JP6947848B2 - A method for producing a polyamic acid resin having easy laser peeling and high heat resistance, and a polyimide resin film produced using the same. - Google Patents

Description

The present invention relates to a method for producing a polyamic acid resin having easy laser peeling and high heat resistance and a polyimide resin film produced by using the polyamide resin produced by the method, and specifically, it has an appropriate adhesive force with glass or the like. Since laser peeling is possible with low energy while maintaining a high level, it is possible to peel without damage to the thin film (curl, polyimide, breakage, etc.) and a polyamic acid resin with high heat resistance. Can be usefully used as a flexible display substrate material, a semiconductor material, or the like.

Flexible polymer materials are attracting attention as substrate materials for flexible displays, which are in the limelight as next-generation display devices.

The flexible device generally uses an organic light emitting diode (OLED) display and uses a high process temperature (300-500 ° C.) TFT process. Polymer materials that can withstand such high process temperatures are extremely limited, but in particular, polyimide (PI) resin, which is a polymer having excellent heat resistance, is mainly used.

An organic light emitting diode (OLED) display is manufactured by a method in which a resin is applied to a glass substrate, then heat-cured to form a film, and then peeled off from the glass substrate after several steps.

Among such manufacturing processes, the viscosity of the resin in the process of applying the resin to the glass substrate is a very important factor in film production. If the viscosity is too high, it is difficult to remove the resin solvent during heat treatment, which reduces the physical characteristics of the thin film, or it is difficult to apply the thin film uniformly during coating, which reduces the uniformity of the thin film, resulting in product defects in OLED panel manufacturing. May lead to. On the other hand, if the viscosity is too low, it is difficult to obtain the thickness required for coating, and it is difficult to control the uniformity of the thin film.

Therefore, it can be said that a resin having an appropriate viscosity is advantageous in producing a thin film. Then, during the TFT process, product defects may occur due to thermal shock due to a high process temperature (> 350 ° C.).

Therefore, defects in the product can be minimized only by having a coefficient of thermal expansion comparable to that of a glass substrate. At present, the thin film is generally peeled from the glass substrate by a laser peeling method after the thin film is manufactured. However, due to the characteristics of the resin, it is a non-polar molecule and has a high adhesive force with the glass after the heat treatment. When the film is peeled off after being made into a film, problems such as curl, product defects, and product breakage occur, and even if the film is not peeled off well at the time of laser peeling, irradiation with high energy leads to damage to the film.

On the other hand, Korean Publication No. 1998-015679 relates to a method for producing an aromatic polyimide resin film, in which an excess acid dianhydride monomer is added to the aromatic diamine in several portions to make it organic. Since a polyimide resin film is produced from a polyamic acid resin obtained by polymerizing at a temperature of about 5 to 20 ° C. using a polar solvent, it has excellent physical properties such as heat resistance, but the polyamic acid viscosity at room temperature while maintaining the physical properties. Also, since the polyamic acid solution has a high viscosity, there is a limit in that a step of raising the temperature of the solution to lower the viscosity at the time of film casting is further required.

Therefore, if the laser is easily peeled off at the time of laser peeling, the above problem does not occur. This can be peeled off without damaging the thin film by laser peeling with low energy.

Therefore, it is desired to develop a polyamic acid resin having a low viscosity, adjusted to an appropriate adhesive force with glass, capable of laser peeling with low energy, high heat resistance and a low coefficient of thermal expansion.

Therefore, in view of the above problems, the present inventors consider the above-mentioned problems, and in order to develop a polyamic acid resin having high heat resistance and easy laser peeling, the composition is charged in a step of adding a composition used for producing a polyamide resin, or dividedly charged. It was found that the excess molar ratio of acid dianhydride can be minimized and the viscosity can be easily adjusted by optimally adjusting the charging time interval and the polymerization temperature conditions of the above. In comparison, they have found that the molar ratio of the composition used can be minimized and a polyamic acid resin having better physical characteristics can be produced, and the present invention has been completed. Further, by optimizing such a divided charging step, a charging time interval (time from the previous charging time to the next charging time), and the polymerization temperature, a polyamic acid resin having a low viscosity without deterioration of physical properties can be obtained. It turned out to be obtained.

Therefore, an object of the present invention is to provide a method for producing a polyamic acid resin having easy laser peeling and high heat resistance.

Further, the present invention is a film produced by heat-treating the polyamic acid resin obtained by the above-mentioned production method, and has an adhesive force of 0.2 to 2.0 N / cm and peeling based on a film thickness of 10 to 15 μm. An object of the present invention is to provide a polyimide resin film having an energy of 200 mJ / cm ² or less and a coefficient of thermal expansion of 10 ppm / ° C. or less in the range of 100 to 350 ° C.

The present invention is a method for producing a polyamic acid resin produced by polymerizing a composition containing a diamine compound monomer, an acid dianhydride monomer, and an organic solvent. A polyamide having easy laser peeling and high heat resistance, characterized in that the diamine compound monomer is dissolved in the organic solvent and then divided and polymerized four or more times at intervals of 30 to 60 minutes. This is a method for producing an acid resin.
The present invention also produces a polyamic acid resin, wherein the acid dianhydride monomer is divided and added 4 times or more and 6 times or less and polymerized at a polymerization temperature of 40 ° C. to 60 ° C. The method.
Further, the present invention is a method for producing a polyamic acid resin, characterized in that the acid dianhydride monomer is added in 5 portions at intervals of 30 minutes at a polymerization temperature of 40 ° C.
Further, in the present invention, 5,50 mol% of 2,2'-bis (trifluoromethyl) -benzidine (2,2'-bis (trifluoromethyl) benzidine) is contained in 100 mol% of the diamine compound monomer. It is a method for producing a polyamic acid resin, which is characterized by containing it.
Further, the present invention is a method for producing a polyamic acid resin, which comprises setting the viscosity of the polyamic acid resin to 1,000 to 7,000 cp.
Further, the present invention is a polyimide resin film produced by heat-treating a polyamic acid resin produced by any of the above production methods, and the adhesive strength is 0 based on the polyimide resin film thickness of 10 to 15 μm. A polyimide resin film characterized by having a peeling energy of 200 mJ / cm ² or less and a thermal expansion coefficient of 10 ppm / ° C. or less in the range of 100 to 350 ° C. of 2 to 2.0 N / cm.

The polyimide resin produced by the production method of the present invention is a polyimide resin film having low viscosity, exhibiting excellent laser peeling power with low energy by thermosetting, and having excellent mechanical properties and heat resistance properties. can get. The obtained polyimide resin film can be usefully used as a flexible display substrate material, a semiconductor material, and the like.

It is a graph which shows the change of the viscosity by the split-adding condition at the time of manufacturing the polyamic acid resin which concerns on this invention.

The result of testing the presence or absence of peeling of the film by irradiating the polyimide resin film produced by applying the polyamic acid resin according to the present invention on a glass substrate and then heat-treating it with an individual energy magnitude (photo). be.

Hereinafter, the present invention will be described in more detail with reference to an embodiment.

The present invention provides a method for producing a polyamic acid resin produced by polymerizing a composition containing a diamine compound monomer, an acid dianhydride monomer, and an organic solvent. A polyamide resin produced by a predetermined method is used in order to obtain a polyimide resin film having an appropriate laser peeling property, excellent heat resistance, and a low coefficient of thermal expansion during film production while having a low viscosity. ..

Specifically, in the method for producing a polyamic acid resin of the present invention, an acid dianhydride monomer is obtained by dissolving a diamine compound monomer in an organic solvent and then dividing the acid dianhydride monomer into four or more. Each weight is charged at intervals of charging time.

The charging time interval of charging is, for example, 30 to 60 minutes. FIG. 1 is a graph showing a change in viscosity due to split-adding conditions during the production of the polyamic acid resin according to the present invention.

Generally, when adjusting the viscosity of a polyamic acid resin, the target is to add an excess amount of the molar ratio of the acid dianhydride monomer and the diamine compound monomer so that one of them is -5 to 5 mol%. It is preferable to reach the viscosity, but this is to ensure proper viscosity control and storage stability. However, if one of these molar ratios is excessively excessive, it causes various deteriorations in characteristics during the production of the polyimide resin film.

Therefore, in order to solve the above problems, in the production of the polyamic acid resin of the present invention, the molar ratio of the composition to be used is excessive by optimizing the number of times the monomer is added, the time interval between the addition of the monomers, and the polymerization temperature. When the viscosity is adjusted and the viscosity at the same level is used as a reference, the molar ratio is minimized as compared with the existing method, so that a polyamic acid resin having further excellent properties can be produced.

In addition, a polyamic acid resin having a low viscosity can be obtained without deterioration of physical properties.

Furthermore, at the time of polymerization of the polyamide resin, it is preferable to dissolve the diamine compound monomer in an organic solvent and then add the acid dianhydride monomer in four or more divided portions. More preferably, it is 4 to 6 times. More preferably, it is 5 times. At this time, the polymerization temperature of the diamine-containing solution into which the acid dianhydride monomer is added is preferably 40 to 60 ° C. More preferably, it is 40 ° C.

When 100 mol% of the acid dianhydride monomer is used as a reference, it is preferable to add the acid dianhydride monomer with a time difference of 30 to 60 minutes in the case of equal division 4 to 6 times. After the addition 4 to 6 times, the acid dianhydride monomer is added while adjusting the amount of the acid dianhydride monomer based on the target viscosity of the polyamic acid solution. In such a split injection method, the growth of the molecular chain is made into the form of an oligomer having an appropriate molecular weight level instead of a high molecular weight, so that the viscosity in a solution state is possible, and a polyimide resin film is produced by heat treatment. At times, the oligomeric form of the molecule can be bound at high molecular weight during the imidization process.

Therefore, the polyamic acid resin of the present invention can exhibit excellent mechanical properties, high heat resistance, and low coefficient of thermal expansion when manufactured as a polyimide resin film, while having a low viscosity. This can be confirmed from the experimental example described later. The composition used for producing the polyamic acid resin according to the present invention is as follows.

(A) Diamine-based compound In the production of the polyamic acid resin of the present invention, the diamine compound monomer as a basic constitution contains a fluorinated aromatic diamine and a non-fluorinated diamine. When the polyamic acid resin contains a fluorinated aromatic diamine in which a fluorine substituent is introduced, the fluorine substituent increases the surface tension and lowers the adhesive force with the glass substrate, which may occur when the polyimide resin film is peeled off. Problems such as curl, product defects, and product breakage can be improved, and excellent laser peeling characteristics can be exhibited with low energy. Further, when such a fluorinated aromatic diamine and a non-fluorinated aromatic diamine are mixed and used, the peeling property is given by the fluorine substituent of the fluorinated aromatic diamine, and at the same time, the non-fluorinated aromatic diamine is used. Due to the toughness of the aromatic structure of the diamine, a polyimide resin film having excellent heat resistance and a low thermal expansion coefficient can be provided, and damage to the polyimide resin film can be minimized during laser peeling.

The fluorinated aromatic diamine used in the present invention is not particularly limited as long as it is an aromatic diamine containing fluorine. For example, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-Bis (trifluoromethyl) -4,4'-Diaminobiphenyl, TFMB), bisaminohydroxyphenylhexafluoropropane (2,2'-Diaminobiphenyl, TFMB). bisaminohydroxyphenyl hexafluoropropane, DBOH, bisaminophenoxyphenyl hexafluoropropane, 4BDAF, 2,2'-bis (trifluoromethyl) -4,3'-bi-bi-bi-bi-bi-bi-bi-bi-bi-bi-bi-bi-bi-bi-bi-bi-bi-bi-bi-bi ) -4,3'-Diaminobiphenyl), 2,2'-bis (trifluoromethyl) -5,5'-diaminobiphenyl (2,2'-Bis (trifluoromethyl) -5,5'-Diaminobiphenyl), etc. However, it is not limited to this. These can be used alone or in combination of two or more. Of these, when TFMB is used, it is preferable because the peeling property and the heat resistance property can be improved at the same time.

The content of such a fluorinated aromatic diamine is not particularly limited, but if it is 5 to 50 mol%, preferably 5 to 30 mol% based on 100 mol% of the total diamine compound, the heat resistant characteristics are maintained. However, the peeling property can be exhibited.

The polyamic acid resin of the present invention can further contain a non-fluorinated aromatic diamine as an aromatic diamine component. For example, para-phenylenediamine (PPD), meta-phenylenediamine (MPD), 4,4'-oxydianiline (ODA), bisaminophenoxyphenylpropane (6HMDA), 4,4'-diaminodiphenylsulfone (4, 4'-DDS), 9,9'-bis (4-aminophenyl) fluorene (FDA), para-xylylenediamine (p-XDA), meta-xylylenediamine (m-XDA), 4,4'- Methylenedianiline (MDA), 4,4'-diaminobenzoate (4,4'-DABA), 4,4'-bis (4-aminophenoxy) biphenyl (4,4'-BAPP), etc. Can be used alone or in combination of two or more. Of these, PPD is preferable because it can exhibit excellent heat resistance characteristics and low coefficient of thermal expansion characteristics.

The content of such a non-fluorinated aromatic diamine is not particularly limited, but may be about 50 to 95 mol%, preferably 70 to 95 mol% based on 100 mol% of the diamine compound.

(B) Acid dianhydride monomer The polyamic acid resin of the present invention contains an aromatic acid dianhydride monomer as an acid dianhydride monomer component.

When an aromatic acid dianhydride monomer is used in the polyamic acid resin, the heat resistance characteristics and the low coefficient of thermal expansion characteristics of the polyimide can be improved. Due to the tough molecular structure of aromatic acid dianhydride, a polyimide resin film having excellent heat resistance can be produced. The aromatic acid dianhydride monomer is not particularly limited, and is, for example, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 4,4'-(4,4'-. Hexafluoroisopropyridene diphenoxy) bis- (phthalic anhydride) (6-FDPDA), pyromeritic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic hydride (BPDA) , 3,3', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic anhydride (ODPA), 2,2-bis [4-3,4-dicarboxyphenoxy) ] Phenyl] Propane dianhydride (BPADA), 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (DSDA), ethylene glycol bis (4-trimeritate anhydride) (TMEG), etc. , Not limited to this. These can be used alone or in combination of two or more. Of these, it is preferable to use PMDA or BPDA as the aromatic acid dianhydride monomer.

The content of the above-mentioned aromatic acid dianhydride monomer is not particularly limited, but is BPDA 50 to 90 mol% and PMDA 10 to 50 mol% based on a total of 100 mol% of the acid dianhydride monomer. , Preferably, when BPDA is 70 to 100 mol% and PMDA is 0 to 30 mol%, excellent heat resistance can be exhibited.

(C) Organic Solvent The solvent used for producing the polyamic acid resin of the present invention may be any solvent as long as the polyamic acid resin is dissolved, and its structure is not particularly limited. For example, m-cresol, N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), N, Polar solvents such as N-dimethylacetamide (DMAc), N, N-diethylacetamide (DEAc), dimethylsulfoxide (DMSO), diethylacetate (DEA), 3-methoxy-N, N-dimethylpropanamide (DMPA), It is preferable to use a low boiling solvent such as tetrahydrofuran (THF), chloroform or the like, or a low water absorption solvent such as gamma-butyrolactone (GBL). These can be used alone or in combination of two or more.

(D) Reaction catalyst The polyamic acid resin of the present invention further contains one or more reaction catalysts from the group consisting of trimethylamine, xylene, pyridine and quinoline depending on the reactivity. Can be, and is not necessarily limited to this. Further, the polyamic acid resin is composed of a group consisting of a plasticizer, an antioxidant, a flame retardant, a dispersant, a viscosity modifier, and a leveling agent, if necessary, within a range that does not significantly impair the object and effect of the present invention. It can contain a small amount of one or more selected additives.

The contents of the aromatic diamine (B), the aromatic acid dianhydride monomer (C), the organic solvent (D), and the catalyst (E) in the above-mentioned polyamic acid resin of the present invention are not particularly limited. The total amount of the acid dianhydride monomer component and the diamine component is 5% by mass or more with respect to the total amount of the solvent, the acid dianhydride monomer component and the diamine component, including the polyamic acid resin and the solvent of the present invention. The ratio is preferably 10% by mass or more, more preferably 15% by mass or more. Further, usually, 60% by mass or less, preferably 50% by mass or less is preferable. If this concentration is too low, it is difficult to control the thickness of the obtained polyimide resin film during the production of the polyimide resin film, and if it is too high, there is a limit to adjusting the viscosity of the polyamic acid resin, which is within the above range. do.

At this time, the reaction is carried out by mixing 95 to 100 mol% of the diamine compound monomer and 100 to 105 mol% of the acid dianhydride monomer under the organic solvent conditions and for 8 to 24 hours at a temperature condition of 10 to 70 ° C. It is preferable to do so. Here, it is preferable to add an excess amount of -5 to 5 mol% of the acid dianhydride monomer to the diamine compound monomer to reach the target viscosity, which is appropriate for viscosity adjustment and storage stability. This is to secure. Further, if the reaction time is less than 4 hours, there is a limit in terms of storage stability of the polyamic acid resin, and if it exceeds 24 hours, there is a limit in terms of productivity. Therefore, it is preferable to manufacture within the above range. ..

The polyamic acid resin produced by such a reaction preferably has a viscosity in the range of 1,000 to 7,000 cP. If the viscosity is less than 1,000 cP, there is a problem in obtaining an appropriate polyimide resin film thickness, and if it exceeds 7,000 cP, there is a problem in uniform coating and effective solvent removal. preferable.

The method for producing the polyimide resin film in the present invention is as follows. The present invention provides a polyimide resin film produced by thermally imidizing the above-mentioned polyamic acid resin. The polyamic acid resin according to the present invention has viscosity, and is produced by coating a substrate having a flat surface such as a glass substrate by an appropriate method and then heat-treating it at the time of producing a polyimide resin film.

As the coating method, a well-known ordinary method can be used without limitation, for example, spin coating (Spin coating), dip coating (Dip coating), solvent casting (Solvent casting), slot die coating (Slot die coating), spraying. There are, but are not limited to, coatings (Spray coating) and the like.

The polyamic acid resin of the present invention can be produced as a polyimide resin film by heat treatment in a high-temperature convection oven. At this time, the heat treatment conditions are carried out in a nitrogen atmosphere, and are carried out under the conditions of 100 to 500 ° C. for 60 to 300 minutes. More preferably, the polyimide resin film is obtained under the temperature and time conditions of 100 ° C./30 minutes, 150 ° C./10 minutes, 300 ° C./15 minutes, and 500 ° C./10 minutes. This is due to imidization, which allows for proper solvent removal and maximization of properties.

Since the transparent polyimide resin film of the present invention is produced using the polyamic acid resin, it exhibits high transparency and at the same time has a low coefficient of thermal expansion.

The polyimide resin film of the present invention has an adhesive force of 0.2 to 2.0 N / cm, a peeling energy of 200 mJ / cm ² or less, and a coefficient of thermal expansion in the range of 100 to 350 ° C. based on a film thickness of 10 to 15 μm. It is 10 ppm / ° C or less. Preferably, it is as low as 5 ppm / ° C. or less. The polyimide resin film of the present invention can suppress defects of elements on the substrate due to curling, expansion and contraction at the time of laser peeling from the glass substrate.

FIG. 2 shows a polyimide resin film produced by applying the polyamic acid resin according to the present invention on a glass substrate and then heat-treating it by irradiating it with a laser at an individual energy magnitude to test whether or not the polyimide resin film is peeled off. This is the result (photo). Lower energy when irradiated with laser (160mJ / cm ²⁾ Polyimide is well peeled, as the energy of the irradiating laser is high (220mJ / cm ^2), a phenomenon that a polyimide resin film on the glass substrate may be damaged It was observed.

The polyimide resin film of the present invention can be used in various fields, and is used as a material for OLED displays, liquid crystal element displays, TFT substrates, flexible printing circuit substrates, flexible OLED surface lighting substrates, and electronic paper substrates. It can be provided as a substrate for a flexible display and a protective film.

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are for exemplifying the present invention and do not limit the scope of the present invention.

<Split loading process>
Comparative Example 1
The compositions shown in Table 1 below include PPD19, which is a diamine compound monomer. 141 g (0.177 mole) and TFMB 2. 882 g (0.009 mole) was placed in NMP 455.04 g, which is an organic solvent, and dissolved in a nitrogen atmosphere at room temperature for 30 minutes to 1 hour to prepare a diamine-containing solution. Then, 7.961 g (0.197 mole) of BPDA5, which is an acid dianhydride monomer, was put into a diamine-containing solution and stirred for 6 hours to produce a polyamic acid resin polymerization temperature (polymerization temperature: 23 ° C., this). At the time, the solid content is maintained so as to be 15% by weight based on the total weight of the reaction solvent). As a result of measurement with a viscosity measuring device (Blockfield DV2T, SC4-27), the viscosity was 5,900 cP.

Comparative Examples 2 and 3
Comparative example except that the number of times the acid dianhydride monomer was added to the diamine-containing solution (2 to 3 times), the addition time interval (30 minutes), and the acid dianhydride excess molar ratio were used. The polyamic acid resin was produced by the same method as in 1.

Examples 1-3
The polyamic acid resin was added in the same manner as in Comparative Example 1 except that the number of times the acid dianhydride monomer was added (4 to 6 times), the addition time (30 minutes), and the acid dianhydride excess molar ratio were shown in Table 1 below. Manufactured.
That is, PPD 19.1 41 g (0.177 mole), which is a diamine compound monomer, and TFMB 2. 882 g (0.009 mole) was placed in NMP 455.04 g, which is an organic solvent, and dissolved in a nitrogen atmosphere at room temperature for 30 minutes to 1 hour. Then, BPDA, which is an acid dianhydride monomer, was added at the number of times of addition in Table 1, the addition time, and the amount of excess acid dianhydride, and stirred for 6 hours to produce a polyamic acid resin (polymerization). Temperature: 23 ° C., at this time, the solid content is maintained so as to be 15% by weight based on the total weight of the reaction solvent.)

<Experimental example 1: Measurement of physical properties>
The polyamic acid resins of Comparative Examples and Examples were coated on a glass plate using a bar coater, and then heat-treated in a high-temperature convection oven. The heat treatment conditions were carried out in a nitrogen atmosphere, and the final polyimide resin film was obtained under the temperature and time conditions of 100 ° C./30 minutes, 150 ° C./10 minutes, 300 ° C./15 minutes, and 500 ° C./10 minutes. The physical properties of the polyimide resin film thus obtained were measured by the following methods, and the results are shown in Table 1 below.

(A) Viscosity measurement The viscosity was measured using a Brookfield viscometer (Blockfield DV2T, SC4-27).

(B) Adhesive strength measurement (peel test)
A 100 mm × 100 mm glass substrate was heat-treated with a polyamic acid resin to produce a polyimide resin film, cut to a width of 25 mm, and then subjected to a 90 ° adhesive force test at a speed of 300 mm / min using a UTM manufactured by Instron.

(C) Thermal Characteristics The coefficient of thermal expansion (CTE) of the polyimide resin film was measured using TMA 402 F3 manufactured by Netzsch. The force of the tension mode is set to 0.05 N, the measurement temperature is raised from 30 ° C to 500 ° C at a rate of 5 ° C / min, and the average value in the range of 100 to 350 ° C is a line. The coefficient of thermal expansion was measured.

The thermal decomposition temperature (T _d , 1%) was measured using TG 209 F3 manufactured by Netzsch. The measurement temperature is raised from 30 ° C. to 120 ° C. and maintained for 10 minutes → raised to 220 ° C. and maintained for 1 hour → maintained at 460 ° C. for 3 hours → raised to 700 ° C. (10 ° C. per minute). The weight loss% after maintaining at 460 ° C. for 3 hours was measured.

(D) Mechanical properties An Instron UTM was used to measure the mechanical properties of the polyimide resin film. The width of the polyimide resin film test piece was set to 10 mm, the distance between the grips was set to 100 mm, and the test piece was measured while pulling the test piece at a speed of 50 mm / min.

As shown in Table 1, in the case of Example 2 in which the acid dianhydride monomer was added evenly divided 5 times to the composition having the same level of viscosity, the heat resistance characteristics, Td after maintaining at 460 ° C. for 3 hours. (%) And CTE are superior to those of Comparative Examples 1 to 3 in which the acid dianhydride monomer was added in an evenly divided manner 1 to 3 times, and Examples 1 and 3 in which the acid dianhydride monomer was added in an evenly divided manner 4 times and 6 times. It can be seen that it exhibits the same level of characteristics as.

This is an excellent result in terms of heat resistance and mechanical properties while having the same level of viscosity by minimizing the acid dianhydride excess molar ratio by changing the method of adding the acid dianhydride monomer. It can be said that it shows.

From the above results, the number of times the acid dianhydride monomer according to the present invention is divided and added is appropriately 4 to 6 times, preferably 5 times divided and added.

<Split input time>
Comparative Example 4
The compositions shown in Table 2 below include PPD 19.1 41 g (0.177 mole), which is a diamine compound monomer, and TFMB 2. 882 g (0.009 mole) was placed in NMP 455.04 g, which is an organic solvent, and dissolved in a nitrogen atmosphere at room temperature for 30 minutes to 1 hour to prepare a diamine-containing solution.

Then, 56.64 g (0.193 mole) of BPDA, which is an acid dianhydride monomer, was added into the diamine-containing solution in equal divisions 5 times. At this time, the divided injection was added at an interval of 10 minutes, and the mixture was stirred for 6 hours to produce a polyamic acid resin (the polymerization temperature, which is the temperature of the diamine-containing solution, was set to 23 ° C., at this time, the solid content was increased. It was maintained so as to be 15% by weight based on the total weight of the reaction solvent). Since the charging time interval for split charging was short, the acid dianhydride monomer was not sufficiently dissolved.

Comparative Example 5
The polyamic acid resin was produced by the same method as in Comparative Example 4 except for the charging time interval (20 minutes) in which the acid dianhydride monomer was dividedly charged in Table 2 below. Similarly, the acid dianhydride monomer was not sufficiently dissolved due to the short charging time interval of the divided charging.

Examples 2-1 to 2-4
A polyamic acid resin was produced under the same conditions as in Comparative Example 4 except for the charging time interval of the divided charging of the acid dianhydride monomer in Table 2 below.
That is, as the composition shown in Table 2 below, a diamine-containing solution was prepared by adding the same amount of the diamine compound monomers PPD and TFMB as in Comparative Example 1 to the same amount of NMP as the organic solvent to prepare nitrogen. It was dissolved in an atmosphere at room temperature for 30 minutes to 1 hour.
The same amount of BPDA, which is an acid dianhydride monomer, was added to the diamine-containing solution at the number of divided additions (5 times) and the divided addition time interval (minutes) shown in Table 2, and the mixture was stirred for 6 hours to obtain a polyamic acid resin. (Polymerization temperature: 23 ° C., at this time, the solid content was maintained so as to be 15% by weight based on the total weight of the reaction solvent).

<Experimental example 2: Measurement of physical properties>
A polyimide resin film was produced by the same method as in Experimental Example 1, the physical properties were measured, and the results are shown in Table 2 below.

As shown in Table 2 above, the number of divided injections of the acid dianhydride monomer was fixed at 5 times, and the optimization of the divided charging time interval was evaluated. In Comparative Examples 4 and 5, the charged acid dianhydride monomer is not sufficiently dissolved because the divided charging time interval is short. Therefore, it was not possible to produce a polyamic acid resin having good characteristics.

On the other hand, as in Examples 2-1 to 2-4, when the monomer of the acid dianhydride monomer is added at a time interval of 30 to 60 minutes, the added acid dianhydride is added. The monomer was sufficiently dissolved, and a polyamic acid resin having good characteristics was obtained.

As can be seen in the characteristic results of Examples 2-1 to 2-4, the divided charging time intervals in which the acid dianhydride monomer can be sufficiently dissolved are at the same level regardless of the increase in the divided charging time intervals. Shows the characteristics of. From this result, it is appropriate that the split charging time interval of the monomer of the acid dianhydride monomer is 30 to 60 minutes, preferably 30 minutes.

<Polymerization temperature>
Examples 2-1 and 2-5 to 2-7, and Comparative Example 6
A polyamic acid resin was produced by the same method as in Example 1 except for the polymerization temperature and the acid dianhydride excess molar ratio shown in Table 3 below.

<Experimental example 3: Measurement of physical properties>
A polyimide resin film was produced by the same method as in Experimental Example 1, the physical properties were measured, and the results are shown in Table 3 below.

As shown in Table 3 above, the number of times the acid dianhydride monomer was added (5 times) and the addition time interval (30 minutes) were fixed, and the optimization of the polymerization temperature was evaluated. As seen in the results of Examples 2-5 to 2-7 as compared with Example 2-1 by decreasing the acid dianhydride overdose molar ratio while increasing the polymerization temperature, while exhibiting the same level of viscosity. However, the heat resistance and mechanical properties increased. It can be seen that the same level of characteristics is exhibited at the polymerization temperature of 40 to 60 ° C. in Examples 2-5 to 2-7. On the other hand, as seen in the results of Comparative Example 6, at a polymerization temperature of 70 ° C., the acid dianhydride excess molar ratio was small, and despite having the same level of viscosity, Examples 2-5-2. The characteristics are lower than -7. From this result, the polymerization temperature is appropriately 40 to 60 ° C, preferably 40 ° C.

From the above results, after dissolving the diamine compound monomer in an organic solvent, the acid dianhydride monomer is added in 4 or more divided portions at a polymerization temperature of 40 to 60 ° C., but at intervals of 30 to 60 minutes. In the case of the polyamic acid resin obtained by charging and polymerizing with a time difference of the above, it can be seen that a polyimide resin film having easy laser peeling and high heat resistance can be produced.

<Reference example>
Comparative Example 7
The compositions shown in Table 4 below include TFMB 41, which is a diamine compound monomer. 630 g (0.130 mole) was placed in NMP 455.04 g, which is an organic solvent, and dissolved in a nitrogen atmosphere at room temperature for 30 minutes to 1 hour. Then, BPDA, which is an acid dianhydride monomer, 38. 837 g (0.132 mole) was added in 5 portions and stirred for 6 hours to produce a polyamic acid resin (polymerization temperature: 60 ° C./6 hours followed by 25 ° C., at which time the solid content was the total weight of the reaction solvent. As a result of measurement with a viscosity measuring device (Blockfield DV2T, SC4-27), the viscosity was 6,000 cP.

Comparative Example 8
As the composition shown in Table 4 below, PPD 21.3 04 g (0.197 mole), which is a diamine compound monomer, was added to NMP 455.04 g, which is an organic solvent, and dissolved in a nitrogen atmosphere at room temperature for 30 minutes to 1 hour. To prepare a diamine-containing solution. Then, BPDA, which is an acid dianhydride monomer, 58. 844 g (0.200 mole) was added in 5 portions and stirred for 6 hours to produce a polyamic acid resin (polymerization temperature: 60 ° C./6 hours followed by 25 ° C., at which time the solid content was the total weight of the reaction solvent. It is maintained so as to be 15% by weight.) As a result of measurement with a viscosity measuring device (Blockfield DV2T, SC4-27), the viscosity was 6,100 cP.

Example 4
The compositions shown in Table 4 below include PPDs, which are diamine compound monomers. 681 g (0.182 mol), TFMB 3. 202 g (0.010 mole) was placed in NMP 455.04 g, which is an organic solvent, and dissolved in a nitrogen atmosphere at room temperature for 30 minutes to 1 hour. Then, BPDA 57., Which is an acid dianhydride monomer. 373 g (0.195 mole) was added in 5 portions and stirred for 6 hours to produce a polyamic acid resin (polymerization temperature: 40 ° C./6 hours followed by 25 ° C., at which time the solid content was the total weight of the reaction solvent. It is maintained so as to be 15% by weight.) As a result of measurement with a viscosity measuring device (Blockfield DV2T, SC4-27), the viscosity was 5,800 cP.

Example 5
As the composition shown in Table 4 below, PPD 18.2 76 g (0.169 mol) and TFMB 6.0 84 g (0.019 mole), which are diamine compound monomers, were added to NMP 455.04 g, which is an organic solvent. , Nitrogen atmosphere, dissolved at room temperature for 30 minutes to 1 hour. Then, 55.9 01 g (0.190 mole) of BPDA, which is an acid dianhydride monomer, was added in 5 portions and stirred for 6 hours to produce a polyamic acid resin (polymerization temperature: 60 ° C. / 6 hours stirring). Later, at 25 ° C., the solid content is maintained at 15% by weight based on the total weight of the reaction solvent). As a result of measurement with a viscosity measuring device (Blockfield DV2T, SC4-27), the viscosity was 5,300 cP.

Example 6
As a composition shown in Table 4, was placed a diamine compound monomer PPD 8.4 35 g (0.078mol), TFMB 2 4.978 g of (0.078mole) in NMP 455.04G an organic solvent , Nitrogen atmosphere, dissolved at room temperature for 30 minutes to 1 hour. Then, BPDA 46.7 81 g (0.159 mole), which is an acid dianhydride monomer, was added in 5 portions and stirred for 6 hours to produce a polyamic acid resin (polymerization temperature: 60 ° C. / 6 hours stirring). Later, at 25 ° C., the solid content is maintained at 15% by weight based on the total weight of the reaction solvent). As a result of measurement with a viscosity measuring device (Blockfield DV2T, SC4-27), the viscosity was 5,500 cP.

Example 7
As the composition shown in Table 4 below, 21.304 g (0.197 mol) of PPD as a diamine compound monomer and 3.202 g (0.010 mole) of TFMB were added to 455.04 g of NMP as an organic solvent, and a nitrogen atmosphere was formed. It was dissolved at room temperature for 30 minutes to 1 hour. Then, 37.071 g (0.126 mole) of BPDA and 18.322 g (0.084 mol) of PMDA, which are acid dianhydride monomers, were added in 5 portions and stirred for 6 hours to produce a polyamic acid resin (). Polymerization temperature: 60 ° C./25 ° C. after stirring for 24 hours, at which time the solid content is maintained so as to be 15% by weight based on the total weight of the reaction solvent). As a result of measurement with a viscosity measuring device (Blockfield DV2T, SC4-27), the viscosity was 5,900 cP.

<Experimental example 4: Measurement of physical properties>
A polyimide resin film was produced by the same method as in Experimental Example 1, the physical properties were measured, and the results are shown in Table 4 below.

As shown in Table 4, in the case of Examples 4 to 7 containing 5 to 50 mol% of 2,2'-bis (trifluoromethyl) -benzidine (TFMB), the adhesive force to the glass substrate is 0.5. It can be confirmed that it is ~ 2.0 (N / cm). The adhesive strength can be adjusted by adjusting the content of TFMB, the adhesive strength can be adjusted to the glass substrate, and curl and product defects can be minimized at the time of peeling.

In addition, since it can be peeled off with low energy during laser peeling, it can be peeled off without damaging the polyimide resin film. Moreover, it can be confirmed that it is also excellent in heat resistance and mechanical aspects. In Comparative Example 7, the adhesive strength is less than 0.2 (N / cm) and the adhesive strength is too weak, and in Comparative Example 8, the adhesive strength is 2.3 (N / cm) and the adhesive strength is high. too strong. Moreover, since the laser peeling energy is too high, the polyimide resin film may be damaged at the time of peeling. Thus, if the adhesive strength is too weak or too strong, it will lead to curl or product defects during film peeling.

Therefore, the polyamic acid resin produced by the present invention has an adhesive strength of 0.2 to 2.0 N / cm, a peeling energy of 200 mJ / cm ² or less, and a coefficient of thermal expansion of 10 ppm / ° C or less in the range of 100 to 350 ° C. It can be provided as a polyimide resin film characterized by being present.

Based on the above results, the polyamic acid resin of the present invention produced by monomer division charging, charging time adjustment and optimization of polymerization temperature has low viscosity, excellent mechanical properties, heat resistance and low heat. Since it has an expansion coefficient, maintains an appropriate adhesive force, and can be laser-peeled with low energy, it does not cause curl or product defects during peeling, and can be widely used as an adhesive film on a glass substrate of an organic light emitting diode. ..

Claims (5)

A polyamic acid produced by polymerizing the diamine compound monomer and the acid dianhydride monomer in a composition containing a diamine compound monomer, an acid dianhydride monomer, and an organic solvent. It is a resin manufacturing method
In the polyamic acid resin, the diamine compound monomer is dissolved in the organic solvent to prepare a diamine-containing solution, and then the acid dianhydride monomer is added to the diamine-containing solution at intervals of 30 minutes. It was added in 5 portions and polymerized at a temperature of 40 ° C., and the diamine compound monomer contained 5 to 50 mol% of fluorinated aromatic diamine and 50 to 95 mol% of non-fluorinated aromatic diamine. The acid dianhydride monomers are 50 to 90 mol% of 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and 10 to 50 mol% of pyromelitoic acid dianhydride (PMDA). including the door, and wherein the method of polyamides acid resin. It is characterized in that 2,2'-bis (trifluoromethyl) -benzidine (2,2'-bis (trifluoromethyl) benzidine) is contained in 100 mol% of the diamine compound monomer in an amount of 5 to 50 mol%. The method for producing a polyamic acid resin according to claim 1. The method for producing a polyamic acid resin according to claim 1, wherein the viscosity of the polyamic acid resin is set to 1,000 to 7,000 cp. A method for producing a polyimide resin film, which is produced by coating a substrate with a polyamic acid resin produced by any of the production methods of claims 1 to 3 and heat-treating the substrate. The method for producing a polyimide resin film according to claim 4 , wherein the adhesive force is 0.2 to 2.0 N / cm and the peeling energy is 200 mJ / based on the produced polyimide resin film thickness of 10 to 15 μm. A method for producing a polyimide resin film, characterized in that the coefficient of thermal expansion in the range of 100 to 350 ° C. of ^{cm 2} or less is 10 ppm / ° C. or less.

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