CN109370299B - Black ink and preparation method and application thereof - Google Patents
Black ink and preparation method and application thereof Download PDFInfo
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- CN109370299B CN109370299B CN201811246602.XA CN201811246602A CN109370299B CN 109370299 B CN109370299 B CN 109370299B CN 201811246602 A CN201811246602 A CN 201811246602A CN 109370299 B CN109370299 B CN 109370299B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
Abstract
The invention provides a black ink, which comprises components of soluble polyimide, a flame retardant, resin, DMAC (dimethylacetamide), carbon black and talcum powder, wherein the black covering film prepared by using the ink provided by the invention has the advantages of low price and wide source of production raw materials, and the performances of blackness, light transmittance, light shielding property, matte degree and the like can be adjusted according to the requirements of customers.
Description
Technical Field
The invention belongs to the technical field of flexible circuit boards, and particularly relates to black ink as well as a preparation method and application thereof.
Background
Compared with the common covering film, the black covering film is opaque and has no reflection, and is mainly used for preparing LED lamp panels, automobile lamps and the like; in addition, the black cover film is also widely used for manufacturing mobile phones.
As for the preparation technique of the black cover film, there are two common technical approaches: firstly, coating a common covering film on a black polyimide film (PI film) by using glue solution; secondly, coating a special black glue solution on a common PI film. For mass production, the first way only needs to replace raw materials, and the operation is simple and convenient; the second approach starts with glue formulation.
However, the first approach has problems in that: black PI films with a thickness of more than 25 μm are sold at home and abroad, black PI films with a thickness of 12.5 μm are produced by manufacturers and in small supply, the black PI films are expensive and have immature production processes, in order to achieve the required blackness, a large amount of carbon black powder needs to be added into the black PI films, which causes the reduction of surface insulation performance and the occurrence of adverse phenomena such as short circuit, so that the blackness and the insulation performance are contradictory, and the actual PI film production is seriously affected by too high proportion of the filler, so that a plurality of manufacturers can produce black PI, but the production of the black PI films with a thickness of 12.5 μm is difficult, and the specification is often required by customers.
The second approach, starting from the glue formulation, has the problems: the requirements of the cover film on the glue layer are very complex, multiple properties are mutually contradictory, the difficulty in obtaining a cover film meeting the requirements is very high, the contradiction is more complicated by developing a black glue solution, the problem of the cover film is solved, the contradiction among blackness, light transmittance and insulativity caused by adding carbon black is also reconciled, the basic properties of the final black cover film are poor compared with those of a common cover film, the storage property, the adhesion property, the coverage property, the electrical property and the like are reduced in different degrees, and the performances such as the matte degree (surface roughness, one appearance property) and the like of the black cover film cannot meet the requirements of mobile phone manufacturers.
Disclosure of Invention
In order to solve the problems of the black covering film in the prior art, the invention aims to provide black ink.
The invention also aims to provide a preparation method of the black ink.
The invention also aims to provide application of the black ink.
In order to achieve the purpose, the invention adopts the following technical scheme:
the black ink comprises the following components in parts by weight:
2 to 20 parts of soluble polyimide,
1-2 parts of a flame retardant,
2-5 parts of resin,
1-5 parts of DMAC (dimethylacetamide),
1 to 2 parts of carbon black,
0.1-0.5 part of talcum powder.
Preferably, the preparation method of the soluble polyimide comprises the following steps:
(1) adding diamine and tetracarboxylic dianhydride into an NMP solvent according to a molar ratio of 1:1, and uniformly mixing in a water bath at 5 ℃ to obtain PAA acid;
(2) and (2) adding acetic anhydride and a catalyst into the PAA acid obtained in the step (1), and dehydrating at 90 ℃ to obtain the soluble polyimide.
Further preferably, the diamine is one or more of 2, 2-bis (4- (4-aminophenoxy) phenyl) propane, ODA and 3, 3' -DDS.
Further preferably, the tetracarboxylic dianhydride is one or more of BPADA, BTDA, PMDA and ODPA.
Further preferably, the catalyst is one or more of pyridine, picoline, triethylamine and isoquinoline.
Preferably, the flame retardant is coyen OP-935.
Preferably, the resin is a modified epoxy resin, and the modified epoxy resin is XD-1000, Jiashend 3501L or CV company C431A 70.
The preparation method of the black ink comprises the following steps: and sequentially adding the soluble polyimide, the flame retardant, the resin, the DMAc, the carbon black and the talcum powder into a container, and uniformly stirring at a high speed.
Use of black ink in a cover film.
Preferably, the cover film comprises a first protective layer, a black ink layer, an insulating layer, an adhesive layer and a second protective layer which are sequentially connected.
Preferably, the first protective layer is a matte release film layer.
Preferably, the insulating layer is one of a liquid crystal polymer layer, a polyimide layer, a polyester film, and a polynaphthalene film.
Preferably, the thickness of the insulating layer is 5-50 mu.
Preferably, the adhesive layer is one of an epoxy glue layer, an acrylic acid layer, a polyester glue layer and a polyimide glue layer.
Preferably, the thickness of the adhesive layer is 8-100 mu.
Preferably, the second protective layer is a release film layer.
The preparation method of the covering film comprises the following steps: after the black ink is prepared, the black ink is coated on a common PI film and then is solidified.
The black covering film prepared by the black ink provided by the invention is low in price and wide in source of production raw materials, and can adjust performances such as blackness, light transmittance, light shielding property, matte degree and the like according to the requirements of customers. The degree of blackness, light transmittance and light shielding property are controlled by the addition amounts and fineness of carbon powder and silica, and the degree of mattness is controlled by the roughness of the protective film of the black layer. The specific method comprises the following steps: more fillers are needed to be added and the fineness of the fillers is controlled to be lower if the black rubber with blacker color, lower light transmittance and better light shading property is needed to be obtained. And a surface roughness with a degree of dumb of 30 is required to be obtained by transferring the black layer release film with the degree of dumb of 30 onto the black layer to realize a black cover film with the degree of dumb of 30.
The black covering film prepared by the black ink provided by the invention has the advantages that the black ink layer is separated from the glue layer for protecting the circuit, so that the problem of short circuit between circuits in the circuit board to be protected is effectively avoided. And the protective layer above the black ink layer can effectively protect the black ink layer from being polluted and avoid the possibility of pollution, and in addition, as the selected protective layer has better roughness with the surface contacted with the black ink layer, better matte degree or even a dull black covering film can be easily obtained by utilizing the transfer printing principle.
In the covering film, the first protective layer is a matte release film or a matte micro-adhesive film, and the thickness of the first protective layer is preferably 25-200 micrometers, and more preferably 38-100 micrometers. Its main function is to provide a stable matte finish to the black ink layer. The matte degree of the contact surface of the protective layer 1 and the adhesive surface is preferably 30 or less, more preferably 10 or less (matte product). The bright release film can also be selected, and the product is a bright black covering film.
The black ink layer provides the black degree of the black covering film, and the thickness range of the black ink layer is 3-40 micrometers. Its main function is to provide the properties of black covering film such as shading rate, blackness, etc,
The insulating layer is one of LCP, polyimide, polyester film and polynaphthalene film, and the thickness of the insulating layer is 3-50 micrometers, and more preferably 5-25 micrometers.
The adhesive layer is one of epoxy adhesive, acrylic adhesive, polyester adhesive, polyurethane adhesive, polyimide adhesive and the like or a doped adhesive, and the thickness of the adhesive layer is 8-100 micrometers, preferably 10-40 micrometers.
The second protective layer is made of protective materials such as release paper, release film and micro-adhesive film, and has the main function of protecting the low dielectric loss adhesive layer from being polluted.
The invention has the advantages of
1. The black covering film prepared by using the ink provided by the invention is low in price and wide in source of production raw materials, and can adjust performances such as blackness, light transmittance, light shielding property, matte degree and the like according to the requirements of customers;
2. the black covering film prepared by the black ink provided by the invention has the advantages that the black ink layer is separated from the glue layer for protecting the circuit, so that the problem of short circuit between circuits in the circuit board to be protected is effectively avoided.
Drawings
FIG. 1 is a schematic view of the structure of a coverlay film prepared using the black ink of the present invention.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1
This example prepares a black ink, numbered a, having the components and preparation method as follows:
two diamines ODA, 2, 2-bis (4- (4-aminophenoxy) phenyl) propane; with BPADA, BTDA anhydride as anhydride: diamine molar ratio of 1:1 into NMP solvent with solid content of 20%, and mixing and stirring in water bath at 5 deg.C for 8hr to obtain PAA acid;
mixing acetic anhydride and pyridine according to a molar ratio of 2:1: adding into PAA acid synthesized in the first step at a ratio of 1, and dehydrating at 90 deg.C for 7hr to obtain soluble polyimide 1.
32g of the above soluble polyimide 1 solution, 3.84g of Kelaien OP-935, 7.72g of traded XD-1000 resin, 8 g of DMAC solvent, 4.5g of Mitsubishi MA-100 and 0.6g of talc were added in this order, and the mixture was stirred at high speed for 2 hours to obtain black ink A.
Example 2
This example prepares a black ink, numbered B, having the components and preparation method as follows:
two diamines 3, 3' -DDS and 2, 2-bis (4- (4-aminophenoxy) phenyl) propane; and BPADA and PMDA anhydride in a molar ratio of 1:1 into NMP solvent with solid content of 10%, and mixing and stirring in water bath at 5 deg.C for 8hr to obtain PAA acid;
mixing acetic anhydride and isoquinoline according to a molar ratio of 2:1: adding into PAA acid synthesized in the first step at a ratio of 1, and dehydrating at 90 deg.C for 7hr to obtain soluble polyimide 2.
30g of the above soluble polyimide 2 solution, 3.2g of Kelaien OP-935, 7.72g of traded rice XD-1000 resin, 8 g of DMAc solvent, 4.3g of Mitsubishi MA-100 and 0.4g of talc were added in this order, and the mixture was stirred at high speed for 2 hours to obtain black ink B.
Example 3
This example prepares a black ink, numbered C, having the components and preparation method as follows:
two diamines ODA, 2, 2-bis (4- (4-aminophenoxy) phenyl) propane; and BPADA and BTDA anhydride in a molar ratio of 1:1 in NMP solvent, wherein the solid content is 20%, and fully mixing and stirring in a water bath at 5 ℃ for 8hr to obtain PAA acid.
Mixing acetic anhydride and pyridine according to a molar ratio of 2: adding into the PAA acid synthesized in the first step at a ratio of 1:1, and dehydrating at 90 deg.C for 7hr to obtain soluble polyimide 3.
32g of the above soluble polyimide 3 solution, 4.2g of Kelaien OP-935, 7.72g of traded XD-1000 resin, 8 g of DMAc solvent, 0.5g of nigrosine and 1.0g of talc were added in this order, and the mixture was stirred at high speed for 2 hours to obtain black ink C.
Example of detection
Three black cover films were prepared using black inks A, B and C, numbered AD-1, AD-2 and AD-3,
the structure is shown in fig. 1, wherein 1 is a first protective layer, 2 is a black ink layer, 3 is an insulating layer, 4 is an adhesive layer, and 5 is a second protective layer.
The preparation method comprises the following steps: and coating 2-25 mu m on the surface of the PI film, drying by an oven, curing, and attaching a matte release film or release paper to obtain the first surface of the black covering film. And coating a covering film adhesive on the other side of the PI film and attaching release paper to obtain a black covering film. The properties are shown in Table 1.
TABLE 1 test results of three types of mulch film properties
Compared with the black covering film in the prior art, the black covering film has the advantages that the black ink layer is separated from the adhesive layer for protecting the circuit, so that the problem of short circuit between circuits in the protected circuit board is effectively solved. And the protective layer above the black ink layer can effectively protect the black ink layer from being polluted and avoid the possibility of pollution, and in addition, as the selected protective layer has better roughness with the surface contacted with the black ink layer, better matte degree or even a dull black covering film can be easily obtained by utilizing the transfer printing principle.
Claims (4)
1. The black ink is characterized by being prepared from the following components in parts by weight:
2 to 20 parts of soluble polyimide,
1-2 parts of a flame retardant,
2-5 parts of resin,
1-5 parts of DMAC (dimethylacetamide),
1 to 2 parts of carbon black,
0.1-0.5 part of talcum powder;
the flame retardant is Kelaien OP-935;
the resin is modified epoxy resin, and the modified epoxy resin is XD-1000, Jiashengde 3501L or CVC 431A 70;
the preparation method of the soluble polyimide comprises the following steps:
(1) adding diamine and tetracarboxylic dianhydride into an NMP solvent according to a molar ratio of 1:1, and uniformly mixing in a water bath at 5 ℃ to obtain PAA acid;
(2) adding acetic anhydride and a catalyst into the PAA acid obtained in the step (1), and dehydrating at 90 ℃ to obtain the soluble polyimide;
the diamine is one or more of 2, 2-bis (4- (4-aminophenoxy) phenyl) propane, ODA and 3, 3' -DDS;
the tetracarboxylic dianhydride is one or more of BPADA, BTDA, PMDA and ODPA;
the catalyst is one or more of pyridine, picoline, triethylamine and isoquinoline;
the molar ratio of the acetic anhydride to the catalyst to the tetracarboxylic dianhydride is 2:1: 1;
the black ink is used for polyimide films.
2. The method for preparing the black ink according to claim 1, comprising the steps of: and sequentially adding the soluble polyimide, the flame retardant, the resin, the DMAC, the carbon black and the talcum powder into a container, and stirring at a high speed to mix uniformly.
3. Use of a black ink according to claim 1 or a black ink prepared by the method according to claim 2 in a cover film.
4. The use of the black ink in a cover film according to claim 3, wherein the cover film comprises a first protective layer, a black ink layer, an insulating layer, an adhesive layer, and a second protective layer, which are connected in this order.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811246602.XA CN109370299B (en) | 2018-10-24 | 2018-10-24 | Black ink and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811246602.XA CN109370299B (en) | 2018-10-24 | 2018-10-24 | Black ink and preparation method and application thereof |
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| CN109370299A CN109370299A (en) | 2019-02-22 |
| CN109370299B true CN109370299B (en) | 2021-07-16 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017159914A1 (en) * | 2016-03-18 | 2017-09-21 | 국도화학 주식회사 | Low-glass black polyimide transfer film and manufacturing method therefor |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017159914A1 (en) * | 2016-03-18 | 2017-09-21 | 국도화학 주식회사 | Low-glass black polyimide transfer film and manufacturing method therefor |
Non-Patent Citations (1)
| Title |
|---|
| "可溶性聚酰亚胺用于无胶双面挠性覆铜板的研究";胡启彬等;《绝缘材料》;20170227;第50卷(第2期);第30-34页 * |
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