WO2008050704A1

WO2008050704A1 - Polyimide film and method for production thereof

Info

Publication number: WO2008050704A1
Application number: PCT/JP2007/070521
Authority: WO
Inventors: Koichi Sawasaki; Toshihiro Teshiba
Original assignee: Du Pont-Toray Company, Ltd.
Priority date: 2006-10-25
Filing date: 2007-10-22
Publication date: 2008-05-02
Also published as: TW200833785A; KR20090073135A; JP2008106139A

Abstract

A polyimide film produced mainly by the imidization of para-phenylenediamine and 4,4'-diaminodiphenyl ether as diamine components and pyromellitic acid dianhydride and 3,3'-4,4'-biphenyltetracarboxylic acid dianhydride as acid dianhydride components, wherein an inorganic particle having a particle diameter of 0.01 to 1.5 μm, an average particle diameter of 0.05 to 0.7 μm, and such a particle size distribution that inorganic particles having a particle diameter of 0.15 to 0.60 μm account for 80 vol% or more of the total particle volume is dispersed in the film at a ratio of 0.1 to 0.9 wt% relative to the weight of the film resin.

Description

Specification

Polyimide film and method for producing the same

Technical field

[0001] The present invention relates to a polyimide film and a method for producing the same. More specifically, the added inorganic particles are not exposed, and surface protrusions can be generated in a state of being uniformly dispersed in the film, so that the surface state can be well controlled, and the running property, adhesiveness and dimensional stability of the film are improved. The present invention relates to a polyimide film that can be applied to an AOI and a manufacturing method thereof.

Background art

[0002] Polyimide films are known to have excellent characteristics in heat resistance, cold resistance, chemical resistance, electrical insulation and mechanical strength. Electrical insulation materials for wires, heat insulating materials, flexible printed wiring It is widely used for base films for substrates (FPC), carrier tape films for IC automated tape bonding (TAB), and IC lead frame fixing tapes. Of these, polyimide film and copper foil are usually bonded to each other through various adhesives, especially in applications such as FPC, TAB carrier tape and lead fixing tape.

[0003] An important practical property when a polyimide film is used in these applications is the slipperiness (slidability) of the film. In various film processing processes, the slidability between the film support (for example, roll) and the film and the slidability between the films are ensured to improve the operability and handling in each process. This is because it is possible to avoid the occurrence of defects such as scratches on the film.

[0004] On the other hand, for flexible printed wiring board applications, which are the main uses of polyimide films, the force polyimide film bonded to copper foil via various adhesives usually has its chemical structure and Due to chemical resistance (solvent) stability, adhesion to the copper foil is often insufficient. Currently, polyimide films are subjected to surface treatment such as alkali treatment, corona treatment, plasma treatment, and sand blast treatment, and then copper Glued with foil! [0005] In addition, in recent finer pitches of electronic components, especially FPC inspections, inspection of line widths and foreign matters has been the mainstream in the past, but an automatic optical inspection system (AOI) was introduced. After that, the heat-resistant finalem manufactured with the conventional formulation mixed with inorganic powder was sufficiently satisfactory in terms of runnability, but the inorganic powder was too large for AOI. For this reason, with the recent narrowing of pitches such as FPC, inorganic particles may be judged as foreign matter, which has become a major obstacle to automatic inspection systems.

[0006] Conventionally, as an easy-sliding technology for polyimide films, inert inorganic compounds (for example, orthophosphoric acid of alkaline earth metal, dicalcium phosphate dibasic, calcium pyrophosphate, silica, talc) are used as polyamic acid. A method of adding (for example, see Patent Document 1), and a method of performing plasma treatment after forming fine protrusions on the film surface with fine particles (for example, see Patent Document 2) are known. However, since the inorganic particles shown in these figures have a large particle size, they are not suitable for automatic optical inspection systems! / And! //.

[0007] In addition, inorganic particles having an average particle diameter of 0.01 to 100 m are held in the polyimide surface layer by embedding a part of each particle! / From the partially exposed inorganic particles A method is known in which 1 × 10 to 5 × 10 ⁸ pieces / mm ² are present on the surface layer of the film (for example, see Patent Document 3). This method actively exposes inorganic particles on the surface and reduces the coefficient of friction on the film surface to effectively obtain a slippery effect. As a result, there was a problem in that the surface of the film on the other side of the contact surface was scratched, resulting in poor appearance.

Patent Document 1: Japanese Patent Laid-Open No. 62-68852

Patent Document 2: JP 2000-191810 A

Patent Document 3: Japanese Patent Laid-Open No. 5-25295

Disclosure of the invention

Problems to be solved by the invention

[0008] The present invention has been achieved as a result of studying the solution of the problems in the above-described prior art as an object.

[0009] Therefore, the object of the present invention is excellent in the runnability, adhesiveness and dimensional stability of the film. The object is to provide a polyimide film applicable to an optical inspection system (AOI) and a method for manufacturing the polyimide film.

Means for solving the problem

[0010] In order to achieve the above goal, according to the present invention, paradiamine diamine and 4,4'-diaminodiphenyl ether as diamine components, pyromellitic acid dianhydride and 3,4'-diaminodiphenyl ether as acid dianhydride components, and 3 ', 4, 4'—Biphenyltetracarboxylic dianhydride as a constituent component, a polyimide film produced mainly by imidization, having a particle size of 0.0;! To 1.5 m And an average particle size of 0.05-0.7 m, and particles having a particle size of 0.15-0.60 111 have a particle size distribution occupying 80% by volume or more of all particles. Inorganic particle force A polyimide film is provided which is dispersed in a film at a ratio of 0.;! To 0.9% by weight per film resin weight.

[0011] In the polyimide film of the present invention,

Ratio power S of each component in the polyimide film, 4 Parafue two Renjiamin and 50-90 mole ^_0/0 10-50 mode Honoré percent Jiamin component, 4 'over-diamino diphenyl ether, acid dianhydride component pyromellitic dianhydride as 50-99 mole ^_0/0, and 3, 3 ', 4, 4

'-Biphenyltetracarboxylic dianhydride 1-50 mol%,

The inorganic particles are contained at a ratio of 0.3 to 0.8% by weight per film resin weight;

The average particle size of the inorganic particles is 0.;!-0.6 m;

The average particle size of the inorganic particles is 0.3 to 0.5 m,

Protrusions caused by the inorganic particles are present on the film surface, and the number of the protrusions having a height of 2 μm or more is 5 pieces / 40 cm square or less, and

The film thickness is 5 to 75 am

, Both are mentioned as preferable conditions.

[0012] The method for producing the polyimide film of the present invention includes a diamine component comprising paraphenylene diamine and 4,4'-diaminodiphenyl ether, pyromellitic dianhydride, and 3, 3 ', 4, The polycarboxylic acid dianhydride component consisting of 4'-biphenyltetracarboxylic dianhydride is reacted in a polar organic solvent to produce polyamic acid, which is imidized. Then, when forming into a film, the particle diameter is within the range of 0 · 01-1.5 m, the force and the average particle diameter is 0.05-0.7 mm, and the particle diameter is 0. A slurry in which inorganic particles having a particle size distribution in which 15-60.111 inorganic particles occupy 80% by volume or more of all particles is dispersed in the same polar organic solvent as the polar organic solvent is produced by polyimide. It is characterized in that the inorganic particles are added to the polyamic acid solution in the process at a ratio of 0.;! To 0.9% by weight per resin weight.

The invention's effect

[0013] According to the present invention, as described below, the added inorganic particles are not exposed, and surface protrusions can be generated in a state of being uniformly dispersed in the film, so that the surface state can be controlled well. In addition to excellent film runnability, adhesion, and dimensional stability, it is possible to obtain a polyimide film that can be applied to flexible optical printed circuit boards (FPC) and chip-on-film (COF) automatic optical inspection systems (AOI).

BEST MODE FOR CARRYING OUT THE INVENTION

[0014] Hereinafter, the present invention will be described in detail.

[0015] First, the polyamic acid that is a precursor for obtaining the polyimide film of the present invention will be described.

[0016] In the present invention, an aromatic tetracarboxylic dianhydride component and an aromatic diamine component or a chemical substance mainly composed of these components are subjected to addition polymerization in an organic solvent. A varnish-like polyamic acid is obtained. Paraphenylenediamine and 4,4′-diaminodiphenyl ether are used as aromatic diamine components, and pyromellitic dianhydride and 3 are used as aromatic tetracarboxylic dianhydride components. , 3 ', 4, 4'-biphenyltetracarboxylic acid dihydrate are used as main components. That is, four kinds of essential components are paraphenylenediamine, 4,4'-diaminodiphenyl ether, pyromellitic dianhydride, and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride. These four types can be obtained by adding only a small amount of other ingredients in addition to these four types. Preferably, using 4, 4 'over diamino diphenyl ether 10-50 mole% of Parafue two Renjiamin and 50 to 90 mol% Jiamin component, 50 to 99 mole ^_0/0 pins Romeritto as an acid dianhydride component Dianhydride and;! ~ 50 mol% 3,3 ', 4,4'-biphenyltetracarboxylic acid Obtained using dianhydride. Roh Rafue two Renjiamin becomes hard and is too large, since too soft too small, 1-70 Monore% strength S Preferably, still more preferably 5 to 60 mol ^_0/0, the more favorable Mashiku 10-50 mole ^_0/0 It is. When 4,4'-diaminodiphenyl ether is too much, it becomes soft and soft, and when it is too little, it becomes hard, so 20-99 mono %% << preferably, more preferably 40-95 monole%, more preferably 50-90 Monore%. Becomes hard and pyromellitic dianhydride is too large, too small straw force, so Kunar, more preferably preferably 50 to 99 mol% instrument 6 0-90 Monore ^_0/0, more preferably (or 65 85 Monore ^_0/0. 3, 3 ,, 4, 4, Bifue two Norete us soft power becomes base when dianhydride is too large, since the hard and too small, 1-50 molar percent preferably fixture further preferably 10 to 40 mole ^_0/0, more preferably 15 to 35 mole ^_0/0

Yes

In the present invention, as described above, a small amount of other diamines may be added in addition to 4,2'-diaminodiphenyl ether. In addition to pyromellitic dianhydride and 3, 3 ', 4, 4'-biphenyltetracarboxylic dianhydride, a small amount of other acid dianhydride may be added! Specific other diamines and dianhydrides include, but are not limited to, force S, including:

[0018] (1) Acid dianhydride

3, 3 ', 4, 4'—Bipheninotetratetranorebonic dianhydride, 2, 3', 3, 4'—Bifeniole tetracarboxylic dianhydride, 3, 3 ', 4, 4' Benzov Enone tetracarboxylic dianhydride, 2, 3, 6, 7 Naphthalene dicarboxylic dianhydride, 2, 2 bis (3,4 dicarboxyphenyl) ether, pyridine 2, 3, 5, 6 tetracarboxylic dianhydride Anhydride, 1, 2, 4, 5 Naphthalenetetracarboxylic dianhydride, 1, 4, 5, 8-Naphthalenetetracarboxylic dianhydride, 1, 4, 5, 8-Decahydronaphthalenetetracarboxylic dianhydride Anhydride, 4,8-dimethyl-1,2,5,6 Hexahydronaphthalenetetracarboxylic dianhydride, 2,6 dichloro-1,4,5,8 Naphthalenetetracarboxylic dianhydride, 2,7 dichloro-1 , 4, 5, 8 Naphthalene tetracarboxylic dianhydride, 2, 3, 6, 7 Tetrachloro-1, 4, 5, 8 Naphthalene tetra Rubonic dianhydride, 1,8,9,10 phenanthrenetetracarboxylic dianhydride, 2,2 bis (2,3 dicarboxyphenenole) propane dianhydride, 1,1 bis (3,4 Dicanoloxyphenyl) ethane anhydride, 1,1 bis (2,3-dicarboxyphenyl) ethane Dianhydride, bis (2,3 dicarboxyphenyl) methane dianhydride, bis (3,4 dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, benzene 1 2, 3, 4 Tetracarboxylic dianhydride, 3, 4, 3 ', 4' Benzophenone tetracarboxylic dianhydride.

(2) Jimin

3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, metaphenydidiamine, 4,4'-diaminodiphenylpropane, 3,4'-diaminodiphenylpropan, 3, 3'- Diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenylsulfide, 3, 4 '—Diaminodiphenylsulfide, 3, 3'-Diaminodiphenylsulfide, 4, 4'-Diaminodiphenylsulfone, 3, 4'-Diaminodiphenylsulfone, 3, 3'-Diaminodiphenylsulfone, 2 , 6 Diaminopyridine, bis (4-aminophenyl) jetylsilane, 3,3'-dichlorobenzidine, bis (4-aminophenol) ethylphosphine oxide Bis-1- (4-aminophenyl) phenylphosphinoxide, Bis-1- (4-aminophenyl) N Phenylamine, Bis-1- (4-aminophenyl) N-Methylenoleamine, 1,5-Diaminonaphthalene, 3,3'-Dimethylolene 4, 4'-diaminobiphenyl, 3, 4 'dimethyl-3', 4 diaminobiphenyl 3, 3 'dimethoxybenzidine, 2, 4-bis (p-β-amino-tert-butylphenyl) ether, bis (p-β-amino) 1 t-butylphenol) ether, p-bis (2-methyl-4-aminopentinole) benzene, p-bis (1,1-dimethyl-5-aminopentinole) benzene, m-xylylenediamine, p-chimantane, 3, 3'-diaminomethinole 1 , 1'-diadamantane, bis (p-aminocyclohexylene) methane, hexamethylenediamine, heptamethylenediamine, ota Methylene diamine, nonamethylene diamine, decamethylene diamine, 3-methylheptamethylene diamine, 4, 4'-dimethylheptamethylene diamine, 2, 11-diaminododecane, 1, 2 bis (3 amino propoxy) ) Ethane, 2,2 dimethylpropylenediamine, 3 methoxyhexaethylenediamine, 2,5 dimethylhexamethylenediamine, 2,5 dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1, 4-diaminocyclohexane, 1,12-diamino Octadecane, 2, 5 Diamino 1, 3, 4, Oxadiazole, 2, 2 Bis (4-aminophenole) hexafluoropropane, N— (3-Aminophenyl) -4-aminoaminobenzamide, 4-Aminophenol 3- Amino Benzoate etc.

[0020] Further, specific examples of the organic solvent used in the present invention for forming a polyamic acid solution include sulfoxide solvents such as dimethyl sulfoxide and jetyl sulfoxide, N, N Formamide solvents such as dimethylformamide and N, N jetylformamide, N, N dimethylacetamide, and acetateamide solvents such as N, N jetylacetamide, N-methyl 2-pyrrolidone, N-but-2-pyrrolidone Pyrrolidone solvents such as phenolone, phenol, o-, m-, or p Cresol mononole, xylenol, halogenated phenol, catechol, and other phenolic solvents, or hexamethylphosphoramide, γ petit-mouthed ratatones, etc. Protic polar solvents can be mentioned, and these are preferably used alone or as a mixture. Aromatic hydrocarbons such as silene and toluene can also be used.

[0021] The polymerization method may be any known method, for example, the following method.

[0022] (1) A method in which the total amount of the aromatic diamine component is first put in a solvent, and then the aromatic tetracarboxylic acid component is added so as to be equivalent to the total amount of the aromatic diamine component.

[0023] (2) A method in which the entire amount of the aromatic tetracarboxylic acid component is first put in a solvent, and then the aromatic diamine component is added in an amount equal to the amount of the aromatic tetracarboxylic acid component for polymerization.

[0024] (3) After putting the aromatic diamine compound in the solvent, the aromatic tetracarboxylic acid compound was mixed at a ratio of 95 to 105 mol% with respect to the reaction components for the time required for the reaction. Thereafter, another aromatic diamine compound is added, and then the aromatic tetracarboxylic acid compound is added and polymerized so that the total aromatic diamine component and the total aromatic tetracarboxylic acid component are approximately equal.

[4] (4) After the aromatic tetracarboxylic acid compound is placed in the solvent, the aromatic diamine compound is mixed at a ratio of 95 to 105 mol% with respect to the reaction components for the time required for the reaction. A method in which an aromatic tetracarboxylic acid compound is added, and then the other aromatic diamine compound is added and polymerized so that the total aromatic diamine component and the total aromatic tetracarboxylic acid component are approximately equal. [0026] (5) A polyamic acid solution (A) is prepared by reacting one aromatic diamine component and aromatic tetracarboxylic acid in a solvent so that either one becomes excessive, and the other in another solvent. The polyamic acid solution (B) is prepared by reacting the aromatic diamine component and the aromatic tetracarboxylic acid in an excess amount. A method in which the polyamic acid solutions (A) and (B) thus obtained are mixed to complete the polymerization. At this time, when adjusting the polyamic acid solution (A), if the aromatic diamine component is excessive, in the polyamic acid solution (B), the aromatic tetracarboxylic acid component is excessive, and in the polyamic acid solution (A), the aromatic tetraamine component is excessive. When the carboxylic acid component is in excess, the polyamidic acid solution (B) makes the aromatic diamine component excess, and the polyamic acid solutions (A) and (B) are mixed together with the wholly aromatic diamine component used in these reactions. Adjust so that the aromatic tetracarboxylic acid components are approximately equal.

[0027] The polymerization method is not limited to these, and other known methods may be used.

Yes

[0028] The polyamic acid solution thus obtained contains 5 to 40% by weight, preferably 10 to 30% by weight of solid content, and its viscosity is 10 to 2000 Pa ′ as measured by a Brookfield viscometer. s, preferably from 100; lOOOPa 's strength is preferably used for stable liquid delivery. The polyamic acid in the organic solvent solution may be partially imidized.

[0029] The inorganic particles added to the resin in order to form protrusions on the film surface of the present invention must be insoluble in all chemical substances that come into contact in the polyimide film manufacturing process.

[0030] Inorganic particles that can be used in the present invention include SiO (silica), TiO 2, CaHPO 2, C 3

Preferable examples include 2 2 4 a PO. Above all, it was manufactured by the wet grinding method of sol 'gel method

2 2 7

Silica is preferably used because it is stable and physically stable in the varnish-like polyamic acid solution and does not affect the properties of the polyimide.

[0031] Further, the fine silica powder should be used as a silica slurry uniformly dispersed in a polar solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, n-methylpyrrolidone. Therefore, it is preferable because aggregation can be prevented. Since this slurry has a very small particle size, the sedimentation rate is slow and stable. Also, even if it sinks It can be easily redispersed by re-stirring.

In the present invention, the inorganic particles added to form protrusions on the surface of the polyimide film have a particle size in the range of 0.01 to 1.5 m and an average particle size of 0.00. 05 μ ΐΐΐ-Ο. 7 〃 m, more preferably 0.1—0.6 〃 m, even more preferably 0.3 to 0.5 m. Not only can it be applied to optical inspection systems without causing any problems in inspection, but it can also be used without causing any deterioration in the mechanical properties of the film. On the other hand, if the average particle size is below these ranges, sufficient slipperiness to the film cannot be obtained, and if it exceeds the average particle size, the automatic inspection system will judge the inorganic particles as foreign matter and cause trouble. Therefore, it is not preferable. Further, since the normal film thickness is 5 Hm to 75 [Im], inorganic particles in this particle diameter range are not exposed on the surface of the polyamide film.

[0033] The addition amount of the inorganic particles is preferably from 0.3 to 0.8% by weight, more preferably from 0.3 to 0.8% by weight per film resin weight. 0. When the content is 1% by weight or less, the film surface is insufficient in number of protrusions, so that sufficient slipperiness to the film cannot be obtained, the transportability is deteriorated, and the film winding shape when wound on a roll is also deteriorated. Therefore, it is not preferable. On the other hand, if it is 0.9% by weight or more, the slipperiness of the film is improved, but coarse protrusions due to abnormal aggregation of inorganic particles increase, and this is judged as foreign matter by the automatic inspection system as a result. It is not preferable because it causes trouble.

[0034] By forming surface protrusions with inorganic particles, the surface area of the film is also increased, and the film is sufficiently roughened to exhibit an anchor effect without impairing the adhesiveness.

[0035] Regarding the particle size distribution of the inorganic particles, it is preferable that the particle size distribution is narrow, that is, the proportion of particles of similar size in the total particle is higher. Specifically, the particle size is 0.15 to 0.60. It is preferable that 111 particles occupy 80% by volume or more of all particles. If the proportion of particles below this range and 0.15 m or less increases, the slipperiness of the film decreases, which is not preferable. In addition, when sending inorganic particles, the force S that can remove coarse particles with a 5 m cut filter or 10 m cut filter, and the proportion of particles over 0.60 m increases, Not only is clogging frequently caused and process stability is deteriorated, but also coarse aggregation of particles tends to occur, which is not preferable. [0036] In the film surface protrusions caused by inorganic particles, the number of protrusions having a height of 2 m or more is 5 pieces / 40 cm square or less, more preferably 3 pieces / 40 cm square or less, and even more preferably 1 piece / It is desirable that it is 40 cm square or less. If the amount is larger than this, it is not preferable because the inorganic particles are judged as foreign matter by the automatic inspection system and cause trouble.

In the present invention, a slurry in which such inorganic particles are dispersed in the same polar solvent as the organic solvent used in the production of the polyimide film is added to the polyamic acid solution in the polyimide production process, and then removed. It is preferable to obtain a polyimide film by cyclization and desolvation. However, after adding the inorganic particle slurry to the organic solvent before polyamic acid polymerization, the polyimide film is subjected to polyamic acid polymerization and decyclization desolvation. It is possible to add the inorganic particle slurry in any step before the decyclization and desolvation, such as obtaining.

[0038] Next, a method for producing the polyimide film of the present invention will be described.

[0039] As a method of forming a polyimide film, a polyamic acid solution is cast into a film and thermally decyclized and desolvated to obtain a polyimide film, and a cyclization catalyst and dehydration are added to the polyamic acid solution. Force that includes a method of obtaining a polyimide film by mixing a chemical agent and chemically decyclizing it, and then heating and desolvating the gel film The latter method Keeping the thermal expansion coefficient of the polyimide film low Is preferable.

[0040] In the chemical decyclization method, first, the polyamic acid solution is prepared.

[0041] The polyamic acid solution can contain a cyclization catalyst (imidization catalyst), a dehydrating agent, a gelation retarder, and the like.

[0042] Specific examples of the cyclization catalyst used in the present invention include aliphatic tertiary amines such as trimethylamine and triethylenediamine, aromatic tertiary amines such as dimethylaniline, isoquinoline and pyridine. Among the powers such as heterocyclic tertiary amines such as / 3-picoline, it is preferable to use at least one amine selected from heterocyclic tertiary amines.

[0043] Specific examples of the dehydrating agent used in the present invention include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride. Of these, acetic anhydride and / or benzoic anhydride are preferred. [0044] As a method for producing a polyimide film from a polyamic acid solution, a polyamic acid solution containing a cyclization catalyst and a dehydrating agent is cast on a support from a die with a slit, and is then formed into a film. The imidization is partially advanced to obtain a gel film having self-supporting property, and then peeled off from the support, heat-dried / imidized, and subjected to heat treatment.

[0045] The polyamic acid solution is formed into a film shape through a slit-shaped base, cast onto a heated support, undergoes a thermal ring-closing reaction on the support, and has a self-supporting gel film. And peeled off from the support.

[0046] The support is a metal rotating drum or an endless belt, and its temperature is controlled by radiant heat from a liquid or gas heat medium and / or an electric heater.

[0047] The gel film is heated to 30 to 200 ° C, preferably 40 to 150 ° C by heat reception from the support and / or heat from a heat source such as hot air or an electric heater, and undergoes a ring-closing reaction. The volatile matter such as the liberated organic solvent is dried to become self-supporting and peeled off from the support.

[0048] The gel film peeled from the support is usually stretched in the running direction while regulating the running speed with a rotating roll. Stretching is carried out at a temperature of 140 ° C or lower at a magnification of 1.05 ~; 1. 9 times, preferably 1.;! ~ 1.6 times, more preferably 1.;! ~ 1.5 times The The gel film stretched in the running direction is introduced into the tenter device, and both ends in the width direction are held by the tenter clip, and stretched in the width method while running with the tenter clip.

[0049] The film dried in the drying zone is heated for 15 seconds to 10 minutes with hot air, an infrared heater or the like. Next, heat treatment is performed at a temperature of 250 to 500 for 15 seconds to 20 minutes using hot air and / or an electric heater. It is preferable to adjust the film thickness of the resulting polyimide film to 5 to 75,1 m while adjusting the draw ratio in the running direction and the draw ratio in the width direction. If it is thicker or thinner than this range, the film forming property is remarkably deteriorated, which is not preferable.

Example

[0050] The present invention will be described below with reference to examples.

[0051] Methods for measuring various physical properties in the present invention will be described below.

[0052] [Friction coefficient (Static friction coefficient)] The processed surfaces of the film were overlapped and measured according to JIS K-7125 (1999). That is, using a slip coefficient measuring device Slip Tester (manufactured by Technonez Corporation), the film processing surfaces are overlapped, a 200 g weight is placed on top, one side of the film is fixed, and the other side is fixed at 100 mm / min. And the coefficient of friction was measured.

[0053] [Adhesive strength]

Specifically, the adhesion evaluation method is based on the method of IPC-FC-241. Bond polyimide film and copper foil with commercially available thermoplastic polyimide adhesive, fix the film on the hard board, and measure. Was determined by

[0054] [Automatic Optical Inspection (AOI)]

The base film was inspected using SK-75 manufactured by Onorepo Tech. The case where foreign matter and fine particles can be distinguished is evaluated as `` A '', while the size of foreign matter and fine particles is similar and the two cannot be distinguished! /, The case is evaluated as `` C '', and the middle is `` B '' It was evaluated.

[0055] [Evaluation of inorganic particles]

The result of measurement and analysis of a sample dispersed in a polar solvent using the Horiba laser round / scattering particle size distribution analyzer LA-910. Force Particle size range, average particle size, particle size 0.15-0.60 The occupation ratio of m in all particles was read.

[0056] [Number of abnormal protrusions]

The number of protrusions with a height of 2 m or more was counted per 40 cm square area of the film. For height measurement, use a scanning laser microscope “1LM15W” manufactured by Lasertec Co., Ltd., using a Nikon 100x lens (CF Plan ΙΟΟ Χ / Ο. 95 ∞ / 0 EPI) in “SURFACE1” mode. This was confirmed by photographing and analyzing the surface.

[0057] [Film thickness]

Measurement was performed using a Mitutoyo lightmatic (Series 318).

[0058] [Linear expansion coefficient]

TMA-50 manufactured by Shimadzu Corporation was used, and measurement was performed under the conditions of a measurement temperature range: 50 to 200 ° C. and a heating rate: 10 ° C./min.

[0059] Next, a synthesis example of a polyamic acid solution will be described.

[0060] [Synthesis Example 1] Pyromellitic dianhydride (Molecular weight 218.12) / 3, 3 ', 4, 4'-Biphenyltetracarboxylic dianhydride (Molecular weight 294 · 22) / 4, 4'-Diaminodiphenyl ether (Molecular weight 200.24) / paraphenylene diamine (molecular weight 108 · 14) at a monore ratio of 65/35/80/20, 18.5 wt% solution in DMAc (N, N-dimethylacetamide) Thus, a 3000 poise polyamic acid solution was obtained.

[0061] [Synthesis Example 2]

Pyromellitic dianhydride (Molecular weight 218.12) / 3, 3 ', 4, 4'-Biphenyltetracarboxylic dianhydride (Molecular weight 294 · 22) / 4, 4'-Diaminodiphenyl ether (Molecular weight 200.24) / paraphenylene diamine (molecular weight 108 · 14) prepared in a molar ratio of 3/1/3/1, 18.5 wt% solution in DMAc (N, N-dimethylacetamide) In this way, 3000 poise polyamic acid solution was obtained.

[0062] [Synthesis Example 3]

Pyromellitic dianhydride (Molecular weight 218.12) / 3, 3 ', 4, 4'-Biphenyltetracarboxylic dianhydride (Molecular weight 294 · 22) / 4, 4'-Diaminodiphenyl ether (Molecular weight 200.24) / paraphenylene diamine (molecular weight 108 · 14) at a molar ratio of 9/1/8/2 and prepared as a 18.5% by weight solution in DMAc (N, N-dimethylacetamide). Polymerization was performed to obtain a 30 OOpoise polyamic acid solution.

[0063] [Synthesis Example 4]

Pyromellitic dianhydride (Molecular weight 218.12) / 3, 3 ', 4, 4'-Biphenyltetracarboxylic dianhydride (Molecular weight 294 · 22) / 4, 4'-Diaminodiphenyl ether (Molecular weight 200.24) / paraphenylene diamine (molecular weight 108 · 14) in a molar ratio of 4/1/3/2 and prepared as a 18.5 wt% solution in DMAc (N, N-dimethylacetamide). Polymerization was performed to obtain a 30 OOpoise polyamic acid solution.

[0064] [Synthesis Example 5]

Pyromellitic dianhydride (Molecular weight 218.12) / 3, 3 ', 4, 4'-Biphenyltetracarboxylic dianhydride (Molecular weight 294 · 22) / 4, 4'-Diaminodiphenyl ether (Molecular weight 200.24) / paraphenylene diamine (molecular weight 108 · 14) prepared at a molar ratio of 95/5/85/15, 18.5 wt% solution in DMAc (N, N-dimethylacetamide) Then polymerize 3000 poise polyamic acid solution was obtained.

[0065] [Synthesis Example 6]

Pyromellitic dianhydride (molecular weight: 218.12) / 4,4'-diaminodiphenyl ether (molecular weight: 200.24) was mixed at a molar ratio of 50/50, and DMAc (N, N dimethylacetamide was added. ) Polymerized to 18.5 wt% solution to obtain 3000poise polyamic acid solution.

[0066] [Example 1]

The total particle size is 0. Ol rn or more and 1.5 m or less, and particles with an average particle size of 0.3 2〃111 and a particle size of 0.15—0.60 m are contained in all particles. volume ^_0/0 of the silica in N, N-dimethyl § Seto amide slurry, the polyamic acid solution obtained in synthesis example 1 were added the resin weight per 0.3 wt%, sufficiently stirred and dispersed. To this polyamic acid solution, a conversion agent composed of acetic anhydride (molecular weight 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight with respect to the polyamic acid solution. At this time, it prepared so that acetic anhydride and isoquinoline might be 2.0 and 0.4 molar equivalent with respect to the amic acid group of a polyamic acid, respectively. The obtained mixture was cast on a 90 ° C stainless steel drum rotated by a T-shaped slit die to obtain a gel film having a self-supporting property of 55% by weight of residual volatile components and a thickness of about 0.05 mm. . The gel film is peeled off from the drum, and both ends thereof are gripped, and processed at 200 ° CX for 30 seconds, 350 ° CX for 30 seconds, and 550 ° CX for 30 seconds in a Karo heat furnace to obtain a polyimide film with a thickness of 38 μm. It was. The properties of the obtained polyimide film are shown in Table 1.

[0067] [Examples 2 to 7]

Except that the ratio of the polyamic acid solution used, the average particle size of silica, the amount of silica added, and the particle size of 0.15 to 0.60 in of all particles was set as shown in Table 1, respectively. The characteristics of the 38 m thick polyimide films obtained in the same manner as in 1 were evaluated and are shown in Table 1.

[Example 8]

The particle size of all particles is within the range of 0.01 to 1.5 m, and particles with an average particle size of 0.3 to 7 mm and a particle size of 0.15 to 0.60 m are included in all particles. volume ^_0/0 of the silica in N, N-dimethyl § Seto amide slurry, the polyamic acid solution obtained in synthesis example 1 were added the resin weight per 0.35 wt%, sufficiently stirred and dispersed. Acetic anhydride (molecule The conversion agent consisting of 102.09) and isoquinoline was mixed and stirred at a ratio of 50% by weight to the polyamic acid solution. At this time, it prepared so that acetic anhydride and isoquinoline might be 2.0 and 0.4 molar equivalent with respect to the amic acid group of a polyamic acid, respectively. The obtained mixture was cast on a 90 ° C stainless steel drum rotated by a T-shaped slit die to obtain a self-supporting gel film having a residual volatile component of 55 wt. ⁰ / o and a thickness of about 0.05 mm. It was. The gel film was peeled off from the drum, and both ends were gripped and treated in a heating furnace at 200 ° CX for 30 seconds, 350 ° CX for 30 seconds, and 550 ° CX for 30 seconds to obtain a polyimide film with a thickness of 25 μm. . The properties of the resulting polyimide film are shown in Table 2.

[0069] [Example 9]

The rotation speed of the drum was the same as in Example 8, except that the gel film transport speed (film formation speed) after peeling from the drum was twice as fast as in Example 8 to obtain a 12.5 in thick film. The characteristics of the polyimide films obtained in the same manner as in Example 8 were evaluated and are shown in Table 2.

[0070] [Example 10]

The rotation speed of the drum is the same as in Example 8, except that the gel film transport speed (film formation speed) after peeling from the drum is 4 times faster than in Example 8 to obtain a film with a thickness of 7.5 ^ 111 The characteristics of the polyimide films obtained in the same manner as in Example 8 were evaluated and are shown in Table 2.

[0071] [Example 11]

The rotation speed of the drum is the same as in Example 8, except that the gel film transport speed (film formation speed) after peeling from the drum is half that of Example 8 and a film with a thickness of 50 am is obtained. Table 2 shows the characteristics of the polyimide films obtained in the same manner as in Example 8.

[Example 12]

The rotating speed of the drum is the same as in Example 8, except that the gel film transport speed (film forming speed) after peeling from the drum is 1/3 of that in Example 8, and a film with a thickness of 7511 m is obtained. Table 2 shows the characteristics of the polyimide films obtained in the same manner as in Example 8. [0073] [Comparative Example 1]

A 38-m thick polyimide film was obtained in the same manner as in Example 1 except that silica was not added. The properties of the obtained polyimide film were evaluated and are shown in Table 3. A film with a high coefficient of static friction and poor slip was obtained. Also, the adhesive strength was low.

[0074] [Comparative Example 2]

The particle size of all particles is 0.1 l rn or more and 4.5 m or less, and particles with an average particle size of 1. ,, ι m and a particle size of 0.15—0.60 m are included in all particles. A volume% calcium hydrogen phosphate N, N-dimethylacetamide slurry was added to the polyamic acid solution obtained in Synthesis Example 6 in an amount of 0.2% by weight per resin weight, and the mixture was sufficiently stirred and dispersed. To this polyamic acid solution, an acetic anhydride (molecular weight 102.09) and isoquinoline conversion agent were mixed and stirred at a ratio of 50% by weight to the polyamic acid solution. At this time, it was prepared such that acetic anhydride and isoquinoline were 2.0 and 0.4 molar equivalents relative to the amic acid group of the polyamic acid. The obtained mixture was cast on a 90 ° C stainless steel drum rotated by a T-shaped slit die, and a self-supporting gel film having a residual volatilization component of 55% by weight and a thickness of about 0.05 mm was obtained. Obtained. This gel film is peeled off from the drum, and both ends thereof are gripped and heated in a heating furnace at 200 ° C. for 30 seconds, 350. C X 30 seconds, 550. C X was treated for 30 seconds to obtain a 38 μm-thick polyimide film. The properties obtained are shown in Table 3. In the AOI inspection, there were many abnormal projections that could not distinguish between foreign particles and fine particles. Moreover, since the linear expansion coefficient is high, the dimensional change is large.

[0075] [Comparative Example 3]

Particle size range of 0.01—0.3 ^ 111, average particle size 0.08 μΐ ^ addition amount 0.35% by weight, particle size 0.15-0. 60 in of all particles Table 3 shows the characteristics of a 38-m thick polyimide film obtained in the same manner as in Comparative Example 2 except that 31.4% by volume of silica was used. A film with a high coefficient of static friction and slightly poor sliding properties was obtained. Also, the dimensional change was significant due to the high linear expansion coefficient.

[0076] [Comparative Example 4]

Particle size range is 0.01 — 1. δ μΐ ^ average particle size 0.4 ^ 111, added amount 0.35 wt%, particle size 0.15-0. A 38-m thick polyimide film obtained in the same manner as in Comparative Example 2 except that 72.6% by volume of silica was used. The characteristics were evaluated and are shown in Table 3. In this example, the occupancy ratio of 0.9 to 1.3 m particle size accounted for 22.3% by volume of the whole, and this increased the number of abnormal projections. In addition, A OI inspection showed that it was difficult to distinguish between foreign particles and fine particles. Furthermore, the linear expansion coefficient was high! /, So the dimensional change was large.

[0077] [Comparative Example 5]

A polyimide film having a thickness of 38 111 was obtained in the same manner as in Comparative Example 2 except that the polyamic acid solution obtained in Synthesis Example 1 was used. The properties of the obtained polyimide film were evaluated and are shown in Table 3. In the AOI inspection, there were many abnormal protrusions that could not distinguish between foreign particles and fine particles.

[0078] [Table 1]

] [

Table 2

As is apparent from the results in Tables 1 to 3, paradiamine diamine and ⁴ '' -diaminodiphenyl ether as the diamine component, pyromellitic dianhydride and 3 '4'-biphenyl as the acid dianhydride component Mainly by imidization from tetracarboxylic dianhydride

Replacement kite («26) A manufactured polyimide film, mainly composed of inorganic particles having a particle size in the range of 0.01-1.5 mm and an average particle size of 0.05-0.7 m. The polyimide film of the present invention uniformly distributed in the film at a ratio of 0.;! To 0.9% by weight per film resin weight maintains excellent slipperiness, dimensional stability, and adhesiveness. In addition, since the number of protrusions due to coarse particles is small, there is no obstacle that the particles are judged as foreign matter by AOI inspection. Therefore, applications such as flexible printed circuit boards (FPC) and chip-on-film (COF) that form fine wiring It is suitable for.

Industrial applicability

The polyimide film of the present invention can be applied to an academic inspection system (AOI) that has excellent film runnability, adhesiveness, and dimensional stability. It is suitable for applications such as flexible printed wiring boards (FPC) and chip-on-film (COF) that form fine wiring.

Claims

The scope of the claims

[1] Paraphenylenediamine and 4,4, -diaminodiphenyl ether as diamine components, pyromellitic dianhydride and 3, 3 ', 4, 4'-biphenyltetra-force rubonic acid dianhydride as acid dianhydride components Is a polyimide film produced by imidization, having a particle size in the range of 0.01 — 1.5 m and an average particle size of 0.05 to 0.7 m. In addition, an inorganic particle force having a particle size distribution in which particles having a particle size of 0.15 to 0.60 m occupy a ratio of 80% by volume or more of all particles is 0.;! To 0.9% by weight A polyimide film characterized by being dispersed in the film.

[2] 4, 4 'over-diamino diphenyl ether, acid dianhydride of the Parafue two Renjiamin and 50-90 mole ^_0/0 10-50 mode Norre% as a percentage force Jiamin component of each component in the polyimide film pyromellitic dianhydride as component 50-99 mole ^_0/0, and 3, 3 ', 4, 4, characterized in that it consists an over Biff enyl dianhydride 1-50 mol%請Motomeko 1. The polyimide film according to 1.

[3] The polyimide film according to [1] or [2], wherein the inorganic particles are contained at a ratio of 0.3 to 0.8% by weight per film resin weight.

[4] The polyimide film as set forth in any one of [1] to [3], wherein the inorganic particles have an average particle size of 0 .;! To 0.6 m.

[5] The polyimide film according to any one of [1] to [4], wherein an average particle diameter of the inorganic particles is 0.3 to 0.5 m.

[6] The protrusions attributed to the inorganic particles are present on the film surface, and the number of protrusions having a height of 2 μm or more is 5 pieces / 40 cm square or less. The polyimide film as described in 1 above.

[7] The polyimide or film according to any one of [1] to [6], wherein the film thickness is 5 to 75 m.

[8] Diamine component consisting of parafenylenylenediamine and 4,4'-diaminodiphenyl ether, pyromellitic dianhydride and 3, 3 ', 4, 4'-biphenyltetracarboxylic dianhydride A tetracarboxylic dianhydride component consisting of the following is reacted in a polar organic solvent to produce a polyamic acid, which is imidized and then molded into a film with a particle size of 0 · 0;!

1. Within the range of 5 m, the average particle size is 0 · 05—0.7 m, and particles with a particle size of 0.15-0.60 111 account for 80% by volume or more of all particles. A slurry in which inorganic particles having an occupied particle size distribution are dispersed in the same polar organic solvent as the polar organic solvent is added to the polyamic acid solution in the polyimide production process, and the inorganic particles are added to the resin weight by weight of 0.00; It adds so that it may become a ratio of 9 weight%, The manufacturing method of the polyimide film of any one of Claims 1-7 characterized by the above-mentioned.