CN113671794A - Positive photoresist and preparation method thereof, preparation method of glass shell and electronic equipment - Google Patents
Positive photoresist and preparation method thereof, preparation method of glass shell and electronic equipment Download PDFInfo
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- CN113671794A CN113671794A CN202110985128.8A CN202110985128A CN113671794A CN 113671794 A CN113671794 A CN 113671794A CN 202110985128 A CN202110985128 A CN 202110985128A CN 113671794 A CN113671794 A CN 113671794A
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- positive photoresist
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K5/00—Casings, cabinets or drawers for electric apparatus
- H05K5/02—Details
- H05K5/0217—Mechanical details of casings
- H05K5/0243—Mechanical details of casings for decorative purposes
Abstract
The application provides a positive photoresist, which comprises phenolic resin, a photosensitizer, an auxiliary agent and a solvent, wherein the weight average molecular weight of the phenolic resin is more than or equal to 18000, the auxiliary agent comprises a cross-linking agent, and the structural formula of the cross-linking agent is shown as the formula (I):
the positive photoresist has excellent acid resistance, adhesion performance and thermal stability, can protect the surface of glass which does not need to be etched in the process of etching the glass by the acid etching solution, and can be stably positioned in the acid etching solution for a long time, thereby being beneficial to enhancing the etching depth of the surface of the glass and ensuring that the glass etching effect is more obvious. The application also provides a preparation method of the positive photoresist, a preparation method of the shell and electronic equipment.
Description
Technical Field
The application belongs to the technical field of electronic products, and particularly relates to a positive photoresist and a preparation method thereof, a preparation method of a glass shell and electronic equipment.
Background
With the continuous development of electronic devices, users have higher and higher requirements on the appearance effect of the electronic devices. Therefore, in order to meet the higher and higher aesthetic requirements of users, the appearance of the electronic device also needs to be developed continuously to provide better use experience for users. Electronic devices that employ a glass housing and that are textured on the glass housing have become a popular design. In order to realize the texture on the glass shell, a high-precision photoresist is needed to be used as protection, and then the photoresist is etched and removed to obtain the texture.
Disclosure of Invention
In view of this, the present application provides a positive photoresist, a method of preparing the same, a method of preparing a glass housing, and an electronic device.
In a first aspect, the present application provides a positive photoresist, including a phenolic resin, a photosensitizer, an auxiliary agent and a solvent, wherein a weight average molecular weight of the phenolic resin is greater than or equal to 18000, the auxiliary agent includes a cross-linking agent, and a structural formula of the cross-linking agent is represented by formula (I):
in a second aspect, the present application provides a method for preparing a positive photoresist, comprising:
uniformly mixing phenolic resin, a photosensitizer, an auxiliary agent and a solvent to obtain a mixed solution, wherein the weight average molecular weight of the phenolic resin is greater than or equal to 18000, the auxiliary agent comprises a cross-linking agent, and the structural formula of the cross-linking agent is shown as a formula (I):
and filtering the mixed solution to obtain the positive photoresist.
In a third aspect, the present application provides a method of making a glass housing, comprising: coating the positive photoresist of the first aspect or the positive photoresist prepared by the preparation method of the second aspect on the first surface of the glass substrate, and curing to form a photoresist layer; exposing the photoresist layer; developing and hard baking the exposed photoresist layer to form a patterned photoresist layer; and etching the first surface by using acid etching liquid to form a plurality of concave structures on the first surface, thereby obtaining the glass shell.
In a fourth aspect, the present application provides an electronic device including the glass housing manufactured by the manufacturing method of the third aspect.
The application provides a positive photoresist, can be used to glass sculpture, and this positive photoresist has excellent acid resistance, adhesion performance and thermal stability, can be at the surface that acid etching liquid etching glass's in-process need not to carry out the sculpture to glass and protect, and this positive photoresist can be in acid etching liquid for a long time steadily simultaneously, is favorable to the enhancement of glass surface sculpture degree of depth for glass sculpture effect is more obvious. The preparation method of the positive photoresist is simple, convenient to operate and beneficial to industrial production. The positive photoresist is used for etching the surface of the glass, the etching depth selection range is wider, and the glass shell with clear surface textures can be prepared. The electronic equipment with the glass shell has obvious appearance texture effect, improves the product competitiveness and can meet the requirements of users.
Drawings
In order to more clearly explain the technical solution in the embodiments of the present application, the drawings that are required to be used in the embodiments of the present application will be described below.
Fig. 1 is a flowchart of a method for preparing a positive photoresist according to an embodiment of the present disclosure.
Fig. 2 is a flowchart of a method for manufacturing a glass housing according to an embodiment of the present disclosure.
Fig. 3 is a schematic structural diagram of an electronic device according to an embodiment of the present application.
Fig. 4 is a schematic structural diagram of an electronic device according to an embodiment of the present application.
Detailed Description
The following is a preferred embodiment of the present application, and it should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present application, and these improvements and modifications are also considered as the protection scope of the present application.
The following disclosure provides many different embodiments or examples for implementing different features of the application. In order to simplify the disclosure of the present application, specific example components and arrangements are described below. Of course, they are merely examples and are not intended to limit the present application. Moreover, the present application may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present application provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or use of other materials.
The application provides a positive photoresist, which comprises phenolic resin, a photosensitizer, an auxiliary agent and a solvent, wherein the weight average molecular weight of the phenolic resin is more than or equal to 18000, the auxiliary agent comprises a cross-linking agent, and the structural formula of the cross-linking agent is shown as a formula (I):
in the related art, glass materials are more and more selected for the electronic device 200 because of their high variability in permeability, shape structure, and appearance effect. In the process of changing the appearance of the glass shell, a decorative layer can be manufactured on the surface of the glass, part of the surface of the glass can be etched through acid etching liquid to form textures on the surface of the glass, and the part which does not need to be etched needs to be shielded and protected in the process. The inventor of the application finds that the photoresist is often used as a protective layer in the manufacturing process of a semiconductor device, such as in the manufacturing of a thin film transistor, and the like, when the existing photoresist is used for glass etching, the acid resistance is poor, the etching is often carried out for less than one minute, the photoresist layer can fall off from the surface of the glass, the protection cannot be continuously carried out, the etching depth is less than 3 mu m, the etching depth range cannot be increased, and the texture with large depth and obvious visual effect cannot be formed on the surface of the glass. The application provides a positive photoresist, it can form stable and acidproof photoresist layer on the glass surface to can be for a long time, stably adhere to on the glass surface at glass sculpture in-process, play the guard action to glass, be favorable to the glass surface to etch out the texture that the degree of depth is big, visual effect is obvious, thereby can improve glass's outward appearance effect. Specifically, the positive photoresist provided by the application forms a photoresist layer on the surface of glass, the solubility of the photoresist layer is improved under 365nm-405nm illumination, the photoresist layer can be dissolved by a developing solution, so that part of the surface of the glass is covered by the photoresist layer, and part of the surface is exposed; meanwhile, the photoresist formed by the positive photoresist is excellent in acid resistance and strong in adhesive force with a glass substrate, so that the glass substrate can be protected for a long time, the etching time of the acid etching liquid can be prolonged, and an obvious texture effect is formed on the surface of the glass.
In the present application, the phenolic resin is used as a main component of the positive photoresist, and the acid resistance, adhesion and stability of the positive photoresist are improved. In the present application, the weight average molecular weight (Mw) of the phenolic resin is 18000 or more, and when the weight average molecular weight is too small, the acid resistance (such as hydrofluoric acid) is poor, and the requirement of glass etching cannot be satisfied. Further, the weight average molecular weight of the phenolic resin is 18000-30000. The phenolic resin in the range can improve the acid resistance of the positive photoresist and ensure the dissolution rate and the development speed of the resin in the glass etching process. It is understood that the effect of the positive photoresist in the present application is the effect of the photoresist layer formed after the positive photoresist is cured. Further, the weight average molecular weight of the phenolic resin may be 22000-29000. Further, the weight average molecular weight of the phenolic resin may be 22000-, 28000-, 20000-, 25000-, 27000-or the like.
In the embodiment of the present application, the softening point of the phenolic resin is greater than 160 ℃, so that the positive photoresist has excellent thermal stability, and long-term stable adhesion performance between the positive photoresist and the glass substrate can be ensured. It will be appreciated that the softening point is the temperature at which the phenolic resin begins to soften. Specifically, the softening point of the phenolic resin is 165 ℃, 166 ℃, 168 ℃, 170 ℃, 172 ℃, 175 ℃, 178 ℃ or the like.
In the present application, the phenolic resin is formed by the polycondensation of a phenolic substance and an aldehyde substance. In embodiments herein, phenolics include meta-substituted phenols and para-substituted phenols. In this application, meta-and para-substituted phenols undergo polycondensation with aldehydes to form phenolic resins. In one embodiment, the substituents in the meta-substituted phenol and the para-substituted phenol comprise hydrocarbyl groups. Specifically, the number of carbon atoms of the alkyl group may be, but is not limited to, 1 to 10, such as 1, 2,3,4, 5, 6, 7, 8, 9, or 10, and the like, for example, the hydrocarbon group may be, but is not limited to, at least one of an alkyl group, an alkenyl group, and an alkynyl group. The substituent is favorable for the reaction between the phenolic substance and the aldehyde substance, and the simplicity and the convenience of preparing the phenolic resin are ensured. Further, the molar ratio of the meta-substituted phenol to the para-substituted phenol is 1:1 to 7: 3. The developing precision is influenced by the excessively high content of the meta-substituted phenol, the developing difficulty is caused by the excessively high content of the para-substituted phenol, the development process is ensured by adopting the above contrast range, the resolution is improved, and meanwhile, the acid resistance of the positive photoresist can be improved. Specifically, the molar ratio of the meta-substituted phenol to the para-substituted phenol may be, but is not limited to, 1:1, 2:1, 3:2, 7:3, or the like. In one embodiment, the phenolic material comprises m-cresol and p-cresol in a molar ratio of m-cresol to p-cresol of 1:1 to 7: 3.
In embodiments herein, the phenolic material comprises a polyhydric phenol. That is, the phenolic group in the phenolic resin has a plurality of hydroxyl groups, thereby contributing to the improvement of the thermal stability of the phenolic resin, and the development speed. In one embodiment, the phenolic material may be, but is not limited to, 2, 6-bis (hydroxymethyl) p-cresol.
In embodiments of the present application, the phenolic resin comprises a novolac phenolic resin. The photosensitive performance of the positive photoresist can be improved by adopting the linear phenolic resin, and the photoetching efficiency is improved. Furthermore, the phenolic resin comprises high-ortho phenolic resin, namely high-ortho linear phenolic resin, so that the regularity and rigidity of the phenolic resin can be improved, the hydrogen bonding acting force between the photosensitizer and the high-ortho phenolic resin is enhanced, the dissolution difference between an exposed part and an unexposed part in the photoresist layer in a developing solution is further enhanced, the solvent speed of the exposed part is higher, and the resolution of the positive photoresist is improved. It is understood that the high ortho phenolic resin is a phenolic resin in which the ratio of ortho-bonding positions of methylene groups or substituted methylene groups in the aldehyde substance to phenolic hydroxyl groups of the phenolic substance is 50% or more. In one embodiment of the present application, the mass ratio of the high ortho phenolic resin in the phenolic resin is greater than or equal to 90%, so as to improve the acid resistance, the developing precision and the stability of the positive photoresist. Furthermore, the mass ratio of the high ortho phenolic resin in the phenolic resin is more than or equal to 95 percent. Specifically, the mass ratio of the high-ortho phenol resin in the phenol resin may be, but not limited to, 92%, 93%, 96%, 97%, 98%, 99%, 100%, or the like. In the present application, a commercially available high ortho phenol resin may be selected as necessary, or a high ortho phenol resin may be synthesized according to a condensation polymerization reaction. In one embodiment, the high ortho phenolic resin may be represented by the formula
Wherein R' may be, but is not limited to, at least one of alkyl, alkenyl, alkynyl, halogen, aryl, hydroxyl, etc.
In embodiments of the present application, the terminal groups of the phenolic resin comprise a dimethylol group. By using xylenol group as a terminal group, more high-ortho phenolic resin can be obtained in the process of manufacturing the phenolic resin, and meanwhile, the softening point and the heat resistance of the phenolic resin are improved, and the photosensitive speed and the resolution of the positive photoresist are improved. Specifically, the xylenol group may be, but is not limited to, at least one group including 2, 4-dimethylol group, 2, 5-dimethylol group, 2, 6-dimethylol group, 3, 4-dimethylol group, and the like.
In the present application, the phenolic substance may be, but not limited to, at least one of phenol, cresol, xylenol, ethylphenol, butylphenol, and polyphenol, and the aldehyde substance may be, but not limited to, at least one of formaldehyde, paraformaldehyde, acetaldehyde, trioxymethylene, and propionaldehyde, and the specific may be selected as needed.
In the embodiment of the application, the mass ratio of the phenolic resin in the positive photoresist is 20-25%. The phenolic resin with the content can ensure the film forming performance of the positive photoresist and simultaneously ensure that the positive photoresist has certain acid resistance. Furthermore, the mass ratio of the phenolic resin in the positive photoresist is 21-24.5%. Furthermore, the mass ratio of the phenolic resin in the positive photoresist is 22-24%. Specifically, the mass ratio of the phenolic resin in the positive photoresist may be, but not limited to, 20%, 21%, 22%, 22.8%, 23%, 23.5%, 24%, 25%, or the like.
In the application, the photosensitizer acts as a dissolution inhibitor before being irradiated by light, so that the dissolution of the positive photoresist in a developing solution is inhibited, the photosensitizer is photolyzed under the irradiation condition to become a dissolution promoter, the solubility of the positive photoresist in the developing solution is greatly improved, and the positive photoresist in an exposure area is removed. In embodiments herein, the photosensitizer comprises a diazonaphthoquinone sulfonate. Specifically, the diazonaphthoquinone sulfonate comprises at least one of 2,3, 4-trihydroxybenzophenone-2, 1, 5-diazonaphthoquinone sulfonate and 2,2',4,4' -tetrahydroxybenzophenone-2, 1, 5-diazonaphthoquinone sulfonate. In one embodiment of the present application, the esterification rate of the hydroxyl groups in the diazonaphthoquinone sulfonate ester is 66% to 88%. The higher the esterification rate of hydroxyl groups in diazonaphthoquinone sulfonate esters, the higher the dissolution inhibition of the positive photoresist during development, the higher the resolution of the positive photoresist, the too high esterification rate of hydroxyl groups in diazonaphthoquinone sulfonate esters, the reduced photosensitivity and poor solubility of diazonaphthoquinone sulfonate esters, and the difficulty in removing the positive photoresist. When the diazonaphthoquinone sulfonate within the range of the esterification rate of the hydroxyl is used as a photosensitizer, the photosensitivity and the solubility of the positive photoresist are ensured, and the improvement of the resolution is facilitated. Furthermore, the esterification rate of the hydroxyl in the diazonaphthoquinone sulfonate ester is 70-85%. Furthermore, the esterification rate of the hydroxyl groups in the diazonaphthoquinone sulfonate ester is 73 to 80 percent. Specifically, the esterification rate of the hydroxyl group in the naphthoquinone diazide sulfonate ester may be, but not limited to, 72%, 74%, 75%, 76%, 77%, 78%, 81%, 83%, 87.5%, or the like. Specifically, according to the esterification rate of hydroxyl in diazonaphthoquinone sulfonate ester, 2,3, 4-trihydroxybenzophenone-2, 1, 5-diazonaphthoquinone sulfonate ester and 2,2',4,4' -tetrahydroxybenzophenone-2, 1, 5-diazonaphthoquinone sulfonate ester can be selected from commercially available diazonaphthoquinone sulfonate ester photosensitizers, for example, 2,3, 4-trihydroxybenzophenone-2, 1, 5-diazonaphthoquinone sulfonate ester can be, but is not limited to, PAC-320, PAC-325 and the like available from KISCO; the 2,2',4,4' -tetrahydroxybenzophenone-2, 1, 5-diazonaphthoquinone sulfonate can be, but is not limited to, PAC-425, PAC-430, PAC-435 and the like of KISCO company, and further, the 2,2',4,4' -tetrahydroxybenzophenone-2, 1, 5-diazonaphthoquinone sulfonate is PAC-435, and the esterification rate is 87.5%.
In the embodiment of the application, the mass of the photosensitizer in the positive photoresist accounts for 16-25% of the mass of the phenolic resin. Within the range, the dissolution rates of the positive photoresist in the exposed area and the non-exposed area can be obviously different, and the positive photoresist in the non-exposed area can be conveniently removed. Furthermore, the mass of the photosensitizer in the positive photoresist accounts for 18-23% of the mass of the phenolic resin. Specifically, the mass of the photosensitizer in the positive photoresist may be, but is not limited to, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, or the like, based on the mass of the phenolic resin.
In the embodiment of the application, the mass ratio of the photosensitizer in the positive photoresist is 4-5%. The phenolic resin with the content can ensure that the dissolution rates of the positive photoresist in the exposed area and the non-exposed area have obvious difference, and ensure the development process. Specifically, the mass ratio of the photosensitizer in the positive photoresist may be, but not limited to, 4.1%, 4.2%, 4.5%, 4.6%, 4.8%, 5%, or the like.
In the present application, the auxiliary agent comprises a cross-linking agent having the structural formula
When hard baking is carried out, alkoxy in the cross-linking agent can be bonded with phenolic hydroxyl of phenolic resin, so that the cross-linking degree and molecular weight of the resin are improved, bonding is generated between the alkoxy and the photosensitizer, and acting force is generated on the surface of glass, so that the acid resistance and the adhesion performance of the positive photoresist are improved, the positive photoresist can stably exist in acid etching liquid, and the etching time of the glass is prolonged.
In the embodiment of the application, the mass of the cross-linking agent accounts for 2-10% of the mass of the phenolic resin. Within the range, the acid resistance of the positive photoresist can be greatly improved, and the crosslinking agent and the phenolic resin can not react before development, so that the development is ensured. Furthermore, the mass of the cross-linking agent accounts for 2-7% of the mass of the phenolic resin. Specifically, the mass of the crosslinking agent may be, but is not limited to, 2%, 3%, 5%, 6%, 8%, 9%, 10%, or the like based on the mass of the phenol resin.
In the embodiment of the application, the mass ratio of the cross-linking agent in the positive photoresist is 0.5-2%, so that the cross-linking agent and the phenolic resin are fully reacted, and the acid resistance of the positive photoresist is further improved. Furthermore, the mass ratio of the cross-linking agent in the positive photoresist is 0.7-1.5%. Specifically, the mass ratio of the crosslinking agent in the positive photoresist may be, but not limited to, 0.8%, 0.9%, 1%, 1.2%, 1.3%, 1.5%, or the like.
In an embodiment of the present application, the auxiliary agent further includes at least one of a dissolution promoter, a coupling agent, and a leveling agent. The dissolution promoter can improve the adhesion of the positive photoresist on the glass surface and improve the photosensitivity, and the increase of the dissolution speed of an exposed area in the positive photoresist is greater than that of a non-exposed area; the coupling agent can improve the adhesive force of the positive photoresist on the surface of the glass; the leveling agent can improve the leveling effect in the coating process of the positive photoresist, avoid the generation of surface scratches of the photoresist layer and ensure the surface smoothness and the thickness uniformity of the formed photoresist layer.
In an embodiment of the application, the dissolution promoter comprises 4- [4- [1, 1-bis (4-hydroxyphenyl) ethyl ] ] - α, α -dimethylbenzylphenol, 2-cyclohexyl-4- [2- [3- [2- (5-cyclohexyl-4-hydroxy-2-methylphenyl) propan-2-yl ] phenyl ] propan-2-yl ] -5-methylphenol, 2, 6-bis (4-hydroxy-2, 5-dimethylbenzyl) -4-methylphenol, 4, 6-bis [2- (4-hydroxyphenyl) propan-2-yl ] benzene-1, 3-diol, 2, 6-bis [ (4-hydroxy-3, at least one of 5-dimethylphenyl) methyl-4-methylphenol, 4' - (cyclohexane-1, 1-diyl) diphenol and a substance represented by the formula (II),
In the embodiment of the present application, the mass of the dissolution accelerating agent accounts for 2% to 10% of the mass of the phenolic resin, and specifically, the mass of the dissolution accelerating agent may be, but is not limited to, 5%, 6%, 7%, 8%, 9%, 10%, or the like of the mass of the phenolic resin. The dissolution promoter with the content can improve the adhesive force of the positive photoresist on the surface of the glass, and is beneficial to the processes of exposure and development.
In the embodiment of the application, the mass ratio of the dissolution promoter in the positive photoresist is 1-2%, so that the adhesion performance of the positive photoresist can be better improved. Furthermore, the mass ratio of the dissolution accelerator is 1.2-1.7%. Specifically, the mass of the dissolution promoter may be, but not limited to, 1%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, or the like.
In the embodiment of the present application, the coupling agent includes a silane coupling agent containing at least one of an amino group, an amide group, a urea group, a ketimine group, an isocyanate group, a mercapto group, an isocyanuric ring skeleton, a methacryl group, and a styryl group. In one embodiment, the coupling agent comprises r-glycidoxytrimethylsilane, which may be KBM-403 from Japan.
In the embodiment of the present application, the mass of the coupling agent accounts for 0.2% to 2.5% of the mass of the phenolic resin, and specifically, the mass of the coupling agent may be, but is not limited to, 0.5%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3%, or the like of the mass of the phenolic resin. The coupling agent with the content can further improve the adhesion of the positive photoresist on the glass surface.
In the embodiment of the application, the mass ratio of the coupling agent in the positive photoresist is 0.1-0.5%, so that the adhesion performance of the positive photoresist can be better improved. Further, the mass ratio of the coupling agent is 0.15-0.45%. Specifically, the mass of the coupling agent may be, but not limited to, 0.2%, 0.25%, 0.3%, 0.33%, 0.4%, 0.42%, or the like.
In an embodiment of the present application, the leveling agent includes at least one of a fluorine-containing surfactant, a silicone-containing surfactant, a polyalkylene oxide-containing surfactant, and a polymethacrylate-containing surfactant. In an embodiment of the present application, the leveling agent includes a surfactant containing fluorine, thereby facilitating further improvement of the acid resistance of the positive photoresist. In one embodiment, the fluorine-containing surfactant is a basf-EFKA-3600 leveling agent.
In the embodiment of the present application, the mass of the leveling agent accounts for 0.4% to 2.5% of the mass of the phenolic resin, and specifically, the mass of the leveling agent may be, but is not limited to, 0.5%, 1%, 1.2%, 1.6%, 1.8%, 2%, 2.3%, or the like of the mass of the phenolic resin. The leveling agent with the content can further improve the leveling effect of the positive photoresist.
In the embodiment of the application, the mass ratio of the leveling agent in the positive photoresist is 0.1-0.5%, so that the leveling effect of the positive photoresist can be better improved. Further, the mass percentage of the flatting agent is 0.15-0.45%. Specifically, the mass of the leveling agent may be, but not limited to, 0.2%, 0.25%, 0.3%, 0.33%, 0.4%, 0.42%, or the like.
In the embodiment of the application, the mass ratio of the auxiliary agent in the positive photoresist is 2-5%. The aid with the content can improve the acid resistance, the adhesion and other properties of the positive photoresist, and is more beneficial to the use of the positive photoresist. Specifically, the mass ratio of the auxiliary agent in the positive photoresist may be, but not limited to, 2.5%, 3%, 3.6%, 4%, 4.2%, 4.8%, or the like. In an embodiment of the present application, the auxiliary agent includes a cross-linking agent, a dissolution promoter, a coupling agent, and a leveling agent. It will be appreciated that the auxiliary agent may also comprise other functional agents, the particular of which may be selected as required. Furthermore, the mass percentage of the cross-linking agent in the positive photoresist is 0.5-2%, the mass percentage of the dissolution accelerating agent is 1-2%, the mass percentage of the coupling agent is 0.1-0.5%, and the mass percentage of the flatting agent is 0.1-0.5%.
In the present application, the positive photoresist has a solvent to ensure viscosity of the positive photoresist to facilitate coating of the positive photoresist. In an embodiment of the present application, the solvent is an organic solvent, and the organic solvent includes at least one of an ester compound, an alcohol compound, and a ketone compound. In an embodiment of the present application, the esters include at least one of propylene glycol methyl ether acetate, ethylene glycol methyl ether acetate, butyl acetate, amyl acetate, and ethyl lactate. In one embodiment, the solvent is Propylene Glycol Methyl Ether Acetate (PGMEA). In the embodiment of the application, the mass ratio of the solvent in the positive photoresist is 65-75%, so that the viscosity of the positive photoresist is ensured to be proper. Furthermore, the mass ratio of the solvent in the positive photoresist is 68-73%. Specifically, the ratio of the solvent in the positive photoresist may be, but not limited to, 66%, 67%, 69%, 70%, 72%, 74%, or the like. In the embodiment of the application, the boiling point of the solvent is 120-170 ℃, so that the drying time is appropriate, the coating process is ensured, and the solvent in the photoresist layer is completely volatilized. Specifically, the boiling point of the solvent may be, but not limited to, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, or the like.
In an embodiment of the present application, the viscosity of the positive photoresist is greater than or equal to 5mpa · s. Further, the viscosity of the positive photoresist is 5mpa · s to 30mpa · s. Further, the viscosity of the positive photoresist is 5mpa · s to 20mpa · s. Specifically, the viscosity of the positive photoresist may be, but not limited to, 5mPa · s, 6mPa · s, 10mPa · s, 12mPa · s, 15mPa · s, 18mPa · s, or the like. The positive photoresist with the viscosity is beneficial to coating, and a photoresist layer with good surface smoothness is formed.
In an embodiment of the present application, the positive photoresist includes, by mass, 20% to 25% of a phenolic resin, 4% to 5% of a photosensitizer, 0.5% to 2% of a crosslinking agent, 1% to 2% of a dissolution promoter, 0.1% to 0.5% of a coupling agent, 0.1% to 0.5% of a leveling agent, and 65% to 75% of a solvent. In another embodiment of the present application, the positive photoresist comprises, by mass, 21% to 24.5% of a phenolic resin, 4% to 5% of a photosensitizer, 0.7% to 1.5% of a crosslinking agent, 1.2% to 1.7% of a dissolution promoter, 0.15% to 0.45% of a coupling agent, 0.15% to 0.45% of a leveling agent, and 68% to 73% of a solvent. In another embodiment of the present application, a positive photoresist includes, by mass, 22% to 24% of a phenolic resin, 4.2% to 4.8% of a photosensitizer, 0.8% to 1.2% of a crosslinking agent, 1.2% to 1.7% of a dissolution promoter, 0.15% to 0.45% of a coupling agent, 0.15% to 0.45% of a leveling agent, and the balance of a solvent. Specifically, the contents of the components can be matched and selected according to the descriptions of the components.
In the related technology, the etching time of the glass with the photoresist layer is less than 1min in the etching process, the photoresist layer can fall off from the glass, so that the depth of the texture generated on the surface of the glass is less than 3 mu m, the acid resistance of the photoresist layer formed by curing the positive photoresist is improved, the etching time of the glass with the photoresist layer is more than 6min, the depth of the generated texture is more than 10 mu m, the etching time and the selection range of the texture depth are greatly improved, and the glass can obtain richer appearance effect; the glass etching is carried out by adopting mixed acid etching liquid, and the mixed acid etching comprises 4% of hydrofluoric acid, 5% of nitric acid and 5% of sulfuric acid in percentage by mass.
The application also provides a preparation method of the positive photoresist, and the photoresist in any one of the above embodiments can be prepared. Referring to fig. 1, a flow chart of a method for preparing a positive photoresist according to an embodiment of the present disclosure includes:
s101: mixing phenolic resin, a photosensitizer, an auxiliary agent and a solvent to obtain a mixed solution, wherein the weight average molecular weight of the phenolic resin is greater than or equal to 18000, the auxiliary agent comprises a cross-linking agent, and the structural formula of the cross-linking agent is shown as the formula (I):
s102: and filtering the mixed solution to obtain the positive photoresist.
The preparation method of the positive photoresist is simple and convenient to operate, and the positive photoresist with excellent acid resistance and adhesion performance can be obtained.
In S101, a phenolic resin, a photosensitizer, an auxiliary agent, and a solvent are mixed to obtain a mixed solution, and each component is uniformly dispersed in the mixed solution. In an embodiment of the present application, the mixed solution includes, by mass, 20% to 25% of the phenolic resin, 4% to 5% of the photosensitizer, 0.5% to 2% of the crosslinking agent, and 65% to 75% of a solvent. In another embodiment herein, the adjuvant further comprises at least one of a dissolution promoter, a coupling agent, and a leveling agent. In an embodiment of the application, the mass ratio of the dissolution promoter in the positive photoresist is 1% to 2%, the mass ratio of the coupling agent is 0.1% to 0.5%, and the mass ratio of the leveling agent is 0.1% to 0.5%.
In the present application, the phenolic resin is formed by the polycondensation of a phenolic substance and an aldehyde substance. In embodiments herein, the phenolics include meta-substituted phenols and para-substituted phenols, with the molar ratio of meta-substituted phenol to para-substituted phenol being from 1:1 to 7: 3. The contrast range ensures the development process, improves the resolution ratio and can also improve the acid resistance of the positive photoresist.
In S102, the mixed solution is filtered to obtain a positive photoresist. In the embodiment of the present application, the filtering includes multi-stage filtering, thereby obtaining a fine positive photoresist. In one embodiment of the present application, the filtration comprises filtration through a filter having a pore size of 4 μm to 5 μm, followed by filtration through a filter having a pore size of 1 μm to 2 μm, and finally filtration through a filter having a pore size of 400nm to 500 nm. In one embodiment, the filtration comprises filtration through a filter having a pore size of 5 μm, followed by filtration through a filter having a pore size of 1 μm and finally filtration through a filter having a pore size of 500 nm.
The present application further provides a method for manufacturing a glass housing 100, in which a positive photoresist in any of the above embodiments is used to form a texture on a surface of a glass substrate, so as to obtain the glass housing 100.
Referring to fig. 2, a flow chart of a method for manufacturing a glass housing according to an embodiment of the present disclosure includes:
s201: coating positive photoresist on the first surface of the glass substrate, and forming a photoresist layer after curing.
S202: and exposing the photoresist layer.
S203: and developing and hard baking the exposed photoresist layer to form a patterned photoresist layer.
S204: and etching the first surface by using the acid etching liquid to form a texture on the first surface.
S205: and removing the patterned photoresist layer to obtain the glass shell.
The preparation method of the glass shell 100 provided by the application is simple to operate, is easy for large-scale production, can obtain the glass shell 100 with textures, improves the appearance effect of the glass shell 100, and is beneficial to application of the glass shell.
In S201, before coating the positive photoresist, the method further includes performing a cleaning process on the first surface of the glass substrate to remove stains on the surface. In the embodiment of the application, the photoresist layer is formed by soft baking and curing, wherein the temperature of the soft baking is 80-120 ℃, and the time of the soft baking is 5-10 min. In the embodiment of the present application, the photoresist layer has a thickness of 5 μm to 10 μm. Specifically, the thickness of the photoresist layer may be, but is not limited to, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm, etc.
In S202, the photoresist layer may be exposed to ultraviolet light using Laser Direct Imaging (LDI) so that the exposed photoresist can be dissolved in a developing solution. And the laser direct imaging is adopted for exposure, so that the exposure accuracy can be improved. In the embodiment of the present application, the energy of the ultraviolet light is 200mj/cm2-500mj/cm2Therefore, complete exposure can be ensured, the development process is facilitated, overexposure is avoided, and the texture effect is ensured.
In S203, the developing includes developing with an alkaline developer to remove the photoresist layer in the exposed region. Specifically, the pH value of the alkaline developing solution is 8-14, and the developing temperature is 20-40 ℃, so that the developing process can be ensured. In the embodiment of the application, the hard baking temperature is 150-180 ℃ and the hard baking time is 30-60 min, so that the phenolic resin in the photoresist layer of the non-exposure area is subjected to reaction crosslinking, the acid resistance of the photoresist layer is improved, and the patterned photoresist layer is obtained. In one embodiment, the hard bake comprises a treatment at 160 ℃ for 50 min. In embodiments of the present application, the adhesion between the glass substrate and the patterned photoresist layer is greater than or equal to 4B according to ASTM D3359. That is to say, the adhesion between the patterned photoresist layer and the glass substrate is strong, so that the glass substrate can be better protected, and the glass etching duration is prolonged. That is, the adhesion between the glass substrate and the photoresist layer formed by curing and hard baking the positive photoresist on the glass surface is greater than or equal to 4B. Further, the adhesion between the glass substrate and the patterned photoresist layer was 5B.
In S204, the first surface of the glass is etched with an acidic etching solution to form a texture on the first surface at a location not protected by the photoresist layer. In the embodiment of the application, the acidic etching solution comprises hydrofluoric acid, nitric acid and sulfuric acid, wherein hydrofluoric acid accounts for 2-4% of the acidic etching solution by mass, nitric acid accounts for 3-5% of the acidic etching solution by mass, and sulfuric acid accounts for 3-5% of the acidic etching solution by mass. In the present application, the etching time can be selected as desired. In the embodiment of the application, the etching time is 3min-15min, so that clear textures can be formed on the surface of the glass substrate, and meanwhile, the fine texture of the textures is guaranteed. Further, the etching time is greater than or equal to 6 min. Furthermore, the etching time is 6min-8 min. Specifically, the etching time may be, but is not limited to, 3min, 6min, 7min, 8min, 10min, 12min, or the like. In an embodiment of the present application, the texture includes a plurality of recessed structures. The application provides a photoresist layer's acid resistance promotes, can be as required control the sculpture long to obtain the sunk structure of the different degree of depth. In an embodiment of the present application, the maximum depth of the concave structure is greater than or equal to 10 μm, so that the clarity of the texture can be improved, and the appearance effect of the glass housing 100 can be improved. Specifically, the maximum depth of the recess structure may be, but not limited to, 10 μm, 12 μm, 15 μm, 16 μm, 17 μm, 18 μm, or the like. It is understood that by reducing the etching time, a texture depth of 10 μm or less can be obtained.
In S205, the patterned photoresist layer is removed using a photoresist stripper, resulting in the glass housing 100. In the embodiment of the application, the photoetching stripping liquid is a potassium hydroxide aqueous solution with the mass content of 4% -6%, so that the patterned photoresist layer can be quickly and effectively removed.
The application also provides the glass shell 100 prepared by the preparation method, and the surface of the glass shell 100 has textures and rich appearance effects, so that the glass shell 100 is beneficial to application in the electronic equipment 200. In an embodiment of the present application, the texture of the surface of the glass housing 100 is a glittering sand texture, that is, the portion of the glass housing 100 having the texture can realize a glittering visual effect in the process of light rotation, and the product competitiveness is further improved. It is understood that the shape of the glass housing 100 in the present application can be, but is not limited to, a plane shape or a curved surface shape, which can be selected according to the requirement, and of course, a decorative layer, such as a color layer, an optical film layer, etc., can be formed on the surface of the glass housing 100 to further enhance the appearance effect thereof.
The present application further provides an electronic device 200 including the glass housing 100 of any of the above embodiments. It is understood that the electronic device 200 may be, but is not limited to, a cell phone, a tablet computer, a notebook computer, a watch, an MP3, an MP4, a GPS navigator, a digital camera, etc. Referring to fig. 3, a schematic structural diagram of an electronic device according to an embodiment of the present disclosure is shown, in which the electronic device 200 includes a glass housing 100. The glass housing 100 can improve the appearance of the electronic device 200. Referring to fig. 4, which is a schematic view illustrating a structure of an electronic device according to an embodiment of the present disclosure, a structure of the electronic device 200 may include an RF circuit 210, a memory 220, an input unit 230, a display unit 240, a sensor 250, an audio circuit 260, a WiFi module 270, a processor 280, a power supply 290, and the like. The RF circuit 210, the memory 220, the input unit 230, the display unit 240, the sensor 250, the audio circuit 260, and the WiFi module 270 are respectively connected to the processor 280; the power supply 290 is used to supply power to the entire electronic device 200. Specifically, the RF circuit 210 is used for transmitting and receiving signals; the memory 220 is used for storing data instruction information; the input unit 230 is used for inputting information, and may specifically include other input devices such as a touch panel and operation keys; the display unit 240 may include a display screen or the like; the sensor 250 includes an infrared sensor, a laser sensor, etc. for detecting a user approach signal, a distance signal, etc.; the speaker 261 and the microphone 262 are connected with the processor 280 through the audio circuit 260 and used for emitting and receiving sound signals; the WiFi module 270 is configured to receive and transmit WiFi signals; the processor 280 is used for processing data information of the electronic device 200.
The properties of the positive photoresist provided by the practice of the present application are further illustrated by the following specific examples and comparative examples.
Example 1
A positive photoresist comprises, by weight, 20 parts of a phenol-formaldehyde novolac resin (the phenol-formaldehyde novolac resin is formed by condensation polymerization of m-cresol and p-cresol with formaldehyde, the molar ratio of m-cresol groups to p-cresol groups is 7:3, Mw is 20000, and the softening point is 168 ℃), 71.6 parts of propylene glycol monomethyl ether acetate, 5 parts of 2,2',4,4' -tetrahydroxybenzophenone 2,1, 5-diazonaphthoquinone sulfonate (PCA-435, the esterification rate is 87.5%), 2 parts of a dissolution promoter PAPS-20, 0.2 part of a coupling agent KBM-403, 0.2 part of a leveling agent EFKA-3600, and 1 part of a crosslinking agent shown in formula (I).
Example 2
A positive photoresist was substantially the same as example 1 except that 20 parts of a novolak resin having a xylenol end group was used.
Example 3
A positive photoresist was substantially the same as example 1 except that the molar ratio of the phenolic resin intermediate cresol groups to the p-cresol groups was 1: 1.
Example 4
A positive photoresist was substantially the same as example 1, except that 20 parts of a phenol novolac resin was used and Mw was 35000.
Example 5
A positive photoresist was prepared in substantially the same manner as in example 1, except that 20 parts of a phenol novolac resin was used and the softening point was 150 ℃.
Example 6
A positive photoresist comprises, by weight, 20 parts of a phenol novolac resin (the ratio of m-cresol groups to p-cresol groups is 7:3, Mw is 20000, and the softening point is 168 ℃), 74 parts of propylene glycol methyl ether acetate, 5 parts of 2,2',4,4' -tetrahydroxybenzophenone 2,1, 5-diazonaphthoquinone sulfonate (PCA-435, the esterification rate is 87.5%), and 1 part of a crosslinking agent represented by the formula (I).
Example 7
A positive photoresist comprises, by weight, 25 parts of a phenol novolac resin (the ratio of m-cresol groups to p-cresol groups is 7:3, Mw is 20000, and the softening point is 168 ℃), 68.5 parts of propylene glycol methyl ether acetate, 4 parts of 2,2',4,4' -tetrahydroxybenzophenone 2,1, 5-diazonaphthoquinone sulfonate (PCA-435, the esterification rate is 87.5%), 1 part of a dissolution accelerator PAPS-20, 0.5 part of a coupling agent KBM-403, 0.5 part of a leveling agent EFKA-3600, and 0.5 part of a crosslinking agent shown in a formula (I).
Example 8
A positive resist was prepared in substantially the same manner as in example 1, except that 70.6 parts of propylene glycol monomethyl ether acetate and 2 parts of the crosslinking agent represented by the formula (I) were used.
Example 9
A positive resist was fabricated substantially as in example 1, except that 72.4 parts of propylene glycol monomethyl ether acetate and 0.2 part of the crosslinking agent of the formula (I) were used.
Comparative example 1
A positive photoresist comprises, by weight, 20 parts of a phenol novolac resin (Mw is 10000, softening point is 153 ℃), 72.6 parts of propylene glycol methyl ether acetate, 5 parts of 2,2',4,4' -tetrahydroxybenzophenone 2,1, 5-diazonaphthoquinone sulfonate (PCA-435, esterification rate is 87.5%), 2 parts of a dissolution accelerator PAPS-20, 0.2 part of a coupling agent KBM-403 and 0.2 part of a leveling agent EFKA-3600.
Comparative example 2
A positive photoresist comprises, by weight, 20 parts of a phenol formaldehyde novolac resin (Mw is 6000 and the softening point is 153 ℃), 71.6 parts of propylene glycol methyl ether acetate, 5 parts of 2,2',4,4' -tetrahydroxybenzophenone 2,1, 5-diazonaphthoquinone sulfonate (PCA-435, the esterification rate is 87.5%), 2 parts of a dissolution accelerator PAPS-20, 0.2 part of a coupling agent KBM-403, 0.2 part of a leveling agent EFKA-3600 and 1 part of hexamethoxymethylmelamine resin Cymel-303.
Comparative example 3
A positive photoresist was substantially the same as example 1 except that the phenolic resin Mw was 15000.
Comparative example 4
A positive photoresist, substantially the same as example 1, except that no crosslinking agent was included.
Performance detection
The viscosity of the positive type photoresists in examples and comparative examples was measured by using a viscometer; coating the positive photoresist in the examples and the comparative examples on the surface of a glass substrate under the same conditions, curing and hard baking to form a photoresist layer, and detecting the adhesion of the photoresist layer according to the ASTM D3359 standard; and (3) placing the glass substrate with the photoresist layer in mixed acid, wherein the mixed acid comprises 4% hydrofluoric acid, 5% nitric acid and 5% sulfuric acid in percentage by mass, and recording the falling time of the photoresist layer from the glass substrate as a detection index of acid resistance.
TABLE 1 Performance test results
| Viscosity/mpa.s | Adhesion force | Acid resistance/min | |
| Example 1 | 10-15 | ≥4B | ＞6 |
| Example 2 | 10-15 | ≥4B | ＞6 |
| Example 3 | 10-15 | ≥4B | ＞6 |
| Example 4 | 25-30 | ≥4B | ＞6 |
| Example 5 | 10-15 | ≥4B | ＞6 |
| Example 6 | 10-15 | ≥4B | ＞6 |
| Example 7 | 10-15 | ≥4B | ＞6 |
| Example 8 | 10-15 | ≥4B | ＞6 |
| Example 9 | 10-15 | ≥4B | ＞6 |
| Comparative example 1 | 10-15 | ≥4B | ＜1 |
| Comparative example 2 | 10-15 | ≥4B | ＜1 |
| Comparative example 3 | 10-15 | ≥4B | 3-4 |
| Comparative example 4 | 10-15 | ≥4B | ＜3 |
As can be seen from table 1, the positive photoresists provided in comparative examples 1 to 4 have poor acid resistance, cannot be left in an acid environment for a long time, and thus cannot etch deep texture on the glass surface; the positive photoresist provided by the embodiment of the application can be soaked in mixed acid for more than 6min, even can reach 15min, still cannot fall off from a glass substrate, has excellent acid resistance, and is beneficial to the etching process of glass, so that diversified textures can be formed on the surface of the glass, and the appearance effect of the glass is improved.
The foregoing detailed description has provided for the purposes of providing a thorough understanding of the present embodiments, and has illustrated and described the principles and embodiments of the present application, but it is to be understood that this disclosure is only illustrative of the methods and their core concepts; meanwhile, for a person skilled in the art, according to the idea of the present application, the specific embodiments and the application range may be changed. In view of the above, the description should not be taken as limiting the application.
Claims (20)
1. The positive photoresist is characterized by comprising a phenolic resin, a photosensitizer, an auxiliary agent and a solvent, wherein the weight average molecular weight of the phenolic resin is greater than or equal to 18000, the auxiliary agent comprises a cross-linking agent, and the structural formula of the cross-linking agent is shown as the formula (I):
2. the positive photoresist of claim 1, wherein the phenolic resin is present in an amount of 20% to 25% by mass and the crosslinking agent is present in an amount of 0.5% to 2% by mass.
3. The positive photoresist of claim 1, wherein the weight average molecular weight of the phenolic resin is 18000-30000, and the softening point of the phenolic resin is greater than 160 ℃.
4. The positive photoresist of claim 1, wherein the terminal groups of the novolac resin comprise a bisphenol group.
5. The positive photoresist of claim 1, wherein the phenolic resin comprises a high ortho phenolic resin, and the mass proportion of the high ortho phenolic resin in the phenolic resin is greater than or equal to 90%.
6. The positive photoresist of claim 1, wherein the photosensitizer is present in an amount of 4% to 5% by weight of the positive photoresist;
the photosensitizer comprises diazonaphthoquinone sulfonate, the diazonaphthoquinone sulfonate comprises at least one of 2,3, 4-trihydroxybenzophenone-2, 1, 5-diazonaphthoquinone sulfonate and 2,2',4,4' -tetrahydroxybenzophenone-2, 1, 5-diazonaphthoquinone sulfonate, and the esterification rate of hydroxyl in the diazonaphthoquinone sulfonate is 66% -88%.
7. The positive photoresist of claim 1, wherein the additive is present in an amount of 2% to 5% by weight of the positive photoresist;
the auxiliary agent also comprises at least one of a dissolution promoter, a coupling agent and a flatting agent, wherein the dissolution promoter accounts for 1-2% by mass, the coupling agent accounts for 0.1-0.5% by mass, and the flatting agent accounts for 0.1-0.5% by mass in the positive photoresist.
8. The positive photoresist of claim 7, wherein the dissolution promoter comprises 4- [4- [1, 1-bis (4-hydroxyphenyl) ethyl ] ] - α, α -dimethylbenzylphenol, 2-cyclohexyl-4- [2- [3- [2- (5-cyclohexyl-4-hydroxy-2-methylphenyl) propan-2-yl ] phenyl ] propan-2-yl ] -5-methylphenol, 2, 6-bis (4-hydroxy-2, 5-dimethylbenzyl) -4-methylphenol, 4, 6-bis [2- (4-hydroxyphenyl) propan-2-yl ] benzene-1, 3-diol, di (t-butyl-ethyl) -phenyl ] -n-butyl-ethyl-phenyl-1, 3-diol, di (t-butyl-phenyl) -n-2-yl ] -propyl-phenyl-2-yl-methyl-phenyl-1, 6-bis [2- (4-hydroxyphenyl) propan-2-yl ] -propyl-2-phenyl-2, 5-methyl-phenyl-ol, At least one of 2, 6-bis [ (4-hydroxy-3, 5-dimethylphenyl) methyl ] -4-methylphenol, 4' - (cyclohexane-1, 1-diyl) diphenol and a substance represented by the formula (II),
9. the positive photoresist of claim 7, wherein the coupling agent comprises a silane coupling agent containing at least one of an amino group, an amide group, a urea group, a ketimine group, an isocyanate group, a mercapto group, an isocyanuric ring skeleton, a methacryl group, and a styryl group.
10. The positive photoresist of claim 7, wherein the leveling agent comprises at least one of a fluorine-containing surfactant, a silicone-containing surfactant, a polyalkylene oxide-containing surfactant, and a polymethacrylate-containing surfactant.
11. The positive photoresist of claim 1, wherein the solvent is 65-75% by mass, the solvent has a boiling point of 120-170 ℃, the solvent comprises at least one of esters, alcohols and ketones, and the esters comprise at least one of propylene glycol methyl ether acetate, ethylene glycol methyl ether acetate, butyl acetate, amyl acetate and ethyl lactate.
12. A method of making a positive photoresist, comprising:
mixing phenolic resin, a photosensitizer, an auxiliary agent and a solvent to obtain a mixed solution, wherein the weight average molecular weight of the phenolic resin is greater than or equal to 18000, the auxiliary agent comprises a cross-linking agent, and the structural formula of the cross-linking agent is shown as a formula (I):
and filtering the mixed solution to obtain the positive photoresist.
13. The method according to claim 12, wherein the mixed solution comprises, by mass, 20% to 25% of the phenol resin, 4% to 5% of the photosensitizer, 0.5% to 2% of the crosslinking agent, and 65% to 75% of the solvent.
14. The method of claim 12, wherein the phenolic resin is formed by the polycondensation of a phenolic material and an aldehyde material, wherein the phenolic material comprises a meta-substituted phenol and a para-substituted phenol, and wherein the meta-substituted phenol and the para-substituted phenol are present in a molar ratio of from 1:1 to 7: 3.
15. The method of claim 12, wherein the filtering comprises filtering through a filter having a pore size of 4 μm to 5 μm, filtering through a filter having a pore size of 1 μm to 2 μm, and filtering through a filter having a pore size of 400nm to 500 nm.
16. A method of making a glass housing, comprising:
coating a positive photoresist according to any one of claims 1 to 11 or a positive photoresist prepared by the preparation method according to any one of claims 12 to 15 on a first surface of a glass substrate, and curing the coating to form a photoresist layer;
exposing the photoresist layer;
developing and hard baking the exposed photoresist layer to form a patterned photoresist layer;
etching the first surface by using an acidic etching liquid to form a texture on the first surface;
and removing the patterned photoresist layer to obtain the glass shell.
17. The method of claim 16, wherein the etching time is greater than or equal to 6 min.
18. The method of claim 16, wherein the texture comprises a plurality of recessed features having a maximum depth of 10 μ ι η or greater.
19. The method of claim 16, wherein the adhesion between the glass substrate and the patterned photoresist layer is greater than or equal to 4B according to ASTM D3359.
20. An electronic device comprising a glass housing produced by the production method according to any one of claims 16 to 19.
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| CN202110985128.8A CN113671794A (en) | 2021-08-25 | 2021-08-25 | Positive photoresist and preparation method thereof, preparation method of glass shell and electronic equipment |
| PCT/CN2022/107387 WO2023024783A1 (en) | 2021-08-25 | 2022-07-22 | Positive photoresist and preparation method, preparation method for glass housing, and electronic device |
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| WO2023024783A1 (en) * | 2021-08-25 | 2023-03-02 | Oppo广东移动通信有限公司 | Positive photoresist and preparation method, preparation method for glass housing, and electronic device |
| WO2023236681A1 (en) * | 2022-06-08 | 2023-12-14 | 比亚迪股份有限公司 | Decorative plate and manufacturing method therefor, and electronic device |
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