 'Ε1 is the thermal expansion coefficient (Ppm/0c) of the first polyamidite resin layer, E2 is the thermal expansion coefficient (ppm/〇c) of the second polyamic acid amine resin layer, and T1 is the first polyarylene The thickness of the amine resin layer (pm), and Τ2 is the second polyamidamine resin The thickness of the layer (gm). The conductor laminate according to claim 1 or 2, wherein the at least one layer of the adhesive resin-containing layer, the first polyimide layer, and the second polyimide layer The thickness of the amine resin layer satisfies the following Equation 2: Equation 2 44 200806100 [0·01 X (ΤΙ + Τ2)] <Τ3<[3·0 χ(Τ1 + Τ2)], and 〇·5<Τ3 , ΤΙ is the thickness of the first polyamidamine resin layer (μιη), Τ2 is the thickness of the β-polyimide resin layer (μ)^, and Τ3 is the thickness of the layer containing 5 Take melon). The conductor layer according to claim 1 or 2, wherein the first conductor or the second conductor comprises copper, aluminum, gold, silver, nickel, zinc, iron, cobalt, Lead, button, bismuth, and alloys of the foregoing metals, or oxides of the foregoing metals. The method of manufacturing the flexible double-sided conductor layer according to claim 1, comprising: laminating an adhesive resin-containing layer on one side of the polyimide film; The second polyimide film is pressed onto the adhesive resin containing layer under a high temperature/high pressure atmosphere. The method of claim 18, further comprising depositing a conductor on the other side of the first polyamido film and the second polyimide film. A method of manufacturing a flexible double-sided conductor laminate as described in claim 1 or 2, comprising: 20 coating a first polyamido resin on one side of the first conductor or a precursor thereof, followed by drying, applying an adhesive resin thereon, followed by drying, and performing a mercaptomination reaction under a high temperature atmosphere to prepare a first conductor, a first polyamido resin and an adhesive The resin comprises a first layer of the layer; a second polyimide resin or its precursor 45 200806100 is coated on one side of the second conductor, dried, and then the adhesive resin is coated thereon, and then dried to ^ performing a mercaptomination reaction under a warm atmosphere to separately prepare a laminate comprising a first conductor, a second polyimide resin and an adhesive resin-containing layer; and 5 # under temperature and pressure The first layer and the second layer are pressed together such that the adhesive resin-containing layer of the first layer and the adhesive resin-containing layer of the second layer are joined to each other. The method of claim 20, further comprising coating the layer 10 or its precursor on the adhesive resin containing layer of the laminate or the second laminate, followed by drying to prepare the third And a resin layer, and pressing the first layer and the second layer at a temperature of 1 degree and high pressure to bond the third layer of the Uygur adhesive resin to each other. A method of manufacturing a resistant double-sided conductor laminate as described in claim 2 or 2, comprising: 15 coating the first polyamine on one side of the first conductor After the resin or its precursor is dried, the third resin or its precursor is applied to it, and Zhang Yizhang, _, first, Γ '-Asia are sub-alkalized under two-temperature atmosphere. Reacting to prepare a first layer comprising a first conductor, a first polyimide resin and a third resin layer; 2, coating a second polyimide resin on one side of the second conductor or a precursor thereof 2 〇 2 = post-drying, then applying an adhesive resin thereon, and then drying, and performing a mercapto amination reaction under a w wrinkle atmosphere to separately prepare a resin containing the ninth The adhesive tree wax comprises a second reed of the layer; and the first layer and the second layer are pressed under high temperature and high pressure to make the third resin of the first layer of the 2008 2008100100 and the second layer The adhesive resin of the board comprises layers bonded to each other. The method of claim 5, wherein the high temperature is equal to or greater than a glass transition temperature of the adhesive resin-containing layer, and the pressure of the 5 south pressure is 1 to 200 kgf/cm 2 or 1 to 200 kgf/cm. The method of claim 2, wherein the high temperature is equal to or higher than a glass transition temperature of the adhesive resin-containing layer, and the high pressure is in a range of from 1 to 200 kgf/cm 24 i to 200 kgf. /crn. The method of claim 21, wherein the high temperature system is equal to or higher than a glass transition temperature of the adhesive resin-containing layer, and the high pressure has a pressure range of 1 to 2 〇〇 kgf / Cm2 or 1 to 200 kgf/cm. The method of claim 22, wherein the high temperature is equal to or higher than a glass transition temperature of the adhesive resin-containing layer, and the high pressure pressure range is 〖to 2〇〇1^ price 1112 Or 1 to 200 吆 111. 47