KR20140057956A - Photosensitive transparent-polyimide and composition of the same - Google Patents

Photosensitive transparent-polyimide and composition of the same Download PDF

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KR20140057956A
KR20140057956A KR1020120124363A KR20120124363A KR20140057956A KR 20140057956 A KR20140057956 A KR 20140057956A KR 1020120124363 A KR1020120124363 A KR 1020120124363A KR 20120124363 A KR20120124363 A KR 20120124363A KR 20140057956 A KR20140057956 A KR 20140057956A
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formula
polyimide
photosensitive transparent
group
transparent polyimide
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KR1020120124363A
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Korean (ko)
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이정환
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도레이케미칼 주식회사
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The present invention relates to a photosensitive transparent polyimide and a composition thereof, and more specifically, it is insoluble in an alkali solvent without using a dissolution inhibitor such as DNQ (diazonaphthoquinone), thereby reducing manufacturing costs and simplifying the manufacturing process And a photosensitive polyimide excellent in economical efficiency and a composition thereof.

Description

Photosensitive transparent polyimide and composition thereof [0002]

The present invention relates to a photosensitive transparent polyimide and a composition thereof, and more specifically to a photosensitive transparent polyimide insoluble in an alkali solvent without using a dissolution inhibitor such as DNQ (diazonaphthoquinone).

Polyimide is prepared by polycondensation of a tetracarboxylic acid and a diamine as a polymer having a heterodimer in the main chain. The polyimide has excellent light transmittance, excellent mechanical properties, thermal properties and adhesion to a substrate, Lt; / RTI > Polyimide is widely used as a substitute for metals and glass in various fields such as electric, electronic, automobile, airplane, and semiconductor. In particular, polyimide is excellent in thermal characteristics and mechanical properties, tape automated bonding (CSP), chip scale package (CSP), wafer level package (WLP), and the like.

Since polyimide is mostly poor in solubility, it is generally prepared by a method of obtaining a polyimide precursor solution, coating it on a glass substrate or the like, and then curing it by heat treatment. The commercialized polyimide product is a polyimide precursor solution polyimide film state And is supplied mainly in the form of a polyimide precursor solution in the field of semiconductor devices.

The photosensitive polyimide is largely classified into a negative type and a positive type. As a negative type example, U.S. Patent No. 3,957,512 by Rubner et al. Of Siemens Co., Ltd. discloses that a photosensitive functional group is a polyimide precursor Discloses a polyamic acid linked by an ester linkage to a polyamic acid, and U.S. Patent No. 4,243,743 to Toray, Japan discloses a photosensitive polyimide in which a photosensitive group and a compound having an amino component are ion-bonded to a polyamic acid. In the case of both of the patented inventions, when a resist composition solution containing polyimide is coated on a substrate and exposed to light, photopolymerization occurs in the exposed portion, crosslinking is formed between the precursor molecules and is insolubilized, and then developed with an organic solvent to remove non- By completing the imidization reaction by the heat treatment, a polyimide layer having a desired pattern is obtained.

However, in the case of the above negative-type photosensitive polyimide, the resolution is generally inferior to that of the positive type, and the possibility of occurrence of defects is high. N-methyl-2-pyrrolidone (NMP) Since an organic solvent such as dimethylacetamide (DMAc) is used as a developing solution, a positive photosensitive polyimide which is developable in an alkali aqueous solution is preferred in a semiconductor process because it is not only expensive but also is not preferable from an environmental point of view.

As examples of the positive photosensitive polyimide, JP-A-52-13315 and JP-A-62-135824 disclose a mixture of a naphthoquinone diazide compound and a phenol resin compound, which are dissolution inhibitors of polyamic acid and an alkali aqueous solution, as a polyimide precursor And mixing the mixture to prepare a pattern by a difference in dissolution rate between the exposed portion and the non-exposed portion.

However, the conventional photosensitive polyimide manufacturing process using the dissolution inhibitor has disadvantages such as difficulty in controlling the ratio of the solution inhibitor itself, complexity in the manufacturing process, difficulty in economics due to the use of expensive naphthoquinonediazide compounds There is an urgent need to develop a new photosensitive polyimide which solves the problem.

Accordingly, the present inventors intend to provide a photosensitive transparent polyimide in which an alkali insoluble group is introduced into a side chain so as to be insoluble in an alkali solvent without using a dissolution inhibitor, and a composition thereof.

In order to solve the above problems, the present invention relates to a photosensitive transparent polyimide, and may include a compound represented by the following general formula (1).

[Chemical Formula 1]

Figure pat00001

In the above Formula 1, X is -CH 2 -, -O-, -S-, -CO-, -CH (CH 3) -, C (CH 3) 2 -, -CH (CF 3) -, - C (CF 3 ) 2 - or -SO 2 -, R 1 is a C1-C6 alkyl group or a C2-C6 alkylene group, and R 2 is

Figure pat00002
,
Figure pat00003
or
Figure pat00004
R 3 is a hydrogen atom or a C 1 to C 4 alkoxy group, m is an integer of 1 to 3, and n is a rational number satisfying a weight average molecular weight of the compound of 5,000 to 200,000.

As a preferred embodiment of the present invention, the photosensitive transparent polyimide of the present invention may include a compound represented by the following formula (2)

(2)

Figure pat00005

In Formula 2, R 1 is a C1-C6 alkyl group or a C2-C6 alkylene group, and R 2 is

Figure pat00006
,
Figure pat00007
or
Figure pat00008
R 3 is a hydrogen atom or a C 1 to C 4 alkoxy group, m is an integer of 1 to 3, and n is a rational number satisfying a weight average molecular weight of the compound of 5,000 to 200,000.

In another preferred embodiment of the invention, the photosensitive transparent polyester of the present invention R 1 in the general formula (2) imide is an alkyl group of C1 ~ C6, R 2 is

Figure pat00009
or
Figure pat00010
R 3 is a hydrogen atom or a C 1 to C 2 alkoxy group, and m is an integer of 1 to 2. In another embodiment, the photosensitive transparent polyimide of the present invention is a compound wherein R 1 is a C 2 to C 4 Alkyl group, R < 2 &
Figure pat00011
And R < 3 > is a hydrogen atom.

Another aspect of the present invention relates to a photosensitive transparent polyimide composition comprising: a polyimide powder represented by the following general formula (3); And a compound represented by the following formula (4).

(3)

Figure pat00012

For Formula 3, X is -CH 2 -, -O-, -S-, -CO-, -CH (CH 3) -, -C (CH 3) 2 -, -CH (CF 3) -, -C (CF 3 ) 2 - or -SO 2 -, and n is a rational number satisfying the weight average molecular weight of the compound of 5,000 to 200,000.

[Chemical Formula 4]

Figure pat00013

In the formula (4), R 1 is a C1-C6 alkyl group or a C2-C6 alkylene group, and R 2 is

Figure pat00014
,
Figure pat00015
or
Figure pat00016
And R 3 is a hydrogen atom or a C 1 to C 4 alkoxy group.

As a preferred embodiment of the present invention, the polyimide composition of the present invention may contain the polyimide powder and the compound represented by Formula 4 in a molar ratio of 0.7 to 0.2: 0.3 to 0.8.

In a preferred embodiment of the present invention, the polyimide composition of the present invention is 1,8-diazabicyclo [5,4,0] undec-7-ene (1,8-Diazabicyclo [ 7-ene, 1,5-diazabicyclo (4,3,0) -non-5-ene (1,5-Diazabicyclo (4,3,0) trimethylamine, N-methylimidazole, and diisopropylethylamine. The reaction catalyst may be at least one selected from the group consisting of trimethylamine, trimethylamine, N-methylimidazole, and diisopropylethylamine.

In another preferred embodiment of the present invention, in the polyimide composition of the present invention, the polyimide powder is a polyamic acid represented by the following general formula (5); An imidation catalyst and a dehydrating agent.

[Chemical Formula 5]

Figure pat00017

In the above Formula 5, X is -CH 2 -, -O-, -S-, -CO-, -CH (CH 3) -, -C (CH 3) 2 -, -CH (CF 3) -, -C (CF 3 ) 2 - or -SO 2 -, and n is a rational number satisfying the weight average molecular weight of the compound of 5,000 to 200,000.

In another preferred embodiment of the present invention, the polyimide composition of the present invention is characterized in that X in the above Chemical Formula 3 and Chemical Formula 5 is -C (CF 3 ) 2 - or -SO 2 -.

As a preferred embodiment of the present invention, the imidization catalyst, which is one of the polyimide compositions of the present invention, is at least one selected from the group consisting of pyridine, isoquinoline, and? -Quinoline And the dehydrating agent may include at least one selected from acetic anhydride, phthalic anhydride, and maleic anhydride.

Another aspect of the present invention relates to a photosensitive transparent polyimide film, which comprises the above-described photosensitive transparent polyimide, and the film further comprises a photosensitive transparent polyimide containing a polymer represented by the following formula .

[Chemical Formula 8]

Figure pat00018

For Formula 8, X is -CH 2 -, -O-, -S-, -CO-, -CH (CH 3) -, C (CH 3) 2 -, -CH (CF 3) -, - C (CF 3 ) 2 - or -SO 2 -, R 1 is a C1-C6 alkyl group or a C2-C6 alkylene group, and R 2 is

Figure pat00019
,
Figure pat00020
or
Figure pat00021
R 3 is a hydrogen atom or a C 1 to C 4 alkoxy group, m is an integer of 1 to 3, and a and b are rational numbers satisfying a: b = 0.7 to 0.2: 0.3 to 0.8.

The final cured product prepared from the photosensitive transparent polyimide of the present invention has excellent physical properties, particularly excellent transparency and excellent low temperature curability, and is insoluble in an alkali solvent, so that no separate dissolution inhibitor is used The manufacturing cost can be reduced, and the manufacturing process can be simplified.

The term " C1 ","C2", etc. used in the present invention means a carbon number. For example," C1 to C5 alkyl "means an alkyl group having 1 to 5 carbon atoms. The random copolymer used in the present invention is a copolymer of two or more monomers, meaning that the order of the monomers is randomly polymerized. For example, a random copolymer of monomers A and B The term "(A) a - (B) b -" means randomly copolymerized in various forms such as - (ABAABA) -, - (AABB) -, - (AAABAAB) a - (B) In b -, a and b mean the ratio of A and B.

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

The present invention relates to a photosensitive transparent polyimide comprising a compound represented by the following formula (1), and the present invention will be described in more detail below.

[Chemical Formula 1]

Figure pat00022

In the above Formula 1, X is -CH 2 -, -O-, -S-, -CO-, -CH (CH 3) -, C (CH 3) 2 -, -CH (CF 3) -, - -S-, -CH (CF 3 ) -, -C (CF 3 ) 2 - or -SO 2 -, and preferably an electron withdrawing group for improving transparency. 3 ) 2 - or -SO 2 -, more preferably -C (CF 3 ) 2 - or -SO 2 -. For example, when X is -C (CF 3 ) 2 -, the compound may be represented by the following general formula (2).

(2)

Figure pat00023

In Formula 1 and / or Formula 2, R 1 is an alkyl group having 1 to 6 carbon atoms or an alkylene group having 2 to 6 carbon atoms. Preferably, R 1 is a C1 to C6 alkyl group, more preferably a C2 Which is advantageous in view of the non-solubility and the synthesis of an aqueous alkaline solution which is an alkyl group of a to C4.

In the above general formulas (1) and / or (2), wherein R 2 is

Figure pat00024
,
Figure pat00025
or
Figure pat00026
, Preferably
Figure pat00027
or
Figure pat00028
, More preferably
Figure pat00029
Is better in terms of alkali insolubility. R 3 is a hydrogen atom or a C 1 to C 4 alkoxy group, and m is an integer of 1 to 3.

In the above formula (1) and / or formula (2), n is a rational number satisfying a weight average molecular weight of the compound of 5,000 to 200,000, preferably a weight average molecular weight of 10,000 to 150,000. When the weight average molecular weight is less than 1,000, There may be a problem of deterioration in solubility. When the weight average molecular weight exceeds 200,000, there may be a problem that the solubility is deteriorated. Therefore, it is preferable that the weight average molecular weight is within the above range.

Hereinafter, the photosensitive transparent polyimide composition of the present invention will be described.

The photosensitive transparent polyimide composition of the present invention comprises: a polyimide powder represented by the following formula (3); And a compound represented by the following general formula (4), and the amount of the polyimide powder to be used is: And the compound represented by the following formula (4) in a molar ratio of 0.7 to 0.2: 0.3 to 0.8 to synthesize the polyimide represented by the above formula (1). If the amount of the compound represented by the following formula (4) is less than 0.7: 0.3 by mole based on the polyimide powder, there may be a problem that the dissolution inhibiting effect is poor with respect to the aqueous alkaline solution. If the ratio exceeds 0.2: 0.8, It is uneconomical.

(3)

Figure pat00030

For Formula 3, X is -CH 2 -, -O-, -S-, -CO-, -CH (CH 3) -, C (CH 3) 2 -, -CH (CF 3) -, - C (CF 3) 2 - or -SO 2 - recommended in, preferably -O-, -S-, -CH (CF 3 ) -, -C (CF 3) 2 - or -SO 2 - in that , More preferably -C (CF 3 ) 2 - or -SO 2 -. And n is a rational number satisfying the weight average molecular weight of the compound of 5,000 to 200,000, preferably the weight average molecular weight of 10,000 to 150,000.

[Chemical Formula 4]

Figure pat00031

In Formula 4, R 1 is an alkyl group having 1 to 6 carbon atoms or an alkylene group having 2 to 6 carbon atoms, preferably R 1 is a C1 to C6 alkyl group, more preferably an alkaline aqueous solution having a C2 to C4 alkyl group Which is advantageous in terms of non-solubility and synthesis.

In the above formula (4), R 2 is

Figure pat00032
,
Figure pat00033
or
Figure pat00034
, Preferably
Figure pat00035
or
Figure pat00036
, More preferably
Figure pat00037
Is preferable in view of the non-solubility of the aqueous alkali solution.

In the formula (4), R 3 is a hydrogen atom or a C 1 to C 4 alkoxy group, and m is an integer of 1 to 3.

The polyimide composition of the present invention comprises the polyimide powder; And a compound represented by the following general formula (4), wherein the reaction catalyst is selected from the group consisting of 1,8-diazabicyclo [5,4,0] undec-7-ene (1,8-diazabicyclo [ 4,0] undec-7-ene, hereinafter referred to as DBU), 1,5-diazabicyclo (4,3,0) -non-5-ene), trimethylamine, N-methylimidazole, and diisopropylethylamine.

In the polyimide composition of the present invention, the polyimide powder may include a polyamic acid represented by the following general formula (5).

[Chemical Formula 5]

Figure pat00038

In the above Formula 5, X is -CH 2 -, -O-, -S-, -CO-, -CH (CH 3) -, C (CH 3) 2 -, -CH (CF 3) -, - C (CF 3) 2 - or -SO 2 - recommended in, preferably -O-, -S-, -CH (CF 3 ) -, -C (CF 3) 2 - or -SO 2 - in that , More preferably -C (CF 3 ) 2 - or -SO 2 -. And n is a rational number satisfying the weight average molecular weight of the compound of 5,000 to 200,000, preferably the weight average molecular weight of 10,000 to 150,000.

The polyimide powder may further include at least one selected from an imidation catalyst and a dehydrating agent in addition to the polyamic acid. The imidization catalyst may include pyridine, isoquinoline, and? -Quinoline (? quinoline, and the dehydrating agent may include at least one selected from the group consisting of acetic anhydride, phthalic anhydride, and maleic anhydride.

The photosensitive transparent polyimide composition of the present invention may further include various types of additives, and specifically includes at least one additive selected from a flame retardant, an adhesion promoter, an inorganic particle, an antioxidant, a plasticizer and an antistatic agent . In addition to the above additives, the present invention may further include additives such as an antioxidant, an ultraviolet absorber, an antistatic agent and a pigment depending on the application.

Various types of molded products can be produced using the photosensitive transparent polyimide prepared by the above-described composition. For example, a multilayer printed circuit board, a flexible circuit board, a stack for a semiconductor, an OLED device Sensitive organic insulating material for a light-sensitive material. Specifically, for example, the film, the protective film, the insulating film or the like may be characterized by including a photosensitive transparent polyimide containing a polymer represented by the following formula (8).

[Chemical Formula 8]

Figure pat00039

For Formula 8, X is -CH 2 -, -O-, -S-, -CO-, -CH (CH 3) -, C (CH 3) 2 -, -CH (CF 3) -, - C (CF 3) 2 - or -SO 2 -, preferably -O-, -S-, -CH (CF 3 ) -, -C (CF 3) 2 - or -SO 2 - which is, more preferably from -C (CF 3) 2 - or -SO 2 - is preferably

R 1 is preferably a C 1 to C 6 alkyl group or a C 2 to C 6 alkylene group, preferably R 1 is a C 1 to C 6 alkyl group, more preferably a C 2 to C 4 alkyl group, And is advantageous in terms of synthesis.

In the above general formulas (1) and / or (2), wherein R 2 is

Figure pat00040
,
Figure pat00041
or
Figure pat00042
, Preferably
Figure pat00043
or
Figure pat00044
, More preferably
Figure pat00045
Is better in terms of alkali insolubility. R 3 is a hydrogen atom or a C 1 to C 4 alkoxy group, and a and b are rational numbers satisfying the ratio of a: b = 0.7 to 0.2: 0.3 to 0.8.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, it goes without saying that the scope of the present invention is not limited by the following examples.

[ Example ]

Preparation Example  : Synthesis of Polyimide Powder

(One) Polyamic acid  Solution preparation

440 ml of N-methyl-2-pyrrolidone was charged into a 1 L reactor equipped with a stirrer, a nitrogen inlet, a dropping funnel, a temperature controller and a condenser while passing nitrogen through the reactor, Lt; RTI ID = 0.0 > 10 C. < / RTI > Next, 19.77 g (0.13 mol) of 3,5-diaminobenzoic acid was added to the reactor to completely dissolve it. Next, 57.75 g of 4,4- (hexafluoroisopropylidene) diphthalic-3,5-diamino benzoic acid (4,4- (Hexafluoroisopropylidene) diphthalic anhydride-3,5-diamino benzoic acid) 0.13 mol) was added and stirred for 3 hours to obtain a polyamic acid solution containing a compound represented by the following formula (6).

[Chemical Formula 6]

Figure pat00046

In Formula 6, n is a rational number satisfying a weight average molecular weight of 40,000 to 45,000.

(2) Preparation of polyimide powder

20.56 g of pyridine (imidization catalyst) and 26.54 g of acetic anhydride (dehydrating agent) were added to the polyamic acid solution, stirred at 60 ° C for 6 hours and cooled at room temperature (25 ° C) to obtain a reaction solution.

Next, the reaction solution was slowly added to distilled water to precipitate. The precipitated solid was filtered, washed with methanol, and then dried in a vacuum oven for 24 hours to obtain 100 g of a polyimide powder containing a compound represented by the following general formula (7).

(7)

Figure pat00047

In Formula 7, n is a rational number satisfying a weight average molecular weight of 40,000 to 45,000.

Example  1: Synthesis of photosensitive transparent polyimide solution

10 g of the polyimide powder prepared in the above preparation example was dissolved in 60 ml of dimethylformamide (DMF), and then 4- (2-bromoethoxy) -4-nitrobiphenyl (4- (2-bromoethoxy) -4- (DBU, reaction catalyst) of 12.94 g and 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU, reaction catalyst) were placed in a nitrogen atmosphere at 60 ° C. for 24 hours To prepare a reaction solution.

Next, the reaction solution was slowly added to distilled water to precipitate, and the precipitated solid was dissolved in DMF and re-precipitated in methanol to obtain a solid.

The resulting solid was dried in an oven for 24 hours and pulverized. The powder was dissolved in DMF to prepare a 20 wt% photosensitive polyimide solution containing a polymer represented by the following formula (8-1) , The content of the aromatic nitro compound used in the preparation is as shown in Table 1 below.

[Formula 8-1]

Figure pat00048

In the formula (8-1), a is 0.3 and b is a rational number of 0.7.

Example  2

11.0 g of BENP and 10.8 g of DBU were added in the same manner as in Example 1 to prepare a photosensitive transparent polyimide solution containing the polymer (a = 0.4, b = 0.6) represented by Formula 8-1.

Example  3

9.24 g of BENP and 9.13 g of DBU were added in the same manner as in Example 1 to prepare a photosensitive transparent polyimide solution containing the polymer (a = 0.5, b = 0.5) represented by Formula 8-1.

Example  4

7.39 g of BENP and 7.3 g of DBU were added in the same manner as in Example 1 to prepare a photosensitive transparent polyimide solution of the polymer (a = 0.6, b = 0.4) represented by Formula 8-1.

Example  5

5.54 g of BENP and 5.47 g of DBU were added in the same manner as in Example 1 to synthesize the polymer (a = 0.7, b = 0.3) represented by the formula 8-1.

Example  6

Except that 1.16 g of 4,5-dimethoxy-2-nitrobenzyl bromide (DNMB) instead of BENP and 5.42 g of DBU were added in the same manner as in Example 1, -2 < / RTI > was prepared.

[Formula 8-2]

Figure pat00049

In the formula (8-2), a is 0.3 and b is a rational number of 0.7.

Comparative Example  One

The procedure of Example 1 was repeated except that 4- (2-4- (2-bromoethoxy) -4'-nitrobiphenyl (4- (2-4- (2-Bromoethoxy) and 3.64 g of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene).

Comparative Example  2

The polyimide powder represented by the above formula (7) prepared in Preparation Example was dissolved in DMF to prepare a photosensitive transparent polyimide solution.

division The ratio of a and b in formulas (8-1) and (8-2) Example 1 0.3: 0.7 Example 2 0.4: 0.6 Example 3 0.5: 0.5 Example 4 0.6: 0.4 Example 5 0.7: 0.3 Example 6 0.3: 0.7 Comparative Example 1 0.8: 0.2 Comparative Example 2 1: 0

Experimental Example  1: Measurement of solubility of photosensitive transparent polyimide solution

The photosensitive transparent polyimide solution (containing 20% by weight of the polymer) prepared in the above Examples and Comparative Examples was added to the solvent shown in Table 2 at 25 캜 to prepare a mixed solution (containing 3% by weight of polymer) And the results are shown in Table 2 below.

menstruum Example 1 Example 2 Example 3 Example 4 Example
5 Example
6 Comparative Example 1 Comparative Example
2 DMF ○ ○ ○ ○ ○ ○ ○ ○ DMAc ○ ○ ○ ○ ○ ○ ○ ○ DMSO ○ ○ ○ ○ ○ ○ ○ ○ 1 wt% NaOH aqueous solution ● ● ● ● ● ● ◐ ○ CHCl 3 ● ● ● ● ● ● ● ● MeOH ● ● ● ● ● ● ● ● toluene
(Toluene) ● ● ● ● ● ● ● ● ○: soluble ●: not soluble (insoluble)
◐: Partially soluble

From the results of the solubility test in Table 2, it can be confirmed that the PI solution (Example) of the present invention is insoluble in an alkaline solvent. However, in the case of Comparative Example 1 in which the ratio of a and b in the general formula (8) was 0.8: 0.2, it was confirmed that the alkali insoluble group was insufficient in the side chain and was partially dissolved in the aqueous sodium hydroxide solution. It is preferable to synthesize the polyimide powder and BENP (corresponding to Formula 4) so as to be 0.3-0.3: 0.7. In the case of Comparative Example 2 in which the alkali insoluble group was not present in the side chain, it was confirmed that it dissolves in an aqueous solution of sodium hydroxide unlike the present invention.

Manufacturing example  1 to 6 and Comparative Manufacturing Example  1 to 2: PI  Production of film

Each of the aforesaid positive photosensitive polyimide solutions prepared in Examples 1 to 6 and Comparative Examples 1 and 2 was coated on a silicon wafer using a spin coater and prebaked at 100 ° C for 10 minutes to obtain an average thickness of 4 μm Of a polyimide precursor film was obtained. This precursor film was irradiated with ultraviolet rays having a light intensity of 150 mW / cm < 2 > at 365 nm for a predetermined time using an ultra-high pressure mercury lamp, and then heated at 120 DEG C for 5 minutes. Then, development was carried out for 1 minute at 2.degree. C. with a 2.38% aqueous solution of tetramethylammonium hydroxide to prepare Preparative Examples 1 to 6 and Comparative Preparative Examples 1 and 2. The test results are shown in Table 3.

(One) Residual film ratio  Measure

The film residual ratio was measured by the following equation (1), and the film thickness was measured using an STM-602 instrument (manufactured by Sukuren Company, Japan).

[Equation 1]

(%) = Film thickness after development / film thickness after free bake 占 100

(2) Resolution measurement

The film was subjected to i-line (365 nm) exposure and development, and a 50 μm line-and-space pattern (1L / 1S) Was measured as the resolution.

division Remaining film ratio (%) Light dose (mJ / cm 2) Resolution (탆) Production Example 1 84 1,500 5 Production Example 2 80 1,500 5 Production Example 3 82 1,500 10 Production Example 4 80 1,500 5 Production Example 5 78 1,500 10 Production Example 6 83 1,500 6 Comparative Preparation Example 1 38 1,500 Not measurable Comparative Production Example 2 Dissolution - Not measurable

From the results of the experiment of Table 3, it can be confirmed that the present invention of Production Examples 1 to 6 has a very high residual film ratio and resolution. However, in Comparative Production Example 1, the film was measured at a very low residual film ratio, and thus the resolution could not be obtained. In Comparative Production Example 2 and in the aqueous tetramethylammonium hydroxide solution, the measurement was impossible.

The final cured product prepared from the photosensitive transparent polyimide of the present invention has excellent physical properties through the above Examples and Experimental Examples. In particular, it has excellent transparency, is excellent in low temperature curing property, and is insoluble in alkali solvents. It has been confirmed that pattern formation is easy because it has a high residual film ratio and a low resolution.

Claims (13)

A photosensitive transparent polyimide comprising a compound represented by the following formula (1):
[Chemical Formula 1]
Figure pat00050

In the above Formula 1, X is -CH 2 -, -O-, -S-, -CO-, -CH (CH 3) -, C (CH 3) 2 -, -CH (CF 3) -, - C (CF 3 ) 2 - or -SO 2 -, R 1 is a C1-C6 alkyl group or a C2-C6 alkylene group, and R 2 is
Figure pat00051
,
Figure pat00052
or
Figure pat00053
R 3 is a hydrogen atom or a C 1 to C 4 alkoxy group, m is an integer of 1 to 3, and n is a rational number satisfying a weight average molecular weight of the compound of 5,000 to 200,000. A photosensitive transparent polyimide according to claim 1, which comprises a compound represented by the following formula (2):
(2)
Figure pat00054

In Formula 2, R 1 is a C1-C6 alkyl group or a C2-C6 alkylene group, and R 2 is
Figure pat00055
,
Figure pat00056
or
Figure pat00057
R 3 is a hydrogen atom or a C 1 to C 4 alkoxy group, m is an integer of 1 to 3, and n is a rational number satisfying a weight average molecular weight of the compound of 5,000 to 200,000. The method of claim 2, wherein, R 1 is an alkyl group of C1 ~ C6, R 2 is
Figure pat00058
or
Figure pat00059
, R 3 is a hydrogen atom or a C 1 to C 2 alkoxy group, and m is an integer of 1 to 2. The method of claim 3 wherein, R 1 is an alkyl group of C2 ~ C4, R 2 is
Figure pat00060
And R < 3 > is a hydrogen atom. A polyimide powder represented by the following formula (3); And a compound represented by the following general formula (4);
(3)
Figure pat00061

For Formula 3, X is -CH 2 -, -O-, -S-, -CO-, -CH (CH 3) -, -C (CH 3) 2 -, -CH (CF 3) -, -C (CF 3 ) 2 - or -SO 2 -, and n is a rational number satisfying the weight average molecular weight of the compound of 5,000 to 200,000,
[Chemical Formula 4]
Figure pat00062

In the formula (4), R 1 is a C1-C6 alkyl group or a C2-C6 alkylene group, and R 2 is
Figure pat00063
,
Figure pat00064
or
Figure pat00065
And R 3 is a hydrogen atom or a C 1 to C 4 alkoxy group. The photosensitive transparent polyimide composition according to claim 5, wherein the polyimide powder and the compound represented by Formula 4 are contained in a molar ratio of 0.7 to 0.2: 0.3 to 0.8. 6. The polyimide resin composition according to claim 5, wherein the polyimide powder is a polyamic acid represented by the following formula (5): Imidation catalyst; And a dehydrating agent; and a photosensitive transparent polyimide composition comprising:
[Chemical Formula 5]
Figure pat00066

In the above Formula 5, X is -CH 2 -, -O-, -S-, -CO-, -CH (CH 3) -, -C (CH 3) 2 -, -CH (CF 3) -, -C (CF 3 ) 2 - or -SO 2 -, and n is a rational number satisfying the weight average molecular weight of the compound of 5,000 to 200,000. The photosensitive transparent polyimide composition according to claim 5 or 7, wherein X is -C (CF 3 ) 2 - or -SO 2 -. 6. The method of claim 5,
Diazabicyclo [5.4.0] undec-7-ene (1,8-Diazabicyclo [5,4,0] undec-7-ene), 1,5-diazabicyclo 5-ene), trimethylamine, N-methylimidazole, and di-naphthylamine. Wherein the photosensitive transparent polyimide composition further comprises at least one reaction catalyst selected from the group consisting of isopropyl ethylenediamine and diisopropylethylamine. The photosensitive transparent polyimide composition according to claim 7, wherein the imidation catalyst comprises at least one selected from the group consisting of pyridine, isoquinoline, and? -Quinoline. The photosensitive transparent polyimide composition according to claim 7, wherein the dehydrating agent comprises at least one selected from the group consisting of acetic anhydride, phthalic anhydride, and maleic anhydride. A film comprising the photosensitive transparent polyimide of any one of claims 1 to 4. 13. The method of claim 12,
A film comprising a photosensitive transparent polyimide containing a polymer represented by the following formula (8);
[Chemical Formula 8]
Figure pat00067

For Formula 8, X is -CH 2 -, -O-, -S-, -CO-, -CH (CH 3) -, C (CH 3) 2 -, -CH (CF 3) -, - C (CF 3 ) 2 - or -SO 2 -, R 1 is a C1-C6 alkyl group or a C2-C6 alkylene group, and R 2 is
Figure pat00068
,
Figure pat00069
or
Figure pat00070
R 3 is a hydrogen atom or a C 1 to C 4 alkoxy group, m is an integer of 1 to 3, and a and b are rational numbers satisfying a: b = 0.7 to 0.2: 0.3 to 0.8.

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021060602A1 (en) * 2019-09-23 2021-04-01 에스케이씨코오롱피아이 주식회사 Polyimide powder preparation method, and polyimide powder prepared thereby

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021060602A1 (en) * 2019-09-23 2021-04-01 에스케이씨코오롱피아이 주식회사 Polyimide powder preparation method, and polyimide powder prepared thereby

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