CN117510979A - Titanium black composition, polyamic acid composition, polyimide film, and laminate thereof - Google Patents
Titanium black composition, polyamic acid composition, polyimide film, and laminate thereof Download PDFInfo
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- CN117510979A CN117510979A CN202211226075.2A CN202211226075A CN117510979A CN 117510979 A CN117510979 A CN 117510979A CN 202211226075 A CN202211226075 A CN 202211226075A CN 117510979 A CN117510979 A CN 117510979A
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- titanium black
- polyimide film
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 122
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000010936 titanium Substances 0.000 title claims abstract description 97
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 97
- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 47
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000077 silane Inorganic materials 0.000 claims abstract description 33
- 125000003118 aryl group Chemical class 0.000 claims abstract description 8
- 239000004642 Polyimide Substances 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 238000002834 transmittance Methods 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 5
- 125000003700 epoxy group Chemical class 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 36
- 239000000758 substrate Substances 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002270 dispersing agent Substances 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101001045744 Sus scrofa Hepatocyte nuclear factor 1-beta Proteins 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- RKLXSINPXIQKIB-UHFFFAOYSA-N trimethoxy(oct-7-enyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCC=C RKLXSINPXIQKIB-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/41—Opaque
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a titanium black composition, a polyamic acid composition, a polyimide film and a laminate thereof. Titanium black is coated with a silane having a specific structure of an epoxy group or an aryl group to prepare a titanium black composition excellent in dispersibility. The titanium black composition is added to polyamic acid to obtain a polyamic acid composition, and is used to produce a polyimide film having low dielectric loss and a black shielding effect, and a laminate thereof.
Description
Technical Field
The present invention relates to a polyamic acid composition and a polyimide laminate, and more particularly, to a titanium black composition, a polyamic acid composition, a polyimide film, and a laminate thereof.
Background
Polyimide (PI) films are formed by applying a polyamic acid to a substrate and then cyclizing the substrate at high temperature. The polyimide film has good high and low temperature resistance, good environmental stability, good mechanical property and dielectric property, so the polyimide film has wide application in the scientific and technological industry. For example, polyimide films can be used as protective layers for flexible copper foil substrates (flexible copper clad laminate, FCCL) and flexible circuit boards (flexible printed circuit board, FPCB) of flexible circuit boards, and also as insulating materials for electronic devices, etc.
A known method for producing a black polyimide film is to add a black pigment to a polyamic acid to improve the blackness and light-shielding properties of the polyimide film. The known black pigment is carbon black having good color developing properties, but since carbon black has conductivity, dielectric loss increases. It is known to use other black pigments which are not conductive, but they may have a problem of poor dispersibility, so that a dispersant is required to be added to improve color development. However, the addition of the dispersant also causes an increase in dielectric loss.
In view of the above, it is desirable to provide a polyamic acid composition that includes a black pigment having good dispersibility and that does not cause an increase in dielectric loss.
Disclosure of Invention
In one aspect, the present invention provides a titanium black composition comprising titanium black and titanium black coated silane.
Another aspect of the present invention provides a polyamic acid composition comprising the titanium black composition of the aspect described above.
Another aspect of the present invention is to provide a polyimide film comprising the polyamic acid composition of the above aspect.
In yet another aspect of the present invention, there is provided a laminate comprising a metal layer and a polyimide laminate layer of the polyimide film of the above aspect.
According to one aspect of the present invention, there is provided a titanium black composition comprising titanium black and titanium black coated silane. The silane has the structure of the following formula (1):
R 3 -R 2 -Si-(OR 1 ) 3 ……(1)
in formula (1), R 1 Is methyl or ethyl, R 2 Is a single bond, an alkoxy group having 1 to 6 carbon atoms or an alkylene group having 1 to 6 carbon atoms, and R 3 Is epoxy or aryl.
According to an embodiment of the present invention, the weight ratio of the titanium black to the silane is 1:0.005 to 1:0.05.
according to another aspect of the present invention, there is provided a polyamic acid composition comprising the titanium black composition of the above aspect and a polyamic acid.
According to an embodiment of the present invention, the weight ratio of the polyamic acid to the titanium black composition is 100:2 to 100:20.
according to another aspect of the present invention, there is provided a polyimide film prepared from the polyamic acid composition of the above aspect. The polyimide film has a dielectric loss of less than 0.006 at 10GHz and a light transmittance of less than 10%.
According to yet another aspect of the present invention, a laminate is provided that includes a first metal layer and a polyimide stack layer on the first metal layer. The polyimide stack layer comprises at least one polyimide film of the above-described aspect.
According to an embodiment of the present invention, the laminate further includes a second metal layer. The polyimide stack layer is arranged between the first metal layer and the second metal layer.
According to an embodiment of the invention, the thickness of the first metal layer is 9 μm to 35 μm.
According to an embodiment of the present invention, the total thickness of the polyimide stack layer is 12 μm to 50 μm.
According to an embodiment of the present invention, the polyimide stack layer includes 1 to 3 polyimide films.
The titanium black composition, the polyamic acid composition and the polyimide film are applied, and the polyamic acid is added into the titanium black coated by silane to prepare a laminated body with low dielectric loss and black shielding effect.
Drawings
The aspects of the disclosure are best understood from the following detailed description when read with the accompanying drawing figures. It should be noted that, as is standard in the industry, many features are not drawn to scale. In fact, the dimensions of many of the features may be arbitrarily scaled for clarity of discussion.
Fig. 1A and 1B are cross-sectional views illustrating a laminate according to some embodiments of the invention.
Fig. 2A-2F are cross-sectional views illustrating laminates according to some embodiments of the invention.
Fig. 3A-3L are cross-sectional views illustrating laminates according to some embodiments of the invention.
Reference numerals: 100,200, 300; 110,210,310: a metal substrate; 120, polyimide film; 130,230,330: titanium black composition; 150,250,350 a metal layer; 220 polyimide stack layers; 223,225 polyimide film; a polyimide stack layer 320; 323,325,328 polyimide film.
Detailed Description
The following disclosure provides many different embodiments, or examples, for implementing different features of the invention. Specific examples of components and arrangements are described below to simplify the present disclosure. These are of course merely examples and are not intended to be limiting. For example, descriptions of the first feature being formed on or over the second feature include embodiments in which the first feature and the second feature are in direct contact, as well as embodiments in which other features are formed between the first feature and the second feature such that the first feature and the second feature are not in direct contact. In addition, the present disclosure repeats reference numerals and/or letters in the various embodiments. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
In addition, spatially relative terms, such as "lower", "below" of … "," below "," above "of …", "above", and the like, are used for ease of description of the relationship of the parts or features depicted in the drawings to other parts or features. Spatially relative terms may be intended to encompass different orientations of the component in use or operation in addition to the orientation depicted in the figures. The device may be otherwise oriented (rotated 90 degrees or in other directions), and the spatially relative descriptions used in the present disclosure may be read as such.
As used herein, "about", "near" or "substantially" generally means within 20 percent, or within 10 percent, or within 5 percent of the stated value or range. The numerical values recited herein are approximations that may include the antecedent "about," near, "or" substantially, "even if not explicitly stated.
In view of the above, the present invention provides a titanium black composition, a polyamic acid composition, a polyimide film, and a laminate thereof, in which a polyamic acid (PAA) is added to titanium black coated with silane, and the resultant is cyclized to obtain a polyimide film having a low dielectric loss and a black shielding effect, and a laminate thereof.
The invention provides a titanium black composition, which comprises titanium black and silane coated on the surface of the titanium black. Titanium black is a non-conductive black powder pigment. Titanium suboxide and titanium oxynitride are collectively referred to as titanium black. Silane was used as a surface treatment agent for titanium black. In some embodiments, the silane has the structure of formula (1):
R 3 -R 2 -Si-(OR 1 ) 3 ……(1)
in formula (1), R 1 Is methyl or ethyl, R 2 Is a single bond, an alkoxy group having 1 to 6 carbon atoms or an alkylene group having 1 to 6 carbon atoms, and R 3 Is epoxy (epoxy group) or aryl (aromatic group).
In some embodiments, the silane may be (3-glycidoxypropyl) trimethoxysilane, epoxybutyl trimethoxysilane, phenyl trimethoxysilane, and/or combinations of the foregoing. It should be noted that if the polarity of the functional group of the silane is low (e.g., linear alkyl or alkenyl), the molecular arrangement may be changed due to a large difference in polarity from the polyamic acid, and the dielectric loss of the polyimide film to be produced later may be increased. In addition, the titanium black composition of the present invention does not contain a dispersant, and since the dispersant generally has a polar functional group, it is easy to cause an increase in dielectric loss.
Since the titanium black surface has-OH functional groups, the alkoxy groups of the silane (i.e., -OR in formula (1) 1 Functional groups) can be bonded to the surface of the-OH functional groups to form the silane-coated titanium black composition described above. In some embodiments, the weight ratio of titanium black to silane is 1:0.005 to 1:0.05. when the weight of the silane is less than 0.005 based on 1 weight of the titanium black, the dispersibility of the titanium black composition in the polyamic acid cannot be effectively improved due to insufficient silane coated on the surface of the titanium black, so that the color spreading property after film formation is affected, and the light transmittance is increased; on the other hand, if the weight of silane is more than 0.05, there is an excess of silane that does not react with titanium black, resulting in an increase in dielectric loss of the polyimide film to be produced later.
In some embodiments, the titanium black composition may be prepared using N-methyl-2-pyrrolidone (NMP) as a solvent. In some embodiments, mixing titanium black, silane, and a solvent such as NMP may be mixed using a high-revolution homogenizer or ball mill. In some embodiments, the solvent may be removed by spray drying.
The polyamic acid composition provided by the invention is prepared by adding the titanium black composition into polyamic acid. In some embodiments, the polyamic acid comprises at least 25mol% of a repeating unit of formula (2):
in formula (2), a represents a divalent organic group derived from a cyclohexane-group-containing diamine, wherein the total carbon number of the divalent amine organic group is 6 to 18, formula (3) below; and Ar represents a tetravalent organic group derived from an aromatic group-containing tetracarboxylic dianhydride, which comprises the following formula (4) and formula (5).
B in formula (5) comprises a single bond, -O-, -CH 2 -、-C(CH 3 ) 2 -、SO 2 -or-CO-.
In some embodiments, the weight ratio of polyamic acid to titanium black composition is 100:2 to 100:20. when the weight ratio of the polyamic acid to the titanium black composition is in the aforementioned range, a Polyimide (PI) film to be produced later can have an appropriate light transmittance without causing an increase in dielectric loss.
The black polyimide film on the substrate can be obtained by coating the polyamic acid composition on the substrate (for example, a metal substrate) and cyclizing at high temperature. In some embodiments, the aforementioned high temperature cyclization step is performed at a temperature of about 270 ℃ to about 370 ℃. Some embodiments of the present invention provide a laminate comprising a metal substrate and a polyimide stack layer on the metal substrate. In some embodiments, the metal substrate has a thickness of about 9 μm to about 35 μm. In some embodiments, a metal layer on the polyimide stack layer may be optionally included. In other words, polyimide is stacked between the metal substrate and the metal layer. In some embodiments, the metal substrate and the metal layer comprise the same material, such as copper.
In some embodiments, the total thickness of the polyimide stack layer is from about 12 μm to about 50 μm. In some embodiments, the polyimide stack layer comprises at least one black polyimide film. In some embodiments, the polyimide stack layer comprises 1 to 3 polyimide films, wherein the black polyimide film may be 1, 2, or 3 layers. The black polyimide film contains the silane-modified titanium black composition of the present invention. In some embodiments, the black polyimide film of the present invention has a light transmittance of less than 10%, wherein the light transmittance is measured using the ultraviolet-visible light spectrum (UV-Vis) at 550 nm. In some embodiments, the black polyimide films of the present invention have a dielectric loss of less than 0.006 at 10GHz, where the dielectric loss is defined by dissipation factors (dissipation factor, df).
Referring to fig. 1A and 1B, a cross-sectional view of a laminate 100 according to some embodiments of the invention is shown, wherein the polyimide stack layer comprises 1 polyimide film. As shown in fig. 1A, the laminate 100 includes a metal substrate 110 and a polyimide film 120, wherein the polyimide film 120 includes a titanium black composition 130. The stack 100 of other embodiments shown in fig. 1B further comprises a metal layer 150 on the polyimide film 120 over the structure of fig. 1A.
Referring to fig. 2A-2F, a cross-sectional view of a laminate 200 according to some embodiments of the invention is shown, wherein the polyimide stack comprises 2 polyimide films. As shown in fig. 2A to 2F, the laminate 200 includes a metal substrate 210 and a polyimide stack layer 220, wherein the polyimide stack layer 220 includes a polyimide film 223 and a polyimide film 225. Fig. 2B, 2D and 2F further include a metal layer 250 on the structures of fig. 2A, 2C and 2E, respectively.
In fig. 2A and 2B, only the polyimide film 225 includes the titanium black composition 230; in fig. 2C and 2D, only the polyimide film 223 includes the titanium black composition 230; in fig. 2E and 2F, both polyimide film 223 and polyimide film 225 comprise titanium black composition 230. The thickness of each of the polyimide stack layers 220 (i.e., polyimide film 223 and polyimide film 225) may be the same or different. Although fig. 2A to 2F illustrate that the thickness of the polyimide film 225 is greater than that of the polyimide film 223, the present invention is not limited thereto.
Referring to fig. 3A-3L, cross-sectional views of a laminate 300 according to some embodiments of the invention are shown, wherein the polyimide stack layer comprises 3 polyimide films. As shown in fig. 3A to 3L, the laminate 300 includes a metal substrate 310 and a polyimide stack layer 320, wherein the polyimide stack layer 320 includes a polyimide film 323, a polyimide film 325, and a polyimide film 328. Fig. 3B, 3D, 3F, 3H, 3J, and 3L further include a metal layer 350 on the structures of fig. 3A, 3C, 3E, 3G, 3I, and 3K, respectively.
In fig. 3A and 3B, only the polyimide film 325 includes the titanium black composition 330; in fig. 3C and 3D, only the polyimide film 323 includes the titanium black composition 330; in fig. 3E and 3F, only the polyimide film 328 includes the titanium black composition 330; in fig. 3G and 3H, the polyimide film 323 and the polyimide film 325 include a titanium black composition 330; in fig. 3I and 3J, polyimide film 325 and polyimide film 328 comprise titanium black composition 330; in fig. 3K and 3L, the polyimide film 323, the polyimide film 325, and the polyimide film 328 each include a titanium black composition 330. The thickness of each of the layers in polyimide stack 320 (i.e., polyimide film 323, polyimide film 325, and polyimide film 328) may be the same or different. Although fig. 3A to 3L illustrate that the thickness of the polyimide film 325 is greater than the thickness of the polyimide film 323 and the polyimide film 328, and the polyimide film 323 and the polyimide film 328 have similar thicknesses, the present invention is not limited thereto.
The following examples are set forth to illustrate the practice of the invention and are not intended to limit the invention thereto, as various modifications and adaptations may be made by those skilled in the art without departing from the spirit and scope of the invention.
Example 1
Titanium black, (3-glycidoxypropyl) trimethoxysilane and N-methyl-2-pyrrolidone are mixed according to the weight ratio of 100:0.5:900 and a reaction was carried out for one hour using a homogenizer to carry out a silane-coated titanium black procedure. When (3-glycidoxypropyl) trimethoxysilane is used as a surface treating agent, the surface treating agent has methoxy (-OCH) 3 ) Can bond with the-OH functional groups of the titanium black surface to form the titanium black composition of example one. The titanium black composition is stably suspended in NMP, and the mixture can be spray dried to obtain the NMP-removed titanium black composition. The D95 particle diameter of the titanium black composition, the D95 particle diameter of the titanium black composition after one week, and the D95 particle diameter of the titanium black composition in the polyamic acid were measured by a laser particle diameter analyzer, respectively, and the obtained results are shown in table one below.
Since NMP is also a solvent for the polyamic acid, the titanium black composition/NMP mixture can be added directly to the polyamic acid, example one in which the titanium black composition and the polyamic acid are mixed in a weight ratio of 10:100 to obtain a polyamic acid composition. And (3) coating the polyamic acid composition on a copper foil substrate, and cyclizing at high temperature to obtain a black polyimide film on the copper foil substrate. Next, the copper foil was removed with an etching solution to obtain a black polyimide film having a thickness of 12 μm. The SPDR tool was connected using a network analyzer to measure the dissipation factor (Df) and dielectric constant (Dk) at 10 GHz. In addition, transmittance at 550nm was measured using ultraviolet-visible light spectrum to obtain transmittance of the black polyimide film. The measurement results are shown in the following table one.
Examples two to ten
Examples two to ten titanium black compositions and polyimide films were prepared using the same process as in example one. The difference is that the weight ratio of titanium black to silane in example two is 100:5, a step of; example three using a spray dried titanium black composition; the thickness of the polyimide films of the fourth to sixth embodiments was 25 μm, in which the weight ratio of the polyamic acid to the titanium black composition of the fifth and sixth embodiments was 100:2 and 100:20, a step of; examples seven to ten were changed to phenyltrimethoxysilane as the silane of the titanium black composition, wherein the thickness of the polyimide films of examples seven and eight was 12 μm (example eight using the titanium black composition after spray drying), the thickness of the polyimide films of examples nine and ten was 25 μm, and the weight ratio of the polyamic acid of examples nine and ten to the titanium black composition was 100, respectively: 2 and 100:20. conditions of examples two to ten and various measurement results are shown in the following table one.
Comparative examples one to seven
Comparative examples one to seven titanium black compositions (and polyimide films) were prepared using the same process as in example one. The difference is that the weight ratio of titanium black to silane in comparative example one is 100:0.1; the silanes (or surface treatments) of the titanium black compositions used in comparative examples two to seven were hexyl trimethoxysilane, 7-octenyl trimethoxysilane, dispersant, commercially available titanium black, 3-aminopropyl trimethoxysilane, and N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, respectively; wherein the weight ratio of titanium black to the dispersing agent in the fourth comparative example is 100:10. conditions of comparative examples one to seven and various measurement results are shown in the following table one.
List one
Examples one to ten coat titanium black with silane containing an epoxy group or an aryl group, and mix the silane and the titanium black in a specific weight ratio, so that the obtained titanium black composition has a good dispersibility; in addition, the polyamide acid and the titanium black composition are mixed in a specific weight ratio, so that the obtained polyimide film has low light transmittance and dielectric loss property. The polyimide film has better black shielding effect due to low light transmittance.
In contrast, in the comparative example, too little silane was used, the dispersibility of the titanium black composition could not be effectively improved, and the color development of the obtained polyimide film was further affected, resulting in an increase in light transmittance (light transmittance greater than 10%). In the second and third comparative examples, silane containing alkyl and alkenyl groups was used, and the polarity difference from the polyamide acid was large because of the low polarity of the functional groups, and the molecular arrangement was changed, so that the dielectric loss of the polyimide film was increased (Df value was more than 0.006). In comparative example IV, a known dispersant was mixed with titanium black, and the dispersant had a polar functional group, so that the dielectric loss of the polyimide film obtained was increased (Df value was more than 0.006). In comparative example five, commercially available titanium black was directly used without any surface treatment, and the dispersibility of titanium black in polyamic acid was poor, so that the transmittance of the obtained polyimide film was high (transmittance was more than 10%). The silane having an amine group used in comparative examples six and seven had poor dispersibility in titanium black, and thus the particle diameter of the obtained titanium black composition was too high, and thus it was not added to the polyamic acid to prepare a polyimide film.
According to the above, the titanium black composition, the polyamic acid composition, the polyimide film and the laminate thereof according to the present invention are prepared by coating titanium black with a silane having a specific structure of an epoxy group or an aryl group, thereby obtaining a titanium black composition having excellent dispersibility. The titanium black composition is added to polyamic acid to obtain a polyamic acid composition, and is used to produce a polyimide film having low dielectric loss and a black shielding effect, and a laminate thereof.
While the present invention has been described with reference to several embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and it is intended that the invention be limited only by the terms of the appended claims.
Claims (10)
1. A titanium black composition comprising:
titanium black; and
a silane coating the titanium black, wherein the silane has a structure of the following formula (1):
R 3 -R 2 -Si-(OR 1 ) 3 ……(1)
in formula (1), R 1 Is methyl or ethyl, R 2 Is a single bond, an alkoxy group having 1 to 6 carbon atoms or an alkylene group having 1 to 6 carbon atoms, and R 3 Is epoxy or aryl.
2. The titanium black composition of claim 1, wherein the weight ratio of the titanium black to the silane is 1:0.005 to 1:0.05.
3. a polyamic acid composition comprising the titanium black composition according to claim 1 or 2 and a polyamic acid.
4. The polyamic acid composition according to claim 3, wherein the weight ratio of the polyamic acid to the titanium black composition is 100:2 to 100:20.
5. a polyimide film prepared from the polyamic acid composition of claim 3 or 4, wherein the polyimide film has a dielectric loss of less than 0.006 at 10GHz and a light transmittance of less than 10%.
6. A laminate, comprising:
a first metal layer; and
a polyimide stack layer on the first metal layer, wherein the polyimide stack layer comprises at least one polyimide film of claim 5.
7. The laminate of claim 6, further comprising:
and the polyimide stacking layer is arranged between the first metal layer and the second metal layer.
8. The laminate of claim 6, wherein the first metal layer has a thickness of 9 μm to 35 μm.
9. The laminate of claim 6, wherein the polyimide laminate layer has a total thickness of from 12 μm to 50 μm.
10. The laminate of claim 6, wherein the polyimide laminate layer comprises 1 to 3 layers of the polyimide film.
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| TW111127961A TWI827161B (en) | 2022-07-26 | 2022-07-26 | Titanium black composition, polyamic acid composition, polyimide film and laminate thereof |
| TW111127961 | 2022-07-26 |
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| TWI558556B (en) * | 2013-10-22 | 2016-11-21 | 達邁科技股份有限公司 | Multilayered polyimide film incorporating polyimide powder delustrant, and manufacture thereof |
| WO2017159190A1 (en) * | 2016-03-14 | 2017-09-21 | 富士フイルム株式会社 | Composition, film, cured film, optical sensor, and film production method |
| US11028270B2 (en) * | 2016-12-08 | 2021-06-08 | Merck Patent Gmbh | Black matrix composition, black matrix, and black matrix production method |
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