TW201233548A - Matte finish polyimide films and methods relating thereto - Google Patents

Abstract

The present disclosure is directed to a base film having a thickness from 8 to 152 microns, a 60 degree gloss value from 2 to 35, an optical density greater than or equal to 2 and a dielectric strength greater than 1400 V/mil. The base film comprises a chemically converted (partially or wholly aromatic) polyimide in an amount from 71 to 96 weight percent of the base film. The base film further comprises a pigment and a matting agent. The matting agent is present in an amount from 1.6 to 10 weight percent of the base film, has a median particle size from 1.3 to 10 microns, and has a density from 2 to 4.5 g/cc. The pigment is present in an amount from 2 to 9 weight percent of the base film. The present disclosure is also directed to coverlay films comprising the base film in combination with an adhesive layer.

Description

201233548 VI. Description of the Invention: [Technical Field] The present invention relates to matte finish base films which can be used for cover and have excellent dielectric and optical properties. . More specifically, the matte surface treatment base film of the present invention comprises a relatively low concentration of a pigment and a matting agent in a polyimine film which is converted by chemical (relative to thermal procedures). The procedure is imidized by hydrazine. [Prior Art] In summary, coverlays are known as barrier films for protecting electronic materials, such as lead frames for protecting flexible printed circuit boards, electronic parts, integrated circuit packages, and the like. However, there is still a need for a thinner and less costly coverage, and not only requires acceptable electrical properties (e.g., dielectric strength), but also acceptable structural and optical properties to provide for coverage. Protected electronic parts provide safety protection 'avoid unnecessary visual inspection and damage. SUMMARY OF THE INVENTION The present invention is directed to a base film. The base film comprises a chemically converted polyimine in an amount of from 71 to 96% by weight of the base film. The chemically converted polyimide is derived from: i. at least 50 mole percent of aromatic dianhydride' based on the total dianhydride content of the polyimine, and at least 5 mole percent of the aromatic Group diamines, based on the total diamine content of the polyimine. The base film further comprises: a low conductivity carbon black 'which is present in an amount of from 2 to 9 weight percent of the base film; and a matting agent: 154225.doc

S 201233548 a_ is present in an amount of from 1.6 to 10% by weight of the base film, b. has a median diameter of from 1.3 to 10 μm, and c· has a density of from 2 to 4.5 g/cc. In one embodiment, the base film has: L thickness of 8 to 152 microns; 11.60 degree gloss value (6°degree gi〇ss vaiue) of 2 to 35; iii. Optical density of 2 or more; and iv. The dielectric strength is greater than 1400 V/mil. The present invention also relates to a cover film which comprises the base film and incorporates an adhesive layer. The invention also relates to a base film comprising: 一· a chemically converted polyimine in an amount of from 40 to 90% by weight of the base film. The chemically converted poly nitrite is derived from: a. Calculating an aromatic dianhydride of at least 5 mole percent, based on the total amount of the dianhydride of the brewed imine, and b. an aromatic of at least 5 mole percent based on the total amount of the diamine of the polyimine Diamine; Β· A filler, in addition to carbon black and pigment, is present in an amount of from 1 to 60 weight percent of the base film; and wherein the base film has a thickness of from 8 to 152 microns. [Embodiment] Definitions As used herein, the term "comprising" - /, force" is intended to cover non-exclusive inclusions. For example, when the method private order, object, or injury contains a list of components, it is not limited to the difference of the number of the squadrons, but may include other non-express list or methods. Elements that are inherent to the order, object, or equipment. □ J54225.doc 201233548 Unless otherwise stated, (4) “or” means a stipulated or non-exclusive OR. For example, any of the following cases satisfies condition A or B: A is true (or exists) and B is pseudo (or non-existent), A is pseudo (or non-existent) and B is true (or exists) and A and B All are true (or exist). Also, "-" or "one" is used to describe the elements and components of the present invention. This is done for convenience only and provides a general meaning to the invention. This description should be understood to include one or at least one, and the singular also includes the plural. As used herein, "two-needle" is meant to include a precursor or derivative thereof which is technically not a dianhydride but reacts with a diamine to form a polyamic acid which can be subsequently converted. It is a polyimine. As used herein, "diamine" is meant to include a precursor or derivative thereof which is technically not a diamine but which is reacted with a dianhydride to form a poly-proline which can then be converted to a polyruthenium. amine. As used herein, "polylysine" is meant to include any polyamidiamine precursor material derived from a combination of a dianhydride and a diamine monomer or a functional equivalent thereof, and capable of undergoing a chemical conversion procedure. Converted to polyimine. As used herein, "prepolymer" is intended to mean a relatively low molecular weight polyamic acid solution prepared using a stoichiometric excess of diamine to give a viscosity of from about 50 to about 100 poise. Solution. As used herein, "chemical conversion" or "chemical conversion" means the use of a catalyst (accelerator) or a dehydrating agent (or both) to convert the polyamic acid to a polyimine, and is meant to include Part of the chemically converted polyimine' is then dried at elevated temperatures to a degree of solidity greater than 98 Å/〇. 154225.doc 201233548 As used herein, "transformation chemical" or "deuterated chemical" means a catalyst (accelerator) capable of converting polyplycine to polyimine and/or capable of polylysine A dehydrating agent that is converted to a polyimine. As used herein, "Finishing s〇luti〇n" means a dianhydride in a polar aprotic solvent which is added to the prepolymer solution to increase molecular weight and viscosity. The dianhydride used is usually the same as the dianhydride used to make the prepolymer (or one of the same dianhydrides may be used when more than one is used). When a specified content, concentration, or other value or parameter is recited as a range, a preferred range, or an upper preferred value and a lower preferred value, it should be construed as a specific disclosure by any All ranges formed by any pairing of lower or preferred values, whether or not the ranges are separately disclosed. The scope of the present invention is to be understood as being limited to the singular range of the range and the integers and fractions thereof. The present invention: Fan Zhuan and u want to define the specific value of the meaning of the formula. In describing some polymers, it is understood that the applicant sometimes uses the monomers used to make the polymers, or the monomers used to make the polymers: Refer to the polymers. Although this is the name of the polymer, or may not include the final term of the material, any = etc.: the product - the polymer is from the list: two:: mention should be interpreted. Unless otherwise indicated or indicated in the text, it is not intended to limit the present invention to the nature of the invention, unless otherwise specifically described or equivalent to the method or material described in the 154 225. doc 201233548. The speaker is the appropriate method and material. Base Film The base film of the present invention comprises a filled polyimine matrix, wherein the polyimine is created by a chemical conversion procedure. One advantage of the chemical conversion procedure (compared to the separate thermal conversion procedure) is that the amount of matting required to achieve a sufficiently low gloss is at least 10, 20, 30 lower than if the thermal conversion procedure is used. , 40 or 50 percent. The generally accepted 60-degree gloss value is: <10 flat (〇) 肖/ 肖光(四)站切), mercin (satin), semi-gloss (using various terms) >7〇 gloss (glossy) In some embodiments, the base film has a 60 degree gloss value between and optionally including any of the following: 2, 3, 4, 5, 1 〇, 15, 2 〇, 25, 30 and 35. In certain embodiments, the base film has a 6-degree gloss value of 2 to 35. In certain embodiments, the base film has a 6-degree gloss value of (7) to ". The 60-degree gloss value is measured using a Micro_TRI_G1 〇ss gloss meter. A smaller amount of matting agent is used (by means of the chemical conversion Made) has its advantages because it: i. reduces the overall cost; ii. simplifies the process of dispersing the matting agent to the poly-proline (or other polyimide precursor material); and iu makes the base film formed Has better mechanical properties (eg, lower brittleness). Another advantage of the chemical conversion procedure (compared to the separate thermal conversion procedure) is that the chemically converted base film has a higher dielectric strength. In some embodiments, the base film has a dielectric strength of 154225.doc 201233548 of greater than 1400 V/mil (55 V/micron). In certain embodiments, the chemically converted polyimine is polymerized The proline solution is prepared by a step of mixing a catalyst or a dehydrating agent capable of converting polyproline to polyimine. In another embodiment, the chemically converted polyimine is by Poly-proline solution and one capable of converting poly-proline into poly The step of mixing the amine catalyst or dehydrating agent. In the chemical conversion procedure, the polyamic acid solution is impregnated or mixed with a conversion (imidization) chemical. In one embodiment The conversion chemistry is a tertiary amine catalyst (accelerator) and an anhydride dehydration material. In one embodiment, the anhydride dehydration material is acetic anhydride, which is often in the amide relative to the poly phthalic acid. The acid) group is used in molar excess, typically from about 1.2 to 2.4 moles per equivalent of polyamic acid. In one embodiment, a comparable amount of tertiary amine catalyst is used. Acetic anhydride as the anhydride dehydration material Alternatives include: 丨·other aliphatic anhydrides such as propionic anhydride, butyric anhydride, valeric anhydride and mixtures thereof; π. aromatic monocarboxylic acid anhydrides; iii_ mixture of aliphatic anhydrides and aromatic anhydrides; iv carbodiimides (carbodimides); and V. aliphatic ketene (the ketene can be regarded as a carboxylic anhydride derived from an extremely dehydrated acid). In a consistent application, the tertiary amine catalyst is a bite than a 3 _methyl stone bite. (beta-picoline), and its amount is usually similar to the anhydride dehydration material The amount of lower or higher enthalpy may be used depending on the desired conversion rate and the catalyst used. It is also possible to use a tertiary amine having a slightly the same activity as the singular bite and a beta pyridine. . These tertiary amines include 2_mercaptoline; 3,4-dimethylpyridine; 3,5-dipyridinium; 4-methyloxime 154225.doc 201233548 pyridine; 4-isopropyl acridine N, N_: methylbenzylamine; isoquinoline; 4 benzylpyridine, N,N-didecyldodecylamine, triethylamine and the like. Other different catalysts for the ruthenium imidization are well known in the art, such as the "sitting' and can be used in accordance with the present invention. The conversion chemistry is typically carried out at about room temperature or above to convert the polyproline to the polyimine. In one embodiment, the chemical conversion occurs at a temperature of 15 C to 12 Torr, and the reaction is very fast at higher temperatures and relatively slow at lower temperatures. In one embodiment, the chemically treated polyamic acid solution can be sputum-type or extruded onto a heated conversion surface or substrate. In one embodiment, the chemically-treated polyamic acid solution can be cast. Type on the belt or drum. The solvent can be evaporated from the solution and the polyamic acid can be locally chemically converted to polyimine. The resulting solution is then in the form of a polylysine-polyimine colloid. Alternatively, the polyamic acid solution can be extruded into a bath of a conversion chemical consisting of an anhydride component (dehydrating agent), a tertiary amine component (catalyst), or both. Or no dilution solvent. In either case, the film is formed and the percentage of conversion of the guanamine group to the quinone group is dependent on the contact time and temperature, but is typically about 10 to 75 percent complete. In order to cure to a solids level of greater than 98%, the film must be dried at a temperature of from about 2 °C to up to about 550 °C, thus tending to complete the hydrazine imidization. In certain embodiments, it is preferred to use both a dehydrating agent and a catalyst to facilitate the formation of the film and achieve the desired conversion. Although the film has a high solvent content, it still tends to be able to self-support 154225.doc

S 201233548 support (seif-supp〇rting). The film is typically dried to remove water, residual solvent and residual conversion chemicals, and in this procedure the polyamine acid is substantially completely converted to polyimine (i.e., greater than 98% quinone imidization). The drying can be carried out under relatively mild conditions without the need to completely convert the polyamidamine to polyimine at this point, or the drying and conversion can be carried out simultaneously using a higher temperature. Because the colloid contains a number of liquids that must be removed during the drying and conversion steps, the colloids typically must be limited during drying to avoid undesired shrinkage. The base film can be held at its edges during continuous manufacture, for example in a tent frame, using a tenter clip or a tenter pin to limit it. The base film can be dried using a short time of high temperature and the imidization of the film can be induced to convert the film into a polyimide film in the same step. In one embodiment, the base film is heated to a temperature of from 2 Torr to 55 Torr. In general, films require less heating and time than thick films. During such drying and conversion (conversion from polyglycolic acid to polyimine), the base film can be limited to avoid excessive shrinkage and can actually be stretched up to 150 percent of its original size. When the film is prepared, it may be stretched in the length direction or the width direction or both. If necessary, adjust the limit to allow for limited shrinkage. Another advantage of the chemically-transformed base film of the present invention is that both sides are matt, even if it is cast on a smooth surface. If both sides of the base film are matted, any additional layers can be applied to either side of the base film. Different from the above situation, when the film system which is also filled with the polyimide precursor is only thermally converted, 154225.doc 201233548, the side of the mold tends to be luster, and when the air is cast on a smooth surface, the side tends to be extinction. Again - the advantage is that the chemically converted base film has a higher dielectric strength than the base film which is only thermally converted. Typically, the dielectric strength decreases with increasing matting dose so that in a person using only thermal procedures, although a low 60 degree gloss value (only to the air side) can be achieved by increasing the matting dose, the dielectric is dielectric The intensity is also reduced. In one embodiment, the polyamic acid is prepared by the following procedure, with a molar amount of dianhydride and diamine in a solvent, and stirred under controlled temperature conditions. The resulting solution is until the polymerization of the dianhydride and the diamine is complete. Typically, one of the monomers (usually a diamine) is used in a slight excess to initially control molecular weight and viscosity, and then the molecular weight and viscosity can be increased via an additional small amount of insufficient monomer. Examples of the dianhydride suitable for the polyimine of the present invention include aromatic dianhydrides, aliphatic dianhydrides, and mixtures thereof. In one embodiment, the aromatic dianhydride is selected from the group consisting of: pyromellitic dianhydride; 3,3,4,4-diphenyltetracarboxylic acid (tetracarb® Xy) ic dianhydride 3,3',4,4'-diphenylphosphonium tetracarboxylic acid dianhydride; 4,4-oxy oxydiphthalic anhydride; 3,3,4,4 Two-needle; 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane; bisphenol A dianhydride; and mixtures and derivatives thereof Things. 154225.doc 12

S 201233548 in another embodiment

The aromatic dianhydride is selected from the group consisting of 2,3,6,7-naphthalene tetraphthalic acid dianhydride; 1,2,5,6-naphthalene tetraphthalic acid dianhydride; 2,2',3, 3'-biphenyltetracarboxylic dianhydride; (3,4-diphenyl)propanol; bis(3,4-di-hydroxyphenyl)$ wind traitor; 3,4,9, 1〇-茈tetracarboxylic dianhydride; 1'1 (2,3-a slow-base stupid) E-baked two-neck; 1'1 (3,4--re- phenyl) Ethylene; Bis(2,3-dibuylphenyl) sulfonated dianhydride; bis(3,4-dicarboxyphenyl)methane dianhydride; oxydiphthalic acid dianhydride; bis(3,4-dicarboxyphenyl) Sulfone dianhydride; mixtures and derivatives thereof. Examples of aliphatic dianhydrides include: Dingzhu two needles; (10), 5Κ*, 6δ*]-3-indole bicyclo[3.21] Xindong Dongming-3(tetrahydrofuran-2,5-dione); , a mixture thereof. Group of diamines and mixtures thereof < group consisting of: 3,4'-oxydiphenylamine; - 4 π saponin in one embodiment, 兮芸 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Doc -13· 201233548 1,3-bis-(4-aminophenoxy)benzene; 4,4'-oxydiphenylamine; 1,4-diaminobenzene; 1,3-diaminobenzene; 2,2'-bis(trifluoromethyl)benzidine; 2,4'-diaminobiphenyl; 4,4'-diaminodiphenylsulfide Ether; 9,9'-bis(4-amino)fluoro; mixtures and derivatives thereof. In another embodiment, the aromatic diamine is selected from the group consisting of: 4,4'-diaminodiphenylpropane; 4,4'-diaminodiphenylmethane; benzidine 3,3'-di-cyclobenzidine; 3,3'-diaminodiphenyl sulfone; 4,4'-diaminodiphenyl sulfone; 1,5-diaminonaphthalene; 4,4' -diaminodiphenyldiethyldecane; 4,4'-diaminodiphenylnonane; 4,4'-diaminodiphenylethylphosphine oxide (4,4·-diamino diphenyl ethyl Phosphine oxide); 4,4·-diaminodiphenyl N-methylamine; 154225.doc -14-

S 201233548 4,4'-diaminodiphenyl N-phenylamine; 1,4-aminobenzene (p-phenylenediamine); 1,2_-aminobenzene; its compounds and derivatives . Examples of suitable aliphatic diamines include: hexamethylenediamine, eleven-diamine, cyclohexene diamine; and mixtures thereof. In a consistent embodiment, the chemically converted polyimide is derived from pyromellitic dianhydride ("PMDA") and 4,4-dioxydiphenylamine ("4,4 〇DA"). In an embodiment, the polylinimide of the present invention is a cop〇iyimides derived from any of the above-described diamines and dianhydrides. In an embodiment, the co-(i)imide is derived from 15 to 85 mole % of biphenyl tetracarboxylic dianhydride, 15 to 85 mole % of pyruvate dianhydride, 30 to 100 moles of 0/ The p-phenylenediamine of hydrazine and optionally 4,4,-diaminodiphenyl ether and/or 4,4,-diaminodiphenyl ether having a hydrazine to 7 〇 mol%. Such copolyimines are further described in U.S. Patent No. 4,778,872 and U.S. Patent No. 5, ι 66, No. 3, No. 8. In one embodiment, the polyamidiamine dianhydride component is pyromellitic dianhydride ("PMDA") and the polyamidimide diamine component is 4,4,-oxydiphenylamine (" 4,4 ODA") in combination with p-phenylenediamine ("ppD"). In one embodiment, the component is a pyromellitic dianhydride ("PMDA j ) and the polyamidiamine diamine component is 4 〆 1-oxydiphenylamine ("4 , 4 154225.doc 15 201233548 ODA") in combination with p-phenylenediamine ("PPD"), where the ratio of 〇DA to PPD (ODA:PPD) is any of the following molar ratios: 〖20 to 80: 80 To 20; ii. 50 to 70:50 to 30; or in 55 to 65: 45 to 35. In one embodiment, the polyamidiamine dianhydride component is PMDA and the molar ratio of the diamine component to ODA to PPD (ODA:PPD) is about 6 〇:4 〇. In one embodiment, the polyamidiamine dianhydride component is 3,3i, 4,4i-biphenyltetracarboxylic dianhydride ("BPDA") and the polyamidimide diamine component is 4,4 , _oxydiphenylamine ("4,4 ODA") and p-phenylenediamine (r PPDj ) combination. In the examples, the polyacrylonitrile dianhydride component is BPDA and the polyamidimide diamine component is a combination of 4,4 ODA and PPD, wherein the ratio of 〇DA to ppD (ODA:PPD) is For any of the following molar ratios: 丨2〇 to 8〇: 8〇 to 20; ii. 50 to 70:50 to 30; or iii.55 to 65:45 to 35. In one embodiment, the polyamidiamine dianhydride component is BPDA, and the diamine component has an ODA to PPD molar ratio (〇da:PPD) of about 60:40. In one embodiment, the polylysine solvent must be capable of dissolving one or both of the polymerization reactants, and in one embodiment, is capable of dissolving the polyglycolic acid polymerization product. The solvent should be almost non-reactive with all polymeric reactants and polyglycolic acid polymerization products. In one embodiment, the polylysine solvent is a liquid hydrazine, N'N-chalkylcarboxylamide, such as a low molecular weight guanamine, particularly n, n-diindenyl hydrazine. Amine with N,N-diethylacetamide. Other useful compounds for such solvents are N,N-diethylguanamine and hydrazine, hydrazine diethylamine. Other solvents which may be used are cyclobutyl hydrazine, hydrazine-methyl-2 "pyrophase, tetramethylurea, dimercaptosulfone and the like. These solvents may be used alone or in combination with their solvents 154225.doc 201233548. The solvent is preferably used in an amount ranging from 75 to 90% by weight of the polyamic acid. The polyaminic acid solution is generally formed by dissolving the diamine in a dry solvent and slowly adding a dianhydride in an inert gas atmosphere of agitation and temperature control. In practice, any pigment (or combination of pigments) may be used in the practice of the invention. In certain embodiments, useful pigments include, but are not limited to, the following: Barium Lemon Yellow, Calmium Yellow Lemon), Cadmium Yellow Light, Cadmium Yellow Middle, Cadmium Yellow Orange, Scarlet Lake, Cadmium Red, Cadmium Vermilion , Alizarin Crimson, Permanent Magenta, Van Dyke brown, Raw Umber Greenish or Burnt Umber. In some examples The black pigments used include: c〇balt oxide, Fe-Mn-Bi black, Fe-Mn oxide spinel black, (Fe, Mn) 203 black, copper chromium Copper chromite black spinel, lampblack, bone black, bone ash, bone char (b〇ne char), hematite, black iron oxide , mica-like iron oxide, black miscellaneous inorganic pigment (CICP), CuCr204 black, (Ni, Mn, Co) (Cr, Fe) 204 black, aniline black, black, black, green and black hematite , ferrochrome oxide, pigment green 17, pigment black 26, pigment black 27, pigment black 28, pigment brown 29, pigment black 30, pigment black 32, pigment black 33 or mixtures thereof. 154225.doc 17· 201233548 in certain In the examples, a low conductivity carbon black is used. The amount of the low conductivity carbon black and the thickness of the base film generally affect the optical density. If the low conductivity carbon black is loaded too high, even if it has been used low Conductivity carbon black, the base film will still be conductive. If it is too low, the base film may not reach the desired optical density and color. The low conductivity carbon black is used in the present invention to impart a black color to the base film and achieve a desired optical density, the base film having a thickness between and optionally including any of the following: 8, 15, 20 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 1 〇〇, 110, 120, 130, 140 and 152 microns. In certain embodiments, the base film thickness is from 8 to 152 microns. In certain embodiments, the base film has a thickness of from 8 to 127 microns. In still another embodiment, the base film has a thickness of from 1 Å to 4 Å. Low conductivity carbon black means channel type black or furnace black. In certain embodiments, bone black can be used to impart black color. In one embodiment, the low conductivity carbon black is present in an amount and optionally comprises any two of: 2, 3, 4, 5, 6, 7, 8, and 9 weight percent of the base film. In some embodiments, the optical density (opacity) is desirably (e.g., concealing the conductor pattern in the flex circuit to avoid being seen) greater than or equal to two. An optical density of 2 means that 1 X 1 〇 2 or 1% of light can pass through the base film. In some embodiments, the low conductivity carbon black is a surface oxidized carbon black. One method of assessing the extent of surface oxidation (referred to as carbon black) is to measure the volatile content of the carbon black. The measurement of the volatile content can be obtained by calculating the weight loss after calcination at 950 ° C for 7 minutes. In general, the highly oxidized carbon black (high volatile content) of the surface can be easily dispersed in a poly-proline solution (polyimine precursor), which can then be imidized into the present invention (dispersed) 154225.doc

S -18- 201233548 Good) Polyimide-filled matrix polymer. It is generally believed that if the carbon black particles (aggregates) are not in contact with each other, electron tunneling, ectron hopping or other electron flow mechanisms are generally suppressed, resulting in low electrical conductivity. In certain embodiments, the low conductivity carbon black has a volatile content of greater than or equal to 1% beta. In certain embodiments, the low conductivity f carbon black has a volatile content greater than or equal to 5, 9, or 13. %. In some embodiments, the furnace black may be surface treated to increase the volatile content. The uniform dispersion of individual particles (aggregates) not only reduces the conductivity, but also tends to produce a uniform color intensity. In certain embodiments, the low conductivity carbon black is ground. In certain embodiments, the average particle size of the conductivity carbon is between (and optionally includes) any two of the following: 〇.2, H 〇·4 ' 〇·5, 〇·6, 〇7 , 〇 8, 〇 9 and 〇 〇 micron. The base film can be adjusted for a specific application. A dye can be used in a certain target. Examples of useful dyes are, but are not limited to, nigr〇sin blaek, mono- chrome-chromic black (m〇n coffee ch_lum complex black), or mixtures thereof. In certain embodiments, a mixture of dye and pigment can be used. Matting Agents Polymeric materials generally have a surface gloss in their own right. To control gloss (7): to produce matte surface features) there are various possible ways to add surface and low gloss surface features. In a nutshell, these addition methods are based on the physical surface of the modified surface, which (in microscopic = key and irregular shape ' thus causes less light energy to be reversed (eg greater than 50 cm). ^ ^ 'Ding, the person. § The light of the shinning surface 154225.doc 201233548, most of the light is reflected at the same angle, so a relatively high degree of light reflectivity can be observed. When the same light source hits the extinction (ie irregular) surface when the light system is scattered to many different directions and also has a higher proportion of absorption. Therefore, on rough surfaces, light tends to diffusely scatter to all directions, and its image formation quality is greatly reduced (reflection The resulting object is no longer clear but blurred.) The gloss meter used to characterize the gloss of a particular surface is based on the same principle. In general, the light source hits the surface at a fixed angle, and the reflected light reflects It is read by photocells and can be read at multiple angles. Maximum gi〇ss performance tends to appear as 100% reflection, but no Glossy surfaces tend to appear as 0% reflection. Ceria is an inorganic particle that can be ground and filtered to a specific particle size range. The very irregular shape or porosity and low cost of cerium oxide make it a common matting agent. "Other possible matting agents may include: L other ceramics such as borides, nitrides, carbides and other oxides (eg, alumina, titanium oxide, etc.); and cerium. Organic particles, provided that the organic particles are capable of withstanding treatment The temperature at which the polyimine is chemically converted (the treatment temperature is from about 250 ° C to about 550 t, depending on the particular polyimine procedure selected). It can be used as a matting agent for polyimine applications (acceptable poly The thermal condition for the synthesis of the quinone imine is a polyimine particle. The amount, median particle size and density of the matting agent must be sufficient to produce the desired 6-degree gloss value. In some embodiments, the base film is 6 The gloss value is between and optionally includes any of the following: 2, 5, 1〇, 15, 2〇, 25, 3〇 and 154225.doc

S -20· 201233548 35. In certain embodiments, the base film has a 60 degree gloss value of from 1 〇 to 35. In certain κ embodiments, the amount of shai matting agent is present and optionally includes any of the following: 1.6, 2, 3, 4, 5, 6, 7, 8, 9 of the base film 10 weight percent. In certain embodiments, the matting agent has a median particle size between and optionally includes any of the following: 丨3, 2, 34, 5, 6, 7, 8, 9, and 10 microns "The matting agent The particles should have an average particle size of less than (or equal to) about 10 microns and greater than (or equal to) about 13 microns. Larger matting agent particles can have a negative impact on the mechanical properties of the final base film. In certain embodiments, the matting agent has a density between and optionally includes any of the following: 2, 3, 4, and 4.5 g/cc. In some embodiments, when the amount of the matting agent is less than 0.6% by weight of the base film, even if the matting agent median particle size and density are in a desired range, the desired degree cannot be achieved. Gloss value. In some embodiments, ' when the median particle size is below Μmicron, even if the amount and density of the matting agent are in the desired range, the & method achieves the desired 60 degree gloss value. In certain embodiments, the matting agent is selected from the group consisting of cerium oxide, aluminum oxide, barium sulfate, and mixtures thereof. The base film can be prepared by any of the methods known in the art for producing chemically converted and filled polyimine. In such embodiments, a slurry comprising a low conductivity carbon black and a matting agent are prepared. The slurries may or may not be ground (using a ball mill) to achieve the desired particle size. The slurries may or may not be crucible to remove any remaining large particles. The polyamine liquid can be dreamed by methods well known in the art. The poly-aramidic acid solution may or may not be filtered. In some embodiments, the solution is mixed with the low conductivity carbon black body and the extinction i54225.doc -21·201233548 agent slurry. When the polyamic acid solution is produced under conditions of a slight excess of diamine, then an additional dianhydride solution may or may not be added to increase the viscosity of the mixture to the desired extent of the film mold. The amount of the polyamic acid solution, the low conductivity carbon black slurry and the matting agent slurry can be adjusted to achieve the desired loading level in the cured base film. In certain embodiments, the mixture is cooled to below 〇 c and mixed with the conversion chemistry and then conditioned to a heated rotating drum or belt to produce a partially yttrium-imided film. The film can be peeled off from the drum or belt, placed on a tent frame, and cured in an oven using convection and radiation heat to remove the solvent and complete the oxime imidization to greater than 98% solids. Adhesive In some embodiments, the base film is a multilayer film and comprises the base film and an adhesive layer. The adhesive layer is adjacent to and in direct contact with the base film. The base film of the present invention may comprise an adhesive layer to maintain the base film in position when the base film is applied. In one embodiment, the adhesive consists of an epoxy resin and a hardener, and optionally further contains additional components such as an elastomer, a hardening accelerator (catalyst), a hardener, a filler, and a flame retardant. . In some embodiments, the adhesive is an epoxy resin. In one embodiment, the epoxy resin is selected from the group consisting of: bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, biphenyl type Epoxy resin, biphenyl aryl-based epoxy resin, 154225.doc

S -22* 201233548 Aralkyl-based epoxy resin, cyclopentadiene epoxy resin' polyfunctional epoxy resin, naphthalene epoxy resin, rubber modified epoxy resin and mixtures thereof. , δ 玄 adhesive is epoxy resin, and is selected from

~q > coat rolling rouge compound. In another embodiment, a phenolic A type epoxy resin, in some embodiments, the epoxy adhesive comprises a hardener. In the example, the a-binder is a phenolic compound. In certain embodiments, the compound is selected from the group consisting of: ', novolac type phenol resin, aralkyl type phenol resin, biphenyl aryl-based resin, polyfunctional A phenol resin, a nitrogen-containing phenol resin, a bicyclononadiene type phenol resin, a phosphorus-containing phenol resin, and a triazine phenol phenol resin. In another embodiment, the hardener is an aromatic diamine compound. , #• Stay some of the examples, the aromatic diamine compound is a diaminobiphenyl compound. In some embodiments of 154225.doc -23- 201233548, the diaminobiphenyl compound is 4,4'-diaminobiphenyl or 4,4'-diamino 2,2'-didecyl. Biphenyl. In certain embodiments, the aromatic diamine compound is a diaminodipheny lalkane compound. In certain embodiments, the diaminodiphenylalkane compound is 4,4,diaminodiphenylnonane or 4,4,-diaminodiphenylethane. In certain embodiments, the aromatic diamine compound is a diaminodiphenyl ether compound. In certain embodiments, the diaminodiphenyl ether compound is 4,4,diaminodiphenylether or di(aminoamine-3-ethylphenyl)ether. In certain embodiments, the aromatic diamine compound is a diaminodiphenyl sulfide compound. In certain embodiments, the diaminodiphenyl sulfide compound is 4,4,-diaminodiphenyl sulfide or bis(4-amino-3-propyl phenyl) sulfide. In certain embodiments, the aromatic diamine compound is a diaminodiphenyl sulfonate. In certain embodiments, the diaminodiphenyl sulfone compound is 4,4,-:aminodiphenyl stone or bis(4.amino-3-phenylisopropyl) hard. In some solid examples, the aromatic diamine compound is a phenylenediamine. In one embodiment, the hardener is an amine compound. In this case, in some poor practices, the amine compound is hydrazine. In certain embodiments, the hydrazine is dicyanamide - DICY). In another embodiment, the compound of (d) is (iv) in some embodiments, the aliphatic 隹 隹 一 amine is ethylenediamine or diethylenediamine » In some embodiments, Yin, ancient Xuan child flute &;#衣氧粘剂 Contains a catalyst. In some embodiments, the catalyst is selected from the group consisting of a taste saliva, a three-ton type, a 2-ethyl group, a tri-type, and a mixture thereof. In % of the examples, the epoxy doting agent contains an elastomeric agent. At 154225.doc

• 24· 201233548 In certain embodiments, the elastic toughening agent is selected from the group consisting of ethylene-propylene rubber, acrylonitrile-butadiene rubber, carboxy terminated acrylonitrile-butadiene rubber, and mixtures thereof. The group that makes up. In certain embodiments, the epoxy adhesive contains a flame retardant. In certain embodiments, the flame retardant is selected from the group consisting of aluminum trihydroxide, melamine polyphosphate, concentrated poly-salt ester, other flame retardants, and mixtures thereof. Group of. In certain embodiments, the adhesive layer is selected from the group consisting of: polyimine, butyral phenolic, polyoxyalkylene, polyamidoxane, fluorinated Ethylene propylene copolymer, perfluoroalkoxy copolymer, ethylene vinyl acetate copolymer, ethylene vinyl acetate glyceryl acrylate "ethylene vinyl acetate glycidyl acrylate terpolymer" (ethylene vinyl acetate glycidyl methacrylate terpolymer) ethylene alkyl acrylate copolymer and adhesion promoter, ethylene methacrylate Alkyl ester copolymers and adhesion promoters, glycidyl methacrylate, 154225.doc -25- 201233548 ethylene glycidyl methacrylate, ethylene alkyl acrylate glycidyl acrylate triester, vinyl Alkyl acrylate acrylate glycidyl ester tri copolymer, ethylene alkyl acrylate maleic anhydride tri copolymer, Alkenyl methacrylate maleic anhydride tri copolymer, ethylene alkyl acrylate, glycidyl methacrylate tri copolymer, ethylene alkyl methacrylate, glycidyl acrylate, triacrylate, acrylic acid Acrylic acrylonitrile triacrylate copolymer, acrylonitrile acrylonitrile methacrylate triester, ethylene acrylate copolymer including salt thereof, ethylene methacrylic acid copolymer including salt, acrylic acid Alkyl ester acrylonitrile glycidyl methacrylate tri copolymer, alkyl methacrylate acrylonitrile glycidyl methacrylate tri copolymer, alkyl acrylate acrylonitrile glycidyl acrylate triester, methacrylic acid Alkyl ester acrylonitrile glycidyl acrylate tri copolymer, polyvinyl butyral, ethylene methacrylate methacrylic acid tri copolymer and its salt, ethylene thiol acrylate acrylate methacrylate And its salt, ethylene alkyl acrylate triacrylate and its salt, ethylene alkyl methacrylate acrylic copolymer and its salt, ethylene hydrogen maleate Ethyl ethyl hydr〇gen maleat, 154225.doc -26, s 201233548 ethylene acrylate alkyl ester hydrogen maleate, ethylene alkyl methacrylate hydrogen maleate, And mixtures thereof. In certain embodiments, the multilayer film is a cover film. Although the base film of the present invention can be used for covering applications, a chemically converted polyimine (wherein the chemically converted polyimine is capable of converting polylysine into a poly by mixing a polyamic acid solution The catalyst and/or dehydrating agent of the quinone imine, or the step of casting or extruding the polyglycolic acid into a mixture or solution of one of the catalyst and/or dehydrating agent, is beneficial for filling with any type of filler. Polyimine film. US 5,166,308 to Kreuz et al. discloses an aromatic copolymerized polyimide film having a modulus of elasticity of 6 to 12 Kpsi, a coefficient of thermal expansion of 5 to 25 ppm/t > c, 2 to ppm. /% RH has a coefficient of hygroscopic expansion, a water absorption of less than 3 % at 1% RH, and a copolymerization ratio of the same copolymerized polyimide film which is larger than that obtained by a thermal conversion procedure using the same time and temperature conditions. The rate of surnames is not excessive, and Kreuz et al. did not disclose the addition of fillers to the polyimide film. Despite the high solvent content, the film produced by the chemical conversion process has a self-supporting effect. It is believed that the use of a film with so many liquids that must be removed 'any filler will migrate with the removal of a large amount of liquid, or even with the solvent - from the film. If the polyimine rubber filler does not migrate with the removal of the solvent, the film will have a tendency to curl. What is needed is a homogenous dispersion. Therefore, the chemical conversion of Xianxin will not occur and there will be enough to fill the polyimine of the homogenous dispersion throughout the properties of the film. Therefore, Kreuz et al. did not intend to use a large amount of filler. Unexpectedly, 154225.doc •27-201233548, the chemically converted polyimine film is not as brittle as the polyimide film prepared by thermal conversion with the same filler, and can be chemically converted. A more uniform filler dispersion is achieved. Figure 1 is a transmission electron micrograph of a cross section of a three-layer thermally converted polyimine film containing 20% by weight of fucecj oxide, which can be obtained Since I. du Pont de Nemours and Company, Wilmington, DE. Figure 2 is a transmission electron micrograph of a cross-section of a single layer of chemically converted PMDA/4,4-ODA with 13% by weight of fumed alumina. A more uniform dispersion of the polyimide film produced by thermal conversion as shown in Figure 。. In certain embodiments, in addition to carbon black or pigment, the filler that can be used in the polyimide film produced by chemical conversion is selected from the group consisting of talc, titanium dioxide, acicular titanium dioxide, zinc oxide, boron nitride, A group consisting of cerium oxide, gas phase cerium oxide, aluminum oxide, gas phase alumina, sepiolite, apatite, and mixtures thereof. The choice of filler depends on the desired use of the polyimide film. For example, boron nitride can be added to increase the thermal conductivity of the polyimide film. The more boron nitride added, the greater the thermal conductivity of the polyimide film. In certain embodiments, the filler is a thermally conductive filler. In another embodiment the filler is a dielectric filler. In another embodiment, the filler is a conductive filler. In some specific examples, the filler may be any amount of filler that can be included in the polythene oxide film which can be used for the polythene imine. When the denier exceeds this amount, the filled polyimine film becomes difficult to handle due to the brittleness of the film. In certain embodiments, when the filler is selected from the group consisting of talc, dioxide, oxidized, acicular titanium dioxide, oxidized, boron nitride, 154225.doc

S -28- 201233548 When the group consisting of sulphur dioxide, gas phase sulphur dioxide, oxidation, gas phase oxidation, dream limestone and its mixture, the packing up to 9 ^ knife ratio can be low. Conductive carbon black or pigment to replace. The thinner the I-polyimine film, the more difficult it is to fill the film without making the film brittle. To overcome this problem, a three-layer film is typically fabricated. : New fill, while the inner (core) layer is unfilled or contains less than 5 parts by weight of filler. The core layer allows the multilayer film to maintain acceptable mechanical properties. When chemical conversion is used, it can be made into a yttrium film filled with an early layer, and it still has good mechanical properties. An additional advantage of chemical conversion is that a single layer of filled polyimide film produced by chemical conversion can produce a thinner film than can be produced by thermal conversion. In certain embodiments, the base comprises a chemically converted polyamidiamine in an amount from 40 to 90 weight percent of the base; a filler (or a mixture of fillers) in an amount from 10 to 60 of the base film Percent by weight, and wherein the thickness of the base film is from 8 to 152 microns. The lightly chemically converted polynitrite is derived from an aromatic dianhydride having a total of at least 50 mole percent based on the total amount of the two needles of the polyimine, and at least 5 G calculated based on the total amine of one of the polyimine The percentage of the ear is the family diamine. In another example - the base film comprises - chemically converted (four) practice, the amount from the base film:: 〇 to 90% by weight; a filler (or a mixture of fillers), which is from the base film U) to 5G Percent by weight, and wherein the thickness of the base film is from 8 to 76 microns. (d) 彳t Description 'All parts and percentages of the following examples are by weight. EXAMPLES 154225.doc 29. 201233548 The invention will be further described in the following examples, which are not intended to be limited to the scope of the invention described in the claims. Optical density was measured on a Macbeth TD904 optical densitometer. The logger is an average of 5 to 10 individual measurements. The 60-degree gloss value is based on the Micro-TRI-Gloss gloss meter (Gardner USA,

Columbia, MD) measured. The record is the average of 5 to 1 individual measurements. The surface resistivity was measured using an Advantest Model R8340 ultra-high resistance meter and a UR-type concentric ring probe at 1000 volts. The loggers are the average of 3 to 5 individual measurements. The dielectric strength was measured using a Beckman Industrial AC Dielectric Breakdown Tester in accordance with ASTM D149. The loggers are the average of 5 to 1 各 individual measurements. The median particle size was measured using a Horiba LA-930 particle size analyzer.

Horiba, Instruments, Inc., Irvine CA. DMAC (dimethylacetamide) is used as a carrier fluid. When a continuous film casting procedure is used to produce a sample, an ashing procedure is used to determine the amount of matting agent in the film. The film was heated and ashed at 900 ° C in an oven to burn off all of the polymer and low conductivity carbon black leaving only the white matting agent residue. The weight before and after ashing was compared to show the amount of matting agent contained in the film. The polystyrene viscosity measurement was performed on a Brookfield Programmable DV-II + viscometer using rV/HA/HB #7 spindle or LV #5 spindle. The viscometer speed is varied from 5 to 100 rpm to provide an acceptable amount of 54225.doc, 3〇.

S 201233548 The ratio of torque values. The readings were temperature corrected to 25 °C. Tensile properties were measured according to ASTM D-882-91, Method A. The specimen size is 25 mm X 150 mm; the jaws are separated by 100 mm; the jaw speed is 50 mm/min. 100CR is a three-layer, thermally converted polyimine film containing 20% by weight of gas phase oxidation. Available from E. I. du Pont de Nemours and Company, Wilmington, DE. Examples 1 through 5 show that chemical conversion achieves a low 60 degree gloss value (matte appearance) and high dielectric strength on both sides of the base film at low levels of matting agent. Example 1 A carbon black slurry was prepared from 80 weight percent DMAC, 10 weight percent polyglycolic acid prepolymer solution (20.6 weight percent polyglycolic acid solids in DMAC) and 10 weight percent low conductivity carbon Black powder (Special Black 4, available from Evonik Degussa). The ingredients are thoroughly mixed in a rotor stator high speed dispersion mill. The slurry is then processed in a ball mill to disperse any large binder and achieve the desired particle size. The slurry had a median particle size of 0.3 microns. A cerium oxide slurry was prepared from 75.4 weight percent DMAC, 9.6 weight percent poly phthalic acid prepolymer solution (20.6 weight percent polyglycolic acid solids in DMAC) and 15.0 weight percent cerium oxide powder ( Syloid® C 803, available from WR Grace Co.). The ingredients are thoroughly mixed in a high shear rotor stator type mixer. The median particle size is from 3.3 to 3.6 microns. Mix 16_4 kg of this carbon black slurry with 158 kg of PMDA/4,4 ODA prepolymerized 154225.doc -31- 201233548 solution (20.6 weight percent polyglycolic acid solid, about 50 poise viscosity) mixed with 50 Gallon (189.3 liters) in the tank. The tank is equipped with three independently controlled agitator shafts: a low speed anchor mixer, a high speed disc disperser and a high shear rotor stator emulsifier. The mixture was "finished" by adding and incrementally mixing about 7 kg. of a 5.8 weight percent PMDA solution in DMAC to increase molecular weight and viscosity to about 3,000 poise. The speed of the anchor mixer, disperser and emulsifier can be adjusted as necessary to ensure efficient mixing and dispersion without excessive heating of the mixture. By passing the cooled ethylene glycol through the jacket of the mixing tank, The temperature of the mixture is further adjusted. The completion solution was filtered through a 2 〇 micron filter' and vacuum degassed to remove the enclosed air. The monoxide system is metered into the metered stream of the finished polymer/carbon black mixture and thoroughly mixed using a high shear rotor tweezers. The combined liquid stream is cooled to about 6 C, and the conversion chemical acetic anhydride (〇 14 cm 3 /cm 3 polymer solution) and pyridinium (〇·15 cm 3 /cm 3 polymer solution) are metered into and mixed. And the film was cast to a hot rotating drum of 90 ° C using a slit die. The resulting film is peeled from the drum and conveyed to a tenter oven, wherein the film is dried using convection and radiant heat and solidified to a greater extent than solids. The base film contained 5 wt% of carbon black and 35 wt% of bismuth dioxide. The results are not shown in Table 1. Tensile strength and elongation at break are shown in Table 3. Example 2 154225.doc

S -32· 201233548 Preparation of an alumina slurry consisting of 41.7 weight percent DMAC, 23.3 weight percent polylysine prepolymer solution (20.6 weight percent polyglycolic acid solids in DMAC) and 3 5.0 weight percent The Avalan alumina powder (with a median particle size of about 2.2 microns) is composed. The ingredients are thoroughly mixed in a rotor stator high speed dispersion mill. The alumina slurry was metered into the cooled (-7 ° C.) metering stream of the Example 1 completed polymer/carbon black mixture along with the conversion chemistry and using essentially the same procedure as in Example 1. To mold and cure polyimine film. The resulting base film contained 5 weight percent carbon black and 7 weight percent alumina. The results are not in Table 1. Example 3 A carbon black and cerium oxide slurry system was prepared as in Example 1. The slurry system is mixed with a PMDA/4,4 ODA prepolymer solution (20.6 weight percent polyglycolic acid solid, about 50 poise viscosity) in an amount to produce 5 weight percent carbon black on the cured film basis. 2 weight percent of cerium oxide. The mixture was prepared by metering a 6 weight percent pMDA solution in DMAC and mixing at the same time to achieve a final viscosity of about U 5 Torr. The finished polymer mixture was degassed by vacuum. The /I D mixture was manually cast using a stainless steel mold bar on (4) glyme terephthalate W attached to a glass plate. The Myl_poly-p-citric acid ethylene glycol ester sheet containing the wet cast film was immersed in a bath consisting of a mixture of 3 bismuth and a 5G/5G mixture. The bath was gently mixed for 3 to 4 minutes of 昧pq '曰' to initiate the ruthenium iodization and gelation of the film. The gel 154225.doc •33·201233548 film was peeled off from the Mylar® polyethylene terephthalate sheet and placed on a plug frame to limit the film and prevent shrinkage. After the residual solvent was discharged from the film, the plug containing the film was placed at 12 Torr. Hey. In the oven. The oven temperature was raised to 32 Torr over a period of 60 to 75 minutes. (:, held at 320 ° C for 10 minutes) and then transferred to a 400 ° C oven and held for 5 minutes, after which it was removed from the oven and allowed to cool. The results are shown in Table 1. Example 4 The film system was prepared as in Example 3 and had 3 weight percent of sulphur dioxide on the basis of the cured film. The results are shown in Table 1. Example 5 Preparation of a carbon black slurry as in Example 1. Preparation of a synthetic barium sulfate (Blanc Fixe F, from Sachtleben Chemie GmbH) a polymer consisting of 51.7 weight percent DMAC, 24.1 weight percent prepolymer solution (2 〇 6 weight percent polyglycolic acid solids in DMAC) and 24.1 weight percent barium sulfate powder The composition "completely mixes the ingredients in a high shear rotor stator type mixer. The median diameter is 1.3 microns. The pulp system is 卩]\/1〇8/4,4|〇〇八聚酿An amine acid solution (20.6 weight percent polyglycolic acid solid, about 50 poise viscosity) was mixed in an amount to produce 7 weight percent carbon black and 1 weight percent barium sulfate on a cured film basis. By adding 6 weights in the DMAC incrementally The percentage of PMDA solution was completed by simultaneous mixing to achieve a final viscosity of about 2400 poise. The finished polymer mixture was vacuum degassed. -34- 154225.doc

S 201233548 The polymer mixture was cast on Mylar® polyethylene terephthalate sheet and chemically ruminated and cured as described in Example 3. The results are shown in Table 1. Comparative Example 1 Comparative Example 1 shows the same amount of matting agent as in Example 5 for thermal conversion, producing a high (unwanted) 60 degree gloss value and a low dielectric strength on both sides of the base film. Preparation of slave black polymer such as Example 1. A synthetic sulfuric acid lock (Blanc Fixe F' from Sachtleben Chemie GmbH) slurry was prepared from 51-7 weight percent DMAC, 24.1 weight percent polylysine prepolymer solution (20.6 weight percent polylysine solids in dmaC) Medium) consists of 24.1 weight percent barium sulfate powder. The ingredients are thoroughly mixed in a high shear rotor stator type mixer. The median particle size is 13 microns. These systems are mixed with PMDA/4,4, ODA prepolymer solution (20.6 weight percent polyglycolic acid solids, viscosity of about 5 Torr) in an amount of 7 weight percent based on the cured film. The carbon black and barium weight percent of barium sulfate. The mixture was completed by incrementally adding a 6 weight percent PMDA solution in DMAC and mixing at the same time to achieve a final viscosity of about 150,000 poise. The finished polymer mixture was degassed by vacuum. The film was manually cast onto a glass plate using a stainless steel mold bar. The glass plate containing the wet cast film was placed on a hot plate and placed at 8 to 100 C for 30 to 45 minutes to form a partially dried and partially yttrium-immobilized green crucible. The green film was peeled off from the glass plate and placed on the frame. The frame containing the green film was placed in a K12 (rc oven. The temperature of the oven 154225.doc • 35-201233548 was raised to 32 〇t in the period of 60 to 75 minutes at 32 〇. <: holding temperature After 10 minutes, it was transferred to a 400 ° C oven and held for 5 minutes, after which it was removed from the oven and allowed to cool. The results are shown in Table 1. Comparative Example 2 Comparative Example 2 is shown at 4 weight percent The matting dose is thermally converted to produce a high (unwanted) 6-degree gloss value on both sides of the base film, and has a low dielectric strength. The carbon black and cerium oxide slurry system is prepared as an example. Mix with PMDA/4,4' ODA prepolymer solution (2 6% viscous solids viscosity of about 50 poise) in an amount to produce 5 weight percent carbon black and 4 on the cured film basis Percent by weight of cerium oxide. The mixture is completed by incrementally adding 6 weight percent of PMDA solution in DMAC and mixing at the same time to achieve a final viscosity of about 225 Torr. The finished polymer mixture is passed through. Vacuum degassing. Use stainless steel cast rods to apply the film manually The glass plate containing the wet cast film was placed on a hot plate' and placed at 80 to loot for 30 to 45 minutes to form a "green" film which was dried and partially yttrium. The green film is peeled off from the glass plate and placed on the plug frame. The plug frame containing the green film is placed in a 120 C supply box. The oven temperature is raised to 6 to 75 minutes to 320C 'temperature held at 320 C for 10 minutes' and then transferred to a 4 ° ° oven and held for 5 minutes, after which it was removed from the oven and allowed to cool. The results are shown in Table 1. Comparative Example 3 154225. Doc

S •36· 201233548 shows that the thermal conversion requires a high amount of matting agent to produce a low 60 degree light thickness value (/Shaw light appearance) on the air side, but has an undesired (10) degree gloss value. On the other (non-air) side. A carbon black slurry was prepared as in Example 1. Preparation of oxidized homopolymer, which consists of 51.72 liters of DMAC, 24.14% by weight of polyaminic acid prepolymer solution (20.6 weight percent polyglycolic acid solid in dmac) and Agra Oxidized powder (median particle size of about 2.3 microns), and these components are completely mixed in the rotor stator high speed dispersion mill. The body is then added to the ball mill to break up the large cohesive mass. The carbon black is oxidized to remove any residual large particles or cohesive polymers. PMDA/4,4,〇DA prepolymer solution (20.6% polyglycolic acid solid, about 5 Torr) by mixing with 5.8 wt% PMDA solution in DMAC in a high shear mixer Viscosity) "Complete" to add molecular weight and viscosity to about 1500 poise. The completed solution is filtered and mixed with the low conductivity carbon black and alumina slurry in a high shear mixer, along with additional PMDA completion solution, and a small amount of stripping agent (which causes the cast green film) Can be easily stripped from the mold belt). The amount of the pMDA completion solution was adjusted to achieve a viscosity of 1200 poise. The polymer, slurry and the completion solution can be adjusted to achieve the desired loading of carbon black and alumina, as well as the pressure in the mold. The finished polymer/slurry mixture is forced through a filter and to a slot die where the liquid stream is split to form an outer layer of a three layer coextruded film. The second stream of PMDA/4,4 ODA prepolymer polymer solution is completed 154225.doc -37-201233548 in a shear mixer to achieve a viscosity of 500 poise, and is passed through the filter and to the casting In the mold, an intermediate non-filled polyimine core layer of a three-layer co-extruded film is formed. The flow rate of the outer layer of 6 kel and the solution of the unfilled polyimine core layer is adjusted to achieve the desired layer thickness. A three-layer co-extruded film was produced by casting the above assembly from the slit die onto a moving stainless steel belt. The tape is passed through a convection oven to evaporate the bath and partially iridize the polymer to produce a "green" film. The green film solid (which was heated to 300 t: and its weight loss was measured) was 72 6%. The green film was peeled off from the tantalum mold tape and wound up. The green film is then passed through a tenter oven to produce a cured polyimide film. The film is restrained at the edge by the film during the tentering process to control shrinkage. The solidification degree of the cured film (heating it to 300 ° C and measuring its weight loss) was 98.8% » The intermediate unfilled layer contained a total thickness of 33% or 1/3 of the multilayer film and the outer layer contained an equal thickness Alumina and low conductivity carbon black. The outer layer contained 7 weight percent of low conductivity carbon black and 3 weight percent of aluminum oxide. The total film thickness is 0.49 mils. The results are not in Table 1. Tensile strength and elongation at break are shown in Table 3. Comparative Examples 4 and 5 show that some amount of matting agent is required to achieve a low 6-degree gloss value (matting appearance) on both sides of the base film, and further exhibiting a matting agent having a particle size of less than 13 μm produces a glossy base film. Comparative Example 4 A carbon black slurry system having a median diameter of 0.3 μm was prepared as in Example 1. The slurry system is mixed with PMDA/4,4, ODA prepolymer solution (2〇·6% poly lysine 154225.doc •38· 201233548 solid, viscosity of about 50 poise), the amount of which can be 7 weight percent of carbon black was produced on the basis of the cured film. The mixture was completed by incrementally adding a 6 weight percent PMDA solution in DMAC and mixing simultaneously to achieve a final viscosity of about 1900 poise. The finished polymer mixture was degassed by vacuum. The polymer mixture was cast onto Mylar® polyethylene terephthalate sheets and chemically imidized and cured as described in Example 3. The results are shown in Table 1. Comparative Example 5 The metered liquid stream _ of the completed polyglycine/3⁄4 black mixture was metered into an additional carbon black slurry to increase the carbon black content to 7 weight percent based on the cured film. 'And the two streams are thoroughly mixed using a high shear rotor stator mixer. The base film system which was chemically imidized was produced as described in Example 1. The results are shown in Table 1. Comparative Example 6 Comparative Example 6 shows that when chemical conversion using 30% by weight of BaS04 was carried out, Example 5, which was chemically converted using 10% by weight of BaS?4, did show a decrease in dielectric strength as expected. Surprisingly, however, the chemical conversion was carried out using 30 weight percent of BaS04, which resulted in a higher dielectric strength than Comparative Example 1 which used 10% by weight of BaS04 for thermal conversion. A carbon black slurry was prepared as in Example 1. A synthetic barium sulfate (Blanc Fixe F, from Sachtleben Chemie GmbH) slurry was prepared from 51 7 weight percent 154225.doc •39·201233548 ratio DMAC, 24.1 weight percent prepolymer solution (20.6 weight percent poly The proline acid solids were in DMAC and consisted of 24.1 weight percent barium sulfate powder. The ingredients are thoroughly mixed in a high shear rotor stator type mixer. The median particle size is 1.3 microns. The pulp systems were mixed with a PMDA/4,4' ODA polyaminic acid solution (20.6 weight percent polyglycolic acid solid, about 50 poise viscosity) in an amount of 7 weight percent based on the cured film. Carbon black with 30 weight percent barium sulfate. The mixture was completed by incrementally adding a 6 weight percent PMDA solution in DMAC while mixing to achieve a final viscosity of about 2400 poise. The finished polymer mixture was degassed by vacuum. The polymer mixture was cast on a Mylar® polyethylene terephthalate sheet and chemically imidized and cured as described in Example 3. The results are shown in Table 1. Examples 6 through 7 show that using a lower amount of matting agent and chemical conversion, a low 60 degree gloss value (matte appearance) and high dielectric strength can still be achieved on both sides of the base film. Example 6 A chemically yttrium-imided black polyimine-based film system was prepared as in Example 1, except that the metered flow rate of the cerium oxide slurry was reduced by 37°/. . According to the ash analysis, the base film contained 2.2% by weight of cerium oxide. The results are shown in Table 1. Tensile strength and elongation at break are shown in Table 3. Example 7 A carbon black and cerium oxide slurry system was prepared as in Example 1. By high shear mixing 154225.doc • 40-

S 201233548 combiner with 5.8 wt% PMDA solution in DMAC, and make PMDA/4,4' ODA prepolymer solution (20.6% polyamic acid solid, viscosity about 50 poise) "complete" To increase molecular weight and viscosity to about 25 00 poise. The metered liquid stream of the completed polyamic acid solution is cooled to about 1 〇 C. The conversion chemical needle (0.18 cm3/cm3 polymer solution) was cooled in the same manner as the metered solution of 3-methylpyridine (0.17 cm3/cm3 polymer solution), along with carbon black (0.095 cm3/cm3 polymer solution) and A metered stream of cerium oxide slurry (0.029 cm3/cm3 polymer solution) was mixed into the polyamic acid solution in a high shear mixer. The cooled mixture was filtered and immediately cast into a film on a hot rotating drum at 10 °C using a slit die. The resulting film was peeled from the drum and conveyed to a tenter oven wherein the film was dried using convection and radiant heat and solidified to a degree of solids greater than 98%. The base film contains about 5.5 weight percent carbon black. According to the ash analysis, the base film contained 1.8% by weight of cerium oxide. The results are shown in Table 1. Tensile strength and elongation at break are shown in Table 3. Example 8 A carbon black slurry system was prepared as in Example 丨. The alumina slurry system was prepared as in Comparative Example 3. The slurry systems are mixed with PMDA/4,4, 〇DA prepolymer solution (2〇6% polyamic acid solid, about 50 poise viscosity) in an amount of 5 weights on the cured film basis. Percentage of carbon black with 1% by weight of cerium oxide. The mixture was completed by incrementally adding 6 weight percent of the PMDA solution in the DMAC and mixing at the same time to achieve a final viscosity of 190 poise and 5 liters of the finished polymer mixture was vacuum degassed. The 154225.doc •41 - 201233548 polymer blend was aged on My lar® polyethylene terephthalate tablets and chemically amided and cured as described in Example 3. The results are not in Table 1. Comparative Example 7 Comparative Example 7 shows thermal conversion using the same matting dose as used in Example 8, producing high (unwanted) 6-degree gloss values on both sides of the base film, and having a low dielectric strength. A carbon black slurry system was prepared as in Example 1. Alumina slurry system preparation as in Comparative Example 3 » The slurry systems were mixed with PMda/4,4, 〇DA prepolymer solution (20.6% polyamic acid solids 'about 50 poise viscosity), the amount of which was 5 parts by weight of carbon black and 10% by weight of silica dioxide were produced on the basis of the cured film. The mixture was completed by incrementally adding 6 weight percent of PMDA solution in DMAC and mixing at the same time to achieve a final viscosity of about 1900 poise. The finished polymer mixture was degassed by vacuum. The film was cast and heat-imided as described in Comparative Example 2. The results are not in Table 1. Comparative Examples 8 and 9 show that a matting dose of more than 15 weight percent is required to achieve a low 6 twist gloss value (matte appearance) on both sides of the base film. Comparative Example 8 This base film was prepared as in Example 3, and had 1 weight percent of cerium oxide based on the cured film. The results are not in Table 1. Comparative Example 9 This base film was prepared as in Example 3 and had i 5 154225.doc on the basis of the cured film.

S -42· 201233548 Percent by weight of cerium oxide. The results are shown in Table 1. It is shown that the median particle size of the matting agent has a lower limit than that of the fathers 10 and 11 to achieve a low 60 degree gloss value. Comparative Example 10 A carbon black slurry was prepared as in Example 1. An alumina slurry was prepared from 8 丨 4 weight percent DMAC, 8.3 weight percent pmda/BPDA//4, 4'-ODA/PPD prepolymer solution (14.5 weight percent polyglycolic acid solids in DMAC), 0.1% by weight of the dispersant was composed of 1% by weight of fumed alumina powder. The ingredients were thoroughly mixed in a rotor stator high speed dispersion mill. The slurry was then processed in a media mill to break up the large cohesive mass and achieve a median particle size of about 0.35 μιη. The slurry systems are mixed with a PMDA/4,4 ODA prepolymer solution (20-6% polyamic acid solid, about 5 Torr) in an amount to produce 5 weight percent carbon black on a cured film basis. With 2 weight percent alumina. The mixture was completed by incrementally adding a 6 weight percent PMDA solution in DMAC while mixing to achieve a final viscosity of about 21 50 poise. The finished polymer mixture was degassed by vacuum. The polymer mixture was cast on Mylar® polyethylene terephthalate sheet and chemically ruminated and cured as described in Example 3. The results are shown in Table 1. Comparative Example 11 An anhydrous calcium hydrogen phosphate (CaHP〇4) slurry was prepared, which consisted of 11.5 weight percent of calcium hydrogen phosphate, 64.7 weight percent of a polyamido acid prepolymer solution 154225.doc -43·201233548 (20.6 weight percent The polyglycolic acid solids were composed in DMAC with 23.8 weight percent DMAC. These ingredients are thoroughly mixed in a high shear rotor stator type mixer. The order particle size is 1,25 microns. The calcium hydrogen phosphate slurry system is metered into and mixed with the cooled (-8 ° C) metered liquid stream of the completed Example 1 polymer/carbon black mixture, along with the conversion chemical, and used substantially as in Example 1. The procedure casts and cures the polyimide film. The resulting base film contained 5 weight percent carbon black and 2.8 weight percent calcium hydrogen phosphate. The results are shown in Table 1. Comparative Example 12 Comparative Example 12 shows that a high density matting agent produces a high (unwanted) 60 degree gloss value on both sides of the base film. Preparation of a carbon black slurry as in Example 1 ^Preparation of a titanate lock (Sakai, BT-05) slurry from 75 weight percent, 1 weight percent polyphosphoric acid prepolymer solution (20.6 weight percent polyamine) The acid solid is in dmaC) and 15% by weight of barium titanate powder. The ingredients were thoroughly mixed in a tantalum shear rotor stator type mixer and then sonicated to a median particle size of 15 microns. The pulp systems are mixed with a PMDA/4,4, 〇DA prepolymer solution (20.6% of a polyamidamine S-solids viscosity of about 5 〇$) in an amount of 5 weights on a cured film basis. Percentage of carbon black with 2 weight percent barium titanate. The mixture was completed by incrementally adding 6 weight percent PMDA solution in DMAC and mixing at the same time to achieve a final viscosity of about 0 poise. The polymer mixture was vacuum degassed. The polymer mixture 154225.doc 201233548 mixture was cast onto Mylar® polyethylene terephthalate sheets and chemically imidized and cured as described in Example 3. The results are shown in Table 1. Examples 9, 10 and 11 The base film was prepared as in Example 3 except that the amount of the cerium oxide slurry was adjusted to produce 5 weight percent, 7.5 weight percent, and 10 weight percent, respectively, based on the cured film. Ceria. The results are not in Table 1. Examples 12 and 13 The film system was prepared as in Example 1. The pulp system with? ] ^ 〇 8 / 4, 4 '00 eight prepolymer solution (20.63⁄4 polyamic acid solid, about 5 Torr viscosity) mixed in an amount of 5 weight percent carbon on the basis of the cured film Black with 22 weight percent cerium oxide. The mixture was completed, cast into a film, chemically imidized and cured as in Example 1. Conditions can be adjusted to produce a base film of 2 mils and 5 mils thick. The results are shown in Table 1. Examples 14 and 15 cerium oxide powder (Syloid® C 803) was treated in an air classifier to remove a portion of the largest particles. The bulk was prepared from the air classified cerium oxide as described in Example 1. The median particle diameter was 2.1 microns. The carbon black slurry system was prepared as in Example 1 ^ The carbon black and cerium oxide slurry system was mixed with PMDA/4,4 ODA prepolymer solution (20.6% polyamic acid solid, about 50 poise viscosity), and the amount was 5 weight percent carbon black and 2 weight percent and 4 weight percent 154225.doc -45·201233548 cerium oxide were produced on a cured film basis. The mixture was completed and the base film was prepared as in Example 3. The results are shown in Table 1. Example 16 Example 16 shows chemical conversion using different low conductivity carbon blacks, still achieving a low 60 degree gloss value (matte appearance) and high dielectric strength on both sides of the base film. A black pulp body was prepared which consisted of 80 weight percent DMAC, 10 weight percent prepolymer solution (20.6 weight percent polyglycolic acid solids in DMAC) and 1 weight percent of the tank and had 6% volatilization The content of carbon black (Printex U, from Evonik Degussa). These components are completely mixed in the rotor stator disperser. The slurry was then treated with an ultrasonic processor (Sonics & Materials, Inc., Model VCX-500) to deaggl〇merate the carbon black. The cerium oxide slurry system was prepared as in Example 1. The poly system is mixed with 卩]\40/4,4,00 eight prepolymer solution (20.6% polyamic acid solids 'about 50 poise viscosity), the amount of which can be based on the cured film 5 weight percent carbon black and 2 weight percent cerium oxide were produced. The mixture was completed by incrementally adding a 6 weight percent PMDA solution in DMAC while mixing to achieve a final viscosity of about 2250 poise. The procedure described in Example 3 was used to prepare the chemically imidized base film. The results are shown in Table 1. Comparative Example 13 Comparative Example 13 was not subjected to the same extinction dose as in Example 热6 for thermal transfer. 46-154225.doc

S 201233548 produces a high (unwanted) 60 degree gloss value and low dielectric strength on both sides of the base film. . The preparation system was prepared as in Example 16. Using a stainless steel mold bar, the finished mixture is manually cast onto a glass plate and will contain the '..., cast! The glass plate of the crucible was placed on a hot plate and placed at 80 to 1 C for 30 to 45 minutes to form a partially dried and partially pyriminated "green" film. The green film was peeled off from the glass plate and placed on a frame. The frame containing the 彔 film was placed in a 丨2〇 oven. The oven temperature was raised to 32 ° C for a period of (9) to 75 knives, held at 32 (TC for 10 minutes, then transferred to a 4 GG ° C box and held for 5 minutes, after which it was taken from The oven was removed and allowed to cool. The results are shown in Table 1. Example 17 Example 17 exhibited a low 6-degree gloss value on both sides of the base film without chemical conversion of different low-conductivity carbon blacks. The matte appearance) and the high dielectric strength. The base film was prepared as in Example 16 'except that the carbon black slurry system was prepared from Furnace Black' with a volatile content of 3.5% (Spedal Black 55〇 from Evonik Degussa) » Results The scheme is shown in Table 1. Comparative Example 14 Comparative Example 14 shows the same extinction dose as in Example 17 for thermal conversion 'produces high (unwanted) 6-degree gloss values on both sides of the base film and low dielectric 154225.doc •47· 201233548 The base film was prepared as in Comparative Example 13, except that the carbon black slurry system was prepared from Furnace Black with a volatile content of 3.5% (Special Black 550 from Evonik Degussa). The system is shown in Table 1. Example 18 Example 1 8 shows the use of different low pass Chemical conversion of carbon black can still achieve a low 60 degree gloss value (matte appearance) and high dielectric strength on both sides of the base film. The base film is prepared as in Example 16, except that the carbon black slurry system is prepared from the furnace. Black, which has a volatile content of 1.2% (Printex 55, derived from (10) to Degussa). The results are shown in Table 1. Comparative Example 15 Comparative Example 15 shows the same amount of matting as in Example ι8 for thermal conversion, A high (unwanted) 6-degree gloss value and a low dielectric strength were produced on both sides of the base film. The base film was prepared as in Comparative Example 13, except that the carbon black slurry system was prepared from Furnace Black, which had 1.2%. Volatile content (printex 55 from Evonik Degussa) ° The results are not shown in Table 1. Comparative Example 16 Comparative Example 16 shows that by using a high loading (3 重量% by weight) matting agent, thermal conversion can achieve the desired The 60 degree gloss value is on the air side of the base film but the other side of the base film has a high (unintended) 6 degree gloss value, and its 154225.doc

S •48- 201233548 Dielectric strength is low. The carbon black and cerium oxide slurry system was prepared as in Example 1. The slurry systems are mixed with a PMDA/4,4' ODA prepolymer solution (20.6% polyamic acid solid, about 4,500 poise viscosity) in an amount to produce 5 weight percent carbon on a cured film basis. Black with 30% by weight of cerium oxide. The mixture was adjusted to a viscosity of 300 poise by incrementally adding 6 wt% of the PMDA solution in the DMAC and mixing at the same time. The finished polymer mixture was degassed by vacuum. The film was manually cast onto a glass plate using a stainless steel mold bar. The glass plate containing the wet cast film was placed on a hot plate and placed at 80 to 1 Torr for 3 to 45 minutes to form a partially dried "green" film which was acid-imidized. The green film was peeled off from the glass plate and placed on the frame. Place the test frame containing the green film in the (4) generation box. The chamber temperature was raised to 32 generations over a period of 60 to 75 minutes, and was removed from the oven after 32 (TC held at 1 G minutes, then transferred to a 4 (four) oven and held at a temperature of 'clock' It was cooled. The results are shown in Table 1. 154225.doc -49- 201233548

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S 201233548 3-pyridinium consists of a mixture of 5〇/5〇 of acetic anhydride. The bath was gently stirred for a period of 3 to 4 minutes to initiate the hydrazine imidization and gelation of the film. The film was peeled off from the Mylar® polyethylene terephthalate sheet and placed on a plug frame to limit the film and prevent shrinkage. After the residual solvent was discharged from the film, the plug containing the film was placed in a 12-inch oven. The oven temperature was raised to 32 〇〇c over a period of 60 to 75 minutes, held at 32 Torr for ι min, then transferred to a 400 t oven and held for 5 minutes, after which it was baked from - Remove and let it cool. Based on the composition of the completed polymer mixture, the base film contained 25 weight percent cerium oxide and b weight percent pigment. The results are shown in Table 2. Comparative Example 17 was not thermally converted by the same matting dose as in Example 19, and a high (unwanted) (9) gloss value was produced on both sides of the base film. The degassed finished polymer mixture from Example 19 was manually cast onto a glass plate using a non-recorded steel casting bar. The glass plate containing the wet cast film was placed on a hot plate and placed at 8 to just t for a minute to a minute, and the crucible was formed into a partially dried and partially immated "green" crucible. The green film was peeled off from the glass plate and placed on the frame. The test frame containing the green film was placed in a 120 C flood. The temperature of the flood box is raised to 320 C in 60 to 75 minutes, held at 320 C for 1 minute, and then transferred to a 4 °c oven and held at a temperature of 5 minutes. It is then removed from the oven and allowed to cool. The results are shown in Table 2. 154225.doc -53· 201233548 v〇ά 卜ON ό CN ww stay 49.5 53.3 iTi 〇\ 丨H 畸 1 1 < Dielectric strength (V/mi 3792 3423 ON VO U^i 60 degree gloss to the air side 55.2 ί light agent density g / cc Γ " Ή < N CN matting agent D50 (micro | m) 3.3-3.6 3.3-3.6 isrf Ί Ί <N (N ah: s _ _ _ _ _ _ 3 ^ 蜩: i2 %% ^^ φ和进: .〇难: ON 〇 〇 154225.doc -54- s 201233548 It should be thought of 'not the above--the general description or the actions described in the examples are necessary, specific actions Part of it may not be necessary, and in addition to the actions described, the order in which the actions can be performed in other steps is not necessarily the order in which the actions must be followed. After studying this specification, the skilled artisan will be able to determine which actions are available for their particular needs or needs. In the foregoing description, the invention has been described by reference to specific embodiments. __like technical people can understand, not Various modifications and changes can be made in the present invention as described in the following claims. All the features disclosed in the present specification can be replaced with alternative features which can achieve the same, equivalent or similar purpose. Therefore, the present specification and drawings are to be regarded as illustrative and not restrictive, and all such modifications are intended to be included in the scope of the invention. A transmissive electron micrograph of a cross section of a layer of thermally transformed polyimine film. The polyimide film contains 20% by weight of fumed alumina. Figure 2 is a single layer of chemically converted PMDA. Transmissive electron micrograph of the cross section of /4.4-QDA, the PMDA/4.4-QDA contains 13% by weight of gas phase oxidation. 154225.doc •55-

Claims (1)

201233548 VII. Patent application scope: 1. A base film comprising: A. - chemically converted polyimine, in an amount of from 4 to 90% by weight of the base film, the chemically converted poly The amine is derived from: i. at least 50 mole percent of the aromatic liver, and ii. based on the total amount of the polydiamine dianhydride, and at least 50 moles based on the total amount of the polyamine of the polyimine. Percent of the aromatic diamine; B. - filler 'except for low conductivity carbon black and pigment, the amount is 10 to 60 weight percent of the base film; and wherein the thickness of the base film is from 8 to 152 micrometers . 2. The base film of claim 1, wherein the chemically converted polyimine is a catalyst or a dehydrating agent capable of converting a polyproline to a polyimine by using a polyamic acid solution. The mixing step is made. 3. The base film of claim 1, wherein: a. the aromatic dianhydride is selected from the group consisting of: pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid Anhydride, 3,3',4,4'-diphenyl ketone four acid dianhydride; 4,4, oxydiphthalic anhydride, 3,3',4,4·-diphenyl sulfone tetracarboxylic acid a group consisting of diiso 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, bisphenol A dianhydride, and mixtures of the foregoing; and 154225.doc 201233548 b. the aromatic diamine Is selected from: 3,4'-oxydiphenylamine, 1,3-bis-(4-aminophenoxy)benzene, 4,4'-oxydiphenylamine, M-diaminobenzene, 1, 3 _ -Aminobenzene, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenylthiophene, 9,9' - bis(4-amino)fluoro and mixtures thereof. 4. The base film of claim 3, wherein the chemically converted polyimide is derived from pyromellitic dianhydride and 4,4,-oxydiphenylamine. 5. If requested! The base film, the filler in the crucible is selected from the group consisting of talc, titanium dioxide, needle-shaped di-drying, oxidation, nitriding, trioxite, gas phase cerium oxide, aluminum oxide, gas phase oxidation A group of aluminum, sepiolite, limestone, and mixtures thereof. 154225.doc