Novel bearing dry film for producing single-sided thin plate and use method of novel bearing dry film

Abstract

The invention relates to the technical field of flexible circuit boards, and particularly discloses a novel bearing dry film for producing a single-sided thin plate and a use method of the novel bearing dry film. The novel bearing dry film for producing the single-sided thin plate comprises the following raw materials in parts 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 binding force auxiliary agent, 1-10 parts of an acid-resistant toughening agent and 1-2 parts of other auxiliary agents. Compared with a traditional bearing film with glue, the photosensitive dry film is adopted, the photoinitiator in the dry film generates active particles after being irradiated by ultraviolet light, dry film monomers are initiated to be subjected to a cross-linking reaction, then the dry film monomers are firmly combined with the product, and the bearing effect is achieved. And the film is automatically removed through chemical reaction with a strong alkali solution or an organic film removing solution at the DES station, and film stripping by pulling force is not needed, so that the product is prevented from wrinkling.

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 circuit boards or FPC (Flexible Printed Circuit), are electronic components with high bendability and flexibility. They are widely used in various electronic devices, such as smartphones, tablets, wearable devices, medical devices, etc. In recent years, with the rapid development of science and technology and the increasing demand of consumers for the portability, functionality and aesthetics of electronic devices, the market size has continued to grow. According to data from market research institutions, the market size of flexible circuit boards has shown a continuous growth trend in recent years. It is estimated that by 2025, the global flexible circuit board market size will reach 150 billion US dollars. Driven by the rapid development of science and technology and the growing market demand, its development prospects are very broad.

[0003] With the integration and upgrading of electronic product functions, flexible circuit boards have become thinner (several microns) and more sophisticated in order to meet space constraints, weight requirements, flexibility needs and thermal management considerations. On the other hand, in order to improve production capacity and efficiency, most manufacturers use roll-to-roll processes to produce the outer layer of multilayer board products. However, in the roll-to-roll process, the tension of the reel needs to reach about 0.5MPa. Thinner products are prone to abnormal expansion and contraction, which affects the conduction of the circuits between multilayer circuit boards. In severe cases, it can also cause obvious wrinkles, resulting in poor appearance and function.

[0004] At present, in order to overcome this problem, most manufacturers use PET film with adhesive as the carrier film to help share the tension of the circuit board during the rolling process and provide support. After the rolling process, an additional film stripping process is added to peel the carrier film from the thin circuit board under heating conditions. However, during the film stripping process, the product is very easy to wrinkle due to the thinness of the product and the large pulling force required, resulting in poor appearance and function. 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 carrier dry film for producing single-sided thin plates and a method of using the same.

[0006] A novel dry film for bearing single-sided thin plates, the raw materials of which include, by weight: 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;

[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: the 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 for 1-2 hours at the same temperature, and hydroxylated hexagonal boron nitride is added and stirred for 5-10 hours.

[0009] The above-mentioned bonding additives 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 salt 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] Wherein, the mass ratio of hexagonal boron nitride powder and quaternary ammonium salt surfactant is 1-5:1-2.

[0013] Hydroxylated hexagonal boron nitride uses quaternary ammonium surfactant to activate hexagonal boron nitride powder and ball mill, which can not only effectively increase the interlayer spacing to form a nanostructure, but also further hydroxylates its surface, so that the obtained hydroxylated hexagonal boron nitride has a good bonding effect with butanediol diglycidyl ether, and has good dispersibility. The reinforced polyamide amine uses a dendritic polyamide-amine with dense amino functional groups on the surface and highly branched, with a specific three-dimensional structure, and diethanolamine to react with butanediol diglycidyl ether, which has a good curing effect on epoxy resin and excellent flexibility. Since the highly branched macromolecules are spherical in structure and there is no chain entanglement between molecules, they form a strong bond with the product in the dry film and have a good supporting effect. With the action of hydroxylated hexagonal boron nitride, it can effectively avoid abnormal expansion and contraction and wrinkles of the product due to tension. At the same time, the automatic peeling effect is good, which further avoids the problems of abnormal expansion and contraction and product wrinkles.

[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 min, degassing, keeping at 100-120° C. for 1-2 h, and cooling to room temperature.

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

[0018] The present invention adopts isopropyl glycidyl ether and graphene oxide to compound, and combines 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. It is then combined with a reinforced polyamide amine with a dendritic macromolecular structure to 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 and have good chemical stability. They are resistant to acids and weak alkalis and can be chemically cleaned, developed and etched without being corroded or dissociated.

[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, and can also improve the adhesion of the photosensitive dry film to the surface of the substrate, 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 surface of the substrate, 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 defoamer, 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 inhibit 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-hydroxyphenylboric 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, and then combines it with glucose and polylysine in situ on mesoporous silica through a hydrothermal method. It not only contains abundant 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, and have excellent repairing effects and excellent stability.

[0036] The method for using the new type of dry film for bearing used in producing single-sided thin plates comprises laminating a single-sided copper foil coil with the new type of dry film for bearing used in producing single-sided thin plates to obtain a dry film coil; the dry film coil is exposed to obtain a reinforced bearing dry film coil, and the reinforced bearing dry film coil is then chemically cleaned, hot rolled and exposed to obtain a circuit coil; the circuit coil is developed and etched to remove the film to obtain a single-sided thin plate.

[0037] Preferably, during the process of pressing and laminating the coiled material with the above-mentioned novel load-bearing 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, hole-capping ability, etc. However, the dry film used in the present invention is only used for support and is not used for etching circuits, so it has more and specific polymer matrix and more bonding promoters, plasticizers, etc.

[0042] Compared with the traditional use of adhesive carrier film, the present invention uses photosensitive dry film. The photoinitiator in the dry film generates active particles after being irradiated by ultraviolet light, which triggers the dry film monomer to undergo a cross-linking reaction, and then firmly combines with the product to play a bearing role. At the DES station, the film is automatically removed by chemical reaction with a strong alkaline solution or an organic film removal liquid, without the need for pulling to peel the film, thereby avoiding product wrinkles.

[0043] The present invention uses a new type of dry film for bearing, which eliminates the film stripping process and solves the problems of easy floating and product wrinkling in the traditional bearing film wet process compared to the traditional bearing film production process of thin single-sided board. The dry film for bearing replaces the traditional bearing film and is attached to the non-copper surface of the single-sided board. After exposure, it has excellent mechanical properties and chemical stability. It is closely combined with the product and provides good support for the product to avoid abnormal expansion and contraction of the product. In addition, after conventional chemical cleaning, circuit dry film pressing, circuit exposure, development and etching to remove the film, the dry film for bearing is directly removed in the film stripping process without film stripping, so as to avoid poor appearance and function caused by product wrinkles. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 This is a box plot of the average values ​​of the expansion and contraction 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 values ​​of the expansion and contraction 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 values ​​of the expansion and contraction 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 values ​​of the expansion and contraction 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 values ​​of the expansion and contraction 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 values ​​of the expansion and contraction 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 values ​​of the expansion and contraction 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 values ​​of the expansion and contraction of the two edges in the TD and MD directions after the film is removed in Example 7.

[0052] Fig. 9 This is a comparison chart of the shape recovery rates of the new type of supporting 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 in conjunction with specific embodiments.

[0054] Example 1

[0055] A new type of dry film for supporting 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 bearing used in producing single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for bearing used in producing single-sided thin plates are pressed and laminated to obtain a dry film coil, and the laminating speed of the dry film for bearing is 1.0 m / min; the dry film coil is exposed to light to obtain a reinforced bearing dry film coil, and the exposure energy is 100 mJ / cm 2 The strengthened bearing dry film coil is then chemically cleaned (there is no floating and liquid seepage of the dry film 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 coil; the circuit coil is developed and etched to remove the film to obtain a single-sided thin plate.

[0057] The film removal liquid is a 3% NaOH solution by mass, the film removal speed is 2.2 m / min, the film removal liquid spray pressure is 1.5 bar, the film removal section temperature is 50°C, and 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 shrinkage value of the A test sample in the TD direction is 100.050%, and the target expansion and shrinkage value in the MD direction is 100.110%. The expansion and shrinkage 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 are different from the target expansion and contraction values. and This shows that the product has obvious abnormal expansion and contraction, and also has a more serious trapezoidal expansion and contraction.

[0060] The expansion and contraction after the film is removed in this embodiment is as follows Figure 2 As shown, the average values ​​of the two sides in the TD direction are 100.051% and 100.049%, which are different from the target values. and In comparison, it is more consistent with the target expansion and contraction value, and the trapezoidal expansion and contraction is significantly improved. The concentration of the expansion and contraction data of each edge also shows 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 gamma-methacrylate modified silane, 3 parts of vinyl trimethoxysilane, 1 part of photochromic agent, 10 parts of polyether amine, and 1 part of inhibitor.

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

[0064] The film removal liquid is a 5% NaOH solution by mass, 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 after film removal in this embodiment is as follows Figure 3 As shown, the average values ​​of the expansion and contraction in the TD direction are 100.052% and 100.050% respectively, which are in line with the preset expansion and contraction values, and the trapezoidal expansion and contraction is The maximum and minimum expansion and contraction values ​​of the same edge are and This shows that the internal expansion and contraction of the product is 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 bearing used in producing single-sided thin plates is as follows: a single-sided copper foil coil is pressed and laminated with the novel dry film for bearing used in producing single-sided thin plates to obtain a dry film coil. Loading use Dry film Pressing speed The dry film roll is exposed to obtain a strengthened load-bearing dry film roll, and the exposure energy is 100mJ / cm 2 The strengthened bearing dry film coil 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 coil; the circuit coil 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 film removal in this embodiment is as follows Figure 4 As shown, the average expansion and contraction values ​​in the TD direction are 100.051%, and the average expansion and contraction values ​​in the MD direction are 100.110% and 100.111% respectively. There is almost no ladder-shaped expansion and contraction in both directions and they are close to the preset values.

[0071] Example 4

[0072] A new type of carrier dry film used for producing 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 new type of dry film for bearing used in producing single-sided thin plates is as follows: a single-sided copper foil coil and the new type of dry film for bearing used in producing single-sided thin plates are pressed and laminated to obtain a dry film coil, and the laminating speed of the dry film for bearing is 1.0 m / min; the dry film coil is exposed to obtain a reinforced bearing dry film coil, and the exposure energy is 75 mJ / cm 2 The strengthened bearing dry film coil is then chemically cleaned (the surface of the dry film 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 coil; the circuit coil is developed and etched to remove the film to obtain a single-sided thin plate.

[0074] The film removal liquid is a 3% NaOH solution by mass, 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 after film removal in this embodiment is as follows Figure 5 As shown in the figure, the average expansion and contraction values ​​in the TD direction are 100.050%, which is completely in line with the preset expansion and contraction values, 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 supporting dry film used for producing 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 di(epoxypropyl) carbonate, 1 part of polyimide, 1 part of photochromic agent, 1 part of inhibitor, and 5 parts of polyether amine.

[0078] The method for using the new type of dry film for bearing used in producing single-sided thin plates is as follows: a single-sided copper foil coil and the new type of dry film for bearing used in producing single-sided thin plates are pressed and laminated to obtain a dry film coil, and the laminating speed of the dry film for bearing is 1.0 m / min; the dry film coil is exposed to obtain a reinforced bearing dry film coil, and the exposure energy is 75 mJ / cm 2 The strengthened bearing dry film coil is then chemically cleaned (the surface of the dry film 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 coil is exposed; the circuit coil is developed and etched to remove the film to obtain a single-sided thin plate.

[0079] The film removal liquid is a 3% NaOH solution by mass, 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 after film removal in this embodiment 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 bearing 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 phthalates, 1 part of photochromic agent, 1 part of inhibitor, and 1 part of polyether alcohol.

[0083] The method for using the novel dry film for bearing used in producing single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for bearing used in producing single-sided thin plates are pressed and laminated to obtain a dry film coil, and the laminating speed of the dry film for bearing is 0.5 m / min; the dry film coil is exposed to light to obtain a reinforced bearing dry film coil, and the exposure energy is 100 mJ / cm 2 The reinforced bearing dry film coil is then chemically cleaned (the surface of the dry film 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 coil; the circuit coil is developed and etched to remove the film to obtain a single-sided thin plate.

[0084] The film removal liquid is a 3% NaOH solution by mass, 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 after film removal in this embodiment is as follows Figure 7 As shown, its expansion and contraction range in the TD direction is larger than that in other embodiments, but is still significantly better than traditional carrier film products, and there is no obvious trapezoidal expansion and contraction, and 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 supporting 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 is prepared by the following specific steps: 150g of 1.5-generation dendritic polyamide-amine, 150g of diethanolamine, and 350g of dimethylethanolamine are mixed, stirred at a temperature of 55°C for 1.5h, 800g of butanediol diglycidyl ether is added thereto under stirring, the mixture is stirred for 1.5h at the same temperature, 1.5g of hydroxylated hexagonal boron nitride is added, and stirring is continued for 8h.

[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, ball milled at a speed of 800r / min for 1.5h, 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.

[0090] The method for using the novel dry film for bearing used in producing single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for bearing used in producing single-sided thin plates are pressed and laminated to obtain a dry film coil, and the laminating speed of the dry film for bearing is 0.5 m / min; the dry film coil is exposed to light to obtain a reinforced bearing dry film coil, and the exposure energy is 100 mJ / cm 2 The reinforced bearing dry film coil is then chemically cleaned (the surface of the dry film 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 coil; the circuit coil is developed and etched to remove the film to obtain a single-sided thin plate.

[0091] The film removal liquid is a 3% NaOH solution by mass, 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 film removal 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 bearing dry film used for producing 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-glycidoxy)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 min, degassed, kept at 110° C. for 1.5 h, and cooled to room temperature.

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

[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, ball milled at a speed of 800r / min for 1.5h, 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.

[0099] The boron-containing microspheres are prepared by the following steps: 8 g of mesoporous silica, 1.5 g of glucose, 1.5 g of polylysine, and 0.5 g of 4-hydroxyphenylboric acid are mixed, stirred at a speed of 3000 r / min for 15 min, hydrothermally reacted at a temperature of 210° C. for 5 h, cooled to room temperature, filtered, washed, and vacuum dried.

[0100] The method for using the novel dry film for bearing used in producing single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for bearing used in producing single-sided thin plates are pressed and laminated to obtain a dry film coil, and the laminating speed of the dry film for bearing is 0.5 m / min; the dry film coil is exposed to light to obtain a reinforced bearing dry film coil, and the exposure energy is 100 mJ / cm 2 The reinforced bearing dry film coil is then chemically cleaned (the surface of the dry film 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 coil; the circuit coil is developed and etched to remove the film to obtain a single-sided thin plate.

[0101] The film removal liquid is a 3% NaOH solution by mass, 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 for producing 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 is prepared by the following steps: 15 g of bis(4-glycidoxy)diphenyl disulfide, 3 g of isopropyl glycidyl ether, and 2 g of polyoxyethylene diamine are added to 30 g of ethanol, stirred at 85° C. for 45 min, degassed, kept at 110° C. for 1.5 h, and cooled to room temperature.

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

[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, ball milled at a speed of 800r / min for 1.5h, 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.

[0108] The boron-containing microspheres are prepared by the following steps: 8 g of mesoporous silica, 1.5 g of glucose, 1.5 g of polylysine, and 0.5 g of 4-hydroxyphenylboric acid are mixed, stirred at a speed of 3000 r / min for 15 min, hydrothermally reacted at a temperature of 210° C. for 5 h, cooled to room temperature, filtered, washed, and vacuum dried.

[0109] The method for using the novel dry film for bearing used in producing single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for bearing used in producing single-sided thin plates are pressed and laminated to obtain a dry film coil, and the laminating speed of the dry film for bearing is 0.5 m / min; the dry film coil is exposed to light to obtain a reinforced bearing dry film coil, and the exposure energy is 100 mJ / cm 2 The reinforced bearing dry film coil is then chemically cleaned (the surface of the dry film 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 coil; the circuit coil is developed and etched to remove the film to obtain a single-sided thin plate.

[0110] The film removal liquid is a 3% NaOH solution by mass, 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, the expansion and contraction values ​​in the TD direction are 100.051%, and the expansion and contraction values ​​in the MD direction are 100.110%, which are basically in line with the preset values.

[0112] Comparative Example 2

[0113] A new type of supporting dry film used for producing 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, 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-glycidoxy)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 min, degassed, kept at 110° C. for 1.5 h, 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, 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] The boron-containing microspheres are prepared by the following steps: 8 g of mesoporous silica, 1.5 g of glucose, 1.5 g of polylysine, and 0.5 g of 4-hydroxyphenylboric acid are mixed, stirred at a speed of 3000 r / min for 15 min, hydrothermally reacted at a temperature of 210° C. for 5 h, cooled to room temperature, filtered, washed, and vacuum dried.

[0117] The method for using the novel dry film for bearing used in producing single-sided thin plates is as follows: a single-sided copper foil coil and the novel dry film for bearing used in producing single-sided thin plates are pressed and laminated to obtain a dry film coil, and the laminating speed of the dry film for bearing is 0.5 m / min; the dry film coil is exposed to light to obtain a reinforced bearing dry film coil, and the exposure energy is 100 mJ / cm 2The reinforced bearing dry film coil is then chemically cleaned (the surface of the dry film 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 coil; the circuit coil is developed and etched to remove the film to obtain a single-sided thin plate.

[0118] The film removal liquid is a 3% NaOH solution by mass, 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 are basically in line with the preset values.

[0120] The new type of dry film for bearing used in producing single-sided thin plates obtained in Example 8 and Comparative Examples 1-2 was subjected to shape recovery test. Each group of samples was hung with a 200g weight for 5 minutes to deform, and then the weight was removed and the length of the sample was measured after waiting for 1 minute at 30°C to calculate the shape recovery rate.

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

[0122] like Fig. 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), proving that it has excellent self-repairing properties.

[0123] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A new type of dry film for bearing used in producing 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 at least one of vinyl trimethoxy silane, vinyl silicone oil, polyimide, phthalate, and reinforced polyamide amine; The reinforced polyamide amine is prepared by the following specific steps: the 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 for 1-2 hours at the same temperature, and hydroxylated hexagonal boron nitride is added and stirred 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; preferably at least one of bisphenol A epoxy resin, epoxy neophenol resin, epoxy acrylic resin and self-healing epoxy resin.

3. The novel dry film for supporting single-sided sheets according to claim 2, characterized in that: 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 30-60min, degassing, keeping at 100-120°C for 1-2h, and cooling to room temperature; Preferably, the mass ratio of bis(4-glycidoxy)diphenyl disulfide, isopropyl glycidyl ether, graphene oxide and polyoxyethylene diamine is 10-20:1-5:1-2:1-3.

4. 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.

5. 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.

6. The novel dry film for supporting single-sided thin plates 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.

7. The novel dry film for supporting single-sided thin plate 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 salt 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.

8. The novel dry film for supporting single-sided sheets 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.

9. The novel dry film for supporting a single-sided sheet according to claim 8, characterized in that: The boron-containing microspheres are prepared by the following steps: mixing mesoporous silica, glucose, poly-lysine and 4-hydroxyphenylboric acid, hydrothermally reacting at 200-220° C. for 3-7 hours, cooling to room temperature, filtering, washing and vacuum drying; Preferably, the mass ratio of mesoporous silica, glucose, polylysine and 4-hydroxyphenylboronic acid is 5-10:1-2:1-2:0.1-1.

10. 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 9, characterized in that: The single-sided copper foil coil is laminated with the novel bearing dry film for producing the single-sided thin plate as claimed in any one of claims 1 to 9 to obtain a dry film coil; the dry film coil is exposed to obtain a reinforced bearing dry film coil, and the reinforced bearing dry film coil is then chemically cleaned, hot rolled, and exposed 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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