Low-water-permeable oxygen-permeable photoresist protective film and preparation method thereof

Abstract

The application discloses a low-water-permeation and oxygen-permeation photoresist protective film and a preparation method thereof, relates to the technical field of dry film photoresist protective films, and the protective film comprises an inner layer, an intermediate layer and an outer layer; the inner layer is made of 100 parts of low-density polyethylene and 0.1-0.3 parts of a release agent; the intermediate layer is made of 20-80 parts of low-density polyethylene, 10-40 parts of high-density polyethylene, 10-30 parts of a bonding agent, 6-12 parts of modified silicon dioxide and 1-2 parts of an antistatic agent; and the outer layer is made of 10-90 parts of low-density polyethylene, 10-40 parts of metallocene low-density polyethylene and 0.1-0.5 parts of an anti-sticking agent; the application realizes excellent water and oxygen double barrier properties, can provide excellent protection for a dry film photoresist film, and has the characteristics of high mechanical strength, antistatic property and clean peeling, thereby effectively guaranteeing the process stability and product yield in chip manufacturing and having remarkable application value.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of dry film photoresist protective film, and particularly relates to a low water permeation and oxygen permeation photoresist protective film and a preparation method thereof. BACKGROUND

[0002] Dry film photoresist is an indispensable key pattern transfer material in the fields of printed circuit board (PCB) manufacturing, semiconductor packaging and precision metal processing. It usually presents a "sandwich" type multi-layer composite structure, that is, the middle is a core layer with photochemical reactivity, that is, a photoresist layer, and a polyester support film (usually a PET film) and a polyethylene protective film (PE protective film) are covered on the upper and lower sides of the photoresist layer respectively to play a supporting role and a protective role. In use, the PE protective film is first removed, the photoresist layer is attached to the surface of the substrate (such as a copper-clad plate) by hot pressing, then the substrate is exposed to ultraviolet light through a negative film carrying a circuit pattern, and finally the PET support film is removed and developed, so that the precise circuit pattern is transferred from the negative film to the substrate.

[0003] In the above structure, the outermost PE protective film plays a crucial role in all aspects of the production, transportation, storage and use of dry film photoresist. Its main function is to protect the middle sensitive photoresist layer from physical damage such as scratching, extrusion and wear; at the same time, it isolates dust, oil stains and other pollutants in the environment to prevent them from polluting the glue surface and causing defects such as open circuit or short circuit in the final circuit. In addition, the protective film also needs to have good release performance to ensure that it can be smoothly and cleanly removed before the film is attached, without any residue.

[0004] In the prior art, the protective film for dry film photoresist is relatively simple in structure. The most common one is a single-layer film structure with low-density polyethylene (LDPE) as the main raw material, and sometimes a small amount of traditional additives such as slip agents and anti-blocking agents are added to improve its physical properties or processing properties. Some existing technologies also use simple multi-layer co-extrusion composite structure, for example, by co-extruding two or three different polyethylene materials to obtain specific mechanical strength or surface properties. However, whether it is a single layer or a simple composite structure, the core of its design is mainly to provide physical protection, prevent pollution and achieve clean peeling, and the material system itself is not specially designed for water vapor and oxygen permeation.

[0005] Therefore, with the rapid development of electronic products towards high density, high integration and high reliability, the requirements for the fineness and yield of circuit patterns have reached an unprecedented height, and the traditional PE protective film with such a simple structure has gradually exposed its inherent performance defects, mainly in:

[0006] Insufficient barrier performance: the barrier ability of traditional PE protective film to water vapor and oxygen is limited. The photoinitiator and active monomer in the photoresist layer are very sensitive to water vapor and oxygen in the environment. If the humidity in the environment is too high, water molecules will penetrate the protective film and be absorbed by the photoresist, causing the photoresist to lose its photosensitivity, resolution, and adhesion to the substrate. Oxygen will inhibit the free radical polymerization reaction during exposure (i.e., the "oxygen inhibition effect"), resulting in incomplete curing of the photoresist surface, rough edges of the lines, and serious impact on the precision and quality of pattern transfer. This problem is particularly pronounced under high-temperature and high-humidity storage or transportation conditions.

[0007] Static problem: high molecular materials such as PE are prone to generate and accumulate static electricity during production and peeling, which can attract a large number of dust particles in the air. Once these particles adhere to the surface of the photoresist, they can form fatal defects such as pinholes and pits in subsequent processes, directly leading to product rejection.

[0008] Therefore, the technical problem to be solved by the present application is how to overcome the deficiencies of existing dry film photoresist protective film, such as insufficient water and oxygen barrier performance and easy generation of static electricity, and develop a new type of photoresist protective film with extremely low water and oxygen permeability, excellent antistatic performance, and mechanical and physical properties, thereby significantly improving the environmental tolerance and storage stability of dry film photoresist, and ensuring its high reliability and high yield in precision patterning processes. SUMMARY

[0009] To solve the problems in the prior art, the present application provides a low water and oxygen permeable photoresist protective film and a preparation method thereof. Through the synergistic design of a three-layer co-extrusion structure and a new type of modified silica, excellent water and oxygen barrier properties are achieved. The protective film can provide excellent protection for dry film photoresist film, and has high mechanical strength, antistatic and clean peeling properties, effectively ensuring the process stability and product yield in chip manufacturing, and has significant application value.

[0010] To achieve the above-mentioned purposes, the technical scheme adopted by the present application is as follows:

[0011] A low water and oxygen permeable photoresist protective film, comprising an inner layer, a middle layer, and an outer layer, wherein the inner layer is made of low-density polyethylene 100 parts and release agent 0.1-0.3 parts, the middle layer is made of low-density polyethylene 20-80 parts, high-density polyethylene 10-40 parts, adhesive 10-30 parts, modified silica 6-12 parts, and antistatic agent 1-2 parts, and the outer layer is made of low-density polyethylene 10-90 parts, metallocene low-density polyethylene 10-40 parts, and anti-adhesive agent 0.1-0.5 parts.

[0012] Preferably, the modified silica is prepared by the following method steps:

[0013] (1) slowly drop tetraethyl orthosilicate solution into PVA aqueous solution, adjust the pH of the system, hydrolysis, to obtain PVA / SiO2 composite sol;

[0014] Preparation of organic-inorganic composite precursor: tetraethyl orthosilicate (TEOS) hydrolysis under acidic conditions, to generate an intermediate with active silicon hydroxyl (Si-OH). These silicon hydroxyls are further condensed to form a silica network with a silicon-oxygen-silicon (Si-O-Si) backbone. In this process, the polyvinyl alcohol (PVA) macromolecular chain, with its rich hydroxyl groups, physically entangles and penetrates the generated silica network through hydrogen bonding, forming a uniformly dispersed PVA / SiO2 composite sol at the molecular level.

[0015] Preferably, in step (1), the tetraethyl orthosilicate solution is an ethanol solution of tetraethyl orthosilicate with a concentration of 30-50wt%, and the PVA aqueous solution has a concentration of 5-10wt%; the volume ratio of tetraethyl orthosilicate solution to PVA aqueous solution is 100-250mL:150-300mL.

[0016] Preferably, in step (1), the pH of the system is adjusted to 1.5-2.5 with hydrochloric acid; the hydrolysis reaction conditions are 55-70℃ for 18-24h.

[0017] (2) rapeseed oil is added to the PVA / SiO2 composite sol, high-speed shearing emulsification is performed to form an emulsion, the pH of the system is adjusted, then dodecanediamine and glutaraldehyde are added, stirring and reaction are performed, crosslinking and solidification are performed to form a gel, and after aging, washing and drying, an intermediate silica is obtained;

[0018] Emulsion template method to construct porous framework and introduce reaction sites: rapeseed oil, which is insoluble in water, is dispersed in the above sol as a template agent to form an oil-in-water emulsion. In a weakly acidic environment, glutaraldehyde is added as a bifunctional crosslinking agent, and its two aldehyde groups simultaneously undergo acetal reaction with the hydroxyl groups of PVA and Schiff base reaction with the amino groups of dodecanediamine. These two reactions crosslink the organic polymer PVA and dodecanediamine with amino functional groups into a three-dimensional network, which encapsulates rapeseed oil droplets and silica network. After solidification, the rapeseed oil template is washed away, and a porous intermediate with active amino groups on the surface is obtained.

[0019] Preferably, in step (2), the amount ratio of rapeseed oil, PVA / SiO2 composite sol, dodecanediamine, and glutaraldehyde is 10-15g:100mL:2-8g:3-9g.

[0020] Preferably, in step (2), the high-speed shearing emulsification condition is 3000-5000 r / min for 10-30 min; the pH of the system is adjusted to 5.0-6.0 with dilute ammonia water; and the stirring reaction condition is 50-65℃ for 12-24 h.

[0021] (3) dispersing the intermediate silica into DMF, ultrasonic treatment, then adding 2,2-difluoro-3-hydroxyvaleric acid, and then adding EDC and NHS successively, stirring and reacting under the protection of nitrogen and in the dark, centrifuging, washing and drying the product to obtain the modified silica.

[0022] The amidation reaction is used for functional modification: under the activation of EDC / NHS condensing agent, the carboxyl group of 2,2-difluoro-3-hydroxyvaleric acid is converted into a highly active intermediate. The active intermediate can react with the primary amino group provided by dodecanediamine on the surface of the porous silica intermediate to form a stable amide bond (-CO-NH-) efficiently. This step successfully grafts the fluorine-containing group to the pore surface of the material in a chemical bonding manner.

[0023] Preferably, in step (3), the amount ratio of the intermediate silica, DMF, 2,2-difluoro-3-hydroxyvaleric acid, EDC and NHS is 10 g: 100-200 mL: 2-5 g: 3-9 g: 1.5-4.5 g.

[0024] Preferably, in step (3), the ultrasonic treatment is performed for 10-30 min; and the stirring reaction condition is 20-35℃ for 24-36 h.

[0025] Preferably, the binder is one of polyolefin-based elastomer, polyurethane-based thermoplastic elastomer and polyamide-based thermoplastic elastomer; the release agent is one or more of silicone powder and / or polyvinyl alcohol; the antistatic agent is one or more of polyethylene oxide, polyether ester amide, polyethylene glycol, methyl acrylate and quaternary ammonium salt-based methacrylate copolymer; and the anti-adhesive agent is one of diatomite, talc powder and silicon dioxide.

[0026] The application also claims a preparation method of the low-water-permeable and oxygen-permeable photoresist protective film, which comprises the following steps: mixing materials according to a formula, melting through three single-screw extruders respectively, connecting through a batching block connector, co-extruding through a die and cooling to form a film; and then cooling, shaping, detecting thickness, cutting online, winding and packaging the product to obtain the low-water-permeable and oxygen-permeable photoresist protective film.

[0027] Compared with the prior art, the application has the following beneficial effects:

[0028] 1、The three-layer co-extrusion structure protective film of the present application realizes excellent comprehensive performance through the synergistic effect of each layer of material. First, the inner layer uses pure low-density polyethylene (LDPE) and adds a release agent, which ensures that the layer has excellent flexibility and adhesion when it is in contact with the precise photoresist surface, and the presence of the release agent ensures that the protective film can be easily and cleanly peeled off after use without any residue or static damage, effectively protecting the fine circuit pattern. Second, the middle layer, as the core functional layer, builds a substrate with both rigidity and flexibility by blending high-density polyethylene (HDPE) with LDPE. The addition of HDPE significantly improves the density of the material, providing a preliminary physical barrier to water and oxygen. The key is that the layer introduces special modified silica, whose internal porous structure forms a "labyrinth effect", greatly extending the penetration path of water and oxygen molecules. Combined with its hydrophobic surface properties, it builds a strong barrier performance, achieving the core goal of "low water vapor transmission and oxygen transmission". At the same time, the adhesive ensures good compatibility and interfacial bonding force between the inorganic filler and the polyolefin matrix, and the antistatic agent eliminates the risk of static accumulation during production and use, avoiding the problem of dust adsorption and static breakdown. Finally, the outer layer introduces metallocene low-density polyethylene (mLLDPE), which gives the protective film excellent mechanical strength, puncture resistance and wear resistance, making it less likely to be scratched or damaged during transportation and operation. The addition of the anti-adhesive agent effectively prevents the adhesion between the layers after the film is wound, ensuring the smoothness of the product processing and use.

[0029] 2、The present application provides a modified silica, the first step is to prepare PVA / SiO2 organic-inorganic hybrid by sol-gel method, first of all, the good gas barrier property of PVA itself is utilized to provide the material with basic barrier ability; at the same time, the inorganic network of silica formed as a rigid filler can effectively reinforce the final polymer film, improving its mechanical strength and dimensional stability. The second step introduces dodecanediamine containing long-chain alkyl while building a porous framework, which significantly improves the compatibility between silica and non-polar polyolefin resin matrix, thereby greatly improving its dispersion effect in the matrix, avoiding the agglomeration of inorganic fillers and ensuring the uniformity of barrier performance. In addition, the introduction of long-chain alkyl also plays the role of internal lubricant, which can improve the release property of the composite film during processing. Of course, the terminal amino group also provides a key reaction site for subsequent modification. The third step introduces fluorine-containing functional monomers through chemical grafting, which effectively and significantly reduces the surface energy of the material, making it have excellent strong hydrophobic and oleophobic properties, which can effectively alleviate the fatal defect of traditional silica filler that is prone to moisture absorption and swelling under high temperature and humidity conditions, thereby avoiding the problem of damage to the microstructure of the film due to water absorption of the filler, ultimately leading to a sharp decline in the barrier performance of the film, ensuring the long-term service stability and reliability of the protective film in harsh environments. DETAILED DESCRIPTION

[0030] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to examples. Of course, the specific examples described herein are only used to explain the present application and should not be used to limit the present application.

[0031] Unless otherwise specified, the chemicals and materials in the present application are purchased through market channels or synthesized from raw materials purchased through market channels.

[0032] Low-density polyethylene was purchased from LG, Korea, with the brand BF415E;

[0033] High-density polyethylene was purchased from Samsung-Dow, with the brand 920A;

[0034] Metallocene low-density polyethylene was purchased from Mitsui Chemical, with the brand SP2020;

[0035] EVA was purchased from Saudi National Petrochemical, with the brand eva2005;

[0036] The silica particle size used in Comparative Example 3 was 50-100 nm.

[0037] A preparation method of a low-water-permeable oxygen-permeable photoresist protective film, comprising the following steps:

[0038] (1) 100-250 mL of 30-50 wt% tetraethyl orthosilicate ethanol solution was slowly added to 150-300 mL of 5-10 wt% PVA aqueous solution, the pH of the system was adjusted to 1.5-2.5 with hydrochloric acid, and hydrolysis was carried out at 55-70°C for 18-24 h to obtain a PVA / SiO2 composite sol;

[0039] (2) 10-15 g of rapeseed oil was added to 100 mL of PVA / SiO2 composite sol, emulsified at 3000-5000 r / min for 10-30 min to form an emulsion, the pH of the system was adjusted to 5.0-6.0 with dilute ammonia water, then 2-8 g of dodecanediamine and 3-9 g of glutaraldehyde were added, and the mixture was stirred and reacted at 50-65°C for 12-24 h to form a gel, which was washed and dried after aging to obtain an intermediate silica;

[0040] (3) 10 g of the intermediate silica was dispersed in 100-200 mL of DMF, ultrasonically treated for 10-30 min, then 2-5 g of 2,2-difluoro-3-hydroxyvaleric acid was added, followed by the addition of 3-9 g of EDC and 1.5-4.5 g of NHS, and the mixture was stirred and reacted at 20-35°C for 24-36 h under nitrogen atmosphere and in the dark, and the product was centrifuged, washed and dried to obtain modified silica;

[0041] (4) the inner layer raw material is 100 parts of low-density polyethylene and 0.1-0.3 parts of a release agent, the middle layer raw material is 20-80 parts of low-density polyethylene, 10-40 parts of high-density polyethylene, 10-30 parts of a bonding agent, 6-12 parts of modified silicon dioxide and 1-2 parts of an antistatic agent, and the outer layer raw material is 10-90 parts of low-density polyethylene, 10-40 parts of metallocene low-density polyethylene and 0.1-0.5 parts of an anti-sticking agent; the materials are mixed according to the formula, then melt through three single-screw extruders, and then film is formed through a material distribution block connector, a die head co-extruder and cooling; the product is subsequently cooled, shaped, thickness detected, cut online, wound and packaged to obtain the low-water-permeation and oxygen-permeation photoresist protective film.

[0042] The bonding agent is one of polyolefin-based elastomers, polyurethane-based thermoplastic elastomers and polyamide-based thermoplastic elastomers; the release agent is silicone powder and / or polyvinyl alcohol; the antistatic agent is one or more of polyethylene oxide, polyether ester amide, polyethylene glycol, methyl acrylate and quaternary ammonium salt-based methacrylate copolymer; and the anti-sticking agent is one of diatomite, talc and silicon dioxide.

[0043] The application will be further described below through specific examples.

[0044] Example 1

[0045] A preparation method of a low-water-permeation and oxygen-permeation photoresist protective film includes the following steps:

[0046] (1) 250 mL of 40wt% tetraethyl orthosilicate ethanol solution is slowly dropped into 300 mL of 8wt% PVA aqueous solution, the pH of the system is adjusted to 2.0 with hydrochloric acid, and hydrolysis is carried out at 70℃ for 18 h to obtain a PVA / SiO2 composite sol;

[0047] (2) 15 g of rapeseed oil is added to 100 mL of the PVA / SiO2 composite sol, emulsified at 4000 r / min for 20 min to form an emulsion, the pH of the system is adjusted to 5.5 with dilute ammonia water, then 8 g of dodecanediamine and 9 g of glutaraldehyde are added, and stirring reaction is carried out at 65℃ for 12 h to form a gel after cross-linking and solidification; after aging, the gel is washed and dried to obtain intermediate silica;

[0048] (3) 10 g of the intermediate silica is dispersed into 150 mL of DMF, ultrasonic treatment is carried out for 20 min, then 5 g of 2,2-difluoro-3-hydroxyvaleric acid is added, and then 9 g of EDC and 4.5 g of NHS are added in sequence, stirring reaction is carried out at 35℃ for 24 h under the protection of nitrogen and in the dark, and the product is centrifuged, washed and dried to obtain modified silica;

[0049] (4) The inner layer raw material is 10000g of low-density polyethylene, 30g of release agent silicone powder, the middle layer raw material is 8000g of low-density polyethylene, 4000g of high-density polyethylene, 3000g of adhesive EVA, 1200g of modified silica, 200g of antistatic agent polyethylene oxide, the outer layer raw material is 9000g of low-density polyethylene, 4000g of metallocene low-density polyethylene, 50g of anti-adhesive diatomite, the materials are mixed according to the formula, then melt through three single-screw extruders respectively, then film forming through the batching block connector, die co-extrusion and cooling; the product is subsequently cooled, shaped, thickness detected, cut online, wound and packaged to obtain the low-water-permeable and oxygen-permeable photoresist protective film.

[0050] Example 2

[0051] A preparation method of a low-water-permeable and oxygen-permeable photoresist protective film, comprising the following steps:

[0052] (1) 200mL of 40wt% tetraethyl orthosilicate ethanol solution is slowly dropped into 250mL of 8wt% PVA aqueous solution, the pH of the system is adjusted to 2.0 with hydrochloric acid, and hydrolysis is carried out at 65℃ for 22h to obtain a PVA / SiO2 composite sol;

[0053] (2) 14g of rapeseed oil is added to 100mL of PVA / SiO2 composite sol, emulsified at 4000r / min for 20min to form an emulsion, the pH of the system is adjusted to 5.5 with dilute ammonia water, then 6g of dodecanediamine and 7g of glutaraldehyde are added, and stirring reaction is carried out at 60℃ for 16h to form a gel after cross-linking and solidification, and the gel is washed and dried after aging to obtain an intermediate silica;

[0054] (3) 10g of the intermediate silica is dispersed into 150mL of DMF, ultrasonic treatment is carried out for 20min, then 4g of 2,2-difluoro-3-hydroxyvaleric acid is added, and then 7g of EDC and 3.5g of NHS are added in sequence, stirring reaction is carried out at 30℃ for 28h under the protection of nitrogen and in the dark, and the product is centrifuged, washed and dried to obtain modified silica;

[0055] (4) The inner layer raw material is 10000g of low-density polyethylene, 30g of release agent silicone powder, the middle layer raw material is 8000g of low-density polyethylene, 4000g of high-density polyethylene, 3000g of adhesive EVA, 1200g of modified silica, 200g of antistatic agent polyethylene oxide, the outer layer raw material is 9000g of low-density polyethylene, 4000g of metallocene low-density polyethylene, 50g of anti-adhesive diatomite, the materials are mixed according to the formula, then melt through three single-screw extruders respectively, then film forming through the batching block connector, die co-extrusion and cooling; the product is subsequently cooled, shaped, thickness detected, cut online, wound and packaged to obtain the low-water-permeable and oxygen-permeable photoresist protective film.

[0056] Example 3

[0057] A preparation method of a low-water-permeable and oxygen-permeable photoresist protective film, comprising the following steps:

[0058] (1) 150 mL of 40wt% tetraethyl orthosilicate ethanol solution is slowly added dropwise into 200 mL of 8wt% PVA aqueous solution, the pH of the system is adjusted to 2.0 with hydrochloric acid, and hydrolysis is carried out at 60°C for 20 h to obtain a PVA / SiO2 composite sol;

[0059] (2) 12 g of rapeseed oil is added to 100 mL of the PVA / SiO2 composite sol, emulsified at 4000 r / min for 20 min to form an emulsion, the pH of the system is adjusted to 5.5 with dilute ammonia water, then 4 g of dodecanediamine and 5 g of glutaraldehyde are added, and the mixture is stirred and reacted at 55°C for 20 h to form a gel, which is washed and dried after aging to obtain an intermediate silica;

[0060] (3) 10 g of the intermediate silica is dispersed into 150 mL of DMF, ultrasonic treatment is performed for 20 min, then 3 g of 2,2-difluoro-3-hydroxyvaleric acid is added, and then 5 g of EDC and 2.5 g of NHS are added in sequence, and the mixture is stirred and reacted at 25°C for 32 h under the protection of nitrogen and in the dark, and the product is centrifuged, washed and dried to obtain modified silica;

[0061] (4) The inner layer raw materials are 10000 g of low-density polyethylene and 15 g of release agent silicone powder, the middle layer raw materials are 4000 g of low-density polyethylene, 2000 g of high-density polyethylene, 1500 g of adhesive EVA, 800 g of modified silica, and 140 g of antistatic agent polyethylene oxide, and the outer layer raw materials are 3000 g of low-density polyethylene, 2000 g of metallocene low-density polyethylene, and 20 g of anti-adhesive diatomite, the materials are mixed according to the formula, then melt through three single-screw extruders, and then film is formed through a material block connector, a die co-extrusion and cooling; the product is subsequently cooled, shaped, thickness detected, cut online, wound and packaged to obtain the low-water-permeable and oxygen-permeable photoresist protective film.

[0062] Example 4

[0063] A preparation method of a low-water-permeable and oxygen-permeable photoresist protective film, comprising the following steps:

[0064] (1) 100 mL of 40wt% tetraethyl orthosilicate ethanol solution is slowly added dropwise into 150 mL of 8wt% PVA aqueous solution, the pH of the system is adjusted to 2.0 with hydrochloric acid, and hydrolysis is carried out at 55°C for 24 h to obtain a PVA / SiO2 composite sol;

[0065] (2) 10 g of rapeseed oil was added to 100 mL of PVA / SiO2 composite sol, emulsified at 4000 r / min for 20 min, an emulsion was formed, the pH of the system was adjusted to 5.5 with dilute ammonia water, then 2 g of dodecanediamine and 3 g of glutaraldehyde were added, and the gel was formed after crosslinking and solidification at 50°C for 24 h, and after aging, the gel was washed and dried to obtain intermediate silica;

[0066] (3) 10 g of intermediate silica was dispersed into 150 mL of DMF, and ultrasonic treatment was performed for 20 min, then 2 g of 2, 2-difluoro-3-hydroxyvaleric acid was added, followed by the addition of 3 g of EDC and 1.5 g of NHS, and the reaction was performed at 20°C for 36 h under the protection of nitrogen and in the dark, and the product was centrifuged, washed and dried to obtain modified silica;

[0067] (4) The inner layer raw material was 10000 g of low-density polyethylene and 10 g of silicone powder as a release agent, the middle layer raw material was 2000 g of low-density polyethylene, 1000 g of high-density polyethylene, 1000 g of EVA as an adhesive, 600 g of modified silica and 100 g of polyethylene oxide as an antistatic agent, and the outer layer raw material was 1000 g of low-density polyethylene and 1000 g of metallocene low-density polyethylene, and 10 g of diatomite as an anti-adhesive agent, the materials were mixed according to the formula, then melted through three single-screw extruders, and then formed into a film through a material block connector, a die head co-extrusion and cooling; and the product was subsequently cooled, shaped, thickness detected, cut online, wound and packaged to obtain the low-water-permeable and oxygen-permeable photoresist protective film.

[0068] Comparative Example 1

[0069] A preparation method of a low-water-permeable and oxygen-permeable photoresist protective film, comprising the following steps:

[0070] (1) 250 mL of 40 wt% tetraethyl orthosilicate ethanol solution was slowly added dropwise into 300 mL of 8 wt% PVA aqueous solution, the pH of the system was adjusted to 2.0 with hydrochloric acid, and hydrolysis was performed at 70°C for 18 h to obtain a PVA / SiO2 composite sol;

[0071] (2) 15 g of rapeseed oil was added to 100 mL of PVA / SiO2 composite sol, emulsified at 4000 r / min for 20 min to form an emulsion, the pH of the system was adjusted to 5.5 with dilute ammonia water, then 8 g of dodecanediamine and 9 g of glutaraldehyde were added, and the gel was formed after crosslinking and solidification at 65°C for 12 h, and after aging, the gel was washed and dried to obtain intermediate silica;

[0072] (3) The inner layer raw material is low-density polyethylene 10000g, release agent silicone powder 30g, the intermediate layer raw material is low-density polyethylene 8000g, high-density polyethylene 4000g, adhesive EVA 3000g, intermediate silica 1000g, 2, 2-difluoro-3-hydroxyvaleric acid 200g, antistatic agent polyethylene oxide 200g, the outer layer raw material is low-density polyethylene 9000g, metallocene low-density polyethylene 4000g, anti-adhesive diatomite 50g, the materials are mixed according to the formula, then melt through three single screw extruders respectively, then film forming through the batching block connector, die co-extrusion and cooling; the product is subsequently cooled, shaped, thickness detected, cut online, wound and packaged to obtain the low-water-permeable and oxygen-permeable photoresist protective film.

[0073] Comparative Example 2

[0074] A preparation method of a low-water-permeable and oxygen-permeable photoresist protective film, comprising the following steps:

[0075] (1) 250mL 40wt% tetraethyl orthosilicate ethanol solution is slowly dropped into 300mL 8wt% PVA aqueous solution, the pH of the system is adjusted to 2.0 with hydrochloric acid, and hydrolysis is carried out at 70℃ for 18h to obtain a PVA / SiO2 composite sol;

[0076] (2) 15g rapeseed oil is added to 100mL PVA / SiO2 composite sol, emulsified at 4000r / min for 20min to form an emulsion, the pH of the system is adjusted to 5.5 with dilute ammonia water, then 9g glutaraldehyde is added, and stirring reaction is carried out at 65℃ for 12h to form a gel after cross-linking and solidification, and the gel is washed and dried after aging to obtain intermediate silica;

[0077] (3) The inner layer raw material is low-density polyethylene 10000g, release agent silicone powder 30g, the intermediate layer raw material is low-density polyethylene 8000g, high-density polyethylene 4000g, adhesive EVA 3000g, intermediate silica 1000g, dodecanediamine 200g, antistatic agent polyethylene oxide 200g, the outer layer raw material is low-density polyethylene 9000g, metallocene low-density polyethylene 4000g, anti-adhesive diatomite 50g, the materials are mixed according to the formula, then melt through three single screw extruders respectively, then film forming through the batching block connector, die co-extrusion and cooling; the product is subsequently cooled, shaped, thickness detected, cut online, wound and packaged to obtain the low-water-permeable and oxygen-permeable photoresist protective film.

[0078] Comparative Example 3

[0079] A preparation method of a low-water-permeable and oxygen-permeable photoresist protective film, comprising the following steps:

[0080] The inner layer raw material is 10000 g of low-density polyethylene, 30 g of release agent silicone powder, the middle layer raw material is 8000 g of low-density polyethylene, 4000 g of high-density polyethylene, 3000 g of adhesive EVA, 1200 g of silicon dioxide, 200 g of antistatic agent polyethylene oxide, the outer layer raw material is 9000 g of low-density polyethylene, 4000 g of metallocene low-density polyethylene, and 50 g of anti-adhesive diatomite, the materials are mixed according to the formula, then melt through three single-screw extruders, then film forming through a material block connector, a die head co-extrusion and cooling; the product is subsequently cooled and shaped, thickness detected, cut online, wound and packaged to obtain the low-water and oxygen permeability photoresist protective film.

[0081] The thickness of the photoresist protective film is measured according to GB / T 6672-2001 “Plastic films and sheets-Determination of thickness-Mechanical method”; the tensile strength and elongation at break are tested according to GB / T 1040.3-2006 “Determination of tensile properties of plastics-Part 3: Test conditions for films and sheets”; the number of crystal points on the sample is detected by a crystal point detector, and the test is performed in parallel for three times; the water vapor permeability g / (m 2 ·24h) is tested under the conditions of a temperature of 23 DEG C and a relative humidity of 85% by using a BASIC301 water vapor permeability tester according to GB / T 26253-2010 “Determination of water vapor transmission rate of plastic films and sheets-Infrared detector method”, and the lower the permeability, the better the performance; the oxygen permeability cm 3 / (m 2 ·24h·0.1MPa) is tested under the conditions of a temperature of 23 DEG C and a relative humidity of 0% by using a VACV1 oxygen permeability tester, and the lower the permeability, the better the performance; the specific data are shown in Table 1.

[0082] Table 1: Performance test results of photoresist protective film

[0083]

[0084] The above merely describes the preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto, any person skilled in the art can make equivalent replacements or changes to the technical solution and the inventive concept of the present application within the technical range disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A low water permeable oxygen permeable photoresist protective film comprising an inner layer, an intermediate layer, and an outer layer, characterized in that, The inner layer is made of 100 parts of low-density polyethylene and 0.1-0.3 parts of a release agent, the intermediate layer is made of 20-80 parts of low-density polyethylene, 10-40 parts of high-density polyethylene, 10-30 parts of a bonding agent, 6-12 parts of modified silica and 1-2 parts of an antistatic agent, and the outer layer is made of 10-90 parts of low-density polyethylene, 10-40 parts of metallocene low-density polyethylene and 0.1-0.5 parts of an anti-sticking agent; The modified silica is prepared by the following steps: (1) slowly drop tetraethyl orthosilicate solution into PVA aqueous solution, adjust the pH of the system, hydrolysis reaction, and obtain PVA / SiO2 composite sol; (2) add rapeseed oil into the PVA / SiO2 composite sol, high-speed shear emulsification, form an emulsion, adjust the pH of the system, then add dodecanediamine and glutaraldehyde, stirring reaction, cross-linking and curing to form a gel, after aging, wash and dry to obtain intermediate silica; (3) disperse the intermediate silica into DMF, ultrasonic treatment, then add 2,2-difluoro-3-hydroxyvaleric acid, and then add EDC and NHS successively, stirring reaction under nitrogen atmosphere and avoiding light, centrifugal, washing and drying to obtain modified silica. In step (3), EDC and NHS refer to condensing agents.

2. The low-water permeable oxygen permeable photoresist protective film according to claim 1, characterized by, In step (1), the tetraethyl orthosilicate solution is an ethanol solution of tetraethyl orthosilicate with a concentration of 30-50 wt%, and the concentration of the PVA aqueous solution is 5-10 wt%; the volume ratio of the tetraethyl orthosilicate solution to the PVA aqueous solution is 100-250 mL:150-300 mL.

3. The low-water permeable oxygen permeable photoresist protective film according to claim 1, characterized by, In step (1), the pH of the system is adjusted to 1.5-2.5 with hydrochloric acid; the hydrolysis reaction conditions are 55-70℃ for 18-24 h.

4. The low-water permeable oxygen permeable photoresist protective film according to claim 1, characterized by, In step (2), the amount ratio of rapeseed oil, PVA / SiO2 composite sol, dodecanediamine and glutaraldehyde is 10-15 g:100 mL:2-8 g:3-9 g.

5. The low-water permeable oxygen permeable photoresist protective film according to claim 1, characterized by, In step (2), the high-speed shear emulsification conditions are 3000-5000 r / min for 10-30 min; the pH of the system is adjusted to 5.0-6.0 with dilute ammonia water; the stirring reaction conditions are 50-65℃ for 12-24 h.

6. The low-water permeable oxygen permeable photoresist protective film according to claim 1, characterized by, In step (3), the amount ratio of intermediate silica, DMF, 2,2-difluoro-3-hydroxyvaleric acid, EDC and NHS is 10 g:100-200 mL:2-5 g:3-9 g:1.5-4.5 g.

7. The low-water permeable oxygen permeable photoresist protective film according to claim 1, characterized by, In step (3), the ultrasonic treatment is 10-30 min; the stirring reaction conditions are 20-35℃ for 24-36 h.

8. The low-water permeable oxygen permeable photoresist protective film according to claim 1, characterized by, The bonding agent is one of polyolefin-based elastomers, polyurethane-based thermoplastic elastomers and polyamide-based thermoplastic elastomers; the release agent is silicone powder and / or polyvinyl alcohol; the antistatic agent is one or more of polyethylene oxide, polyether ester amide, polyethylene glycol, methyl acrylate and quaternary ammonium salt-based methacrylate copolymer; and the anti-sticking agent is one of diatomite, talc and silicon dioxide.

9. A method for producing the low water permeable and oxygen permeable photoresist protective film according to any one of claims 1 to 8, characterized by, It comprises the following steps: after mixing the materials according to the formula, melt through three single-screw extruders respectively, then pass through a material block connector, die co-extrusion and cooling to form a film; the product is subsequently cooled and shaped, thickness detected, cut on line, wound and packaged to obtain the low-water-permeable and oxygen-permeable photoresist protective film.

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