WO2018214366A1 - 高雾度的有色超薄高频覆盖膜及制备方法 - Google Patents

高雾度的有色超薄高频覆盖膜及制备方法 Download PDF

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WO2018214366A1
WO2018214366A1 PCT/CN2017/104414 CN2017104414W WO2018214366A1 WO 2018214366 A1 WO2018214366 A1 WO 2018214366A1 CN 2017104414 W CN2017104414 W CN 2017104414W WO 2018214366 A1 WO2018214366 A1 WO 2018214366A1
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colored ink
layer
ink layer
colored
adhesive layer
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PCT/CN2017/104414
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English (en)
French (fr)
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杨立志
李韦志
李建辉
林志铭
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昆山雅森电子材料科技有限公司
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0274—Optical details, e.g. printed circuits comprising integral optical means
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • 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
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber 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
    • B32B2255/20—Inorganic 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
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/4023—Coloured on the layer surface, e.g. ink
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0183—Dielectric layers
    • H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure

Definitions

  • the invention relates to the field of FPC (flexible circuit board) cover film and preparation technology thereof, in particular to a high haze colored ultra-thin high-frequency cover film and a preparation method thereof.
  • FPC flexible circuit board
  • the material of the cover film currently on the market is generally a black polyimide film.
  • the bottleneck is that the black polyimide film has a thickness of 5 ⁇ m or less and has great difficulty in processing and handling.
  • Another ink-type colored high-frequency cover film is a colored ink coated with a 5-7.5 ⁇ m yellow ultra-thin polyimide film. This method also has the problems of high cost and large thickness.
  • another manufacturing method is a 5-7.5 ⁇ m yellow ultra-thin polyimide film, the upper layer is coated with a black adhesive or ink, and the black adhesive or the upper layer of the ink is coated with a carrier film, and is non-dull type. (Gloss) Cover film, resulting in high gloss (greater than 50GU), poor processing operability and high cost.
  • Taiwan Patent No. "TW201132714 A1” reveals a low-gloss black polyimide film doped with ceramic powder
  • Taiwan Patent No. "TW1481646 B” reveals a doping A low-gloss polyimide film of powdered polyimide
  • a Korean patent No. "10-2012-0036253” discloses a black polyimide film doped with carbon black.
  • such an approach is not easy to achieve in a 5-7.5 ⁇ m ultra-thin polyimide film.
  • a high-frequency colored ultra-thin cover film composed of a colored ink layer and a high-frequency adhesive is replaced by a colored polyimide cover film.
  • the colored ink layer can be obtained by changing the resin, adding the doped powder, and obtaining various advantages such as high extinction, high flame retardancy and high hardness by changing the powder content and designing the particle size.
  • the present invention provides a high haze color super-high, with high heat dissipation, high flame retardancy, high extinction and high hardness, and low cost development directions, as well as the need for powerful and high-speed signal transmission.
  • the thin high-frequency cover film comprises a colored ink layer and a high-frequency adhesive layer, and the release layer of the release film or the release paper is respectively attached to the upper and lower sides, and has a very low dielectric constant and loss, extremely high ion purity, and super Thin stack thickness, high heat dissipation, high flame retardancy, high extinction, especially suitable for use in high-frequency thin-line circuits; higher reliability and operability compared to general cover films The gloss value of the surface, thus replacing the general cover film material.
  • the present invention adopts a technical solution to provide a high-haze colored ultra-thin high-frequency cover film, including a colored ink layer and a high-frequency adhesive layer, wherein the colored ink layer is located at the high Above the frequency adhesive layer, the colored ink layer is provided with at least one layer;
  • the hardness of the colored ink layer is HB-5H;
  • the colored ink layer has a gloss of 0-60 GU (60°);
  • the colored ink layer has a roughness of 50-1000 nm
  • the colored ink layer has a thickness of from 1 to 10 ⁇ m, and the high frequency adhesive layer has a thickness of from 3 to 25 ⁇ m.
  • the colored ink layer has a hardness of 2H-5H.
  • the colored ink layer has a thickness of 1-3 ⁇ m
  • the high frequency adhesive layer has a thickness of 3-10 ⁇ m.
  • the colored ink layer is provided with two layers, and is a first colored ink layer and a second colored ink layer, respectively, the first colored ink layer is located on an upper surface of the second colored ink layer, a second colored ink layer is located on an upper surface of the high frequency adhesive layer;
  • the first colored ink layer and the second colored ink layer each have a thickness of 2-3 ⁇ m.
  • the colored ultra-thin high frequency cover film further includes an auxiliary adhesive layer between the colored ink layer and the high frequency adhesive layer, and the thickness of the auxiliary adhesive layer is 3-25 ⁇ m.
  • the colored ink layer is an ink layer containing a matting powder having a particle diameter of 2 to 12 ⁇ m (D90).
  • the matting powder in the colored ink layer is at least one of an inorganic powder, an organic powder, a polyimide, and a flame retardant compound
  • the inorganic powder is sulfuric acid.
  • the flame retardant compound is a flame retardant compound containing at least one of a halogen, a phosphorus, a nitrogen, and a boron.
  • the release layer comprising an upper release layer and a lower release layer, the upper release layer being a matte release film layer, and the matte release film layer and the The side in contact with the colored ink layer is a rough surface and has an Rz value of 0.2 to 10 ⁇ m.
  • the high frequency adhesive layer means a Dk value of 2.4 to 3.0 (10 GHz), a Df value of 0.002 to 0.006 (10 GHz), a water absorption ratio of 0.03 to 0.2%, and an interline insulation resistance of more than 10 11 ⁇ .
  • a layer of adhesive having a surface resistance greater than 10 12 ⁇ and a volume resistance greater than 10 13 ⁇ ⁇ cm.
  • the high frequency adhesive layer includes sintered silica, Teflon, a fluorine resin, a phosphorus-based flame retardant, and a polyimide-based resin, and the sintered silica, the Teflon
  • the sum of the ratio of the fluorine-based resin and the phosphorus-based flame retardant is 8 to 50% by weight based on the total solid content, and the ratio of the polyimide-based resin content is 40% to 90% (weight) percentage).
  • the colored ink layer comprises an inorganic pigment or an organic pigment
  • the inorganic pigment is at least one of cadmium red, cadmium citrate, orange cadmium yellow, titanium dioxide, carbon black, black iron oxide and black mismatched inorganic pigment, and the sum of the ratios of the inorganic pigments is a colored ink layer 5-70% by weight of the total solids content;
  • the organic pigment is at least one of aniline black, phthalocyanine, phthalocyanine, benzidine yellow pigment, indigo blue, and indigo green, and the sum of the ratios of the organic pigments is the total solid content of the colored ink layer. 5-70% by weight.
  • the sum of the thicknesses of both the colored ink layer and the high-frequency adhesive layer is 4 to 35 ⁇ m.
  • the upper release layer and the lower release layer are each a release layer composed of at least one of polypropylene, biaxially oriented polypropylene, and polyethylene terephthalate.
  • the resin material in the colored ink layer is an epoxy resin, an acrylic resin, a urethane resin, a silicone rubber resin, a poly-p-xylene resin, or a bismaleimide resin. At least one of a polyimide resin and a polyamideimide.
  • the colored ink layer has a gloss of 5-25 GU (60°) when low haze is required, and the colored ink layer gloss is 0-5 GU (60°) when extremely low haze is required.
  • the matte powder of the colored ink layer is 2-50% of the total solid content.
  • the sum of the proportions of silica, carbon black, talc, calcium carbonate, glass powder and quartz powder in the matting powder is 10-50% by weight of the total solid content, or the phosphorus
  • the ratio of the compound is 2-40% by weight based on the total solid content.
  • the matte powder in the colored ink layer is preferably at least one of titanium dioxide and silicon dioxide, and when high flame resistance is considered, hydrogen peroxide is preferred.
  • Aluminum, alumina, calcium carbonate, phosphorus-containing flame retardant compounds, halogen-containing flame retardant compounds, nitrogen-containing flame retardant compounds, and boron-containing flame retardant compounds At least one of them.
  • the resin material of the high frequency adhesive layer is a fluorine resin, an epoxy resin, an acrylic resin, a urethane resin, a silicone rubber resin, a polyparaxylene resin, and a double horse. At least one of an imide resin, a polyimide resin, and a polyamideimide is used.
  • the resin material in the auxiliary adhesive layer is an epoxy resin, an acrylic resin, a urethane resin, a silicone rubber resin, a polyparaxylene resin, or a bismaleimide resin. At least one of a polyamideimide and the polyimide-based resin.
  • the invention also provides a preparation method of the high haze colored ultra-thin high-frequency cover film, which is one of the following methods:
  • Step 1 Apply colored ink material to the lower surface of the upper release layer and cure at 50-180 ° C at low temperature. Forming a colored ink layer;
  • Step 2 forming a high frequency adhesive layer on the lower surface of the colored ink layer by a coating method or a transfer method;
  • Step 3 attaching the lower release layer to the lower surface of the high frequency adhesive layer to obtain a finished product
  • Step 1 sequentially coating the colored ink raw material on the lower surface of the upper release layer, and curing at 50-180 ° C to form a first colored ink layer and a second colored ink layer;
  • Step 2 forming a high frequency adhesive layer on the lower surface of the second colored ink layer by a coating method or a transfer method;
  • Step 3 attaching the lower release layer to the lower surface of the high frequency adhesive layer to obtain a finished product
  • Step 1 coating the colored ink raw material on the lower surface of the upper release layer, and curing at 50-180 ° C to form a colored ink layer;
  • Step two coating an auxiliary adhesive layer on the surface of the colored ink layer
  • Step 3 forming a high frequency adhesive layer on the lower surface of the auxiliary adhesive layer by a coating method or a transfer method;
  • Step 4 attaching the lower release layer to the lower surface of the high frequency adhesive layer to obtain a finished product.
  • the colored ink layer of the present invention has a surface gloss of 0-60 GU (60°), preferably 25% or less, and a hardness of HB-5H, preferably 2H-5H. Therefore, the present invention not only has Matte characteristics, and its high hardness can prevent surface scratches, and is not easily corroded by chemical reagents in the downstream process, and has good weather resistance;
  • the present invention may add an auxiliary adhesive layer between the colored ink layer and the high frequency adhesive layer, the auxiliary adhesive layer having a thickness of 3-25 ⁇ m.
  • the adhesion of the colored ink layer and the high frequency adhesive layer can be effectively increased to improve the overall hardness and mechanical strength of the product;
  • the invention can adopt the method of double-layer coating ink, that is, the colored ink layer comprises two first ink layers of the first colored ink layer and the second colored ink layer, which can solve the micropore problem existing in the coating process and improve the process yield rate. ;
  • the colored ink layer of the present invention contains a matting powder, and the degree of extinction of the surface of the coating film is adjusted by controlling the particle size of the powder, and the particle size is controlled to be 2-12 ⁇ m, and the particle size of the matting powder is smaller, and the surface gloss is The greater the (glossiness) value, that is, the brighter the surface morphology, by adjusting the particle size, type, and content of the matting powder, it is possible to obtain a desired product (such as gloss, flame resistance, hardness, cost, etc.), and The matting powder can further improve the hardness of the colored ink layer, so that the product has more mechanical properties, electrical properties and operability;
  • the surface of the colored ink layer of the present invention uses a matte release film layer having a surface Rz (roughness) of 0.2-10 ⁇ m.
  • Rz roughness
  • the downstream terminal is operable, and the matte release film layer allows the cover film to be quickly pressed and formed, and after the release film layer is peeled off, the surface morphology of the colored ink layer is helped to be a matte form;
  • the high-frequency adhesive layer contains a polyimide resin, a sintered silica, a Teflon, a fluorine-based resin, and a phosphorus-based flame retardant, so that it has a low water absorption rate and not only absorbs water. It has stable performance, good electrical performance, reduced signal transmission insertion loss, and extremely low Dk/Df value in high temperature and humidity environment, making the invention suitable for low temperature (less than 180 ° C) rapid pressure. The process is strong, and the requirements for the production equipment are low, thereby reducing the production cost;
  • the sum of the thicknesses of the colored ink layer and the high frequency adhesive layer of the present invention is as low as 4-7 ⁇ m, which satisfies the design requirements of the current FPC thin line;
  • the invention has a low rebound force and is suitable for a downstream high-density assembly process.
  • Figure 1 is a schematic view of the structure of the present invention (a layer of colored ink);
  • Figure 2 is a schematic view of another structure of the present invention (two layers of colored ink layer);
  • Figure 3 is a schematic view of still another structure of the present invention (including an auxiliary adhesive layer);
  • 100-up release layer 200-colored ink layer, 201-first colored ink layer, 202-second colored ink layer, 300-high frequency adhesive layer, 400-low release layer and 500-auxiliary adhesion layer.
  • Embodiment 1 A high-haze colored ultra-thin high-frequency cover film, as shown in FIG. 1, includes a colored ink layer 200 and a high-frequency adhesive layer 300, and the colored ink layer 200 is located at the high-frequency adhesive Above the layer 300, the colored ink layer is provided with at least one layer;
  • the hardness of the colored ink layer is HB-5H;
  • the colored ink layer has a gloss of 0-60% (60°);
  • the colored ink layer has a roughness of 50-1000 nm
  • the colored ink layer has a thickness of from 1 to 10 ⁇ m, and the high frequency adhesive layer has a thickness of from 3 to 25 ⁇ m.
  • the colored ink layer has a single layer, and the sum of the thicknesses of both the colored ink layer 200 and the high-frequency adhesive layer 300 is 4-35 ⁇ m.
  • the colored ink layer 200 has a hardness of 2H-5H.
  • the colored ink layer 200 has a thickness of 1-3 ⁇ m
  • the high frequency adhesive layer 300 has a thickness of 3-10 ⁇ m.
  • the colored ink layer 200 is an ink layer containing a matting powder having a particle diameter of 2 to 12 ⁇ m (D90).
  • the matting powder in the colored ink layer is at least one of an inorganic powder, an organic powder, a polyimide, and a flame retardant compound
  • the inorganic powder is calcium sulfate or carbon black.
  • At least one of the flame retardant compounds is a flame retardant compound containing at least one of a halogen, a phosphorus, a nitrogen, and a boron.
  • a release layer is further included, the release layer including an upper release layer 100 and a lower release layer 400, the upper separation layer
  • the type layer 100 is a matte release film layer, and the side of the matte release film layer in contact with the colored ink layer 200 is a rough surface and has an Rz value of 0.2 to 10 ⁇ m.
  • the high frequency adhesive layer 300 refers to a Dk value of 2.4-3.0 (10 GHz), a Df value of 0.002-0.006 (10 GHz), a water absorption ratio of 0.03-0.2%, an inter-line insulation resistance of more than 10 11 ⁇ , and a surface resistance.
  • the high frequency adhesive layer 300 includes sintered silica, Teflon, a fluorine resin, a phosphorus-based flame retardant, a polyamideimide, and a polyimide-based resin, and the sintered silica, the The sum of the ratios of the Teflon, the fluorine-based resin, and the phosphorus-based flame retardant is 8 to 50% by weight based on the total solid content, and the ratio of the polyimide-based resin content is 40% to 90%. % (% by weight).
  • the colored ink layer 200 includes an inorganic pigment or an organic pigment
  • the inorganic pigment is at least one of cadmium red, cadmium citrate, orange cadmium yellow, titanium dioxide, carbon black, black iron oxide and black mismatched inorganic pigment, and the sum of the ratios of the inorganic pigments is a colored ink layer 5-70% by weight of the total solids content;
  • the organic pigment is at least one of aniline black, phthalocyanine, phthalocyanine, benzidine yellow pigment, indigo blue, and indigo green, and the sum of the ratios of the organic pigments is the total solid content of the colored ink layer. 5-70% by weight.
  • the upper release layer 100 and the lower release layer 400 are each a release layer composed of at least one of polypropylene, biaxially oriented polypropylene, and polyethylene terephthalate.
  • the resin material in the colored ink layer is an epoxy resin, an acrylic resin, a urethane resin, a silicone rubber resin, a polyparaxylene resin, a bismaleimide resin, or a polyamide. At least one of an amine resin and a polyamideimide.
  • the colored ink layer has a gloss of 5-25 GU (60°) when low haze is required, and the colored ink layer gloss is 0-5 GU (60°) when extremely low haze is required.
  • the matting powder of the colored ink layer 200 is 2-50% of the total solid content.
  • the sum of the proportions of silica, carbon black, talc, calcium carbonate, glass powder and quartz powder in the matting powder is 10-50% by weight of the total solid content, or the phosphorus
  • the ratio of the compound is 2-40% by weight based on the total solid content.
  • the matting powder in the colored ink layer is excellent At least one of titanium dioxide and silicon dioxide is selected, and when considering high flame resistance, aluminum hydroxide, aluminum oxide, calcium carbonate, phosphorus-containing flame retardant compound, halogen-containing flame retardant are preferred. At least one of a compound, a nitrogen-containing flame retardant compound, and a boron-containing flame retardant compound.
  • the resin material of the high frequency adhesive layer 300 is a fluorine resin, an epoxy resin, an acrylic resin, a urethane resin, a silicone rubber resin, a polyparaxylene resin, or a bismaleimide. At least one of an amine resin, a polyamideimide, and a polyimide resin.
  • Embodiment 2 As shown in FIG. 2, the other is the same as Embodiment 1, except that the colored ink layer is provided with two layers, and is a first colored ink layer 201 and a second colored ink layer 202, respectively.
  • the first colored ink layer 201 is located on the upper surface of the second colored ink layer 202
  • the second colored ink layer 202 is located on the upper surface of the high frequency adhesive layer 300;
  • the thickness of the first colored ink layer 201 and the second colored ink layer 202 are both 2-3 ⁇ m.
  • the resin material in the auxiliary adhesive layer is an epoxy resin, an acrylic resin, a urethane resin, a silicone rubber resin, a polyparaxylene resin, a bismaleimide resin, or a polyamido group. At least one of an imine and the polyimide-based resin.
  • Embodiment 3 As shown in FIG. 3, the other is the same as Embodiment 1, except that the colored ultra-thin high-frequency cover film further includes an auxiliary adhesive layer 500, and the auxiliary adhesive layer 500 is located in the colored ink layer. Between 200 and the high frequency adhesive layer 300, and the auxiliary adhesive layer 500 has a thickness of 3 to 25 ⁇ m.
  • the invention also provides a preparation method of the high haze colored ultra-thin high-frequency cover film, which is one of the following methods:
  • Step 1 coating the colored ink raw material on the lower surface of the upper release layer, and curing at 50-180 ° C to form a colored ink layer;
  • Step 2 forming a high frequency adhesive layer on the lower surface of the colored ink layer by a coating method or a transfer method;
  • Step 3 attaching the lower release layer to the lower surface of the high frequency adhesive layer to obtain a finished product
  • Step one sequentially coating the colored ink raw material on the lower surface of the upper release layer, at a low temperature of 50-180 ° C Curing to form a first colored ink layer and a second colored ink layer;
  • Step 2 forming a high frequency adhesive layer on the lower surface of the second colored ink layer by a coating method or a transfer method;
  • Step 3 attaching the lower release layer to the lower surface of the high frequency adhesive layer to obtain a finished product
  • Step 1 coating the colored ink raw material on the lower surface of the upper release layer, and curing at 50-180 ° C to form a colored ink layer;
  • Step two coating an auxiliary adhesive layer on the surface of the colored ink layer
  • Step 3 forming a high frequency adhesive layer on the lower surface of the auxiliary adhesive layer by a coating method or a transfer method;
  • Step 4 attaching the lower release layer to the lower surface of the high frequency adhesive layer to obtain a finished product.
  • Table 1 shows the specific stacking and basic performance indexes of the high frequency adhesive layer and the colored ink layer of Examples A1 to A12, and the results are as follows.
  • Table 2 shows the addition, gloss and hardness of the matting powder in the colored ink layer of Example B1 to Example B12 of the present invention.
  • Table 3 shows the addition of the matting powder and the glossiness in the colored ink layer of Example C1 to Example C15 of the present invention, and also includes the gloss of the comparative example.
  • the roughness of the upper release layer in Tables 2 and 3 means that the upper release layer is in contact with the colored ink layer. The roughness of one side.
  • the roughened release layer design contributes to a lower gloss finish, and the powder having a larger average particle size can reduce the surface gloss value.
  • the colored ultra-thin high-frequency cover film provided by the present invention comprises a colored ink layer and a high-frequency adhesive layer, and the upper and lower release layers are respectively attached to the upper and lower sides, and have extremely low dielectric constant and loss, and extremely high ions. Purity, ultra-thin laminate thickness, high heat dissipation, high flame retardancy, high extinction, especially suitable for use in high-frequency high-speed, ultra-thin line.
  • the use of colored inks, particularly black inks protects the circuitry, which is used in conjunction with high frequency adhesives to replace costly and problematic black polyimides.

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Abstract

本发明公开了一种高雾度的有色超薄高频覆盖膜及制备方法，包括有色油墨层和高频接着剂层，有色油墨层位于高频接着剂层的上方，有色油墨层设有至少一层；有色油墨层的硬度为HB-5H；有色油墨层的光泽度为0-60％(60°)；有色油墨层的粗糙度为50-1000nm；有色油墨层的厚度为1-10μm，高频接着剂层的厚度为3-25μm。本发明提供的一种高雾度的有色超薄高频覆盖膜，包括有色油墨层与高频接着剂层，上下分别贴合离型膜或离型纸之离型层，具有极低的介电常数与损耗、极高的离子纯度、超薄的叠构厚度、高散热性、高阻燃性、高消旋光性，特别适合在高频细线化线路中使用；相比一般的覆盖膜具有更高的可靠度以及操作性且可以调整表面的光泽度值，从而取代一般覆盖膜材料。

Description

高雾度的有色超薄高频覆盖膜及制备方法 技术领域
本发明涉及FPC(柔性线路板)用覆盖膜及其制备技术领域，特别涉及一种高雾度的有色超薄高频覆盖膜及制备方法。
背景技术
由于电子系统在朝向轻薄短小、高耐热性、多功能性、高密度化、高可靠性且低成本的方向上发展，所以在功能上，则需要强大且高速讯号传输。在高频领域，无线基础设施需要提供足够低的插损、更低的介电常数与损耗，才能有效提高能源利用率。随着5G时代与USB3.1等应用需求来临，射频产品需要提供更宽的带宽，并且向下兼容3G、4G业务。当前市面上的覆盖膜的材料常见的是使用黑色聚酰亚胺薄膜，在薄型化的设计上，其瓶颈之处在于黑色聚酰亚胺膜做出5μm以下的厚度具有巨大困难且加工操作性不好，且使用环氧树脂系的接着剂其离子纯度不佳、电性不良、成本高昂，这些都使得覆盖膜难以应对当前超细线化线路和高频高速传输的趋势。而另一种油墨型的有色高频覆盖膜，是使用5-7.5μm黄色超薄聚酰亚胺薄膜涂布有色油墨，此方法也一样有成本高、厚度较大的问题。
更进一步，另一种制造方法为于5-7.5μm黄色超薄聚酰亚胺薄膜，上层涂布黑色接着剂或油墨，其黑色接着剂或油墨上层需贴上承载膜，且属于非消光型(亮光)覆盖膜，造成高光泽度(大于50GU)，较差加工操作性及高成本。
工业设计上，为了电路设计不外露、美观、视觉保护等方面的要求，对于低光泽度(低雾度、高消旋光性)的薄膜具有需求，市面黑色聚酰亚胺生产商为了降低光泽度常常添加粉体制造表面散射来解决，如台湾专利号“TW201132714 A1”揭示了一种掺杂陶瓷粉体的低光泽黑色聚酰亚胺薄膜、台湾专利号“TW1481646 B”揭示了一种掺杂粉体聚酰亚胺的低光泽聚酰亚胺薄膜、南韩专利号“10-2012-0036253”揭示了一种掺杂碳黑的黑色聚酰亚胺薄膜。但是此类做法在5-7.5μm超薄聚酰亚胺膜中不易做到。
为了克服上述缺陷，藉由将有色聚酰亚胺覆盖膜替换成有色油墨层与高频接着剂组成之高频有色超薄覆盖膜。其中有色油墨层可以通过改换树脂、添加掺杂粉体的方式，并通过粉体含量改变、粒径设计的方式得到高消旋光性、高阻燃性、高硬度等多种优点。
发明内容
为了针对目前细线化线路的设计，并满足极低的介电常数及损耗、极佳离子迁移性、极高离子纯度、良好的接着力、低反发力、高柔软性、可低温加工、高散热性、高阻燃性、高消旋光性及高硬度等特性且低成本的发展方向，以及在功能上需要强大且高速讯号传输的需求，本发明提供了一种高雾度的有色超薄高频覆盖膜，包括有色油墨层与高频接着剂层，上下分别贴合离型膜或离型纸之离型层，具有极低的介电常数与损耗、极高的离子纯度、超薄的叠构厚度、高散热性、高阻燃性、高消旋光性，特别适合在高频细线化线路中使用；相比一般的覆盖膜具有更高的可靠度以及操作性且可以调整表面的光泽度值，从而取代一般覆盖膜材料。
为解决上述技术问题，本发明采用的一个技术方案是：提供一种高雾度的有色超薄高频覆盖膜，包括有色油墨层和高频接着剂层，所述有色油墨层位于所述高频接着剂层的上方，所述有色油墨层设有至少一层；
所述有色油墨层的硬度为HB-5H；
所述有色油墨层的光泽度为0-60GU(60°)；
所述有色油墨层的粗糙度为50-1000nm；
所述有色油墨层的厚度为1-10μm，所述高频接着剂层的厚度为3-25μm。
优选的，所述有色油墨层的硬度为2H-5H。
优选的，所述有色油墨层的厚度为1-3μm，所述高频接着剂层的厚度为3-10μm。
进一步地说，所述有色油墨层设有两层，且分别为第一有色油墨层和第二有色油墨层，所述第一有色油墨层位于所述第二有色油墨层的上表面，所述第二有色油墨层位于所述高频接着剂层的上表面；
所述第一有色油墨层和所述第二有色油墨层的厚度皆为2-3μm。
进一步地说，所述有色超薄高频覆盖膜还包括辅助接着层，所述辅助接着层位于所述有色油墨层和所述高频接着剂层之间，且所述辅助接着层的厚度为3-25μm。
进一步地说，所述有色油墨层为含消光粉体的油墨层，所述消光粉体的粒径为2-12μm(D90)。
进一步地说，所述有色油墨层中的所述消光粉体为无机粉体、有机粉体、聚酰亚胺系和具阻燃性之化合物中的至少一种，所述无机粉体为硫酸钙、碳黑、二氧化硅、二氧化钛、硫化锌、氧化锆、碳酸钙、碳化硅、氮化硼、氧化铝、氢氧化铝、滑石粉、氮化铝、玻璃粉体、石英粉体、金刚砂和黏土中的至少一种，所述具阻燃性之化合物为包含卤素、磷系、氮和硼系中至少一种的具阻燃性之化合物。
进一步地说，还包括离型层，所述离型层包括上离型层和下离型层，所述上离型层为消光离型膜层，且所述消光离型膜层与所述有色油墨层接触的一面为粗糙面且Rz值为0.2-10μm。
进一步地说，所述高频接着剂层是指Dk值为2.4-3.0(10GHz)、Df值为0.002-0.006(10GHz)、吸水率介于0.03-0.2％、线间绝缘阻抗大于1011Ω、表面电阻大于1012Ω且体积电阻大于1013Ω˙cm的胶层。
进一步地说，所述高频接着剂层包括烧结二氧化硅、铁氟龙、氟系树脂、磷系耐燃剂和聚酰亚胺系树脂，且所述烧结二氧化硅、所述铁氟龙、所述氟系树脂和所述磷系耐燃剂的比例之和为总固含量的8-50％(重量百分比)，所述聚酰亚胺系树脂含量的比例为40％-90％(重量百分比)。
进一步地说，所述有色油墨层包括无机颜料或有机颜料；
其中，所述无机颜料为镉红、镉柠檬黄、橘镉黄、二氧化钛、碳黑、黑色氧化铁和黑色错合无机颜料中的至少一种，且所述无机颜料比例之和为有色油墨层的总固含量的5-70％(重量百分比)；
所述有机颜料为苯胺黑、苝黑、蒽醌黑、联苯胺类黄色颜料、酞青蓝和酞青绿中的至少一种，且所述有机颜料比例之和为有色油墨层的总固含量的5-70％(重量百分比)。
进一步地说，具有单层有色油墨层时，所述有色油墨层和所述高频接着剂层两者的厚度之和为4-35μm。
进一步地说，所述上离型层和所述下离型层皆为聚丙烯、双向拉伸聚丙烯和聚对苯二甲酸乙二醇酯中的至少一种构成的离型层。
进一步地说，所述有色油墨层中的树脂材料为环氧树脂、丙烯酸系树脂、氨基甲酸酯系树脂、硅橡胶系树脂、聚对环二甲苯系树脂、双马来酰亚胺系树脂、聚酰亚胺系树脂及聚酰胺酰亚胺中的至少一种。
优选的，当有低雾度要求时，有色油墨层光泽度介于5-25GU(60°)，当有极低雾度要求时，有色油墨层光泽度介于0-5GU(60°)。
进一步地说，所述有色油墨层的消光粉体为总固含量的2-50％。
优选的，所述消光粉体中二氧化硅、碳黑、滑石粉、碳酸钙、玻璃粉体和石英粉体比例之和为总固含量的10-50％(重量百分比)，或者所述磷系化合物的比例为总固含量的2-40％(重量百分比)。
优选的，从成本考虑，当要求较高硬度时，所述有色油墨层中的所述消光粉体优选二氧化钛和二氧化硅中的至少一种，当考虑较高的耐燃性时，优选氢氧化铝、氧化铝、碳酸钙、含磷系的具阻燃性之化合物、含卤素的具阻燃性之化合物、含氮的具阻燃性之化合物和含硼系的具阻燃性之化合物中的至少一种。
进一步地说，所述高频接着剂层的树脂材料为氟系树脂、环氧树脂、丙烯酸系树脂、胺基甲酸酯系树脂、硅橡胶系树脂、聚对环二甲苯系树脂、双马来酰亚胺系树脂、聚酰亚胺系树脂和聚酰胺酰亚胺中的至少一种。
进一步地说，所述辅助接着层中的树脂材料为环氧树脂、丙烯酸系树脂、氨基甲酸酯系树脂、硅橡胶系树脂、聚对环二甲苯系树脂、双马来酰亚胺系树脂、聚酰胺酰亚胺和所述聚酰亚胺系树脂中的至少一种。
本发明还提供了一种所述的高雾度的有色超薄高频覆盖膜的制备方法，所述制备方法为下列方法中的一种:
方法一：按照如下步骤进行：
步骤一、在上离型层的下表面涂布有色油墨原料，50-180℃低温下固化 形成有色油墨层；
步骤二、由涂布法或转印法将高频接着剂层形成于有色油墨层的下表面；
步骤三、将下离型层贴覆于高频接着剂层的下表面，即得成品；
方法二：按照如下步骤进行：
步骤一、依次在上离型层的下表面涂布有色油墨原料，50-180℃低温下固化形成第一有色油墨层和第二有色油墨层；
步骤二、由涂布法或转印法将高频接着剂层形成于第二有色油墨层的下表面；
步骤三、将下离型层贴覆于高频接着剂层的下表面，即得成品；
方法三：按照如下步骤进行：
步骤一、在上离型层的下表面涂布有色油墨原料，50-180℃低温下固化形成有色油墨层；
步骤二、在有色油墨层表面涂布辅助接着层；
步骤三、由涂布法或转印法将高频接着剂层形成于辅助接着层的下表面；
步骤四、将下离型层贴覆于高频接着剂层的下表面，即得成品。
本发明的有益效果是：本发明至少具有以下优点：
一、本发明的有色油墨层其表面光泽度为0-60GU(60°)，较佳可以达到25％以下，且硬度为HB-5H，较佳可以达到2H-5H，因此，本发明不仅具有雾面特性，而且其高硬度可以防止表面刮伤，且不易被下游制程中的化学试剂腐蚀，耐候性佳；
二、若有较高的硬度、机械强度及层间接着力要求时，本发明可以在有色油墨层与高频接着剂层之间增加辅助接着层，其所述辅助接着层厚度为3-25μm，可有效增加有色油墨层与高频接着剂层的接着力，提高产品整体硬度及机械强度；
三、本发明可以采用双层涂布油墨的方式，即有色油墨层包括第一有色油墨层和第二有色油墨层两层油墨层，能够解决涂布制程存在的微孔问题，提高制程良品率；
四、本发明的有色油墨层含有消光粉体，利用控制粉体粒径大小来调整涂布成膜表面消光程度，其粒径控制在2-12μm，消光粉体粒径越小，其表面gloss(光泽度)值越大，即表面形态越亮，通过调整消光粉体的粒径、种类和含量等，能够得到所需(如光泽度、耐燃性、硬度或成本等)的产品，而且加入的消光粉体能进一步提高有色油墨层的硬度，使本产品具有更加的机械性能、电气性能和可操作性能等；
五、本发明的有色油墨层表面使用消光离型膜层，其表面Rz(粗糙度)为0.2-10μm，透过此形态使覆盖膜的有色油墨层与离型层较易分离，从而大大提高了下游终端可操作性，同时该消光离型膜层使覆盖膜快压成型后，撕去离型膜层后，有助于有色油墨层表面形态为消光形态；
六、由于本发明中高频接着剂层的配方中含有聚酰亚胺系树脂、烧结二氧化硅、铁氟龙、氟系树脂和磷系耐燃剂，使其具有较低的吸水率，不仅吸水后性能稳定，具有较佳的电气性能，可减少讯号传输插入损耗，而且具有极低的并且在高温湿度环境下稳定的Dk/Df值，使得本发明适合低温(低于180℃)快速压合，工艺加工性强，而且对制作设备要求低，进而降低生产成本；
七、本发明有色油墨层和高频接着剂层两者的厚度之和最低可达4-7μm，满足目前FPC细线化线路的设计需求；
八、本发明具有较低的反弹力，适合下游高密度组装制程。
本发明的上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合附图详细说明如后。
附图说明
图1是本发明的一种结构示意图(一层有色油墨层)；
图2是本发明的另一种结构示意图(两层有色油墨层)；
图3是本发明的又一种结构示意图(含辅助接着层)；
附图中各部分标记如下：
100-上离型层、200-有色油墨层、201-第一有色油墨层、202-第二有色油墨层、300-高频接着剂层、400-下离型层和500-辅助接着层。
具体实施方式
以下通过特定的具体实施例说明本发明的具体实施方式，本领域技术人员可由本说明书所揭示的内容轻易地了解本发明的优点及功效。本发明也可以其它不同的方式予以实施，即，在不背离本发明所揭示的范畴下，能予不同的修饰与改变。
实施例1：一种高雾度的有色超薄高频覆盖膜，如图1所示，包括有色油墨层200和高频接着剂层300，所述有色油墨层200位于所述高频接着剂层300的上方，所述有色油墨层设有至少一层；
所述有色油墨层的硬度为HB-5H；
所述有色油墨层的光泽度为0-60％(60°)；
所述有色油墨层的粗糙度为50-1000nm；
所述有色油墨层的厚度为1-10μm，所述高频接着剂层的厚度为3-25μm。
本实施例中，有色油墨层具有单层，且所述有色油墨层200和所述高频接着剂层300两者的厚度之和为4-35μm。
优选的，所述有色油墨层200的硬度为2H-5H。
优选的，所述有色油墨层200的厚度为1-3μm，所述高频接着剂层300的厚度为3-10μm。
所述有色油墨层200为含消光粉体的油墨层，所述消光粉体的粒径为2-12μm(D90)。
所述有色油墨层中的所述消光粉体为无机粉体、有机粉体、聚酰亚胺系和具阻燃性之化合物中的至少一种，所述无机粉体为硫酸钙、碳黑、二氧化硅、二氧化钛、硫化锌、氧化锆、碳酸钙、碳化硅、氮化硼、氧化铝、氢氧化铝、滑石粉、氮化铝、玻璃粉体、石英粉体、金刚砂和黏土中的至少一种，所述具阻燃性之化合物为包含卤素、磷系、氮和硼系中至少一种的具阻燃性之化合物。
还包括离型层，所述离型层包括上离型层100和下离型层400，所述上离 型层100为消光离型膜层，且所述消光离型膜层与所述有色油墨层200接触的一面为粗糙面且Rz值为0.2-10μm。
所述高频接着剂层300是指Dk值为2.4-3.0(10GHz)、Df值为0.002-0.006(10GHz)、吸水率介于0.03-0.2％、线间绝缘阻抗大于1011Ω、表面电阻大于1012Ω且体积电阻大于1013Ω˙cm的胶层。
所述高频接着剂层300包括烧结二氧化硅、铁氟龙、氟系树脂、磷系耐燃剂、聚酰胺酰亚胺和聚酰亚胺系树脂，且所述烧结二氧化硅、所述铁氟龙、所述氟系树脂和所述磷系耐燃剂的比例之和为总固含量的8-50％(重量百分比)，所述聚酰亚胺系树脂含量的比例为40％-90％(重量百分比)。
所述有色油墨层200包括无机颜料或有机颜料；
其中，所述无机颜料为镉红、镉柠檬黄、橘镉黄、二氧化钛、碳黑、黑色氧化铁和黑色错合无机颜料中的至少一种，且所述无机颜料比例之和为有色油墨层的总固含量的5-70％(重量百分比)；
所述有机颜料为苯胺黑、苝黑、蒽醌黑、联苯胺类黄色颜料、酞青蓝和酞青绿中的至少一种，且所述有机颜料比例之和为有色油墨层的总固含量的5-70％(重量百分比)。
所述上离型层100和所述下离型层400皆为聚丙烯、双向拉伸聚丙烯和聚对苯二甲酸乙二醇酯中的至少一种构成的离型层。
所述有色油墨层中的树脂材料为环氧树脂、丙烯酸系树脂、氨基甲酸酯系树脂、硅橡胶系树脂、聚对环二甲苯系树脂、双马来酰亚胺系树脂、聚酰亚胺系树脂和聚酰胺酰亚胺中的至少一种。
优选的，当有低雾度要求时，有色油墨层光泽度介于5-25GU(60°)，当有极低雾度要求时，有色油墨层光泽度介于0-5GU(60°)。
所述有色油墨层200的消光粉体为总固含量的2-50％。
优选的，所述消光粉体中二氧化硅、碳黑、滑石粉、碳酸钙、玻璃粉体和石英粉体比例之和为总固含量的10-50％(重量百分比)，或者所述磷系化合物的比例为总固含量的2-40％(重量百分比)。
从成本考虑，当要求较高硬度时，所述有色油墨层中的所述消光粉体优 选二氧化钛和二氧化硅中的至少一种，当考虑较高的耐燃性时，优选氢氧化铝、氧化铝、碳酸钙、含磷系的具阻燃性之化合物、含卤素的具阻燃性之化合物、含氮的具阻燃性之化合物和含硼系的具阻燃性之化合物中的至少一种。
所述高频接着剂层300的树脂材料为氟系树脂、环氧树脂、丙烯酸系树脂、胺基甲酸酯系树脂、硅橡胶系树脂、聚对环二甲苯系树脂、双马来酰亚胺系树脂、聚酰胺酰亚胺和聚酰亚胺系树脂中的至少一种。
实施例2：如图2所示，其它与实施例1相同，不同之处在于：所述有色油墨层设有两层，且分别为第一有色油墨层201和第二有色油墨层202，所述第一有色油墨层201位于所述第二有色油墨层202的上表面，所述第二有色油墨层202位于所述高频接着剂层300的上表面；
所述第一有色油墨层201和所述第二有色油墨层202的厚度皆为2-3μm。
所述辅助接着层中的树脂材料为环氧树脂、丙烯酸系树脂、氨基甲酸酯系树脂、硅橡胶系树脂、聚对环二甲苯系树脂、双马来酰亚胺系树脂、聚酰胺酰亚胺和所述聚酰亚胺系树脂中的至少一种。
实施例3：如图3所示，其它与实施例1相同，不同之处在于：所述有色超薄高频覆盖膜还包括辅助接着层500，所述辅助接着层500位于所述有色油墨层200和所述高频接着剂层300之间，且所述辅助接着层500的厚度为3-25μm。
本发明还提供了一种所述的高雾度的有色超薄高频覆盖膜的制备方法，所述制备方法为下列方法中的一种:
方法一(适用于实施例1)：按照如下步骤进行：
步骤一、在上离型层的下表面涂布有色油墨原料，50-180℃低温下固化形成有色油墨层；
步骤二、由涂布法或转印法将高频接着剂层形成于有色油墨层的下表面；
步骤三、将下离型层贴覆于高频接着剂层的下表面，即得成品；
方法二(适用于实施例2)：按照如下步骤进行：
步骤一、依次在上离型层的下表面涂布有色油墨原料，50-180℃低温下 固化形成第一有色油墨层和第二有色油墨层；
步骤二、由涂布法或转印法将高频接着剂层形成于第二有色油墨层的下表面；
步骤三、将下离型层贴覆于高频接着剂层的下表面，即得成品；
方法三(适用于实施例3)：按照如下步骤进行：
步骤一、在上离型层的下表面涂布有色油墨原料，50-180℃低温下固化形成有色油墨层；
步骤二、在有色油墨层表面涂布辅助接着层；
步骤三、由涂布法或转印法将高频接着剂层形成于辅助接着层的下表面；
步骤四、将下离型层贴覆于高频接着剂层的下表面，即得成品。
表1为实施例A1-A12的高频接着剂层和有色油墨层的具体叠构展示和基本性能指标，结果如下。
表1：
Figure PCTCN2017104414-appb-000001
Figure PCTCN2017104414-appb-000002
表2是本发明的实施例B1-实施例B12的有色油墨层中，消光粉体的添加情况及光泽度和硬度。
表2：
Figure PCTCN2017104414-appb-000003
从表2看出，通过添加的消光粉体的粒径和含量的设计之实施例搭配粗糙度5.5um的上离型层，得到相应的光泽度，总体来说，大粒径、含量多的消 光粉体有助于降低光泽度。
表3是本发明的实施例C1-实施例C15的有色油墨层中，消光粉体的添加情况及光泽度，还包括比较例的光泽度。
Figure PCTCN2017104414-appb-000004
注：表2和表3中的上离型层的粗糙度是指上离型层与有色油墨层接触 的一面的粗糙度。
由表3可知，粗化的上离型层设计有助于得到更低光泽度的成品，平均粒径大之粉体可降低表面光泽值。
由实施例可知，本发明提供的有色超薄高频覆盖膜包括有色油墨层与高频接着剂层，上下分别贴合上下离型层，具有极低的介电常数与损耗、极高的离子纯度、超薄的叠构厚度、高散热性、高阻燃性、高消旋光性，特别适合在高频高速、超细线化线路中使用。有色油墨特别黑色油墨的应用可以保护线路，其与高频接着剂的配合使用以替代成本高且存在技术问题的黑色聚酰亚胺。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (10)

  1. 一种高雾度的有色超薄高频覆盖膜，其特征在于：
    包括有色油墨层和高频接着剂层，所述有色油墨层位于所述高频接着剂层的上方，所述有色油墨层设有至少一层；
    所述有色油墨层的硬度为HB-5H；
    所述有色油墨层的光泽度为0-60GU(60°)；
    所述有色油墨层的粗糙度为50-1000nm；
    所述有色油墨层的厚度为1-10μm，所述高频接着剂层的厚度为3-25μm。
  2. 根据权利要求1所述的高雾度的有色超薄高频覆盖膜，其特征在于：所述有色油墨层设有两层，且分别为第一有色油墨层和第二有色油墨层，所述第一有色油墨层位于所述第二有色油墨层的上表面，所述第二有色油墨层位于所述高频接着剂层的上表面；
    所述第一有色油墨层和所述第二有色油墨层的厚度皆为2-3μm。
  3. 根据权利要求1所述的高雾度的有色超薄高频覆盖膜，其特征在于：所述有色超薄高频覆盖膜还包括辅助接着层，所述辅助接着层位于所述有色油墨层和所述高频接着剂层之间，且所述辅助接着层的厚度为3-25μm。
  4. 根据权利要求1所述的高雾度的有色超薄高频覆盖膜，其特征在于：所述有色油墨层为含消光粉体的油墨层，所述消光粉体的粒径为2-12μm(D90)。
  5. 根据权利要求4所述的高雾度的有色超薄高频覆盖膜，其特征在于：所述有色油墨层中的所述消光粉体为无机粉体、有机粉体、聚酰亚胺系和具阻燃性之化合物中的至少一种，所述无机粉体为硫酸钙、碳黑、二氧化硅、二氧化钛、硫化锌、氧化锆、碳酸钙、碳化硅、氮化硼、氧化铝、氢氧化铝、滑石粉、氮化铝、玻璃粉体、石英粉体、金刚砂和黏土中的至少一种，所述具阻燃性之化合物为包含卤素、磷系、氮和硼系中至少一种的具阻燃性之化合物。
  6. 根据权利要求1所述的高雾度的有色超薄高频覆盖膜，其特征在于：还包括离型层，所述离型层包括上离型层和下离型层，所述上离型层为消光离型膜层，且所述消光离型膜层与所述有色油墨层接触的一面为粗糙面且Rz 值为0.2-10μm。
  7. 根据权利要求1所述的高雾度的有色超薄高频覆盖膜，其特征在于：所述高频接着剂层是指Dk值为2.4-3.0(10GHz)、Df值为0.002-0.006(10GHz)、吸水率介于0.03-0.2％、线间绝缘阻抗大于1011Ω、表面电阻大于1012Ω且体积电阻大于1013Ω˙cm的胶层。
  8. 根据权利要求1所述的高雾度的有色超薄高频覆盖膜，其特征在于：所述高频接着剂层包括烧结二氧化硅、铁氟龙、氟系树脂、磷系耐燃剂和聚酰亚胺系树脂，且所述烧结二氧化硅、所述铁氟龙、所述氟系树脂和所述磷系耐燃剂的比例之和为总固含量的8-50％(重量百分比)，所述聚酰亚胺系树脂含量的比例为40％-90％(重量百分比)。
  9. 根据权利要求1所述的高雾度的有色超薄高频覆盖膜，其特征在于：所述有色油墨层包括无机颜料或有机颜料；
    其中，所述无机颜料为镉红、镉柠檬黄、橘镉黄、二氧化钛、碳黑、黑色氧化铁和黑色错合无机颜料中的至少一种，且所述无机颜料比例之和为有色油墨层的总固含量的5-70％(重量百分比)；
    所述有机颜料为苯胺黑、苝黑、蒽醌黑、联苯胺类黄色颜料、酞青蓝和酞青绿中的至少一种，且所述有机颜料比例之和为有色油墨层的总固含量的5-70％(重量百分比)。
  10. 一种根据权利要求1所述的高雾度的有色超薄高频覆盖膜的制备方法，其特征在于：所述制备方法为下列方法中的一种:
    方法一：按照如下步骤进行：
    步骤一、在上离型层的下表面涂布有色油墨原料，50-180℃低温下固化形成有色油墨层；
    步骤二、由涂布法或转印法将高频接着剂层形成于有色油墨层的下表面；
    步骤三、将下离型层贴覆于高频接着剂层的下表面，即得成品；
    方法二：按照如下步骤进行：
    步骤一、依次在上离型层的下表面涂布有色油墨原料，50-180℃低温下 固化形成第一有色油墨层和第二有色油墨层；
    步骤二、由涂布法或转印法将高频接着剂层形成于第二有色油墨层的下表面；
    步骤三、将下离型层贴覆于高频接着剂层的下表面，即得成品；
    方法三：按照如下步骤进行：
    步骤一、在上离型层的下表面涂布有色油墨原料，50-180℃低温下固化形成有色油墨层；
    步骤二、在有色油墨层表面涂布辅助接着层；
    步骤三、由涂布法或转印法将高频接着剂层形成于辅助接着层的下表面；
    步骤四、将下离型层贴覆于高频接着剂层的下表面，即得成品。
PCT/CN2017/104414 2017-05-23 2017-09-29 高雾度的有色超薄高频覆盖膜及制备方法 WO2018214366A1 (zh)

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