JP2018500211A - Multilayer film - Google Patents

Abstract

The present disclosure relates to multilayer films having an L * color of less than 30 and a 60 degree gloss value of less than 10. The multilayer film has a first polyimide layer and a second polyimide layer. The second polyimide layer comprises 25-50 wt% polyimide, 15-35 wt% polyimide particle matting agent, greater than 0 wt% and less than 20 wt% of at least one submicron carbon black, and 15 -50% by weight of at least one submicron fumed metal oxide.

Description

  The present disclosure relates generally to multilayer films. More specifically, the multilayer film has a first polyimide layer and a second polyimide layer containing a matting agent, submicron carbon black and submicron fumed metal oxide.

A polyimide film for electronic applications has a matte appearance, has a specific color, is durable for handling and circuit processing, and is protected by a coverlay when used as a coverlay There is an increasing industrial need to provide protection against unnecessary visual inspection of parts. Single layer matte films do not have an L ^* color of less than 30 that provides the industrially desirable rich saturated color. Typically, as the amount of matting agent increases, the color of the film is suppressed. The effect of increasing the surface roughness by the matting agent is a dilution of the pigment color so that it appears brighter and less saturated. This is due to the diffuse reflectance dilution (where the pigment color is perceived) due to increased specular reflectance scattering (white light). The rougher the surface, the lower the gloss and the higher the regular reflectance scattering. Thus, L ^* (brightness) typically increases as gloss decreases. Adding more colorant does not reduce the L ^* color. Therefore, it is difficult to achieve low gloss and low L ^* color simultaneously.

  For the reasons described above, it has acceptable electrical properties (eg, dielectric strength), mechanical properties, and durability for handling and circuit processing, but is dull in appearance, has a dense saturated color, and yet has a coverlay. There is a need for polyimide films that also provide sufficient optical density to provide visual protection when used.

This disclosure
a. A polyimide, derived from at least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and polyimide derived from at least 50 mole percent aromatic diamine, based on the total diamine content of the polyimide A first polyimide layer having a thickness of 8 to 130 microns comprising:
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) comprising a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide, having an L ^* color of less than 30 and a 60 degree gloss value of less than 10. Relates to a multilayer film.

FIG. 1 illustrates a bonding layer in direct contact with the first polyimide layer opposite the second polyimide layer, according to one embodiment of the present disclosure. FIG. 2 illustrates a bonding layer that is in direct contact with the second polyimide layer at the surface of the third polyimide layer, the second polyimide layer furthest from the first polyimide layer, according to one embodiment of the present disclosure.

The present disclosure relates to multilayer films that achieve a desired L ^* color of less than 30 and a 60 degree gloss of less than 10 while retaining acceptable electrical properties, mechanical properties, and durability for handling and circuit processing. The multilayer film includes a first polyimide layer and a second polyimide layer.

  Also, the use of “a” or “an” is used to describe elements and components of the invention. This is for convenience only and to give a general sense of the invention. This description should be interpreted to include one, or at least one, and the singular also includes the plural unless it is obvious that it has another meaning.

  The term “polyamic acid” as used herein is intended to include any polyimide precursor material derived from a combination of dianhydride and diamine and capable of conversion to polyimide. The

First polyimide layer The first polyimide layer has at least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and at least 50 mole percent fragrance, based on the total diamine content of the polyimide. Derived from a group diamine. The term “dianhydride” as used herein is technically not a dianhydride but nevertheless reacts with a diamine to form a polyamic acid that can be converted to a polyimide. It is intended to include those precursors, derivatives or analogs obtained. The term “diamine” as used herein is technically not a diamine, but may nevertheless react with a dianhydride to form a polyamic acid that can be converted to a polyimide, It is intended to include their precursors, derivatives or analogs.

In one embodiment, the aromatic dianhydride is
Pyromellitic dianhydride;
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride;
3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride;
4,4'-oxydiphthalic anhydride;
3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride;
2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane;
Selected from the group consisting of bisphenol A dianhydrides; and mixtures and derivatives thereof.

In another embodiment, the aromatic dianhydride is
2,3,6,7-naphthalenetetracarboxylic dianhydride;
1,2,5,6-naphthalenetetracarboxylic dianhydride;
2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride;
2,2-bis (3,4-dicarboxyphenyl) propane dianhydride;
Bis (3,4-dicarboxyphenyl) sulfone dianhydride;
3,4,9,10-perylenetetracarboxylic dianhydride;
1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride;
1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride;
Bis (2,3-dicarboxyphenyl) methane dianhydride;
Bis (3,4-dicarboxyphenyl) methane dianhydride;
Oxydiphthalic dianhydride;
Bis (3,4-dicarboxyphenyl) sulfone dianhydride;
Selected from the group consisting of mixtures and derivatives thereof.

In some embodiments, examples of suitable aliphatic dianhydrides include, but are not limited to, cyclobutane dianhydride; [1S ^* , 5R ^* , 6S ^* ]-3-oxabicyclo [3.2.1] Octane-2,4-dione-6-spiro-3- (tetrahydrofuran-2,5-dione); and mixtures thereof.

  In some embodiments, the aromatic diamine is 3,4′-oxydianiline; 1,3-bis- (4-aminophenoxy) benzene; 4,4′-oxydianiline; paraphenylenediamine; 3-diaminobenzene; 2,2′-bis (trifluoromethyl) benzidene; 4,4′-diaminobiphenyl; 4,4′-diaminodiphenyl sulfide; 9,9′-bis (4-amino) fluorine; Selected from the group consisting of mixtures and derivatives.

  In another embodiment, the aromatic diamine is 4,4′-diaminodiphenylpropane; 4,4′-diaminodiphenylmethane; benzidine; 3,3′-dichlorobenzidine; 3,3′-diaminodiphenylsulfone; '-Diaminodiphenylsulfone; 1,5-diaminonaphthalene; 4,4'-diaminodiphenyldiethylsilane; 4,4'-diaminodiphenylsilane; 4,4'-diaminodiphenylethylphosphine oxide; 4,4'-diaminodiphenyl N-methylamine; 4,4'-diaminodiphenyl N-phenylamine; 1,4-diaminobenzene (paraphenylenediamine); 1,2-diaminobenzene; mixtures and derivatives thereof.

  In some embodiments, examples of suitable aliphatic diamines include hexamethylene diamine, dodecane diamine, cyclohexane diamine, and mixtures thereof.

  In one embodiment, the first polyimide layer comprises polyimide derived from pyromellitic dianhydride and 4,4'-oxydianiline.

  In some embodiments, the first polyimide layer has the following thickness: 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120 and 130 microns thick. Between and including any two. In another embodiment, the first polyimide layer is 8-130 microns thick. In another embodiment, the first polyimide layer is 10-30 microns thick. In another embodiment, the first polyimide layer is 12-25 microns thick.

  The first polyimide layer may optionally contain 1-15% by weight of low conductivity carbon black. In some embodiments, the weight percentage of low conductivity carbon black is between 2 and any one of the following: 1, 5, 10, and 15 wt%. In yet another embodiment, the first polyimide layer contains 2-9 wt% low conductivity carbon black.

  Low conductivity carbon black is intended to mean channel type black, furnace black or lamp black. In some embodiments, the low conductivity carbon black is a surface oxidized carbon black. One way to evaluate the extent of surface oxidation (of carbon black) is to measure the heat loss of carbon black. The loss on heating can be measured by calculating the weight loss when baked at 950 ° C. for 7 minutes. In general, highly surface oxidized carbon black (high heat loss) can then be imidized into the (fully dispersed) filled polyimide base polymer of the present disclosure. It can be easily dispersed in (polyimide precursor). If the carbon black particles (aggregates) do not contact each other, it is believed that electron tunneling effects, electron hopping or other electron flow mechanisms are generally suppressed and low conductivity is obtained. In some embodiments, the low conductivity carbon black has a loss on heating of 1% or more. In some embodiments, the low conductivity carbon black has a loss on heating of 5, 9 or 13% or more. In some embodiments, the furnace black may be surface treated to increase heat loss. As a typical example, low conductivity carbon black has a pH of less than 6.

  A uniform dispersion of isolated low conductivity carbon black particles (aggregates) not only reduces conductivity, but additionally tends to produce uniform color strength. In some embodiments, the low conductivity carbon black is milled. In some embodiments, the average particle size of the low conductivity carbon black has the following diameters: 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, Between any two of 0.9 and 1.0 microns (and optionally including it).

  The first polyimide layer may optionally contain 1 to 40% by weight pigment or dye. In some embodiments, the first polyimide layer contains 1 to 40 weight percent of a mixture of pigments and dyes. In some embodiments, the first polyimide layer has a weight percent between and including any two of the following: 1, 5, 10, 15, 20, 25, 30, 35, and 40 weight percent. Pigments, dyes or mixtures thereof. In some embodiments, the first polyimide layer contains 1 to 40% by weight of a mixture of any two of the following: low conductivity carbon black, pigment or dye.

Virtually any pigment (or combination of pigments) can be used in the practice of the present invention. In some embodiments, useful pigments include, but are not limited to: barium lemon yellow, cadmium yellow lemon, cadmium yellow lemon, cadmium yellow light, cadmium yellow middle, cadmium yellow orange, scarlet lake, cadmium red, cadmium Includes Vermilion, Alizarin Limson, Permanent Magenta, Van Dyke Brown, Roamberg Linish or Burnt Amber. In some embodiments, useful black pigments include cobalt oxide, Fe—Mn—Bi black, Fe—Mn oxide spinel black, (Fe, Mn) ₂ O ₃ black, copper chromite black spinel, lamp. Black, bone black, bone ash, bone char, hematite, black iron oxide, mica iron oxide, black complex inorganic color pigment (CICP), (Ni, Mn, Co) (Cr, Fe) ₂ O ₄ black, aniline black Perylene black, anthraquinone black, chrome green black hematite, chrome iron oxide, pigment green 17, pigment black 26, pigment black 27, pigment black 28, pigment brown 29, pigment brown 35, pigment black 30, pigment black 3 2, Pigment Black 33 or a mixture thereof.

  In some embodiments, the pigment is lithopone, zinc sulfide, barium sulfate, cobalt oxide, yellow iron oxide, orange iron oxide, red iron oxide, brown iron oxide, hematite, black iron oxide, mica iron oxide, chromium ( III) Green, ultramarine blue, ultramarine violet, ultramarine pink, iron cyanide blue, cadmium pigment or lead chromate pigment.

In some embodiments, the pigment is a complex inorganic color pigment (CICP) such as spinel pigment, rutile pigment, zircon pigment or bismuth yellow vanadate. In some embodiments, useful spinel pigments include, but are not limited to, Zn (Fe, Cr) ₂ O ₄ brown, CoAl ₂ O ₄ blue, Co (AlCr) ₂ O ₄ blue green, Co ₂ TiO ₄ green. CuCr ₂ O ₄ black or (Ni, Mn, Co) (Cr, Fe) ₂ O ₄ black. In some embodiments, useful rutile pigments include, but are not limited to, Ti—Ni—Sb yellow, Ti—Mn—Sb brown, Ti—Cr—Sb buff, zircon pigment or bismuth yellow vanadate.

  In another embodiment, the pigment is an organic pigment. In some embodiments, useful organic pigments include, but are not limited to, aniline black (Pigment Black 1), anthraquinone black, monoazo type, diazo type, benzimidazolone, diarylide yellow, monoazo yellow salt, dinitani Phosphorus orange, pyrazolone orange, azo red, naphthol red, azo condensation pigment, lake pigment, copper phthalocyanine blue, copper phthalocyanine green, quinacridone, diarylpyrrolopyrrole, aminoanthraquinone pigment, dioxazine, isoindolinone, isoindoline, quinophthalone, phthalocyanine pigment, Idantron pigment, Pigment Violet 1, Pigment Violet 3, Pigment Violet 19 or Pigment Violet 23 are included. In yet another embodiment, the organic pigment is a vat dye pigment such as, but not limited to, perylene, perylene black, perinone or thioindigo.

  A uniform dispersion of isolated individual pigment particles (aggregates) tends to produce a uniform color intensity. In some embodiments, the pigment is milled. In some embodiments, the pigment has an average particle size of the following diameters: 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and Between any two of 1.0 micron (and optionally including it). In some embodiments, luminescent (fluorescent or phosphorescent) or glossy pigments can be used alone or in combination with other pigments or dyes.

In some embodiments, the first polyimide layer is 1-20% by weight matting agent selected from silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof. Is further included. In another embodiment, the first polyimide layer further comprises 1-20% by weight matting agent, which is carbon black having an average particle size of 2-9 micrometers. In yet another embodiment, the first polyimide layer is
i) carbon black having an average particle size of 2-9 microns; and ii) silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof, 1-20% by weight And further comprises a matting agent.

  In some embodiments, the first polyimide layer is a Kapton® MBC polyimide film from DuPont.

In some embodiments, the first polyimide layer is
i) a chemically converted polyimide in an amount of 71-96% by weight,
a. At least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and b. A chemically converted polyimide in an amount of 71-96 wt% derived from at least 50 mole percent aromatic diamine, based on the total diamine content of the polyimide;
ii) a low conductivity carbon black present in an amount of 2-9 weight percent; and iii) a matting agent comprising:
a. Present in an amount of 1.6 to 10 weight percent;
b. Has a median particle size of 1.3 to 10 microns, and c. A matting agent having a density of 2 to 4.5 g / cc.

  In the chemical conversion process, the polyamic acid solution is immersed in or mixed with the conversion (imidization) chemical. In one embodiment, the conversion chemical is a tertiary amine catalyst (accelerator) and an anhydride dehydrating material. In one embodiment, the anhydride dehydrated material is acetic anhydride, which is in molar excess compared to the amount of amic acid (amidic acid) groups in the polyamic acid, typically about 1. Often used at 2 to 2.4 moles. In one embodiment, a substantial amount of tertiary amine catalyst is used.

  As an alternative to acetic anhydride as an anhydrous dehydration material, i. Other aliphatic anhydrides such as propionic acid, butyric acid, valeric acid and mixtures thereof; ii. Aromatic monocarboxylic acid anhydrides; iii. A mixture of aliphatic and aromatic anhydrides; iv. Carbodiimide; and v. Aliphatic ketenes (ketenes can be related as carboxylic acid anhydrides derived from the rapid dehydration of acids).

  In one embodiment, the tertiary amine catalyst is pyridine and beta picoline and is typically used in an amount similar to the moles of anhydride dehydrated material. Depending on the desired conversion rate and the catalyst used, lower or higher amounts may be used. Tertiary amines having approximately the same activity as pyridine and betapicoline may also be used. These include: alphapicoline; 3,4-lutidine; 3,5-lutidine; 4-methylpyridine; 4-isopropylpyridine; N, N-dimethylbenzylamine; isoquinoline; 4-benzylpyridine, N, N-dimethyldodecyl Amine, triethylamine and the like are included. Various other catalysts for imidization, such as imidazole, are known in the art and may be useful according to the present disclosure.

  Conversion chemicals can generally be reacted at temperatures above room temperature to convert polyamic acid to polyimide. In one embodiment, the chemical transformation reaction occurs at a temperature between 15 ° C. and 120 ° C., the reaction is very fast at higher temperatures and the reaction is relatively slow at lower temperatures.

  In one embodiment, the chemically treated polyamic acid solution can be cast or extruded onto a heated conversion surface or substrate. In one embodiment, the chemically treated polyamic acid solution can be cast on a belt or drum. The solvent can be evaporated from the solution and the polyamic acid can be partially chemically converted to polyimide. The resulting solution then takes the form of a polyamic acid-polyimide gel. Alternatively, the polyamic acid solution is extruded into a bath of conversion chemical consisting of an anhydride component (dehydrating agent), a tertiary amine component (catalyst), or both, with or without a diluent solvent. be able to. In either case, a gel film is formed, and the conversion of amic acid groups to imide groups in the gel film is usually about 10 to 75 percent complete, depending on contact time and temperature. In order to cure to a solids level higher than 98%, the gel film must typically be dried at elevated temperatures (about 200 ° C., up to about 550 ° C.), which tends to complete imidization. In some embodiments, the use of dehydrating agents and catalysts is preferred to promote gel film formation and to achieve the desired conversion rate.

Second polyimide layer The second polyimide layer is 25-50 wt% polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and the total diamine of the polyimide Based on content, it comprises 45-67 wt% polyimide derived from at least 50 mole percent aromatic diamine. In some embodiments, the second polyimide layer comprises weight percent polyimide between and including any of the following: 25, 30, 35, 40, 45, and 50 weight percent. . In another embodiment, the second polyimide layer comprises 33-39% by weight polyimide.

In one embodiment, the aromatic dianhydride is
Pyromellitic dianhydride;
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride;
3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride;
4,4'-oxydiphthalic anhydride;
3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride;
2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane;
Selected from the group consisting of bisphenol A dianhydrides; and mixtures and derivatives thereof.

In another embodiment, the aromatic dianhydride is
2,3,6,7-naphthalenetetracarboxylic dianhydride;
1,2,5,6-naphthalenetetracarboxylic dianhydride;
2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride;
2,2-bis (3,4-dicarboxyphenyl) propane dianhydride;
Bis (3,4-dicarboxyphenyl) sulfone dianhydride;
3,4,9,10-perylenetetracarboxylic dianhydride;
1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride;
1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride;
Bis (2,3-dicarboxyphenyl) methane dianhydride;
Bis (3,4-dicarboxyphenyl) methane dianhydride;
Oxydiphthalic dianhydride;
Bis (3,4-dicarboxyphenyl) sulfone dianhydride;
Selected from the group consisting of mixtures and derivatives thereof.

In some embodiments, examples of suitable aliphatic dianhydrides include, but are not limited to, cyclobutane dianhydride; [1S ^* , 5R ^* , 6S ^* ]-3-oxabicyclo [3.2.1] Octane-2,4-dione-6-spiro-3- (tetrahydrofuran-2,5-dione); and mixtures thereof.

  In some embodiments, the aromatic diamine is 3,4′-oxydianiline; 1,3-bis- (4-aminophenoxy) benzene; 4,4′-oxydianiline; paraphenylenediamine; 3-diaminobenzene; 2,2′-bis (trifluoromethyl) benzidene; 4,4′-diaminobiphenyl; 4,4′-diaminodiphenyl sulfide; 9,9′-bis (4-amino) fluorine; Selected from the group consisting of mixtures and derivatives.

  In another embodiment, the aromatic diamine is 4,4′-diaminodiphenylpropane; 4,4′-diaminodiphenylmethane; benzidine; 3,3′-dichlorobenzidine; 3,3′-diaminodiphenylsulfone; '-Diaminodiphenylsulfone; 1,5-diaminonaphthalene; 4,4'-diaminodiphenyldiethylsilane; 4,4'-diaminodiphenylsilane; 4,4'-diaminodiphenylethylphosphine oxide; 4,4'-diaminodiphenyl N-methylamine; 4,4'-diaminodiphenyl N-phenylamine; 1,4-diaminobenzene (paraphenylenediamine); 1,2-diaminobenzene; mixtures and derivatives thereof.

  In some embodiments, examples of suitable aliphatic diamines include the following: hexamethylene diamine, dodecane diamine, cyclohexane diamine, and mixtures thereof.

In one embodiment, the second polyimide layer is a polyimide derived from pyromellitic dianhydride and 4,4′-oxydianiline, or pyromellitic dianhydride, 4,4′-oxydianiline and Polyimide derived from paraphenylenediamine. In another embodiment, the second polyimide layer comprises 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine. A polyimide derived from In another embodiment, the second polyimide layer is derived from i) a block of pyromellitic dianhydride and 4,4′-oxydianiline, and ii) a block of pyromellitic dianhydride and paraphenylenediamine. Comprising polyimide. In yet another embodiment, the second polyimide layer comprises 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylene. Polyimide derived from diamine. In yet another embodiment, the first polyimide layer comprises a polyimide derived from pyromellitic dianhydride and 4,4′-oxydianiline, and the second polyimide layer comprises:
i) derived from pyromellitic dianhydride and 4,4'-oxydianiline or ii) derived from pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine Or iii) derived from a block of pyromellitic dianhydride and 4,4′-oxydianiline, and a block of pyromellitic dianhydride and paraphenylenediamine, or iv) 3,3 ′, 4 , 4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-oxydianiline and polyimide derived from paraphenylenediamine.

  In some embodiments, the second polyimide layer is thinner than the first polyimide layer. Typically, the second polyimide layer is highly filled and the first polyimide layer must provide mechanical support. Therefore, it is desirable that the second polyimide layer is thin. In some embodiments, the second polyimide layer is 0.5-20 microns thick. In some embodiments, the second polyimide layer is between and includes any two of the following thicknesses: 0.5, 1, 5, 10, 15 and 20 microns thick. In yet another embodiment, the second layer is 0.7-10 microns thick. In some embodiments, the second layer is 0.7-3 microns thick.

  The second layer is in direct contact with the first polyimide layer. The term “in direct contact” is intended to mean that two surfaces are adjacent to each other without an intervening material or bonding layer between the two surfaces.

  The second polyimide layer comprises greater than 0% and less than 20% by weight of at least one submicron carbon black. The term “submicron” is intended to mean that all dimensions are less than 1 micron. In another embodiment, the second polyimide layer comprises 5-17% by weight of at least one submicron carbon black. In another embodiment, the second polyimide layer comprises greater than 7% and less than 11% by weight of at least one submicron carbon black. In another embodiment, the second polyimide layer comprises 8-10% by weight of at least one submicron carbon black. Submicron carbon black for the purposes of this disclosure is intended to be a colorant. One skilled in the art could envision the use of other colorants (pigments or dyes) to create any desired color. In some embodiments, the same pigment or dye used in the second polyimide layer may be used in the first polyimide layer. In yet another embodiment, the colorant of the second polyimide layer could be different from any colorant that may be used in the first polyimide layer.

  The second polyimide layer comprises 15 to 35 wt% polyimide particle matting agent. In some embodiments, the second polyimide layer is between any two of the following: 15, 16, 17, 18, 19, 20, 25, 30, 31, 32, 33, 34, and 35 wt% And comprises a weight percent polyimide particle matting agent containing the same. In another embodiment, it comprises 19-31% by weight polyimide particle matting agent. In some embodiments, the second polyimide layer comprises a mixture of polyimide particle matting agents, or polyimide particle matting agents, and another gloss such as silica, alumina, zirconia, boron nitride, barium sulfate, calcium phosphate and talc. It comprises a mixture with an eraser.

  The polyimide particle matting agent has a median particle size of 2 to 11 microns. In some embodiments, the polyimide particle matting agent is a center between and including any of the following: 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11 microns Have a particle size. In some embodiments, the polyimide particle matting agent has an average particle size of 2 to 11 microns. The particle size of the polyimide particle matting agent is either a Horiba LA-930 (Horiba, Instruments, Inc., Irvine CA) or a Malvern Mastersizer 3000 (Malvern Instruments, Inc., Westbord, Mass.) Laser slurry. Can be measured in.

  The polyimide particle matting agent is derived from at least one aromatic dianhydride and at least one aromatic diamine. In one embodiment, the polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline.

  In some embodiments, the polyimide particle matting agent is a colored polyimide particle matting agent. Colored polyimide particles are composed of polyimide and a colorant. The colored polyimide particles have a color different from that of polyimide alone. Indeed, any colorant can be used including, but not limited to, inorganic pigments, complex inorganic colored pigments, organic pigments and dyes. Useful black colorants include carbon black, graphite, aniline black and perylene black. Useful white colorants include titanium dioxide. The colorant can be incorporated into the polyimide particles, such as by absorption, or can be dispersed as a separate phase within the polyimide particles. Some or all of the colorant may be on the surface of the polyimide particles. The surface of the particles may be partially or fully coated with a colorant. Colored polyimide particles include, but are not limited to: incorporation of colorant into polyimide particles during the process of particle formation by precipitation from solution; absorption, swelling or diffusion of colorant into polyimide particles; polyimide particles It can be made by a variety of methods, including coating colorants on top. The colored polyimide particles can contain 1% to 70% by weight of a colorant. In some embodiments, the colored polyimide particles may contain 1 wt% to 50 wt% colorant. Colored polyimide particle matting agents useful in the present disclosure include those disclosed in US Patent Application Publication No. 2014/0220335, the disclosure of which is incorporated herein by reference.

  In some embodiments, the second polyimide layer comprises 15 to 35 wt% colored polyimide particle matting agent. In some embodiments, the second polyimide layer is between any two of the following: 15, 16, 17, 18, 19, 20, 25, 30, 31, 32, 33, 34, and 35 wt% And comprises, by weight, a weighted colored polyimide particle matting agent. In another embodiment, it comprises 19-31% by weight of colored polyimide particle matting agent.

  In some embodiments, the colored polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline. In some embodiments, the colored polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline and graphite as a colorant (pigment).

  In some embodiments, the polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4′-oxydianiline, and the polyimide of the second polyimide layer is pyromellitic dianhydride, Derived from 4,4'-oxydianiline and paraphenylenediamine. In some embodiments, the colored polyimide particle matting agent is derived from pyromellitic dianhydride, 4,4′-oxydianiline and a colorant and the polyimide of the second polyimide layer is Derived from merit acid dianhydride, 4,4'-oxydianiline and paraphenylenediamine. In some embodiments, the colored polyimide particle matting agent is derived from pyromellitic dianhydride, 4,4′-oxydianiline and graphite, and the polyimide of the second polyimide layer is pyromellitic. Derived from acid dianhydride, 4,4'-oxydianiline and paraphenylenediamine.

Multilayer Film The multilayer film according to the present disclosure has a first polyimide layer and a second polyimide layer as described above. This multilayer film has an L ^* color of less than 30 and a 60 degree gloss value of less than 10, as well as durability for handling and circuit processing. L ^* color was measured in a mode including reflectance, specular reflection using a HunterLab ColorQuest® XE color meter (Hunter Associates Laboratory, Inc.) and CIELAB 10 ° as L ^* , a ^* , b ^* . / D65 system is reported. An L ^* value of 0 is pure black, while an L ^* value of 100 is pure white. The 60 degree gloss was measured using a Micro-TRI-Gloss meter (BYK-Gardner).

  FIG. 1 includes a bonding layer 60 in direct contact with the first polyimide layer 10 opposite the second polyimide layer 20, which is an embodiment of the present disclosure, where the second polyimide layer is a polyimide particle. Illustrated is a multilayer film comprising matting agent 30, submicron carbon black 40 and submicron fumed metal oxide 50. In some embodiments, the bonding layer is an epoxy adhesive selected from the group consisting of bisphenol A type epoxy resins, cresol novolac type epoxy resins, phosphorus-containing epoxy resins, and mixtures thereof. Typically, the bonding layer is thicker or thicker than the first polyimide layer or the second polyimide layer. In some embodiments, the bonding layer is 8 to 300 microns thick.

  In some embodiments, the adhesive is a mixture of two or more epoxy resins. In some embodiments, the adhesive is a mixture of identical epoxy resins having different molecular weights.

  In some embodiments, the epoxy adhesive contains a curing agent. In some embodiments, the epoxy adhesive contains a catalyst. In some embodiments, the epoxy adhesive contains an elastomeric reinforcing agent. In some embodiments, the epoxy adhesive contains a flame retardant.

  In some embodiments, the multilayer film further comprises a third polyimide layer. In some embodiments, the third polyimide layer is 0.5 to 20 microns thick. In another embodiment, the third polyimide layer is between and includes any two of the following thicknesses: thickness 0.5, 1, 5, 10, 15 and 20 microns. In some embodiments, the third polyimide layer is 0.7-10 microns thick. In some embodiments, the third polyimide layer is 0.7-3 microns thick. In some embodiments, the multilayer film further comprises a third polyimide layer having a thickness of 0.5 to 20 microns in direct contact with the first polyimide layer opposite the second polyimide layer.

  The third polyimide layer is particularly desirable when a multilayer film is coextruded. The third polyimide layer serves to prevent wrapping if it is similar or identical to the second polyimide layer. The third polyimide layer may be the same as or different from the second polyimide layer.

In some embodiments, the multilayer film further comprises a third polyimide layer having a thickness of 0.5-20 microns in direct contact with the first polyimide layer opposite the second polyimide layer; The third polyimide layer is
i) a polyimide, derived from at least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and at least 50 mole percent aromatic diamine, based on the total diamine content of the polyimide. And ii) a matting agent or a mixture thereof.

In one embodiment, the matting agent in the third polyimide layer is selected from silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof. In another embodiment, the matting agent for the third polyimide layer is carbon black having an average particle size of 2-9 microns. In yet another embodiment, the matting agent in the third polyimide layer is
i) carbon black having an average particle size of 2-9 microns, and ii) a mixture of silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof. In another embodiment, the matting agent in the third polyimide layer is a polyimide particle matting agent. In yet another embodiment, the matting agent in the third polyimide layer is a colored polyimide particle matting agent.

  In another embodiment, the third polyimide layer comprises 15 to 35% by weight polyimide particle matting agent. In some embodiments, the third polyimide layer is between any two of the following: 15, 16, 17, 18, 19, 20, 25, 30, 31, 32, 33, 34 and 35 wt% And comprises a weight percent polyimide particle matting agent containing the same. In another embodiment, the third polyimide layer comprises 19-31% by weight polyimide particle matting agent. In some embodiments, the third polyimide layer comprises a mixture of polyimide particle matting agents, or polyimide particle matting agents, and another gloss such as silica, alumina, zirconia, boron nitride, barium sulfate, calcium phosphate and talc. It comprises a mixture with an eraser.

  The polyimide particle matting agent has a median particle size of 2 to 11 microns. In some embodiments, the polyimide particle matting agent is a center between and including any of the following: 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11 microns Have a particle size. In some embodiments, the polyimide particle matting agent has an average particle size of 2 to 11 microns. The particle size of the polyimide particle matting agent is either a Horiba LA-930 (Horiba, Instruments, Inc., Irvine CA) or a Malvern Mastersizer 3000 (Malvern Instruments, Inc., Westbord, Mass.) Laser slurry. Can be measured in.

  The polyimide particle matting agent is derived from at least one aromatic dianhydride and at least one aromatic diamine. In one embodiment, the polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline.

  In some embodiments, the polyimide particle matting agent is a colored polyimide particle matting agent. Colored polyimide particles are composed of polyimide and a colorant. The colored polyimide particles have a color different from that of polyimide alone. Indeed, any colorant can be used including, but not limited to, inorganic pigments, complex inorganic colored pigments, organic pigments and dyes. Useful black colorants include carbon black, graphite, aniline black and perylene black. Useful white colorants include titanium dioxide. The colorant can be incorporated into the polyimide particles, such as by absorption, or can be dispersed as a separate phase within the polyimide particles. Some or all of the colorant may be on the surface of the polyimide particles. The surface of the particles may be partially or fully coated with a colorant. Colored polyimide particles include, but are not limited to: incorporation of colorant into polyimide particles during the process of particle formation by precipitation from solution; absorption, swelling or diffusion of colorant into polyimide particles; polyimide particles It can be made by a variety of methods, including coating colorants on top. The colored polyimide particles can contain 1% to 70% by weight of a colorant. In some embodiments, the colored polyimide particles may contain 1 wt% to 50 wt% colorant. Colored polyimide particle matting agents useful in the present disclosure include those disclosed in U.S. Patent Application Publication No. 2014/0220335, the disclosure of which is incorporated herein by reference.

  In some embodiments, the third polyimide layer comprises 15 to 35% by weight of colored polyimide particle matting agent. In some embodiments, the third polyimide layer is between any two of the following: 15, 16, 17, 18, 19, 20, 25, 30, 31, 32, 33, 34 and 35 wt% And comprises, by weight, a weighted colored polyimide particle matting agent. In another embodiment, it comprises 19-31% by weight of colored polyimide particle matting agent.

  In some embodiments, the colored polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline. In some embodiments, the colored polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline and graphite as a colorant (pigment).

  In some embodiments, the polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4′-oxydianiline, and the polyimide of the third polyimide layer is pyromellitic dianhydride, Derived from 4,4'-oxydianiline and paraphenylenediamine. In some embodiments, the colored polyimide particle matting agent is derived from pyromellitic dianhydride, 4,4′-oxydianiline and a colorant, and the polyimide of the third polyimide layer is Derived from merit acid dianhydride, 4,4'-oxydianiline and paraphenylenediamine. In some embodiments, the colored polyimide particle matting agent is derived from pyromellitic dianhydride, 4,4′-oxydianiline and graphite, and the polyimide of the third polyimide layer is pyromellitic. Derived from acid dianhydride, 4,4'-oxydianiline and paraphenylenediamine.

  In one embodiment, the third polyimide layer comprises polyimide derived from pyromellitic dianhydride and 4,4'-oxydianiline. In another embodiment, the third polyimide layer comprises polyimide derived from pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine. In another embodiment, the second polyimide layer comprises 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine. A polyimide derived from In another embodiment, the third polyimide layer is derived from i) a block of pyromellitic dianhydride and 4,4′-oxydianiline, and ii) a block of pyromellitic dianhydride and paraphenylenediamine. Comprising polyimide.

In another embodiment, the multilayer film further comprises a third polyimide layer having a thickness of 0.5-20 microns in direct contact with the first polyimide layer opposite the second polyimide layer, 3 polyimide layer
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black; and iv) 15-50% by weight of at least one submicron fumed metal oxide.

  FIG. 2 illustrates another embodiment of the present disclosure, a third polyimide layer 70 in direct contact with the first polyimide layer 10, a second polyimide surface on the surface of the second polyimide layer furthest from the first polyimide layer 10. Bonding layer 60 in direct contact with the polyimide layer 20, the second polyimide layer and the third polyimide layer comprising polyimide particle matting agent 30, submicron carbon black 40, and submicron fumed metal oxide 50. The multilayer film which comprises is illustrated. In yet another embodiment, the bonding layer 60 may be in direct contact with the third polyimide layer 70 at the surface of the third polyimide farthest from the first polyimide layer 10.

In one embodiment, the multilayer film is
a. A polyimide, derived from at least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and polyimide derived from at least 50 mole percent aromatic diamine, based on the total diamine content of the polyimide A first polyimide layer having a thickness of 8 to 130 microns comprising:
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) comprising a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide, having an L ^* color of less than 30 and a 60 degree gloss value of less than 10. .

In one embodiment, the multilayer film is
a. A polyimide, derived from at least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and polyimide derived from at least 50 mole percent aromatic diamine, based on the total diamine content of the polyimide A first polyimide layer having a thickness of 8 to 130 microns comprising:
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide;
c. An epoxy resin that is in direct contact with the first polyimide layer on the opposite side of the second polyimide layer and is selected from the group consisting of bisphenol A type epoxy resin, cresol novolac type epoxy resin, phosphorus-containing epoxy resin, and mixtures thereof. And has a L ^* color of less than 30 and a 60 degree gloss value of less than 10.

In one embodiment, the multilayer film is
a. A polyimide, derived from at least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and polyimide derived from at least 50 mole percent aromatic diamine, based on the total diamine content of the polyimide A first polyimide layer having a thickness of 8 to 130 microns comprising:
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide;
c. A third polyimide layer 0.5 to 20 microns thick, in direct contact with the first polyimide layer opposite the second polyamide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) a third polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide.

In one embodiment, the multilayer film is
a. A polyimide, derived from at least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and polyimide derived from at least 50 mole percent aromatic diamine, based on the total diamine content of the polyimide A first polyimide layer having a thickness of 8 to 130 microns comprising:
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide;
c. A third polyimide layer 0.5 to 20 microns thick, in direct contact with the first polyimide layer opposite the second polyamide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) a third polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide;
d. A group comprising a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, a phosphorus-containing epoxy resin, and a mixture thereof in direct contact with the second polyimide layer on the surface of the second polyimide layer opposite to the first polyimide layer And a bonding layer that is an epoxy resin selected from: having an L ^* color of less than 30 and a 60 degree gloss value of less than 10.

In one embodiment, the multilayer film is
a. A polyimide, derived from at least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and polyimide derived from at least 50 mole percent aromatic diamine, based on the total diamine content of the polyimide A first polyimide layer having a thickness of 8 to 130 microns comprising:
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide;
c. A third polyimide layer 0.5 to 20 microns thick, in direct contact with the first polyimide layer opposite the second polyamide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) a third polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide;
d. A group consisting of a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, a phosphorus-containing epoxy resin, and a mixture thereof in direct contact with the third polyimide layer on the surface of the third polyimide layer opposite to the first polyimide layer And a bonding layer that is an epoxy resin selected from: having an L ^* color of less than 30 and a 60 degree gloss value of less than 10.

In one embodiment, the multilayer film is
a. A first polyimide layer having a thickness of 8 to 130 microns,
i) a polyimide, derived from at least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and at least 50 mole percent aromatic diamine, based on the total diamine content of the polyimide. Polyimide;
ii) a first polyimide layer having a thickness of 8 to 130 microns comprising 1 to 15% by weight of a low conductivity carbon black, or 1 to 40% by weight of a pigment or dye;
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) comprising a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide, having an L ^* color of less than 30 and a 60 degree gloss value of less than 10. .

In one embodiment, the multilayer film is
a. A first polyimide layer having a thickness of 8 to 130 microns,
i) a polyimide, derived from at least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and at least 50 mole percent aromatic diamine, based on the total diamine content of the polyimide. Polyimide;
ii) 1-15 wt% low conductivity carbon black, or 1-40 wt% pigment or dye;
iii) 8 to 130 microns thick comprising 1 to 20% by weight of a matting agent selected from silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof. A first polyimide layer;
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) comprising a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide, having an L ^* color of less than 30 and a 60 degree gloss value of less than 10. .

In one embodiment, the multilayer film is
a. A first polyimide layer,
i) 71-96% by weight of polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 moles based on the total diamine content of the polyimide Chemically converted polyimide in an amount of 71-96% by weight derived from percent aromatic diamine;
ii) a low conductivity carbon black present in an amount of 2-9% by weight; and iii) a matting agent comprising:
a. Present in an amount of 1.6 to 10% by weight;
b. Has a median particle size of 1.3 to 10 microns, and c. A first polyimide layer comprising a matting agent having a density of 2 to 4.5 g / cc;
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) comprising a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide, having an L ^* color of less than 30 and a 60 degree gloss value of less than 10. .

In one embodiment, the multilayer film is
a. A first polyimide layer,
i) 71-96% by weight of polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 moles based on the total diamine content of the polyimide Chemically converted polyimide in an amount of 71-96% by weight derived from percent aromatic diamine;
ii) a low conductivity carbon black present in an amount of 2-9% by weight; and iii) a matting agent comprising:
a. Present in an amount of 1.6 to 10% by weight;
b. Has a median particle size of 1.3 to 10 microns, and c. A first polyimide layer comprising a matting agent having a density of 2 to 4.5 g / cc;
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide;
c. A third polyimide layer 0.5 to 20 microns thick, in direct contact with the first polyimide layer opposite the second polyamide layer,
i) a polyimide, derived from at least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and at least 50 mole percent aromatic diamine, based on the total diamine content of the polyimide. Polyimide;
ii) comprising a third polyimide layer comprising a matting agent or mixtures thereof and having an L ^* color of less than 30 and a 60 degree gloss value of less than 10.

In one embodiment, the multilayer film is
a. A first polyimide layer,
i) 71-96% by weight of polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 moles based on the total diamine content of the polyimide Chemically converted polyimide in an amount of 71-96% by weight derived from percent aromatic diamine;
ii) a low conductivity carbon black present in an amount of 2-9% by weight; and iii) a matting agent comprising:
a. Present in an amount of 1.6 to 10% by weight;
b. Has a median particle size of 1.3 to 10 microns, and c. A first polyimide layer comprising a matting agent having a density of 2 to 4.5 g / cc;
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide;
c. A third polyimide layer 0.5 to 20 microns thick, in direct contact with the first polyimide layer opposite the second polyamide layer,
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) a third polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide, having an L ^* color of less than 30 and a 60 degree gloss value of less than 10. Have.

In one embodiment, the multilayer film is
a. A first polyimide layer having a thickness of 8 to 130 microns comprising a polyimide derived from pyromellitic dianhydride and 4,4'-oxydianiline;
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25-50% by weight of polyimide,
a) pyromellitic dianhydride and 4,4′-oxydianiline,
b) pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine,
c) a block of pyromellitic dianhydride and 4,4′-oxydianiline, and a block of pyromellitic dianhydride and paraphenylenediamine, or d) 3,3 ′, 4,4′-biphenyltetracarboxylic 25-50% by weight of polyimide derived from acid dianhydride, pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) comprising a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide, having an L ^* color of less than 30 and a 60 degree gloss value of less than 10. .

In one embodiment, the multilayer film is
a. A first polyimide layer,
i) a chemically converted polyimide in an amount of 71-96 wt% derived from pyromellitic dianhydride and 4,4'-oxydianiline;
ii) a low conductivity carbon black present in an amount of 2-9% by weight; and iii) a matting agent comprising:
a. Present in an amount of 1.6 to 10% by weight;
b. Has a median particle size of 1.3 to 10 microns, and c. A first polyimide layer comprising a matting agent having a density of 2 to 4.5 g / cc;
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25-50% by weight of polyimide,
a) pyromellitic dianhydride and 4,4′-oxydianiline,
b) pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine,
c) a block of pyromellitic dianhydride and 4,4′-oxydianiline, and a block of pyromellitic dianhydride and paraphenylenediamine, or d) 3,3 ′, 4,4′-biphenyltetracarboxylic 25-50% by weight of polyimide derived from acid dianhydride, pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) comprising a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide, having an L ^* color of less than 30 and a 60 degree gloss value of less than 10. .

In one embodiment, the multilayer film is
a. A first polyimide layer,
i) a chemically converted polyimide in an amount of 71-96 wt% derived from pyromellitic dianhydride and 4,4'-oxydianiline;
ii) a low conductivity carbon black present in an amount of 2-9% by weight; and iii) a matting agent comprising:
a. Present in an amount of 1.6 to 10% by weight;
b. Has a median particle size of 1.3 to 10 microns, and c. A first polyimide layer comprising a matting agent having a density of 2 to 4.5 g / cc;
b. A second polyimide layer 0.5 to 20 microns thick in direct contact with the first polyimide layer,
i) 25-50% by weight of polyimide,
a) pyromellitic dianhydride and 4,4′-oxydianiline,
b) pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine,
c) a block of pyromellitic dianhydride and 4,4′-oxydianiline, and a block of pyromellitic dianhydride and paraphenylenediamine, or d) 3,3 ′, 4,4′-biphenyltetracarboxylic 25-50% by weight of polyimide derived from acid dianhydride, pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide, wherein the multilayer film has an L ^* color of less than 30 and a 60 degree gloss value of less than 10 ;
c. A third polyimide layer 0.5 to 20 microns thick, in direct contact with the first polyimide layer opposite the second polyamide layer,
i) 25-50% by weight of polyimide,
a) pyromellitic dianhydride and 4,4′-oxydianiline,
b) pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine,
c) a block of pyromellitic dianhydride and 4,4′-oxydianiline, and a block of pyromellitic dianhydride and paraphenylenediamine, or d) 3,3 ′, 4,4′-biphenyltetracarboxylic 25-50% by weight of polyimide derived from acid dianhydride, pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) comprising a third polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide, having an L ^* color of less than 30 and a 60 degree gloss value of less than 10. .

In one embodiment, the multilayer film is
a. A first polyimide layer having a thickness of 20-30 microns comprising a polyimide derived from pyromellitic dianhydride and 4,4'-oxydianiline;
b. A second polyimide layer 0.7-3 microns thick in direct contact with the first polyimide layer,
i) 25-50 wt% polyimide derived from pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine;
ii) 19-31% by weight of polyimide particle matting agent;
v) at least one submicron carbon black of greater than 7% and less than 11% by weight;
vi) comprising a second polyimide layer comprising 20-25% by weight of at least one submicron fumed metal oxide, having an L ^* color of less than 30 and a 60 degree gloss value of less than 10. .

In one embodiment, the multilayer film is
c. A first polyimide layer having a thickness of 20-30 microns comprising a polyimide derived from pyromellitic dianhydride and 4,4'-oxydianiline;
d. A second polyimide layer 0.7-3 microns thick in direct contact with the first polyimide layer,
i) 25-50 wt% polyimide derived from pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine;
ii) 19-31% by weight of polyimide particle matting agent;
vii) 8-10% by weight of at least one submicron carbon black;
viii) comprising a second polyimide layer comprising 20-25% by weight of at least one submicron fumed metal oxide, having an L ^* color of less than 30 and a 60 degree gloss value of less than 10 .

Another embodiment of the present disclosure is a method of producing a multilayer film having an L ^* color less than 30 and a 60 degree gloss value less than 10.
a. Providing a first polyimide layer having a thickness of 8 to 130 microns;
b. Coating a second polyimide layer having a thickness of 0.5 to 8 microns on the first polyimide layer, wherein the second polyimide layer comprises:
i) 25 to 50 weight percent polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 mole percent based on the total diamine content of the polyimide 25-50 wt% polyimide derived from aromatic diamines;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black; and iv) 15-50% by weight of at least one submicron fumed metal oxide. is there.

  The first polyimide layer and the second polyimide layer of the present disclosure can be produced by any method known in the technical field related to the production of filled polyimide films. In some embodiments, the first polyimide layer and the second polyimide layer may heat the polyamic acid solution to a temperature typically above 250 ° C. to convert the polyamic acid to polyimide (thermal Produced by imidization). In another embodiment, the first polyimide layer and the second polyimide layer are produced by a chemical conversion process (chemical imidization). In one embodiment, such a method includes preparing a pigment slurry. The slurry may or may not be milled using a ball mill or continuous media mill to achieve the desired particle size. The slurry may or may not be filtered to remove any remaining large particles. The polyamic acid prepolymer solution is prepared by reacting a slight excess of diamine with dianhydride. The polyamic acid solution is mixed with the pigment slurry in a high shear mixer. The amount of polyamic acid solution, pigment slurry and finish solution can be adjusted to achieve the desired loading concentration of pigment and the desired viscosity for film formation. “Finishing solution” refers herein to a dianhydride in a polar aprotic solvent that is added to a prepolymer solution to increase molecular weight and viscosity. The dianhydride used is typically the same as the dianhydride used to produce the prepolymer (or the same as one of the dianhydrides if more than one is used). The mixture can be metered through a slot die and cast or hand cast onto a smooth stainless steel belt or substrate to produce a gel film. The conversion chemical can be surveyed prior to casting using a slot die. In order to convert to a solids level higher than 98 percent, the gel film typically must be dried at elevated temperatures (convection heating at 200-300 ° C and radiant heating at 400-800 ° C). This tends to complete imidization. In yet another embodiment, the first polyimide layer and the second polyimide layer are independently manufactured by a thermal conversion process or a chemical conversion process.

  The multilayer films of the present disclosure can be prepared by any well-known method such as, but not limited to, coextrusion, lamination (laminating single layers together), coating, and combinations thereof. A description of a coextrusion forming process for preparing multilayer polyimide films is provided in European Patent Application 0 659 553 A1 to Sutton et al. Coating methods include, but are not limited to, spray coating, curtain coating, knife over roll, air knife, extrusion / slot die, gravure, reverse gravure, offset gravure, roll coating and dip / dipping.

  In some embodiments, the multilayer film is prepared by simultaneously extruding (coextrusion) the first polyimide layer and the second polyimide layer. In some embodiments, the multilayer film is prepared by simultaneously extruding (co-extruding) the first polyimide layer, the second polyimide layer, and the third polyimide layer. In some embodiments, the layer is extruded by a single-piece or multi-piece extrusion die. In another embodiment, the multilayer film is manufactured using a single die. If a single die is used, the laminar flow of fluid must be high enough in viscosity to prevent fluid mixing and provide stratification. In some embodiments, the multilayer film is prepared by casting onto a moving stainless steel belt from a slot die. In one embodiment, the belt is then passed through a convection oven and the solvent is evaporated to partially imidize the polymer to produce a “green” film. The green film can be peeled off from the casting belt and wound. The green film can then be passed through a tenter oven to produce a fully cured polyimide film. In some embodiments, during tentering (ie, using clips or pins) shrinkage can be minimized by restricting the film along the edge.

  In some embodiments, the multilayer film is produced by coating a silica matting agent, submicron carbon black and submicron fumed metal oxide slurry, and a solution of polyamic acid on the first polyimide layer. The coating is heated and dried. The resulting multilayer film is placed on a pin frame to hold it flat. The coating can be cured in a batch or continuous oven capable of heating to at least 250 ° C. The oven temperature is increased to 320 ° C over 45-60 minutes, then transferred to a 400 ° C oven and held for 5 minutes. In some embodiments, a chemical imidization catalyst and / or a dehydrating agent can be added to the coating solution.

Another embodiment of the present disclosure is a method for reducing the amount of colorant in a multilayer film and achieving an L ^* color of less than 30 and a 60 degree gloss value of less than 10.
a) providing a first polyimide layer or a first polyamic acid solution or a first polyamic acid green film;
b) providing a second polyamic acid solution containing polyamic acid, silica matting agent and submicron carbon black;
c) adding at least one submicron fumed metal oxide to the second polyamic acid solution;
d) Coating the polyamic acid solution formed in step c on the first polyimide layer, or coating the polyamic acid solution formed in step c on the first polyimidic acid green form, or step c. Coextruding the polyamic acid solution formed in step 1 and the first polyimidic acid solution;
f) Imidize the coating formed in step d to form a second polyimide layer on the first polyimide layer, or imidize the coating formed in step d and the first polyamic acid green film. Forming a first polyimide layer and a second polyimide layer, or imidizing the coextruded layer formed in step d to form a first polyimide layer and a second polyimide layer A method comprising:

Yet another embodiment of the present disclosure is a method for reducing the amount of colorant in a multilayer film and achieving an L ^* color of less than 30 and a 60 degree gloss value of less than 10.
a) providing a first polyimide layer or first polyamic acid solution or first polyamic acid green film derived from pyromellitic dianhydride and 4,4′-oxydianiline;
b) providing a second polyamic acid solution containing polyamic acid, polyimide particle matting agent and submicron carbon black, wherein the polyamic acid is pyromellitic dianhydride and 4,4′-oxydi Derived from aniline or derived from pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine, or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride , Pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine, or i) block of pyromellitic dianhydride and 4,4′-oxydianiline, and ii ) A step derived from a block of pyromellitic dianhydride and paraphenylenediamine;
c) adding 15-50% by weight of at least one submicron fumed metal oxide to the second polyamic acid solution;
d) Coating the polyamic acid solution formed in step c on the first polyimide layer, or coating the polyamic acid solution formed in step c on the first polyimidic acid green form, or step c. Coextruding the polyamic acid solution formed in step 1 and the first polyimidic acid solution;
f) Imidize the coating formed in step d to form a second polyimide layer on the first polyimide layer, or imidize the coating formed in step d and the first polyamic acid green film. Forming a first polyimide layer and a second polyimide layer, or imidizing the coextruded layer formed in step d to form a first polyimide layer and a second polyimide layer And the second polyimide layer is in direct contact with the first polyimide layer.

Another embodiment of the present disclosure is a method for reducing the amount of colorant in a multilayer film and achieving an L ^* color of less than 30 and a 60 degree gloss value of less than 10.
a) providing a component selected from the group consisting of a first polyimide layer, a first polyamic acid solution, and a first polyamic acid green film;
b) providing a second polyamic acid solution containing polyamic acid, polyimide particle matting agent and submicron carbon black;
c) adding at least one submicron fumed metal oxide to the second polyamic acid solution;
d) Coating the polyamic acid solution formed in step c on the first polyimide layer, or coating the polyamic acid solution formed in step c on the first polyimidic acid green form, or step c. Forming a multilayer composite by co-extrusion of the polyamic acid solution formed in step 1 and a first polyimide acid solution;
f) imidizing the composite material formed in step d to produce a first polyimide layer and a second polyimide layer.

  The submicron fumed metal oxide or a mixture thereof can be added directly to the second polyamic acid solution or is then added to the second polyamic acid solution to prepare a submicron fumed metal oxide slurry. Can be added. In some embodiments, the second polyamic acid solution is added to the submicron fumed metal oxide slurry. In some embodiments, before coating the first polyimide layer with the polyamic acid solution formed in step c, or before coextruding the polyamic acid solution formed in step c and the first polyamic acid solution. The polyimide particle matting agent, submicron carbon black and submicron fumed metal oxide (and their slurries) may be combined in any order.

  The polyamic acid formed in step c is not limited to those skilled in the art such as spray coating, curtain coating, knife over roll, air knife, extrusion / slot die, gravure, reverse gravure, offset gravure, roll coating and dip / dip Can be coated by a well-known method.

  The coated or coextruded layer can be imidized by thermal or chemical conversion as described above.

  In some embodiments, the first polyamic acid solution is partially dried or partially imidized to form a first polyamic acid green film. The polyamic acid solution formed in step c is then coated on the first polyamic acid green and both layers are imidized.

Another embodiment of the present disclosure is a method for reducing the amount of colorant in a multilayer film and achieving an L ^* color of less than 30 and a 60 degree gloss value of less than 10.
a) providing a component selected from the group consisting of a first polyimide layer, a first polyamic acid solution, and a first polyamic acid green film;
b) providing a second polyamic acid solution containing polyamic acid, polyimide particle matting agent and submicron carbon black;
c) adding at least one submicron fumed metal oxide to the second polyamic acid solution;
d) Coating the polyamic acid solution formed in step c on the first polyimide layer, or coating the polyamic acid solution formed in step c on the first polyimidic acid green form, or step c. Forming a multilayer composite by co-extrusion of the polyamic acid solution formed in step 1 and a first polyimide acid solution;
f) imidizing the composite material formed in step d to produce a first polyimide layer and a second polyimide layer, wherein the second polyimide layer is in direct contact with the first polyimide layer. Is the method.

Another embodiment of the present disclosure is a method for reducing the amount of colorant in a multilayer film and achieving an L ^* color of less than 30 and a 60 degree gloss value of less than 10.
a) a component selected from the group consisting of a first polyimide layer, a first polyamic acid solution and a first polyamic acid green film and derived from pyromellitic dianhydride and 4,4′-oxydianiline Providing a step;
b) providing a second polyamic acid solution containing polyamic acid, polyimide particle matting agent and submicron carbon black;
c) adding at least one submicron fumed metal oxide to the second polyamic acid solution;
d) Coating the polyamic acid solution formed in step c on the first polyimide layer, or coating the polyamic acid solution formed in step c on the first polyimidic acid green form, or step c. Forming a multilayer composite by co-extrusion of the polyamic acid solution formed in step 1 and a first polyimide acid solution;
f) imidizing the composite material formed in step d to produce a first polyimide layer and a second polyimide layer.

  In yet another embodiment, in a method for reducing the amount of colorant in a multilayer film, the second polyimide layer is derived from pyromellitic dianhydride and 4,4′-oxydianiline, or Derived from pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine, or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, Derived from 4,4'-oxydianiline and paraphenylenediamine, or i) block of pyromellitic dianhydride and 4,4'-oxydianiline, and ii) pyromellitic dianhydride and para Polyimide derived from a block of phenylenediamine.

Another embodiment of the present disclosure is a method for reducing the amount of colorant in a multilayer film and achieving an L ^* color of less than 30 and a 60 degree gloss value of less than 10.
a) a component selected from the group consisting of a first polyimide layer, a first polyamic acid solution and a first polyamic acid green film and derived from pyromellitic dianhydride and 4,4′-oxydianiline Providing a step;
b) providing a second polyamic acid solution containing polyamic acid, polyimide particle matting agent and submicron carbon black, wherein the polyamic acid is pyromellitic dianhydride and 4,4′-oxydi Derived from aniline or derived from pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine, or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride , Pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine, or i) block of pyromellitic dianhydride and 4,4′-oxydianiline, and ii ) A step derived from a block of pyromellitic dianhydride and paraphenylenediamine;
c) adding at least one submicron fumed metal oxide to the second polyamic acid solution;
d) Coating the polyamic acid solution formed in step c on the first polyimide layer, or coating the polyamic acid solution formed in step c on the first polyimidic acid green form, or step c. Forming a multilayer composite by co-extrusion of the polyamic acid solution formed in step 1 and a first polyimide acid solution;
f) imidizing the composite material formed in step d to produce a first polyimide layer and a second polyimide layer.

Another embodiment of the present disclosure is a method for reducing the amount of colorant in a multilayer film and achieving an L ^* color of less than 30 and a 60 degree gloss value of less than 10.
a) providing a component selected from the group consisting of a first polyimide layer, a first polyamic acid solution, and a first polyamic acid green film;
b) providing a second polyamic acid solution containing polyamic acid, polyimide particle matting agent and submicron carbon black;
c) adding 15-50% by weight of at least one submicron fumed metal oxide to the second polyamic acid solution;
d) Coating the polyamic acid solution formed in step c on the first polyimide layer, or coating the polyamic acid solution formed in step c on the first polyimidic acid green form, or step c. Forming a multilayer composite by co-extrusion of the polyamic acid solution formed in step 1 and a first polyimide acid solution;
f) imidizing the composite material formed in step d to produce a first polyimide layer and a second polyimide layer.

Another embodiment of the present disclosure is a method for reducing the amount of colorant in a multilayer film and achieving an L ^* color of less than 30 and a 60 degree gloss value of less than 10.
a) a component selected from the group consisting of a first polyimide layer, a first polyamic acid solution and a first polyamic acid green film and derived from pyromellitic dianhydride and 4,4′-oxydianiline Providing a step;
b) providing a second polyamic acid solution containing polyamic acid, polyimide particle matting agent and submicron carbon black, wherein the polyamic acid is pyromellitic dianhydride and 4,4′-oxydi Derived from aniline or derived from pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine, or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride , Pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine, or i) block of pyromellitic dianhydride and 4,4′-oxydianiline, and ii ) A step derived from a block of pyromellitic dianhydride and paraphenylenediamine;
c) adding 15-50% by weight of at least one submicron fumed metal oxide to the second polyamic acid solution;
d) Coating the polyamic acid solution formed in step c on the first polyimide layer, or coating the polyamic acid solution formed in step c on the first polyimidic acid green form, or step c. Forming a multilayer composite by co-extrusion of the polyamic acid solution formed in step 1 and a first polyimide acid solution;
f) imidizing the composite material formed in step d to produce a first polyimide layer and a second polyimide layer.

  Where an amount, concentration or other value or parameter is presented as a range, preferred range, or list of preferred and lower preferred values, this is either regardless of whether the ranges are disclosed separately It is understood that all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value are specifically disclosed. When numerical ranges are listed herein, unless otherwise specified, the ranges are intended to include their endpoints and all integers and fractions within the range. Numeric values are understood as having the precision of the number of significant digits provided. For example, the number 1 is understood to encompass a range of 0.5 to 1.4, whereas the number 1.0 is a range of 0.95 to 1.04 including the end of the specified range. Will be understood to encompass. When defining a range, the scope of the present invention is not intended to be limited to the particular values recited.

  In describing specific polymers, it should be understood that Applicants may refer to the polymers, optionally by the amount of monomers used to produce them or the monomers used to make them. is there. Such a description may not include the specific nomenclature used to describe the final polymer, or may not contain product-by-process terms, but such references to monomers and amounts are Unless the context indicates otherwise, it should be construed to mean that the polymer is made from those monomers.

  The materials, methods, and examples herein are illustrative only and not intended to be limiting, unless explicitly stated. Although methods and materials similar or equivalent to those described herein can be used, suitable methods and materials are described herein.

  All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

  An exemplary preparation and evaluation of the film is described below.

Carbon black slurry (SB6 carbon):
A carbon black slurry was prepared consisting of 82% by weight DMAC, 12% by weight carbon black powder (from Special Black 6, from Orion Engineered Carbons LLC) and 6% by weight dispersion aid (from Byk 9077, Byk Chemie). The ingredients were thoroughly mixed in a high shear moving vane type mixer. The agglomerates were then dispersed and the slurry processed in a bead mill to achieve the desired particle size. The median particle size was 0.14 microns.

Fumed Alumina Slurry Fumed door consisting of 76.3 wt% DMAC, 19.8 wt% fumed alumina powder (Alu C805 from Evonik) and 3.9 wt% dispersant (Disperbyk 180 from Byk Chemie) Lumina slurry was prepared. The ingredients were thoroughly mixed in a high speed disk disperser. The slurry was then processed in a bead mill so that any agglomerates were dispersed and the desired particle size was achieved. The median particle size was 0.3 microns.

Polyimide particle slurry:
A polyimide particle slurry was prepared from a solution of PMDA / 4,4′ODA polyamic acid in pyridine by heating the solution to precipitate the polymer. The pyridine solvent was replaced with deionized water and then ground in a high shear environment. Deionized water was replaced with DMAc to a solids concentration of 3.6% by weight. The median particle size was 4.0 microns.

Colored polyimide particle slurry:
A colored polyimide particle slurry was prepared. Graphite powder was dispersed in a solution of PMDA / 4,4′ODA polyamic acid in pyridine. The mixture was heated to form a precipitate of polyimide particles containing 40 wt% graphite. The pyridine solvent was replaced with deionized water, ground in a high shear environment and then dried. The resulting powder was passed through a 325 mesh screen. The median particle size of the powder that passed through the screen was 9.9 microns. The powder was dispersed in DMAC to form a dispersion of 10% by weight colored polyimide particles.

  Kapton® MBC is an opaque matte black polyimide film manufactured by DuPont. It is based on PMDA / 4,4'ODA polyimide and contains about 5% by weight carbon black and about 2% by weight silica matting agent. This is available in various thicknesses.

PMDA / 4,4′ODA / PPD (molar ratio 100/70/30) copolyamic acid solution:
PPD was dissolved in DMAC to a concentration of about 2.27 wt% at 40-45 ° C. After reducing the temperature to 30-40 ° C., solid PMDA was added with stirring to achieve a PMDA: PPD stoichiometric ratio of about 0.99: 1. The mixture was allowed to react for 90 minutes with stirring. The mixture was diluted to about 5.8-6.5% solids by addition of DMAC. Then, 4,4′ODA was added and reacted at 40-45 ° C. for about 30 minutes to achieve a 70:30 4,4′ODA: PPD molar ratio. Solid PMDA was added sequentially with stirring and reacted at 40-45 ° C. for about 2 hours to achieve a polymer viscosity of 75-250 poise. The polyamic acid solid was 19.5% to 20.5%. The polymer solution was stored in the refrigerator until use.

Preparation of multilayer films Examples 1-4:
As shown in Table 1, the first polyimide layer was composed of Kapton® MBC film.

  The second polyimide layer was prepared using the filler slurry described above and shown in Table 1. The slurry was thoroughly mixed with the polyamic acid solution described above and shown in Table 1 at the appropriate ratio to produce the desired composition after curing. The resulting mixture was coated onto the first polyimide layer using a stainless steel casting rod. The coating was dried on a hot plate at 100 ° C. until dry by visual inspection. The resulting multilayer film was then placed on a pin frame to hold it flat and placed in a 120C oven. The oven temperature was raised to 320C over 45-60 minutes, then transferred to a 400C oven and held for 5 minutes, then removed from the oven and allowed to cool.

  The composition of the cured film is calculated from the composition of the components in the mixture, eliminating the DMAC solvent (removed during curing) and taking into account the removal of water during the conversion of polyamic acid to polyimide. It was.

  The 60 degree gloss was measured using a Micro-TRI-Glossmeter (from BYK-Gardner).

L ^* color was measured using a HunterLab ColorQuest® XE color meter (Hunter Associates Laboratory, Inc.) in a mode that includes reflectivity, specular reflection. This instrument was standardized before each use. Color data from the instrument was reported in the CIELAB 10 ° / D65 system as L ^* , a ^* , b ^* . An L ^* value of 0 is pure black, while an L ^* value of 100 is pure white. As a typical example, the difference in the L ^* value of one unit can be identified visually.

  The particle size of the filler particles in the slurry was either Horiba LA-930 (Horiba, Instruments, Inc., Irvine CA) or Malvern Mastersizer 3000 (Malvern Instruments, Inc., Westborough, Mass.) Particle size analyzer. Measured by laser diffraction. DMAC was used as a dispersion medium.

Alcohol wipe test:
The film was wiped three times with a towel moistened with isopropyl alcohol. If any colorant was observed to move from the film to the towel, a “fail” grade was given. This test is a measure of the film's suitability for durability against the process conditions of electronic circuit manufacturing.

  The results are shown in Table 1.

  The materials, methods, and examples herein are illustrative only and not intended to be limiting, unless explicitly stated. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

  Not all of the operations described above in the summary or examples are required, some specific operations may not be required, and in addition to those described, additional operations may be performed. Please keep in mind. Still further, the order in which each task is listed is not necessarily the order in which they are performed. After reading this specification, one of ordinary skill in the art can determine operations that can be used for their specific needs or requirements.

  In the foregoing specification, the invention has been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below. All features disclosed in this specification may be replaced by other features useful for the same, equivalent, or similar purposes.

  Accordingly, this description is intended to be illustrative rather than limiting and all such modifications are intended to be included within the scope of the present invention.

  Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, benefits, other advantages and solutions to problems, as well as any elements that may yield or make more emphasis on benefits, other advantages and problems, are important in any or all claims. It is not required or interpreted as an essential feature or element.

Claims (24)

a. A polyimide, derived from at least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and at least 50 mole percent aromatic diamine, based on the total diamine content of the polyimide. A first polyimide layer having a thickness of 8 to 130 microns, comprising
b. A second polyimide layer having a thickness of 0.5 to 20 microns in direct contact with the first polyimide layer,
i) 25-50% by weight polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 moles based on the total diamine content of the polyimide 25-50% by weight polyimide derived from percent aromatic diamine;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black;
iv) comprising a second polyimide layer comprising 15-50% by weight of at least one submicron fumed metal oxide, having an L ^* color of less than 30 and a 60 degree gloss value of less than 10. , Multilayer film. The first polyimide layer is
i. ) 1-15% by weight of low conductivity carbon black, or ii. 2. The multilayer film of claim 1 further comprising 1 to 40% by weight pigment or dye.   The first polyimide layer further comprises 1-20% by weight of a matting agent selected from silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof; The multilayer film according to claim 2.   The multilayer film of claim 2, wherein the first polyimide layer further comprises 1-20 wt% matting agent, which is carbon black having an average particle size of 2-9 micrometers. The first polyimide layer further comprises 1 to 20% by weight of a matting agent, and the matting agent comprises:
3. A carbon black having an average particle size of 2) to 9 microns, and ii) a mixture of silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof. Multilayer film. The first polyimide layer is
i. 2) 9% by weight of a low conductivity carbon black; and ii) a matting agent,
a. Present in an amount of 1.6 to 10% by weight;
b. Has a median particle size of 1.3 to 10 microns, and c. The multilayer film of claim 1 further comprising a matting agent having a density of 2 to 4.5 g / cc.   The polyimide of the second polyimide layer is derived from pyromellitic dianhydride and 4,4′-oxydianiline, or pyromellitic dianhydride, 4,4′-oxydianiline and para The multilayer film of claim 1 derived from phenylenediamine.   The polyimide of the second polyimide layer is derived from i) pyromellitic dianhydride and 4,4′-oxydianiline block, and ii) pyromellitic dianhydride and paraphenylenediamine block. The multilayer film according to claim 1. The polyimide of the first polyimide layer is derived from pyromellitic dianhydride and 4,4′-oxydianiline, and the polyimide of the second polyimide layer is
i) pyromellitic dianhydride and 4,4′-oxydianiline,
ii) pyromellitic dianhydride, 4,4′-oxydianiline and paraphenylenediamine,
iii) block of pyromellitic dianhydride and 4,4′-oxydianiline, and block of pyromellitic dianhydride and paraphenylenediamine, or iv) 3,3 ′, 4,4′-biphenyltetracarboxylic The multilayer film of claim 1 derived from acid dianhydride, pyromellitic dianhydride, 4,4'-oxydianiline and paraphenylenediamine. And further comprising a third polyimide layer having a thickness of 0.5 to 20 microns in direct contact with the first polyimide layer on the opposite side of the second polyimide layer, the third polyimide layer comprising:
i) a polyimide comprising at least 50 mole percent aromatic dianhydride, based on the total dianhydride content of the polyimide, and at least 50 mole percent aromatic diamine, based on the total diamine content of the polyimide. The multilayer film of claim 1 comprising a derived polyimide; and ii) a matting agent or a mixture thereof.   11. A multilayer film according to claim 10, wherein the matting agent in the third polyimide layer is selected from silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof.   The multilayer film according to claim 10, wherein the matting agent in the third polyimide layer is carbon black having an average particle diameter of 2 to 9 microns. The matting agent in the third polyimide layer is
11. A carbon black having an average particle size of 2-9 microns, and ii) a mixture of silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof. Multilayer film. And further comprising a third polyimide layer having a thickness of 0.5 to 20 microns in direct contact with the first polyimide layer on the opposite side of the second polyimide layer, the third polyimide layer comprising:
i) 25-50% by weight polyimide, based on the total dianhydride content of the polyimide, at least 50 mole percent aromatic dianhydride, and at least 50 moles based on the total diamine content of the polyimide 25-50% by weight polyimide derived from percent aromatic diamine;
ii) 15-35 wt% polyimide particle matting agent;
iii) greater than 0% and less than 20% by weight of at least one submicron carbon black; and iv) 15-50% by weight of at least one submicron fumed metal oxide. 2. The multilayer film according to 1. The first polyimide layer is
15. The multilayer film of claim 14, further comprising i) 1-15 wt% low conductivity carbon black, or ii) 1-40 wt% pigment or dye.   The first polyimide layer further comprises 1-20 wt% matting agent selected from silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof; The multilayer film according to claim 14.   The multilayer film of claim 14, wherein the first polyimide layer further comprises 1-20 wt% matting agent, which is carbon black having an average particle size of 3-9 micrometers. The first polyimide layer is
i) carbon black having an average particle size of 2-9 microns, and ii) further comprising a matting agent mixture of silica, alumina, zirconia, boron nitride, barium sulfate, polyimide particles, calcium phosphate, talc or mixtures thereof. The multilayer film according to claim 14. The first polyimide layer is
i) 2-9 wt% low conductivity carbon black;
ii) a matting agent,
a. Present in an amount of 1.6 to 10% by weight;
b. Has a median particle size of 1.3 to 10 microns, and c. 15. A multilayer film according to claim 14, further comprising a matting agent having a density of 2 to 4.5 g / cc.   The multilayer film of claim 1, wherein the submicron fumed metal oxide is fumed alumina, fumed silica, or a mixture thereof.   The multilayer film of claim 1, wherein the polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline.   The multilayer film according to claim 1, wherein the polyimide particle matting agent is a colored polyimide particle matting agent.   24. The multilayer film of claim 22, wherein the colored polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4'-oxydianiline.   The polyimide particle matting agent is derived from pyromellitic dianhydride and 4,4′-oxydianiline, and the polyimide of the second polyimide layer is pyromellitic dianhydride, 4,4′- The multilayer film of claim 1 derived from oxydianiline and paraphenylenediamine.

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