CN115960458A - Bio-based resin film and cover film prepared by using same - Google Patents
Bio-based resin film and cover film prepared by using same Download PDFInfo
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- CN115960458A CN115960458A CN202211269608.5A CN202211269608A CN115960458A CN 115960458 A CN115960458 A CN 115960458A CN 202211269608 A CN202211269608 A CN 202211269608A CN 115960458 A CN115960458 A CN 115960458A
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Abstract
The invention discloses a bio-based resin film, which comprises: a carrier film; and an insulating layer having a bio-based resin formed on the carrier film; wherein the content of the bio-based resin in the insulating layer is more than 20%. The invention also provides a covering film using the bio-based resin film. The bio-based resin film is prepared by adopting renewable raw materials so as to reduce the dependence on petrochemical resources; the bio-based resin film has good mechanical characteristics, so that the bio-based resin film can provide good heat dissipation performance, meets the requirement of thinned design, is also suitable for a circuit board assembled at high density, and has industrial application value.
Description
Technical Field
The invention belongs to the technical field of covering films, and particularly relates to a bio-based resin film with a carrier film and a covering film.
Background
Polyimide (PI) is a special engineering material, has the advantages of wide application temperature, chemical corrosion resistance, high strength and the like, and is widely applied to the fields of aviation, aerospace, microelectronics, nano-scale, liquid crystal, separation membranes, lasers and the like. However, most of the polyimide monomers are derived from petrochemical products and derivatives thereof, and some common monomers generally have the problems of high toxicity, carcinogenicity and the like, which threaten human health. Therefore, polyimide prepared from bio-based materials is attractive to industrial industries and research institutions.
The Bio-based (Bio-based) is an important renewable material, has the characteristics of repeated use and reproducibility like resources such as solar energy, wind energy, geothermal heat and the like, can absorb carbon dioxide and reduce the accumulation of greenhouse gases during plant growth, gradually replaces the existing petrochemical products along with the development of various Bio-based alternative material technologies, and meets the actual requirements of energy saving, carbon reduction and earth resource failure in the future.
Nowadays, research and research units have carried out relevant work on the development of bio-based polyimide films, such as the preparation of a series of bio-based polyimide resins from renewable raw materials such as isosorbide, isomannide, lignin derivatives, etc. (Acta polymeric Sinica,2006 (2): 284-288, polymer,2015, 74. From the above data, there exists a technology for preparing polyimide resin from recyclable and recyclable raw materials, but there is still a problem that the prepared polyimide film still has insufficient properties.
On the other hand, the market electronic products are becoming thinner and thinner, and the polyimide film is too thin, which makes the processing operation difficult, and the general technical indexes such as bending property and the like can not meet the requirements of the industry standard, and the preparation yield is low.
In view of the above, it is necessary to provide a bio-based resin film and a cover film with high mechanical properties, which meet the environmental protection trend of carbon neutralization and the requirement of thin design, so as to solve the above problems of the prior art.
Disclosure of Invention
In order to solve the technical problems, the invention adopts a technical scheme that: a bio-based resin film comprising a support film; and an insulating layer having a bio-based resin, the insulating layer being formed on the carrier film;
wherein, according to specification ASTM D6866-12, the content of the bio-based resin in the insulating layer is more than 20%.
Further, the insulating layer is formed by stacking a plurality of insulating layers.
Furthermore, the surface roughness value of the side of the insulating layer in contact with the carrier film is 0.001-10 μm.
More specifically, the surface of the side of the insulating layer in contact with the carrier film comprises inorganic powder with a particle size of 10nm-20 μm, wherein the inorganic powder is at least one selected from the group consisting of calcium sulfate, carbon black, silica, titanium dioxide, zinc sulfide, zirconia, calcium carbonate, silicon carbide, boron nitride, alumina, talc powder, aluminum nitride, glass powder, quartz powder and clay, and the weight percentage of the inorganic powder is 0-50% based on the weight of the insulating sublayer.
Further, the bio-based resin is a resin having an imide bond synthetically prepared from bio-based monomers.
More particularly, the bio-based resin is at least one selected from the group consisting of polyimide resin and polyamideimide.
The bio-based resin is a resin having a structure of the following formula (I), wherein n is 15 to 25.
Further, the insulating layer further comprises petrochemical resin, and the weight percentage of the petrochemical resin is 0-80%;
wherein the petrochemical resin is at least one selected from the group consisting of epoxy resin, acrylic resin, urethane resin, silicone rubber resin, poly-p-xylylene resin, bismaleimide resin, styrene-ethylene-butylene-styrene block copolymer, polyimide resin, and polyamideimide.
The petrochemical resin is a polyamideimide resin having the following formula (II), wherein n is 20 to 30.
Further, the insulating layer also comprises an inorganic filler, and the weight percentage of the inorganic filler is 0-50%;
wherein the inorganic filler is at least one selected from the group consisting of calcium sulfate, carbon black, silicon dioxide, titanium dioxide, zinc sulfide, zirconium oxide, calcium carbonate, silicon carbide, boron nitride, aluminum oxide, talc powder, aluminum nitride, glass powder, quartz powder and clay.
Further, the insulating layer further comprises a pigment, and the weight percentage of the pigment is 0-50%.
More specifically, the pigment is an inorganic pigment selected from at least one of cadmium red, cadmium lemon yellow, orange cadmium yellow, titanium dioxide, carbon black, black iron oxide, and black complex.
More specifically, the pigment is an organic pigment selected from at least one of the group consisting of aniline black, perylene black, anthraquinone black, benzidine-based yellow pigments, phthalocyanine blue and phthalocyanine green.
The insulating layer further comprises an additive, and the weight percentage of the additive is 0-20%, wherein the additive is a curing agent, a catalyst or a surfactant.
Further, the carrier film is at least one selected from the group consisting of polypropylene, biaxially oriented polypropylene, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polyurethane, and polyamide.
Further, the surface roughness value of the surface of the carrier film in contact with the insulating layer is 0.001 to 10 μm.
More specifically, the carrier film further comprises an inorganic powder with a particle size of 20 μm to 10nm, wherein the inorganic powder is at least one selected from the group consisting of calcium sulfate, carbon black, silicon dioxide, titanium dioxide, zinc sulfide, zirconium oxide, calcium carbonate, silicon carbide, boron nitride, aluminum oxide, talc powder, aluminum nitride, glass powder, quartz powder and clay, and the weight percentage of the inorganic powder is 0-50% based on the weight of the carrier film.
A cover film comprising the bio-based resin film;
an adhesive layer having a bio-based resin formed on the insulating layer of the bio-based resin film;
the release layer is formed on the bonding layer, so that the bonding layer is positioned between the insulating layer and the release layer;
wherein, according to the specification ASTM D6866-12, the content of the bio-based resin in the covering film is more than 20%.
Further, the bio-based resin in the adhesive layer and the insulating layer is a resin having an imide bond synthesized from a bio-based monomer.
More particularly, the bio-based resin is at least one selected from the group consisting of polyimide resin and polyamideimide.
Further, at least one of the adhesion layer and the insulation layer further comprises petrochemical resin, and the weight percentage of the petrochemical resin is 0-80%;
wherein the petrochemical resin is at least one selected from the group consisting of epoxy resin, acrylic resin, urethane resin, silicone rubber resin, poly-p-xylylene resin, bismaleimide resin, styrene-ethylene-butylene-styrene block copolymer, polyimide resin, and polyamideimide.
Further, the adhesion layer also comprises a flame retardant, and the weight percentage of the flame retardant is 0-50%.
More specifically, the flame retardant is a compound having flame retardancy, which is at least one selected from the group consisting of halogen, phosphorus, nitrogen and boron.
More specifically, the flame retardant is an inorganic substance having a particle size of 2 μm to 10nm, and is at least one selected from the group consisting of calcium sulfate, carbon black, silica, teflon, fluorine-based resin, titanium dioxide, zinc sulfide, zirconia, calcium carbonate, silicon carbide, boron nitride, aluminum hydroxide, alumina, talc, aluminum nitride, glass powder, phosphorus-based flame retardant, quartz powder, and clay.
More specifically, the flame retardant is organic powder containing polyimide resin.
Further, at least one of the adhesion layer and the insulating layer further includes a pigment, and the pigment is an inorganic pigment selected from at least one of the group consisting of cadmium red, cadmium lemon yellow, orange cadmium yellow, titanium dioxide, carbon black, black iron oxide, and black complex; the pigment is at least one organic pigment selected from the group consisting of aniline black, perylene black, anthraquinone black, benzidine yellow pigments, phthalocyanine blue and phthalocyanine green.
Further, at least one of the adhesion layer and the insulation layer further comprises an additive, and the additive is a curing agent, a catalyst or a surfactant.
Further, the release layer is at least one selected from the group consisting of polypropylene, biaxially oriented polypropylene, and polyethylene terephthalate.
The preparation method of the bio-based resin film comprises the following steps:
coating a varnish having a bio-based resin on a carrier film;
and curing the varnish with the bio-based resin at a temperature of 50-180 ℃ to form the insulating layer with the bio-based resin.
Furthermore, the method for preparing the bio-based resin film further comprises the step of repeating the steps of coating the varnish with the bio-based resin and curing after curing the varnish with the bio-based resin, so as to form the insulating layer with a plurality of insulating sub-layers.
The preparation method of the covering film comprises the following steps:
the preparation method of the bio-based resin film is implemented;
forming an adhesive layer with bio-based resin on the insulating layer by using a coating method or a transfer method;
and forming an off-layer on the adhesion layer.
The invention has the beneficial effects that:
1. according to the invention, the components extracted from natural animals and plants are selected to replace the prior resin with high content, and the defects of insufficient mechanical strength and other properties of the bio-based resin film are effectively improved through the addition proportion of the resin and additives, so that the invention can be applied to cover films, printing ink, copper-clad plates, electromagnetic interference shielding films, polyimide reinforcing plates, heat-conducting products (such as consisting of a heat-conducting substrate, a resin-coated copper foil and heat-conducting insulating glue) and the like. Moreover, by means of the design of the bio-based resin film and the adhesion layer containing bio-based components, the covering film not only meets the environmental protection trend of the existing carbon neutralization policy, but also has the advantages of insulating surface glossiness, color adjustability, good adhesion, high flame retardance, high shielding property, high dimensional stability, high heat dissipation, high surface hardness and the like, and is suitable for being applied to the fields of ultra-density assembly lines, wireless charging and the like;
2. on the other hand, by utilizing the carrier film and the process of multilayer coating, the preparation method of the invention also solves the thickness limitation of the stretching method process of the colored film on the market at present, meets the design requirement of the thinning industry, also solves the difficulty of single specification production, is easy to produce various thicknesses and can replace the thinned polyimide film with high unit price and thickness less than 12.5 microns on the market; meanwhile, the preparation method has no residual tensile stress, so the preparation method has the advantages of better size stability, easier processing for downstream processing, low cost and the like, and has industrial application value.
Drawings
FIG. 1 is a schematic structural view of a first embodiment of a bio-based resin film according to the present invention;
FIG. 2 is a schematic structural view of a second embodiment of the bio-based resin film of the present invention;
FIG. 3 is a schematic structural view of a first embodiment of a coverfilm of the present invention;
FIG. 4 is a schematic structural view of a second embodiment of a coverfilm of the present invention;
the reference numbers are as follows:
1. bio-based resin film
10. 20 carrier film
11. 21 insulating layer
111. 112, 211, 212 insulating sub-layer
2. Covering film
22. Adhesive layer
23. And a release layer.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention.
Example (b): a bio-based resin film comprising a support film; and an insulating layer having a bio-based resin, the insulating layer being formed on the carrier film;
wherein, according to specification ASTM D6866-12, the content of the bio-based resin in the insulating layer is more than 20%.
In particular embodiments, the bio-based resin content in the insulating layer is 20-100%, such as 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%.
Herein, the bio-based resin is prepared by refining and processing natural animal and plant raw materials, such as gum rosin, castor oil, rapeseed, tall oil, soybean oil, lignin, isosorbide and cardanol, or is synthesized by including bio-based monomers obtained by refining natural animal and plant raw materials, and has a weight average molecular weight (Mw) of 10,000 to 500,000.
In a first embodiment, the bio-based resin is at least one selected from the group consisting of epoxy resin, acrylic resin, urethane resin, silicone rubber resin, parylene resin, bismaleimide resin, styrene-ethylene-butylene-styrene block copolymer, polyimide resin, and polyamideimide.
In a second embodiment, the bio-based resin is a resin having imide linkages made synthetically from bio-based monomers; the bio-based resin is at least one selected from the group consisting of polyimide resin and polyamideimide.
The bio-based resin is a resin having a structure of the following formula (I), wherein n is 15 to 25.
Herein, the content of the bio-based resin can be measured by using JORA certification standard or USDA certification standard; wherein the JORA certification standard is measured by a weight ratio of bio-based derived components to petrochemical fuel derived components; the USDA standard is measured by measuring bio-based derived carbon and petrochemical fuel derived carbon through specification ASTM D6866-12 14 C ratio calculation; in the present invention, the content of the bio-based resin in the insulation layer is measured by the specification ASTM D6866-12.
The total thickness of the insulating layer is 1-150 μm.
In a first embodiment, as shown in fig. 1, the structure of the bio-based resin film 1 includes: a carrier film 10; and an insulating layer 11 with bio-based resin formed on the carrier film 10, wherein the insulating layer is a single layer body formed by one-time curing.
The insulating layer is formed by laminating a plurality of insulating layers, and the composition of each layer can be the same or different. In a second embodiment, as shown in fig. 2, another structure of the bio-based resin film 1 includes: a carrier film 10; and insulating sublayers 111 and 112 with bio-based resin sequentially formed on the carrier film 10. In other embodiments, the insulating layer may also include three or four insulating sublayers, but is not limited thereto.
The insulating layer is formed by multilayer coating and multiple curing of varnish type resin, which is not only beneficial to controlling the content of the biobased resin, but also can solve the surface micropore problem existing in the prior coating process and further improve the mechanical property.
When the insulating layer comprises a plurality of insulating sublayers, in addition to solving the defects of coating appearance and improving the defects of mechanical characteristics and the operability and appearance of production and processing, inorganic powder with the particle size of 10nm-20 mu m is added into the insulating layer or the insulating sublayers in contact with the carrier film, so that the surface roughness (Rz) value of the surface of the insulating layer or the surface of the insulator layer in contact with the carrier film is 0.001-10 mu m, and other layers are not added with powder, so that the overall mechanical characteristics are better maintained; by the addition mode, the whole shielding performance is improved, and the carrier film is easy to separate.
In this embodiment, the inorganic powder is at least one selected from the group consisting of calcium sulfate, carbon black, silica, titanium dioxide, zinc sulfide, zirconia, calcium carbonate, silicon carbide, boron nitride, alumina, talc powder, aluminum nitride, glass powder, quartz powder, and clay, and the weight percentage of the inorganic powder is 0-50%, for example, 10%, 20%, 30%, 40%, or 50% based on the weight of the insulating sub-layer.
Preferably, the surface roughness (Rz) of the surface of the insulating layer or the surface of the insulator layer in contact with the carrier film has a value of 0.1 to 5 μm, for example, 0.001. Mu.m, 0.003. Mu.m, 0.005. Mu.m, 0.007. Mu.m, 0.009. Mu.m, 0.1. Mu.m, 0.3. Mu.m, 0.5. Mu.m, 0.7. Mu.m, 0.9. Mu.m, 1.0. Mu.m, 1.1. Mu.m, 1.2. Mu.m, 1.3. Mu.m, 1.4. Mu.m, 1.5. Mu.m, 1.6. Mu.m, 1.7. Mu.m, 1.9. Mu.m, 2.0. Mu.m, 2.1. Mu.m, 2.2. Mu.m, 2.3. Mu.m, 2.4. Mu.m, 2.5. Mu.m, 2.6. Mu.m, 2.7. Mu.m, 2.8. Mu.m, 2.9. Mu.m, 3.0. Mu.m, 4.0. Mu.m, 5.0. Mu.m, 6.m, 7.0. Mu.m, 8.0. Mu.m, 9.0. Mu.m, or 10. Mu.m.
The insulation layer further comprises a petrochemical resin, and the weight percentage of the petrochemical resin is 0-80%, such as 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 80%; wherein the petrochemical resin is at least one selected from the group consisting of epoxy resin, acrylic resin, urethane resin, silicone rubber resin, parylene resin, bismaleimide resin, styrene-ethylene-butylene-styrene block copolymer, polyimide resin, and polyamideimide.
The petrochemical resin is a polyamideimide resin having the following formula (II), wherein n is 20 to 30.
The insulating layer further comprises an inorganic filler, and the weight percentage of the inorganic filler is 0-50%, such as 10%, 20%, 30%, 40% or 50%. Wherein the inorganic filler is at least one selected from the group consisting of calcium sulfate, carbon black, silicon dioxide, titanium dioxide, zinc sulfide, zirconium oxide, calcium carbonate, silicon carbide, boron nitride, aluminum oxide, talc powder, aluminum nitride, glass powder, quartz powder and clay.
The insulating layer further comprises a pigment, and the weight percentage of the pigment is 0-50%, such as 10%, 20%, 30%, 40%, or 50%. The pigment is at least one inorganic pigment selected from the group consisting of cadmium red, cadmium lemon yellow, orange cadmium yellow, titanium dioxide, carbon black, black iron oxide and black complex. The pigment is at least one organic pigment selected from the group consisting of aniline black, perylene black, anthraquinone black, benzidine yellow pigments, phthalocyanine blue and phthalocyanine green.
The insulating layer further comprises an additive, and the weight percentage of the additive is 0-20%, wherein the additive is a curing agent, a catalyst or a surfactant.
The carrier film is used outside the insulating layer and is made of at least one material selected from the group consisting of polypropylene, biaxially oriented polypropylene, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polyurethane and polyamide.
The surface roughness value of the surface of the carrier film in contact with the insulating layer is 0.001 to 10 μm.
The carrier film also comprises inorganic powder with the grain diameter of 20 mu m to 10nm, the inorganic powder is selected from at least one of the group consisting of calcium sulfate, carbon black, silicon dioxide, titanium dioxide, zinc sulfide, zirconia, calcium carbonate, silicon carbide, boron nitride, alumina, talcum powder, aluminum nitride, glass powder, quartz powder and clay, and the weight percentage of the inorganic powder is 0 to 50 percent based on the weight of the carrier film.
The insulating layer and the carrier film are easy to separate through the form control of the surface roughness, so that the operability of a downstream terminal is improved, and meanwhile, the colored bio-based resin film prepared by rapid press molding also has better product appearance.
The invention also comprises a covering film which comprises the bio-based resin film;
an adhesive layer having a bio-based resin formed on the insulating layer of the bio-based resin film;
the release layer is formed on the bonding layer, so that the bonding layer is positioned between the insulating layer and the release layer;
wherein, according to the specification ASTM D6866-12, the content of the bio-based resin in the covering film is more than 20%.
The content of the bio-based resin in the insulating layer is 20-100%.
In a first embodiment, the insulating layer is a single layer formed by one-time curing. As shown in fig. 3, the structure of the cover film 2 includes: a carrier film 20; an insulating layer 21 with bio-based resin; an adhesive layer 22 with bio-based resin; and a release layer 23.
The insulating layer is formed by stacking a plurality of insulating layers. In the second embodiment, as shown in fig. 4, another structure of the cover film 2 includes: a carrier film 20; insulating sublayers 211, 212 with bio-based resin; an adhesion layer 22 with bio-based resin formed on the insulating sub-layer 212; and a release layer 23 formed on the adhesive layer 22. In other embodiments, the insulating layer may also be three or four layers, but is not limited thereto.
At least one of the adhesive layer and the insulating layer further comprises a petrochemical resin, and the weight percentage of the petrochemical resin is 0-80%;
wherein the petrochemical resin is at least one selected from the group consisting of epoxy resin, acrylic resin, urethane resin, silicone rubber resin, poly-p-xylylene resin, bismaleimide resin, styrene-ethylene-butylene-styrene block copolymer, polyimide resin, and polyamideimide.
The adhesive layer further comprises a flame retardant, and the weight percentage of the flame retardant is 0-50%, such as 10%, 20%, 30%, 40% or 50%.
The flame retardant is a compound having flame retardancy selected from at least one of the group consisting of halogen, phosphorus, nitrogen and boron.
The fire retardant is an inorganic substance with the particle size of 2 mu m to 10nm, and is at least one selected from the group consisting of calcium sulfate, carbon black, silicon dioxide, teflon, fluorine resin, titanium dioxide, zinc sulfide, zirconium oxide, calcium carbonate, silicon carbide, boron nitride, aluminum hydroxide, aluminum oxide, talcum powder, aluminum nitride, glass powder, phosphorus flame retardant, quartz powder and clay. However, the higher the proportion of inorganic powder such as titanium dioxide, silica, alumina, aluminum hydroxide, or calcium carbonate added, the higher the flame resistance.
The flame retardant is organic powder containing polyimide resin.
Preferably, the flame retardant is at least one selected from the group consisting of silica, carbon black, talc, calcium carbonate, glass powder and quartz powder, and the weight percentage of the flame retardant is 0-50%, such as 10%, 20%, 30%, 40% or 50%.
More preferably, the flame retardant is present in an amount of 5 to 35% by weight.
When high flame resistance is required, the flame retardant is a flame retardant compound selected from at least one of the group consisting of aluminum hydroxide, aluminum oxide, calcium carbonate and halogen, phosphorus, nitrogen or boron series.
Meanwhile, the addition of the powder is also beneficial to improving the hardness of the powder to ensure that the hardness of the powder reaches 2H to 6H, and compared with a commercially available varnish layer with the hardness of HB to 2H, the layer body of the invention is not easy to scratch and influence the appearance and the mechanical property of the layer body.
At least one of the adhesion layer and the insulation layer also includes a pigment, and the weight percentage of the pigment is 0-50%, such as 10%, 20%, 30%, 40%, or 50%.
The pigment is at least one inorganic pigment selected from the group consisting of cadmium red, cadmium lemon yellow, orange cadmium yellow, titanium dioxide, carbon black, black iron oxide and black complex.
The pigment is at least one organic pigment selected from the group consisting of aniline black, perylene black, anthraquinone black, benzidine yellow pigments, phthalocyanine blue and phthalocyanine green.
At least one of the adhesion layer and the insulation layer further comprises an additive, and the weight percentage of the additive is 0-20%, wherein the additive is a curing agent, a catalyst or a surfactant.
The release layer is at least one selected from the group consisting of polypropylene, biaxially oriented polypropylene and polyethylene terephthalate.
The preparation method of the bio-based resin film comprises the following steps:
the method comprises the following steps: coating a varnish having a bio-based resin on a carrier film;
step two: curing the varnish with the bio-based resin at a temperature of 50-180 ℃ to form the insulating layer with the bio-based resin.
The preparation method of the bio-based resin film can repeat the coating and curing conditions of the first step, namely the steps of coating the varnish with the bio-based resin and curing after the insulating layer is cured and formed according to the number of the layers of the insulating layer, so as to form the insulating layer with a plurality of insulating sub-layers.
The preparation method of the covering film comprises the following steps:
the method comprises the following steps: coating varnish with bio-based resin on a carrier film, and curing the varnish with the bio-based resin at a low temperature of between 50 and 180 ℃ to form an insulating layer with the bio-based resin;
step two: forming the adhesive layer with bio-based resin on the surface of the insulating layer by coating or transfer printing;
step three: and taking a release layer, and attaching the release layer to the adhesive layer to obtain the cover film.
According to the preparation method of the cover film, the number of the layer bodies of the insulating layer can be determined according to the requirement, and after the insulating layer is solidified and formed, the coating and solidifying conditions in the first step are repeated to form a plurality of insulating layers on the insulating layer.
The features and effects of the present invention will be further described in detail with reference to the following specific examples, which are not intended to limit the scope of the present invention.
Example 1: preparation of bio-based resin film
The preparation of the bio-based resin thin film of the present example includes slit coating of a varnish having a bio-based resin on a carrier film, and the composition of the varnish used for forming the insulating layer used in each example is as follows; and curing the varnish with the bio-based resin in an oven at 50-180 ℃ for 10 minutes to form the insulating layer with the bio-based resin.
For comparative examples B1 and B2, a commercially available polyimide film (dupont black polyimide film Kapton) which is a uniaxially stretched film was used. In comparative examples B3 and B4, a polyimide film (HB-N) of Shenzhen Ruihita was used.
The material of the carrier film used in each example was polyethylene terephthalate (Dupont Teijin film, YG 0).
The bio-based resin used in each example is a resin having a structure of the following formula (I) wherein n is 15 to 25.
The petrochemical resin in each embodiment is a polyamideimide resin having the following structure (II), wherein n is 20 to 30.
The curing agent used in each example was 4,4' diamino diphenyl sulfone and the flame retardant was Clariant, type:
OP 935 and the inorganic filler is SiO 2 The inorganic pigment is carbon black.
The insulating layers for the embodiments A1 to A3 are in a double-layer stack; in the first insulating sublayer, the weight percentage of the bio-based resin is 70%, the weight percentage of the petrochemical resin is 10%, the weight percentage of the inorganic filler is 5%, the weight percentage of the inorganic pigment is 10%, the weight percentage of the curing agent is 5%, and the solvent is cyclohexanone.
In the second insulating sub-layer, the weight percentage of the bio-based resin is 50%, the weight percentage of the petrochemical resin is 40%, the weight percentage of the inorganic filler is 5%, the weight percentage of the inorganic pigment is 0%, the weight percentage of the curing agent is 5%, and the solvent is cyclohexanone.
The insulating layer according to embodiments A4 and A5 is a single layer, and includes: the weight percentage of the bio-based resin is 80%, the weight percentage of the petrochemical product resin is 0%, the weight percentage of the inorganic filler is 5%, the weight percentage of the inorganic pigment is 10%, the weight percentage of the curing agent is 5%, and the solvent is cyclohexanone.
The insulating layer according to embodiments A6 and A7 is a single layer, and includes: 30 percent of bio-based resin, 50 percent of petrochemical product resin, 5 percent of inorganic filler, 10 percent of inorganic pigment, 5 percent of curing agent and 5 percent of cyclohexanone as solvent.
Test method
Coefficient of thermal conductivity: thermal conductivity was measured using a hot disk (hot disk) and was performed according to the ASTM D5470 specification.
Breakdown voltage resistance: a pressure resistant analyzer was used and was conducted in accordance with ASTM D149.
Size stability: a two-dimensional coordinate measuring machine is used and the method is carried out according to the IPC-TM-650.2.4C specification.
The tensile strength, elastic modulus and elongation were measured by using an electronic universal tensile machine in accordance with the IPC-TM-650.4.19 specification.
TABLE 1
As shown in the results of table 1, the examples have a certain bio-based content, the bio-based content of the total bio-based resin measured under USDA certification can be greater than 20% of the content of the actual bio-based resin, and bio-based plastic certification of various countries can be obtained, and all have better thermal conductivity and dimensional stability, and the overall performance meets the industry requirements, wherein in examples A1 to A7, the tensile strength, elongation and elastic modulus of the film can be improved through the adjustment of the formula ratio; in contrast, the polyimide films B1 and B2 produced by the tape casting method and not biaxially stretched maintain the mechanical strength, but show the worst dimensional stability of the final products.
Example 2: preparation of colored bio-based resin film
The bio-based resin films of the following examples were prepared as in example A4, except that the composition of the inorganic pigments in the insulating layer was changed as in table 2, and the carrier used was polyethylene terephthalate (Dupont Teijin film, YG 0) having a thickness of 25 μm and containing the pigments in table 2. In addition, each of examples 1 to 16 was prepared in two separate sets of samples, for example, example 1 was divided into a carbon black/carbon black set and a black dye/black dye set; examples 12, 13 and 16 have the same additive composition, but different proportions of the respective groups of samples, wherein the black dye is an inorganic black pigment with carbon black added.
Test method
Surface roughness: the measurement was carried out using an Atomic Force Microscope (AFM for short) in accordance with JIS B0601-2002.
Release force: tensile tester was used and was performed according to ASTM D3330.
TABLE 2
As shown in the results of table 2, the roughness matching between the insulating layer and the carrier film is mainly achieved by adding powder to make the insulating layer or the carrier film or both have a certain roughness to reduce the release force to the required range. In addition, the rougher the surface roughness of the carrier film, the rougher the surface of the insulating layer of the carrier film, the roughening effect is also provided.
In the case of example 14, the release force was too large to release the film without the addition of the release agent; to solve this problem, the known technology is different from the technology of the present invention in that more release agent is added to the carrier film. In order to further reduce the release force, the bio-based resin film of the present invention may further include an inorganic powder, an inorganic filler, or a pigment in at least one of the insulating layer and the carrier film. The inorganic powder, the inorganic filler or the pigment comprise the material disclosed herein, and the weight percentage of each material is 0-50%.
Example 3: preparation of cover film
The preparation of the coverlay film of the following examples was comprised of: the bio-based resin film was prepared as in the above example; then, coating an adhesive layer with bio-based resin on the insulating layer of the bio-based resin film, and heating for 5 minutes in an oven at the temperature of 50-130 ℃; and forming an off-layer on the adhesion layer.
The bio-based resin used in each example is a resin having a structure according to formula (I) wherein n is 15 to 25. The petrochemical resin in each embodiment is a polyamideimide resin having a structure of formula (II), wherein n is 20 to 30.
The curing agent used in the examples was 4,4' diamino diphenyl sulfone and the flame retardant was Clariant, type:
OP 935 and the inorganic filler is SiO 2 The inorganic pigment is carbon black.
The covering film prepared by the bio-based resin layer comprises a carrier film, a bio-based resin layer, a bio-based adhesive layer and a release layer, and related characteristic examples C1 to C7 are as follows; the insulating layers of examples C1 to C3 were in a double-layer stack; the insulating layers of embodiments C4 to C7 use a single layer such as the first insulating sublayer.
The coverlay films of comparative examples D1 and D2 were prepared using the polyimide film HB-N of shenzhenrehuatai as the insulating layer, and the coverlay films of comparative examples D3 and D4 were prepared using the black polyimide film Kapton of dupont as the insulating layer; then, coating and forming an adhesive layer on the insulating layer, namely replacing the bio-based adhesive layer material of the embodiment with a petrochemical resin adhesive layer material, wherein the composition of the bio-based adhesive layer material comprises 55 wt% of petrochemical resin (polyamide-imide resin with a structure of formula (II), wherein n is 20 to 30), 30 wt% of flame retardant, 0 wt% of inorganic pigment, 15 wt% of curing agent and cyclohexanone as solvent, and heating the bio-based adhesive layer material in an oven at 50 to 130 ℃ for 5 minutes; and forming an off-layer on the adhesion layer.
The material of the carrier film used in each example is polyethylene terephthalate (Dupont Teijin film, YG 0); the release layer is a selective laminating release paper (Taibo, T30).
The first insulating sublayer comprises 70 wt% of bio-based resin, 10 wt% of petrochemical resin, 5 wt% of inorganic filler, 10 wt% of inorganic pigment, 5 wt% of curing agent and cyclohexanone as solvent.
The second insulating sub-layer is prepared from 50 wt% of bio-based resin, 40 wt% of petrochemical resin, 5 wt% of inorganic filler, 0 wt% of inorganic pigment, 5 wt% of curing agent and cyclohexanone as solvent.
The insulating layers of examples C4 and C5 used were a resin composition including 80 wt% of bio-based resin, 0 wt% of petrochemical resin, 5 wt% of inorganic filler, 10 wt% of inorganic pigment, 5 wt% of curing agent, and cyclohexanone as solvent.
The insulating layers of examples C6 and C7 used were the layers comprising 30 wt% bio-based resin, 50 wt% petrochemical resin, 5 wt% inorganic filler, 10 wt% inorganic pigment, 5 wt% curing agent, and cyclohexanone as solvent.
The adhesive layer with the bio-based resin comprises 30 weight percent of the bio-based resin, 25 weight percent of the petrochemical product resin, 30 weight percent of the flame retardant, 0 weight percent of the inorganic pigment, 15 weight percent of the curing agent and cyclohexanone serving as a solvent.
TABLE 3
As shown in the results of table 3, the insulating layer and the adhesive layer of the embodiment have a certain content of bio-based resin, and the total bio-based content thereof can be greater than 20% of the actual bio-based resin content determined under USDA certification, so that bio-based plastic certification of various countries can be obtained, and the bio-based plastic has good dimensional stability, and the overall performance meets the requirements of the industry. The polyimide films of comparative examples D1, D2 produced by casting method and not biaxially stretched exhibited the worst dimensional stability of the finished products.
In summary, the present invention uses high content bio-based resin to replace the prior resin, and effectively improves the defect of insufficient mechanical strength of bio-based resin film by the addition ratio of the resin and the additives, so that the present invention can be applied to cover films, inks, copper clad laminates, electromagnetic interference shielding films, polyimide reinforcing plates, heat conductive products (such as composed of heat conductive substrates, resin coated copper foils, and heat conductive insulating adhesives).
By the design of the bio-based resin film and the adhesion layer containing bio-based components, the covering film not only meets the environmental protection trend of the existing carbon neutralization policy, but also has the advantages of insulating surface glossiness, color adjustability, good adhesion, high flame retardance, high shielding property, high dimensional stability, high heat dissipation, high surface hardness and the like, and is suitable for being applied to the fields of ultra-density assembly lines, wireless charging and the like.
In addition, by utilizing the carrier film and the multi-layer coating process, the preparation method also solves the thickness limitation of the stretching process of the colored film on the market at present, meets the design requirement of the thinning industry, also solves the difficulty of single specification production, is easy to produce various thicknesses, and can replace the thinned polyimide film with high unit price and the thickness less than 12.5 microns on the market; meanwhile, the preparation method has no tensile stress residue, so the preparation method has the advantages of better dimensional stability, easier processing for downstream processing, low cost and the like, and has industrial application value.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to other related technical fields, are included in the scope of the present invention.
Claims (29)
1. A bio-based resin film, characterized by: comprises a carrier film; and an insulating layer having a bio-based resin, the insulating layer being formed on the carrier film;
the content of the bio-based resin in the insulating layer is greater than 20%.
2. The bio-based resin film according to claim 1, wherein: the insulating layer is formed by stacking a plurality of insulating layers.
3. The bio-based resin film according to claim 1, wherein: the surface roughness value of the side of the insulating layer in contact with the carrier film is 0.001-10 μm.
4. The bio-based resin film according to claim 2, wherein: the surface of one side of the insulating layer, which is in contact with the carrier film, comprises inorganic powder with the particle size of 10nm-20 microns, wherein the inorganic powder is selected from at least one of the group consisting of calcium sulfate, carbon black, silicon dioxide, titanium dioxide, zinc sulfide, zirconium oxide, calcium carbonate, silicon carbide, boron nitride, aluminum oxide, talcum powder, aluminum nitride, glass powder, quartz powder and clay, and the weight percentage of the inorganic powder is 0-50% based on the weight of the insulating sublayer.
5. The bio-based resin film according to claim 1, wherein: the bio-based resin is a resin having imide bonds that is synthetically prepared from bio-based monomers.
6. The bio-based resin film according to claim 5, wherein: the bio-based resin is at least one selected from the group consisting of polyimide resin and polyamideimide.
7. The bio-based resin film according to claim 1, wherein: the insulating layer further comprises petrochemical resin, and the weight percentage of the petrochemical resin is 0-80%;
wherein the petrochemical resin is at least one selected from the group consisting of epoxy resin, acrylic resin, urethane resin, silicone rubber resin, parylene resin, bismaleimide resin, styrene-ethylene-butylene-styrene block copolymer, polyimide resin, and polyamideimide.
8. The bio-based resin film according to claim 1, wherein: the insulating layer also comprises inorganic filler, and the weight percentage of the inorganic filler is 0-50%;
wherein the inorganic filler is at least one selected from the group consisting of calcium sulfate, carbon black, silicon dioxide, titanium dioxide, zinc sulfide, zirconium oxide, calcium carbonate, silicon carbide, boron nitride, aluminum oxide, talc powder, aluminum nitride, glass powder, quartz powder and clay.
9. The bio-based resin film according to claim 1, wherein: the insulating layer further comprises a pigment, and the weight percentage of the pigment is 0-50%.
10. The bio-based resin film according to claim 9, wherein: the pigment is at least one inorganic pigment selected from the group consisting of cadmium red, cadmium lemon yellow, orange cadmium yellow, titanium dioxide, carbon black, black iron oxide and black complex.
11. The bio-based resin film according to claim 9, wherein: the pigment is at least one organic pigment selected from the group consisting of aniline black, perylene black, anthraquinone black, benzidine yellow pigments, phthalocyanine blue and phthalocyanine green.
12. The bio-based resin film according to claim 1, wherein: the insulating layer further comprises an additive, and the weight percentage of the additive is 0-20%, wherein the additive is a curing agent, a catalyst or a surfactant.
13. The bio-based resin film according to claim 1, wherein: the carrier film is at least one selected from the group consisting of polypropylene, biaxially oriented polypropylene, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polyurethane and polyamide.
14. The bio-based resin film according to claim 1, wherein: the surface roughness value of the surface of the carrier film in contact with the insulating layer is 0.001 to 10 μm.
15. The bio-based resin film according to claim 14, wherein: the carrier film also comprises inorganic powder with the grain diameter of 20 mu m to 10nm, the inorganic powder is selected from at least one of the group consisting of calcium sulfate, carbon black, silicon dioxide, titanium dioxide, zinc sulfide, zirconia, calcium carbonate, silicon carbide, boron nitride, alumina, talcum powder, aluminum nitride, glass powder, quartz powder and clay, and the weight percentage of the inorganic powder is 0 to 50 percent based on the weight of the carrier film.
16. A cover film, characterized by: comprising the bio-based resin film of claim 1;
an adhesive layer having a bio-based resin formed on the insulating layer of the bio-based resin film;
the release layer is formed on the bonding layer, so that the bonding layer is positioned between the insulating layer and the release layer;
the content of the bio-based resin in the cover film is greater than 20%.
17. The cover film of claim 16, wherein: the bio-based resin in the adhesive layer and the insulating layer is a resin having an imide bond synthetically prepared from a bio-based monomer.
18. The coverfilm of claim 17, wherein: the bio-based resin is at least one selected from the group consisting of polyimide resin and polyamideimide.
19. The coverfilm of claim 16, wherein: at least one of the adhesive layer and the insulating layer further comprises a petrochemical resin, and the weight percentage of the petrochemical resin is 0-80%;
wherein the petrochemical resin is at least one selected from the group consisting of epoxy resin, acrylic resin, urethane resin, silicone rubber resin, poly-p-xylylene resin, bismaleimide resin, styrene-ethylene-butylene-styrene block copolymer, polyimide resin, and polyamideimide.
20. The cover film of claim 16, wherein: the adhesion layer also comprises a flame retardant, and the weight percentage of the flame retardant is 0-50%.
21. The coverfilm of claim 20, wherein: the flame retardant is a compound having flame retardancy selected from at least one of the group consisting of halogen, phosphorus, nitrogen and boron.
22. The coverfilm of claim 20, wherein: the fire retardant is an inorganic substance with the particle size of 2 mu m to 10nm, and is at least one selected from the group consisting of calcium sulfate, carbon black, silicon dioxide, teflon, fluorine resin, titanium dioxide, zinc sulfide, zirconium oxide, calcium carbonate, silicon carbide, boron nitride, aluminum hydroxide, aluminum oxide, talcum powder, aluminum nitride, glass powder, phosphorus flame retardant, quartz powder and clay.
23. The coverfilm of claim 20, wherein: the flame retardant is organic powder containing polyimide resin.
24. The coverfilm of claim 16, wherein: at least one of the adhesion layer and the insulation layer further comprises a pigment, and the pigment is an inorganic pigment selected from at least one of cadmium red, cadmium lemon yellow, orange cadmium yellow, titanium dioxide, carbon black, black iron oxide, and black complex; the pigment is at least one organic pigment selected from the group consisting of aniline black, perylene black, anthraquinone black, benzidine yellow pigments, phthalocyanine blue and phthalocyanine green.
25. The coverfilm of claim 16, wherein: at least one of the adhesion layer and the insulation layer further comprises an additive, and the additive is a curing agent, a catalyst, or a surfactant.
26. The coverfilm of claim 16, wherein: the release layer is at least one selected from the group consisting of polypropylene, biaxially oriented polypropylene and polyethylene terephthalate.
27. A method for preparing a bio-based resin film according to claim 1, wherein: the method comprises the following steps:
coating a varnish having a bio-based resin on a carrier film;
and curing the varnish with the bio-based resin at a temperature of 50-180 ℃ to form the insulating layer with the bio-based resin.
28. The method of manufacturing according to claim 27, wherein: the method further comprises the step of repeating the steps of coating the varnish with the bio-based resin and curing after curing the varnish with the bio-based resin to form the insulating layer with a plurality of insulating sub-layers.
29. A method of making the coverfilm of claim 16, wherein: the method comprises the following steps:
carrying out the method of producing a bio-based resin film according to claim 27 or 28;
forming an adhesive layer with bio-based resin on the insulating layer by using a coating method or a transfer method;
and forming an off-layer on the adhesion layer.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102711428A (en) * | 2012-06-21 | 2012-10-03 | 广州方邦电子有限公司 | Ultrathin shielding film with high shielding efficiency and production method thereof |
| CN104672448A (en) * | 2014-06-30 | 2015-06-03 | 广东丹邦科技有限公司 | Polyimide resin and application thereof, two-layer adhesiveless base material and preparation method of two-layer adhesiveless base material |
| CN105246313A (en) * | 2015-09-29 | 2016-01-13 | 朱春芳 | Electromagnetic wave shielding film, printed circuit board including shielding film and preparation method of circuit board |
| CN105585671A (en) * | 2016-03-23 | 2016-05-18 | 江南大学 | Biologic photosensitive polyimide resin and coating prepared from same |
| CN108841004A (en) * | 2018-06-29 | 2018-11-20 | 常州储能材料与器件研究院 | A kind of biology base dianhydride monomer, biological poly imide resin and preparation method thereof |
| CN108976457A (en) * | 2018-07-25 | 2018-12-11 | 深圳市弘海电子材料技术有限公司 | Using Kapton as FPC electromagnetic shielding film of insulating layer and preparation method thereof |
| CN109054480A (en) * | 2018-08-01 | 2018-12-21 | 太仓斯迪克新材料科技有限公司 | A kind of thermostable photosensitive and corrosion-resistant film and its preparation and application |
| CN110054894A (en) * | 2019-05-13 | 2019-07-26 | 东华大学 | A kind of biological poly imide membrane and its preparation method and application |
| CN113637202A (en) * | 2021-10-08 | 2021-11-12 | 齐鲁工业大学 | Bio-based polyimide-halloysite nanotube composite film and preparation method thereof |
| CN114507345A (en) * | 2022-01-28 | 2022-05-17 | 华南理工大学 | Gallic acid bio-based polyimide and preparation and application thereof |
-
2022
- 2022-10-18 CN CN202211269608.5A patent/CN115960458A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102711428A (en) * | 2012-06-21 | 2012-10-03 | 广州方邦电子有限公司 | Ultrathin shielding film with high shielding efficiency and production method thereof |
| CN104672448A (en) * | 2014-06-30 | 2015-06-03 | 广东丹邦科技有限公司 | Polyimide resin and application thereof, two-layer adhesiveless base material and preparation method of two-layer adhesiveless base material |
| CN105246313A (en) * | 2015-09-29 | 2016-01-13 | 朱春芳 | Electromagnetic wave shielding film, printed circuit board including shielding film and preparation method of circuit board |
| CN105585671A (en) * | 2016-03-23 | 2016-05-18 | 江南大学 | Biologic photosensitive polyimide resin and coating prepared from same |
| CN108841004A (en) * | 2018-06-29 | 2018-11-20 | 常州储能材料与器件研究院 | A kind of biology base dianhydride monomer, biological poly imide resin and preparation method thereof |
| CN108976457A (en) * | 2018-07-25 | 2018-12-11 | 深圳市弘海电子材料技术有限公司 | Using Kapton as FPC electromagnetic shielding film of insulating layer and preparation method thereof |
| CN109054480A (en) * | 2018-08-01 | 2018-12-21 | 太仓斯迪克新材料科技有限公司 | A kind of thermostable photosensitive and corrosion-resistant film and its preparation and application |
| CN110054894A (en) * | 2019-05-13 | 2019-07-26 | 东华大学 | A kind of biological poly imide membrane and its preparation method and application |
| CN113637202A (en) * | 2021-10-08 | 2021-11-12 | 齐鲁工业大学 | Bio-based polyimide-halloysite nanotube composite film and preparation method thereof |
| CN114507345A (en) * | 2022-01-28 | 2022-05-17 | 华南理工大学 | Gallic acid bio-based polyimide and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈沁;杜杰毫;谢海波;赵宗保;郑强;: "生物基可聚合单体及其聚合物制备与性能研究进展", 高分子学报, no. 10, pages 1131 - 1137 * |
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