KR20120007431A - Low Temperature Curing Polyimide Resin and Manufacturing Method Thereof - Google Patents

Abstract

The present invention In the method for producing a polyimide resin by reacting diamine and dianhydride, a polymer is polymerized in the presence of a solvent having a boiling point of 130 to 180 ° C to provide a polyimide resin capable of low temperature curing in a temperature range of 150 to 250 ° C.
The polyimide according to the method of the present invention can be cured even at low temperatures, so that when used as an electronic material, it is possible to minimize equipment damage caused by a high temperature process, and can also be used on a plastic substrate. Do.

Description

Low temperature curable polyimide resin and method of preparing the same

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

Recently, in the semiconductor device field mainly on semiconductors and liquid crystal display devices, as the movement of high integration, high density, high reliability, and high speed of electronic devices are rapidly spreading, there is an attempt to take advantage of the advantages of organic materials that are easy to process and high purity. Research is actively underway.

In particular, the polyimide resin has good flattening characteristics of the coating surface in addition to excellent electrical properties such as high heat resistance, excellent mechanical strength, low dielectric constant, and high insulation, and has a very low content of impurities that degrades the reliability of the device. There is an advantage that can be made, the use of a photosensitive insulating film including a photosensitive resin containing the same has recently been extended to the display field as well as semiconductor.

As a method of synthesizing polyimide, it is a two-stage condensation polymerization method in which the diamine component and the dianhydride component have the same polarity as N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc) and dimethylformamide (DMF). It is common to polymerize in an organic solvent to obtain a polyimide precursor solution, which is coated on a silicon wafer or glass and then cured by heat treatment at high temperature.

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

However, this method of preparing a polyimide polymer requires a high curing temperature (300 ° C. or higher) and thus cannot be used in a process that is susceptible to heat, and even after high temperature curing, the polyimide precursor solution is completely converted into polyimide. There is a difficult problem to switch.

In order to solve such a problem, a polymerization method for chemical imidization in a liquid phase using a catalyst has been developed in the conventional process, but such a process still requires a high temperature process, and the solvent also uses a high boiling point solvent as it is. In order to remove the solvent after the process, there is a problem that only the high-temperature curing process has to go through again.

In addition, in order to increase the production efficiency in order to perform a high temperature heat treatment for the production of the polyimide resin, there is also a problem that the heat facilities must be enlarged.

The present invention has been made to solve the problems of the prior art as described above, the inventors have a low temperature by using a low boiling point solvent in the manufacturing process of the polyimide or by adding a low boiling point, high reactivity amine catalyst with the low boiling point solvent Also, it was found that the polyimide can be prepared, and the low-temperature polyimide prepared in this manner was confirmed to maintain excellent properties in heat resistance and processability, thereby completing the present invention.

Accordingly, one object of the present invention is to provide a method for producing a polyimide resin which can be imidized even at low temperature by using a solvent having a low boiling point.

In addition, the present invention provides a method for producing a polyimide resin capable of imidization even at low temperature by using a low boiling point solvent and a specific catalyst having a low boiling point and high reactivity.

Further, another object of the present invention is to provide a photosensitive composition and an ink composition for printing comprising the polyimide resin.

In addition, another object of the present invention to provide a polyimide resin capable of low-temperature curing.

Method for producing a polyimide resin of the present invention for achieving the above object may include the step of polymerizing the polyimide resin using a low boiling point solvent having a boiling point of 130 ~ 180 ℃.

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-methoxy propionate, ethyl 3-ethoxy propionate, propylene glycol Methyl ether propionate, dipropylene glycol dimethyl ether, cyclohexanone and It may be at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA).

The low boiling point solvent may be included in 20 to 2000 parts by weight based on 100 parts by weight of the monomer for producing a polyimide resin.

According to the method of the present invention, the polyimide may be to prepare a polyimide resin directly, without passing through the polyamic acid precursor manufacturing step.

The polyimide resin may be prepared in the presence of a catalyst having a boiling point of 60 to 100 ℃.

The catalyst is selected from the group consisting of N, N-diethylmethylamine, N, N-dimethylisopropylamine, N-methylpyrrolidine, pyrrolidine, and triethylamine. It may be one or more.

The catalyst may be included in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of diamine and dianhydride which are starting materials of the polyimide resin.

According to the method of the present invention, the polymerization may be carried out at a temperature of 120 ~ 200 ℃.

The polyimide resin

및 3,5-디아미노벤조산으로부터 유래되는 2가의 유기기 등 페놀성 수산기, 카르복실기 또는 수산기를 포함하는 2가의 유기기로 이루어진 그룹으로부터 선택된 1종 이상의 방향족 디아민; p-페닐렌디아민, m-페닐렌디아민, 2,4,6-트리메틸-1,3-페닐렌디아민, 2,3,5,6-테트라메틸-1,4-페닐렌디아민, 4,4'-디아미노디페닐에테르, 3,4'-디아미노디페닐에테르, 3,3'-디아미노디페닐에테르, 4,4'-디아미노디페닐설피드, 4,4'-디아미노디페닐메탄, 3,4'-디아미노디페닐메탄, 3,3'-디아미노디페닐메탄, 4,4'-메틸렌-비스(2-메틸아닐린), 4,4'-메틸렌-비스(2,6-디메틸아닐린), 4,4'-메틸렌-비스(2,6-디에틸아닐린), 4,4'-메틸렌-비스(2-이소프로필-6-메틸아닐린), 4,4'-메틸렌-비스(2,6-디이소프로필아닐린), 4,4'-디아미노디페닐술폰, 3,3'-디아미노디페닐술폰, 벤지딘, o-톨리딘, m-톨리딘, 3,3',5,5'-테트라메틸벤지딘, 2,2'-비스(트리플루오로메틸)벤지딘, 1,4-비스(4-아미노페녹시)벤젠, 1,3-비스(4-아미노페녹시)벤젠, 1,3-비스(3-아미노페녹시)벤젠, 비스[4-(4-아미노페녹시)페닐]술폰, 비스[4-(3-아미노페녹시)페닐]술폰, 2,2-비스[4-(4-아미노페녹시)페닐]프로판, 및 2,2-비스[4-(3-아미노페녹시)페닐]프로판으로 이루어진 그룹으로부터 선택된 1종 이상의 방향족 디아민; 1,6-헥산디아민, 1,4-시클로헥산디아민, 1,3-시클로헥산디아민, 1,4-비스(아미노메틸)시클로헥산, 1,3-비스(아미노메틸)시클로헥산, 4,4'-디아미노디시클로헥실메탄, 및 4,4'-디아미노-3,3'-디메틸디시클로헥실메탄 및 4,4'-디아미노-3,3'-디메틸디시클로헥실메탄, 1,2-비스-(2-아미노에톡시)에탄, 비스(3-아미노프로필)에테르, 1,4-비스(3-아미노프로필)피페라진, 3,9-비스(3-아미노프로필)-2,4,8,10-테트라옥사스피로[5.5]운데칸, 1,3-비스(3-아미노프로필)테트라메틸디실록산으로 이루어진 그룹으로부터 선택된 1종 이상의 지방족 디아민으로 이루어진 그룹으로부터 선택되는 1종 이상의 디아민을 출발 원료로 사용하는 것일 수 있다.

And at least one aromatic diamine selected from the group consisting of a phenolic hydroxyl group, a carboxyl group or a divalent organic group including a hydroxyl group, such as a divalent organic group derived from 3,5-diaminobenzoic acid; p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4 '-Diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodi Phenylmethane, 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'-methylene-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] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 2,2-bis [4- (3-aminophenoxy) phenyl] propane At least one aromatic diamine selected from the group consisting of; 1,6-hexanediamine, 1,4-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, 1,4-bis (3-aminopropyl) piperazine, 3,9-bis (3-aminopropyl) -2, At least one diamine selected from the group consisting of at least one aliphatic diamine selected from the group consisting of 4,8,10-tetraoxaspiro [5.5] undecane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane It may be to use as a starting material.

The polyimide resin 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'-diphenylethertetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4 '-Benzophenonetetracarboxylic dianhydride, 4,4'-hexafluoroisopropylidenediphthalic anhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride, 1,2 , 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-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracar Dissolved dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclo Hexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentane acetic dianhydride, bicyclo [2.2.2] octo-7-ene-2,3,5,6 1 selected from the group consisting of tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuranthracarboxylic dianhydride and 3,5,6-tricarboxy-2-norbornane acetic dianhydride At least one dianhydride selected from the group consisting of at least one acid anhydride and derivatives thereof may be used as a starting material.

The present invention may be to provide a polyimide resin prepared using a low boiling point solvent having a boiling point of 130 ~ 180 ℃ in order to achieve the other object.

It is preferable that the glass transition temperature of the said polyimide is 150-400 degreeC.

It is preferable that the weight average molecular weight of the said polyimide resin is 1,000-100,000.

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

The present invention can provide a photosensitive resin composition capable of low-temperature curing, including the polyimide resin prepared by the above method, in order to achieve the above further another object.

The photosensitive resin composition is characterized in that it is curable at 150 ~ 250 ℃.

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

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

The photosensitive film using the photosensitive resin composition has a feature that can be removed by an EBR solvent (edge bead removal solvent) after pre-bake.

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

The present invention can also provide a printing ink composition comprising a polyimide resin prepared by the above method.

The present invention can provide a printing ink composition comprising a polyimide resin prepared by the above method, in order to achieve the above further another object.

The present invention can also provide an OLED, LCD or semiconductor insulating film prepared by including the photosensitive resin composition,

In addition, it can provide an OLED, LCD or a semiconductor insulating film prepared by including the printing ink composition.

According to the present invention, it is possible to prepare a polyimide resin directly without using a low boiling point solvent to prepare a polyamic acid as a polyimide precursor.

In addition, the polyimide resin prepared in this way can be cured even at low temperatures, and when used as an electronic material, can minimize equipment damage caused by high temperature processes, and can also be used as a plastic substrate, which can be used as a wider electronic material. Do.

The polyimide resin according to the manufacturing method of the present invention also has a sufficient mechanical strength and excellent workability and high production efficiency, so that the polyimide resin can be used not only for photosensitive resin compositions of various displays, but also for printing ink compositions and the like.

When the polyimide resin according to the present invention is included in the photosensitive resin composition and used as a photosensitive film of an electronic material, the polyimide resin may be easily removed even at low temperature by an EBR solvent (edge bead removal solvent) after pre-bake.

In addition, the photosensitive resin composition including the polyimide resin according to the present invention has a feature of dissolving without mixing when drain mixed.

1 and 2 are graphs of the residual solvent amount after curing of the photosensitive resin composition according to the Examples and Comparative Examples of the present invention.

Hereinafter, the present invention will be described in more detail.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an" and "the" may include the plural forms as well, unless the context clearly indicates otherwise.

Also, as used herein, "comprise" and / or "comprising" specifies the presence of the mentioned shapes, numbers, steps, actions, members, elements and / or groups of these. It is not intended to exclude the presence or the addition of one or more other shapes, numbers, acts, members, elements and / or groups.

In the present invention, in preparing a polyimide resin by reacting diamine and dianhydride, by using a specific catalyst and a solvent having a low boiling point, low temperature curing is possible, and a soluble polyimide resin can be produced.

The polyimide resin of the present invention does not prepare a polyamic acid precursor from diamine and dianhydride (anhydride) as in the prior art, and harden it at high temperature to prepare a polyimide film, but directly polyimide from the diamine and dianhydride. It is to prepare a resin.

This is characterized by using a low boiling point solvent having a boiling point of 130 ~ 180 ℃ to enable the synthesis of polyimide resin at low temperature in the present invention.

Typically, the synthesis of polyimide resin was prepared by preparing a polyamic acid precursor and curing it at a high temperature of 320 ° C or higher. In the present invention, however, the polyimide resin is directly manufactured without passing through the polyamic acid precursor step, but a low boiling point solvent is used as described above for the synthesis of the polyimide resin at a lower temperature than before.

As mentioned above, the specific example of the low boiling point solvent which has a boiling point of 130-180 degreeC is diethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, methyl 3-methoxy 1 type selected from the group consisting of propionate, ethyl 3-ethoxy propionate, propylene glycol methyl ether propionate, dipropylene glycol dimethyl ether, cyclohexanone and propylene glycol monomethyl ether acetate (PGMEA) It is not limited to this as long as it is above and the low boiling point solvent which has a boiling point of the said temperature range.

When the boiling point of the solvent according to the present invention is less than 130 ℃ may not be enough energy to make a polyimide conversion may fall, and if the boiling point of the solvent exceeds 180 ℃ higher than 200 ℃ higher than this at the time of curing There is a problem that the solvent does not remain, which makes it difficult to lower the curing temperature, which is not preferable.

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, most preferably 200 to 400 parts by weight, based on 100 parts by weight of the total monomer including diamine and dianhydride. If the content is less than 20 parts by weight, the polyimide may not be sufficiently dissolved, and if it exceeds 2000 parts by weight, there is a problem in that a coating film having a sufficient thickness cannot be formed when applied to the substrate.

In the present invention, the polyimide resin may include a low boiling point catalyst.

The catalyst is a catalyst capable of imidization at a low temperature and easily removed after the reaction, and a catalyst having a low boiling point and high reactivity is preferable.

Specifically, the catalyst may have a boiling point of 60 to 120 ℃, preferably 70 to 100 ℃, most preferably 80 to 90 ℃. If the boiling point of the catalyst is too low, less than 60 ℃ all the evaporation during the polymerization is not preferable, and if it exceeds 120 ℃ may be a highly reactive catalyst after the end of the reaction to cause side reactions in the preparation of the composition.

Specific examples of the catalyst according to the present invention include N, N-diethylmethylamine, N, N-dimethylisopropylamine, N-methylpyrrolidine, pyrrolidine and tri One or more selected from the group consisting of ethylamine is not limited thereto.

The catalyst is used for the synthesis of polyimide resin 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 monomers of diamine and dianhydride combined, and the content of the catalyst is 0.5 parts by weight. If it is less than the amount of the catalyst is insufficient conversion of the polyimide falls, if more than 30 parts by weight of the addition reaction due to the remaining of the unreacted catalyst may occur is not preferable.

In addition, diamine and dianhydride which are monomers used for the polyimide resin of this invention will not be specifically limited if it is those used at the time of manufacture of a normal polyimide resin, However, It can select and use suited for a predetermined use.

For example, as an acid anhydride or its derivative (s), pyromellitic anhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, butane-1,2,3,4- tetracarboxylic acid Dianhydrides, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3 ', 4,4 '-Diphenylsulfontetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride, 3,3', 4,4'-biphenyltetracarboxylic Acid dianhydrides, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-hexafluoroisopropylidenediphthalic anhydride, 3,3', 4,4'-di Phenylsulfontetracarboxylic dianhydride, 1,2,3,4-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-cyclopentanetetracarboxylic Dianhydrides, 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-cyclopentane acetic dianhydride, bicyclo [2.2 .2] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetetracarboxylic dianhydride and 3,5,6-tricarboxy And at least one acid anhydride selected from the group consisting of -2-norbornane acetic dianhydride and derivatives thereof.

As the diamine may be used an aromatic and aliphatic diamine, specific examples of the diamine compound,

And at least one aromatic diamine selected from the group consisting of a phenolic hydroxyl group, a carboxyl group or a divalent organic group including a hydroxyl group, such as a divalent organic group derived from 3,5-diaminobenzoic acid; p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4 '-Diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodi Phenylmethane, 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'-methylene-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] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 2,2-bis [4- (3-aminophenoxy) phenyl] propane At least one aromatic diamine selected from the group consisting of; 1,6-hexanediamine, 1,4-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 And at least one aliphatic diamine selected from the group consisting of 8,10-tetraoxaspiro [5.5] -undecane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and the aromatic and aliphatic diamines. It may be used by mixing, but is not limited thereto.

On the other hand, the polymerization of the polyimide resin according to the present invention may be carried out at a low temperature of 120 ~ 200 ℃, preferably 130 ~ 180 ℃, most preferably 140 ~ 160 ℃.

When manufacturing a polyimide by the above process, it is preferable that the conversion rate at the time of superposition | polymerization is 90 to 100%, and the residual catalyst amount in a polyimide resin is 0.001 to 0.1 weight% of a total polyimide resin.

The polyimide manufacturing method according to the present invention can be confirmed that despite the polymerization at a relatively low temperature, the conversion is high, and the amount of residual catalyst in the final polyimide resin produced is low. It can be seen that the mid resin can be produced effectively.

The polyimide resin according to the present invention produced according to this series of processes is capable of low temperature curing in the temperature range of 150 ~ 250 ℃ and is soluble.

Therefore, problems such as difficulties in the process of curing the polyimide at a high temperature of 320 ° C. or higher, problems that cannot be used in a process that is susceptible to heat, and problems such as low conversion rate from the polyamic acid precursor solution to the polyimide resin even after high temperature curing Will be able to solve.

While polyimide resins are generally known to have extremely limited solubility in solvents, the polyimide resins prepared according to the present invention may be soluble in solvents having low solubility.

In general, polyimide has a very low solubility so that a monomer capable of providing a solubility function must be introduced in order to have solubility. Even so, they tend to dissolve better in highly polar, high boiling solvents.

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

Therefore, in order to make the imid ring, it is not necessary to perform imidization at high temperature after application, and only the solvent is removed to obtain a polyimide membrane. In addition, the chemical imidization has a high conversion rate, so that the reliability of the device is not deteriorated by out-gassing generated from unimidized polyamic acid or polyamic acid ester. In particular, when a low boiling point solvent is used, this temperature can be further lowered according to the boiling point of the solvent, and thus, it may have an advantage of forming a thin film having high mechanical and thermal stability similar to that of a conventional polyimide by applying to a device process requiring a low temperature process. Can be.

The glass transition temperature of the polyimide resin according to the present invention may be 150 ~ 400 ℃. In addition, the polyimide resin may have a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000.

It can provide a photosensitive resin composition capable of low-temperature curing comprising a polyimide resin prepared by the above method, and has a feature capable of curing at a low temperature of 150 ~ 250 ℃.

In addition, in the photosensitive resin composition according to the present invention, the amount of residual solvent in the photosensitive resin composition after curing may be less than 0.05% by weight, and more preferably, no residual solvent is present in the photosensitive resin composition after curing (0% by weight). Can be.

The photosensitive film using the photosensitive resin composition has a feature that can be easily removed by an EBR solvent (edge bead removal solvent) after pre-bake. Although it is not used for general polyimide polymerization, it is polymerized using solvents such as glyme solvent, propionate, PGMEA, etc., which are commonly used for general photoresist, and can be easily removed at low temperature by general purpose EBR solvent. Have

Therefore, it can be removed with other solvents used for rework during manufacturing processes in other semiconductor lines, OLED, LCD, etc., and it can be dissolved without sedimentation generated when mixing drains to prevent clogging of pipes. Has the characteristics.

In addition, in the case of the printing composition, solvents such as NMP, GBL, DMAc, DMF, etc., which are used for the conventional polyamide polymerization, cannot be used. However, the polyamide resin of the present invention does not use such a solvent, and thus printing ink It can be used advantageously in the composition.

In conclusion, the polyimide resin according to the present invention may be used as a binder resin of the photosensitive resin composition and printing ink composition of various electronic materials including OLED and LCD, but is not limited thereto.

Accordingly, the present invention can provide a polyimide film prepared by including the photosensitive resin composition, or a polyimide film prepared by including the printing ink composition, and further, an OLED and an LCD manufactured using the polyimide films. Alternatively, a semiconductor insulating film can be provided.

Hereinafter, the present invention will be described in more detail with reference to Examples. The embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art, and the following examples can be modified in various other forms, and the scope of the present invention is It is not limited to an Example. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the inventive concept to those skilled in the art.

Example  1: Low Temperature Polyimide Polymerization Example

12.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 60 g of propylene glycol monomethyl ether acetate were sequentially added to a 100 ml round bottom flask, followed by slow stirring to completely dissolve the flask. 10.2 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride was slowly added while maintaining in water at room temperature. 11 g of toluene and 4 g of triethylamine were added to the mixed solution, and the mixture was installed to remove water through a dean-stark distillation and refluxed at 150 ° C. for 5 hours. After removing water from the Dean-Stark distillation apparatus, the mixture was further refluxed for 2 hours to remove the catalyst, and then cooled to room temperature to obtain a soluble polyimide solution.

The polyimide production peak was confirmed through IR, and the polyimide resin measured through GPC had a weight average molecular weight of 40,000 and a poly disperse index (PDI) of 1.5.

Example  2: Low Temperature Polyimide Polymerization Example

12.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 60 g of propylene glycol monomethyl ether acetate were sequentially added to a 100 ml round bottom flask, followed by slow stirring to completely dissolve the flask. 6.5 g of butane-1,2,3,4-tetracarboxylic dianhydride was slowly added while maintaining the temperature in water. 11 g of toluene and 4 g of triethylamine were added to the mixed solution, and the mixture was installed to remove water through a dean-stark distillation and refluxed at 150 ° C. for 5 hours. After removing water from the Dean-Stark distillation apparatus, the mixture was further refluxed for 2 hours to remove the catalyst, and then cooled to room temperature to obtain a soluble polyimide solution.

The polyimide production peak was confirmed through IR, and the weight average molecular weight of the polyimide resin measured through GPC was 35,000, and the polydisperse index (PDI) was 1.7.

Comparative example  1: high temperature polyimide polymerization example

12.1 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 60 g of γ-butyrolactone were sequentially added to a 100 ml round bottom flask, and slowly stirred to completely dissolve the flask. 10.2 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride was slowly added while maintaining in water at room temperature. After the mixture solution was stirred at room temperature for 16 hours, 7 g of toluene was added and installed to remove water through dean-stark distillation, and then refluxed at 180 ° C. for 3 hours. After removing water from the Dean-Stark distillation apparatus, the mixture was further refluxed for 2 hours to remove the catalyst, and then cooled to room temperature to obtain a soluble polyimide solution.

The polyimide production peak was confirmed through IR, and the weight average molecular weight of the polyimide resin measured through GPC was 40,000, and the poly disperse index (PDI) was 1.6.

Comparative example  2: polyimide precursor Polymerization example

Into a 1 L round bottom jacket reactor, 73.3 g of 4,4'-oxydianiline and 300 g of γ-butyrolactone were sequentially added and slowly stirred to completely dissolve. Then, the jacket temperature of the reactor was maintained at 20 ° C. and 3,3 ' 55.8 g of, 4,4'-diphenylsulfontetracarboxylic dionehydride were slowly added with stirring. The mixed solution was stirred for 2 hours to fully react, followed by further stirring at room temperature for 16 hours to prepare a polyamic acid. The polyamic acid production peak was confirmed through IR, and the weight average molecular weight of the polyimide resin measured by GPC was 50,000, and the polydisperse index (PDI) was 1.6.

Experimental Example  One

One. Imidization rate  evaluation

After prebake at 120 ° C. for 4 minutes, after hardbake at 250 ° C. for 1 hour, use FT-IR in each case.

-Assuming the CN band integral of the sample cured at 300 ° C for 1 hour at 100% conversion rate, the imidation ratio was confirmed through the CN band integral of the sample cured under each curing condition.

After Prebake (120 ℃, 4min) After Hardbake (250 ℃ 1hr) Example 1 100% 100% Example 2 98% 98% Comparative Example 1 98% 98% Comparative Example 2 0% 0%

As shown in the results of Table 1, in Examples 1 and 2 in which the polyimide resin was directly manufactured at low temperature as in the method of the present invention, the imidation ratio was maintained to be equivalent to that of Comparative Example 1 prepared at high temperature, or rather. It can be seen that it is confirmed to be excellent.

2. Residue Catalytic amount  analysis

: Quantitative analysis of residual catalyst amount through GC-MS analysis, the results are shown in Table 2 below.

Residual Catalyst Example 1 Triethylamine 0.02% Comparative Example 1 Pyridine 0.5%

As shown in Table 2, when using a low boiling point catalyst as in the present invention it can be seen that the amount of catalyst remaining in the polyimide resin is significantly reduced compared to Comparative Example 1. From these results, it turns out that it is effective to manufacture polyimide resin like the method of this invention.

Example  3: of photosensitive resin composition Manufacturing example  (Polyimide Composition)

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

Comparative example  3: of photosensitive resin composition Manufacturing example  (Polyimide Composition)

To 1.6 g of the soluble polyimide synthesized in Comparative Example 1, a diazonaptoquinone ester compound (TPPA 320: OD / (OD + OH) = 2/3 is selectively given among OH and OD as a photoactive compound.) 0.5 g and 4 g of γ-butyrolactone (GHL) were added thereto, stirred at room temperature for 1 hour, and then filtered through a filter having a pore size of 1 μm to prepare a photosensitive resin composition.

Experimental Example  2: residual Solvent  analysis

: Analysis of residual solvent amount using Purge & Trap-GC / MSD equipment

After coating the composition of Example 3 and Comparative Example 3 on the substrate, and prebake for 2 minutes at 120 ℃, hard bake for 1 hour at 200 ℃ to form a coating film. The coating films were analyzed in the amount of solvent collected after 2 hours, 3 hours, and 4 hours at 280 ° C., respectively, as shown in FIGS. 1 and 2.

1 is an analysis graph of the residual solvent amount according to Example 3, and FIG. 2 is an analysis graph of the residual solvent amount of Comparative Example 3. FIG. As shown in FIG. 1, in Example 3, it was confirmed that no peak was generated by the residual solvent, and only a peak due to decomposition of the composition was confirmed. On the other hand, in Figure 2 it can be seen that the peak of the GBL by the peak (peak) due to the residual solvent until the capture of 280 ℃ 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 method of claim 1, wherein 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-methoxy propionate, ethyl 3-ethoxy At least one member selected from the group consisting of propionate, propylene glycol methyl ether propionate, dipropylene glycol dimethyl ether, cyclohexanone and propylene glycol monomethyl ether acetate (PGMEA). Method for producing a polyimide resin.
The method of claim 1, wherein the low boiling point solvent is characterized in that it comprises 20 to 2000 parts by weight based on 100 parts by weight of the monomer for producing a polyimide resin Method for producing a polyimide resin.
The method of manufacturing a polyimide resin according to claim 1, wherein the polyimide resin is directly prepared without passing through the polyamic acid precursor manufacturing step.
The method for producing a polyimide resin according to claim 1, wherein the polyimide resin is produced in the presence of a catalyst having a boiling point of 60 to 100 ° C.
6. The method of claim 5, The catalyst is selected from the group consisting of N, N-diethylmethylamine, N, N-dimethylisopropylamine, N-methylpyrrolidine, pyrrolidine, and triethylamine. It is characterized by one or more Manufacturing method.
6. The method of claim 5, The catalyst is characterized in that it comprises 0.5 to 30 parts by weight based on 100 parts by weight of diamine and dianhydride which are starting materials of the polyimide resin. Manufacturing method.
The method of claim 1, wherein the polymerization comprises the step of performing at a temperature of 120 ~ 200 ℃. The method of claim 1, The polyimide resin

And at least one aromatic diamine selected from the group consisting of a phenolic hydroxyl group, a carboxyl group or a divalent organic group including a hydroxyl group, such as a divalent organic group derived from 3,5-diaminobenzoic acid; p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 4,4 '-Diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodi Phenylmethane, 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'-methylene-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] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 2,2-bis [4- (3-aminophenoxy) phenyl] propane At least one aromatic diamine selected from the group consisting of; 1,6-hexanediamine, 1,4-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, 1,4-bis (3-aminopropyl) piperazine, 3,9-bis (3-aminopropyl) -2, At least one diamine selected from the group consisting of at least one aliphatic diamine selected from the group consisting of 4,8,10-tetraoxaspiro [5.5] undecane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane Is used as a starting material.
The method of claim 1, The polyimide resin 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'-diphenylethertetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4 '-Benzophenonetetracarboxylic dianhydride, 4,4'-hexafluoroisopropylidenediphthalic anhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride, 1,2 , 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-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracar Dissolved dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclo Hexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentane acetic dianhydride, bicyclo [2.2.2] octo-7-ene-2,3,5,6 1 selected from the group consisting of tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuranthracarboxylic dianhydride and 3,5,6-tricarboxy-2-norbornane acetic dianhydride At least one dianhydride selected from the group consisting of at least one acid anhydride and derivatives thereof is used as a starting material. Method for producing a polyimide resin.
A polyimide resin prepared by the method of claim 1.
The polyimide resin according to claim 11, wherein the polyimide has a glass transition temperature of 150 to 400 ° C.
12. The polyimide resin according to claim 11, wherein the polyimide resin has a weight average molecular weight of 1,000 to 100,000.
12. The polyimide resin according to claim 11, wherein the residual catalyst amount in the polyimide resin is 0.001 to 0.1 wt% of the total weight of the polyimide resin.
A photosensitive resin composition capable of low temperature curing comprising a polyimide resin prepared by the method of claim 1.
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 does not have a residual solvent in the photosensitive resin composition after curing.
The photosensitive resin composition according to claim 15, wherein the amount of the solvent remaining in the photosensitive resin composition after curing is less than 0.05% by weight.
The photosensitive resin composition according to claim 15, wherein the photosensitive film using the photosensitive resin composition can be removed by an EBR solvent (edge bead removal solvent) after pre-bake.
The photosensitive resin composition according to claim 15, wherein the photosensitive resin composition is dissolved without mixing when the drain is mixed.
A printing ink composition comprising a polyimide resin prepared by the method of claim 1.
An OLED, LCD or semiconductor insulating film prepared by comprising the photosensitive resin composition according to claim 15. An OLED, LCD or semiconductor insulating film prepared by including the printing ink composition according to claim 21.

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