TW201206696A - Flexible metal-clad laminate - Google Patents

Abstract

This invention provides a flexible metal-clad laminate at a low cost that is excellent in feasibility of installation, visibility, patterning ability and peeling strength. In this laminate, a polyamide imide resin film(Layer A) is laminated on a copper foil directly or through the medium of an adhesive layer, and thereon another polyamide imide resin film(Layer B) is further laminated. Layer A includes a polyamide imide resin ( Ι ) containing an amine component having a naphthalene bone and a polyamide imide resin ( Π ) containing an amine component having an O-tolidine bone, the weight ratio of ( Ι )/( Π ) is 95 to 70/5 to 30, and the number-average molecular weight of ( Ι )and/or ( Π ) is 25000 to 100000. Layer B includes a polyamide imide resin containing an amine component having an O-tolidine bone. The copper foil has a surface coarseness under 3 μ m on the side facing Layer A, and the degree of luster thereof is over 300, and the reflection index thereof for a light with a wavelength of 400nm to 800nm is over 20%.

Description

201206696 - Conductor pattern, wafer, etc. For example, a visible image of about 400 to 800 nm, a laser beam, a substrate, and a turtle pattern are image-processed. Therefore, the accuracy of the position adjustment is largely caused by the so-called visibility represented by the transparency or haze value of the heat-resistant film. With the increase in mounting density or fine pitch, the pattern formability or peel strength is increased, and high accuracy is required for positioning. In recent years, c〇F substrates have been paid attention to safety, visibility, and peel strength. Characteristics such as narrow pitch pattern formability. The COF substrate is produced by patterning a flexible copper-clad laminate (FCCL) in which a copper layer is laminated on a heat-resistant film. In general, FCCL is classified into three types: metallization type, flood casting type, and lamination type according to the manufacturing method. In the foregoing, a metallization type is used in COF applications. In the metallization type, a metal such as Ci. is directly vapor-deposited on a polyimide film by sputtering or the like, and is produced by electroless ore or/or surface. The metallization type has a good visibility because of the transparent and transparent poly S! imine film, but the mineral coating layer has many disadvantages and is lacking, and has a fundamental problem caused by a manufacturing method of peeling off. For example, Patent Document 1 discloses the peeling strength of the bismuth imine. Μ 个 个 剃 ί 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 And the enamel is made of a thermoplastic resin laminated with a polyimide film. "Because the wafer-mounted polyimine is reduced after the pattern is formed, the thermoplastic is a polyamine-type. Its manufacture, because it is easy to show the strong sound of peeling, agriculture & Thinking of the above-mentioned peeling strength or Anzhen·Ma-shenzhi's sputum, in addition to the installation and peeling strength, in addition to the installation and peeling strength, it is not possible to use the type in the traitor. Made by hardening. Please cast 201206696 j?CCI with visibility and pattern formability. This must be a 丨* = good stability is the premise 'but not the same,: ^^ For example, 'Patent Document 3, there is a note that the Portuguese will be covered with copper on the copper, and the polyamine-acid imide resin coated度 刻 刻 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后 后No, the polyimide layer of the polyamide-imine resin has a good thermal property. (4) The problem of the manufacturing stability of the poor stability of the county. _ 曰 曰 t itself saves 々 f ^ document 4 has a winding metal-clad laminate, after the surface roughness H And copper red has a hetero-imine insulating layer composed of a plurality of layers. However, the stacking property of the tantalum body is not sufficient for the mountability of the bare crystal and the copper or the high reflectance of the gloss or the reflectance. Moreover, since the polyimide solution of the polyimide precursor is dried at a high temperature, the imine is dried. It is not suitable for processing. Further, in order to heat-treat to the temperature, the copper box itself is recrystallized, and there is a problem that it is not suitable for pattern formability requiring a narrow pitch, which is a problem. Patent Document 5 discloses a method for producing a metal-clad laminate in which the flexible layer and the layered body are coated with a polyamide-imide resin/column solution on a copper foil having a low surface roughness. The sub-layer has two resin layers, and by coating the second layer with a resin having high heat resistance, the second layer is coated with a resin having good moisture absorption properties, thereby satisfying mountability and wet workability. However, in the method of Patent Document 5, when the copper foil having the same gloss or inverse rate as that of the mirror surface is used, as shown in Comparative Example 7 and Comparative Example 8 of the present invention, the storage stability of the peeled 201206696 fr ΐ 树脂 resin paint is poor. The door rhyme is studied to improve the visibility or pattern formability, but the patent text and the first degree, and the low strength problem? Moreover, the storage stability of the resin paint for washing is poor [this is a technical literature] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-251741 [Patent Document 3] Japanese Patent Laid-Open No. Hei. [Patent Document 5] PCT International Patent Publication No. WO 〇 〇〇 〇〇 〇 〇 42 42 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 〇 〇 〇 〇 〇 〇 〇 〇 [Problem to be Solved by the Invention] The object of the present invention is to solve the problems of the prior art, and to provide a metal-coated body of a high-frequency circuit board with a pitch, ^ ^ a flexible metal-clad for a film-carrying tape The laminate, in particular, is required for inexpensive flexible printed substrates The ideal flexible metal-clad laminate has good storage stability and good visibility, security, flaw, degree and pattern. , 狮强 [Technical means to solve the problem] The inventors of the present invention carefully studied the results of the foregoing, and found that two kinds of polyamine-acid imide resin film layers were laminated on the metal box, and the two ▲ 1 醯The imide resin film layer comprises: two polyamido-imine resin containing a specific and specified number average molecular weight in a layer near the metal foil; and a polyamine containing a specific amine component in a farther layer of gold - The yttrium imine resin can be fully washed to maintain the storage stability, mountability, visibility, pattern formability, and peeling properties of the 201206696 strength and achieve the object of the present invention. In detail, the present invention has the following structure: (). (1) A flexible metal-clad laminate which is formed by directly or laminating a layer of copper on a copper foil, and having a flexibility of an imine resin film (ruthenium layer) thereon a metal-clad laminate characterized by a full range of * _ Β α 1 to (iv); a a (i) A layer comprising: a polyamine-quinone imine resin (I) comprising a naphthalene skeleton ( An amine component of naphthalenes; and j polyamine-quinone imine resin (π) 'containing an amine component having a t-toluidine skeleton; and polyamine-imine resin (I) / The weight ratio of the polyamidamine-imine resin (9) is 95 to 70/5 to 30; ',, ' (ii) The polyamidoamine-imine resin (I) has a number average molecular weight of 25000 to 100000' And/or the polyamido-resinimide resin (π) has a number average molecular weight of 25000 to 100000; (iii) a B layer comprising: a polyamidamine-quinone imine resin comprising an amine component having a phthalic acid skeleton And (iv) the surface roughness of the copper foil A layer side is 3 μm or less, the glossiness is 300 or more, and the light reflectance of the wavelength of 400 nm to 800 nm is 20% or more. (2) As described in (1) Flexible gold Laminate where polyamide - (PEI) resin (I) comprising the following general formula [1], general formula [2], and the general formula [3] of the repeating units; 201206696

201206696 Polyamido-imine resin (ιι) is dispersed or phase separated. (6) The thickness ratio (layer A/layer B) of the resin film of the flexible metal-clad laminate according to any one of (1) to (5) is _~·. UA layer and B layer film-foamed metal-clad, wherein a-layer age-old film-replaceable metal-clad laminate, wherein B-layer resin (9) is a two-sided flexible metal-clad laminate, by a viscous metal-clad stack A layered body, which is formed by forming a metal on both sides. The flexible printed circuit board of the laminated type is a flexible covering metal of any one of (1) to (9) [effect of the invention] Ze Z is laminated The A layer and the B layer of the polyamide-yttrium imide resin soil are set to 'the storage stability of the resin paint or the copper for the mirror surface. The resin composition used in the 'washing scale method', due to: 2:== It is necessary to heat-treat at a high temperature, which contributes to inexpensive brushing, and the flexible printed substrate can maintain the original excellent performance. However, it is not easy to use a conventional technique. (3) Therefore, according to the present invention, it is possible to inexpensively manufacture a high-transparency flexible substrate which requires fine pitch, and is a flexible printed substrate which is used by CGF Boonna (four). Industrially, it is extremely advantageous. [Embodiment] As shown in Fig. 1, the flexible metal-clad layer of the present invention has Paving a film of A. sinensis-yttrium imine resin (A egg, and stacking it on top of it) 201206696 - Amine resin film (B layer) 3. The layer A can be laminated directly. It can be laminated on the copper foil 1 through the adhesive layer. The polyamidamine-imine resin film (Azhan) comprises: a polyamide-imine resin (1) comprising an amine component having a naphthalene skeleton; Polyamine-St imine resin (Π) 'containing an amine component having a bi-toluidine skeleton. The polyamidoximine resin (I) comprises the following general formula [1], general formula [2], and The repeating unit of the formula [3] is preferably in the molecular chain. The units represented by the following general formula [1], the general formula [2], and the general formula [3] may be one type or two or more types. And the substituent may be bonded to the naphthalene skeleton or the benzene skeleton.

0 Λ

2

[3] The generalized state of the polyamine-ruthenium imine resin (1) in the general formula (1) / general formula [2] / general formula [3] 201206696 is more ideally 10~5〇/2 2〇T ;m〇i"5 5 25 35/5^; when t12 is lower than the above ratio, the solubility of the organic solvent of the general formula [2] and the general formula [3] may be deteriorated, When the resin is applied to the layer body, it is necessary to form the shape of the resin paint of the precursor, and the heat treatment is performed under n, and the workability is deteriorated. As a result, energy costs are high. i, ^ ί ϊ 对于 对于 对于 对于 对于 对于 对于 对于 对于 :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: When the ratio is lower than the above ratio, or the Moby of the general formula [3], the Tg of the resin becomes low, the lead wiring L3 rl is collapsed during the bare crystal mounting. Further, the peel strength tends to decrease, and peeling of the wiring and the resin layer may occur. The preferred form is from benzoic acid and naphthalene diisocyanate. The preferred form of the formula [2] is derived from biphenyl tetraruthenic dianhydride and acid ester. The repeating unit, and the repeating unit derived from the diphenyl ketone tetraphthalic acid dianhydride and the acid anhydride (as the general formula [2']), the preferred core of the general formula [3] is from the uniform A repeating unit of naphthalene diisocyanide. The general formula [1] / / general formula [2,] / general formula [2] / general formula [3] in the pin = i · 醯 f amine resin (1) is preferably 5 to 6 〇 / 1~6〇/1~4〇/1~3〇, and the more reasonable form is KM0/KM0/5~3〇//5~2〇, more ideal form is 20~40/30~50/ 10~3〇/5~15. When the molar ratio of the general formula [1] is more than the above upper limit, when the term "term" of the general formula [2], the general formula p, and the general formula (3) is lower than the lower limit, the Tg of the formula becomes It is low, and the lead wiring may cause collapse in the resin layer during die mounting. Further, the peel strength tends to be lower than IV, and peeling of the wiring and the resin layer may occur. Further, the molar ratio of the general formula (1) is lower than the aforementioned T limit, and any of the molar ratios of the general formula [2] 'the general formula [2,] and the general formula p] is more than the aforementioned upper limit, and is lacking For the solubility of the solvent, the workability of the flexible metal-clad laminate may be deteriorated. Moreover, the storage stability of the blended resin may be deteriorated. 201206696 ' According to the metal-clad laminate, the T-bucket, εϊ & amine-flavored dough can be dissolved in the organic solvent: N_methyl as the ratio =; f month ^ month 曰 is also the same. Furthermore, there is a beauty, 醯mm, Gambian, ketone, N,N-dimethyl decylamine, N,N-di-gammamethyl, fine, four-coat, cyclopentide, dimethyl A stone that is fine, and also contains a portion of the compounds. Moreover, the soluble form of the present day is dissolved in 曰5 7 . 10% by weight or more, and the preferred prototype solvent contains at least one of (4)% by weight of the above-mentioned materials, and is carried out as follows. When the resin is in a solid shape, it passes through 8〇 in a 2〇〇ml beaker. The resin powder of the mesh will be gently stirred 3 times under the pit (10). It was allowed to stand under c for 24 hours, and if it was _ ̄ = white turbid or precipitated, it was judged to be dissolved. The object of the matter (11), the total amount of the acid component is 1 〇 0 mol%, the amine component state < 80 苴 莫 耳 ' ' has a clear toluene bone (four) single test ideal sample & ^ for to it' The more desirable state is 120% or more, and the most desirable ΐ 恶 is 170% or less. The most desirable form is when the amount other than (10) Mo % exceeds the above upper limit, except that the peel strength is lowered. JT has a decrease in the solubility of the granules and a deterioration in brittle stability. The heavy-duty, the butterfly [4] 201206696 Ο

(In the formula [4], the crucible and the ruler 6 may be the same or different, and the crucible of the crucible 1 to 4 or the silk base.) Each independently represents hydrogen or carbon number.

r 0 -N

[5]

1 to 4 alkyl or alkoxy 0 〇 N

Lim can be deleted, the nitrogen or carbon number of the butterfly field is C6] (R1 and R2 in the formula [6] can be the same or different, 烧1~4 of the alkyl group or alkoxy group. Further, Y means direct From "2, or, bond (-0-).) (10) bond (), or; polyamine amide resin (Π) in the formula [4] / general formula [5] / pass The ear is ideal (4) is 5G~99/1~50/uo, and the more ideal one is 6〇~9〇/5~4〇/5~3〇, more ideally, it is 65~85/1〇 ~3〇>5 2 2', the molar ratio of the general formula [4] is more than the above upper limit. Any of the general formula [5] and the general formula [6] is lower than the lower limit, and the surface is rough. The strength of the copper flaps with low degrees of gloss and reflection may be reduced. In the case where the molar ratio lower limit of the general formula [4] and the molar ratio of the general formula [5] and the general formula [6] are more than the above upper limit, the solubility of the fat to the organic solvent is lowered. The storage stability of the mixed resin may be deteriorated. The polyamine-quinone imine resin (II) is preferably an acid component comprising benzotricarboxylic anhydride, bis and 14 201206696 sulphur benzene tetracarboxylic dianhydride, and a component having a linked toluene moon virgin wood. Specifically, the acid component is a combination of benzene partial three===3, W biphenyl four-hat items, and = the state of the knife is 3,3,_dimethyl_4,4,-diamine Biphenyl. The oxime group is produced in the polyamine resin® field of the amine _L i f). The manufacturing method can be carried out by a conventional method, and (II) two, Rong, = Γ醯yf 面___聚_•咖安树脂 ^ Γ blending and manufacturing. The exfoliation strong layer is increased by the size of the granular phase of the two (8) components of the polypyridyl imino tree: tree =;: = r original cohesive force "two =" household == ίΐ; poly, quinone imine resin (1), _ molecular weight, a kg is likely to increase the particle size due to the increase in molecular weight. The particle size of the post-&&> can be determined by specifying the molecular weight of the two resins. The body contains amine 7 == turn) / poly-handling amine = the above «more than the former nail _, accompanied by resistance; low and _ degree and high reflectivity of the copper bismuth it's storage stability of the blended resin solution Will deteriorate. When the above-mentioned weight ratio of the stripped amine resin® is more than the above-mentioned upper limit, there is a case where the strong father returns, but since the heat resistance is lowered, the installation is reasonable: ί==: the quantity is more _ and: ==r The average molecular month::=_ is 3 to 9 faces, and the more ideal is to measure 0 to 7 faces. = pure imine _), _ number average molecular weight is less than the lower limit, ^ table = 201206696 The roughness is low, and the higher the gloss and reflectance, the better the average molecular weight, there is no upper limit. According to : system is reduced. The number is flat, but the average molecular weight of around 100,000 is already awkward. 'Although it is not possible to use the polyamine-based imide resin film (layer A), the most condensed polyamine in the granular phase of the yttrium imine resin (II) is calculated to be in diameter. Ομιη above, and more ideally, the bear A' intersection ideal is a circle change of 2.5μιη or more. When the diameter of the circle is more than ideal for the needle = 士', the roughness is low and the gloss and reflectance are high. The higher the surface rough diameter, the better. There is no upper limit. According to it will be reduced. The round change but the round conversion diameter is about the left and right, she has been born 'material energy' - in general, the B layer of polyamido- quinone imine resin, the total amount of the acid component of the bismuth component is in the case of Mox%, with (4) "" An's face

J moisture absorption dimensional change rate, and the characteristics of the JJL surface (low temperament) may also deteriorate. Further, under ^Momo*, the most desirable (four) is a 16G material% of the amine skeleton, and when the amount exceeds the above upper limit, the organic lion is dissolved low and the storage stability may be deteriorated. Poly layer B. The guanamine-containing imine resin comprises the above-mentioned general formula [4], the general formula [study, and the general [6], and the complex unit is preferably in the knife chain. The b layer of poly-tank yttrium imine resin ^ general formula [4] / general formula [study / general formula [sentence of the sentence is more ideally 5 〇 ~ 99 / 1 ~ 50/1 ~ 50, The more ideal form is 6〇~9〇//5~4〇/5~3〇, and the more ideal form is 65~85/10~3〇/5~20. The molar ratio of the general formula [4] is more than the above upper limit, and when any two of the molar ratios of the general formula [5] and the general formula [6] are lower than the aforementioned lower limit, the surface roughness is low and the gloss and reflection are low. The peel strength of the copper smear tends to decrease, and the characteristics such as the moisture absorbing dimensional change rate and the planarity (low warpage property) of the laminate may be deteriorated. Further, when the 201206696 • J ear ratio of the general formula [4] is less than the aforementioned lower limit, and any one of the molar ratios of the general formula [5] or the general formula [6] is more than the above upper limit, dissolution of the organic solvent Sex, storage stability may be woven. R, the amine is bound to the imide and the ugly count is the same as the bismuth layer of polyamine-imine resin (II). ^, layer B of polyamine-imine resin in N_methyl_2_pyr0^5〇Γ 〇51= It sub-quantity ', and more ideally, it has the equivalent of logarithmic viscosity S physical properties Insufficient, and the peel strength is also reduced by two. When the upper limit is reached, the viscosity of the solution is increased, so that the production of the above-mentioned polyamine-imine resin can be carried out by a method such as an isocyanic acid method or an amine method. For example, the lipid needs to be soluble in an organic solvent, and the tree coated coating is ideal. The belly b can be directly chemically reacted with the aromatic tri-salt anhydride and the aromatic amount, and the oxime, force, and monoisocyanate can be used in an organic solvent to determine the chemistry. It can be mentioned that the benzene is biased: the poly-_imine resin used. Aromatic three:;;:;?: For reason j: Cyanide agent in (4) 4 hours compared with: r_, alkali metal: ==== Manufacture of polyamido- 醯 胜 抖 该 该 该 该 该 该The polymerization solvent can be used to dissolve methyl-2-port ratios, NN_. _ organic solvent, for example, may be exemplified by N- '-indenyl hydrazine _$, hydrazine, hydrazine dimethyl hydrazine, ι, 3- 17 201206696 dimercapto-2-imidazolidinone, tetrahydrofuran, ring Ding 飒, dimethyl hydrazine, γ _ _ _ vine vinegar, cyclohexanone, cyclopentanone, etc., and the ideal form is Ν-mercapto-2- 比 咯 。. ^ ^ ^ may also be part of these compounds as a hydrocarbon-based organic solvent such as toluene, diphenylbenzene; diethylene glycol dioxime ether, triethylene glycol dioxime ether, tetrahydrofuran and other ether-based organic solvents; A ketone-based organic solvent such as thiol isobutyl ketone is substituted. The polyamine-imine resin of the present invention is used as a laminate for heat resistance, flame retardancy, adhesion, dimensional stability, flexibility, insulation properties, moisture absorption properties, and the like. In addition to the acid component and the isocyanate component shown above, the acid component and the amine component shown below can be copolymerized in the balance of the performance of the present invention. Further, in combination with the acid component and the amine component, it may be used in combination with a resin which is additionally polymerized. , the acid component, (8) tricarboxylic acid, diphenyl terminal 3, 3,, 4'-three: carboxylic acid, diphenyl -3,3', 4'-tricarboxylic acid, benzophenone _ a monoanhydride or an esterified product such as a tricarboxylic acid such as 3,3', 4,-tricarboxylic acid, naphthalenetricarboxylic acid or monobutane-1,2,4-tricarboxylic acid, or a mixture of two or more thereof. (8) a concave carboxylic acid, diphenyl sulfone _3, 3, 4, stilbene tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, -1,2,4,5-tetracarboxylic acid, Naphthalene-1,4,5,8-tetracarboxylic acid, butadiene-1,2,3,4-tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, etc. Anhydride, esterified product, etc. alone or in combination of two or more; (c) dicarboxylic acid, terephthalic acid, isophthalic acid, biphenyl dicarboxylic acid, diphenyl ^ ditoxin, diphenyl stone Carboxylic acid, adipic acid, azelaic acid, sebacic acid, cyclohexene [dicarboxylic acid of dicarboxylic acid, and monoanhydride or self-agent of such acids. The amine component may, for example, be 3,3,-diethyl-4,4,-diamine biphenyl, 2,2'-dimercapto-4,4'-diamine biphenyl, 2,2' -diethyl-4,4,-diamine biphenyl, 3,3,-dimethoxy_4,4,-February female biphenyl, 3,3-ethoxy _4,4'_ Diamine biphenyl, p-phenylenediamine, m-phenylenediamine, 3,decylamine, monophenyl ether, 4,4'-diaminodiphenyl ether, 4,4,-diaminodiphenyl sulfone, 3 , 3,-diaminomonophenyl hydrazine, 3,4'-diamine biphenyl, 3,3'-diamine biphenyl, 3,3,-diaminobenzimidil, 4,4'-di Aminobenzamide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3^4'-diaminobenzophenone, 2,6_ Toluene diamine, 2,4-nonylphenylenediamine, 4, succinimide, sulphur, 3,3'-diaminodiphenyl sulphide, 4,4, _diamine propylene , 3,3,-diamine, phenylpropan, 3,3'-diaminodiphenyl decane, 4,4'-diaminodiphenylmethane, p-xylene-amine, m-diphenylene diamine , 2,2'_bis(4-aminophenyl)propane, 1,3_bis(3-aminophenoxy 201206696 it amine oxy)benzene, bis(4-aminophenoxy)benzene, 2,2 -Double [4_(4_ Ϊίίί ]propane, bis[t(xylamine phenoxy)) Sulfhydryl, bis[4-(3-aminophenoxy i ϋι bis[4_(3-aminophenoxy)phenyl]propane, 4,4,_bis(4-aminophenoxy) hydrazine Phenoxy)biphenyl, tetramethylenediamine, hexamethylenediamine, isophorhexylamine diamine, cyclohexanyl], 4-diamine, diamine Wei, iifi, diisocyanate alone or Two or more kinds of mixtures. From the point of view of the brothers, the polyimine 醯 醯 imine resin of the present invention is more ideal than the non-recorded system of m-lin halogen. 3 w: ΐ 2 to be For the purpose of the metal-coated (four) body or the flexible printing base 5 spoons, for example, mechanical properties, electrical properties, smoothing agents, and i should be used at the same time. For example, the lubricating stupid car can be used at the same time, 4' Adhesive accelerator, flame retardant (filled or triazole), stabilizer (antioxidant-;:::: ^ ^ resin, poly Jr 丄 丄! ^ purpose, propyl acid Vinegar resin, ethyl urethane fiber, oxyamine, #夫#$ -&> should, if necessary, add aliphatic tertiary aliphatic anhydride, aromatic fiber, amine-imine resin, It is more reasonable to choose ,^, 仃, but no matter which kind of The mode is (4) heavy autumn weight / around, and most ideally, because the solvent is also the aforementioned organic solvent. The viscosity of the solution, the suitable viscosity of the 25t: ht amine-enamel resin solution is 1~l〇〇〇dpa · S range. 19 201206696 The metal used in the flexible metal-clad laminate is copper enamel. The surface of the copper enamel can be treated with organic rust (stupid thiazole, Benzotriazole, imidazole, etc., inorganic = rust, (zinc chrome, zinc alloy, etc.), decane coupling agent treatment (epoxy decane coupling, virgin virgin mixture, thiol-based couplant, etc.) ), coated electric key processing, calcined electric ore processing, and the like. The surface of the surface of the copper A-layer instrument _ stomach M is thicker than 3·0μιη = lower', and the ideal image of the father is 2 〇 or less, and the more ideal form is [O Array below. When the surface roughness exceeds the above upper limit, the pattern formability is inferior, and the lower limit of the surface roughness of the resin layer after the copper smear is not limited, but 〇1 2 is sufficient. The gloss of the copper foil is 3 Å or more, and the more desirable state is · or more, and more preferably 600 or more. Gloss was measured according to muscle Z874]_1997, = angle 60. Irradiated ' and measured 6 〇. The reflected light below. The higher the gloss, the lower the surface roughness, and the smoothness of the surface 4 is because there are not many corrugations or the like which are not reflected in the surface roughness. Therefore, the higher the gloss, the better, but _ is enough. , > human but the gloss, the so-called gloss value is determined by the measured light of the human-shot radiation, and the intensity of the reflected light relative to this is measured at an angle of, for example, JIS-Z874]: 1997 2〇. 45. 6〇. 75. 85. Wait for the angle of incidence, reflection =. Under the circumstance, if a high gloss cloth is used, in the flexible printed circuit board, the substrate layer of the copper 4-like ruthenium removal reflects the surface state of the copper, and the film layer with less diffusion and transparency is good. And the low gloss of the love & the opposite '. However, the transparency when the gloss is used as an index is strictly the angle of the incident angle at the two fixed angles and the amount of the scattered light at the reflection-fixation degree. Therefore, the wire material = the index of transparency is not practical. In detail, (7) the position adjustment of the FA plate, for example, irradiation of visible light of about 40 〇 nm to 800 nm on the substrate, and the pattern is discriminated by image processing, but it is not necessarily 60. The angle 'is rather the angle of incidence and angle of reflection closer to the vertical angle. Therefore, reflecting the surface state of the copper matte, the amount of the substrate of the copper box is close to the diffuse of the drum, and may also be glossy.

20 (D 201206696 ^ The value is irrelevant. For example, under the vertical reflection angle of the human angle of 5. The diffuser also speculates that the surface state is at the angle of the person and the angle of reflection is (6). 1 Conversely, in terms of position adjustment, the former is closer to practical. According to the point of view, choose as the better visibility] [7 (: (; ^ required copper foil, save the light autumn money] 'money irradiation 4. The position of the job is _nm, and the reflection of the substrate when the substrate is dead is effective, and the reflectance in the visible f-region f of 4GGnm~_nm of the present invention is 2G% or more, and the ideal state is 25% or more, more like evil, more than 30%. When the reflectance is low, the visibility is poor. The higher the reflectivity, the better, but about 80% is enough. The thickness of the handle is not limited, for example, 3~ 5 () μ Γ η is ideal. t official band shape 'and its length is not particularly limited ^. In addition, the forged band shape is not limited, but generally 25 ~ or so, and preferably the flexible cover The metal laminate, for example, can be coated on the copper by straight, over-adhesively coating the two kinds of polyamido-imine resins (Α layer: Β 4, and dried) The coating film (initial drying) and, if appropriate, heat treatment and solvent removal (secondary drying) are produced. The method of laminating two types of polyg__light amine resin on H33, the fat solution 'after initial drying' is applied to the B layer. The resin solution is initially dried, and the second dry method is applied as the case may be. Alternatively, the B layer resin solution may be applied after drying and secondary drying, : ^-human green, or may be coated A. Layer resin 1 ^ : tree knives two scraping, coating machine, gravure coater, die coater, reverse: cloth, on or directly coated with the adhesive layer to coat poly-imine wide-band machine巧 剂 剂 严 严 严 严 严 严 严 严 严 严 严 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 Department, poly 醯 ^ 峨 峨 亚 亚 亚 亚 亚 旨 旨 旨 亚 前 前 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 前 亚 前 前 前 前Left and right. For the ideal, it is better to use the Si coating == to make the flexible printed circuit board more interesting, and when the other circuit is processed π, The drying time will be lower than the type of the heart, and the temperature will be about 5 to 40%. The solvent residual rate is about 5 to 40%, and the amount of time is about 3 minutes in the coating film, preferably 2 ~15 minutes or so, and -1 to 30. In addition, the secondary drying conditions are not particularly limited, and the temperature above the boiling point of the dragon can be dried, and generally, as the two: near the point or 疋 200 (:~33 (TC. Go to two p, w #, C~400 C, the ideal pattern will decrease, and when it is too high, w drying time will become longer, productivity: brittle condition. Moreover, copper foil Crystallization of itself: two into: thin under 'in the smear image = tens of hours or so. ' A ff willow '❿-like for a few minutes ~ = force under the order' and more ideal form is in ίο·1~ island The pressure of the left and right; into the 22 8 201206696 early dry sister, a dry can be used in the field 3 habit 4a - mining pro-support or floating side use the method of drying, such as continuous heat treatment, or in the shape of curled Under the condition that the batching type of the heating furnace is used, the oven heat treatment is better than the batch type. Touch, Also, heating side; can be used ===: face: meeting, infrared heater, near infrared heater, etc. In the flexible metal-clad laminate of the present invention, the layer A of the layer A of the present invention is preferably a layer of _~, and the layer of the layer is poor, and is more visible when the upper limit is exceeded.达^下=, the thickness of the lion, the thickness of the installed polyamine-imine resin film (A^ ft = good ΜΟΟμιη =, polyimide 醯 胺 imine resin film (4)), more reasonable G f. 25~40μηι. The thickness of the a layer and the enamel layer / f „ is the inch, the rate becomes larger, and when it exceeds the above-mentioned one-limit time, the Πϊΐ: Ϊ has a tendency to be distorted and the folding resistance is degraded. Just when the upper limit is stated, the characteristics or the degree of addition of flexibility etc.

3;;:, Furthermore, the flexibility of the present invention is as follows: T is required to be applied to two laminates, and the two laminates are laminated, and the laminate is twisted, laminated, and laminated. Tangle #等, 3° '可23 201206696 The evil is 30〇c~50〇c, and the more ideal form is 35(rc~450. The state is 38〇t: ~430°c. More ideally # ' When the temperature is too low, the adhesion is insufficient, and when it is too high, the probability of the = i characteristic is lowered. The time of the lamination, and: the limit is particularly limited, but usually 1. seconds ~ 1 () hours, and ideal : After the clock ~ 3G minutes. When the time is too short, the two sides are bonded, and the mixture is mixed; "=The possibility of the mechanical properties being degraded by f. The above-mentioned etc. which can be used when the layer is laminated by the adhesive is used. The flexible metal-clad layer can be manufactured by a subtractive process circuit ί::4: ΐΓ program'. The edge of the edge-contained conductor circuit is called #1 (4). The thin film is applied to the circuit board (the method of forming the circuit, or the liquid coating agent is applied to the circuit amine-based ink by screen printing, and the preferred form is a polyamidene system.) Amine H bonding The film is directly attached to the circuit board. As described above, the brush substrate can be used for high-density road use applications requiring fine pitch, especially for liquid crystal screens such as flat display and mobile phones. The film-bearing tape is used. The wiring pattern of the '' τ circuit can form an arbitrary pattern. Especially in a circuit with a fine = line pattern, the flexible printed circuit board of the present invention also exhibits a high level of performance. In other words, the thickness of the wiring of the circuit may be 50 μΓη or less, or may be 3 μm or less, 20 μm or less, or less than 1 μmη. The interval of the wiring may be 5 〇 or less, or may be 30 μm or less, 20 μm or less, ΙΟμιη. [Embodiment] Hereinafter, the excellent effects of the present invention will be exhibited based on the examples, but the present invention is not limited to the embodiments. ▲ Further, the evaluation method of the characteristic values in the examples is as follows Further, the powdery polymer sample used in the method is prepared by reprecipitating and refining the polymerized dopants obtained in the respective examples and comparative examples in a large amount of acetone. 8 201206696 • <Adhesive strength> According to IPC-FC241 (IPC_TM-650, 2.4. 9(A)), a circuit pattern is formed by a subtractive process, and a tensile tester (product name ΓΤΕΝ8ΙΙΌ]Ν^ώ is used. Stretch test

The machine, manufactured by Toyo Baldwin Co., Ltd., measures the bonding strength between the circuit pattern and the resin layer. J &lt;Visibility&gt; Visibility, the light penetration group and the value are used as indicators, and the silk transmittance is above and the haze is 25 or less, and the evaluation is 乂. The line, the rate of incidence, and the intensity of the transmitted light are measured by irradiating light onto the resin film layer after stripping the copper flute from the flexible metal-clad laminate. Specifically, the intensity of the transmitted light with respect to the intensity of the transmitted light was measured by a percentage table * manufactured by UV-3150, and measured at a wavelength of ~12 〇〇 · island ^ 1600 nm / min. Frightenedness is divided by, ΐ ΐ 表示 表示 表示 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂 树脂. . Carry out, <use term>, use =, evaluate the increase in the viscosity of the solution after 3 months of storage at 5 为. The increase rate is 0 within 1.2 times of the initial value, and is χ when it exceeds. The β-type viscometer made by T. sinensis C (strand) is hunted by a number of rotations. &lt;Pattern Formability&gt; The photosensitive optical barrier layer is bonded to the copper wire of the flexible metal-clad laminate. Upper exposure, seeding, development and transfer of 2Q, Shishi 3 paste copper chloride solution, butterfly removal = two use first resistance by the test substance to remove. Pattern forming = shape, forming a circuit board according to the linearity of the pattern, the residual of copper, etc., etc., and the root &lt;amplitude&gt; Glass 4=:====^Tg of the film layer ^ TMA(^,^^„/Seik〇Eps〇n is determined under the conditions of 25 201206696. Load: 5g Sample size: 4 (width) &gt;&lt; 20 (length) mm Heating rate: l〇°C/min Environment: Nitrogen &lt;Quantum Average Molecular Weight&gt; The number average molecular weight was determined by GPC (gel permeation chromatography) under the following conditions: Column: TSKgel GMTiXLx2 + TSKgel G2000HXL (manufactured by TOSOI-I) Flow rate: 0.7 ml/min Temperature: 40 ° C Solvent: 0.1% lithium bromide / DMAc solution calibration line: The molecular weight is calculated in terms of standard PEG. The following values are used for the peg molecular weight. ', Peak No PEG molecular weight 1 920000 2 250000 3 170000 4 140000 5 107000 6 50000 7 24000 8 4000 9 1080 &lt;Logarithmic viscosity&gt; 'Prepare a powdery polymer sample and dissolve it in N-methyl-2-pyrrole. The ketone is ketone so that the polymer concentration is 0.5 g/d]. At 30. (: The viscosity of the solution and the viscosity of the solution are determined by Ubbelohde viscosity tube, and are calculated by the following formula Logarithmic viscosity (dl/g) = [lnM/VdA^ where the viscosity of the solution is measured, % indicates the measured solvent viscosity, and Vl and V2 are the solution and solvent (N-methyl _ 2-α ratio p σ deterministic ketone) is obtained by the time of the capillary phenomenon of the viscosity tube, and 'V3 is the polymer concentration (g/dl). 201206696 - <Gloss> Root, j!S-Z8741 -1997 The method for measuring the specular gloss is described as an incident angle of 60. The light source is irradiated at a reflection angle of 6 〇. The intensity of the reflected light is measured. The incident angle here is defined as a direction perpendicular to the irradiation surface of the light.测定. The measurement system uses a VG2 〇〇 gloss meter of Nippon Electric Co., Ltd. &lt;Surface roughness&gt; Measured according to JIS-B-0601. &lt;Reflectance (positive reflectance)&gt; Specular reflectance measuring device (for incident angle 5), which is measured by the UV-3150 manufactured by Shimadzu Corporation at a measurement wavelength of 300 to 1200 nm and a scanning speed of 1600 nm/min, and the positive reflectance at an angle of 5. The value of the reflectance is represented by 55 〇 nm. &lt;Maximum particle diameter of blue imine resin (Π)&gt; Polyamide-醯亚The maximum size of the particulate phase ([pi) of the resin component, based by the use of scanning electron microscope (SEM) at 25. (The temperature of the film was observed at the temperature of the cut surface. Synthesis Example 1 In the reaction vessel, 153 g of trimellitic anhydride (TMA) (manufactured by Rhombus Chemical Co., Ltd.), 3, 3', 4, 4' was added. -diphenyl ketone tetraf-acid dianhydride (BTDA) 4〇g (Daicdchemical

Industries, Ltd.), 3,3',4,4'-biphenyltetraphthalic acid dianhydride (3?〇8) 22笆 (manufactured by Mitsubishi Chemical Corporation), and indole anilide diisocyanate (T〇) DI) 264g (made by Nippon Soda Co., Ltd.), 3g of ethyl diamine (made by Nacalai Tesque, Inc.), and 720g of N-mercapto-2-pyrrolidone (NMP) (Mitsubishi Chemical Co., Ltd.) The X polymer concentration was 15% by weight), and the temperature was raised to 120 ° C in 2 hours, and the reaction was maintained for 5 hours. Next, 211 g of NMP (polymer concentration: 12% by weight) was added and cooled to room temperature. The resulting resin is yellow-brown and the polymer dissolves MNMP. The resin component, logarithmic viscosity, and number average molecular weight of the resin varnish of the synthesis example are shown in Table 1. Synthesis Example 2 A resin lacquer was produced in the same manner as in Synthesis Example 1 except that the resin component was changed to the contents shown in Table 1. Resin composition of resin paint of Synthesis Example 2, logarithmic viscosity, 27 201206696 The number average molecular weight is shown in Table 1 [Table 1] Resin component (Mohr ratio) - Synthesis Example 1 TMAyBTDA/BPDA/TODI=80/12.5/7.5/100 Synthesis Example 2 TMA/BTDA/BPDA/PMA/NDI=30/40/20/l〇/l〇〇ΤΜΑ: benzene trimellitic acid needle 1.8 1.2 number average 40100 31000 BTDA : 3,3,,4,4'- Diphenyl ketone tetraphthalic acid dianhydride BPDA : 3,3:4,4'-biphenyltetraphthalic acid dianhydride PMA: pyromellitic anhydride TODI : ortho-anisidine diisocyanate NDI : 1,5-naphthalene diisocyanate (Comparative Examples 1 to 4) The resin paint obtained in the synthesis example 2 was applied to the surface of the copper foil having the thickness of the copper foil as shown in Table 2, 2 to 5 μm, using a knife coater. The thickness after the bath (layer A) was ΙΟμιπ ' and dried at 1003⁄4 for 5 minutes. Then, the same method was applied, and the resin varnish obtained in the synthesis example was applied, and the thickness of the layer was set to 25, ' and dried at 1 G (1 Torr for 1 minute to obtain a "dry flexible coating". Next, the initially dried flexible metal-clad laminate is fixed to a metal crucible. The vacuum dryer and the inert oven are used to reduce the heat in the following conditions. Press drying conditions: 200 ° C x 24 hr (variation according to the volatilization of the solvent, the degree of decompression between 10 and 100 Pa) Heating under nitrogen (flow rate; 20 L / min): 260 ° C &gt;&lt; 10 hr The finally obtained flexible metallization The laminate was completely removed from the solvent in the coating film, and the properties and peel strength were as shown in Table 2. According to Table 2, a mirror-coated copper foil was used to obtain a flexible metal-clad laminate having good visibility. However, it is difficult to have both peel strength. 201206696 [Table 2] Visibility

X

X 〇 iifSMBiili' Surface roughness (μηι)

Thickness (μηι) Ajf/B layer 10/25 10/25 10/25 10/25 Peel strength (N/cm) 8.5_ 8.9 3.8 Synthesis Example 3 Adding trimellitic anhydride (TMA) 17 29g to the reaction vessel ( 9〇莫耳%, Sanqi Gas Chemical Co., Ltd., 3,3',4,4'-biphenyltetracarboxylic acid diterpene BpDA) 2 94g (1〇莫% 'Mitsubishi Chemical Co., Ltd.), 1,5-naphthalene diisocyanate (M) I) 21. 〇g (1 〇〇 mol%, manufactured by Sumitomo Bayer Urethane Co., Ltd.), diazabicycloundecene, surface apex辰反15重里%), warmed up to 1〇〇t in 2 hours: it will last for 5 hours. Next, add 6 weights (6) and cool to room temperature. The paint is colored; the compound is dissolved in NMP. ~ 界巴巴回5和聚(Comparative Example 5) In Comparative Example 4 Surface ===俾The thickness after solvent removal (2 = interface two flexible metal-clad laminate. Ming can, make the coated surface into a body Mosquitoes are heat treated at the time indicated by the internal temperature of 164 真 4 real work machine and inert oven under the following conditions: 2001x24^ (j艮j Kang solvent volatilization, decompression degree at 1 () ~ gallbladder &amp; Flow rate; 20L/min): 260tx3hr text and figure ====,=,"The solvent of all materials _ will deteriorate, the peel strength is also ==lip == 装二29 201206696 There is one ingredient (polyamide only - brewed The imide resin (I)) or the laminate having no B layer could not achieve the object of the present invention. Synthesis Example 4 193 g (90 mol%) of a trimellitic anhydride (TMA) was added to the reaction vessel, Mitsubishi Gas Chemical (share) system, 3,3',4,4 bisbiphenyltetraphthalic acid dianhydride (BPDA) 29g (10mol%, manufactured by Mitsubishi Chemical Corporation), 1,5-naphthalene diisocyanate (NDI) 2].0g0:00% by mol, manufactured by Sumitomo Bayer Urethane Co" Ltd., diazabicycloundecene ig (manufactured by San-Apro Ltd.), and N-mercapto-2-pyrrolidone ( NMP) 1944gg Ling Chemical Co., Ltd., polymer concentration 15% by weight ), the temperature was raised to l〇〇°c in 2 hours, and the reaction was maintained in this state for 5 hours. Next, NMP 571 g (polymer tears 12% by weight) was added and cooled to room temperature. The resulting resin paint was yellowish brown and the polymer was dissolved in NMP. The resin component and logarithmic viscosity of the resin varnish of Synthesis Example 4 are shown in Table 3. Synthesis Example 5 In the reaction vessel, trimellitic anhydride (TMA) 144 g (manufactured by Mitsubishi Gas Chemical Co., Ltd.), 3,3', 4,4f-diphenyl ketone tetraphthalic acid dianhydride (BTDA) 64 g (Daicel) was added. Chemical Industries, Ltd.), 3,3',4,4'-biphenyltetraphthalic acid dianhydride (BPDA) 15g (manufactured by Mitsubishi Chemical Corporation), and o-anisidine diisocyanate (TODI) 264g (Japan) Cao Da (share) system), Sanshen ethyl 'January female 3g (manufactured by Nacalai Tesque, Inc.), and ]si-mercapto-2-° piroxime α (NMP) 23〇Og (Mitsubishi Chemical) (Production) (polymer concentration: 1 S weight%), the temperature was raised to 100 ° C in 2 hours, and the reaction was maintained for 5 hours. Next, 726 g of NMP (polymer weight 12% by weight) was added and cooled to room temperature. The resulting tree was a yellow-brown transparent paint and the polymer was dissolved in NMP. The resin component and logarithmic viscosity of the resin varnish of Synthesis Example 5 are shown in Table 3. The number average molecular weight of the resin varnish of Synthesis Example 5 was 24,000. Synthesis Example 6 Addition of trimellitic anhydride (TMA) 58 g (30 mol%, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 3,3',4,4'-diphenyl ketone tetraphthalic acid dianhydride to a reaction vessel Moer%, Daicel Chemical IndUstrieS, Ltd.), 3,3,,4,4'-biphenyltetradecanoic acid anhydride (BPDA) 59g (2〇 mol%, manufactured by Mitsubishi Chemical Corporation) Pyromellitic anhydride 22 § (1〇201206696 mol%, manufactured by Daicel Chemical Industries, Ltd.), 1,5-naphthalene diisocyanate (NDI) 210g (100 mol%, Sumitomo Bayer Urethane Co) , manufactured by Ltd., diazabicycloundecene lg (manufactured by San-Apro Ltd.), and N-mercapto-2-pyrrolidone (NMP) 2210 g (Mitsubishi Chemical Co., Ltd. X polymer concentration) 15% by weight), the temperature was raised to 100 ° C in 2 hours, and the reaction was maintained for 5 hours. Next, 650 g of NMP (polymer concentration: 12% by weight) was added and cooled to room temperature. The obtained resin is yellow-brown and transparent, and the polymer is dissolved in ]^&gt;. The resin composition and logarithmic viscosity of the resin varnish of Synthesis Example 6 are shown in Table 3. Synthesis Examples 7 to 9 A resin lacquer was produced in the same manner as in Synthesis Example 6, except that the resin component was changed to the contents shown in Table 3. The resin composition and logarithmic viscosity of the resin varnishes of Synthesis Examples 7 to 9 are not shown in Table 3. Synthesis Example 10 19 g (10 mol%, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 3,3',4,4'-diphenyl ketone tetraphthalic acid dianhydride were added to a reaction vessel. (BTDAUMgGo Moer % ' Daicel chemical Iiidustries, Ltd.), 3,3',4,4'-biphenyltetradecanoic acid dianhydride (BPDA) 59g (20mol%, manufactured by Mitsubishi Chemical Corporation) Pyromellitic anhydride (卩祖) 22 政1〇莫耳%, manufactured by Daicd Chemical Industries, Ltd.), terephthalic acid (TPA) ng (2 〇 mol% 'Mitsubishi Gas Chemical Co., Ltd.), U_naphthalene diisocyanate (NDI) 210 g (100 mol%, manufactured by Sumitomo Bayer Urethane Co., Ltd.), diazabicycloundecene lg (manufactured by San-Apr〇 Ltd.), and N-fluorenyl group- 2] Pyrrolidinone (NMP) 2085 g (manufactured by Ershi Chemical Co., Ltd., polymer concentration Μ% by weight), and the temperature was raised to 10 ° C in 2 hours, and the reaction was maintained for 5 hours. Next, N613 613 g (polymer concentration: 12% by weight) was added and cooled to room temperature. The resulting resin is yellow-brown and the polymer dissolves MNMP. Next, the resin varnish obtained in Synthesis Example 5 was blended at a ratio of 20% by weight based on the solid content of the polyamide-imine resin. The resin component of the resin varnish of Synthesis Example 1 is shown in Table 3 ? 201206696 [Table 3] Resin component (Mohr ratio) - Logarithmic viscosity synthesis Example 4 TMA/BPDA/NDI = 90/10/100 1.6 Synthesis Example 5 TMA/BTDA/BPDA/]ODI=80/12.5/7.5/100 1.3 Synthesis Example 6 TMA/BTDA/BPDA/PM: A/NDI=30/40/20/10/1.0〇1.4 Synthesis Example 7 TMA/BTDA /BPDA//TODI=70/10/20/100 1.5 Synthesis Example 8 TMA/NDI/MDI=100/90/.10 ------- 1.7 Synthesis Example 9 TMA/BTDA/BPDA/TODI=55/ 15/30/100 1.6 Synthesis Example 10 TMA/BTDA/BPDA/PMA/TPA/NDI=10/40/20/10/20/100 + Resin TMS of Synthesis Example 5: trimellitic anhydride BTDA: 3, 3VMT- Diphenyl ketone tetracarboxylic dianhydride BPDA : 3,3',4,4'-biphenyltetradecanoic acid dianhydride PMA. Pyromellitic acid field TODI: o-toluidine diisocyanate ΝΌΙ · 1,5-Cai II Isocyanate TPA: terephthalic acid (Comparative Example 6) VPU flat , column, compare the use of the knife on the 落 surface of the copper drop used by m ==, 俾 to make the thick layer after solvent removal) , · square, 10 = lower, 5 minutes, to obtain an initial dry flexible metal-clad laminate. The dry and flexible metal-clad laminate is turned over, and the 16-to-1 set is the outer side, and the vacuum dryer and the vacuum drying machine are used to reduce the variation: 20 〇t &gt; 241 ir Initial dry flexible metal coating, QCT|^ 5 minutes, for the outside, and treated with true ^ '. New, her plum "Liang Gu ^ strip 32 201206696 Qian Can conditions. 2 according to solvent volatilization, decompression The team talked about the heating under nitrogen (flow rate; 2〇17 points): 26〇3 change) (Comparative examples 7~9) In addition to the thickness of the resin paint of the A and B layers, the heating time under nitrogen was changed to The final flexible metal-clad laminate was obtained as shown in Table 4, except for 10 hours. In the same manner as in Comparative Example 6, the flexible metal-clad obtained in Comparative Examples 6 to 9 was completely removed, and the mold formability and visibility were good, and the solvent in the ash was also excellent in mountability. However, in either of the above cases, A sound = other than Comparative Example 6, the duration of use is short, and her intensity (4) shows health. 〖W resin lacquer composition (polyamide-imine resin 1), or even though the A layer has only one resin (II) molecular weight (four), and * can achieve this hair -醯 imine [Table 41 clever. Polyamide-imine resin (I) Α layer ~ ^ amine - quinone imine resin 01) B layer thick diamond, (_) (A layer / B layer) Comparison of use period ό Comparative example 7 Comparative example 8 Comparison EXAMPLE 9 Synthesis Example Synthesis Example 6 Synthesis Example 8 Synthesis Example 11 Synthesis Example 10 Synthesis Example 5 Synthesis Example 7 Synthesis Example 9 Synthesis Example 1 25/10 1^25~10/25 10/25

XXXX Peel strength (N/cm) 4 4 4 Add benzene trimellitic anhydride (TM^) 58g (3 〇 mol%, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 3, 3', 4, 4 to the reaction bar. '-Diphenyl ketone tetraphthalic acid dianhydride (BTDA) 129 g (4 〇 mol % 'made by Daicel Chemical Industries, Ltd.), 3,3', 4,4'-biphenyltetraphthalic acid dianhydride (BPDA) 59 g (2% Moer%, manufactured by Mitsubishi Chemical Co., Ltd.), pyromellitic anhydride sand ^) 2 (1 〇 mol%, manufactured by Daicel Chemical Indus 1: ries, Ltd.), 1,5-naphthalene diisocyanate ( NDI) 208 g (99 mol%, manufactured by Sumitomo Bayer Urethane Co. Ltd.), diazabicycloundecene lg (manufactured by Saii-Apro Ltd.), and N-mercapto-2-pyrrolidone (NMP) 2210 gg The concentration of the X polymer in the chemical system was 15% by weight, and the temperature was raised to 100 ° C in 2 hours, and the reaction was maintained for 5 hours. Then, 33 201206696 NMP 650g (polymer concentration) 2% by weight was added. The resin paint was yellow-brown and transparent, and the polymer was dissolved in NMP. The resin composition, logarithmic viscosity, and number average molecular weight of the resin paint of Synthesis Example 11 are shown in Table 5. Synthesis Example 12~ 15 A resin lacquer was produced in the same manner as in the synthesis example η except that the resin component was changed to the content shown in Table 5. The molecular weight was appropriately adjusted according to the acid component, the molar ratio of the isocyanate component, the reaction time, and the like. The resin component, logarithmic viscosity, and number average molecular weight of the resin varnishes of Synthesis Examples 12 to 15 are shown in Table 5. [Table 5] Resin Component Mohr Ratio) Logarithmic Viscosity 3 Amount Average Molecular Weight Synthesis Example 11 TMA/BTDA/BPDA/PMA/ NDI=30/40/20/10/100 0.9 23000 Synthesis Example 12 TMA/BTDA/BPDA/PMA/NDT=30/40/20/10/1〇〇1.2 * 31000 Synthesis Example 13 TMA/BTDA/BPDA/PMA /NDI=30/40/20/1〇/1〇〇1.5 ' 37000 Synthesis Example 14 TMA/BTDA/BPDA/TODI=80/12.5/7.5/100 1.8 40000 Synthesis Example 15 TMA/BTDA/BPDA/PMA/NDI =30/40/2O/10/]00 1.6 40000 (Comparative Example 10) In the resin varnish obtained in Synthesis Example 11, the stag varnish obtained in Synthesis Example 14 was used in relation to polyamine-imine. The solid content of the resin is 1 〇〇 by weight and the ratio of ^ = is blended (polyamine-quinone imine resin (1) / polyamine-imine resin j 1%) = 80/20). In the M surface of the copper foil used in Comparative Example 4, ί^ cerebral palsy was used, and the thickness (layer A) after solvent removal was made into 1^ + dry 5" clock. Next, in the same manner as in the same manner, the thickness of the solvent-removed layer (B layer) was 25 μm, and it was obtained by the same method. Drying under c gives an initially dried flexible metal-clad laminate. "The knife and the bell are connected to J, and the initially dried flexible metal-clad laminate is fixed to a metal post-drying machine and an inert oven under the conditions shown below. After the lack, the service is shown in Table 6. The metal-clad laminate. After the decompression drying conditions: 2〇〇t: x24hr = 艮 ^ Kang; the volatility of the gluten 胄 1丨, the degree of decompression in 1G ~ between the variable nitrogen oxygen heating (flow; 20L / Sub)): 260t: xl0hr 34 8 201206696 (Examples 1 to 3) A flexible metal-clad laminate was obtained in addition to the case where the layer A was difficult to be compared with the example of the yarn 6. Polyamide amide 2, amine- 1 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The mounting property was good. ^Yes, the short-term use period of the resin lacquer used in the enamel layer of Comparative Example 10 also showed that Hunting 1 followed. According to the above, it is known that layer a; when the amount of amine-eucalyptus is low, Α The layer formed by the layer. II = (1 ^ 3 grains will become smaller, and the result is the peel strength or the use period is reduced. Moreover, the molecular weight of the polyamine (I) followed by (I) is ideal, *25_The purpose of the invention is 1 [Table 6] 1 Ί Α layer B layer polyamine-imine resin (10) maximum particle size ----------- j life-------- - Peel strength (N/cm) Polyamine-imine resin (I) Polyamine-imine resin (II) Comparative Example 10 Synthesis Example 11 Synthesis Example 14 Synthesis Example 14 0.3 X - 5 Example 1 Synthesis Example 12 Synthesis Example 14 Synthesis Example 14 2.0 〇10 Example 2 Synthesis Example 13 ----· Synthesis Example 14 Synthesis Example 14 3.0 〇10 Example 3 Synthesis Example 15 Synthesis Example 14 Synthesis Example 14 3.1 〇10 Thickness: A Layer /: 8 layers = 1 〇 / 250111 Synthesis Examples 16 to 20 A resin lacquer was produced in the same manner as in Synthesis Example 11 except that the resin component was changed to the content shown in Table 7. The molecular weight was based on the acid component and the isocyanate component. The molar ratio, reaction time, and the like were appropriately adjusted and adjusted. The resin component, logarithmic viscosity, and number average molecular weight of the resin varnish of Synthesis Examples 16 to 20 are shown in Table 7. [Table 7] . . . . Composition (Morby) Logarithmic viscosity number average synthesis Example 16 TMA/BTDA/BPDA/PMA/NDI=30/40/20/10/100 -------- 1.3 31000 Synthesis Example 17 TMA/BTDA/ BPDA/ TODI=80/12.5/7.5/100 — 1.6 34000 ~~ Synthesis Example 18~1 TMA/BTDA/BPDA/TODI=80/12.5/7.5/100 ------- 1.9 39000 ~~~ Synthesis Example 19 TMA /BTDA/BPDA/TODI=80/12.5/7.5/100 2.6 45000 35 201206696 Synthesis Example 20 50000 (Comparative Example 11, Example 4 to 7) The flexibility was obtained by changing the thickness of the A-layer resin varnish to the same as in Comparative Example 1G. The resin-coated lacquer used in the metal-clad laminate/ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ low value. _In the above, it can be seen that when the molecular weight of the polyamine-imine M used in the layer A is low, the particle size of the polyamine-containing imine resin (Π) component formed in the layer A becomes small. The result is a reduction in peel strength or life. Further, the polyamine-quinone imine resin (II) has a high molecular weight, and more than 25 Å can achieve the object of the invention. [Table 8] Maximum particle size of the B-layer polyamine-imine resin (II) of the Fufu period. Peel strength (N/cm) Polyamine-imine resin (I) Polyamide-imine Resin (Π) Comparative Example 11 Synthesis Example 16 Synthesis Example 5 Synthesis Example 14 0.35 X 5 «Example 4 Synthesis Example 16 Synthesis Example 17 Synthesis Example 14 1.5 〇 9 15 Example 5 Synthesis Example 16 Synthesis Example 18 Synthesis Example 14 3.0 〇 10 Example 6 Synthesis Example 16 Synthesis Example 19 Synthesis Example 14 3.8 〇12 Example 7 Synthesis Example 16 Synthesis Example 20 Synthesis Example 14 3.7 〇11 Thickness: A layer/B layer = 〇 25 / 25 μ Γ Synthesis Example 21, 22 In addition to The resin composition was changed to the content shown in Table 9 and the resin composition was prepared in the same manner as in the synthesis example 1. The molecular weight is adjusted as appropriate depending on the acid component, the molar ratio of the isocyanate component, the reaction time, and the like. The resin component, logarithmic viscosity, and number average molecular weight of the resin varnishes of Synthesis Examples 21 and 22 are shown in Table 9. [Table 9] Resin component (Mohr ratio) Logarithmic viscosity number Annual average liver mass synthesis Example 21 TMA/BTDA/BPDA/PMA/NDI=30/40/20/10/100 1.2 31000 Synthesis Example 22 TMA/BTDA/BPDA /TODI=80/12.5/7.5/100 1.9 39000

(D 201206696, (Comparative Examples 12, 13, 8, 8, % Comparative Examples 12, 13, and Examples 8 and 9 were completely removed, and the pattern forming property and the visibility of the four-body coating were used for the three layers. Resin paint has a short service life, stacking ^1 = 5N/cm 〇X 5 12 According to the description, it can be seen that the A-layer used in the A layer is used. The service life and mountability will decrease. ...The strength of the carving or [Table 10 A layer of polyamine-imine resin (1) Polyamido- quinone imine resin (Π) Polyamide - quinone imine · shed (I) / polyamine - quinone imine resin (II) Solid content weight ratio B layer lifespan Peel strength (N/cm) Comparative Example 12 Comparative Example 13 Example 8 Example 9 Synthesis Example 21 Synthesis Example 21 Synthesis Example 21 Synthesis Example 21 Synthesis Example 22 Synthesis Example 22 Synthesis Example 22 Synthesis Example 22 60/40 97/3 80/20 85/15 Synthesis Example 22 Synthesis Example 22 Synthesis Example 22 Synthesis Example 22

XX 〇 ' ' ' A layer / B layer =]. 〇 / 25μτη [Industrial use] & The flexible metal-clad laminate of the present invention can be used for high-speed board applications requiring fine pitching' It contributes to inexpensive manufacture of a flexible printed circuit board which can be used for a C〇F film-carrying tape, and is of great industrial value. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A schematic view showing a cross-sectional structure of a flexible metal-clad laminate of the present invention. ^'No. Description [Main component code 37 201206696 1.....copper 羯2.. Polyamide- quinone imine resin film (layer A) 3.. Polyamide-quinone imine Resin film (B layer) 201206696 Patent description # (This manual's format and order, please do not change it arbitrarily. ※Please note the number of the mark ※Application number·· 1^0 〖, ' ※Application 曰: (price t沦※工p C classification: b Ρ (2〇〇6·Zha (2006.01, I. Invention name _爯: (Chinese / English) &gt;7/1

*Sexual metal-clad laminate

FLEXIBLE METAL-CLAD LAMINATE II. Abstract of the Invention: The present invention provides a flexible metal-clad laminate which is excellent in mountability, visibility, and pattern C). 〉 The present invention is a laminate of a polyimide/imine resin film (layer A) laminated on a copper foil directly or through a binder, and a laminate of a polyamidamine film on top of it. a layer body, wherein the layer A comprises: a polyamidamine-quinone imine resin q comprising an amine component having a skeleton; and a polyamine-quinone imine resin (II) comprising a linked/anthracene &amp; The amine component, and the weight ratio of (I) / (II) is 95 to 70/5 to 30; (I) and / or (Π) has a number average molecular weight of 25000 to 100000, and the layer B contains: a polyamine The indigo imine resin 'containing an amine component having a benzidine skeleton; and having a surface roughness of 3 μm or less on the side of the copper layer A layer and a wavelength of 300 or more and 4 to nm nm to 800 nm t' The reflectance of light is 20% or more. Third, the English invention summary:

This invention provides a flexible metal-clad laminate at a low cost that is excellent in feasibility of installation, visibility, patterning ability and peeling strength. In this laminate, a polyamide imide resin film(Layer A) is laminated on a copper foil directly or Layer A includes a polyamide imide resin (I ) containing an amine component having a naphthalene bone and a polyamide imide resin (Π) containing an alkali component containing a naphthalene bone and a polyamide imide resin An

Claims (1)

[2] [2]201206696 (Y in the formula [2] is c = 0, and η is 0 or 1). 3. The flexible metal-clad laminate according to claim 2, wherein the molybdenum of the general formula (1) / general formula [2] / general formula [3] in the polyamidoamine-imine resin (I) The ratio is 1〇~5〇/20-80/5-20 〇4· The flexible metal-clad laminate according to claim 1 or 2, wherein the poly-monthly acid-acid imide resin (Π) contains An acid component composed of trimellitic anhydride, benzophenone tetracarboxylie dianhydride, and blPhenyltetracarboxylic dianhydride, and an amine component having a benzidine skeleton. /, 秘秘 t such as the flexible metal-clad laminate of claim 1 or 2 of the patent, wherein in the t-imine resin film (4)), the imine of the maximum size of the circle-converted diameter (Secondary dispersion or phase separation. -7b ^ a layer of tree money "golden pro, a layer of fine, its μ 201206696 . 9. A two-sided flexible metal-clad laminate, by bonding patent application scope The flexible metal-clad laminate according to any one of the items 1 to 8, which is obtained by forming a metal foil on both sides. 10. A flexible printed circuit board is used in the first to ninth claims. Flexible metallization laminate of any one Figure: 41 4 201206696 . 9. A two-sided flexible metal-clad laminate, which is bonded to a flexible metal-clad laminate according to any one of claims 1 to 8, to form a metal on both sides. Get it from foil. 10. A flexible printed circuit board using the flexible metallization laminate of any one of claims 1 to 9. Schema: 41 4