阅读说明：本技术 具有激光剥离容易性及高耐热性的聚酰胺酸树脂的制造方法及利用其制造的聚酰亚胺膜 (Method for producing polyamic acid resin having ease of laser peeling and high heat resistance, and polyimide film produced by using same ) 是由 姜镇洙 金镇慕 安龙昊 韩丞镇 于 2017-08-07 设计创作，主要内容包括：本发明涉及具有激光剥离容易性及高耐热性的聚酰胺酸树脂的制造方法及利用由此制造的聚酰胺树脂制造的聚酰亚胺膜,具体而言,与玻璃等的粘合力维持在适定水平,能在低能量进行激光剥离而能无薄膜的损伤(卷曲(curl),缺陷(defect),破损等)地进行剥离,制造具有高耐热性的聚酰胺酸树脂,利用其制造的聚酰亚胺膜可有用地适用于柔性的显示基板材料,半导体材料等。(The present invention relates to a method for producing a polyamic acid resin having ease of laser peeling and high heat resistance, and a polyimide film produced from the polyamide resin produced by the method, and more particularly, to a method for producing a polyamic acid resin having high heat resistance, which can maintain adhesion to glass or the like at a proper level, can be subjected to laser peeling at low energy, and can be peeled without damage (curl, defect, breakage, etc.) of a thin film, and a polyimide film produced by the method can be usefully applied to a flexible display substrate material, a semiconductor material, or the like.)

1. A method for producing a polyamic acid resin having ease of laser peeling and high heat resistance, which comprises polymerizing a composition comprising a diamine monomer, an acid dianhydride compound, and an organic solvent, wherein the polyamic acid resin is obtained by dissolving the diamine monomer in the organic solvent, and then adding the acid dianhydride compound to the resulting solution 4 or more times, and the addition is carried out with a time difference of 30 to 60 minutes.

2. The method according to claim 1, wherein the acid dianhydride compound is equally fed in 4 to 6 times at a polymerization temperature of 40 to 60 ℃.

3. The method of claim 1, wherein the dosing is 5 dosing at 30 minute intervals of the acid dianhydride compound at a polymerization temperature of 40 ℃.

4. The method according to claim 1, wherein the diamine monomer comprises 5 to 50 mol% of 2,2' -bis (trifluoromethyl) -benzidine based on 100 mol% of the diamine monomer.

5. The method of claim 1, wherein the polyamic acid resin has a viscosity of 1,000 to 7,000 cP.

6. A polyimide resin film produced by heat-treating a polyamic acid resin produced by the method according to any one of claims 1 to 5, wherein the film has an adhesive force of 0.2 to 2.0N/cm and a peeling energy of 200mJ/cm in terms of a thickness of 10 to 15 μm²The thermal expansion coefficient is 10 ppm/DEG C or less at 100 to 350 ℃.

[ technical field ] A method for producing a semiconductor device

The present invention relates to a method for producing a polyamic acid resin having ease of laser peeling and high heat resistance, and a polyimide film produced from the polyamide resin produced by the method, and more particularly, to a method for producing a polyamic acid resin having high heat resistance, which can maintain an appropriate level of adhesion to glass or the like, can be subjected to laser peeling at low energy, and can be peeled without damage (curl, defect, breakage, etc.) of a thin film, and a polyimide film produced by the method can be usefully applied to a flexible display substrate material, a semiconductor material, or the like.

[ background of the invention ]

As a substrate material for a flexible display, which is favored for a next-generation display device, a flexible polymer material has attracted attention.

The flexible device generally uses an Organic Light Emitting Diode (OLED) display, and uses a TFT process with a high process temperature (300-500 ℃). Polymer materials that can withstand such high process temperatures are extremely limited, and Polyimide (PI) resins, which are polymers having excellent heat resistance, are also mainly used.

An Organic Light Emitting Diode (OLED) display is manufactured by a method in which a glass substrate is coated with a resin, thermally cured to form a film, and then peeled off from the glass substrate through a plurality of steps.

In the process of coating a resin on a glass substrate in such a manufacturing process, the viscosity of the resin is a very important factor for film manufacturing. If the viscosity is too high, removal of the solvent of the resin upon heat treatment is not easy, thereby reducing the properties of the film, or it is difficult to uniformly coat upon coating and the uniformity of the film is reduced, which causes product defects (defects) during the OLED panel manufacturing process. On the contrary, if the viscosity is too low, it is difficult to apply a desired thickness at the time of application, and thus it is also difficult to control the uniformity of the film.

Thus, it is considered that having an appropriate viscosity is advantageous for the resin to produce a film. Furthermore, in the TFT process, product defects (defects) can be produced by Thermal shock (Thermal shock) due to a high process temperature (>350 ℃).

Thus, only with a thermal expansion coefficient at the glass substrate level, product defects can be minimized. Further, conventionally, it is common that after the production of a thin film, the thin film is peeled from a glass substrate by a laser peeling method, and the resin is a nonpolar molecule in characteristics, so that the adhesion to glass is high after heat treatment, and when the thin film is produced and peeled, problems such as curl (curl), product defect (defect), and product breakage occur, and the thin film is not easily peeled at the time of laser peeling, and the thin film is damaged when high energy is irradiated.

On the other hand, korean laid-open patent No. 1998-015679 relates to a method for producing an aromatic polyimide film, in which an excessive amount of acid dianhydride is added to an aromatic diamine in several portions, and a polyamic acid resin obtained by polymerization at a temperature of about 5 to 20 ℃ is polymerized using an organic polar solvent to produce a polyimide film having excellent properties such as heat resistance, but has limitations in adding a process in which the viscosity of polyamic acid at room temperature needs to be reduced while maintaining the properties, and the viscosity of the polyamic acid solution is high, so that the temperature of the solution during film casting is increased to reduce the viscosity.

In contrast, the above-described problem does not occur unless the peeling is easily performed by laser peeling. This enables the laser peeling to be performed without damaging the film only if the laser peeling is performed at a low energy.

Therefore, it is required to develop a polyamic acid resin which has a low viscosity and adjusts an appropriate level of adhesion to glass, and can be laser-peeled at low energy, and has high heat resistance and a low thermal expansion coefficient.

[ detailed description of the invention ]

[ technical problem ] to provide a method for producing a semiconductor device

In order to solve the above problems, the present inventors have found that a molar ratio of a composition used in excess can be minimized and a viscosity can be easily adjusted by optimizing and adjusting a method of feeding the composition used in the production of a polyamide resin, a time of feeding the composition in divided portions, and a polymerization temperature condition, and have found that a molar ratio of a composition used can be minimized compared to a conventional method when a viscosity of the same level is used as a reference, thereby producing a polyamide resin having more excellent properties, and have completed the present invention. It is also found that by such a method of separately charging, a polyamic acid resin having a low viscosity can be obtained without lowering the properties by optimizing the charging time and the polymerization temperature.

Accordingly, the present invention is directed to a method for producing a polyamic acid resin having ease of laser peeling and high heat resistance.

The present invention also provides a film produced by heat-treating the polyamic acid resin obtained by the above production method, wherein the film has an adhesive strength of 0.2 to 2.0N/cm and a peeling energy of 200mJ/cm based on a film thickness of 10 to 15 μm²The thermal expansion coefficient is 10 ppm/DEG C or less at 100 to 350 ℃.

[ MEANS FOR solving PROBLEMS ] to solve the problems

The present invention provides a method for producing a polyamic acid resin having ease of laser peeling and high heat resistance, comprising polymerizing a composition comprising a diamine monomer, an acid dianhydride compound, and an organic solvent, wherein the polyamic acid resin is produced by dissolving the diamine monomer in the organic solvent, and then adding the acid dianhydride compound 4 or more times for polymerization, wherein the time for adding is set to a time difference of 30 to 60 minutes.

The present invention also provides a polyimide resin film produced by heat-treating the polyamic acid resin produced by the above method, wherein the film has an adhesive strength of 0.2 to 2.0N/cm and a peeling energy of 200mJ/cm based on a film thickness of 10 to 15 μm²The thermal expansion coefficient is 10 ppm/DEG C or less at 100 to 350 ℃.

[ Effect of the invention ]

The polyimide resin produced by the production method according to the present invention has a low viscosity, exhibits excellent laser lift-off at low energy at the time of polyimide film production by thermal hardening, has excellent mechanical properties and heat resistance properties, and thus can be usefully applied to flexible display substrate materials, semiconductor materials, and the like.