A new type of dry film for bearing used in producing single-sided thin plates and its use method

Abstract

The present invention relates to the technical field of flexible circuit boards, and specifically discloses a novel dry film for carrying single-sided thin plates and a method for using the same. The raw materials of the novel dry film for carrying single-sided thin plates include, by mass, 50-85 parts of a polymer matrix, 5-25 parts of a monomer, 0.1-2 parts of a photoinitiator, 1-5 parts of a plasticizer, 1-4 parts of an adhesive, 1-3 parts of a bonding agent, 1-10 parts of an acid-resistant toughening agent, and 1-2 parts of other additives. Compared to the traditional use of a tape-bearing carrier film, the present invention uses a photosensitive dry film. The photoinitiator in the dry film generates active particles after being irradiated with ultraviolet light, which triggers a cross-linking reaction of the dry film monomer, thereby firmly combining with the product and playing a bearing role. At the DES station, the film is automatically removed by chemically reacting with a strong alkaline solution or an organic film-removing liquid, without the need for pulling the film, thereby avoiding wrinkles in the product.

Description

Technical Field

[0001] The present invention relates to the technical field of flexible circuit boards, and in particular to a novel carrier dry film for producing single-sided thin boards and a method for using the dry film. Background Art

[0002] Flexible circuit boards, also known as flexible printed circuits (FPCs), are highly bendable and flexible electronic components. They are widely used in a variety of electronic devices, such as smartphones, tablets, wearables, and medical devices. In recent years, with the rapid development of technology and increasing consumer demand for portability, functionality, and aesthetics in electronic devices, the market has continued to grow. According to market research firms, the flexible circuit board market has shown a sustained growth trend in recent years and is expected to reach $150 billion by 2025. Driven by rapid technological advancements and growing market demand, the market holds a promising future.

[0003] With the integration and upgrading of electronic product functions, flexible circuit boards are becoming increasingly thinner (a few microns) and more sophisticated to meet space constraints, weight requirements, flexibility demands, and thermal management considerations. Furthermore, to improve production capacity and efficiency, most manufacturers use roll-to-roll processes to produce the outer layers of multilayer boards. However, during the roll-to-roll process, the tension required for rewinding and unwinding must be around 0.5 MPa. Thinner products are prone to abnormal expansion and contraction, which can affect the conductivity of the circuits between the multilayer boards. In severe cases, this can cause noticeable wrinkles, resulting in poor appearance and functionality.

[0004] To overcome this problem, most manufacturers currently use adhesive-coated PET film as a carrier film to help distribute the tension and provide support for the circuit boards during the roll-to-roll process. After the roll-to-roll process, an additional stripping step is added to separate the carrier film from the thin circuit board under heated conditions. However, due to the thinness of the product and the high tension required during the stripping process, the product can easily wrinkle, resulting in poor appearance and functionality. Summary of the Invention

[0005] The purpose of the present invention is to solve the shortcomings of the prior art and to propose a new type of dry film for bearing used in the production of single-sided thin plates and a method of using the same.

[0006] A novel dry film for supporting single-sided thin plates, comprising the following raw materials by weight: 50-85 parts of a polymer matrix, 5-25 parts of a monomer, 0.1-2 parts of a photoinitiator, 1-5 parts of a plasticizer, 1-4 parts of an adhesive, 1-3 parts of a bonding agent, 1-10 parts of an acid-resistant toughening agent, and 1-2 parts of other additives;

[0007] The bonding agent is at least one of vinyl trimethoxy silane, vinyl silicone oil, polyimide, phthalate, and reinforced polyamide amine;

[0008] The reinforced polyamide amine is prepared by the following specific steps: dendritic polyamide-amine, diethanolamine and dimethylethanolamine are mixed, stirred at 50-60°C for 1-2 hours, butanediol diglycidyl ether is added thereto under stirring, the mixture is stirred at the same temperature for 1-2 hours, and hydroxylated hexagonal boron nitride is added and the stirring is continued for 5-10 hours.

[0009] The above-mentioned bonding agents can enhance the physical and chemical bonding between the photosensitive dry film and the substrate by improving the surface properties of the film layer, thereby improving the overall mechanical properties of the photosensitive dry film.

[0010] Preferably, the mass ratio of the dendritic polyamide-amine, diethanolamine, dimethylethanolamine, butanediol diglycidyl ether, and hydroxylated hexagonal boron nitride is 1-2:1-2:2-5:5-10:1-2.

[0011] Preferably, hydroxylated hexagonal boron nitride is prepared by the following specific steps: mixing hexagonal boron nitride powder and quaternary ammonium surfactant, ball milling for 1-2 hours, adding to sodium hydroxide solution, stirring at 120-130° C. for 5-10 hours, cooling to room temperature, washing with water, and vacuum drying.

[0012] The mass ratio of hexagonal boron nitride powder to quaternary ammonium salt surfactant is 1-5:1-2.

[0013] Hydroxylated hexagonal boron nitride (HBN) is activated and ball-milled using a quaternary ammonium surfactant. This not only effectively increases the interlayer spacing to form a nanostructure, but also further hydroxylates the surface, resulting in excellent bonding between the HBN and butanediol diglycidyl ether (BDO), while also providing excellent dispersibility. Reinforced polyamidoamine (PAA) utilizes a highly branched, dendritic polyamidoamine with densely distributed amino groups and a specific three-dimensional structure, combined with diethanolamine. This reacts with BDO, resulting in excellent epoxy resin curing and flexibility. Due to the spherical structure of the highly branched macromolecules and the absence of intermolecular chain entanglements, the PAA forms a strong bond with the product in the dry film, providing excellent support. This, combined with the hydroxylated HBN, effectively prevents the product from expanding or contracting under tension, leading to wrinkles. Furthermore, PAA exhibits excellent self-peeling properties, further preventing expansion and shrinkage and wrinkling.

[0014] In particular, the polymer matrix is ​​an epoxy type polymer.

[0015] Preferably, the polymer matrix is ​​at least one of bisphenol A epoxy resin, epoxy neophenol resin, epoxy acrylic resin, and self-healing epoxy resin.

[0016] Preferably, the self-healing epoxy resin is prepared by the following steps: adding bis(4-glycidoxy)diphenyl disulfide, isopropyl glycidyl ether, graphene oxide, and polyoxyethylene diamine to ethanol, stirring at 80-90°C for 30-60 minutes, degassing, keeping warm at 100-120°C for 1-2 hours, and cooling to room temperature.

[0017] Preferably, the mass ratio of bis(4-epoxypropoxy)diphenyl disulfide, isopropyl glycidyl ether, graphene oxide, and polyoxyethylene diamine is 10-20:1-5:1-2:1-3.

[0018] The present invention uses isopropyl glycidyl ether and graphene oxide to compound, and combines it with bis(4-epoxypropoxy)diphenyl disulfide, which can not only significantly improve the strength of the system, but also give the system good self-repairing properties. Combined with the reinforced polyamide amine with a dendritic macromolecular structure, it can provide self-repair of cracks, effectively reduce the occurrence of crack failure, and effectively extend the service life of the dry film.

[0019] These epoxy resins can provide high strength, high toughness and good bonding properties. They still have excellent mechanical strength after exposure. They also have good chemical stability, are resistant to acids and weak bases, and can undergo chemical cleaning, development and etching without corrosion or dissociation.

[0020] Specifically, the monomer is at least one of methyl methacrylate, acrylic acid, hydroxyethyl methacrylate, maleic anhydride, and vinyl pyrrolidone.

[0021] All of the above monomers contain photosensitive groups. When exposed to ultraviolet light or other light sources, these photosensitive groups will undergo polymerization, significantly enhancing the mechanical properties of the dry film layer.

[0022] Specifically, the photoinitiator is at least one of benzophenone, 4,4'-dimethoxybenzophenone, 1-hydroxycyclohexane photooxidized ketone, 2-hydroxy-2-methylpropionitrile-1-phenylpropanone, isopropyl sulfide, and dimethylaminoacetophenone.

[0023] When the above photoinitiators are irradiated by light of a specific wavelength, they absorb light energy and generate free radicals or cations, thereby initiating a polymerization reaction of the monomers.

[0024] Specifically, the plasticizer is at least one of epoxidized soybean oil, fatty acid esters and phosphate esters.

[0025] The above plasticizers can effectively reduce the interaction force between polymer chains, thereby increasing the flexibility of the film layer. They can also improve the adhesion of the photosensitive dry film to the substrate surface, ensuring that the film layer will not peel off or generate bubbles during the exposure and development process.

[0026] Specifically, the adhesive is at least one of γ-methacrylate modified silane, γ-glycine ethyl ester silane, methyl trimethacrylate, methyl dimethacrylate, and bis(epoxypropyl) carbonate.

[0027] The above adhesives can improve the adhesion between the photosensitive dry film and the substrate surface, improve the tolerance of the photosensitive dry film during chemical cleaning, development, and etching, and prevent the film layer from being corroded by chemicals.

[0028] Specifically, the acid-resistant toughening agent is at least one of polyetheramine, polyether alcohol and polyetherimide. These acid-resistant toughening agents can improve the toughness and acid resistance of the photosensitive dry film.

[0029] Specifically, other auxiliary agents include any one or more of a color developer, a defoaming agent, an inhibitor, and boron-containing microspheres.

[0030] Among them, the color developer reveals and enhances the contrast of the pattern through chemical reaction, making the pattern easy to identify.

[0031] Defoaming agents can eliminate and suppress bubbles in the film layer to ensure the uniformity and flatness of the film layer.

[0032] Inhibitors are mainly used to prevent photosensitive dry films from polymerizing prematurely during storage, which would affect their quality.

[0033] Preferably, the boron-containing microspheres are prepared by the following steps: mixing mesoporous silica, glucose, polylysine and 4-hydroxyphenylboronic acid, hydrothermally reacting at 200-220° C. for 3-7 hours, cooling to room temperature, filtering, washing and vacuum drying.

[0034] Preferably, the mass ratio of mesoporous silica, glucose, polylysine and 4-hydroxyphenylboronic acid is 5-10:1-2:1-2:0.1-1.

[0035] The present invention uses 4-hydroxyphenylboric acid as a boron source, which is then in situ combined with glucose and polylysine on mesoporous silica through a hydrothermal method. It not only contains rich functional groups such as amino, carboxyl, and hydroxyl groups, and has excellent bonding strength with epoxy resin-type polymers and reinforced polyamide amines, but also the dynamic BO bonds therein are compounded with self-healing epoxy resins, resulting in excellent repair effects and excellent stability.

[0036] The method for using the above-mentioned new type of dry film for carrying single-sided thin plates is as follows: a single-sided copper foil roll is laminated with the above-mentioned new type of dry film for carrying single-sided thin plates to obtain a dry film roll; the dry film roll is exposed to light to obtain a reinforced supporting dry film roll, and the reinforced supporting dry film roll is then chemically cleaned, hot rolled, and exposed to light to obtain a circuit roll; the circuit roll is developed and etched to remove the film to obtain a single-sided thin plate.

[0037] Preferably, during the pressing and laminating process of the coiled material and the novel carrier-use dry film for producing single-sided thin plates, the speed is 0.5-2 m / min, the hot rolling pressure is 0.3-1 MPa, and the hot rolling temperature is 90-120°C.

[0038] Preferably, during the exposure process of the dry film roll, the exposure energy is 50-100 mJ / cm 2 .

[0039] Preferably, during the film removal process, a sodium hydroxide aqueous solution with a mass fraction of 2-5% is sprayed, the spray pressure is 1.2-3.0 bar, the temperature is 40-70° C., and the speed is 1.0-3.0 m / min.

[0040] Beneficial effects:

[0041] Traditional dry films are often used for circuit etching, requiring high photosensitivity, resolution, and hole-capping capabilities. However, the dry film used in this invention serves only as a support and is not used for etching circuits. Therefore, it has a more specific polymer matrix and more bonding agents, plasticizers, etc.

[0042] Compared to traditional adhesive carrier films, this invention utilizes a photosensitive dry film. Upon exposure to UV light, the photoinitiator in the dry film generates active particles, triggering a cross-linking reaction between the dry film monomers, which in turn securely bonds to the product and acts as a carrier. During the DES process, the film is automatically removed through a chemical reaction with a strong alkaline solution or organic stripping fluid, eliminating the need for tensile peeling and thus preventing wrinkles in the product.

[0043] This invention utilizes a novel carrier dry film. Compared to traditional carrier film production processes for thin single-sided boards, this eliminates the film stripping step and solves the problems of traditional carrier film wet processes, such as detachment and product wrinkling. The carrier dry film replaces traditional carrier film and is applied to the non-copper surface of the single-sided board. After exposure, it exhibits excellent mechanical properties and chemical stability, tightly bonding to the product while providing excellent support and preventing abnormal product expansion and contraction. Furthermore, after conventional chemical cleaning, circuit dry film lamination, circuit exposure, and development and etching, the carrier dry film is directly removed during the film stripping step, eliminating the need for film stripping. This prevents product wrinkles that could cause poor appearance and functionality. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 This is a box plot of the average expansion and contraction values ​​of the two edges of test sample A in the TD and MD directions.

[0045] Figure 2 This is a box plot of the average expansion and contraction values ​​of the two edges in the TD and MD directions after the film is removed in Example 1.

[0046] Figure 3 This is a box plot of the average expansion and contraction values ​​of the two edges in the TD and MD directions after the film is removed in Example 2.

[0047] Figure 4 This is a box plot of the average expansion and contraction values ​​of the two edges in the TD and MD directions after the film is removed in Example 3.

[0048] Figure 5 This is a box plot of the average expansion and contraction values ​​of the two edges in the TD and MD directions after the film is removed in Example 4.

[0049] Figure 6 This is a box plot of the average expansion and contraction values ​​of the two edges in the TD and MD directions after the film is removed in Example 5.

[0050] Figure 7 This is a box plot of the average expansion and contraction values ​​of the two edges in the TD and MD directions after the film is removed in Example 6.

[0051] Figure 8 This is a box plot of the average expansion and contraction values ​​of the two edges in the TD and MD directions after the film is removed in Example 7.

[0052] Figure 9 This is a comparison chart of the shape recovery rates of the new type of carrier dry film for producing single-sided thin plates obtained in Example 8 and Comparative Examples 1-2. DETAILED DESCRIPTION

[0053] The present invention will be further explained below with reference to specific embodiments.

[0054] Example 1

[0055] A new type of carrier dry film used for producing single-sided thin plates is composed, by weight, of 65 parts of epoxy neophenol resin, 15 parts of methyl methacrylate, 1 part of benzophenone, 4 parts of epoxidized soybean oil, 4 parts of methyl dimethacrylate, 3 parts of polyimide, 1 part of photochromic agent, 6 parts of polyetherimide, and 1 part of surfactant.

[0056] The method for using the novel dry film for supporting single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for supporting single-sided thin plates are pressed and laminated to obtain a dry film coil, and the lamination speed of the dry film for supporting single-sided thin plates is 1.0 m / min; the dry film coil is exposed to light to obtain a reinforced dry film coil, and the exposure energy is 100 mJ / cm 2 The strengthened bearing dry film roll is then chemically cleaned (the dry film does not float or seep after chemical cleaning), hot rolled (the hot rolling pressure is 0.5 MPa and the hot rolling temperature is 100°C), and exposed to obtain a circuit roll; the circuit roll is developed and etched to remove the film to obtain a single-sided thin plate.

[0057] The film removal liquid is a 3% mass fraction NaOH solution, the film removal speed is 2.2m / min, the film removal liquid spray pressure is 1.5bar, and the film removal section temperature is 50℃. After film removal, there is no dry film residue on the product surface and the product has no obvious wrinkles.

[0058] Using test sample A (test sample A is a single-sided thin plate product produced by the applicant using existing technology) as a control, the expansion and contraction of test sample A and this embodiment after film removal were measured.

[0059] The target expansion and contraction value of the test sample A in the TD direction is 100.050%, and the target expansion and contraction value in the MD direction is 100.110%. The expansion and contraction after stripping are as follows: Figure 1 As shown in the figure, the average expansion and contraction values ​​of the two sides in the TD (product tension direction) direction are 100.057% and 100.052% respectively, which differ from the target expansion and contraction values ​​by +7‱ and +2‱ respectively. This indicates that the product has obvious expansion and contraction abnormalities and also has severe trapezoidal expansion and contraction.

[0060] The expansion and contraction after the film is removed in this embodiment are as follows Figure 2 As shown, the average expansion and contraction values ​​for the two edges in the TD direction are 100.051% and 100.049%, with differences of +1° and -1° from the target expansion and contraction values. This is a closer match to the target expansion and contraction values, and the trapezoidal expansion and contraction is significantly improved. The concentration of the expansion and contraction data for each edge also demonstrates the superiority of the present invention.

[0061] Example 2

[0062] A new type of carrier dry film used for producing single-sided thin plates is composed, by weight, of 50 parts of epoxy neophenol resin, 25 parts of methyl methacrylate, 2 parts of 4,4'-dimethoxybenzophenone, 5 parts of epoxidized soybean oil, 3 parts of γ-methacrylate modified silane, 3 parts of vinyltrimethoxysilane, 1 part of photochromic agent, 10 parts of polyetheramine, and 1 part of inhibitor.

[0063] The method for using the novel dry film for supporting single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for supporting single-sided thin plates are pressed and laminated to obtain a dry film coil, and the lamination speed of the dry film for supporting single-sided thin plates is 2.0 m / min; the dry film coil is exposed to light to obtain a reinforced dry film coil, and the exposure energy is 50 mJ / cm 2 The reinforced bearing dry film roll is then chemically cleaned (the dry film surface is flat and free of damage after chemical cleaning, and has good bonding with the product), hot rolled (hot rolling pressure is 1.0 MPa, hot rolling temperature is 110°C), and exposed to obtain a circuit roll; the circuit roll is developed and etched to remove the film to obtain a single-sided thin plate.

[0064] The film removal liquid is a 5% by mass NaOH solution, the film removal speed is 2.7 m / min, the film removal liquid spray pressure is 1.2 bar, and the film removal section temperature is 40°C. After film removal, there is no dry film residue on the product surface and the product has no obvious wrinkles.

[0065] The expansion and contraction of this embodiment after removing the film is as follows Figure 3As shown, the average TD expansion and contraction values ​​are 100.052% and 100.050%, respectively, meeting the preset expansion and contraction values, and the trapezoidal expansion and contraction are within 2‱. The maximum and minimum expansion and contraction values ​​on the same side are 0.5‱ and 0.7‱, respectively, indicating that the product's internal expansion and contraction are very stable.

[0066] Example 3

[0067] A new type of carrier dry film used for producing single-sided thin plates is composed, by weight, of 85 parts of bisphenol A epoxy resin, 5 parts of maleic anhydride, 0.1 parts of 1-hydroxycyclohexane photooxidized ketone, 1 part of fatty acid ester additive, 3 parts of γ-glycine ethyl ester silane, 2.9 parts of vinyl silicone oil, 1 part of photochromic agent, and 2 parts of polyether alcohol.

[0068] The method for using the novel dry film for supporting single-sided thin plates is as follows: a single-sided copper foil coil is pressed and laminated with the novel dry film for supporting single-sided thin plates to obtain a dry film coil. Carrying use dry film Pressing speed The dry film roll is exposed to strengthen the bearing dry film roll, and the exposure energy is 100mJ / cm 2 The reinforced bearing dry film roll is then chemically cleaned (the dry film has no obvious damage after chemical cleaning), hot rolled (the hot rolling pressure is 0.5 MPa, the hot rolling temperature is 120°C), and exposed to obtain a circuit roll; the circuit roll is developed and etched to remove the film to obtain a single-sided thin plate.

[0069] The film removal liquid is a 2% NaOH solution by mass, the film removal speed is 1.0 m / min, the film removal liquid spray pressure is 3.0 bar, and the film removal section temperature is 70°C. After film removal, there is no dry film residue on the product surface and the product has no obvious wrinkles.

[0070] The expansion and contraction after removing the film in this embodiment is as follows Figure 4 As shown, the average increase and decrease in the TD direction is 100.051%, and the average increase and decrease in the MD direction are 100.110% and 100.111% respectively. There is almost no ladder-shaped increase and decrease in both directions and they are close to the preset values.

[0071] Example 4

[0072] A new type of carrier dry film used for the production of single-sided thin plates is composed, by weight, of 65 parts of epoxy acrylic resin, 15 parts of hydroxyethyl methacrylate, 1 part of 2-hydroxy-2-methylpropionitrile-1-phenylpropanone, 3 parts of phosphate ester additives, 1 part of methyl trimethacrylate, 3 parts of vinyl silicone oil, 1 part of photochromic agent, 1 part of defoaming agent, and 10 parts of polyether alcohol.

[0073] The method for using the novel dry film for supporting single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for supporting single-sided thin plates are pressed and laminated to obtain a dry film coil, and the lamination speed of the dry film for supporting single-sided thin plates is 1.0 m / min; the dry film coil is exposed to light to obtain a reinforced dry film coil, and the exposure energy is 75 mJ / cm 2 The reinforced bearing dry film roll is then chemically cleaned (the dry film surface is smooth and free of damage after chemical cleaning), hot rolled (the hot rolling pressure is 0.3 MPa and the hot rolling temperature is 100°C), and exposed to obtain a circuit roll; the circuit roll is developed and etched to remove the film to obtain a single-sided thin plate.

[0074] The film removal liquid is a 3% mass fraction NaOH solution, the film removal speed is 1.0 m / min, the film removal liquid spray pressure is 2.0 bar, and the film removal section temperature is 50°C. After film removal, there is no dry film residue on the product surface and the product has no obvious wrinkles.

[0075] The expansion and contraction of this embodiment after removing the film is as follows Figure 5 As shown in the figure, the average expansion and contraction in the TD direction is 100.050%, which is completely in line with the preset expansion and contraction value, and there is no ladder-shaped expansion and contraction. The expansion and contraction values ​​in the MD direction are 100.010% and 100.011% respectively, which are also basically in line with the preset expansion and contraction values.

[0076] Example 5

[0077] A new type of dry film for supporting single-sided thin plates is composed by weight of 65 parts of bisphenol A epoxy resin, 20 parts of vinyl pyrrolidone, 1 part of isopropyl sulfide, 3 parts of phosphate additives, 3 parts of bis(epoxypropyl) carbonate, 1 part of polyimide, 1 part of photochromic agent, 1 part of inhibitor, and 5 parts of polyetheramine.

[0078] The method for using the novel dry film for supporting single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for supporting single-sided thin plates are pressed and laminated to obtain a dry film coil, and the lamination speed of the dry film for supporting single-sided thin plates is 1.0 m / min; the dry film coil is exposed to light to obtain a reinforced dry film coil, and the exposure energy is 75 mJ / cm 2 The strengthened bearing dry film roll is then chemically cleaned (the dry film surface is flat and free of damage after chemical cleaning), hot rolled (the hot rolling pressure is 0.5 MPa and the hot rolling temperature is 90°C), and the circuit roll is exposed; the circuit roll is developed and etched to remove the film to obtain a single-sided thin plate.

[0079] The film removal liquid is a 3% mass fraction NaOH solution, the film removal speed is 2.0 m / min, the film removal liquid spray pressure is 3.0 bar, and the film removal section temperature is 50°C. After film removal, there is no dry film residue on the product surface and the product has no obvious wrinkles.

[0080] The expansion and contraction of this embodiment after removing the film is as follows Figure 6As shown, the expansion and contraction values ​​in the TD direction are both 100.050%, and the expansion and contraction values ​​in the MD direction are both 100.110%, which are completely in line with the preset values.

[0081] Example 6

[0082] A new type of dry film for supporting single-sided thin plates is composed, by weight, of 70 parts of bisphenol A epoxy resin, 19 parts of maleic anhydride, 1 part of dimethylaminoacetophenone, 3 parts of phosphate additives, 2 parts of methyl trimethacrylate, 2 parts of phthalate, 1 part of photochromic agent, 1 part of polymerization inhibitor, and 1 part of polyether alcohol.

[0083] The method for using the novel dry film for supporting single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for supporting single-sided thin plates are pressed and laminated to obtain a dry film coil, and the lamination speed of the dry film for supporting single-sided thin plates is 0.5 m / min; the dry film coil is exposed to light to obtain a reinforced dry film coil, and the exposure energy is 100 mJ / cm 2 The reinforced bearing dry film roll is then chemically cleaned (the dry film surface is smooth and free of damage after chemical cleaning), hot rolled (the hot rolling pressure is 0.5 MPa and the hot rolling temperature is 100°C), and exposed to obtain a circuit roll; the circuit roll is developed and etched to remove the film to obtain a single-sided thin plate.

[0084] The film removal liquid is a 3% mass fraction NaOH solution, the film removal speed is 2.0 m / min, the film removal liquid spray pressure is 3.0 bar, and the film removal section temperature is 50°C. After film removal, there is no dry film residue on the product surface and the product has no obvious wrinkles.

[0085] The expansion and contraction of this embodiment after removing the film is as follows Figure 7 As shown, its TD direction expansion and contraction range is larger than that of other embodiments, but it is still significantly better than traditional carrier film products, and there is no obvious trapezoidal expansion and contraction. Its expansion and contraction values ​​of 100.051% and 100.051% are also in line with the preset values.

[0086] Example 7

[0087] A new type of carrier dry film used for producing single-sided thin plates is composed, by weight, of 70 parts of bisphenol A epoxy resin, 19 parts of maleic anhydride, 1 part of dimethylaminoacetophenone, 3 parts of phosphate additives, 2 parts of methyl trimethacrylate, 2 parts of reinforced polyamide amine, 1 part of photochromic agent, 1 part of inhibitor, and 1 part of polyether alcohol.

[0088] The reinforced polyamide amine was prepared by the following specific steps: 150 g of 1.5-generation dendritic polyamide-amine, 150 g of diethanolamine, and 350 g of dimethylethanolamine were mixed and stirred at 55° C. for 1.5 h. 800 g of butanediol diglycidyl ether was added thereto under stirring, and the mixture was stirred at this temperature for 1.5 h. 1.5 g of hydroxylated hexagonal boron nitride was added thereto, and stirring was continued for 8 h.

[0089] Among them, hydroxylated hexagonal boron nitride is prepared by the following specific steps: 300g of hexagonal boron nitride powder and 150g of octadecyltrimethylammonium chloride are mixed, placed in a zirconia ball mill, and ball-milled at a speed of 800r / min for 1.5h. The mixture is added to 3000g of 3.5mol / L sodium hydroxide solution, stirred at a temperature of 125°C for 8h, cooled to room temperature, washed twice with water, and vacuum dried.

[0090] The method for using the novel dry film for supporting single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for supporting single-sided thin plates are pressed and laminated to obtain a dry film coil, and the lamination speed of the dry film for supporting single-sided thin plates is 0.5 m / min; the dry film coil is exposed to light to obtain a reinforced dry film coil, and the exposure energy is 100 mJ / cm 2 The reinforced bearing dry film roll is then chemically cleaned (the dry film surface is smooth and free of damage after chemical cleaning), hot rolled (the hot rolling pressure is 0.5 MPa and the hot rolling temperature is 100°C), and exposed to obtain a circuit roll; the circuit roll is developed and etched to remove the film to obtain a single-sided thin plate.

[0091] The film removal liquid is a 3% mass fraction NaOH solution, the film removal speed is 2.0 m / min, the film removal liquid spray pressure is 3.0 bar, and the film removal section temperature is 50°C. After film removal, there is no dry film residue on the product surface and the product has no obvious wrinkles.

[0092] The expansion and contraction after removing the film in this embodiment is as follows Figure 8 As shown, the expansion and contraction values ​​in the TD direction are both 100.050%, and the expansion and contraction values ​​in the MD direction are both 100.110%, which are completely in line with the preset values.

[0093] Example 8

[0094] The applicant has made further improvements based on Example 7.

[0095] A new type of dry film for supporting single-sided thin plates is composed, by weight, of 70 parts of self-healing epoxy resin, 18.5 parts of maleic anhydride, 1 part of dimethylaminoacetophenone, 3 parts of phosphate additives, 2 parts of methyl trimethacrylate, 1.5 parts of reinforced polyamide amine, 1 part of photochromic agent, 1 part of inhibitor, 1 part of polyether alcohol, and 1 part of boron-containing microspheres.

[0096] The self-healing epoxy resin was prepared by the following steps: 15 g of bis(4-epoxypropoxy)diphenyl disulfide, 3 g of isopropyl glycidyl ether, 1.5 g of graphene oxide, and 2 g of polyoxyethylene diamine were added to 30 g of ethanol, stirred at 85°C for 45 minutes, degassed, kept at 110°C for 1.5 hours, and cooled to room temperature.

[0097] The reinforced polyamide amine was prepared by the following specific steps: 150 g of 1.5-generation dendritic polyamide-amine, 150 g of diethanolamine, and 350 g of dimethylethanolamine were mixed and stirred at 55° C. for 1.5 h. 800 g of butanediol diglycidyl ether was added thereto under stirring, and the mixture was stirred at this temperature for 1.5 h. 1.5 g of hydroxylated hexagonal boron nitride was added thereto, and stirring was continued for 8 h.

[0098] Among them, hydroxylated hexagonal boron nitride is prepared by the following specific steps: 300g of hexagonal boron nitride powder and 150g of octadecyltrimethylammonium chloride are mixed, placed in a zirconia ball mill, and ball-milled at a speed of 800r / min for 1.5h. The mixture is added to 3000g of 3.5mol / L sodium hydroxide solution, stirred at a temperature of 125°C for 8h, cooled to room temperature, washed twice with water, and vacuum dried.

[0099] Boron-containing microspheres are prepared as follows: 8 g of mesoporous silica, 1.5 g of glucose, 1.5 g of polylysine, and 0.5 g of 4-hydroxyphenylboronic acid are mixed, stirred at a speed of 3000 r / min for 15 minutes, hydrothermally reacted at a temperature of 210°C for 5 hours, cooled to room temperature, filtered, washed, and vacuum dried.

[0100] The method for using the novel dry film for supporting single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for supporting single-sided thin plates are pressed and laminated to obtain a dry film coil, and the lamination speed of the dry film for supporting single-sided thin plates is 0.5 m / min; the dry film coil is exposed to light to obtain a reinforced dry film coil, and the exposure energy is 100 mJ / cm 2 The reinforced bearing dry film roll is then chemically cleaned (the dry film surface is smooth and free of damage after chemical cleaning), hot rolled (the hot rolling pressure is 0.5 MPa and the hot rolling temperature is 100°C), and exposed to obtain a circuit roll; the circuit roll is developed and etched to remove the film to obtain a single-sided thin plate.

[0101] The film removal liquid is a 3% mass fraction NaOH solution, the film removal speed is 2.0 m / min, the film removal liquid spray pressure is 3.0 bar, and the film removal section temperature is 50°C. After film removal, there is no dry film residue on the product surface and the product has no obvious wrinkles.

[0102] After the film is removed in this embodiment, the expansion and contraction values ​​in the TD direction are both 100.050%, and the expansion and contraction values ​​in the MD direction are both 100.110%, which are completely in line with the preset values.

[0103] Comparative Example 1

[0104] A new type of supporting dry film used to produce single-sided thin plates is composed, by weight, of 65.12 parts of self-healing epoxy resin, 4.88 parts of graphene oxide, 18.5 parts of maleic anhydride, 1 part of dimethylaminoacetophenone, 3 parts of phosphate additives, 2 parts of methyl trimethacrylate, 1.5 parts of reinforced polyamide amine, 1 part of photochromic agent, 1 part of inhibitor, 1 part of polyether alcohol, and 1 part of boron-containing microspheres.

[0105] The self-healing epoxy resin was prepared by the following steps: 15 g of bis(4-epoxypropoxy)diphenyl disulfide, 3 g of isopropyl glycidyl ether, and 2 g of polyoxyethylene diamine were added to 30 g of ethanol, stirred at 85° C. for 45 minutes, degassed, kept at 110° C. for 1.5 hours, and cooled to room temperature.

[0106] The reinforced polyamide amine was prepared by the following specific steps: 150 g of 1.5-generation dendritic polyamide-amine, 150 g of diethanolamine, and 350 g of dimethylethanolamine were mixed and stirred at 55° C. for 1.5 h. 800 g of butanediol diglycidyl ether was added thereto under stirring, and the mixture was stirred at this temperature for 1.5 h. 1.5 g of hydroxylated hexagonal boron nitride was added thereto, and stirring was continued for 8 h.

[0107] Among them, hydroxylated hexagonal boron nitride is prepared by the following specific steps: 300g of hexagonal boron nitride powder and 150g of octadecyltrimethylammonium chloride are mixed, placed in a zirconia ball mill, and ball-milled at a speed of 800r / min for 1.5h. The mixture is added to 3000g of 3.5mol / L sodium hydroxide solution, stirred at a temperature of 125°C for 8h, cooled to room temperature, washed twice with water, and vacuum dried.

[0108] Boron-containing microspheres are prepared as follows: 8 g of mesoporous silica, 1.5 g of glucose, 1.5 g of polylysine, and 0.5 g of 4-hydroxyphenylboronic acid are mixed, stirred at a speed of 3000 r / min for 15 minutes, hydrothermally reacted at a temperature of 210°C for 5 hours, cooled to room temperature, filtered, washed, and vacuum dried.

[0109] The method for using the novel dry film for supporting single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for supporting single-sided thin plates are pressed and laminated to obtain a dry film coil, and the lamination speed of the dry film for supporting single-sided thin plates is 0.5 m / min; the dry film coil is exposed to light to obtain a reinforced dry film coil, and the exposure energy is 100 mJ / cm 2 The reinforced bearing dry film roll is then chemically cleaned (the dry film surface is smooth and free of damage after chemical cleaning), hot rolled (the hot rolling pressure is 0.5 MPa and the hot rolling temperature is 100°C), and exposed to obtain a circuit roll; the circuit roll is developed and etched to remove the film to obtain a single-sided thin plate.

[0110] The film removal liquid is a 3% mass fraction NaOH solution, the film removal speed is 2.0 m / min, the film removal liquid spray pressure is 3.0 bar, and the film removal section temperature is 50°C. After film removal, there is no dry film residue on the product surface and the product has no obvious wrinkles.

[0111] After the film is removed from this comparative example, the expansion and contraction values ​​in the TD direction are both 100.051%, and the expansion and contraction values ​​in the MD direction are both 100.110%, which basically meet the preset values.

[0112] Comparative Example 2

[0113] A new type of dry film for supporting single-sided thin panels is composed, by weight, of 70 parts of self-healing epoxy resin, 18.5 parts of maleic anhydride, 1 part of dimethylaminoacetophenone, 3 parts of phosphate additives, 2 parts of methyl trimethacrylate, 0.155 parts of 1.5-generation dendritic polyamide-amine, 0.0015 parts of hydroxylated hexagonal boron nitride, 1 part of photochromic agent, 1 part of inhibitor, 1 part of polyether alcohol, and 1 part of boron-containing microspheres.

[0114] The self-healing epoxy resin was prepared by the following steps: 15 g of bis(4-epoxypropoxy)diphenyl disulfide, 3 g of isopropyl glycidyl ether, 1.5 g of graphene oxide, and 2 g of polyoxyethylene diamine were added to 30 g of ethanol, stirred at 85°C for 45 minutes, degassed, kept at 110°C for 1.5 hours, and cooled to room temperature.

[0115] Hydroxylated hexagonal boron nitride is prepared by the following specific steps: 300g of hexagonal boron nitride powder and 150g of octadecyltrimethylammonium chloride are mixed, placed in a zirconia ball mill, and ball-milled at a speed of 800r / min for 1.5h. The mixture is added to 3000g of 3.5mol / L sodium hydroxide solution, stirred at 125°C for 8h, cooled to room temperature, washed twice with water, and vacuum dried.

[0116] Boron-containing microspheres are prepared as follows: 8 g of mesoporous silica, 1.5 g of glucose, 1.5 g of polylysine, and 0.5 g of 4-hydroxyphenylboronic acid are mixed, stirred at a speed of 3000 r / min for 15 minutes, hydrothermally reacted at a temperature of 210°C for 5 hours, cooled to room temperature, filtered, washed, and vacuum dried.

[0117] The method for using the novel dry film for supporting single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for supporting single-sided thin plates are pressed and laminated to obtain a dry film coil, and the lamination speed of the dry film for supporting single-sided thin plates is 0.5 m / min; the dry film coil is exposed to light to obtain a reinforced dry film coil, and the exposure energy is 100 mJ / cm 2The reinforced bearing dry film roll is then chemically cleaned (the dry film surface is smooth and free of damage after chemical cleaning), hot rolled (the hot rolling pressure is 0.5 MPa and the hot rolling temperature is 100°C), and exposed to obtain a circuit roll; the circuit roll is developed and etched to remove the film to obtain a single-sided thin plate.

[0118] The film removal liquid is a 3% mass fraction NaOH solution, the film removal speed is 2.0 m / min, the film removal liquid spray pressure is 3.0 bar, and the film removal section temperature is 50°C. After film removal, there is no dry film residue on the product surface and the product has no obvious wrinkles.

[0119] After the film is removed from this comparative example, the expansion and contraction values ​​in the TD direction are both 100.049%, and the expansion and contraction values ​​in the MD direction are both 100.111%, which basically meet the preset values.

[0120] The new dry films for single-sided sheet production obtained in Example 8 and Comparative Examples 1-2 were subjected to shape recovery testing. Each sample was attached with a 200g weight and held for 5 minutes to induce deformation. The weight was then removed and the sample length was measured after a 1-minute wait at 30°C. The shape recovery rate was then calculated.

[0121] Shape recovery rate = [1 - (length after deformation recovery - original length) ÷ original length] × 100%

[0122] like Figure 9 As shown, the shape recovery rate of the new type of dry film for supporting single-sided thin plates obtained in Example 8 is the highest, which is better than that of Comparative Examples 1-2 (P < 0.05), confirming its excellent self-repairing performance.

[0123] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A new type of dry film for bearing used in the production of single-sided thin plates, characterized in that: The raw materials include, by mass: 50-85 parts of polymer matrix, 5-25 parts of monomer, 0.1-2 parts of photoinitiator, 1-5 parts of plasticizer, 1-4 parts of adhesive, 1-3 parts of bonding agent, 1-10 parts of acid-resistant toughening agent, and 1-2 parts of other additives; The bonding agent is a reinforcing polyamidoamine; The reinforced polyamide amine is prepared by the following specific steps: dendritic polyamide-amine, diethanolamine and dimethylethanolamine are mixed, stirred at 50-60°C for 1-2 hours, butanediol diglycidyl ether is added thereto under stirring, the mixture is stirred at the same temperature for 1-2 hours, and hydroxylated hexagonal boron nitride is added and the stirring is continued for 5-10 hours.

2. The novel dry film for supporting single-sided sheets according to claim 1, characterized in that: The polymer matrix is ​​an epoxy resin type polymer.

3. The novel dry film for supporting single-sided sheets according to claim 1, characterized in that: The polymer matrix is ​​at least one of bisphenol A epoxy resin, epoxy acrylic resin, and self-healing epoxy resin; The self-healing epoxy resin is prepared by the following steps: adding bis(4-glycidoxy)diphenyl disulfide, isopropyl glycidyl ether, graphene oxide, and polyoxyethylene diamine to ethanol, stirring at 80-90°C for 30-60 minutes, degassing, keeping at 100-120°C for 1-2 hours, and cooling to room temperature.

4. The novel dry film for supporting single-sided sheets according to claim 3, characterized in that: The mass ratio of bis(4-epoxypropoxy)diphenyl disulfide, isopropyl glycidyl ether, graphene oxide and polyoxyethylene diamine is 10-20:1-5:1-2:1-3.

5. The novel dry film for supporting single-sided sheets according to claim 1, characterized in that: The monomer is at least one of methyl methacrylate, acrylic acid, hydroxyethyl methacrylate, maleic anhydride and vinyl pyrrolidone.

6. The novel dry film for supporting single-sided sheets according to claim 1, characterized in that: The adhesive is at least one of gamma-methacrylate modified silane, gamma-glycine ethyl ester silane, methyl trimethacrylate, methyl dimethacrylate, and bis(epoxypropyl) carbonate.

7. The novel dry film for supporting single-sided sheets according to claim 1, characterized in that: The mass ratio of the dendritic polyamide-amine, diethanolamine, dimethylethanolamine, butanediol diglycidyl ether and hydroxylated hexagonal boron nitride is 1-2:1-2:2-5:5-10:1-2.

8. The novel dry film for supporting single-sided sheets according to claim 1, characterized in that: Hydroxylated hexagonal boron nitride is prepared by the following specific steps: mixing hexagonal boron nitride powder and quaternary ammonium surfactant, ball milling for 1-2 hours, adding to sodium hydroxide solution, stirring at 120-130° C. for 5-10 hours, cooling to room temperature, washing with water, and vacuum drying.

9. The novel carrier dry film for producing single-sided thin plates according to claim 1, characterized in that: The acid-resistant toughening agent is at least one of polyetheramine, polyether alcohol and polyetherimide; Other additives include any one or more of a color developer, a defoamer, an inhibitor, and boron-containing microspheres.

10. The novel dry film for supporting a single-sided sheet according to claim 9, characterized in that: The boron-containing microspheres are prepared by the following steps: mixing mesoporous silica, glucose, polylysine and 4-hydroxyphenylboronic acid, hydrothermally reacting at 200-220° C. for 3-7 hours, cooling to room temperature, filtering, washing and vacuum drying.

11. The novel dry film for supporting a single-sided sheet according to claim 10, characterized in that: The mass ratio of mesoporous silica, glucose, polylysine and 4-hydroxyphenylboronic acid is 5-10:1-2:1-2:0.1-1.

12. A method for using the novel dry film for bearing used in producing single-sided thin plates according to any one of claims 1 to 11, characterized in that: Laminating a single-sided copper foil coil with a novel carrier dry film for producing a single-sided thin plate according to any one of claims 1 to 11 to obtain a dry film coil; exposing the dry film coil to obtain a reinforced carrier dry film coil; and chemically cleaning, hot rolling, and exposing the reinforced carrier dry film coil to obtain a circuit coil; The circuit coil is developed and etched to remove the film to obtain a single-sided thin plate.

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