JP2012021133A - Low temperature curable polyimide resin and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide resin which is curable at a low temperature ranging from 150 to 250°C, by polymerization reaction of diamine and dianhydride in the presence of a solvent having a boiling point of 130-180°C.SOLUTION: Because the polyimide resin is curable even at a low temperature, when the polyimide resin is used as an electronic material, damage to equipment due to a high temperature process can be minimized. In addition, the polyimide resin can be intensively used as an electronic material such as for a plastic substrate.

Description

  The present invention relates to a polyimide resin and a method for producing the same, and more particularly to a polyimide resin capable of being cured at a low temperature and a method for producing the same.

  In recent years, in the field of semiconductor elements such as semiconductors and liquid crystal display elements, with the rapid diffusion of movements such as higher integration, higher density, higher reliability, and higher speed of electronic elements, workability and high purity Research has been actively conducted to use the advantages of organic materials that are easy to make.

  In particular, polyimide resin has good flattening characteristics of the coating surface in addition to excellent electrical characteristics such as high heat resistance, excellent mechanical strength, low dielectric constant, and high insulation, and reduces device reliability. There is an advantage that the content of impurities is very low and it can be easily made into a fine shape. In recent years, photosensitive insulating films including photosensitive resins containing them have been used not only for semiconductors but also for displays. It has expanded to the field.

  In general, as a method for synthesizing polyimide, polar organic solvents such as N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc) and dimethylformamide (DMF) are used as a two-stage condensation polymerization in which a diamine component and a dianhydride component are used. There is a method in which a polyimide precursor solution is obtained by polymerizing in, and this is coated on a silicon wafer or glass and then cured by heat treatment at a high temperature.

  Commercialized polyimide products for electronic materials are supplied in a polyimide precursor solution or polyimide film state, and are mainly supplied in a polyimide precursor solution state in the field of semiconductor devices.

  However, the method for producing such a polyimide polymer requires a high curing temperature (300 ° C. or higher), and thus has a problem that it cannot be used in a heat-fragile process. There is a problem that it is difficult to completely convert the polyimide precursor solution into polyimide.

  In order to solve such problems, in the conventional process, a polymerization method in which chemical imidization is performed in a liquid state using a catalyst has been developed. However, such a process still requires a high-temperature process. Of course, since the high-boiling point solvent is used as it is in the solvent, there is a problem that after the polymerization step, a high-temperature curing step must be performed again to remove the solvent.

  In addition, in order to increase the production efficiency by performing a high-temperature heat treatment for the production of the polyimide resin, there is a problem that the heat equipment is enlarged.

  The present invention has been made to solve the above-mentioned problems of the prior art, and the inventors have used a low-boiling solvent in the polyimide production process, or have a low boiling point and a low boiling point solvent together with the low-boiling solvent. By adding a highly reactive amine-based catalyst, it was found that polyimide can be produced even at low temperatures, and the low-temperature polyimide produced by such a method still has excellent properties in heat resistance and workability. The present invention was completed by confirming that it was held.

  An object of the present invention is to provide a method for producing a polyimide resin that can be imidized even at a low temperature using a low boiling point solvent.

  Another object of the present invention is to provide a method for producing a polyimide resin that can be imidized even at a low temperature by using a low boiling point and highly reactive specific catalyst together with the low boiling point solvent.

  Another object of the present invention is to provide a photosensitive composition and a printing ink composition containing the polyimide resin.

  It is another object of the present invention to provide a polyimide resin that can be cured at a low temperature.

  The method for producing the polyimide resin of the present invention for achieving the above object may include a step of polymerizing the polyimide resin using a low boiling point solvent having a boiling point of 130 to 180 ° C.

  Examples of the low boiling point solvent include diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether propionate, diethylene glycol One or more selected from the group consisting of propylene glycol dimethyl ether, cyclohexanone and propylene glycol monomethyl ether acetate (PGMEA).

  The low boiling point solvent is included, for example, in an amount of 20 to 2000 parts by weight with respect to 100 parts by weight of a monomer for producing a polyimide resin.

  According to the method of the present invention, the polyimide can directly produce a polyimide resin without passing through the production step of the polyamic acid precursor.

  The polyimide resin can be produced in the presence of a catalyst having a boiling point of 60 to 100 ° C.

  The catalyst is at least one selected from the group consisting of N, N-diethylmethylamine, N, N-dimethylisopropylamine, N-methylpyrrolidine, pyrrolidine, and triethylamine, for example. .

  The catalyst is included, for example, in an amount of 0.5 to 30 parts by weight with respect to 100 parts by weight of diamine and dianhydride as starting materials for polyimide resin.

  According to the method of the present invention, the polymerization can be performed at a temperature of 120 to 200 ° C.

The polyimide resin is
For example,
And one or more aromatic diamines selected from the group consisting of dihydric organic groups such as divalent organic groups derived from 3,5-diaminobenzoic acid, such as phenolic hydroxyl groups, carboxyl groups or hydroxyl groups; p-phenylenediamine M-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4' -Methylene-bis (2-methylaniline), 4,4'-methylene-bis (2,6-dimethylaniline), 4,4'-methylene-bis (2,6-diethylaniline), 4,4'- Tylene-bis (2-isopropyl-6-methylaniline), 4,4'-methylene-bis (2,6-diisopropylaniline), 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine O-tolidine, m-tolidine, 3,3 ′, 5,5′-tetramethylbenzidine, 2,2′-bis (trifluoromethyl) benzidine, 1,4-bis (4-aminophenoxy) benzene, , 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl ] One or more aromatics selected from the group consisting of sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 2,2-bis [4- (3-aminophenoxy) phenyl] propane Group diamine; 1,6-hexanediamine, 1, -Cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4'-diaminodicyclohexylmethane, and 4,4'-diamino- 3,3′-dimethyldicyclohexylmethane and 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 1,2-bis- (2-aminoethoxy) ethane, bis (3-aminopropyl) ether, 4-Bis (3-aminopropyl) piperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3-bis (3-amino One or more diamines selected from the group consisting of one or more aliphatic diamines selected from the group consisting of (propyl) tetramethyldisiloxane can be used as starting materials.

  Examples of the polyimide resin include pyromellitic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride, and 3,3. ', 4,4'-Benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4 '-Benzophenonetetracarboxylic dianhydride, 4,4'-hexafluoroisopropylidene diphthalic anhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,2,3, 4-Cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-si Clobutanetetracarboxylic dianhydride 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2,3,4-cyclopentanetetracarboxylic dianhydride Anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2, 5-Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, bicyclo [2.2. 2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride and 3,5,6-tricarboxy-2- From the group consisting of one or more acid anhydrides selected from the group consisting of norbornane acetic dianhydride and derivatives thereof One or more dianhydrides Bareru can be used as a starting material.

  The present invention can provide a polyimide resin produced using a low boiling point solvent having a boiling point of 130 to 180 ° C. in order to achieve the other object.

  The glass transition temperature of the polyimide is preferably 150 to 400 ° C.

  The polyimide resin preferably has a weight average molecular weight of 1,000 to 100,000.

  The amount of residual catalyst in the polyimide resin is preferably 0.001 to 0.1% by weight with respect to the total weight of the polyimide resin.

  In order to achieve the above and other objects, the present invention can provide a photosensitive resin composition that can be cured at a low temperature and includes a polyimide resin produced by the method as described above.

  The photosensitive resin composition can be cured at 150 to 250 ° C.

  The photosensitive resin composition is characterized in that no residual solvent is present in the photosensitive resin composition after curing.

  The photosensitive resin composition is characterized in that after curing, the residual solvent in the photosensitive resin composition is less than 0.05% by weight.

  The photosensitive film using the photosensitive resin composition is characterized in that it can be removed by EBR solvent (edge bead removable solvent) after pre-baking.

  The photosensitive resin composition is characterized in that it is dissolved without precipitation when drain is mixed.

  Moreover, this invention can provide the ink composition for printing containing the polyimide resin manufactured by the said method.

  In order to achieve the above and other objects, the present invention can provide a printing ink composition containing a polyimide resin produced by the above method.

  In addition, the present invention can provide an OLED, an LCD, or a semiconductor insulating film manufactured by including the photosensitive resin composition.

  In addition, it is possible to provide an OLED, an LCD, or a semiconductor insulating film manufactured by including the printing ink composition.

  According to the present invention, a polyimide resin can be directly produced by using a low boiling point solvent without including a production step of a polyamic acid as a polyimide precursor.

  In addition, since the polyimide resin manufactured in this way can be cured even at a low temperature, when used as an electronic material, damage to equipment due to a high-temperature process can be minimized, and also used for a plastic substrate or the like. Therefore, it can be used more widely as an electronic material.

  The polyimide resin produced by the production method of the present invention has sufficient mechanical strength, excellent workability, and high production efficiency. Therefore, not only photosensitive resin compositions for various displays but also printing ink compositions. There is an advantage that it can be used for things.

  When the polyimide resin according to the present invention is contained in a photosensitive resin composition and used as a photosensitive film of an electronic material, it can be easily removed even at a low temperature by EBR solvent after preliminary baking.

  In addition, the photosensitive resin composition containing the polyimide resin which concerns on this invention has the characteristics that it melt | dissolves without generation | occurrence | production of precipitation at the time of mixing of a drain.

It is an analysis graph of the amount of residual solvents after hardening of the photosensitive resin composition by the Example of this invention. It is an analysis graph of the amount of residual solvents after hardening of the photosensitive resin composition by the comparative example of this invention.

  Hereinafter, this embodiment will be described in more detail. The terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting of the invention. As used herein, the singular forms may include the plural forms unless the context clearly indicates a particular case.

  Also, as used herein, “comprising” is to identify the presence of the mentioned shape, number, step, action, member, element and / or group thereof, It does not exclude the presence or addition of other shapes, numbers, actions, members, elements and / or groups.

  In the present embodiment, when a polyimide resin is produced by reacting diamine and dianhydride, by using a specific catalyst and a solvent having a low boiling point, not only low-temperature curing is possible, but also a soluble polyimide resin is produced. be able to.

  The polyimide resin of this embodiment is not a polyamic acid precursor produced from a diamine and a dianhydride as in the prior art, and is cured at a high temperature to produce a polyimide film. The polyimide resin is produced directly from

  This is characterized in that a low boiling point solvent having a boiling point of 130 to 180 ° C. is used in this embodiment in order to enable the synthesis of the polyimide resin even at a low temperature.

  Usually, the synthesis | combination of the polyimide resin manufactured the polyamic-acid precursor, and manufactured this by making it harden at the high temperature of 320 degreeC or more. However, in the present embodiment, the polyimide resin is directly produced without passing through the polyamic acid precursor stage, but a low-boiling solvent is used as described above in order to synthesize the polyimide resin at a temperature lower than the conventional one.

  As described above, specific examples of the low boiling point solvent having a boiling point of 130 to 180 ° C. include diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, methyl 3-methoxypropionate, ethyl 3 -One or more selected from the group consisting of ethoxypropionate, propylene glycol methyl ether propionate, dipropylene glycol dimethyl ether, cyclohexanone and propylene glycol monomethyl ether acetate (PGMEA), or the boiling point of the above temperature range Any low boiling point solvent may be used, and the present invention is not limited to this.

  When the boiling point of the solvent according to this embodiment is less than 130 ° C., there is a possibility that the conversion rate is lowered without sufficient energy in the production of polyimide, and when the boiling point of the solvent exceeds 180 ° C., Since the solvent remains unless a higher temperature of 200 ° C. or higher is applied during curing, it is not desirable because there is a problem that it is difficult to lower the curing temperature.

  The low boiling point solvent may be included in an amount of 20 to 2000 parts by weight, preferably 100 to 1000 parts by weight, and most preferably 200 to 400 parts by weight based on 100 parts by weight of the total monomer containing diamine and dianhydride. If the content is less than 20 parts by weight, polyimide cannot be sufficiently dissolved, and if it exceeds 2000 parts by weight, there is a problem that a coating film having a sufficient thickness cannot be formed when applied to a substrate. Absent.

  In this embodiment, a low boiling point catalyst may be included during the production of the polyimide resin.

  The catalyst is preferably a catalyst that can be imidized at a low temperature and can be easily removed after the reaction, and has a low boiling point and high reactivity.

  Specifically, the catalyst has a boiling point of 60 to 120 ° C, desirably 70 to 100 ° C, and most desirably 80 to 90 ° C. When the boiling point of the catalyst is very low below 60 ° C., it is undesirable to evaporate all during polymerization, and when it exceeds 120 ° C., a highly reactive catalyst remains after completion of the reaction, thereby producing a composition. May cause side reactions.

  Specific examples of the catalyst according to the embodiment include N, N-diethylmethylamine, N, N-dimethylisopropylamine, N-methylpyrrolidine, pyrrolidine, and triethylamine. Although it is 1 or more types chosen from more, it is not limited to this.

  The catalyst is 0.5 to 30 parts by weight, preferably 2 to 20 parts by weight, most preferably 5 to 10 parts by weight based on 100 parts by weight of the total monomer containing the diamine and dianhydride used for the synthesis of the polyimide resin. When the content of the catalyst is less than 0.5 parts by weight, the amount of catalyst is insufficient and the conversion rate to polyimide decreases, and when it exceeds 30 parts by weight, residual unreacted catalyst remains. This is not desirable because of the possibility of an addition reaction due to.

  Further, the diamine and dianhydride of the monomer used in the polyimide resin of the present embodiment are not particularly limited as long as they are used at the time of production of a normal polyimide resin, but are selected according to a predetermined use. Can be used.

  For example, acid anhydrides or derivatives thereof include pyromellitic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetra Carboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′ 4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-hexafluoroisopropylidene diphthalic anhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclo Pentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo [2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, and 3,5,6 One or more acid anhydrides selected from the group consisting of 2-tricarboxy-2-norbornaneacetic acid dianhydride and derivatives thereof, It is below.

Aromatic and aliphatic diamines can be used as the diamine, and specific examples of the diamine compound include:
And one or more aromatic diamines selected from the group consisting of dihydric organic groups such as divalent organic groups derived from 3,5-diaminobenzoic acid, such as phenolic hydroxyl groups, carboxyl groups or hydroxyl groups; p-phenylenediamine M-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4' -Methylene-bis (2-methylaniline), 4,4'-methylene-bis (2,6-dimethylaniline), 4,4'-methylene-bis (2,6-diethylaniline), 4,4'- Tylene-bis (2-isopropyl-6-methylaniline), 4,4'-methylene-bis (2,6-diisopropylaniline), 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine O-tolidine, m-tolidine, 3,3 ′, 5,5′-tetramethylbenzidine, 2,2′-bis (trifluoromethyl) benzidine, 1,4-bis (4-aminophenoxy) benzene, , 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl ] One or more aromatics selected from the group consisting of sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 2,2-bis [4- (3-aminophenoxy) phenyl] propane Group diamine; 1,6-hexanediamine, 1, -Cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4'-diaminodicyclohexylmethane, and 4,4'-diamino- 3,3′-dimethyldicyclohexylmethane 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 1,2-bis- (2-aminoethoxy) ethane, bis (3-aminopropyl) ether, 1,4 -Bis (3-aminopropyl) piperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] -undecane, 1,3-bis (3-amino One or more aliphatic diamines selected from the group consisting of (propyl) tetramethyldisiloxane can be mentioned, and the aromatic and aliphatic diamines can be used in a mixed manner, but are not limited thereto.

  On the other hand, the polymerization of the polyimide resin according to this embodiment can be performed at a low temperature of 120 to 200 ° C., desirably 130 to 180 ° C., most desirably 140 to 160 ° C. When the polyimide is produced in the above-described process, the conversion is 90 to 100% at the time of polymerization, and the residual catalyst amount in the polyimide resin is 0.001 to 0.1% by weight in the total polyimide resin. It is desirable.

  The method for producing the polyimide according to the present embodiment can confirm that the conversion rate is high and the amount of residual catalyst in the final produced polyimide resin is small despite polymerization at a relatively low temperature. It can be seen that the polyimide resin can be effectively produced by the production method according to the embodiment.

  The polyimide resin according to the present embodiment manufactured through such a series of processes can be cured at a low temperature in a temperature range of 150 to 250 ° C. and is soluble.

  As a result, the conventional process is difficult due to the curing of polyimide at a high temperature of 320 ° C. or higher, and the process cannot be used in a process that is vulnerable to heat, and the polyimide resin from the polyamic acid precursor solution even after high temperature curing. Can solve problems such as low conversion rate.

  In general, a polyimide resin is known to have extremely limited solubility in a solvent, whereas a polyimide resin manufactured according to the present embodiment can be soluble in a solvent having low solubility.

  Usually, a polyimide has a very low solubility, and in order to have solubility, a monomer capable of imparting a soluble function must be introduced. In this case as well, it tends to be easily dissolved by a high boiling point solvent having high polarity.

  However, the low-temperature curable polyimide according to this embodiment has excellent solubility characteristics, and has excellent solubility in a low boiling point solvent such as a solvent having a boiling point of 130 to 180 ° C. used in this embodiment.

  Therefore, in order to make an imide ring, it is not necessary to imidize at a high temperature after coating, and a polyimide film can be obtained by removing only the solvent. In addition, since it has already been chemically imidized, it has a high conversion rate, and there is no problem that the reliability of the device decreases due to out-gassing generated from a polyamic acid or a polyamic acid ester that is not imidized. . In particular, when a low-boiling solvent is used, the temperature can be lowered according to the boiling point of the solvent, and it can be applied to an element process that requires a low-temperature process. There is an advantage that a thin film having safety can be formed.

  The glass transition temperature of the polyimide resin according to this embodiment is, for example, 150 to 400 ° C. The polyimide resin has a weight average molecular weight of 1,000 to 500,000, desirably 5,000 to 100,000.

  A photosensitive resin composition that can be cured at a low temperature, including the polyimide resin produced by the method as described above, can be provided, and can be cured at a low temperature of 150 to 250 ° C.

  Further, in the photosensitive resin composition according to the present embodiment, after curing, the residual solvent amount in the photosensitive resin composition is less than 0.05% by weight, and more desirably, after curing, the photosensitive resin composition. There is no residual solvent in (0% by weight).

  A photosensitive film using the photosensitive resin composition is characterized in that it can be easily removed by EBR solvent after preliminary baking. This is not used for normal polyimide polymerization, but for ordinary photoresists, polymerization is performed using a general-purpose solvent such as a glyme solvent, propionate, or PGMEA, and a general-purpose EBR solvent is used. It is easy to remove at low temperatures.

  Therefore, in other semiconductor lines and display lines such as OLEDs and LCDs, it can be removed with a common solvent used for rework during the manufacturing process, and precipitation that occurs when drains are mixed is used. It has a feature that it can be dissolved without being generated to prevent clogging of piping.

  In the case of a printing composition, it is impossible to use a solvent such as NMP, GBL, DMAc, or DMF that is used for normal polymerization of a polymer, but the polymer resin of this embodiment uses such a solvent. Therefore, it can be advantageously used in a printing ink composition.

  In conclusion, the polyimide resin according to this embodiment can be used as a binder resin for photosensitive resin compositions and printing ink compositions of various electronic materials including OLEDs and LCDs, but is not limited thereto. Not.

  Therefore, the present embodiment can provide a polyimide film manufactured by including the photosensitive resin composition and a polyimide film manufactured by including the printing ink composition. An OLED, LCD or semiconductor insulating film manufactured using the same can be provided.

(Embodiment)
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited by these Examples.

(Example 1: Polymerization example of low-temperature polyimide)
To a 100 ml round bottom flask, 12.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 60 g of propylene glycol monomethyl ether acetate were sequentially added, and slowly stirred until completely dissolved. Thereafter, 10.2 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride was slowly added while maintaining the flask at room temperature with a water bath. 11 g of toluene and 4 g of triethylamine were added to the mixed solution, and the mixture was provided so that water could be removed by a Dean-Stark distillation apparatus, and then refluxed at 150 ° C. for 5 hours. After removing water from the Dean-Stark distillation apparatus, the mixture was refluxed for 2 hours to remove the catalyst, and cooled at room temperature to obtain a soluble polyimide solution.

  The production peak of polyimide was confirmed by IR, and the weight average molecular weight of the polyimide resin measured by GPC was 40,000, and the polydispersity index (PDI) was 1.5.

(Example 2: Polymerization example of low-temperature polyimide)
To a 100 ml round bottom flask, 12.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 60 g of propylene glycol monomethyl ether acetate were sequentially added, and slowly stirred until completely dissolved. Thereafter, 6.5 g of butane-1,2,3,4-tetracarboxylic dianhydride was slowly added while maintaining the flask at room temperature with a water bath. 11 g of toluene and 4 g of triethylamine were added to the mixed solution, and the mixture was provided so that water could be removed by a Dean-Stark distillation apparatus, and then refluxed at 150 ° C. for 5 hours. After removing water from the Dean-Stark distillation apparatus, the mixture was refluxed for 2 hours to remove the catalyst, and cooled at room temperature to obtain a soluble polyimide solution.

  The production peak of polyimide was confirmed by IR, and the weight average molecular weight of the polyimide resin measured by GPC was 35,000, and the polydispersity index was 1.7.

(Comparative example 1: Polymerization example of high temperature polyimide)
Into a 100 ml round bottom flask, 12.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 60 g of γ-butyrolactone were sequentially added, and stirred slowly until completely dissolved. While maintaining the flask at room temperature with a water bath, 10.2 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride was slowly added. After stirring the mixed solution for 16 hours at room temperature, 7 g of toluene was added, and water was removed by Dean-Stark, followed by refluxing at 180 ° C. for 3 hours. After removing water from the Dean-Stark distillation apparatus, the mixture was refluxed for 2 hours to remove the catalyst, and cooled at room temperature to obtain a soluble polyimide solution.

  The formation peak of polyimide was confirmed by IR, and the weight average molecular weight of the polyimide resin measured by GPC was 40,000, and the polydispersity index was 1.6.

(Comparative example 2: Polymerization example of polyimide precursor)
After sequentially charging 73.3 g of 4,4′-oxydianiline and 300 g of γ-butyrolactone into a 1 L round bottom jacketed reactor, the mixture was slowly stirred and completely dissolved, and then the jacket temperature of the reactor was adjusted to 20%. While maintaining the temperature at 5 ° C., 55.8 g of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride was slowly added and stirred. The mixed solution was stirred for 2 hours to sufficiently react and then further stirred at room temperature for 16 hours to produce polyamic acid. The formation peak of polyamic acid was confirmed by IR, and the weight average molecular weight of the polyimide resin measured by GPC was 50,000, and the polydispersity index was 1.6.

(Experiment 1)
1. Evaluation of imidization rate
-Prebaked at 120 ° C for 4 minutes, then hardbaked at 250 ° C for 1 hour, and measured using FT-IR in each case.
-The integrated value of CN band of each sample cured at 300 ° C for 1 hour was assumed to be a conversion rate of 100%, and the imidization rate was confirmed by the integrated value of CN band of the sample cured under each curing condition.

  From the results in Table 1, in the case of Examples 1 and 2 in which polyimide resin was directly produced at a low temperature as in the method of the present embodiment, is the imidization rate maintained equivalent to that in Comparative Example 1 produced at high temperature? Or rather, it turns out to be excellent.

2. Analysis of residual catalyst amount
: Quantitative analysis of residual catalyst amount by GC-MS analysis is shown in Table 2 below.

  From Table 2, it can be seen that when a low-boiling point catalyst is used as in this embodiment, the amount of catalyst remaining in the polyimide resin is significantly reduced compared to Comparative Example 1. From such a result, it turns out that it is effective to manufacture a polyimide resin like the method of this embodiment.

(Example 3: Production example of photosensitive resin composition (polyimide composition))
A diazonaphthoquinone ester compound (1.6 mg of TPPA 320: OD / (OD + OH) = 2/3 is selectively given as a photoactive compound) to 1.6 g of the soluble polyimide synthesized in Example 1 above. 0.5 g and 4 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent were added, and the mixture was stirred at room temperature for 1 hour, and then filtered through a filter having a pore size of 1 μm to produce a photosensitive resin composition. did.

(Comparative Example 3: Production Example of Photosensitive Resin Composition (Polyimide Composition))
A diazonaphthoquinone ester compound (1.6 mg of TPPA 320: OD / (OD + OH) = 2/3 is selectively given as a photoactive compound) to 1.6 g of the soluble polyimide synthesized in Comparative Example 1) 0.5 g and 4 g of γ-butyrolactone (GHL) were added, and the mixture was stirred at room temperature for 1 hour, and then filtered through a filter having a pore size of 1 μm to produce a photosensitive resin composition.

(Experimental example 2: Analysis of residual solvent amount)
: Analyze residual solvent using a Charge & Trap-GC / MSD instrument.
After coating the composition of Example 3 and Comparative Example 3 on the substrate, it was pre-baked at 120 ° C. for 2 minutes and hard baked at 200 ° C. for 1 hour to form a coating film. The amount of the solvent collected in the coating film at 280 ° C. after 2 hours, 3 hours and 4 hours was analyzed and shown in FIGS.

  FIG. 1 is an analysis graph of the amount of residual solvent according to Example 3, and FIG. 2 is an analysis graph of the amount of residual solvent according to Comparative Example 3. As shown in FIG. 1, in the case of Example 3, it was confirmed that there was no peak due to the residual solvent, and only the peak due to the decomposition of the composition was confirmed. On the other hand, in FIG. 2, it can be seen that the peak due to the residual solvent confirms the GBL peak at 280 ° C. for 4 hours.

Claims (23)

  A method for producing a polyimide resin, comprising polymerizing a polyimide resin using a low boiling point solvent having a boiling point of 130 to 180 ° C.   The low boiling point solvent is diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propylene glycol methyl ether propionate, dipropylene glycol 2. The method for producing a polyimide resin according to claim 1, wherein the polyimide resin is one or more selected from the group consisting of dimethyl ether, cyclohexanone and propylene glycol monomethyl ether acetate (PGMEA).   The method for producing a polyimide resin according to claim 1 or 2, wherein the low boiling point solvent is contained in an amount of 20 to 2000 parts by weight with respect to 100 parts by weight of a monomer for producing the polyimide resin.   4. The method for producing a polyimide resin according to claim 1, wherein the polyimide resin is produced directly without passing through the production step of the polyamic acid precursor. 5.   The said polyimide resin is manufactured in presence of a catalyst with a boiling point of 60-100 degreeC, The manufacturing method of the polyimide resin of any one of Claim 1 to 4 characterized by the above-mentioned.   The catalyst is at least one selected from the group consisting of N, N-diethylmethylamine, N, N-dimethylisopropylamine, N-methylpyrrolidine, pyrrolidine, and triethylamine. The manufacturing method of the polyimide resin of Claim 5.   The method for producing a polyimide resin according to claim 5 or 6, wherein the catalyst is contained in an amount of 0.5 to 30 parts by weight with respect to 100 parts by weight of diamine and dianhydride as starting materials for the polyimide resin.   The method for producing a polyimide resin according to any one of claims 1 to 7, wherein the polymerization includes a step performed at a temperature of 120 to 200 ° C. The polyimide resin is
And one or more aromatic diamines selected from the group consisting of dihydric organic groups such as divalent organic groups derived from 3,5-diaminobenzoic acid, such as phenolic hydroxyl groups, carboxyl groups or hydroxyl groups; p-phenylenediamine M-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4' -Methylene-bis (2-methylaniline), 4,4'-methylene-bis (2,6-dimethylaniline), 4,4'-methylene-bis (2,6-diethylaniline), 4,4'- Tylene-bis (2-isopropyl-6-methylaniline, 4,4'-methylene-bis (2,6-diisopropylaniline), 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o-tolidine, m-tolidine, 3,3 ′, 5,5′-tetramethylbenzidine, 2,2′-bis (trifluoromethyl) benzidine, 1,4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] One or more aromatics selected from the group consisting of sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 2,2-bis [4- (3-aminophenoxy) phenyl] propane Diamine; 1,6-hexanediamine, 1, -Cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4'-diaminodicyclohexylmethane, and 4,4'-diamino- 3,3′-dimethyldicyclohexylmethane and 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 1,2-bis- (2-aminoethoxy) ethane, bis (3-aminopropyl) ether, 4-Bis (3-aminopropyl) piperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3-bis (3-amino 9. One or more diamines selected from the group consisting of one or more aliphatic diamines selected from the group consisting of (propyl) tetramethyldisiloxane are used as starting materials. Method for producing a polyimide resin according to.   The polyimide resin contains pyromellitic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′- Benzophenone tetracarboxylic dianhydride, 4,4′-hexafluoroisopropylidene diphthalic anhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 1,2,3,4- Cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobuta Tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5 -Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo [2.2.2 Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride and 3,5,6-tricarboxy-2-norbornane Selected from the group consisting of one or more acid anhydrides selected from the group consisting of acetic dianhydride and derivatives thereof The method of producing a polyimide resin according to any one of claims 1 to 8, which comprises using a seed or more dianhydride as the starting material.   The polyimide resin manufactured by the method of any one of Claim 1 to 10.   The polyimide resin according to claim 11, wherein a glass transition temperature of the polyimide is 150 to 400 ° C.   The polyimide resin according to claim 11 or 12, wherein the polyimide resin has a weight average molecular weight of 1,000 to 100,000.   14. The polyimide resin according to claim 11, wherein the amount of residual catalyst in the polyimide resin is 0.001 to 0.1% by weight in the total weight of the polyimide resin.   The photosensitive resin composition in which the low temperature hardening which contains the polyimide resin manufactured by the method of any one of Claim 1 to 10 is possible.   The photosensitive resin composition according to claim 15, wherein the photosensitive resin composition is curable at 150 to 250 ° C.   The photosensitive resin composition according to claim 15, wherein the photosensitive resin composition is free from residual solvent in the photosensitive resin composition after being cured.   The photosensitive resin composition according to any one of claims 15 to 17, wherein the photosensitive resin composition has a residual solvent amount of less than 0.05% by weight in the photosensitive resin composition after curing. Resin composition.   The photosensitive film according to any one of claims 15 to 18, wherein the photosensitive film using the photosensitive resin composition can be removed by EBR solvent (edge bead removable solvent) after prebaking. Resin composition.   The photosensitive resin composition according to any one of claims 15 to 19, wherein the photosensitive resin composition is dissolved without causing precipitation when the drain is mixed.   The ink composition for printing containing the polyimide resin manufactured by the method of any one of Claim 1 to 10.   21. An OLED, an LCD, or a semiconductor insulating film produced by including the photosensitive resin composition according to any one of claims 15 to 20.   An OLED, an LCD, or a semiconductor insulating film produced by including the printing ink composition according to claim 21.