TW200814892A - Manufacturing method of flexible laminated plate - Google Patents

Abstract

Provided is a manufacturing method of flexible laminated plate, wherein a required processing time of a heating step after dispensing a polyimide precursor resin solution on a conductive metal foil is short, so as to provide a flexible laminated plate having a low extension elasticity modulus, an excellent flexibility, and an excellent dimension stability. According to the manufacturing method of flexible laminated plate of the present invention, a polyimide precursor resin solution is dispensed on a conductive metal foil, and the polyimide precursor resin solution is then dried and cured by a heating processing, wherein, a total heating time of not less than 90 DEG C; in the heating processing is in a range of 5-25 minutes; the ratio of a heating time of 90-200 DEG C; to a heating time of more than 200 DEG C is set to be 9:1-7:3; the extension elasticity modulus of the polyimide resin layer formed on the conductive metal foil is controlled to be 3-6 Gpa,and the coefficient of heat expansion is controlled to be in a range of 16-28 ppm/DEG C.

Description

1 200814892 - IX. Description of the Invention: - Technical Field to Which the Invention Is A The present invention relates to a method for producing a flexible laminate comprising an insulating layer made of a polyimide resin on a metal foil. [Prior Art] The flexible laminated board is composed of a metal layer and an insulating layer, and has flexibility, and thus contributes to downsizing and weight reduction of a wiring board used in a portion requiring flexibility and flexibility. Even in the laminated board, the insulating layer is made of a polyimide resin, and it is widely used in a f-substrate such as a mobile phone or an information terminal because of its heat resistance and ruler stability. The method for manufacturing a flexible laminate is, for example, a method in which a polyimide resin film is bonded to a metal by an epoxy resin-specific adhesive, or a polyimide resin is directly coated on a metal foil. Or a method of manufacturing the first (iv) fat solution. In particular, the latter method is obtained, and there is no such a problem that the characteristics caused by the binder are lowered, and it becomes a flexible laminate which utilizes the properties of the poly-amine resin. (For example, in the recent years, the miniaturization and weight reduction of the portable electronic device H are becoming increasingly folded. The wiring substrate is required to be mounted in a very narrow space in the machine. Therefore, the laminated laminate is required. Bending, which is a method of improving the bending property of a flexible laminated board, such as a metal foil or a thinner, or a lowering of the tensile modulus of the insulating layer.卜: Reducing the tensile elasticity of the polyimide resin which is effectively used as an insulating layer ^

Two == In the molecular backbone of the polyimine, a bendable bond: a methyl bond or the like is introduced. For example, a polyiminoimine precursor resin using [4,-diphenylamine (10) A 319059 6 200814892 "oxydiani 1 ine" as a raw material monomer is synthesized and synthesized by yttrium yttrium. A ytterbium imide resin insulating layer having a low modulus of elasticity (see, for example, Patent Documents 2, 3, and 4).

However, in the case of the mono-ruthenium film of the polyacrylonitrile resin described in the patent documents, when the coating is deposited or laminated on the metal to form a dicot, it is difficult to obtain between the polyimide and the metal layer. Full adhesion to strong s degrees. The method for solving the above problem is to multilayer the polyimine resin layer, and to provide a good adhesion of the second thermoplastic resin polyimide layer to the metal foil on the side adjacent to the metal slant, and to turn the thermoplastic in the thermoplastic The outer side of the imide resin layer (the side opposite to the metal side) forms a method of forming an elastic amine-based resin layer. - [Patent Document No. 3] Japanese Patent Laid-Open No. Hei. No. 2003-192788 (Patent Document 3) Japanese Patent Publication No. 2003-192788 (Patent Document 4) Japanese Patent No. 3523952 _ [Summary of the Invention] (Problems to be solved by the invention) Layer 2: The use of thermoplastic polyacrylamide resin to increase the number of insulation, (4) The thermal expansion of the entire insulating layer can be sustained as a scratch The situation in which the stability of the inch deteriorates. In order to maintain a sufficient size when the resin solution is applied, it is necessary to reduce the problem. The time is elongated and will lead to productivity. The present invention has been thoroughly studied in order to solve the problem. The 319059 7 200814892 is to provide a flexible laminate which is manufactured in a flexible laminate. The polyaniline precursor resin solution is coated on the conductive metal drop =, the processing time required for the heating step is short, and the pull-down is good: good property and good dimensional stability. In the method of manufacturing a flexible laminated board by the method of (4), the heat treatment after the application of the imine precursor resin solution is carried out in order to solve the above problems. The steps are set to specifically control the characteristics of the insulating layer to complete the present invention. In other words, the method for manufacturing a flexible laminated board is characterized in that the polyimine precursor 醮 = liquid f is placed on the conductive metal, and the polydiamine kebab resin solution is dried by heat treatment. And the manufacturing of the hardened flexible laminated board is characterized in that, in the heat treatment, the total range of 9 〇〇c or more is heated (the range of 3 minutes) and the force of 9 generations or more and 2 generations or less = The ratio of the time to the heating time at a temperature of more than 20 generations is set to t·1 to 7:3′ and the pull (4) (4) of the polyacid imide layer formed on the conductive metal swash is controlled to 3 to 6 GPa. The coefficient of thermal expansion is controlled in the range of 16 to 28 ppm / ° C. (Effects of the Invention) According to the present invention, it is possible to manufacture a flexible laminate having excellent bending stability of 2 inches with a short heat treatment time, and to improve the production of a flexible laminate having such superiority. The effect of sex. [Embodiment] Hereinafter, the present invention will be described in detail. 319059 8 200814892 A flexible laminate produced by the present invention has a polyimide resin layer on a conductive metal slab (hereinafter referred to as "metal foil"). Further, the method of forming a polyimide layer on a metal foil is carried out by coating a polyimide resin precursor solution on a gold stalk and then performing a drying and hardening heat treatment. This converts the above polyimine precursor into a brewin. Further, the polyimide laminate layer of the manufactured flexible laminate has a tensile modulus of 3 to 6 GPa' and a coefficient of thermal contraction in the range of Μ to 28 ppm/cc. In addition, the term "polyimide resin" as used in the present invention means, for example, a polyacrylimine, a polyamidimide, a polyether quinone, a polydecane ylide, or the like, in a molecular structure. A resin composed of a polymer having a quinone imine group. The conductive metal foil used in the present invention is, for example, a metal foil containing copper, melamine, iron, silver, silver, iridium, nickel, chrome, niobium, crane, or an alloy thereof. . Among the metal foils, copper foil or alloy copper foil is preferred. The thickness of the metal foil is preferably in the range of 5 to 35 / / m, particularly preferably in the range of 9 to 18 / / m. If the metal foil is thicker than 35//111, the laminate will become harder, resulting in deterioration of bendability and f-folding. When the ratio of the metal foil is thin, it is difficult to adjust the tension or the like in the manufacturing step of the laminated board, and it is easy to cause wrinkles and the like. In addition, the metal foils may be subjected to a chemical or mechanical surface treatment on the surface for the purpose of improving the adhesion. The polybendylene precursor resin solution used in the present invention can be produced by a known method. For example, the tetracarboxylic dianhydride and the diamine compound are dissolved in a general molar organic solvent, and stirred for 30 minutes to 24 hours in 〇 to 10 ° C to obtain a reaction. The organic solvent used in the polymerization may, for example, be N,N-didecylguanamine, N,N-dimethyl 9 319059 . 200814892 , acetamidine, N-methyl-N-pyrrolidine Ketone, dimethyl sulfoxide, dimethyl sulfate, phenol, - dentated phenol, cyclohexanone, dioxane, tetrahydrofuran, diglyme, triethylene glycol dimethyl ether and the like. Two or more of the above compounds may also be used in combination. The viscosity of the polyimine precursor resin solution is preferably in the range of 5 〇〇 cp to looooocp. When it exceeds this range, when a coating operation is performed by a coater or the like, it is easy to cause defects such as thickness unevenness and streaking on the film. The tetracarboxylic dianhydride and the diamine compound to be used may be one or more selected from the above-mentioned compounds, as appropriate, in combination with the properties of the polyimine resin layer of the flexible laminate of the present invention. In the present invention, it is necessary to set the tensile modulus of the polyimide film to a range of 3 to 6 GPa, and to set the coefficient of thermal expansion in the range of 16 to 28 Ppm/° C., in order to form a flexible laminate. The adhesion between the metal foil and the polyimide layer is in a good state, and it is preferable to form the polyimide layer into a plurality of layers. When the polyimine resin layer is formed into a plurality of layers, the layer adjacent to the metal foil is preferably set to a high thermal expansion coefficient polyamidene resin layer having a thermal expansion coefficient of 3 〇ppm/t or more. In the case of a high thermal expansion coefficient polyimine resin layer, it is preferred to have a structural unit represented by the general formula (1).

In the formula, the lanthanoid series is selected from the groups shown by the following structural formulas (2) and (3) to a group of >, and R2 is selected from the groups shown by the following (4) and (5). At least one type of base. Further, in the following structural formula (4), the hydrazone refers to any of -s〇2—, —c〇— and a direct bond. 319059 10 (3) (2) 200814892 χ>πχ (4) XX (5) When the layer of the polyimide resin layer is formed into a plurality of layers, it is preferable to thermally expand the "imide resin layer (4) (in contrast to the metal ^:: Γ::: The base of the base polyimide resin layer with a ratio of 4 to 8 GPa. The soil layer _ sub (four) grease layer preferably has the structural unit shown by the general formula (6):

(6) wherein R3 is any one of -CH3, -C2Hs, _〇CH3, or 〇C2H5. The best R3 is -CHs. In addition, 戎φ, γ τ, and the 〆 中 X X 系 系 系 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ 4 4 4 4 4 3 3 3 3 3 3 3 3 3 3 3 3 3 And X + y=1. In the ratio of χ to y, if X is less than 〇·[the thermal expansion coefficient of the polyimine resin becomes large, the dimensional stability of the laminated laminate (4) is lowered, and the laminate tends to be curled. On the other hand, when X is more than 〇6, the tensile modulus of the polyimine will increase, and the bendability at the time of forming the flexible laminate tends to be lowered.

The poly-imine resin layer is formed into a plurality of materials, and the layer structure k of the flexible laminate is preferably configured to set a high thermal expansion coefficient of the polyimine tree in the gold m, and sub-layers are sequentially stacked thereon. The structure of the quinone imine resin layer. Further, the layer structure is a metal foil/high thermal expansion coefficient polyimine resin layer/base yttrium imide resin layer/咼 thermal expansion coefficient polyimine resin layer. Thus, 11 319059 . 200814892 8 After making a single-sided flexible product/layer having a metal foil on one side of the polyimide layer, the metal box is heat-bonded to the resin side, preferably high heat. On the polyacetimimine resin layer, the double-coated flexible laminate having a metal foil on both sides of the polyimide resin layer can be produced. The present invention adopts a production method in which a coating of a polyaniline precursor resin solution is carried out on a metal case and heat treatment is performed, but in the drying and hardening steps in the production step, 9 (the total of rc or more is required) The heating time is set to the valley for 25 minutes, and if the total heating time is shorter than 5 minutes, the polyimine resin is likely to cause problems such as foaming. Conversely, if the total heating time exceeds 25 minutes, the flexible laminate is The productivity is deteriorated. In addition, it is necessary to set the ratio of the heating time in the drying and hardening steps to the order of 9 or more and the heating time of 20 or less and the addition time of more than 2〇〇t: the temperature to 9 : 1 to 7: 3. If the heating time ratio at the temperature of 9 or more and lower than /C is less than the total heating time, the thermal expansion coefficient of the polyimine layer becomes large, or the flexible laminate The dimensional stability of the plate is reduced, or the laminate is curled. Conversely, if the heating time ratio below the temperature of _ °c exceeds 9 (10) of the total heating time, when the heat treatment is performed at more than 20 (TC temperature) ,Rise When the temperature is too high, the polyimine is likely to cause problems such as foaming. Further, when the polyimino resin layer is composed of a plurality of layers, the polyacid precursor precursor resin solution applied to each layer is added in total. The drying time is applied, and the hardening time is taken into account, and the heating time is determined. In addition, regarding the heating temperature of more than 2 Torr, since the polyimide layer begins to deteriorate, it is preferable to heat the temperature. The upper limit is set to 450 ° C. 319059 12 .200814892 : The thickness of the polyimide layer of the flexible laminate is preferably set in the range of 5 • to 40 # m, particularly preferably 8 to 35 # m. When the thickness of the polyimide layer is less than 5 #m, the strength when used as an insulating layer is weak, and when the processing is performed on the sheet, the film is likely to be broken or the like. 40 / / m thick, the film is less likely to bend, resulting in flexibility, laminate, 3 fold reduction. When the polyimine resin layer is set to multiple layers ^ substrate (four) imine resin layer and high scale (4) The imine resin layer, the good ratio is based on the total thickness of each The base polyimine resin layer/high thermal expansion coefficient polyimine resin layer is from i to 4 Å, more preferably 30%. In the manufacturing method of the flexible laminated board, the polyimide layer (i) yield Must be set to 3 to 6 GPa, at the same time, the number of thermal expansions must be ..., 6 to 28 qing. The tensile elasticity of the polyimide resin layer is ι Γ仏 1 & the range is 3.5 to 5.5 GPa. The rate is lower than 3 Gpa, and it is difficult to handle the processing of the flexible laminated board. On the contrary, if the bending property is higher than that of the depleted laminated board, the fineness of the polyimide layer is 17 to 2 W. If the difference between the 酿 靡 靡 超过 超过 超过 超过 超过 , , , , , , , , , , , 超过 超过 超过 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜The elastic modulus and the 埶 胀 系数 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制The manufacture of laminates. (Embodiment) 319059 13 200814892 • Hereinafter, the present invention will be described in more detail by way of examples. In addition, the abbreviations used in the examples/examples are as follows: DMAC · N,N-dimethylacetamide m-TB : 2, 2' ~ dimethyl-4,4'-diaminobiphenyl 0M : 44'-diaminodiphenyl ether BAPP = 2,2'-bis(4-aminophenoxyphenyl)propane PMDA: pyromellitic anhydride 10 steps 1) 8: 3, 3'-4 In the example of 4'-biphenyltetracarboxylic dianhydride, the evaluation of the tensile modulus of elasticity and the coefficient of thermal expansion of the polyimide layer of the polyimide resin was carried out in the following manner. Tensile modulus: The measurement was carried out using a Strograph® R-1 manufactured by Toyo Seiki Co., Ltd. (According to IPC-TM-650, 2. 4. 19) Thermal % expansion coefficient: using a Seiko Instruments thermal analyzer TMA-1, heating up to 255 t^^, after holding at this temperature for 1Q minutes, Further, cooling was carried out at a rate of 5 ° C /min, and the mean thermal expansion coefficient (thermal expansion coefficient) from 24 ° C to i 〇〇 ° c was determined. [Synthesis Example 1] m-TB (6 equivalents) and hydrazine DA (4 equivalents) were stirred at room temperature to dissolve DMAc in a separable flask. Next, PMDA (9 86 equivalents) was added. Then, stirring was continued for about 3 hours to carry out a polymerization reaction to obtain a polyamidene precursor resin solution a. Further, DMAc uses an amount of loading of m-ΤΒ, 0M, and PMDA of 16% by weight. The polyiphthalide precursor resin solution a prepared in the copper foil (the steel foil BHY-22B-T made by Nikko Materials Co., Ltd., thickness: 18/zm. Hereinafter referred to as "copper foil") means the copper 319059 14:200814892 4) Evenly coated to a thickness of 26 〇A m and at 125. The solvent is removed by applying the heat for 3 minutes. Then, at (10). C to the °C temperature range of 8 minutes and 3 seconds, in the temperature range of 2〇11 to 3赃 = j minutes and 30 seconds of heat treatment, and the hydrazine imidization reaction, and the formation on the copper There is a layered body with a thickness of about 28 # m polyimine layer. The copper falling layer of the laminate is removed by a solvent treatment to obtain a polyimide film. The tensile elastic modulus and thermal expansion coefficient of the polyimide film obtained by the measurement were 6.8 GPa and 12.6 ppm/°c, respectively. [Synthesis Example 2] A polymerization reaction was carried out in the same manner as in Synthesis Example 1 except that 5 equivalents of the m-TB system and 5 equivalents of the 0DA system were used, and a polybine imine resin solution b was obtained. Using the prepared polyimine precursor resin solution b, a polyimide film was obtained in the same manner as in Synthesis Example 1, and the tensile modulus and the coefficient of thermal expansion were measured, and the results were 5. 9 GPa, 17·1 ppm/ °C. [Synthesis Example 3] The polymerization reaction was carried out in the same manner as in Synthesis Example 1 except that 4 equivalents of the m-TB system and 6 equivalents of the ODA system were used, and the polyaniline precursor resin solution c was obtained. GPa, 23·lppm/, respectively, the tensile modulus and thermal expansion coefficient were measured, respectively, and the results were 5. 1 GPa, 23·1 ppm/, respectively, using a polyetherimine precursor resin solution c'. 〇C. [Synthesis Example 4] Except that the m-TB system used 1 〇 equivalent and the 〇DA system used 0 equivalent, the 319059 15 200814892 f remainder was in the same manner as in Synthesis Example 1 and was taken as a person. The polymerization was carried out to obtain a poly(indenine) precursor resin solution d. In the same manner as in the synthesis example i, the polyimide film was obtained by the same method as in the synthesis example i, and the tensile modulus and the coefficient of thermal expansion were measured, and the results were 13 birds, respectively. -5·lppm/〇C 〇 [Synthesis Example 5] Except that m-TB is used in the equivalent of 〇, and 〇DA is used in the same amount, the remainder is obtained by the same method as the synthesis. Polyacid imine precursor resin solution e. Using the prepared polyamidamine precursor resin solution e, a polyimide film was obtained in the same manner as in the synthesis example, and the tensile modulus and the coefficient of thermal expansion were measured, and the results were 2.7 〇 ρ & 4.4 ppm, respectively. /°C. [Synthesis Example 6] DMAc was dissolved in a separable flask by stirring BAPPU0 equivalent) at room temperature. Next, pMDA (9.69 equivalents) and BpDA (〇.5l 10 equivalents) were added. Then, the polymerization was carried out by further stirring for about 3 hours to obtain a poly-S&imine precursor resin solution f. Further, dmIc uses an amount of loading of 12% by weight of RAPP, PMDA and BPM. A polythene layer having a thickness of about 28//m was obtained in the same manner as in Synthesis Example 1, except that the prepared polyfluorene resin was used to coat the thickness of 3,500 Å. The average tensile strength and thermal expansion coefficient were 2. 6 GPa, 50 · Tppm / ^ C, respectively. [Example 1] On a copper foil, a solution of the polyimine precursor resin 319059 16 200814892 i prepared according to Synthesis Example 6 was uniformly coated to a thickness of 50 / / m, and heated at i25 ° C / Drying to remove the solvent. Next, the polyimine precursor resin solution 3 prepared in accordance with Synthesis Example 1 was uniformly coated to a thickness of 190 / / m in a manner of being laminated thereon, and dried by heating at 125 ° C. Further, on the top, the polyiminoimine precursor resin solution f was uniformly applied to a thickness of 5 〇 #爪, and heat-dried at 125 °C. The total heating drying time up to this point was set to 3 minutes. Then, it is subjected to heat treatment for 8 minutes and 30 seconds in the range of 13 至 to 2 〇〇, and heat treatment is performed for 3 minutes and 30 seconds in the range of 2 〇 rc to 36 〇, and yttrium imidization is performed. The reaction "; and won the thick layer of about 2 8 // m poly-imine layer in the copper and metallurgy. The copper foil layer of the laminate was removed by an etching treatment to obtain a polyimide film. The results of tensile modulus and coefficient of thermal expansion of the polyimide film obtained by the measurement of yttrium are shown in Table 1. [Example 2] A polyimide film was obtained in the same manner as in the practice of μ except that the polyethylenimine precursor resin solution a was used instead of the solution b, and the tensile modulus and thermal expansion were measured. coefficient. The results are shown in the table. [Example 3] A polyimine film was obtained in the same manner as in Example 1 except that the substituted polyanilin precursor resin solution & was used instead of the solution c, and the tensile modulus and the tensile modulus were measured. Thermal expansion coefficient. The results are shown in the table. [Comparative Example 1] A film of polytheneimide thin 319059 17 200814892 was obtained in the same manner as in Example 1 except that the substituted polyimine precursor resin solution a was used instead of the solution d, and the tensile was measured. Elasticity and coefficient of thermal expansion. The results are shown in the table. ^ [Comparative Example 2] 'A polyimide film was obtained in the same manner as in Example 1 except that the polyethylenimine precursor resin solution a was replaced, and the solution e was used instead, and the tensile modulus was measured. With coefficient of thermal expansion. The results are shown in Table 1. [Comparative Example 3] The procedure was carried out in the same manner as in Example i until the application of the polyimine precursor resin solution and the heating and drying (25 minutes, 3 minutes). Then, heat treatment is carried out for 6 minutes in a temperature range of 13 (TC to 200 ° C, heat treatment is carried out for 6 minutes in a temperature range of 2 〇 to 360 ° C, and hydrazine imidization reaction is carried out to obtain A laminate of about 28 Am polyimine layer is formed on the copper foil. The copper foil layer of the laminate is removed by etching to obtain a polyimide film. The stretch of the polyimide film obtained by measurement is obtained. Elasticity and coefficient of thermal expansion, the results are shown in Table 1.

[Table 1]

319059 18

Claims (1)

200814892 V ^ X. Application for Patent Park: • 1. A method for manufacturing an observational laminate by applying (iv) an imine prior wax solution to a conductive metal crucible and heating it to make it agglomerated A method for producing a leaching laminated plate in which an imine precursor resin solution is dried and hardened is characterized in that, in the heat treatment, a total heating time of 9 (rc or more is set to a range of 5 to 25 minutes, and will be at 9 〇. The ratio of the heating time above 〇c and below _c to the heating time in the temperature above 2 〇〇 is set to 9: 丨 to 7:3, and will be formed on the conductive metal. The tensile modulus of the resin layer is controlled to be 3 to 6 GPa, and the thermal expansion coefficient is controlled to be in the range of 16 to 28 ppm/t: 2. The method for producing a flexible laminate according to the first aspect of the invention, wherein the polyimide resin The thickness of the layer is in the range of 5 to 4 〇" and consists of a plurality of layers, and has at least one layer of thermal expansion coefficient polyimine resin layer having a thermal expansion coefficient of PPm/C or more, and at least one layer of tensile elasticity a layer of a base polyimide layer of 4 to 8 GPa, The layer adjacent to the conductive metal foil is a high thermal expansion coefficient resin layer. 319059 19 % 200814892 ” VII. Designated representative figure: None ^ (1) The representative figure of the case is: () picture. (2) The symbol of the representative figure Brief Description: • 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: The chemical formula that is not represented in this case. 5 319059