TW450982B - Polyimide film and electric/electronic equipment base materials with the use thereof - Google Patents

Abstract

A polyimide film having sufficiently excellent characteristics such as a sufficiently high elastic modulus, a low water absorption, a small coefficient of moisture-absorption expansion, a small coefficient of linear expansion and a nigh dimensional stability; and various electric/electronic equipment bases with the use of the polyimide film. A polyimide film having a tensile elastic modulus of 700 kg/mm<SP>2</SP> or less and a coefficient of moisture-absorption expansion of 20 ppm or less and containing a specific repeating unit as an essential repeating unit is synthesized. Then various electric/electronic equipment bases such as a laminate for flexible print connection boards are produced by using the polyimide film.

Description

V. Description of the invention Q) With i ϊ: about a novel polyimide film. In particular, it is a novel polyimide film with good water properties (high enough elastic modulus, low absorption 7 ;, ', small coefficient of water expansion, small coefficient of linear expansion, and high dimensional stability-, car name δ Used as a base film for a variety of electric iron * / electronic devices such as flexible printing suspensions; ΐΐ: ΐΐ: · For packaging semiconductors, magnetic recording films, hard disks, etc. 4 Polyimide films are commonly used in organic polymers. A variety of excellent properties, such as low temperature properties, chemical resistance, electrical properties, etc.). Therefore, fenfluramine film is widely used in electrical / electronic equipment as materials and in aviation and sub-communications fields. Especially in recent years, these polyimide films have been required to be incompatible with heat resistance and have multiple functions. # If you want polyimide film to be used as a base film for flexible printed connection boards, it has a high elastic modulus, a small water expansion coefficient and a small linear expansion system A 1- Use a large water expansion coefficient and a large linear expansion coefficient In the polymerization, the amine film 'cured or warped when the resulting flexible printed web was curled. The substrate substrate film, which is particularly stable in shape, must be used for a flexible printed board for a plasma display (PDP) 'because the substrate is intended for a larger area than other applications. As for the polyfluorene imine used in the aforementioned electrical / electronic equipment, the polyimide obtained by polycondensation of pyromellitic dianhydride and 4, 4, diaminodiphenyl ether was actually used because of its heat resistance Excellent electrical and electrical insulation properties, so it can be used in high temperature equipment. By using high dimensional stability, this polymer is used

88119324.ptd Page 5 450982 V. Description (2) ''-Films made from imine can also be used for flexible printed plywood, etc. However, in recent years, it has been required that the base film used for IC, LSI, etc. has further improved workability and higher accuracy. Therefore, polyimide as a base film material must have a high elastic modulus, a low linear expansion coefficient, and a low water absorption. ^ 这 多 ^ _ Try to meet these needs. For example, it has been reported that by using p-phenylenediamine as a diamine component, the modulus of elasticity is increased, thereby obtaining phenyltetracarboxylic acid dianhydride, 4'4'-diaminodiphenyl ether, and p-phenylene Three-component fluorene polyimide composed of amines, disclosed in JP-A-60 ~ 21〇629, JP-A-64-16M2, / Pf 64-16833, JF-A-64-16834 'JA-A-1 -131241 and jp-A 131242 (the term "JP-A" is used herein to mean "Japanese Patent Publication"). In addition, 3,3 ', 4,4, -biphenyltetracarboxylic dianhydride was also added to the first three components, thereby obtaining a four-component polyimide having a further increased elastic modulus. For example, JP-A-59-1 643 28 and JP-A-6 1-1 1 1 359 are not such four-component polyfluorene imines. Further attempts have been made to improve the physical properties of the four-component polyimide by adding monomers in a controlled order during the polymerization step. F 'Reported by, for example, JP-A-5-25273. It is also reported that an acid having a similar formula to p-phenylene (trimellitic acid monoester anhydride) is reported in Jp_A_63_189490 (Japanese Patent Publication No. 7__88495), Jp_n6〇182 (Japanese Patent No. 2,712,597), JP -A-9-7787 1 'JP-A-1 0-36506 and JP-A'54862. Increasing demands are being placed on polyimide films for electrical / electronic equipment as previously described ', and therefore various studies are intended to meet these requirements. However, polyimide films that do not have sufficiently excellent characteristics (high enough elastic modulus, low water absorption, small water expansion coefficient, small linear expansion coefficient, and high dimensional stability) have not been mentioned.

88119324.ptd 450982 V. Description of the invention (3)). Summary of the invention Under these circumstances, the object of the present invention is to provide a poly (trimethylamino) amine film with sufficiently excellent characteristics (high enough elastic modulus', low water absorption, small water expansion coefficient, small linear expansion coefficient, and high dimensional stability Sex). Another object of the present invention is to provide various electrical / electronic device substrates using the polyimide film. In order to achieve the foregoing object, the present invention provides a polyimide film, a laminate of a flexible printed connecting plate, and an adhesive Alas, the magnetic recording base film and the hard disk suspension connection substrate are described in detail later. (1) A polyimide film has a tensile elastic modulus of 700 kg / m 2 or less and a water absorption coefficient of 20 ppm or less. (2) The polyimide film described in (1) above has a linear expansion coefficient of 10 to 20 (rc is 5 to 15 ppm.) (3) The polyimide film according to (1) or (2) above The film has a water absorption of 3% or less. (4) The polyimide film described in (3) above has a water absorption of 2.0% or less. (5) As described in any one of (1) to (4) above. A polyimide film containing the repeating unit represented by the following general formula (1) in its molecule:

Where R1 represents a divalent organic group selected from:

88119324.ptd Page 7 450982

88119324, ptd page 8 450982 V. Description of the invention (5) (where Y and Z may be the same or different and each represents a monovalent substituent selected from the group consisting of hydrogen atom, _ atom, carboxyl group, and having 6 or less carbon atoms A lower alkyl group, and a lower alkoxy group having 6 or less carbon atoms; and A represents a divalent bonding group selected from 0-, -S-, -C0-, -S0-, and -CH9_). 〇human Λ N R3 N-R- Υ 〇 〇〇 (6) The polyimide film as described in (5) above, in addition to the repeating unit represented by the general formula (1), further contains the following general formula (2) The repeating unit represented in its molecule: (2) where R is defined as the general formula (1); and R3 represents a tetravalent organic radical

〇 II c-o

»1〇C〇L

〒Η3 ο I u 0 &quot; C

CH, -a

: O ~ S02OC

88119324.ptd Page 9 450982

88119324.ptd Page 10 V. Description of the invention (7) (where R2 has the same meaning as the general formula (4); and R3 has the same definition as the general formula (2)). It contains (9) the polyimide film as described in j 5) or (6) above, wherein the main repeating unit of the molecule is represented by the following general formulae (6) to (9):

〇 η

(10) The polyfluorene imide film described in (9) above can satisfy the following requirements (a + b) / s' (a + c) / s, (b + d) / s and (c + d) / The requirements of s each falling within the range of 0.2 2 0.75, where a, b, c, and d respectively represent the number of repeating units as indicated by (6) ^ (9) above and s represents a + b + c + ( i. 450982__ V. Description of the invention (8) (11) A laminate for a flexible printed connection board, which is obtained by using the polyimide film described in any one of (1) to (10) above— The surface is obtained by opening a metal layer on the surface. Xincheng (1 2) The laminate for a flexible printed connecting board as described in (11) above, wherein the metal layer is laminated through a thermosetting adhesive. (1 3) as above (11) The laminate for a flexible printed connecting board, wherein the metal layer is laminated through a thermoplastic polyimide adhesive. (14) As described in any one of (11) to (13) above A laminate for a flexible printed connection board, wherein at least one side of the polyimide film is subjected to at least one treatment selected from the group consisting of heat treatment, corona treatment, plasma treatment, and coupling agent treatment. (15) — Adhesive film It is obtained by forming an adhesive layer on at least one side of the polyimide film according to any one of (1) to (10) above. (16) The adhesive film according to (1 5) above, wherein the adhesive layer comprises A thermosetting adhesive. (17) The adhesive film according to the above (15), wherein the adhesive layer comprises a thermoplastic polyimide adhesive. (18) The polyurethane according to any one of (1) to (10) above An amine film is used as a base film for magnetic recording. In brief, the figure is clear. Figure 1 is a schematic diagram of a curling property evaluation test for the three-layer laminate of Comparative Example 1 and Examples 22 to 28. Each number in the figure shows As follows: 1: Copper foil

88119324.ptd Page 12 450982 V. Description of the invention (9) 2: Adhesive 3: Film. Fig. 2 is a schematic diagram of a test for measuring the coefficient of water expansion of Comparative Examples 1 and 2 and Examples 1 to 33. Fig. 3 is a device for measuring the coefficient of water expansion of Comparative Examples 1 and 2 and Examples 1 to 33. The symbols in this figure are shown as follows: a: detection b: recorder c: (gain) d: water vapor outlet e: hot water outlet f: nitrogen flow g: sample h: water i: water vapor j: hot water Inlet (hot water tank) k: Humidity sensor 1: Humidity converter m: Water vapor generator η: Thermostat (50 ° C) 〇: Detailed description of the invention of the humidity control unit Polyimide film according to the present invention With tensile elastic modulus of 700 kg /

88119324.ptd Page 13

4 5 Q 9 R P

5. Description of the invention (10) Square millimeters or less and usually 5,000 to 700 kilograms / square millimeter and a water absorption coefficient of 20 ppm or less, preferably i5 ppm or less. Usually has ^ 1 0 0 to 2 0 0. (: The linear expansion coefficient is 5 to 15 ppm and the water absorption is 3.0% or less and preferably 2.0% or less. The aforementioned polyimide film of the present invention is made of a polyimide, which is a polyimide The imine usually contains a repeating unit represented by the following general formula (1) in its molecule. C:

(1) wherein R1 represents a divalent organic group selected from the group consisting of

-ΟτΌτ

, Br-,

(Where R4 represents CH3-, C1-F- or CH30_); and R represents as follows

88119324.ptd Page 14 45 09 8 2 V. Description of the invention (11) Divalent organic group represented by the general formula:

(Where η is an integer from 1 to 3; and X represents-a tooth atom, several groups, a substituent having 6 or less carbon ^ substituents selected from a lower carbon alkoxy group having a hydrogen atom 'and lower carbon atoms), or a lower alkyl group Base and containing 6 or ~ XU) x 5 £ Js Js -r_ _

And Z may be the same or different and each represents a monovalent substituent selected from the group consisting of hydrogen, tooth atom, carboxyl group, lower alkyl group having 6 or less carbon atoms, and lower alkyl group having 6 or less carbon atoms Oxy; and a represents a divalent linking group selected from 0-, -S-, -C0-, -S0-, -S02-, and -CH2-). The polyimide film containing the repeating unit represented by the general formula (1) in the molecule contains a repeating unit represented by the following general formula (2) in addition to the repeating unit of the general formula (1) as a main component. : Ϋ human Λ W—R- ο ο where R is defined as the general formula (l); and R3 represents a tetravalent organic group selected from the group consisting of:

88119324, ptd page 15 450982 V. Description of the invention (12)

DOC.m ch3

ch3

-t〇C

^ as〇2OC

^ 〇n〇:

〇 II C—O — (CHsb

-OC The polyimide film according to the present invention &lt; is manufactured by dehydration and cyclization of a polyimide acid (i.e., a polyimide precursor) solution, thereby obtaining the imine and subsequently processing it into a thin sheet, or simultaneously Imination and thin film formation. Specifically, the polyamic acid solution is mixed with a dehydrating agent, a catalyst, and the like, and then the resulting mixture is cast or applied to a support such as a circulating belt to form a thin film. Secondly, it is converted into fluorene imine by baking at an appropriate temperature, and the thus obtained film is obtained as a polyfluorene imine film. It is used in the manufacture of polyimide film as a precursor, because it is roughly equal in mole ratio to organic ::: liquid can be obtained through ingredients. In this method, if there are two required components, the poly-donkey amine solution made of the acid dianhydride component and two or more diamines as the diamine to form an acid dianhydride is usually obtained as the second component. The fragrant vinegar used in the present invention. Anhydride with #m is combined with the following general formula (1.) It is used as the main dianhydride component and has the following general formula

45 09 R V. Description of invention (13) The polymerization of diamine represented by (11) is obtained: 〇 11 (10) c II o

, C ϊΙ Ο where R1 is defined as the general formula (1): h2n- R-nh2

Where R is defined as the general formula (1) D. In addition to the polymerization reaction, in addition to the general formula (10) as shown in Table 22 of the above formula (10), the dianhydride can also be added, such as the following formula U means tetracarboxylic dianhydride);

〇 II

〇II X 0 C II 0 C II 0 (12) where R3 is defined as the general formula (2). Show IS: 'Aromatic diester dianhydride represented by the general formula (1〇) and epihydride of the general formula (12) It can be used in a proportion appropriately determined according to the purpose of use. Generally, the amount of aromatic diester dianhydride which accounts for the total amount of dianhydride is 25% or more, preferably 35% or more and more preferably 4%. % Molar ratio, but it is preferable to use an appropriate amount of tetracarboxylic dianhydride represented by the general formula (12). When the content of the square group one intentional dianhydride represented by ~ .10) is lower than the M% Molar ratio, the resulting polymer The imine film has higher water absorption and higher water absorption coefficient. The above-mentioned I-combination can be performed by any well-known method, for example, p_A_

450982 V. Description of the invention ¢ 14) 5 9- 1 64328 or JP-A-63-Η6287 is performed using an organic polar solvent. In the polymerization step, the 'initial dianhydride component and the diamine component can be added to the reaction system in any order &quot; 3. 4. In the present invention, the reaction is performed by various methods as follows. In a separate method, the diamine and the dianhydride are initially mixed, and then the mixture is added to the solvent solution with stirring. (b) A method in which the solvent is added to the di- and yixuan mixture under stirring as opposed to the foregoing. (C) ~ a method in which a diamine system is exclusively dissolved in a solvent, and then two are added thereto in a proportion allowing a controlled reaction rate. The latter method is one in which the tetracarboxylic dianhydride is exclusively dissolved in the solvent, and the amine is added thereto in a proportion allowing the reaction rate to be controlled. The other method is to use Bk and ~~ xuanfen. Dissolve in the solvent and then slowly mix the solution in the reactor. 〇) ~ A method in which polyamines containing excess diamine and polydianhydride containing excess dianhydride are initially formed and then react with each other in the reactor. g) A method in which part of the diamine and dianhydride are reacted first and then reacted!--&amp;-shame 'and vice versa. 4 When the aromatic diester dianhydride represented by the general formula (10) and the tetracarboxylic acid represented by the general formula (12) are used as the dianhydride component, a particularly preferred polymerization method is performed first.

A first polyamic acid is obtained from one of the dianhydride and a diamine component, and then a second polyamine is obtained from the other dianhydride and a diamine component. (~ Examples of organic polar solvents useful in the foregoing polymerization reactions include arsenic solvents ~ methylidene, diethylene fluorene, etc.), amine solvents (N, N-dimethyl fluorene 45 09 8 2 5. Description of the invention ( 15) N, N-diethylformamide, etc.), acetamide solvent (N, dimethylacetamide, 〆— ^ ^ iv, ^ U ㈡amine, N, N-diethylacetamide) Etc.), β-pyrrolidone solvents (N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, etc.), phenol solvents (phenol, o-, m- or p-cresol, Xylenol, halogenated phenol, catechol, etc.), hexamethylphosphoramidine and r-butyrolactone. It is necessary to use a solvent or a mixture thereof. Combinations of these solvents with aromatic hydrocarbons such as di-benzene and toluene can also be used. From a processing point of view, is it desirable that the polyamines thus formed are in a weight ratio of 5 to, preferably 10 to 30% reset ratio, and 12 to 1 in weight? 7¾ Tongue θ Organic polar solvent. The rolling degree to 27% by weight Charpy is dissolved in polyimide starting from polyamic acid by the aforementioned method. Characteristics and well-balanced physical properties. The foregoing formula is required to have excellent molecular weight with an average molecular weight of 10,000 to 10,000, 100,000. When the polyamic acid having a rolled average molecular weight of less than 10,000 is obtained, the resulting film becomes brittle. &quot; When the flat molecular weight of glutamic acid exceeds 1,000,000,000, because the viscosity is too high, on the one hand, when the processing properties of the average lacquer are deteriorated, D polyamino acid is manufactured from polyamino acid by the aforementioned method Among the polyfluorene imide in which the molecule contains-repeating units, it is particularly preferable that the polymer contains a polyimide film having the repeating unit represented by the general formula (1): The general formula (3) represents

(3) Intramolecular Λ W formula (U represents

450982 V. Polyimide film of the repeating unit of the description of the invention (16), the polymer containing the repeating unit represented by the following general formula (4) and another repeating unit represented by the following general formula (5) in the molecule醯 Imine film is particularly good:

(4) wherein R2 represents a divalent organic group selected from the group consisting of: ο 〇 (5) λ3λ 2

W—R ο ο (where R2 is defined as the general formula (4); and R3 is defined as the general formula (2)). In the polyimide film containing the repeating unit represented by the above general formula (1) in the molecule, the polyimide film containing the repeating unit represented by the following general formulae (6) to (9) as the main repeating unit For even better:

88119324.ptd Page 20 4 5 0 9 8 2 Five 'invention description (17) 〇 〇

(6) (7)

: νη〇 * · 〇Ό ^ (9) The foregoing polyfluorene imide film can meet the requirements, (a + b) / s, (b + d) / s and (c + d) / s each fall between 0.25 and 0.75 Ranges, where a, b, c, and d respectively represent the number of repeating units represented by the general formulae (6) to (9) above and s represents a + b + c + d. Antioxidants, light stabilizers, flame retardants, antistatic agents, heat stabilizers, ultraviolet light absorbers, inorganic fillers, or various reinforcing agents can also be added to the production of the polyamic acid solution used as a precursor. In order to obtain the polyimide film of the present invention from a polyamic acid solution, a heating method using thermal dehydration or a chemical method using a dehydrating agent can be used. However, Che Jiao used chemical methods because the polyimide film thus obtained showed

88119324.ptd Page 21 450982 V. Description of the invention (18) '— favorable mechanical properties, such as elongation and tensile strength, the aspect is that the imidization reaction can be completed in a short time. It is also possible to combine the fluorene method with the chemical fluoridation method. &quot;, Privatization Now, the method for producing a polyimide film according to the present invention will be described in detail. To the aforementioned polyamic acid or its solution, 'a stoichiometric amount or more' of a water agent and a catalyst is added. The solution thus obtained is subsequently cast or applied to a drum drum strip to form a film. Secondly, the film is dried at a temperature of 500 t or less for about \ f minutes, thus obtaining a self-supporting poly (amino acid) film. This membrane is then separated by the carrier and then solidified.定 both ends. It is then slowly or gradually heated to about 1500 to 55 ^ (preferably 450 ° C or more, more preferably 47.0 or more, and most preferably 507 or more) into amidine. From the viewpoint of film deterioration, the preferred maximum heating temperature does not exceed 600 ° C. After cooling, the film was removed to obtain a polyfluorene = amine film according to the present invention. Examples of the dehydrating agent include aliphatic anhydrides (such as acetic anhydride) and aromatic anhydrides. As for the aforementioned catalysts, for example, aliphatic third amines (triethylamine, etc.), aromatic third amines (dimethylaniline, etc.), and heterocyclic third amines (piperidine, methylpyridine, etc.) can be used. , Isooxoline, etc.). The thickness of the polyfluoreneimide film thus obtained can be appropriately determined depending on the purpose of use and the like. Usually the thickness ranges from 5 to 90 microns. It is preferred that the polyimide film thus obtained has an elastic modulus of 50 (kg) / m 2 or more but not more than 700 kg / m 2 (inclusive), so it can be suitably used as a base film such as a flexible printed connection board Of laminates. The preferred polyimide film has a water absorption coefficient of 20 ppm or less, more preferably 18 ppm or less, and particularly preferably 16 ppm or less. It is also preferred that the polyimide film has a linear expansion coefficient of 200 ppn at 100 to 200 ° C] or less, more preferably 15 ppm or less and most

88119324.ptd Page 22 450982 V. Description of the invention (19) ----------- Jia 12 Qing or 0. It is usually linearly expanded. Better poly, amine thin has a water absorption of 3 shoulders or less, more Gui 2? Or with :, and good! .㈣ or below and special fantasy. = Permittivity of 3.50 or below, and better ^: Relative frequency of 10Hz f range. It is also preferable to have polyimide thin sheet. 〇 to 2 () (^ temperature ^ hertz frequency | &amp; the relative permittivity of the frequency range of 1 kHz to i million Hz at room temperature is 3. 30 or less. The relative between dry conditions and water absorption conditions The permittivity difference is preferably low or 0.3 or lower. In addition, it is preferred that the polyimide film exhibit a ratio of water absorption expansion coefficient (MD) to transverse direction (TD) in the main direction (MD) of 1/5 to 5, 1/3 to 3 And particularly good 1/2 to 2. The density of the polyimide film is preferably about 440 to 1.480 g / cm3. The glass transition temperature of the polyimide film is preferably 200 t or more. 24 ° C or above and particularly good 260 X: or above. F. The polyimide film according to the present invention has excellent characteristics such as sufficient elastic modulus, low water absorption, small water expansion coefficient, and small linear expansion. Coefficient and high dimensional stability. Therefore it can be widely used for a variety of purposes. Among them, it can be fully used as an adhesive film for flexible printed connection boards, or used for packaging semiconductors, magnetic recording films (floppy disks, magnetic recording tapes, etc.), hard disk suspension Hanging the connection substrate, etc. The polyimide film according to the present invention will now be used as the base of the flexible printing connection plate layer. A case is explained. Generally, a 'flexible printed connection board (FPC) is manufactured by the following method and involves the steps of I 歹 j. ① using an adhesive and drying; ② laminating steel foil; ③ hardening the adhesive; and ④ forming a layout pattern (Application of resist 'steel etching, separate the resist.) In the pattern formation step, the size change often occurs during the etching process 88119324.ptd

Page 23 45 〇 9 8 2

change. Therefore, the design of circuit patterns must take into account changes in subsequent steps in advance. In order to achieve the high dimensional stability of the FPC itself, it is necessary to use an FPC base material having a suitably high elastic modulus', low water absorption, small linear expansion coefficient, and small water expansion coefficient. These changes in FPC are caused by: (a) changes in the dimensions of the base film as the FPC insulating material due to water absorption / desorption; (b) strain caused by the difference in thermal expansion between the steel foil and the base film during the copper box lamination step; and ( c) The strain caused by the tension in each step. The degree of dimensional change caused by factor (b) If the base film has a constant linear expansion coefficient, it is easy to expect in the design step. The dimensional change caused by factor (c) can be adjusted by controlling the tension occurring in each step. Therefore, such changes are also easy to anticipate in the design steps. However, the dimensional change induced by factor (a) is almost uncontrollable because the water absorption and drying are repeated in the FPC manufacturing process. Recently, a method for manufacturing multilayer connection boards has been reported. In this method, a polyimide film is first bonded to a copper foil with a thermoplastic polyimide to obtain a copper foil / polyimide film having a laminated structure, in which a thermoplastic polyimide adhesive layer is also formed on the bottom surface. . Next, a copper connection pattern is etched, and the carrier is drilled from the bottom using an excimer laser beam. Secondly, the conductive paste of the carrier (obtained by adding metal powder to the thermoplastic polyimide resin) is filled in the holes. A predetermined number of plates were prepared by stacking each other by the same method. Secondly, these plates were laminated in one pass by a hot-melt method using a hot press to obtain a multi-layer connection plate. In such a method for manufacturing a multi-layered connection board, it is difficult to appropriately control the shape stability of the polyimide film as an insulating layer. On the other hand, the FPC of the plasma display (PDP) itself must have higher dimensional stability 'because it uses a larger area than other applications. It is thus urgently required that the FPC substrate of the present invention can meet these strict requirements.

88119324.ptd Page 24

V. Description of the invention (21) __ 1 has the aforementioned excellent features, so the invention of the present invention solves the problems encountered in the aforementioned FPC field, and can be fully used as the base film of the multilayer connection board reported recently. When the polyimide film of the present invention is used as a three-layer Fpc or a multi-layer spider base film, a polyimide film is particularly preferably used, except for the amine group. The substituted phenylene diamine and the diamine 3 which does not have a substituent other than the amine group are 3 ethers. The use of the aforementioned phenylenediamine can further improve the elastic modulus, and the aforementioned diamine diphenyl ether can further improve the moldability of polyfluorene in the film forming step. Among these phenylenediamines, p-phenylenediamine, ==. Among these diamine diphenyl ethers, 4, 4, _diamino diphenyl ether is particularly preferred. In addition, polyfluorene imine films are preferred. Among them, phenylenediamine and diamine mediphenyl ether. The mixing ratio is 10 to 90% Molar ratio and 10 to 90% Molar ratio, preferably 20 to 80% Molar ratio and 20 to 80% Molar ratio and more preferably 30 to 70%. Mole ratio and 30 to 70 Mole ratio. ^ Take polyimide film as the base film of flexible printed connecting plate as an example. The flexible printed connecting plate will be used under strict conditions (high temperature, high humidity, etc.), so the aforementioned properties of the film must be better. In the polyimide film of the invention, it is particularly good to use a copolymerized polyimide film, which contains the aforementioned aromatic diester dianhydride, an imine component, and two specific diamine components (phenylene diamine: Diamino monophenyl 5 to 40% mole ratio: 60 to 95% mole ratio) molecularly bonded to another two polyimide components containing the aforementioned tetracarboxylic dianhydride and two specific diamine components ( Phenyldiamine: diaminodiphenyl ether; 55 to 90% mole ratio; 10 to 45% mole ratio). The polyimide film of the present invention is used as a base film and a metal formed thereon

4 5 0982_ V. Description of the invention &quot; (22) '------ Flexible printed plywood laminate with layer composition can be selected through well-known

An example of a suitable method in the method of making a flexible printed plywood laminate is given below. . So usually the method of making such a laminate is to apply a solution-type adhesive to the polyimide film, or laminate a sheet-shaped adhesive and then attach a metal foil, etc., and then adhere a metal foil (copper foil, etc.) to On it, and cured at = temperature to harden the adhesive. The appropriate adhesive in this example can be selected from 'well-known adhesives, such as epoxy resin adhesive' polyamidine f-mixture, phenolic resin adhesive, acrylic resin adhesive, polyimide tree adhesive And rubber resin adhesive. Any one of the adhesives or a mixture of two or more of them may be used. Adhesives containing various additives such as hydrating agents, antioxidants, and ultraviolet light absorbers can also be used. When using a solution type adhesive, the 'polyimide film is slit to obtain a fixed width, and then the adhesive solution is applied thereon using a rod coating machine, a "comma" coating machine, etc. to obtain a thickness of 5 to "50 microns" followed by Dry at 50 to 200 ° C for 10 to 600 seconds to remove the organic solvent from the adhesive solution. Secondly, the polyimide film on which the adhesive has been applied is heated to 50 to 200. 〇 Adhesion to copper foil. The thus obtained three-layer laminate consisting of an adhesive, a polyimide film, and a copper foil is heated and cured at an appropriate temperature for an appropriate time, thereby hardening the resin used for the adhesive. When a sheet-shaped adhesive is used, the thin sheet protective layer is removed, the adhesive is adhered to, and the polyimide film is heated to 50 to 200 ° C. Secondly, a two-layer laminate composed of a polyimide film and an adhesive sheet was bonded to a steel reed heated to 50 to 2000c. The three-layer laminate composed of the adhesive, the polyimide film, and the copper foil thus obtained was heated at a high temperature for a sufficient time to harden the tree used for the adhesive.

4 5 0982 V. Description of the Invention (23) Fat. By using these methods', a three-layer laminate for a flexible printed connection board can be obtained. The adhesive strength of the aforementioned laminates can be improved using a variety of well-known techniques to increase the adhesive strength, 'for example, by applying an adhesive to a polyimide film or laminating an adhesive thin film before the step thereon'. The amine film is subjected to pretreatment (heat treatment 'corona treatment', plasma treatment at atmospheric pressure, plasma treatment under reduced pressure 'coupling agent treatment, sandblasting, alkali treatment, acid treatment, etc.). In order to improve the adhesion strength ', it is also possible to add various metal compounds (tin compounds, titanium compounds, etc.) to polyamic acid, or to apply various metal compound solutions to the gel film as disclosed in U.S. Patent No. 4,742,099. Then, the heat treatment used for the pretreatment of the polyimide film can be continuously performed using, for example, a heat treatment system provided with a heating supply box (electric heater, etc.) between the film feeder and the dispenser. If necessary, a heat treatment system provided with a plurality of heating ovens is preferably used. It is also preferable that the maximum heating temperature is controlled so that the highest atmospheric pressure temperature at which the heating oven can be obtained is from 100 to 700. 〇, and more preferably 200 to 600. (:. By adjusting the maximum heating temperature within the aforementioned range, a polyimide film with excellent mechanical strength, adhesion, and shape stability can be obtained. ^ Regarding the heat treatment time, it is preferred that the polyimide film be exposed to the highest heating. Temperature 2 ~ 1 '!.: Seconds' is more preferably 2 to 800 seconds and particularly good 5 to 400 seconds. Heat treatment: The fixed mouth 2 L is gradually changed. 加热 The heating temperature of the heating oven can be 600, 4 ° 0 and 20 ( rc, and the polyimide film lasts 200 seconds. In addition, the heating temperature of the heating box can be a 疋 5 0 C but the heating time of each oven is changed. As described in the pretreatment of polyimide film Corona treatment can be used by industry people

450982 V. Description of the invention (24) Corona treatment system commonly used by scholars. The corona treatment density obtained from the following formula is preferably from 50 to 800 watts / minute / square meter. Corona treatment density (W • min / m2)-Corona output (W) / {linear speed (m / min) &gt; &lt; processing width (m)}. In addition, the plasma treatment used as a pre-treatment for the polyimide film can be performed using a plasma treatment system commonly used by those in the industry. There are two methods including one based on plasma discharge under reduced pressure and the other based on plasma discharge under atmospheric pressure. From the viewpoint of activity cost, the latter is better. Although plasma discharge at atmospheric pressure is not limited to gas type or pressure or processing density, the gas pressure is usually controlled to the range of 1,000 torr. The gas example used to form the plasma gas is an inert gas (helium, Argon, Krypton, Krypton, Neon, Krypton, Nitrogen, etc.), Oxygen, = Carbon monoxide, Carbon dioxide 'Tetragasified Carbon, Chloroform, Hydrogen, Ammonia tetrafluoride, Trichlorofluoroethane and Trifluoromethane. It is also possible to use a well-known fluorine-containing gas or a mixture of the foregoing gases. Preferred gas combinations include argon-argon / ammonia, rat / helium / oxygen, argon / carbon dioxide, argon / atmosphere / carbon dioxide, / helium / nitrogen, argon / helium / nitrogen / carbon dioxide, argon / helium, argon / helium / acetone , Helium /, helium / air, argon / helium / silane, etc. The plasma processing density calculated according to the following formula is preferably from 1 () 0 to 20,000 watt.min / m2 and particularly preferably from 300 to 1 () '000 watt.min / m2. Density of electro-forging treatment (W.min / m2) = Out of the electric wheel (W) M linear velocity (m / min) X processing width (m) 丨. Fifth, it is used as a pretreatment of the polyimide film to use a coupling agent. For example, a coupling agent solution can be applied to the film surface, the coupling agent solution can be used to stand up the film surface, and the coupling agent solution can be sprayed on the film surface. Impregnated film

88119324.ptd

Page 28 swl 1 932- ^ 1 view 30 ㈣

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450982 V. Description of the invention (27) Solve the problem of 'using thermoplastic polyimide as an adhesive when manufacturing FPC using the aforementioned polyimide film of the present invention as a base film' and perform the aforementioned pretreatment such as corona Treatment, plasma treatment, coupling agent treatment, etc. This makes it possible to manufacture FPCs with further improved properties that involve increased adhesive strength and can be used in harsh conditions (high temperature, etc.). The thermoplastic polyimide adhesive used in the aforementioned FPC having further improved characteristics is not particularly limited. Generally, the thermoplastic polyfluorene imide represented by the following general formulae (1 3) and (1 4) can be used.

Where R5 represents a divalent organic group selected from the group consisting of: ch3 ch3 ch3 Ru Shi, —Srh2— ,, ch3 Pop &gt; cf3

88119324.ptd Page 31 450982 V. Description of the invention (28) and R6 indicate that the divalent organic group is selected from the group consisting of:

〇-,

〇 -Ϊ- -hQ ^ c-o ^ ch ^ o-c ^^^ ·

88]] 9324.ptd Page 32

B8119324.ptd Page 33 450982

88119324, ptd page 34 4 δ 098 2 V. Description of the invention (31)

These thermoplastic polyimide resins show an exact glass transition temperature in the range of 100 to 350 ° C, depending on the composition. By using a thermoplastic polyimide adhesive, a polyimide thin film as a base film can usually be bonded to a metal box in the manner described in -p. IT Λ plastic polyimide. When the varnish containing the polyamidic acid to be converted into a thermal polyamic acid is used, a thin layer is formed with one of the amino acids or a partially polyimide-containing polyimide. When used as an adhesive, the varnish is applied to the adherend.

88119324.ptd Page 35 4 5 0 9 8 2 V. Description of the invention (32) 10 0 to 3 0 ° C After a fixed period of time, the excess solvent is removed and the polyamic acid is converted into a compound with higher stability. Polyimide. Next, another adherend was placed thereon and pressure-bonded at 100 to 400 ° C at 1 to 1,000 kg / cm2 and then cured at 100 to 400 ° C. In this way, the adhesives adhere to each other. When a thermoplastic polyimide in the form of a film or powder is used as an adhesive, the film or powder is inserted into the inside of the adherend and is pressure-bonded at 100 to 400 ° C at 1 to 1,000 kg / cm2. It then cures at 1000 to 400 ° C and will adhere to each other. When a solution of thermoplastic polyimide in an organic solvent is used as an adhesive ', this adhesive is applied to one of the adherends. It is then heated by the adhesive to about 1000 to 300 ° C for a fixed period of time to remove the solvent. Next, another adhered structure is placed on the surface of the adherend on which the adhesive has been applied and pressure-bonded at 100 to 400 ° C at 1 to 1,000 kg / cm2, followed by 100 to 400. (: Cured. In this way, the adhesives are bonded to each other. In the aforementioned bonding method, the 'polyimide laminate and the metal foil can be pressure-bonded by using a method appropriately selected from well-known methods, such as using a heat-friendly heating layer or heat Pressing method. The heating conditions depend on the glass transition temperature of the thermoplastic polyimide used. In other words, a heating temperature not lower than the glass transition temperature is preferred, and it is preferably as high as 200 c above the glass transition temperature. The processing pressure is usually 20 To 150 kg / cm2. It is preferable to use a thermoplastic polyimide having a glass transition temperature of 100 to 350 ° C and more preferably 150 to 300. (: a thermoplastic polyimide having a glass transition temperature. Next, the use of a polyimide film according to the present invention will be described in detail. Base film of adhesive film. Recently, it has tended to develop high-performance, high-function and small-sized electronic devices, which require the use of small and lightweight electronic components. This also requires the use of semi-

MS 88119324-ptd Page 36 4 5 〇 9 8 2 V. Description of the invention (33)-Energy and 3 f Ϊ and wiring materials and wiring components have high density and high power. Special requirements for the development of solder heat resistance, formability, and sticky packaging materials (Semiconductor 7 2 ″ material, so that it can be appropriately used in high-density modules), etc. ^ Printing car seal body, COL 'L〇C package , MCM (multi-chip ^ .τ &lt; IP brush connection, 纟. Board material (multi-layer FPC, etc.) and aviation materials. Second, try to improve solder heat resistance. Jp_A_6_ poly ΓΓ: for the board, the adhesive film is made of -The composition of a polyoxymethylene unit is composed of =, month, and mounting oxygen resin. JP ~ A-7_0 975 55 proposal-Improved lipids: mixed with alcohol-soluble polyamine resin and specific naphthalene epoxy resin II, , Aqueous solution as surface treatment of polyimide film to improve solder amphoteric printing far Γ / 9496 proposal "A method to make soft solder with good solder heat resistance: = junction plate method, this method is rolled by AC contact engraving The steel box 2 is prepared. 'Two adhesives are laminated thereon, and then a plastic insulating film is laminated thereon. In addition, a variety of table-type modified adhered surfaces with excellent solder heat resistance have been proposed (polyurethane: surface treatment). , Copper surface treatment, etc.) Or borrow a poly ::: introduce polyimide master Chain to improve adhesion., To the end

ς = satisfactory solder heat resistance and dimensional stability; J adhesive films, insulating materials, etc. β evil test characteristics In order to form the aforementioned adhesive film for packaged semiconductors, it shows spy ^ 醯: Stability and adhesion characteristics of adhesion ί The film can be used according to this :: Adhesion of the polyimide film according to the present invention as the base film can be used.

450982 Five 'Invention Note (34)' ~ When used to fix or insulate electronic parts, electronic circuit boards, etc. in electronic equipment. In particular, it can be suitably used for the bonding of die pads for flexible printed circuit boards or semiconductor devices, or for packaging materials that require high heat resistance such as COL (chip on lead) or dna (chip on lead). The adhesive film of the present invention using the polyimide film according to the present invention as a base film can be manufactured by forming an adhesive layer on one or both sides of the polyimide film as the base film. Adhesive films and the like having a covering film (such as a pET film) also belong to the category of adhesive films of the present invention. From the viewpoint of shape stability, the polyimide film which is preferably used as the base film has a high elastic modulus, so the elastic modulus of the elastic amine film which can be alleviated due to the roll-to-roll molding step stretching is preferably 50. . Kg / mm2 or more, 550 kg / mm2 or more, and particularly preferably 600 kg / mm2 or esteem. Polyimide film also has a low water absorption and can be used for solder heat resistance. Since ^ ί ί, the solder resistance after the original state is improved and the moisture is absorbed; ρDuS, the water absorption of the polyimide film is preferably 3-0% or more, 2 is 2.0% or less, Even more preferably, it is 18% or less and particularly preferred is 醯 Asian L ^ Ί. In addition, from the point of view of improved pattern density and reliability, Ju Guerui has a low coefficient of water expansion and a low coefficient of linear expansion, a heating step for cattle brewing, heating, and etching, laundering, and drying of ladle laminates. Dimensions change. Water swell of the preferred polyimide film: Γ; 12ppm or less, more specifically nnnm +, ΊΤ ^ ^ sparse; m β ppm or u and particularly preferably 8ppm or less. The linear expansion system of the preferred polyimide film is ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ or less and particularly preferably 12 pprn or less. 15 or less, more preferably 14 In order to form the adhesive layer of the adhesive film according to the present invention, an appropriate selection may be used.

4 5 09 8 2 V. Description of the invention (35) Self-contained adhesives similar to those previously described in the case of producing flexible printed connection boards by using the polyimide film of the present invention. Examples of useful adhesives include thermoplastic polyimide adhesives, and thermosetting adhesives such as epoxy resins and phenolic resins. If necessary, a polyimide film can be pre-treated by applying the well-known improved adhesive strength technology (heating treatment, corona treatment, plasma treatment at atmospheric pressure, plasma treatment under reduced pressure, coupling agent treatment, etc.). These heat treatment, corona treatment, plasma treatment at atmospheric pressure, plasma treatment under reduced pressure, and treatment with a coupling agent can each be laminated as described above through the use of the polyimide sheet of the present invention to produce a flexible printed plywood laminate. The case is described as the case. It is also possible to combine two or more pre-treatments (these pre-treatments are preferably performed because the adhesion strength at the interface between the polyimide film and the adhesive layer can be improved. There is no particular limitation on the thermoplastic polyamidine adhesive to be used for forming the adhesive layer. The thermoplastic polyfluorene imide represented by the general formulae (13) and (14) is usually used. Such an adhesive layer made of thermoplastic polyimide can be formed on a polyimide film used as a base film in the same manner as in the case of manufacturing a flexible printed plywood laminate by using the polyimide film of the present invention. In the foregoing, the invention is not limited to this. In other words, a thermoplastic polyimide solution or a polyamic acid (ie, its precursor) solution can be washed and cast on the polyimide film or applied on it using a light coater, a bar coater, etc., and then dried by heating. This forms an adhesive layer. In addition, the thermoplastic polyimide in the form of a film or a powder is press-bonded with a so-called double-belt press equipped with a heating / pressing member and an endless belt to form an adhesive layer on the polyimide film. Examples of thermosetting adhesives that can be used to form the adhesive layer include epoxy resins

V. September instructions (36) _ One -----:, grease, melamine resin, xylene resin and cyanate resin. Other resins and phenol resins are preferred because of their excellent insulation properties. The content of the thermosetting resin relative to the so-called rubber composition per 100 / minute weight ratio, that is, the resin components other than the thermosetting resin is in a range of 5 to 400 parts by weight and preferably 50 to 200 parts by weight. It is preferred to use a thermosetting resin with a content of 5 parts by weight or more, because the high temperature elastic modulus can be prevented. The semiconductor integrated circuit can be prevented from being connected during the operation of the semiconductor packaging instrument, which can improve the processing properties of the process. It is also preferable to use a thermosetting diester in an amount of 400 parts by weight or less because the adhesive layer having a field elastic mold and a sufficiently linear expansion coefficient can be obtained in this way. The present invention is by no means limited to thermosetting resins that add a hardener, an accelerator, and the like to form an adhesive layer. A method for producing an adhesive film using the aforementioned thermosetting adhesive will now be described by way of example. (A) A solution of the adhesive composition in a solvent is applied to a release polyester film or the like and dried. Drying is preferably from 100 to 200. (: Proceed! To 5 minutes. Preferable solvents include aromatic solvents (toluene, dimethylbenzyl, benzene, etc.), ketones (isobutyl ketone and aprotic polar solvents (dimethylformamide, dimethylformamide) (E.g., ethylacetamide, etc.), but the present invention is not limited to this. (B) The film as described in (a) above is laminated on a polyimide film used as a base film. * After the release polyester film is removed The adhesive film is cured from 100 to 2000 for 10 to 20 hours to obtain an adhesive film. 'As stated then' The adhesive film is composed of a polyimide film and an adhesive layer as a base film. Secondly, it is explained that each layer is better. Thickness. The preferred thickness of the base film is in the range of 15 to 90 microns. When the thickness of the base film is less than 5 microns, Polyurethane

88tl9324.ptd Page 40 450982 V. Description of the invention (37) The amine adhesive film is a multilayered layer having greatly different mechanical properties from each other, and often has the disadvantage of flash formation during the stamping step. Often stamping &amp; failure, the opening between the mother stamper and the male stamper is filled with stamping waste material and cannot be evolved. In this case, another kind of misalignment error occurs. On the other hand, when the thickness of the base film exceeds 90 micrometers, the pressing step requires high pressure, which results in deformation or cracking of the film. The preferred adhesive layer thickness is usually made of thermosetting adhesive or thermoplastic polyimide adhesive in the range of 2 to micrometers: when the thickness of the adhesive layer is less than 2 micrometers, a sufficient adhesive force cannot be established, which can damage reliability. On the other hand, when the thickness of the adhesive layer exceeds 30 micrometers, a flash fire is formed after the stamping step. Although the mechanism of flash formation is unknown until now, it is expected to be as follows: When the base film is completely cut before the adhesive layer, the adhesive layer becomes fine under cutting and the extended portion of the adhesive layer turns into a flash flame. : To prevent the flash shape &amp; ‘The preferred base layer is thickened without degrading the machinability &amp; of the stamping’ and the adhesive layer is thinned without deteriorating the adhesion reliability. In particular, the thickness of Erjia's base film accounts for 30 to 90% of the total thickness. So detailed. Ming: The adhesive film according to the present invention. The coating layer formed on the bonding surface or surface of the present invention via a bonded steel box has a thermal property of 3 when the coating layer is formed. Film rate m. This will produce favorable results for packaged semiconductors (quality and quality) 2: The base film using the polyimide film of the present invention as a magnetic recording film is as follows. ^ Xianzhi has a thin metal film formed on the surface of the base film It has been used in the technical field. For example, in the field of magnetic recording, two kinds of magnetic layers made of polymer films have been used to obtain corpses :: 2 ferromagnetic materials for application 2!!

450982 V. Description of the invention (38) Magnetic recording tape, etc.). This field of magnetic recording has led to the study of magnetic recording media of metal application type or vapor deposition type, which is different from the conventional oxide application type and has recently tended to high density recording. In addition, magnetic 5H recording media that have developed magnetic recording systems have exceeded the limits of conventional magnetic recording systems. The manufacturing method of magnetic recording media has changed greatly. For example, conventional methods in which magnetic metal powder is mixed with a binder and the resulting mixture has been replaced by novel thin film stacking methods such as vapor deposition, sputtering or ion plating such as used to form alloys such as cobalt-nickel or diamond-chromium. In these thin film stacking methods, the system encounters a significant high temperature due to the radiant heat from the evaporation source and the kinetic energy emitted by the deposited particles during the step of forming the magnetic layer film on the base film. In order to impart a sufficiently large coercive force as in the case of the cobalt-chromium thin film, it is occasionally necessary to raise the temperature of the base film to 100 or more or 6 or more. The base film of such a metal foil preferably has significantly high heat resistance in a thin film stacking method. Record: ϋ Ϊ such as polyethylene terephthalate film is often used as a conventional magnetic film = S, #cognite = &amp; film. Because the polyester film has low heat resistance, it is necessary to reduce the temperature of the tank. It is necessary to fully adhere the base film to the tank to assist the deposition process. Even if these methods are performed, the poly (isomeric pair: equal part of the thermal damage or the shape of the ester is difficult to use to form i 霡 t to produce small bumps. &Amp; exo-polyethylene terephthalate is also heated as in 2 A magnetic layer with a history of more than 16.0 ° 'even though it's a polyamine ^ ^ amine film on the polymer material φ, and polyamine film is known as a heat-resistant film. Polyamide 250. (:. Known polymer brewing 、 It has extremely high heat resistance, so it can be used continuously in A imine film. Films made of the following components:

450982 V. Description of the invention (39) Polymer of tetraacid dianhydride (hereinafter abbreviated as PMDA) and diamine diphenyl ether (hereinafter abbreviated as 0DA), biphenyltetracarboxylic dianhydride (hereinafter abbreviated as Polymers of BPDA) and 0M, and polymers of BPDA and p-phenylenediamine (hereinafter abbreviated as p-PDA). But the three types of polyimide films have insufficient heat resistance or mechanical properties, that is, they show an excessively high linear expansion coefficient (30 ppm or above at 20 to 300 ° C) or an excessively low linear expansion coefficient (at 20 to 300 ° C). 4ppm or more). Such conventional magnetic recording media composed of polyimide thin film or polyimide thin film often have severe curling problems in alloy films formed on the surface by a deposition or dispersion method. The curling cause of the aforementioned magnetic recording medium seems to be: (a) the stress of the magnetic layer; (b) the difference in the linear expansion coefficient of the base film layer and the magnetic layer, and the thermal stress caused by the thermal contraction of the base film layer; and (c) the magnetic layer Mechanical stress applied to the base film during formation. In the case of magnetic recording media, the temperature of the base film must be significantly increased during the formation of the flexible layer. The reason is that in the case of magnetic properties 2 the same as the cobalt-chromium film, especially the base film layer and magnetic, a major factor that constitutes curl . But no thread was found to be a means other than curl. The conventional polyimide thin effect is free from 300 kw / witch, ^ Qiao Qiu The top modulus is about "square millimeter, which is about the same as that of the rigid square bismuth polyfluorene film of the magnetic recording medium! , 〇〇〇 至 约】 200 ％, and =., In other words, these films compared with polyethylene J square milliliter, so can not show a sufficient tensile elastic modulus. Because :: too soft or too: body Traveling properties ... Irregular winding disturbances often occur. Only the contact failure can be used. The polyimide film according to the present invention is used as a substrate for magnetic recording.

Page 43 4 5 〇 9 8 2

V. Description of the invention (40) 臈 can solve the above-mentioned conventional magnetic problem k 2. The properties of the magnetic recording film that Tong Dang encounters with electrical recording films are as follows: U) The proper properties of the magnetic recording film are as follows: U) legitimate 诶 &amp; β is not wound in the coil 缜 躇 庳 忐 土 土 * soil and right mixed-&gt; 4 X-thickness formation of any irregularities on the surface; (b) with sufficient tensile elastic modulus (500 to 800); excellent properties; and (rn recognized, Tian * * Fan Ding Nai Zhai Wood) 'Cc) It has high dimensional stability under the condition of heat resistance change and humidity change, heat shrinkage ratio, small linear expansion coefficient, small water absorption and does not contain anisotropy in the film. By using the poly-amine film according to the present invention as a base film, a f 14 i recording film that satisfies the aforementioned requirements can be obtained without the curl problem. Sichuan Biomass magnetic stick: = Polyimide film of the base film of raw Λ film, preferably with an elastic mold of 500 kg / mm2 or more (preferably 550 kg / mm2 or more), at 20 To 300. (: The average linear expansion coefficient is] to ', 2 * 0ppm (preferably 1 to 16ppm), and the linear expansion coefficient ratio in the main direction (MD) to the transverse direction (td) is 1/5 to 5 (preferably 1/3) To 3 and even better 1/2 to 2), the average value of the water absorption coefficient in the range of 30% relative humidity to 80% relative humidity is 2 to 20ppm, preferably 1 to 15ppm and more preferably 1 to 10 叩 111). From room temperature to 300, it is heated and then maintained at the same temperature for 2 hours. The measured heat shrinkage ratio of the film at room temperature is _ work. 0% to not more than 1.0%, the thickness is 50 microns or less, even when the thickness is reduced to 2 to 1 These properties are maintained after 5 microns. Preferred specific examples of the present invention will now be described with reference to the following examples. However, it should be understood that the present invention is not limited to these examples. Those skilled in the art can make various changes, changes and modifications without departing from the scope of the present invention. The following abbreviations are used in the examples and comparative examples. PDMD: stupid melamine.

88119324.ptd Page 44 450982

V. Explanation of the invention (41) TMHQ p-phenylene concentrated (benzyltrimonate) QDA 4, 4'-diamine dibenzyl ether. p-PDA p-phenylenediamine. DMF Monomethylamine. DMAc dimethylacetamide. AA acetic anhydride. IQ Comparative Example 1 Heterophilin. DMF was introduced into a separate flask and 1 equivalent of ODA was added. The resulting mixture was stirred thoroughly at room temperature until the 0DA was completely melted. Next, 0,85 equivalents of powdered pMM slow mantle was added thereto and stirred for 40 minutes. Then, 1.5 equivalents of PMDA was dissolved in DMF solution and slowly added thereto, and the resulting mixture was stirred under cooling for 1 hour to obtain a solution of polyamic acid in DMF. The amount of DMF used is 18% by weight to obtain the feed concentration of the diamine and aromatic tetracarboxylic dianhydride monomer. Next, the polyamic acid solution was mixed with AA and IQ and poured onto a glass plate. After drying at about 100 ° C for about 5 minutes, the polyamine film was peeled off from the glass plate. The film was then fixed to the stand and heated for about 5 minutes at about 1000 ° C, about 300 ° C. (: Heating for about 30 seconds' heating at about 400 ° C for about 30 seconds and heating at about 5 10 ° C for about 30 seconds for dehydration and cyclization, thus obtaining a polyimide film having a thickness of about 10 microns

Example 1 Ingredient A: DMAc was introduced into a separation bottle and 2 equivalents of ODA and 3 equivalents of p-PDA were added thereto. The resulting mixture was thoroughly stirred at room temperature until OPA and p-PDA were completely dissolved into

88119324.ptd Page 45 V. Description of the invention (42) Stop ° Secondly, slowly add 4.25 equivalents of powdered TMHQ and stir for 40 minutes. Then, a solution of 0.75 equivalent of TMHQ dissolved in MAc and the resulting mixture were slowly added under stirring for 1 hour to obtain a solution of polyamic acid in DM Ac. The amount of DM Ac can be used to obtain a feed concentration of diamine and aromatic tetracarboxylic dianhydride monomers of 18% by weight. Ingredient B: DMF was introduced into the separation bottle and 3 equivalents of ODA and 1 equivalent of p_PDA ° were added to the mixture. The mixture was thoroughly stirred at room temperature until ODA and p-PDA were completely dissolved. Next, 3.4 equivalents of powdery pMDA was slowly added and stirred for 40 minutes. Then, a solution of 0.6 equivalent of PMDA in DMF was slowly added thereto, and the resulting mixture was stirred under cooling for 1 hour to obtain a solution of polyamic acid in DMF. The amount of DMF can be used to obtain a diamine and an aromatic tetracarboxylic dianhydride monomer feed concentration of 18% by weight. Next, the components A and β are mixed and stirred at a weight ratio of 1: 1. The polyamic acid solution was mixed with AA and 1Q and poured onto a glass plate. After drying at about 100 ° C for about 5 minutes, the polyamic acid film was peeled off from the glass plate. The film was then fixed to the stent and passed sequentially at about 1000. 〇Heating for about 5 minutes, heating at about 3000c for about 30 seconds, heating at about 400 ° c for about 30 seconds, and about 510 ° c for about 30 seconds for dehydration and cyclization, thereby obtaining a thickness of about i. Micron polyimide film. Example 2 DMAc was introduced into a separation bottle and 4 equivalents of ODA and 2 equivalents of p-PDA were added thereto. The resulting mixture was thoroughly stirred at room temperature until the oDA and p_pDA were completely dissolved. Next, 6 equivalents of TMHQ were slowly added thereto, followed by stirring for 40 minutes. 1 equivalent of 0DA and 3 equivalents of p_PDA were added, and the mixture was stirred for 40 minutes. its

88119324.ptd Page 46 450982 V. Description of the invention (43) Add 3.5 equivalents of PMDA and stir the mixture for 40 minutes. Then 0.5 equivalent of a solution in which PMDA was dissolved in DMAc was slowly added, and the resulting mixture was cooled; it was stirred for 1 hour to obtain a solution of polyamic acid in DM Ac. The amount of DMAc can be used to obtain a feed concentration of diamine and aromatic tetracarboxylic dianhydride monomers of 18% by weight. Next, the polyamic acid solution was mixed with AA and I Q and poured onto a glass plate. After drying at about 100 ° C for about 5 minutes, the polyamic acid film was peeled off from the glass plate. The film is then fixed to the stent and heated sequentially at about 100 ° C for about 5 minutes, at about 3 G 0 ° C for about 30 seconds, at about 400 ° C for about 30 seconds, and at about 51 seconds. OX: Dehydration and cyclization by heating for about 30 seconds to obtain a polyimide film having a thickness of about 10 microns. Example 3 DM Ac was introduced into a separation flask and 4.5 equivalents of 0D A and 5.5 equivalents of p-PDA were added thereto. The resulting mixture was thoroughly stirred at room temperature until 0DA and p-PDA were completely dissolved. Next, 5 equivalents of PMDA was added thereto, followed by stirring for 40 minutes. Then 4.5 equivalents of TMHQ was added and the mixture was stirred for 40 minutes. Then, a 0.5 equivalent solution of TMHQ dissolved in DMAc was slowly added thereto, and the resulting mixture was cooled and stirred for 1 hour to obtain a solution of polyamic acid in DMAc. The amount of DMAc can be used to obtain a feed concentration of diamine and aromatic tetracarboxylic dianhydride monomer of 18% by weight. Next, the polyamic acid solution was mixed with AA and IQ and poured onto a glass plate. After drying at about 100 ° C for about 5 minutes, the polyamic acid film was peeled from the glass plate. The film was then fixed to the stent and heated sequentially at about 1000 ° C for about 5 minutes, at about 300 ° C for about 30 seconds', at about 400 ° C for about 30 seconds, and at about 5 ° C. Heat at 10 ° C for about 30 seconds to dehydrate and cyclize to obtain a thin polyimide with a thickness of about 10 microns.

88119324, ptd page 47 450982 V. Description of the invention (44) Membrane. Example 4 DMAc was introduced into a separation bottle and 5 equivalents of 0DA and 5 equivalents of p-PDA were added thereto. The resulting mixture was stirred thoroughly at room temperature until oda and p-PDA were completely dissolved. Next add 5 equivalents of TMHQ and stir for 40 minutes. Then 4.5 equivalents of PMDA was added and the mixture was stirred for 40 minutes. Then 0.5 equivalent of PMDA was dissolved in)) MAc was slowly added thereto, and the resulting mixture was cooled and stirred for 1 hour to obtain a solution of polyamic acid in DMAc. The amount of DMAc can be used to obtain a feed concentration of diamine and aromatic tetracarboxylic dianhydride monomers of 18% by weight.

Next, the polyamine solution was mixed with AA and IQ and poured onto a glass plate. After drying at about 100 ° C for about 5 minutes, the polyacetic acid thin sheet was peeled off from the glass plate. The film was then fixed to the support and heated sequentially at about 100 ° C for about 5 minutes, at about 300 ° C for about 30 seconds, at about 400 ° C for about 30 seconds, and at about 51 ° C for about 30 seconds. Dehydration and cyclization in seconds resulted in a polyimide film having a thickness of about 10 microns. The linear expansion coefficient, water expansion coefficient, elastic modulus, water absorption and relative permittivity of the films obtained in Comparative Example 1 and Examples 1 to 4 were measured. Table 1 summarizes the results. A1

Modulus of Elasticity (kg / mm2) Comparative Example 1 300 Example 1 550 Example 2 680 Example 3 630 Example 4 600 Linear expansion coefficient 32 9 8 9 9 88119324.ptd Page 48 450982 (ppm) Water expansion coefficient (ppm) 21 8 4 5 5 Water absorption (%) 3 1. 5 0. 9 1. 4 1.2 Relative permittivity temperature / frequency-5 0 ° C / 1 kHz 3.50 3.08 3.10 3.09 3.10 -0 ° C / 1 kHz 3.46 3.18 3.20 3.19 3.18 22 ° C / i KHz 3. 48 3. 24 3. 22 3.23 3.23 1 0 0 ° C / 1 KHz 3. 01 3.11 3.10 3.12 3.11 2 0 (TC / 1 KHz 3. 00 3. 16 3. 17 3. 19 3.15 2 2 0C / 1 0 0 Hz 3.51 3. 28 3.25 3.30 3/2 5 22 ° C / 10 kHz 3. 46 3. 20 3.17 3.20 3.21 22 ° C / 100 KHz 3. 43 3. 15 3. 14 3. 14 3. 15 2 2 ° C / 1 megahertz 3.40 3.10 3.10 3.11 3. 10 The linear expansion coefficient is represented by TMA-8 140 manufactured by Rigaku Corporation. The linear expansion coefficient measured under a nitrogen gas flow at 0 to 3 0 0 ° C. The water absorption expansion coefficient is measured by using the following measuring device (2) by the following calculation method (1). (1) Calculation method of water elongation : When as shown in Figure 2 When changing the water, while the length of the sample measured gain and moisture changes, thus calculated moisture elongation (measured temperature: 5 0 ° C) water elongation =

88119324.ptd Page 49 450982 V. Description of the invention (46) {water absorption length gain (d) / {sample length + c)} / moisture change (b). b: 35% relative humidity (low humidity end), 75% relative humidity (high humidity end). c: Thermal expansion after the sample is fixed as the temperature rises from room temperature to the measurement temperature. (2) Measurement device: ① The measurement temperature is controlled by the thermostat of the hot water tank. ② In order to increase the humidity of the thermostat, the nitrogen gas is passed into the water vapor generating tank ’, and the humidity conditions are planned by using a heating bag to raise the temperature program. The temperature of the inlet between the thermostats is controlled to prevent dew formation. ③ The temperature of the humidity sensor is adjusted to the same level as the temperature of the thermostat. The β temperature control unit is a sensor body provided outside the thermostat. ④ The length (gain) is measured using 1 ^ 8 (1 ^ (: _ 14〇) manufactured by Maruzen. The tensile elastic modulus is measured according to ASTM-D882. The water absorption is measured according to the following formula, where W1 is expressed at 150 ° The film sample weight was measured after 30 minutes of drying, and W2 is the weight of the sample measured by immersing in distilled water for 24 hours and then wiping off the water droplets on the surface. Water absorption (%): = (W2_W1) / W1 χ100. Relative permittivity The measurement is performed under the following conditions. The thickness of the sample soil is calculated by the volume specific gravity method. Electrode type: According to JIS-K6911. Test environment: 22 ± 2 ° C, 60 ± 5% relative humidity. Frequency: 100 Hz, 1 KHz, 10 KHz, 100 KHz, 1 MHz.

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88119324.ptd 56th stomach 450982 V. Description of the invention (53) DMAc was introduced into the separation bottle and 4 equivalents of 0DA and 1 equivalent of PDA were added. The resulting mixture was stirred thoroughly at room temperature until the oDA and p-PDA were completely dissolved. Secondly, 4.95 equivalents of powdered TMHQ were slowly added, followed by stirring for 40 minutes. After adding 0.5 equivalent of 0DA and 4.5 equivalent of p-PDA, the mixture was stirred for 40 minutes. Next, 5 equivalents of PMDA powder was slowly added thereto and the mixture was stirred for 1 hour. Then, a solution of 0.5 equivalent of PMDA in DMAc was slowly added thereto, and the resulting mixture was stirred under cooling for 1 hour to obtain a solution of polyamic acid in DM Ac. The amount of DMAc can be used to obtain a feed concentration of diamine and aromatic tetracarboxylic dianhydride monomers of 18% by weight. Next, 'the polyamic acid thus obtained was mixed with AA and I Q and then cast on a stainless steel endless belt. After drying at 100 ° C for 5 minutes, the self-supporting front film thus formed was peeled off from the tape. The front film was continuously fed into the inside of the oven by clamping both ends, and heated in a supply oven at 300 for 30 seconds', heated at 400 ° C for 30 seconds, and 510 X: heated for 30 seconds. Next, slowly cool to room temperature in the annealing chamber. When the film is removed from the annealing chamber ', it is torn off from the needle. Then, various characteristics of the thin film were measured, and the film flow direction was referred to as the MD direction and the lateral direction was referred to as the TD direction. The linear expansion coefficient, water absorption expansion coefficient, and elastic modulus of the films obtained in Comparative Example 2 and Examples 1 2 to 14 were measured. Table 3 summarizes the results. The linear swelling coefficient indicates that Maruichi manufactured by Rigaku Corporation is used. "The coefficient of linear expansion measured under nitrogen flow from 20 to 3007 is determined in the same manner as in Comparative Examples and Examples] to the bucket. The modulus of tensile elasticity is according to ASTM-D882 The water absorption is measured according to the following formula ^ 'wherein they are expressed in l5Q t dry content

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W β β ^ W νΝ t. A Collection of Emperor Jiqi ^ uv ^ r ^ φ ^ s Λν ^ Η MW, 雒 雒 雒 Ψ Ψw, u $ ^ s ο I f «450982 Description of the Five 'Invention (56) Stir for 1 hour to obtain polyamide A solution of acid in MAc. The amount of DMAc can be used to obtain a feed concentration of diamine and aromatic tetracarboxylic dianhydride monomers of 18% by weight. Ingredient B: DMF is introduced into the separation bottle and 3 equivalents of 0DA and 1 equivalent of P-PDA are added to it. The resulting mixture was stirred thoroughly at room temperature until the oDA and p-PDA were completely dissolved. Next, 3.4 equivalents of powdered PMDA was slowly added, followed by stirring for 40 minutes. Then, a solution of 0.6 equivalent of PMDA in DMF was slowly added thereto, and the resulting mixture was stirred under cooling for 1 hour to obtain a solution of polyamic acid in DMF. The amount of DMF can be used to obtain a diamine and aromatic tetracarboxylic dianhydride monomer feed concentration of 18% by weight. Next, components A and B are mixed and stirred at a 1: 1 weight ratio. The polyamic acid thus obtained was then mixed with AA and IQ and then cast on a stainless steel endless belt. After drying at 100 ° C for 5 minutes, the self-supporting front film thus formed was peeled off from the tape. The front film was continuously fed into the inside of the oven by clamping both ends, and heated in the oven at 300 ° C for 30 seconds', heated at 400 ° C for 30 seconds, and heated at 5100 ° C for 30 seconds. Next, slowly cool to room temperature in the annealing chamber. When the film is removed from the annealing chamber ', it is torn off from the needle. Then, various characteristics of the film were measured, and the flow direction of the film was referred to as the MD direction and the lateral direction was referred to as the td direction. JT Example 18 Ingredient A: DMAc was introduced into the separation flask and 2 equivalents of OM and 3 equivalents of p-pda were added to the Tibetan compound, and the mixture was thoroughly stirred at room temperature until 0) A and p_pda were completely dissolved. Next, 4.25 equivalents of powdered TMHQ was added and stirred for 40 minutes. Then slowly add 0.775 of the solution in which TMHQ was dissolved and the resulting mixture was allowed to cool.

88119324.ptd

450982 V. Description of the invention (57) Stir for 1 hour to obtain a solution of polyamic acid in DMAc. The amount of DMAc can be used to obtain a feed concentration of diamine and aromatic tetracarboxylic dianhydride monomers of 18% by weight. Ingredient B: DMF is introduced into the separation bottle and 3 equivalents of 0DA and 1 equivalent of p-PDA are added thereto. The resulting mixture was thoroughly stirred at room temperature until 0DA and p-PDA were completely dissolved. Next, 3.4 equivalents of powdered PMDA was slowly added and stirred for 40 minutes. Then, a solution of 0-6 equivalents of PMM in DMF was slowly added thereto and the resulting mixture was stirred under cooling for 1 hour to obtain a solution of polyamic acid in DMF. The amount of DMF can obtain the diamine and aromatic tetracarboxylic dianhydride monomer feed concentration of 18% by weight. Next, components A and B are mixed and stirred at a 2: 1 weight ratio. The polyamic acid thus obtained was then mixed with AA and IQ and then cast on a stainless steel endless belt. After drying at 100 ° C for 5 minutes, the self-supporting front film thus formed was peeled off from the tape. The front film was continuously fed into the inside of the oven by clamping the two ends, and heated in a coal oven at 300 for 30 seconds, at 400 ° C for 30 seconds, and at 510 ° C for 30 seconds. Next, slowly cool to room temperature in the annealing chamber. When the film is removed from the annealing chamber, it is torn off from the needle. Then, various characteristics of the film were measured, and the direction of film flow was referred to as the MD direction and the transverse direction was referred to as the T D direction. Example 19 DMAc was introduced into a separation flask and 4.5 equivalents of ODA and 5.5 equivalents of p-PDA were added thereto. The resulting mixture was stirred thoroughly at room temperature until ODA and p-PDA were completely dissolved. Next, 5 equivalents of PMDA was added thereto and the mixture was stirred for 40 minutes. After adding 4.5 equivalents of TMHQ, the mixture was stirred for another 40 minutes. Then 0.5 equivalent of a solution of TMHQ dissolved in DMAc was slowly added thereto, and the resulting mixture was cooled down

88119324.ptd Page 61 450982 V. Description of the invention (58) Stir for 1 hour to obtain a solution of polyamic acid in DM Ac ". The amount of DM Ac can obtain the feed of diamine and aromatic tetracarboxylic dianhydride monomers. The concentration is 18% by weight. Next, the polyamic acid thus obtained was mixed with AA and IQ and then cast on a stainless steel endless belt. After drying at 100 ° C for 5 minutes, the self-supporting front film thus formed was peeled off from the tape. The front film is continuously fed into the inside of the oven by holding both ends, and heated in the oven at 300 for 30 seconds, 400 ° C for 30 seconds and 510 t: heating for 30 seconds. Next, slowly cool to room temperature in the annealing chamber. When the film is removed from the annealing chamber, it is torn off from the needle. Then measure various characteristics of the film, and call the film flow direction the MD direction and the transverse direction the TD direction. Example 2 g DMAc was introduced into a separation bottle and 4 equivalents of ODA and 2 equivalents of P-PDA were added thereto. The resulting mixture was stirred thoroughly at room temperature until the oDA and p-PDA were completely dissolved. Then 6 equivalents of TMHQ was added thereto and the mixture was stirred for 40 minutes. Next, 1 equivalent of ODA and 3 equivalents of p-PDA were added thereto and the mixture was stirred for 40 minutes. After adding 3.5 equivalents of PMDA, the mixture was stirred for another 40 minutes. Then, a solution of 0.5 equivalent of PMDA in DMAc was slowly added thereto, and the resulting mixture was stirred under cooling for 1 hour to obtain a solution of polyamic acid in DMAc. The amount of DMAc can be used to obtain a feed concentration of 18% by weight of diamine and aromatic tetracarboxylic dianhydride monomer. Next, 'the polyamic acid thus obtained was mixed with AA and I Q and then cast on a stainless steel endless belt. At 100 t: 5 minutes after drying, the self-supporting front film thus formed was peeled off from the tape. The front film is continuously fed into the inside of the oven by clamping the two ends, and heated in the oven at 300 for 30 seconds, at 400 eC for 30 seconds, and at 510 ° C for 30 seconds.

88119324, ptd Page 62 4 5 0982 V. Description of the invention (59) seconds. Next, slowly cool to room temperature in the annealing chamber. When the film is removed from the annealing chamber, it is torn off from the needle. Then measure various characteristics of the film, and call the film flow direction the MD direction and the transverse direction the TD direction. Example 21 DMAc was introduced into a separation bottle and 5 equivalents of 0DA and 5 equivalents of p-PDA were added thereto. The resulting mixture was stirred thoroughly at room temperature until oda and p-PDA were completely dissolved. Next, 5 equivalents of TMHQ was added thereto and the mixture was stirred for 40 minutes. After adding 4.5 equivalents of PMDA, the mixture was stirred for another 40 minutes. Then, a solution of 0,5 equivalents of TMHQ in DMAc was slowly added thereto, and the resulting mixture was searched under cooling for 1 hour to obtain a solution of polyamic acid in DMAc. The amount of DMAc can be used to obtain a feed concentration of diamine and aromatic tetracarboxylic dianhydride monomers of 18% by weight. Next, 'the polyamic acid thus obtained was mixed with AA and IQ and then cast on a stainless steel endless belt. After drying at 100 ° C for 5 minutes, the self-supporting front film thus formed was peeled off from the tape. The front film is continuously fed into the inside of the oven by clamping both ends, and heated in the oven at 300 for 30 seconds', heated at 400 ° C for 30 seconds, and heated at 5 10 ° C for 30 seconds. Next, slowly cool to room temperature in the annealing chamber. When the film is removed from the annealing chamber ', it is torn off from the needle. Then measure the various characteristics of the film, the film flow direction is called MD direction and the transverse direction is called!) Direction. The linear expansion coefficient, water expansion coefficient and elastic modulus of the films obtained in Comparative Example 2 and Examples 15 to 21 were measured. Table 4 summarizes the results. ^ _4

Coefficient of Linear Expansion (ppm) Coefficient of Water Expansion (ppm) Modulus of Elasticity (kg / flat curl IS IS ί 1 Ϊ 1 i! I 1! Ϊ 1 i 1 1 ί 11 11 II 88119324.ptd Page 63 1450982 V. Invention Explanation (60) Fang Lailai MD TD MD TD Comparative Example 2 30 34 18 22 300 X Example 1 5 12 13 6 8 550 〇 Example 1 6 11 9 4 3 700 〇 Example 1 7 9 9 8 8 550 〇 Example 1 8 7 6 6 6 640 〇Example 1 9 9 10 5 6 63 0 〇Example 2 0 8 8 4 4 660 〇Example 21 9 8 4 4 600 〇, the linear expansion coefficient is expressed by using TMA-8140 manufactured by Rigaku Corporation. Coefficient of linear expansion measured at 20 to 300 ° C under nitrogen flow. The coefficient of water expansion was measured in the same manner as in Comparative Example 1 and Examples 1 to 4. The tensile elastic modulus is measured according to ASTM-D882. The degree of curl was measured by forming a magnetic layer on each of the thin film samples of Comparative Example 2 and Examples 15 to 21 by a common oblique vapor deposition method using an electron beam heating type continuous deposition apparatus. The thickness of the magnetic layer in each case was 0.1 2 microns, and the tank temperature was 250 ° C. The magnetic layer deposition rate is about 0.1 micron / second. Example 22 A polyimide film having a thickness of about 10 m was obtained in the same manner as in Example 5. Example 23 A polyimide film having a thickness of about 10 microns was obtained in the same manner as in Example 6.

88119324.ptd Page 64 ^ 4 5 09 8 2 V. Description of Invention (61). Example 24 A polyimide film having a thickness of about 10 m was obtained in the same manner as in Example 1. Example 25 A polyimide film having a thickness of about 10 m was obtained in the same manner as in Example 8. Example 26 A polyimide film having a thickness of about 10 m was obtained in the same manner as in Example 3. Example 27 A polyimide film having a thickness of about 10 m was obtained in the same manner as in Example 2. Example 28 A polyimide film having a thickness of about 10 m was obtained in the same manner as in Example 4. The linear expansion coefficient, water expansion coefficient, and elastic modulus of the films obtained in Comparative Example 1 and Examples 22 to 28 were measured. Table 5 summarizes the results. Table__5 Linear expansion coefficient (ppm) Water absorption expansion coefficient (ppm) Elastic modulus (kg / mm2) Density (g / cm3) Water absorption (%) Adhesive strength (kg / cm) Comparative example 1 32 20 300 1 . 420 3. 0 0.8

88119324.ptd Page 65 450982 V. Description of the invention (62) Example 2 2 12 — — 7 550 1.456 1. 0 1.1 Example 23 10 4 700 1. 457 0,8 1.1 Example 24 9 8 550 1. 445 1.5 1.2 Example 2 5 8 7 640 1.445 1.4 1.1 Example 26 9 5 630 1.445 1.4 1.3 Example 27 8 4 680 1. 460 0.9 1. 2 Example 28 9 5 600 1. 459 7Γ ~ 1 1.3 The linear expansion coefficient is expressed by using Rigaku Corporation The linear expansion coefficient of TMA-8140 measured at 20 to 300 t under nitrogen flow. The coefficient of water expansion was measured in the same manner as in Comparative Example 1 and Examples 1 to 4. The tensile elastic modulus is measured according to ASTM-D882. Water absorption is measured according to the following formula, where W1 is the weight of the film sample measured after drying at 150 ° C for 30 minutes, and W2 is the weight of the sample measured after immersed in distilled water for 24 hours and then wiped off the water droplets on the surface β water absorption U) KW2-W1) / W1 X100. The density is measured according to JIS.K7112 6.4D method (density gradient centrifugation method). The adhesive strength was measured as follows. Each of the polyimide films thus obtained was laminated on a steel foil (electrolytic copper foil 3EC_VLp manufactured by Mitsui Mining and Metallurgy Co., Ltd.) using a nylon epoxy adhesive to obtain a three-layer laminate (polyimide film / adhesive / Copper foil). The laminate was then subjected to measurement according to JIS ~ 6472-1 995- (8). The degree of curling of the three-layer ladle laminate was evaluated by the following method.

88119324.ptd Page 66 450982 V. Description of the Invention (63) (1) As Comparative Example 1 and Examples 2 to 2 8 a 50 micron film was obtained. (2) Each of the films thus obtained was laminated on a steel sheet (electrolytic copper f | 3EC-VLP manufactured by Mitsui Mining and Metallurgy Co., Ltd.) using a nylon epoxy resin adhesive to obtain a three-layer laminate (polyimide film / adhesion Agent / copper foil). (3) The three-layer laminate thus obtained was cut into a size of 35 mm (TD direction) X40 mm CMD direction) and allowed to stand in an atmosphere of 23 ° C and 55% relative humidity. The sample was then placed with the concave side downward as shown in Figure 1, and the dial was used to measure the highest lifting height. Table 6 summarizes the results. Height in the curling direction (meter) Comparative Example 1 TD 2.4 Example 2 2 TD 1. 3 Factory Example 23 TD 1.3 2 4 TD 1.1 ^ Example 25 TD 1.4 Example 2 6 TD 0.9 Example 27 TD 0. 8 Issue 28 TD 0. 8 gJ ^ J2 9 Polyimide film with a thickness of about 10 microns was obtained in the same manner as in Example 5 ^ # & J30

88119324.Ptd page 67 v 4 5 0 9 8 2 V. Description of the invention (64) A polyimide film having a thickness of about 10 microns was obtained in the same manner as in Example 6. Example 31 A polyimide film having a thickness of about 10 m was obtained in the same manner as in Example 3. Example 32 A polyimide film having a thickness of about 10 m was obtained in the same manner as in Example 2. Example 33 DMAc was introduced into a separation flask and 5 equivalents of 0]) A and 5 equivalents of p-PDA were added thereto. The resulting mixture was thoroughly stirred at room temperature until 0da and p-PDA were completely dissolved. Next, 5 equivalents of TMHQ was added thereto, followed by stirring for 40 minutes. Further, 4-5 equivalents of PMDA was added thereto, followed by stirring for 40 minutes. Then, a solution of 0.5 equivalents of PMDA dissolved in DMAc was slowly added thereto, and the resulting mixture was stirred under cooling for 1 hour to obtain a solution of polyamic acid in DMAc. The amount of DMAc can be used to obtain a feed concentration of diamine and aromatic tetracarboxylic dianhydride monomers of 18% by weight. The polyamic acid solution was mixed with A A and I Q and poured onto a glass plate. After drying at about 1000 ° C for about 1 minute, the polyimide film was peeled off from the glass plate. The film was then fixed to the stent and heated sequentially at about 1000 ° C for about 1 minute, then at about 300 ° C for about 30 seconds', at about 400 ° C for about 30 seconds, and at about 510 X: heating for about Dehydration and cyclization in 30 seconds resulted in a polyimide film having a thickness of about 10 microns. The linear expansion coefficient, water absorption expansion coefficient, and elastic modulus of the films obtained in Comparative Examples 1 and 2 to 9 to 3 3 were measured. Table 7 summarizes the results.

88119324.ptd Page 68 45 09 8 2 V. Explanation of the invention (65) Coefficient of linear expansion (ppm) Coefficient of water expansion (ppm) _ ^ Modulus of elasticity (kg / square meter) Water absorption (%) Comparative example 1 32 20 --- ~~~ -L--300 3. 0 Example 29 12 Ί 550 1.0 Example 30 10 4 Π ~ Ύ〇〇〇78 ~ Example 31 9 5 630 1.4 Example 32 8 4 680 0 · 9 Example 33 9 5 600 1.2 The coefficient of linear expansion refers to the coefficient of linear expansion measured using a TMA-8140 manufactured by Rigaku Corporation at 20 to 300 ° C under a nitrogen stream. The coefficient of water expansion was measured in the same manner as in Comparative Example 1 and Examples 1 to 4. The tensile elastic modulus is measured according to ASTM-D882. The water absorption is determined according to the following formula, where W1 is the weight of the film sample measured after drying at 150 ° C for 30 minutes, and W2 is the weight of the sample measured after immersing in distilled water for 24 hours and then wiping off the water droplets on the surface. . Water absorption (%) = (W2-W1) / W1 X100. Comparative Example 3 A polyamic acid solution was applied to one side of the film (10 μg) obtained in Comparative Example 1. Polyamic acid was a thermoplastic polyimide precursor having a Tg of 190 ° C, containing 3, 3 ', 4 , 4, -Dibenzylidene tetracarboxylic dianhydride, 3, 3, '-4, 4, -ethylene glycol dibenzylate tetracarboxylic dianhydride and 2, 2'-fluorene (4- (4 -Amino stupid oxygen) stupid

88119324, ptd Page 69 450982 V. Description of the invention (66) '' ~~ * -------- based) Propylene sintering is used as the main ingredient in a solution of 1% organic solvent and then dried to obtain a thickness of 1 7 Micron polyfluorene imide laminate. Then the polyimide thus obtained was laminated. The material was placed on a steel foil (electrolytic copper foil 3EC-VLP manufactured by Mitsui Mining and Metallurgy Co., Ltd.) and heated and compressed and bonded (30 kgf / cm2 / 240 ° C / 20) Minutes) to obtain a three-layer laminate, namely #thermoplastic polyimide / thermoplastic polyimide / copper foil. The adhesive strength of the interface (non-thermoplastic polyimide / thermoplastic polyimide) of the obtained laminate was measured. Table 8 shows the results. Table 8 _Coupling strength (kg / cm) Heating corona plasma coupling agent Comparative example 3 Comparative example 1 • _ 0.1 Comparative example 4 Comparative example 1 0--0.2 Comparative example 5 Comparative example 1 0 0 0,2 Comparative Example 6 Comparative Example 1 0 0 0-0, 2 Comparative Example 7 Comparative Example 1 0 0-0 Isophorone Diamine 0, 3 Comparative Example 8 Comparative Example 1 0 _ 0 Ibid. 0.3 Comparative Example 9 Example 29-- 0.3 | Comparative Example 10 Example 3 3 _-0,3 Example 34 Example 29 0--0 Isophoronediamine 1.0 Example 35 Example 2 9 0 0--0.9 Example 36 Example 29 0 0 1.2 丨 Example 37 Example 29 0 0 0 1.2 i Example 3 8 Example 29 0 0 0 Isophoric diamine 1.0 丨 Example 39 Example 2 9 0 0 0 Ibid. 2 丨 Example 40 Example 3 0 0 0 0 1.0 丨 Example 41 Example 3 1 0 0 0 1,1 Example 42 Example 3 2 0 0 0 1,0 11 II 1 1 —- — --- 88119324.ptd Page 70 450982 V. Description of the invention (67) Example 4 3 Example 33 〇--0 Buddha_diamine \ Λ Example 44 Example 3 3 0--0 Diethylenetriamine 1.0 Example 45 Example 33 0--〇N-Aminoethylhexahydropyracine 1.0 Example 4 6 Example 33 0 0 _ 0.9 Example 47 Example 3 3 0 0 1.2 Example 48 Example 33 0 0 0 Drop 1.2 Example 49 Example 33--0 • 1.2 Comparative Example 4 The film (10 micrometers) obtained in Comparative Example 1 was subjected to heat treatment at 50 ° C for 1 minute. Then, the adhesion strength of the obtained polyimide film was measured as in Comparative Example 3. Comparative Example 5 The film (10 micrometers) obtained in Comparative Example 1 was sequentially subjected to a heat treatment at 5000 for 1 minute and a corona treatment at a corona density of 300 watt · minutes / square meter. Then, the adhesive strength of the obtained polyfluoreneimide film was measured as in Comparative Example 3. The thin film (10 micrometers) obtained in Comparative Example 1 was sequentially subjected to 500 heat treatment for 1 minute, and was subjected to a corona density of 300 W.min / m2. Further connected to a plasma treatment with a plasma density of 2000 W.min / m². Then, the adhesive strength of the obtained polyimide film was measured as in Comparative Example 3. … Comparative Example 7 m) Sequentially subjected to a heat treatment at 500 ° C for 1 minute / square meter of corona treatment. Further, the film obtained in Comparative Example 1 (10 microminutes and a corona density of 300 watts

4 5 09 8 2 V. Description of the invention (68) Use a rod coater to apply isophoric diamine in a methanol solution (dry at 5 and 70 C! Minutes. Then, as a comparison ratio), apply the adhesive strength of the film. Polyimide Comparative Example 8 Obtained in Comparative Example 8 The film obtained in Comparative Example 1 (10 micrograms) was sequentially mined and densified in tiles. Min / square heat treatment 1 step Use a rod coater to apply isophorone diamine in a methanol solution Progress: ^ a ^ 70 It ^ ^ # 0 ^ ^ ^ ,, J3 (t; Adhesive strength of amine thin film. $ 利 所 利 聚醯 亚 Comparative Example 9 Measurement of the adhesive strength of the film (j 0 micron) obtained in Example 33 As in Comparative Example 3, the adhesive strength of the film obtained in Comparative Example 10, Example 33, and f Example 34 (not shown) was measured as in Comparative Example 3. Defect: 29: The obtained film (1 ° micron) was accepted at 500. . Heat treatment for 1 minute. 4 Use a cup coater to dry isophorone diamine in a methanol solution (5% weight ratio ·) for t 5 3 5 for 1 minute. Then, the adhesive strength of the obtained polyimide shore film was measured as in Comparative Example 3. Example 35 The film (10 micrometers) obtained in Example 29 was sequentially subjected to a corona treatment at 500 ° C and a corona density of fine G watts per minute / square µ. In Comparative Example 3, the adhesive strength of the obtained polyimide film was measured. Example 36

450982 V. Description of the invention (69) * ----- As measured in Comparative Example 3, the adhesive strength of the obtained polyimide thin fluorene was measured. Example 37 Example 29 = Film (10 · m) is sequentially accepted at 50 ° (rc force clock and corona density of 300 watts per minute per square meter ;; Plasma density of 2000 watts per minute per square half standard Makeup # / amp 卞 is water-treated with plasma. Then directly measure the adhesion strength of the polyimide film obtained as in Comparative Example 3. Example 38 film and Example 29 film αα micro demand) was sequentially accepted at 500. 〇 plus minutes and corona treatment at corona density_W · min / m2. Further—Use a bar coater to apply isophorone diamine to a methanol solution (5% by weight) and dry it on 70 for 1 minute. Then, the adhesive strength of the obtained polyimide-specific film was measured as in Comparative Example 3. Example 39 The film (10 micrometers) obtained in Example 29 was sequentially subjected to 500 hours of heat treatment for 1 minute and corona treatment at a corona density of 300 W.min / m2. Further, plasma treatment was performed at a plasma density of 200 W · min / m 2. Isophorone diamine was then applied to a methanol solution (5% by weight) using a bar coater and dried at 70 ° C for 1 minute. Then, the adhesion strength of the obtained polyimide was measured as in Comparative Example 3. /, Example 4 0 The film (10 microns) obtained in Example 30 was sequentially subjected to 50 ° C heat treatment! It was known to be corona treated at a corona density of 300 watts per minute per square meter.

450982_ V. Description of the invention (70) Plasma density: 200 W · min / m2 Plasma treatment. Then, the adhesion strength of the obtained polyimide film was measured as in Comparative Example 3. Example 41 The film (10 micrometers) obtained in Example 31 was sequentially subjected to a heat treatment at 5000 for 1 minute and a corona treatment at a corona density of 300 W · min / m 2. Then it was treated with plasma at a density of 200 W.min / m². Then, the adhesion strength of the obtained polyimide film was measured as in Comparative Example 3. Example 4 2 The film (10 microns) obtained in Example 3 2 was sequentially subjected to a heat treatment of 500 minutes and a corona treatment of a corona density of 300 watts per minute per square meter. Then, the plasma density was 200 watts per minute per square meter. Then, the adhesion strength of the obtained polyimide film was measured as in Comparative Example 3. Example 43 The film (10 micrometers) obtained in Example 33 was subjected to 500 heat treatment for 2 minutes. Isophorone diamine was then applied to a methanol solution (5% by weight) using a rod coater and dried at 70 ° C for 1 minute. Then, the adhesion strength of the obtained polyfluoreneimide film was measured as in Comparative Example 3. The films (10 microns) obtained in Examples 44 and 33 were subjected to a heat treatment at 5000 for 2 minutes. Diethylene glycol triamine was then applied to a methanol solution (5% by weight) using a bar coater and then heated to 70%. (: Dry for 1 minute. Then measure the adhesive strength of the obtained polyfluorene imine thin film according to Comparative Example 3. Example 45 The film (10 microns) obtained from Example 33 was subjected to heat treatment at 500 ° C for 1 minute.

88119324.ptd Page 74 450982 V. Description of the invention (71) Then use a dry coater to spray N-aminoethylhexahydro "onto a methanol solution ($% by weight) and apply it at 70 ° C. 1 minute. Then the adhesive strength of the obtained polyimide film was measured as in Comparative Example 3. Example 46 The film (10 micron) obtained in Example 33 was sequentially subjected to 500. It was heat-treated for 1 minute and at a corona density of 300 watts. Corona treatment per minute / square meter. Then the adhesive strength of the polyfluoreneimide film obtained was measured as in Comparative Example 3.… Example 47 The film (10 microns) obtained in Example 33 was sequentially subjected to a heat treatment at 500 ° C for 1 minute and Plasma treatment at a plasma density of 2000 W · min / m 2 .The adhesive strength of the obtained polyimide film was then measured as in Comparative Example 3. Example 48 The film (10 μm) obtained in Example 3 3 was sequentially accepted at 50%. 〇 It was heat-treated for ^ minutes and corona treatment at a corona density of 300 watts per minute / square meter.-Plasma treatment at a plasma density of 2000 watts per minute / square meter. Then measured as in Comparative Example 3. Adhesive strength of polyimide film. Example 49 The film (10 microliters) obtained in Example 33 was subjected to plasma treatment at a plasma density of 2,000 watt-meters. Then, the adhesive strength of the film was measured as in Comparative Example 3. The imine polyimide film was manufactured as follows: The procedure is to form. This type 6 polyfluorene imide film (PI films 1 to 6) is measured by the following methods based on the properties of each film. (Linear expansion coefficient)

88119324, ptd Page 75 450982 V. Description of the invention (72) Under nitrogen gas flow, the sample is repeatedly heated and cooled from room temperature to 400 ° C at a rate of 10 ° c per minute "and then manufactured by Rigaku Corporation TMA-8140 measures the average linear expansion coefficient of the second heating step at 20 to 300 ° C. (Coefficient of Water Expansion) The coefficient of water expansion was measured in the same manner as in Comparative Example 1 and Examples 1 to 4. (Tensile elastic modulus) The tensile elastic modulus is measured according to ASTM-D882. (Water absorption) The water absorption was measured according to the following formula, where W1 is the weight of the film sample measured after drying at 150 ° C for 30 minutes, and W2 is the weight of the sample measured after immersion in distilled water for 24 hours and then removing the water droplets on the surface. Water absorption (%) = (W2-W1) / W1 × 100. (PI film-1) DMF was introduced into the separation flask and 10 equivalents of 0 Da were added thereto. The resulting mixture was stirred thoroughly at room temperature until 0DA was completely dissolved. Next, 8.5 equivalents of powdered PMDA was slowly added thereto followed by stirring for 40 minutes. Then, a solution of 5 equivalents of PMDA in DMF was slowly added thereto and the resulting mixture was stirred under cooling for 1 hour to obtain a solution of polyamic acid in DMF. The amount of DMF can be used to obtain a feed concentration of 18% by weight based on the weight of the polyamidic acid solution of diamine and aromatic tetra-acid dianhydride. Second, the polyamic acid solution was mixed with AA and Q and poured onto a glass plate. After drying at about 100 ° C for about 5 minutes, the polyamic acid film was peeled off from the glass plate, and then the film was fixed to a stand and heated at about 300 ° C in order.

4 5 09 8 2 V. Description of the invention (73) minutes, heating at about 400 ° C for about 1 minute and heating at about 5100 ° C for about 1 minute for dehydration and cyclization, thus obtaining a polymer with a thickness of about 10 microns醯 imine film. 0%。 The polyimide film thus obtained showed a linear expansion coefficient of 32 ppm, a water absorption expansion coefficient of 20 ppm, an elastic modulus of 300 kg / mm2 and a water absorption of 3.0%. (PI film-2) DMAc was introduced into the separation bottle and 8 equivalents of 0DA and 5 equivalents of p-PDA were added thereto. The resulting mixture was stirred thoroughly at room temperature until ODA and p-PDA were completely dissolved. Next, 5 equivalents of TMHQ and 6.05 equivalents of powdered PMDA were slowly added thereto, followed by stirring for 40 minutes. Then, a solution of 1.95 equivalents of P M D A in DMA c was slowly added thereto, and the resulting mixture was stirred under cooling for 1 hour to obtain a solution of polyamic acid in DMAc. The amount of DMAc can be used to obtain the diamine and aromatic tetra-acid dianhydride monomer. The feed concentration based on the weight of the polyamine solution is 18% by weight. Next, the polyamic acid solution was mixed with A A and I Q and poured onto a glass plate. After it was dried for about 5 minutes, the polyamic acid film was peeled off from the glass plate. The film is then fixed to the support and heated sequentially at about 300 ° C for about 1 minute, heated at about 400 ° C for about 1 minute, and heated at about 5100 ° C for about one minute for dehydration and cyclization. 10 micron polyimide film. The polyimide film thus obtained exhibited a linear expansion coefficient of 12 ppm, a water absorption expansion coefficient of 7 ppm, an elastic modulus of 550 kg / mm2, and a water absorption of 1.0%. (PI film-3) DMAc was introduced into a separation bottle and 12 equivalents of ODA and 11 equivalents of p-PDA were added thereto. The resulting mixture was stirred thoroughly at room temperature until the ODA and p-PDA were completely dissolved. Next, 15 equivalents of TMHQ and 4.55 equivalents of powdered PMDA were slowly added thereto, followed by stirring for 40 minutes. Then 3.45 equivalents of PMDA dissolved in DMF solution slowly

'45 0982 V. Description of the invention (74)' &quot;-Added to it 'and the resulting mixture was stirred under cooling for 1 hour to obtain a solution of polyamic acid in DMAc. The amount of DMAc can be used to obtain the feed concentration of diamine and aromatic tetracarboxylic acid dixenite based on the weight of the polyamic acid solution is 8% by weight. Next, the polyamic acid solution was mixed with AA and 19 and poured onto a glass plate. After drying at about 100 ° C for about 5 minutes, the polyamic acid film was peeled off from the glass plate. The membrane was then fixed to the stent and heated sequentially at about 300 ° C for about 1 minute, at about 400 ° C for about 1 minute, and at about 5 10 t: heating for about 1 minute for dehydration and cyclization ' In this way, a polyimide film having a thickness of about 10 micrometers was obtained. The polyimide film thus obtained showed a linear expansion coefficient of 0ρρη, a water absorption expansion coefficient of 4 ppm, an elastic modulus of 700 kg / mm2, and a water absorption of 0.8%. (PI film-4) DMAc was introduced into the separation bottle and 4.5 equivalents of ODA and 5.5 equivalents of p-PDA were added thereto. The resulting mixture was thoroughly stirred at room temperature until 0DA and p-PDA were completely dissolved. Next, 5 equivalents of PMDA was added, followed by stirring for 40 minutes, and 4.5 equivalents of TMHQ was added, followed by stirring for 40 minutes. Then, 0.5 equivalent of a solution of TMHQ dissolved in DMAc was slowly added thereto, and the resulting mixture was stirred for j hours under cooling to obtain a solution of polyamic acid in DMAc. The amount of DMAc can be used to obtain a feed concentration of diamine and aromatic tetracarboxylic dianhydride monomer based on the weight of the polyamic acid solution of 18% by weight. Next, the polyamic acid solution was mixed with AA and O and poured onto a glass plate. After drying at about 100 ° C for about 5 minutes, the polyurethane film was peeled off from the glass plate. The film was then fixed to the stent and heated sequentially at about 300 ° C for about 1 minute, then at about 400 ° C for about 1 minute and at about 5 1 0. &lt; Dehydration and cyclization by heating for about 1 minute, thus obtaining a polyimide film having a thickness of about 10 microns. The polyimide film thus obtained exhibited a linear expansion coefficient of 9 ppm and swelling upon absorption of water.

88119324.ptd Page 78 1 ^ ^ 15 09 8? 5. Description of the invention (75) The coefficient is 5 ppm, the elastic modulus is 630 kg / mm2 and the water absorption is 14%. (PI film-5) DMAc was introduced into a separation bottle and 4 equivalents of 0 da and 2 equivalents of p-PDA were added thereto. The resulting mixture was thoroughly stirred at room temperature until ODA and p_pda were completely dissolved. Next, 6 equivalents of TMHQ were added and stirred for 40 minutes. After the addition of} equivalent-0DA and 3 equivalents of p-PDA, the mixture was stirred for another 40 minutes. Next, 3.5 equivalents of PMDA was added followed by stirring for 40 minutes. Then 0.5 equivalent of pMDA was dissolved in DMAc &quot; solution was slowly added thereto, and the resulting mixture was stirred under cooling for 1 hour to obtain a solution of polyamic acid in DMAc. The amount of DMAc can be used to obtain a feed concentration of 18% by weight based on the weight of the polyamidic acid solution of the diamine and the aromatic tetrakisine di-field monomer. Next, the polyamine solution was mixed with AA and I Q and poured onto a glass plate. After drying at about 100 C for about 5 minutes, the polyimide film was peeled off from the glass plate. This film was then fixed on the support and sequentially heated at about 300 ° C for about 1 minute 'heated at about 400 ° C for about 1 minute and heated at about 5107 for about 1 minute for dehydration and cyclization' so as to obtain a thickness of about 1%. Micron polyimide film. The polyimide film thus obtained showed a coefficient of linear expansion of 8 ppra, a coefficient of absorption of water and a coefficient of expansion of 680 kg / mm2 and a water absorption of 0.999 ^ (PI film-6). DMAc was introduced into the separation bottle and 5 equivalents of DA. And 5 equivalents of p_PDA were added to it. The resulting mixture was thoroughly stirred at room temperature until 0j) A and p-PDA were completely dissolved. ) Next add 5 equivalents of TMHQ and stir for 40 minutes. The resulting mixture was stirred for 40 minutes after the addition of 4.5 equivalents of PMDA. Then, a solution of 0.5 equivalent of pMDA in DMAc was slowly added thereto, and the resulting mixture was stirred under cooling for 1 hour to obtain a solution of polyamic acid in DMAc. DMAc dosage can get diamine and aromatic

88119324.ptd Page 79 4 5 09 8 2 V. Description of the invention (76) The feed concentration of the tetracarboxylic dianhydride monomer based on the weight of the polyamino acid solution is 18% by weight. Next, the polyamic acid solution was mixed with A A and IQ and poured onto a glass plate. At about 100 t: after drying for about 5 minutes', the polyamide film was peeled off from the glass plate. This membrane is then fixed to the stent and is sequentially applied at about 300. (: Heating for about 1 minute, heating at about 400 ° C for about 1 minute, and heating at about 5 100 for about 1 minute for dehydration and cyclization, so that a polyimide film having a thickness of about 10 microns is obtained.醯 imine film shows a linear expansion coefficient of 9ppm, water absorption expansion = 5ppffl-elastic modulus of 60. kg / m2 and water absorption 丨. 2%. Treatment of PI 溥 film:

The PI film thus obtained was subjected to the following treatments. (Process A) Heat treatment at 500 ° C for 1 minute. (Treatment B) Corona treatment was then performed at a corona density of 300 at 50 (TC '1 minute. Watt-minutes per square meter for corona treatment. (Treatment C) minutes / square meter for plasma treatment. Plasma density was 2 °. 〇〇watt (treatment D)

It was heated at 50 ° C ′ for 1 minute (5% by weight) and applied to a bell using a bar coater. After the treatment, the production of isophorone diamine on the methanol film and drying at 70 ° C for 1 minute, the adhesive film was produced: Comparative Example 11 Untreated p Irrigation_ 1 + 4 film-1 Amino acid solution, which is

Page 80 4 '450982 V. Description of the invention (77) Thermoplastic polyimide precursor with Tg 19〇t: and 4, viscous: benzophenone tetracarboxylic dianhydride, 3, 3, -4, 4 A solution of 2, -ethylene glycol dibenzoate tetracarboxylic dianhydride and 2, 2'-fluorene (4- (4-aminophenoxy) benzyl) propane as the main december component in an organic solvent, followed by drying to obtain Thickness 60 single-composite film. The adhesive strength and solder heat resistance of the obtained film were measured by the method ^, and the details will be described later. The results show that the adhesive strength is 0.01 kgf = the solder heat resistance at 280 to 300 C is "bad". Comparative Example 1 2] The procedure compared to ϋ11, but using the Π film human amine which has been treated with A! Process PI film -1 as an alternative to obtain a 60 μm thick single-sided adhesive ^ § When measuring in the method described later, Le The composite film showed an adhesive strength of 0.3 kgf / cm. Comparative Example 1 3 ΓComparing to Γ11's procedure 'but using β which has already been processed? 1 film = ίΐΡΙ film: a substitute of 1 to obtain a single-sided adhesive with a thickness of 60 μm: # Λ / 备 Γ · ″ When measured by the V method, the adhesive film showed an adhesive strength of 3 dry strength / cm.

The procedure of Comparative Example U 1 3 11 'but using PI film 1 which has been treated with C as an untreated PI film' J instead of 0 film. It was reported that the thickness of 60 μm was paid when the heart was replaced. Early Sticky

S force // material, the adhesive film shows a hybrid strength of U. Comparative Example 1 5 Follows the sequence of Comparative Example 11, but uses the Π film that has been treated D 4 5 09 8 2 Five 'Description of the Invention (78) 1- 1 As an alternative to the untreated PI film-1, a unilateral adhesive film with a thickness of 60 micrometers was obtained. When measured by the method described later, the 'adhesive film showed an adhesive strength of 0 / kg force / cm. ~ Comparative Example 16 A polyamic acid solution was applied to one side of the untreated PI-film-1, which was a thermoplastic polyimide precursor and had Tg 190. (: And contains 3, 3 ', 4, 4'-benzophenone tetracarboxylic dianhydride' 3, 3 '-4, 4, -ethylene glycol dibenzate tetracarboxylic dianhydride and 2 , 2'-fluorene (4- (4-aminobenzyloxy) phenyl) propane as a main component in an organic solvent solution, followed by drying to obtain a 60-micrometer &quot; &quot; rice unilateral adhesive film. The other side of the film was repeated to obtain a bilateral adhesive film with a thickness of 70 micrometers. The solder heat resistance of the thin foil obtained was measured by the method described below. The results showed that the solder heat resistance at 280 to 300 ° C was "poor" Comparative Example 17 "Nylon epoxy resin adhesive was applied to one side of PET (polyethylene terephthalate) film and dried to obtain a bonded pET sheet with a one-stage B adhesive layer. The resulting bonded PET sheet had a thickness of 10 microns .Second untreated PI film-1 was placed on this adhesive PET sheet to form a PI film / adhesive layer / pET film sequence and heated at 12 ° C for 5 seconds under a pressure of 5 kgf / cm2 to obtain a single edge. Adhesive film, in which the adhesive surface is coated with PET film. The ρΕτ film is a cover film for the adhesive surface and is torn off before use. The adhesive strength and solder heat resistance of the obtained film were measured by the method described later. The results showed that the adhesive strength was 0.1 kgf / cm and the solder heat resistance at 280 to 300 ° C was "not Q good". Comparative Example 1 8

4 5 09 8 2 V. Explanation of the invention (79) ---- Follow the procedure of Comparative Example 17, but use the treatment A that has already been accepted? 1 臈 臈 1 1 is obtained as a substitute for untreated PI 臈 臈 -1. When measured by the method described below, the adhesive film showed an adhesive strength of 0.3 kgf / cm2.

The procedure of Comparative Example 17 was followed, but using the 6 2P 丨 film_J that had been treated as an alternative to the untreated PI film-1 to obtain a single-sided adhesive film. When measured by the method described later, the adhesive film showed an adhesive strength of 0.3 kgf / cm. Up to l-M example 20, follow the procedure of comparative example 17, but use the already accepted treatment c?丨 Film -1 As a substitute for untreated PI film-1, a unilateral adhesive film was obtained. When measured by the method described below, the adhesive film showed an adhesive strength of 0.4 kgf / cm, following the procedure of Comparative Example 17 ', but using p I film 1 which has been treated with D as an alternative to untreated PI film-1. Product to obtain a single-sided adhesive film. When measured by the method described above, the adhesive film showed an adhesive strength of 0.4 kgf / cm.

The untreated film-1 was inserted between the two adhesive pet sheets used in Comparative Example 17 in the order of PET film / adhesive layer / π film / adhesive layer / pET: film. At 120. (: Heating at 5 kgf / cm2 for 5 seconds, to obtain a double-sided adhesive film, in which both sides are coated with PET film. The solder heat resistance of the obtained repeated film was measured by the method described later. The results are shown in 280 to

Page 83 450982

The solder heat resistance r of 300 C was not high. Example 50 The same procedure as in Comparative Example 11 was followed, but a treated PI film-1 was used instead. When measured by the method described below, "good" solder heat resistance. Example 51 The untreated PI film-2 was used as a single-sided adhesive film thus obtaining a thickness of 60 µm, which was shown at 280 ° C to 300 ° C. 〇 Not applicable Follow the procedure of Comparative Example 11 but use the treated PI film-1 as a replacement film. When measured by the method described below, the sticky "good" material has heat resistance. Example 52 Untreated PI film-3 was obtained as a single-sided adhesive film with a thickness of 60 micrometers. Shown at 280 ° C to 300 ° C. Followed the procedure of Comparative Example 11 but used untreated ρ 〖film_ As an alternative to the untreated PI film-1, a single-sided adhesive film with a thickness of 60 microns was thus obtained. When measured by the method described below, the adhesive film showed "good" solder heat resistance from 28 ° C to 300 ° C. Example 53 The procedure of Comparative Example 11 was followed but using untreated ρ I film _ 5 as a substitute for untreated PI thin film -1 and thus a single-sided adhesive film having a thickness of 60 µm was obtained. When measured by the method described below, the adhesive film shows the "good" solder heat resistance of 280 ° C to 300 ° C. Example 54 The procedure of Comparative Example 11 was followed but using untreated p I film-6 as a substitute for untreated PI film-1 thus obtaining a 60 μm thick single-sided adhesive

88119324.ptd Page 84 4 5 09 8 2 V. Description of the invention (81) Membrane. Using the method described later Force / cm and at 280 ° C Example 5 5 Follow Comparative Example 11 as an untreated PI edge adhesive film. When borrowed 9 kgf / cm. Example 5 6 Followed Comparative Example 11 as an untreated PI edge adhesive film. When borrowed 1 kgf / cm. Example 57 Followed Comparative Example 11 as an untreated PI edge adhesive film. When borrowed 1.2 kgf / cm β f Example 58 Followed Comparative Example 11 as an untreated PI edge adhesive film. When borrowed 3 kgf / cm. Repeat Example 5 9 When measuring, the procedure of sticking to 300 ° C but using the alternative method of film-1 is used to measure the program but using the alternative method of film-1 is used to measure # # Use the wisdom of film-1; Method No. 1] The composite film showed an adhesive strength of 0.2 kg and "good" solder heat resistance. The PI film substitute that has already been treated with A thus obtains a single thickness of 60 microns. The adhesive film shows the adhesive strength. The procedure but uses the alternative that has been treated with thin film_6 thin film-1 and thus obtains a single description of 60 microns thick. Method for measuring the 'adhesive strength of the adhesive film}. When the PI film -6 of the C film that has been treated has received a 60 micron thick sheet, the adhesive film shows that the PI film of the D film -6 has been treated and thus obtained When the thickness is 60 μm, the adhesive layer shows an adhesive strength of 1, following the procedure of Comparative Example 16 but using an untreated PI film-2 as

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Mr WN kr My H is ♦ J m 60 0 Han Qin 2000. &lt; / ^ — Q ^ Γ 槔 槔 如 命 rfo · to-f-rush β ο f Ά. 3 0 0 on 4 5 0982 V. Description of the invention (84). Example 6 9 Follow the sequence of Comparative Example 17 However, it is used as an untreated p I thin 臈 -1 substitute edge adhesive film. Measure 1 · 1 kgf / cm by the method described below. Example 70 Followed the procedure of Comparative Example 17 but used as an untreated PI film. When measuring by the method described below 1.2 kgf / cm. f. Example 71 The procedure of Comparative Example 17 was followed but used as an untreated PI film—i instead of an edge-adhesive film. When measuring by the method described below 1.4 kgf / cm. Example 72 The procedure of Comparative Example 22 was followed but used as an untreated PI thin film. We shall measure Qi 4 1.3 kgf / cm by the method described later. 73 Example 73 The procedure of Comparative Example 2 2 was followed but a substitute film of treated PI film-1 was used. When measured by the method described below, the PI film that has been treated with A has been replaced with a 6-generation product and thus has a thickness of 60 micrometers. The 'combined film shows that the adhesive strength has been treated with the PI film with B._6 The product has obtained a thickness of 6 A single time of 0 micron 'adhesive film shows the adhesive strength has been treated with the PI film substitute of c and thus obtains a single thickness of 60 micrometers. A single time' adhesive film has an adhesive strength of the PI film which has received the treatment of D film-6 and thus has a thickness of 70 microns The single-time 'adhesive film showed adhesive strength. The untreated PI film-2 was shown at 280 as a single-sided adhesive film with a thickness of 70 microns. (: To 30 (TC of

88119324.ptd Page 88 45 09 8 2 V. Description of the invention "Good" solder heat resistance. Example 74 The procedure of Comparative Example 22 was followed but an untreated PI film_3 was used as the untreated PI film-; an alternative to this resulted in a single-sided adhesive film with a thickness of 70 microns. When measured by the method described later, the adhesive film was shown at 20.8.匸 to 300 t "Good" solder heat resistance. Example 75 The procedure of Comparative Example 22 was followed but using an untreated p_4 film as an alternative to an untreated P / I film-thus obtaining a single-sided adhesive film having a thickness of 70 µm. When measured by the method described later, the adhesive film showed a "good" solder heat resistance of 280 to 300 t. Example 76 The procedure of Comparative Example 2 2 was followed but an untreated ρ I film „5 was used as an alternative to the PI film -1 without a process, so a single-sided adhesive film with a thickness of 70 μm was obtained. ▲ Measured by the method described later At this time, the adhesive film showed good performance from 280 to 3,000. Example 77 The procedure of Comparative Example 22 was followed but an untreated PI film_6 was used as an alternative to the untreated PI film-thereby obtaining a single-sided adhesive film having a thickness of γ0 µm. When measured by the method described below, the adhesive film showed a temperature of 2800 ° C to 300 t: good. 4) Heat resistance. Measurement method of adhesive strength and solder heat resistance of the adhesive film: First, a copper box (electrolytic copper box 3EC_VLp, 35 microns, manufactured by Mitsui Mining and Metallurgy Co., Ltd.) was bonded to each of the adhesive films obtained in Comparative Examples 11 to 22 and Examples 50 to 77.

45 09 8 2 V. Description of the invention (86) The selection method is based on the type of adhesive layer and film type used (that is, single-sided or double-sided), and the appropriate bonding method is selected from the following methods. (Adhesive film containing thermoplastic polyimide layer on one side: Comparative Examples 丨〗 〖5〗 and Examples 50 to 5 8) Single-sided adhesive film was placed in a copper box (electrolytic copper pig 3EC ~ VLp, 35 microns, Mitsui Mining and Metallurgy (Manufactured by the company) and thermocompression bonded using a hot press (30 kgf / cm2, 24 ° C '20 minutes) to obtain a three-layer laminate consisting of a PI film / thermoplastic polyimide / copper foil. (Adhesive film containing thermoplastic polyimide layer on both sides: Comparative Examples 16 and 63) Steel foil (electrolytic copper foil 3EC-VLP, 35 micron, manufactured by Mitsui Mining and Metallurgy Co., Ltd.) was placed on both sides of the adhesive concrete, using a hot press ( 30 kgf / cm2, 240 ° C for 20 minutes) hot-pressed to obtain a five-layer laminate consisting of steel foil / thermoplastic polyimide masonry film / thermoplastic polyimide / copper foil. (Adhesive film with a thermosetting adhesive layer on one side: Comparative Examples 17 to and Example M. After tearing off the PET film as a cover film, a single-sided adhesive film was placed (electrolytic steel box 3EC-VLP, 35 microns, manufactured by Mitsui Mining & Metallurgy) Top = hot pressing with white, (10 * kgf / cm2, 12 (rc, 丨 minutes) preliminary hot pressing 2: obtaining three layers of PI film / nylon epoxy adhesive / copper foil. Secondly, so The obtained three-layer laminate was cured in three steps (20 hours, 4 hours, 12 (rc 4 hours)) to complete the hardening of the nylon ring agent. A pair of adhesive films with a thermosetting adhesive layer on both sides of the adhesive was known: Comparative Example 22 And examples

45 09 B 2 V. Description of the invention (87) 77) After tearing off the PET film as the cover film, copper foil (electrolytic copper foil 3EC-VLP, 35 micron, manufactured by Mitsui Mining and Metallurgy Co., Ltd.) was placed on both sides of the bilateral adhesive film Five pieces of copper foil / nylon epoxy resin adhesive / PI film / nylon epoxy resin adhesive / copper foil were obtained by preliminary hot pressing using a hot press (10 kgf / cm2, 120 ° C, 1 minute). Layer laminate. Secondly, the five-layer laminate thus obtained was heated in two steps (4 hours at 120 ° C, 4 hours at 160 ° C, 4 hours at 120 eC) to complete the hardening of the nylon epoxy resin adhesive. The thus-obtained steel-clad laminates were evaluated for adhesion strength and solder heat resistance by the following methods. (Adhesive strength) The adhesive strength is measured according to the method specified in JIS 6472-1 995- (8). (Solder heat resistance)

It is known that the heat resistance is based on the original state evaluation. The ladle laminate was cut into blocks (20 mm x 50 mm) and floated on 280 or 300 ° C melted solder for 1 minute. The copper box was then removed by etching and the foam was observed. Samples that do not contain any abnormalities (hair blistering, creping, cracking, tearing, deformation, etc.) are evaluated as "good X = different (foaming, canning, cracking, tearing, deformation, etc.) Sample juice was evaluated as | bad. "

Table 9 summarizes the data of the samples of Comparative Examples 1 to 22 and Examples 50 to 77 and the results of solder heat resistance evaluation. 'Strong X

88119324.ptd Page 91 450982 V. Description of Invention (88) Table

PI film surface adhesive strength (kg force / solder heat resistance cm) 28 0 ° C 30 0 PC Comparative Example 1 1 No single-sided TPI 0.1 Poor Poor Comparative Example 12 A Single-sided TPI 0.3 Comparative Example 13 E Single-sided TPI 0.3 Comparative Example 14 C Single-sided TPI 0.3 Comparative Example 15 1 D Single-sided TPI 0.3 Defective Poor Comparative Example 16 No double-sided-TPJ Poor Defective Comparative Example 1 7 No single-sided ΝΗ 0.1 Comparative Example 18 A Single-sided Ε 0.3 Comparative Example 1 9 B Single-sided NE 0, 3 Comparative Example 20 C Single-sided NE 0.4 Comparative Example 2 1 1 D Single-sided NE 0.4 Comparative Example 22 1 No Double-sided NE E Bad Example 50 2 No Single-sided TPI Good Good Example 51 3 No Single-sided TPI Good Good Examples 52 4 Single-sided TPI Good Good Example 53 5 Single-sided TPI Good Good Example 54 6 Single-sided TPI 0.2 Good Good Example 55 6 A Single-sided TPI 0.9 Example 56 6 B Single-sided TPI 1. 1.1 Example 57 6 C single-sided TP1 1.2 Example 58 6 D single-sided TPI 1.3 Example 59 2 None Good examples of double-sided TPI 60 3 Good examples of double-sided TPI Good examples 61 4 Μ Double-sided TPI Good examples 62 5 No double-sided TPI Good examples 63 6 No double-sided TPI Good examples 64 2 No single-sided ΕΕ Good example 65 3 No single-sided ΝΕ Good good example 66 4 No single-sided ΝΕ Good good example 67 5 No single-sided ΝΕ Good good example 68 6 No single-sided Ν0.2 Good Good 88119324.ptd Page 92 45 09 8 2

V. Description of the invention (89) Example 69 '--- 5 A single-sided NE 1,1 ® example 7 0 6 B single-sided NE 1.2 example 71 6 C single-sided NE 1.4 example 72 6 D single-sided NE 1.3 «example 73 2 Good examples without double-sided NE 74 3 Good examples without double-sided NE 75 4 Good examples without double-sided NE 76 5 Good examples without double-sided NE 77 6 Good examples without double-sided NE Good TPI: thermoplastic polyimide. N E: Nylon epoxy resin wax mixture. Comparative Example 2 3 DMAc was introduced into a separation bottle and 1 equivalent of 0DA and 3 equivalents of p-PDA ° were added to the mixture. The resulting mixture was thoroughly stirred at room temperature until 0 ^^ and storage was completely dissolved. Next, 3.5 equivalents of powdered PMDA was slowly added thereto followed by stirring for 40 minutes. Then, 0.5 equivalent of a solution of pmda dissolved in DMAc was slowly added thereto and the obtained Zhan compound was stirred for 1 hour to obtain a solution of polyamic acid in MAc. In DMAc, 18% by weight of diamine and aromatic tetracarboxylic dianhydride are known. Ma Followed the procedure of Example 1 to obtain 25, 50 and 75 micron thick films. After reaching the frame ', the film was heated under the following conditions: 25 micron thick film: 100 ° C for 5 minutes and 300. (: 50 micron thick film: 400 ° C and 510 ° C for 30 seconds each; _l ^ jog B 2___ V. Invention (go) _----- 100 ° C for 5 minutes and 300 ° C, 400 ° 60 seconds each at ° c and 510 ° C · 75 micron thick film: '100 ° C for 5 minutes and 30 0 ° c, 40 0 t: and 510. (: 90 seconds each. AJ178 compliance, Example 4 procedure to obtain a thickness of 25 , 50 and 75 micron film. After fixing to the frame, 'heated under the following conditions: 25 micron thick film: ° C 5 minutes and 30 0 ° C, 40 0 ° C and 510 ° C 30 seconds each; thickness 5 0 micron film: 100 ° C for 5 minutes and 300 ° c, 40 (TC and 510. (: 60 seconds each; thickness of 75 micron film: 100 ° C for 5 minutes and 300 ° c, 40 0 ° C and 510 t each 90 seconds; By using the films obtained in Comparative Example 23 and Example 78, the water vapor permeability and air permeability were measured according to the Japanese Industrial Standard (JIS). When measuring the temperature dependence of water vapor permeability, use a thickness of 2 5 microns Film. Tables 1 to 12 show the results. Table 10 Water vapor permeability: J IS 0 2 0 8 (cup method) 40 ° C, 90% relative humidity (g / sq. 3 min. 24 hours) Example 78 Comparative Example 23 2 5 μm 8.5 60 50 microns 5.0 ------38 75 microns | 3. 4

45 09 8 2

Water vapor permeability (temperature / moisture correlation): JIS z〇2〇8 (cup method) __ (g / m2. 24 hours) Example 78 Comparative Example 2 3 25 t, 90% 3. 4 30 4 0 ° C, 9 0% 7. 6 60 60 ° C-90% 18 130 85 〇C, 85% 57 300 clothing

IC oxygen permeability: JIS K7126A method) (cubic centimeter / square meter. 24 hours .; Example 78 ~ — Comparative Example 2 3 2 5 microns 18 ~~ ”150 5 0 microns 11 7 5 .7 5 microns 8,3- 5 5 Atmospheric Pressure) (1) Water vapor permeability: When the base film has high water absorption and high water vapor permeability, its dielectric constant changes and the electrical characteristics of the FPC also change. Usually the circuit design is considered; The range of change. However, considering the wider range of these changes, we will reduce the size and thickness of FPC. We will use double-layered jT pc as the base film and contact the steel with susceptibility to water absorption. Therefore, it is highly important that the base film used for the double-layer FPC has low water absorption and low water vapor transmission.

88119324.ptd Page 95 45 09 8 2 V. Description of the invention (92) '— (2) Oxygen permeability: When oxygen penetrates the three layers of FPC from the edge of the basement membrane, the problem of adhesion failure due to the deterioration of the adhesive occasionally occurs. On the other hand, taking double-layer FPC as an example, the electrical characteristics are impaired due to the deterioration of copper. It is therefore desirable to use a polyfluorene imide film having low oxygen permeability. Comparative Example 24 DMAc was introduced into a separation bottle and 1 equivalent and 2 equivalents of P-PDA were added thereto. The resulting mixture was thoroughly stirred at room temperature until the oDA &amp; p_pDA was completely dissolved. Next, 2.5 equivalents of powdery TMHQ was slowly added thereto followed by stirring for 40 knives. Then, a solution of 0.5 equivalent of TMHQ in DMAc was slowly added thereto, and the resulting mixture was stirred for 1 hour to obtain a solution of polyamic acid in DMAc. The amount of DMAc used was 18% by weight to obtain the feed concentration of the diamine and aromatic tetracarboxylic dianhydride monomer. Next, a polyimide film having a thickness of about 0 μm was obtained according to the procedure of Example 1. feA Example 25 5 DMAc was introduced into a separation bottle and 2 equivalents of oDA and 3 equivalents of p_pD a were added thereto. The obtained quinqueline mixture was thoroughly stirred at room temperature until OA and ρ_PM were completely dissolved. Next, 4.5 equivalents of powdered TMHQ was added slowly and then stirred for 40 cents. Then a solution of 0.5 equivalents of TMHQ dissolved in DMAc was slowly added to it and the known mixture was stirred for 1 hour to obtain a solution of polymethane MDMAc. The amount of DMc used is 18% by weight to obtain the feed concentration of the diamine and aromatic tetracarboxylic dianhydride monomer. Secondly, follow the procedure of Example 1 to obtain a polyimide film with a thickness of about 10 microns.

450982_ V. Description of the Invention (93) Comparative Example 2 6 DMAc was introduced into a separation bottle and 1 equivalent of 0DA and 1 equivalent of p-pDA were added thereto. The resulting mixture was stirred at room temperature until the 0DA and p-PDA were completely dissolved. Next, 1.8 equivalents of powdered TMHQ was slowly added thereto followed by stirring for 40 minutes. Then a solution of 0.2 equivalents of TMHQ in DMAc was slowly added thereto and the resulting mixture was stirred for 1 hour to obtain a solution of polyamic acid in DM Ac. The amount of DMAc used was 18% by weight to obtain the feed concentration of diamine and aromatic tetracarboxylic dianhydride monomer. Next, a polyimide film having a thickness of about 10 micrometers was obtained by following the procedure of Example 1. Comparative Example 2 7 DMAc was introduced into a separation bottle and 3 equivalents of 0DA and 1 equivalent of p ~ pDA were added thereto. The resulting mixture was stirred thoroughly at room temperature until the oDA and p-PDA were completely dissolved. Next, 3.6 equivalents of powdered TMHQ was slowly added thereto followed by stirring for 40 minutes. Then a solution of 0.4 equivalent of TMHQ dissolved in MAc was slowly added thereto and the resulting mixture was stirred for 1 hour to obtain a solution of polyamic acid in DMAc ^ The amount of DMAc was the feed concentration of the diamine and aromatic tetrakis dianhydride monomers It is 18% by weight. ~ Second, follow the procedure of Example 1 to obtain a polyimide film with a thickness of about 0 μm. 0 Comparative Example 28 Follow the procedure of Comparative Example 24, but after fixing to the frame, heat it for 5 minutes at 2007 and then at 2000, 300 and "(^^ for 2 minutes each", thus obtaining a polyimide film with a thickness of 12.5 microns.

450982

Example 79 By following the procedure of Example 4, a polyimide film having a thickness of about 0 µm was obtained. Example 80 DMAc was introduced into a separation flask and 5 equivalents of α) α and 5 equivalents of P-PDA were added thereto. The resulting mixture was stirred thoroughly at room temperature until the &amp; ρ_ρ]) A completely dissolved. Next, 6 equivalents of powdered TMHQ were slowly added thereto followed by stirring for 40 minutes. Further, 3.5 equivalents of PMDA was added thereto, followed by stirring for 40 minutes. Then, a solution of 0.5 equivalent of PMDA dissolved in DMAc was slowly added thereto and the resulting mixture was stirred for 1 hour to obtain a solution of polyamic acid in DjjAc. The amount of DMAc used was 18% by weight to obtain the feed concentration of diamine and aromatic tetracarboxylic dianhydride monomer. Next, the procedure of Example 1 was used to obtain a polyimide film having a thickness of about 10 microns. ZM11 DMAc 5 was placed in a separation flask and 5 equivalents of oDA and 5 equivalents of p-pDA were added thereto. The resulting mixture was stirred at room temperature until the ODA and p-PDA were completely dissolved. Next, 7 equivalents of powdered TMHQ was slowly added thereto, followed by stirring for 40 minutes. Further, 2.5 equivalents of PMDA was added thereto, followed by stirring for 40 minutes. Then, a solution of 0.5 equivalent of PMDA in DM Ac was slowly added to the solution and the resulting mixture was stirred for 1 hour to obtain a solution of polyamic acid in DMAc. The amount of DMAc used was 18% by weight to obtain the feed concentration of diamine and aromatic tetracarboxylic dianhydride monomer. Next, the procedure of Example 1 was used to obtain a polyimide film having a thickness of about 10 microns. XM82

4 5 0 9 8 2 V. Description of the invention (95) DMAc was introduced into the separation bottle and 5 equivalents of 0DA and 5 equivalents of P-PDA were added thereto. The resulting mixture was thoroughly stirred at room temperature until 0DA and p-PM were completely dissolved. Next, 4 equivalents of powdered TMHQ was slowly added thereto followed by stirring for 40 minutes. Further, 5.5 equivalents of PMDA was added thereto, followed by stirring for 40 minutes. Then, a solution of 0.5 equivalent of PMDA in DM Ac was slowly added thereto, and the resulting mixture was stirred for 1 hour to obtain a solution of polyamic acid in DMAc. The amount of DMAc used was 18% by weight to obtain the feed concentration of diamine and aromatic tetracarboxylic dianhydride monomer. Next, the procedure of Example 1 was used to obtain a polyimide film having a thickness of about 10 microns. Example 83 DMAc was introduced into a separation flask and 5 equivalents of ODA and 5 equivalents of p-PDA were added thereto. The resulting mixture was thoroughly stirred at room temperature until 0DA and p-PDA were completely dissolved. Next, 3 equivalents of powdered TMHQ was slowly added thereto followed by stirring for 40 minutes. A further 6.5 equivalents of PMDA was added thereto, followed by stirring for 40 minutes. Then 0.5 equivalent of a solution of PMDA dissolved in DMAc was slowly added thereto and the resulting mixture was stirred for 1 hour to obtain a solution of polyamic acid in DMAc. DM Ac was used in an amount to obtain the diamine and aromatic tetracarboxylic dianhydride monomers. The given concentration is 18% by weight. Next, the procedure of Example 1 was used to obtain a polyimide film having a thickness of about 10 microns. Example 84 DMAc was introduced into a separation flask and 7 equivalents of ODA and 3 equivalents of p-PDA were added thereto. The resulting mixture was thoroughly stirred at room temperature until ODA and p-PDA were completely dissolved. Next, 5 equivalents of powdered TMHQ was slowly added thereto followed by stirring for 40 minutes. A further 4.5 equivalents of PMDA was added thereto, followed by stirring for 40 minutes. Of course

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O read &amp; β m 4 5 09 B2 V. Description of the invention (98) Example 89 The procedure of Example 7 9 was followed, but the fixing to the pivot was performed at 480 ° C instead of 510 ° C, so the imine was obtained. film. ijMio followed the procedure of Example 79, but it was fixed to the frame instead of 510 ° C but at 450 ° C, so the imine film was obtained. tMll followed the procedure of Example 79, but was fixed to the pivot instead of 510 ° C but at 400 t: proceeded, and thus the acid imine film was obtained. The dynamic viscoelasticity of the film obtained in the foregoing example was measured by a measuring device: manufactured by Seiko Instruments Inc. Sample form: 9 mm x 40 mm. Profile: 20 ° C-400 ° 〇 3. Frequency: 10 Hz Lamp: 20. Base: 0. Gain: 3 〇 Table 13 shows the smallest observed ΔE ′ / ΔT (that is, the temperature at which the maximum drop is expected), E, (the final thickness after storage elasticity is increased by 12 2.5, and the final thickness is increased by 12. 5 micro-heating step of rice gathering The final thickness of the thermal step-metering gathering is 1 2.5 DMS 200 ° min under the following conditions. 6 Hot-step rice-converging measurement. Check with the increase in temperature modulus) and Tg ( 〇C) information

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88119324

^ 50982 V. Description of the invention (99) Comparative example 2 4 3 -1 1 丄 —2 _—_ — 228 Μ. 1E9 Comparative example 2 5 5-2 3 215 9.8E8 Comparative example 2 6 2 1 "-1 — 1 227 6.6E8 Comparative Example 2 7 4-3 1 211 2.7E8 Comparative Example 28 3 — 1 2 228 1.1E9 Example 79 | 5 | 5 5 5 290 12.1E9 1 Example 80 1 6 I 4 5 5 | 280 | 1. 9E9 Example 81 1 7 1 3 5 5 275 11.7E9 Example 82 1 4 1 6- 5 | 5 | 290 2, 1E9 | Example 83 3 | 7 5 5 I 295 2. 2E9 Example 84 5 5 7 3 280 2. 0E9 Example 85 1 5 | 5 3 7 I 295 I 2. 5E9 (Example 86 I 7 1 3 1 7 3 270 1.9E9 Example 87 t ^ JB8] 3 1 7 I 7 3 390 2.5E9 3 1 7 3 7 | 3 0 0 丨2. 7E9 Example 8 9 1 5 | 5 | 5 5 I 290 2. 1E9 Example 9 0 1 5 1 5 1 5 5 290 2. 1E9 Example 91 | 5 | 5 5 5 1 290 2. 1E9 Next under the following conditions (Film thickness: 12.5 micrometers) The hydrolysis resistance test was performed by using the films of Comparative Examples 24 to 28 and Examples 7 9 to 91. ① As an indicator of hydrolysis resistance, the resistance measured according to ASTM D-1 938 was used Indication of tear propagation. ② The tear propagation resistance is measured as the initial value. ③ In order to evaluate the hydrolysis resistance, the film-like Use PC30 5S (Hirayama

88119324.ptd Page 103 0 9 0 2 V. Description of the Invention (100) (manufactured by Seisakusho) Exposure to 150 ° C / 100% relative humidity / 4 atmospheres for 24 hours. Then measure the tear propagation resistance. ④ After the exposure, the samples of Comparative Examples 2 to 28 were broken into powders and could not be measured. Table 14 summarizes the results. Table 14 Maximum temperature (° 0 Initial value (g / mm) 1 After exposure (g / mm) Percent retention Comparative Example 2 4 510 120 Not measured. 0 Comparative Example 2 5 510 121 Ibid. 0 Comparative Example 2 6 510 125 Ibid. 0 Comparative Example 27 510 119 Ibid. 0 Comparative Example 28 400 120 Ibid. 0 Real Π9 510 150 120 80 Example 80 510 150 121 81 丨 Example 81 510 149 120 81 Example 8 2 510 152 125 82 Example 8 3 510 150 122 81 Example 84 510 150 116 77 Example 85 510 148 120 81 Example 86 510 150 120 81 Example 87 510 153 121 79 Example 88 510 150 119 I 79 Example 8 9 480 155 120 1 77

88119324.ptd Page 104 4509 ^^ V. Description of the invention (101) Example 90 450 154 Example 9 1 400 149 (1) Dynamic viscoelasticity:

Comparative Example 28 corresponds to the example of JP-A-1 0-36506. However, the thickness 5 will be described in advance before the measurement at 3 50 t: E '. Polyimide film is continuously formed under tension at different angles, i j. ^, And in the direction of visibility, while the two ends are clamped in a box for the box, Zhou Xia Yuwen (400

° c or above). When the South Modulus elastic modulus decreases significantly, tension can hardly be applied in the wide production direction, so the film sags in the tenter oven, and X cannot be manufactured stably. The inventor's research results found that this phenomenon has a higher probability ^ ^ when E 'drops to 1.0E9 or below. It is therefore possible that in the inventor's published patent case, the film cannot be continuously manufactured in steady state. "A In the foregoing case, the temperature at which E 'shows the greatest decrease with time is called Tg. At Tg of 25 0 ° C or below, the following problems may occur. 1. When thermoplastic polyimide is used as an adhesive This procedure is performed at an elevated temperature (about 250 to 300 ° C), and the thermal contact bonding system is performed using a press: This base film deforms and curls or warps after cooling. 2. When used at high temperature The FPC thus constructed may be deformed. Therefore, it is considered that the Tg must be at least 250 r and the E ′ must be at least 1.0E9 at 3 50 ° C. (2) Hydrolysis resistance: FPC using polyimide film as the base film will be Use under more divergent conditions. One of the most demanding cases seems to be FPC for high temperature and high humidity. When FPC is used under these conditions, it is estimated that the base film is degraded by hydrolysis

88119324.ptd Page 105 450982 V. Description of the invention (102) The following problems s In other words, the degradation of the film is induced by hydrolysis: ① the adhesive strength at the interface between the PI film and the adhesive FPC decreases; ② between the ρι film and ° 2 ^ (二The bonding strength of the interface between layers (FPC) is reduced; ③ Due to the mechanical 5-drop, it cannot be stored in a bent state or used for movement = 1 degree = poor electrical characteristics of the PI film. Examination of 4 pieces; ④ As mentioned above, the present invention can provide a new polyimide film and board with absolute weight, low water absorption, small water expansion coefficient, small mold stability, etc.): Various kinds of electric / electronic devices of 醯 imine film are used for connecting boards, adhesive films for packaging semiconductors, and printing connection boards. Difficulties Although the film and the hard disk suspension have been described in detail with reference to specific examples, it is obvious that many changes can be made without departing from its essence and scope.

Claims (1)

Bulletin 450982 ~ 6. Patent application scope 1. A polyimide film with a tensile elastic modulus of 70 kg / mm2 or less and a water absorption coefficient of 20 ppm or less. 2. The polyimide film according to item 1 of the scope of patent application, which has a linear expansion coefficient from 100 to 2 G Q ° C of 5 to 15 p p m. 3. The polyimide film according to item 1 of the patent application scope has a water absorption of 3.0% or less. 4. The polyimide film according to item 3 of the patent application, which has a water absorption of 2.0% or less. 5. The polyimide film according to item 1 of the patent application scope, which contains the repeating unit represented by the following general formula (1) in its molecule: 88119324, ptd p. 108 450982 R4 R4 R4 Six, please patent garden. R4. R4 ", &lt;? 〇 &gt; (where R4 represents CH3-, C1-'Br-, F- or CH30-); and R represents a bivalent organic represented by the following general formula base: (Where η is an integer from 1 to 3; and X represents a monovalent substituent selected from the group consisting of a hydrogen atom, a tooth atom, a carboxyl group, a lower alkyl group containing 6 or less carbon atoms, and a lower group containing 6 or less carbon atoms Carboalkoxy), or the formula: C in which Υ and Z may be the same or different and each represents a monovalent 〃 &amp; Budyl is selected from the group consisting of a hydrogen atom, a tooth atom, a carboxyl group, a lower alkyl group containing 6 or less carbon atoms, and 6 or less carbons Atomic low-scorching oxygen; and eight represents a divalent linking group selected from -0-, -S-, -C0 ~, _so-, _s〇2-, and -CH2-). 6. The polyamidamine film according to item 5 of the patent application, which, in addition to the repeating unit represented by the general formula (1), further contains the repeating unit represented by the general formula (2) in the molecule: 乂 88119324.ptd Page 109 4 5 09 8 2 ο c 〇— (ch2) 2—〇— C) α .toe 7. If the polyimide film of the patent application scope item 5 or 6, it further contains the repeating unit represented by the following general formula (3) in Its molecule: 〇 Wherein R is defined as the general formula (1). 8. The polyimide film as claimed in claim 5 or 6, which contains 88119324.ptd Page 110 450982 8S119324.ptd Page 111 450982 6. Scope of Patent Application 10. If the polyimide film according to item 9 of the patent application scope, it can satisfy (a + b) / s, (a + c) / s, (b + d) / s and (c + d) / The requirements of s each falling within the range of 0.25 to 0.75 'where a'b, c and d represent the number of repeating units as represented by the general formulae (6) to (9) above and s represents a + b + c + d. 11. A laminate for a flexible printed connection board, which is obtained by forming a metal layer on at least one side of a polyimide film as described in item 8 of the patent application scope. 1 2. The laminate for a flexible printed connection board according to item 11 of the scope of the patent application, wherein the metal layer is laminated through a thermosetting adhesive. 1 3. The laminate for a flexible printed link board according to item 丨 丨 of the patent application range, wherein the metal layer is laminated through a thermoplastic polyimide adhesive. 1 4. The laminate for flexible printed connection boards according to item 11 of the scope of patent application, wherein at least one side of the polyimide film receives at least one option. 88119324.ptd Page 112 450982 6. The scope of patent application includes at least one of heat treatment, corona treatment, plasma treatment and coupling agent treatment. 1 ··· An adhesive film obtained by forming an adhesive layer on at least one side of a polyimide film such as the item No. 8 of the patent application. 16. The adhesive film according to item 15 of the patent application scope, wherein the adhesive layer comprises a thermosetting adhesive. 1 7. The adhesive film according to item 15 of the patent application scope, wherein the adhesive layer comprises a thermoplastic polyimide adhesive. 1 8. The polyimide film according to item 8 of the scope of patent application, which is used as a base film for magnetic recording. 18119324.ptd Page 113