阅读说明：本技术 一种聚酰亚胺膜硬化导电复合膜的制作工艺 (Manufacturing process of polyimide film hardened conductive composite film ) 是由 刘刚 廖贻河 于 2021-07-12 设计创作，主要内容包括：本发明公开了一种聚酰亚胺膜硬化导电复合膜的制作工艺,具体涉及柔性盖板玻璃、柔性触控折叠屏生产技术领域,具体步骤如下：步骤一：高硬度硬化液制备；步骤二：合成石墨烯纳米银液制备；步骤三：保护层液制备；步骤四：聚酰亚胺硬化膜制备；步骤五：聚酰亚胺硬化导电膜制备。本发明制作的聚酰亚胺膜硬化导电复合膜用于柔性盖板玻璃和折叠柔性折叠屏的防护防折,工艺创新、科学、合理、性能稳定可靠,高温高湿稳定性＞500H,透光率优＞92％,可折弯性能优,硬化硬度最高可达9H,R1mm内折外折可达500K。(The invention discloses a manufacturing process of a polyimide film hardened conductive composite film, and particularly relates to the technical field of production of flexible cover plate glass and flexible touch folding screens, wherein the manufacturing process comprises the following specific steps: the method comprises the following steps: preparing a high-hardness hardening liquid; step two: preparing synthetic graphene nano silver liquid; step three: preparing a protective layer liquid; step four: preparing a polyimide hardened film; step five: and preparing a polyimide hardened conductive film. The polyimide film hardened conductive composite film prepared by the invention is used for protecting and preventing flexible cover plate glass and a folding flexible folding screen, the process is innovative, scientific and reasonable, the performance is stable and reliable, the high-temperature high-humidity stability is more than 500H, the light transmittance is excellent and more than 92%, the bending performance is excellent, the hardening hardness can reach 9H to the maximum, and the R1mm can be folded inwards and outwards to 500K.)

1. A manufacturing process of a polyimide film hardened conductive composite film is characterized by comprising the following steps: the method comprises the following specific steps:

the method comprises the following steps: the preparation method of the high-hardness hardening liquid comprises the following steps:

s1: preparing a group A part: the raw materials are as follows: methyl acrylate, EAC and PGMG, and the preparation steps are as follows: firstly adding PGMG and EAC into a stirring barrel tank, stirring, and then adding a main agent methyl acrylate and stirring;

s2: preparing a group B part: the raw materials are additive and EAC, and the blending steps are as follows: pouring the EAC and the additive into a 250-sand 500ml beaker, and then manually stirring;

s3: mixing and stirring the part A and the part B, namely completing the preparation of the high-hardness hardening liquid, and then carrying out glue test;

step two: the preparation method of the synthetic graphene nano silver solution comprises the following steps:

the raw materials are as follows: ultrapure water, isopropanol and graphene nano silver liquid are prepared by the following steps: mixing and stirring ultrapure water and isopropanol, adding graphene nano silver liquid, stirring, filtering by using a filter bag, adding liquid medicine, and defoaming in vacuum, so that the preparation of the synthesized graphene nano silver is finished;

step three: the preparation method of the protective layer liquid comprises the following steps:

the raw materials are as follows: isopropanol, diacetone alcohol, an additive and acrylic resin, and the preparation steps are as follows: mixing and stirring isopropanol and diacetone alcohol, then adding an additive, stirring, then adding acrylic resin, and stirring to obtain a protective layer liquid;

step four: the preparation method of the polyimide hardened film comprises the following steps:

s1: pouring the high-hardness hardening liquid into a liquid supply barrel, installing an ROKI filter element for filtering, setting the temperature of an oven to be 50-100 ℃, setting the curing energy of a UV lamp to be 600mj/cm, and turning on N220 minutes to ensure that the oxygen content is lower than 200 ppm;

s2: coating a hardening liquid of a glue supply barrel on a polyimide film by a precise Ginesian flowmeter by using a Tacmina pulseless pump in a slit type or micro-concave coating mode, performing surface curing by an air-floating contactless heat drying oven section, and performing UV (ultraviolet) deep curing after the polyimide film is taken out of the oven to form a polyimide hardening film;

step five: the preparation method of the polyimide hardened conductive film comprises the following steps:

s1: pouring the synthesized graphene nano silver liquid into a liquid supply barrel, installing an ROKI filter element for filtering, setting the temperature of an oven to be 50-120 ℃, setting the curing energy of a UV lamp to be 600mj/cm, and turning on N220 min to enable the oxygen content to be lower than 200 ppm;

s2: coating the graphene nano silver solution synthesized by the glue supply barrel on a polyimide film hardened film through a precise Ginesian flowmeter by using a Tacmina pulseless pump in a slit type or micro-concave coating mode, and performing surface curing through an air floating type contactless heat drying oven section;

s3: stirring the protective layer liquid, pouring the protective layer liquid into a liquid supply barrel, installing an ROKI filter element for filtering, setting the temperature of an oven to be 50-110 ℃, setting the curing energy of a UV lamp to be 600mj/cm, and turning on N220 minutes to ensure that the oxygen content is less than 200 ppm;

s4: coating a protective layer liquid of a glue supply barrel on a polyimide film hardened film through a precise Ginese flowmeter by using a Tacmina pulseless pump in a slit type or micro-concave coating mode, and performing surface curing through an air floating type non-contact heat drying oven section;

s5: and (4) taking the polyimide film out of the oven, then carrying out UV deep curing, and finally laminating through a protective film to form the polyimide hardened conductive composite film.

2. The process for manufacturing the polyimide film hardened conductive composite film according to claim 1, wherein: in step one, in S1, stirring speed of PGMG and EAC is 200rpm for 5 minutes, and stirring speed of methyl acrylate is 300rpm for 10 minutes.

3. The process for manufacturing the polyimide film hardened conductive composite film according to claim 1, wherein: EAC was manually stirred with additives for 3 minutes in step one S2, and part A and part B were mixed and stirred for 20 minutes at 300rpm in step one S3.

4. The process for manufacturing the polyimide film hardened conductive composite film according to claim 1, wherein: and mixing and stirring ultrapure water and isopropanol for 5min at the rotating speed of 65rpm in the step two, adding the graphene nano silver liquid, stirring for 15min at the rotating speed of 65rpm, and filtering by using a filter bag with the inner diameter of 75um and the outer diameter of 50 um.

5. The process for manufacturing the polyimide film hardened conductive composite film according to claim 1, wherein: in the third step, isopropanol and diacetone alcohol are mixed and stirred for 5min at the rotating speed of 120rpm, the additive is added and stirred for 5min at the rotating speed of 120rpm, acrylic resin is added and stirred for 15min at the rotating speed of 120 rpm.

6. The process for manufacturing the polyimide film hardened conductive composite film according to claim 1, wherein: the ROKI filter element was 1um in S1 of step four, and the coating speed was 12m/min in S2 of step four.

7. The process for manufacturing the polyimide film hardened conductive composite film according to claim 1, wherein: the ROKI filter element was 50um in S1 of step five, the coating speed was 12m/min in S2 of step five, the ROKI filter element was 1um in S3 of step five, and the coating speed was 12m/min in S4 of step five.

Technical Field

The invention relates to the technical field of production of flexible cover plate glass and flexible touch folding screens, in particular to a manufacturing process of a polyimide film hardened conductive composite film.

Background

Polyimide film (polyimide film) is the film insulating material with the best performance in the world, and is prepared by polycondensation and film-forming of pyromellitic dianhydride (PMDA) and diaminodiphenyl ether (DDE) in a strong polar solvent and imidization. The polyimide film is yellow and transparent in characteristic, the relative density is 1.39-1.45, the polyimide film has excellent high and low temperature resistance, electrical insulation, cohesiveness, radiation resistance and medium resistance, can be used for a long time within the temperature range of-269-280 ℃, and can reach the high temperature of 400 ℃ in a short time. The glass transition temperatures were 280 ℃ (Uplix R), 385 ℃ (Kapton) and 500 ℃ or higher (Uplix S), respectively. The tensile strength is 200MPa at 20 ℃ and is more than 100MPa at 200 ℃. Polyimide is a polymer having an imide ring (-CO-NH-CO-) in the main chain, and among them, a polymer having a phthalimide structure is most important. Polyimide is used as a special engineering material and has been widely applied to the fields of cover plates, flexible folding screens, aviation, aerospace, microelectronics, nano-scale, liquid crystal, separation membranes, lasers and the like. Recently, the research, development and utilization of polyimide are being carried out in various countries as one of the most promising engineering plastics in the 21 st century. Polyimide, because of its outstanding characteristics in performance and synthesis, has been fully recognized as a structural material or a functional material with great application prospects.

Aiming at the core pain point of the folding part of the folding mobile phone in the field of materials, the invention is directed to the invention of a polyimide conductive hardened composite material for a folding terminal, which is used for the protection and folding prevention of flexible cover plate glass and a folding flexible folding screen and has stable reliable performance.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides a manufacturing process of a polyimide film hardened conductive composite film, and the manufactured polyimide film hardened conductive composite film is used for protecting and preventing folding of flexible cover plate glass and a folding flexible folding screen and has stable reliability.

In order to achieve the purpose, the invention provides the following technical scheme: a manufacturing process of a polyimide film hardened conductive composite film comprises the following specific steps:

the method comprises the following steps: the preparation method of the high-hardness hardening liquid comprises the following steps:

s1: preparing a group A part: the raw materials are as follows: methyl acrylate, EAC and PGMG, and the preparation steps are as follows: firstly adding PGMG and EAC into a stirring barrel tank, stirring, and then adding a main agent methyl acrylate and stirring;

s2: preparing a group B part: the raw materials are additive and EAC, and the blending steps are as follows: pouring the EAC and the additive into a 250-sand 500ml beaker, and then manually stirring;

s3: mixing and stirring the part A and the part B, namely completing the preparation of the high-hardness hardening liquid, and then carrying out glue test;

step two: the preparation method of the synthetic graphene nano silver solution comprises the following steps:

the raw materials are as follows: ultrapure water, isopropanol and graphene nano silver liquid are prepared by the following steps: mixing and stirring ultrapure water and isopropanol, adding graphene nano silver liquid, stirring, filtering by using a filter bag, adding liquid medicine, and defoaming in vacuum, so that the preparation of the synthesized graphene nano silver is finished;

step three: the preparation method of the protective layer liquid comprises the following steps:

the raw materials are as follows: isopropanol, diacetone alcohol, an additive and acrylic resin, and the preparation steps are as follows: mixing and stirring isopropanol and diacetone alcohol, then adding an additive, stirring, then adding acrylic resin, and stirring to obtain a protective layer liquid;

step four: the preparation method of the polyimide hardened film comprises the following steps:

s1: pouring the high-hardness hardening liquid into a liquid supply barrel, installing an ROKI filter element for filtering, setting the temperature of an oven to be 50-100 ℃, setting the curing energy of a UV lamp to be 600mj/cm, and turning on N220 minutes to ensure that the oxygen content is lower than 200 ppm;

s2: coating a hardening liquid of a glue supply barrel on a polyimide film by a precise Ginesian flowmeter by using a Tacmina pulseless pump in a slit type or micro-concave coating mode, performing surface curing by an air-floating contactless heat drying oven section, and performing UV (ultraviolet) deep curing after the polyimide film is taken out of the oven to form a polyimide hardening film;

step five: the preparation method of the polyimide hardened conductive film comprises the following steps:

s1: pouring the synthesized graphene nano silver liquid into a liquid supply barrel, installing an ROKI filter element for filtering, setting the temperature of an oven to be 50-120 ℃, setting the curing energy of a UV lamp to be 600mj/cm, and turning on N220 min to enable the oxygen content to be lower than 200 ppm;

s2: coating the graphene nano silver solution synthesized by the glue supply barrel on a polyimide film hardened film through a precise Ginesian flowmeter by using a Tacmina pulseless pump in a slit type or micro-concave coating mode, and performing surface curing through an air floating type contactless heat drying oven section;

s3: stirring the protective layer liquid, pouring the protective layer liquid into a liquid supply barrel, installing an ROKI filter element for filtering, setting the temperature of an oven to be 50-110 ℃, setting the curing energy of a UV lamp to be 600mj/cm, and turning on N220 minutes to ensure that the oxygen content is less than 200 ppm;

s4: coating a protective layer liquid of a glue supply barrel on a polyimide film hardened film through a precise Ginese flowmeter by using a Tacmina pulseless pump in a slit type or micro-concave coating mode, and performing surface curing through an air floating type non-contact heat drying oven section;

s5: and (4) taking the polyimide film out of the oven, then carrying out UV deep curing, and finally laminating through a protective film to form the polyimide hardened conductive composite film.

In a preferred embodiment, in step one S1, the PGMG and EAC are stirred at 200rpm for 5 minutes, and the methyl acrylate is added at 300rpm for 10 minutes.

In a preferred embodiment, the EAC is manually stirred with the additive for 3 minutes in step one S2 and the group a and group B parts are mixed and stirred for 20 minutes at 300rpm in step one S3.

In a preferred embodiment, in the second step, ultrapure water and isopropanol are mixed and stirred for 5min at the rotating speed of 65rpm, the graphene nano silver liquid is added and stirred for 15min at the rotating speed of 65rpm, and the mixture is filtered by using filter bags with the inner diameter of 75um and the outer diameter of 50 um.

In a preferred embodiment, isopropanol is mixed with diacetone alcohol and stirred for 5min at a rotation speed of 120rpm in step three, the additive is added and stirred for 5min at a rotation speed of 120rpm, the acrylic resin is added and stirred for 15min at a rotation speed of 120 rpm.

In a preferred embodiment, the ROKI filter element is 1um at S1 of step four, and the coating speed is 12m/min at S2 of step four.

In a preferred embodiment, the ROKI filter element is 50um at S1 of step five, the coating speed is 12m/min at S2 of step five, the ROKI filter element is 1um at S3 of step five, and the coating speed is 12m/min at S4 of step five.

The invention has the technical effects and advantages that:

1. according to the invention, the first creative reduction of the thickness of the hardening liquid coating and the graphene nano-silver polyimide composite cover plate from the current 100um to 50um in the industry can be realized by using roll-to-roll automatic coating equipment for crack and dimple coating in combination with the most advanced pulse-free pump, so that a layer of OCA is successfully reduced and the use of a layer of CPI film is reduced, thus the cost of the cover plate and the touch layer is reduced by 70%, the price of the flexible screen mobile phone is reduced and domestic in-situ supply is realized;

2. the invention has the advantages of innovative, scientific and reasonable process, stable and reliable performance, high-temperature and high-humidity stability of more than 500H, excellent light transmittance of more than 92 percent, excellent bending performance, highest hardening hardness of 9H and R1mm inward and outward bending of 500K.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1: the polyimide hardened film manufacturing process in the prior art comprises the following specific steps:

the method comprises the following steps: in a hundred-grade clean-grade dust-free plant, part A is prepared: firstly adding 5000g of PGMG (propylene glycol methyl ether) and 4900g of EAC (ethyl acetate) into a stirring barrel tank, stirring at the rotation speed of 200rpm for 5 minutes, and then adding 5000g of methyl acrylate serving as a main agent, stirring at the rotation speed of 300rpm for 10 minutes;

preparing a group B part: pouring 100g of EAC (ethyl acetate) and 7.5g of additive into a 500ml beaker, manually stirring for 3 minutes, pouring into a stirring barrel tank, stirring for 20 minutes at the rotating speed of 300rpm, and finishing the preparation of the hardening liquid;

step two: stirring and mixing the prepared hardening liquid, pouring the mixture into a liquid supply barrel, installing an ROKI filter element with the diameter of 1um for filtering, setting the temperature of an oven at 80 ℃, setting the curing energy of a UV lamp at 600mj/cm, and turning on N for 220 minutes until the oxygen content is lower than 200 ppm;

step three: coating the hardening liquid of the glue supply barrel on the polyimide film by a precision Ginesian flowmeter at the coating speed of 12m/min by using a Tacmina pulseless pump in a slit type or micro-concave coating mode, and carrying out surface curing by an air-floating type contactless heat drying oven section;

step four: and after the cover plate is taken out of the oven, carrying out UV deep curing, and finally laminating through a protective film to form a polyimide hardening film which can be used for protecting a flexible cover plate and a mobile phone folding screen.

Example 2:

the invention provides a manufacturing process of a polyimide film hardened conductive composite film, which comprises the following specific steps:

the method comprises the following steps: the preparation method of the high-hardness hardening liquid comprises the following steps:

s1: preparing a group A part: the raw materials are as follows: methyl acrylate, EAC and PGMG, and the preparation steps are as follows: firstly adding 5000g of PGMG (propylene glycol methyl ether) and 4900g of EAC (ethyl acetate) into a stirring barrel tank, stirring at the rotating speed of 200rpm for 5 minutes, and then adding 5000g of main agent methyl acrylate, stirring at the rotating speed of 300rpm for 10 minutes;

s2: preparing a group B part: the raw materials are additive and EAC, and the blending steps are as follows: pouring 100g of EAC (ethyl acetate) and 7.5g of additive into a 500ml beaker, and manually stirring for 3 minutes;

s3: mixing and stirring the part A and the part B for 20 minutes at the rotating speed of 300rpm, namely completing the preparation of the high-hardness hardening liquid, and then carrying out glue supply test;

step two: the preparation method of the synthetic graphene nano silver solution comprises the following steps:

the raw materials are as follows: ultrapure water, isopropanol and graphene nano silver liquid are prepared by the following steps: 5500g of ultrapure water and 1000g of isopropanol are mixed and stirred for 5min at the rotating speed of 65rpm, then 3500g of graphene nano-silver liquid is added, the mixture is stirred for 15min at the rotating speed of 65rpm, then a filter bag with the inner part of 75um and the outer part of 50um is used for filtering, then the liquid medicine is added for vacuum defoaming, and the negative 0.07MPA is added, thus completing the preparation of the synthesized graphene nano-silver;

step three: preparing a protective layer solution: raw materials of isopropanol, diacetone alcohol, an additive and acrylic resin are prepared by the following steps: 4796g of isopropanol and 4796g of diacetone alcohol are mixed and stirred for 5min at the rotation speed of 120rpm, 108g of additive is added and stirred for 5min at the rotation speed of 120rpm, 300g of acrylic resin is added and stirred for 15min at the rotation speed of 120rpm, and the preparation of the protective layer liquid is finished;

step four: preparing a polyimide hardened film:

s1: pouring the high-hardness hardening liquid into a liquid supply barrel, installing an ROKI filter element of 1um for filtering, setting the temperature of an oven at 80 ℃, setting the curing energy of a UV lamp at 600mj/cm, and turning on N220 minutes to ensure that the oxygen content is lower than 200 ppm;

s2: coating the hardening liquid of the glue supply barrel on the polyimide film by a precise Ginesian flowmeter at the coating speed of 12m/min by using a Tacmina pulseless pump in a slit type or micro-concave coating mode, performing surface curing by an air floating type non-contact heat drying oven section, and performing UV deep curing after the polyimide film is taken out of the oven to form a polyimide hardening film;

step five: preparing a polyimide hardened conductive film:

s1: pouring the synthesized graphene nano silver liquid into a liquid supply barrel, installing an ROKI filter element of 50um for filtering, and setting the temperature of an oven to be 100 ℃;

s2: coating the graphene nano-silver solution synthesized by the glue supply barrel on a polyimide film hardened film by a precise Ginese flowmeter at a coating speed of 12m/min by using a Tacmina pulseless pump in a slit type or micro-concave coating mode, and performing surface curing by an air-floating contactless heat drying oven section;

s3: stirring the protective layer liquid, pouring the protective layer liquid into a liquid supply barrel, installing an ROKI filter element with the diameter of 1um for filtering, setting the temperature of an oven to be 90 ℃, setting the curing energy of a UV lamp to be 600mj/cm, and turning on N220 minutes to ensure that the oxygen content is lower than 200 ppm;

s4: coating a protective layer liquid of a glue supply barrel on a polyimide film hardened film by a precise Ginese flowmeter at a coating speed of 12m/min by using a Tacmina pulseless pump in a slit type or micro-concave coating mode, performing surface curing on the polyimide film hardened film by an air-floating contactless heat drying oven section, and performing UV deep curing after the polyimide film hardened film is taken out of the oven;

s5: and after the film is taken out of the oven, carrying out UV deep curing, and finally laminating through a protective film to form the polyimide hardened conductive film which can be used for flexible large, medium and small touch screens.

The invention has the advantages of innovative, scientific and reasonable process, stable and reliable performance, high-temperature and high-humidity stability of more than 500H, excellent light transmittance of more than 92 percent, excellent bending performance, hardening hardness of 9H at most, R1mm inward-bending and outward-bending of 500K, and the main technical innovation is as follows:

at present, the thickness of the hardening liquid coating and the graphene nano-silver polyimide composite cover plate is creatively reduced from the current 100um to 50um for the first time in the industry by using roll-to-roll automatic coating equipment for crack and dimple coating and matching with the most advanced pulse-free pump, so that a layer of OCA is successfully reduced, and the use of a layer of CPI film is reduced, and the cost of the cover plate and the touch layer is reduced by 70%. Only one company in Japan has the same technology in the world at the present stage, the project has completed research and development and successfully realizes mass production, and the technology and the yield are far ahead of the world. The technology makes great contribution to the popularization and market expansion of the cover plate and the flexible screen mobile phone, changes the situation that the foreign huge monopoly (Japanese inhabitants and Korea Kelong) is changed into China autonomous production, reduces the price of the flexible screen mobile phone and realizes domestic in-situ supply.

And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.