KR101971155B1 - Diamine monomer, transparent polyimide comprising the same, and the preparation method thereof - Google Patents

Abstract

The present invention relates to a diamine monomer having a flexible structure, a transparent polyimide including the same, and a process for producing the same. According to the present invention, a transparent and flexible polyimide thin film can be obtained by using flexible diamine for polyimide synthesis. The produced polyimide thin film has an advantage that it can be used as an optical device material having excellent chemical and mechanical properties.

Description

[0001] The present invention relates to a diamine monomer having a flexible structure, a transparent polyimide containing the same, and a process for producing the same,

The present invention relates to a diamine monomer having a flexible structure, a transparent polyimide including the same, and a process for producing the same.

Polyimide is a polymer material having an imide ring formed by condensation polymerization of a dianhydride with an aromatic diamine or a polyisocyanate in a solvent and may have various molecular structures depending on the type of the monomer used, Physical properties appear.

As the polyimide, pyromellitic dianhydride (PMDA) or biphenyltetracarboxylic dianhydride (BPDA) or the like is used as the dianhydride, oxydianiline (ODA) or p-phenylene diamine (P-PDA) and so on. Such polyimides are widely used as substitutes for metals and glass in various fields such as electric, electronic, semiconductor, automobile, airplane, and optical device due to various properties such as excellent heat resistance, electrochemical and mechanical properties and flame retardancy.

Particularly, weight reduction and miniaturization of the jumba are important in the field of display, so that the polyimide which is lighter in weight than the glass substrate currently used, easy to synthesize, and capable of producing a thin film can be used for a plastic display substrate .

Despite these advantages, they do not satisfy the basic colorless and transparent properties for use in the display field, and are difficult to process due to the curing temperature (400 ° C), high viscosity, insoluble and infusible properties Much effort is being made to solve the same problems.

In the prior art for solving the above problems, US Pat. No. 5,053,480 discloses a technique for using an aliphatic cyclic dianhydride component instead of an aromatic dianhydride. When the above-described technique was applied, transparency and color were improved. However, as described above, it was not remarkable improvement for use as a high-performance optical material, and the polyimide film thus prepared had excellent thermal and physical stability There is a problem in which the temperature is greatly lowered.

Further, in Japanese Patent Laid-Open Nos. 58-208322 and 2006-232960, 1,2,3,4-cyclopentanetetracarboxylic acid-1, 2,3: 4- 2 anhydride has been studied but has a problem of low polymerization degree and heat resistance and low solubility in an organic solvent.

These prior arts do not have high transparency, heat resistance, and flexibility, which are basic conditions in which a polyimide thin film can be used as a material of an optical device, and it is urgent to develop an improved polyimide thin film.

1. U.S. Patent No. 5,053,480 2. Japanese Patent Laid-Open No. 58-208322 3. Japanese Patent Application Laid-Open No. 2006-232960

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art. Accordingly, the present invention provides a polyimide thin film excellent in transparency, heat resistance, and flexibility so that it can be used as a material for an excellent optical device.

The present invention also provides monomers for the production of polyimide, polyamic acid or a composition containing the same, and a process for producing the same.

One aspect of the present invention relates to a monomer for polyimide synthesis.

Another aspect of the present invention relates to a polyamic acid comprising a gastric monomer, a composition thereof, or a polyimide.

Another aspect of the present invention relates to a method for producing a polyamic acid or polyimide using a stomach monomer.

According to the present invention, a transparent and flexible polyimide thin film can be obtained by using flexible diamine for polyimide synthesis. The produced polyimide thin film has an advantage that it can be used as an optical device material having excellent chemical and mechanical properties.

Fig. 1 shows the results of hydrogen-resonance spectroscopy ( ¹ H-NMR) analysis of the structural analysis of the novel diamine prepared in Example 3. Fig.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

An aspect of the present invention relates to a monomer for synthesizing a polyimide having a structure represented by the following formula:

[Formula 1a]

A is (CH ₂ ) _p , and p is a natural number between 1 and 5.

Another aspect of the present invention relates to a polyamic acid characterized by containing the above compound as a monomer.

According to one embodiment, the polyamic acid is represented by the following formula (1b).

[Chemical Formula 1b]

은 하기 화학식 2a 내지 2f 중 어느 하나의 구조를 가지고,remind

Has the structure of any one of formulas (2a) to (2f)

The -Ar ₂ - has the structure of the following formula (1d)

Wherein -Ar ₃ - has the structure of any one of formulas (3a) to (3j)

Wherein -X ₁ and -X ₂ are the same or different and independently represent a structure of any one of the following formulas (4a) to (4d)

N is 0 or 1, m1 is a number of 5 to 1,000 or less, and m2 is a number of 0 to 10,000 or less. When n is 0, it means polyamic acid which is not end-capped, and when n is 1, it means polyamic acid end-capped with X ₁ and X ₂ .

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

(2f)

≪ RTI ID = 0.0 &

[Chemical Formula 3]

(3b)

[Chemical Formula 3c]

(3d)

[Formula 3e]

(3f)

[Formula 3g]

[Chemical Formula 3h]

[Formula 3i]

[Chemical formula 3j]

[Chemical Formula 4a]

(4b)

[Chemical Formula 4c]

[Chemical formula 4d]

.

.

Another aspect of the present invention relates to a polyimide comprising a compound of formula (1a) as a monomer.

According to one embodiment, the polyimide is represented by the following formula (1c).

[Chemical Formula 1c]

, -Ar₂-, -Ar₃-, -X₁, -X₂, n, m1, m2은 제2항에 정의된 바와 같다.remind

_{, -Ar 2 -, -Ar 3 -} , -X 1, -X 2, n, m1, m2 are as defined in claim 2.

According to another aspect of the present invention, there is provided a polyimide preparation composition comprising polyamic acid according to various embodiments of the present invention, 0.1 to 5 parts by weight of a low temperature curing catalyst based on 100 parts by weight of the polyamic acid, and 0.1 to 10 parts by weight of an inorganic filler .

The low temperature curing catalyst may be selected from the group consisting of 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undec-7- Or more.

The inorganic filler may be selected from the group consisting of silica, alumina, titania, manganese oxide, zirconium oxide, tetraethoxysilane, montmorillonite martensitic, zirconium phosphate (ZrP), phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, And multiple acids (HPA).

Another aspect of the present invention relates to a process for preparing a polyamic acid of the above formula (1b), comprising the steps of (A) reacting dianhydride with diamine to obtain the polyamic acid according to claim 3. And more particularly to a method for producing polyamic acid which is not end-capped.

The dianhydride may be at least one selected from the group consisting of pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3 , 3'4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 4,4 '- (hexafluoroisopropylidene) diphthalic acid dianhydride (6FDA), 3,3', 4,4 ' - diphenylsulfone tetracarboxylic acid dianhydride (DSDA).

The diamine may be selected from the group consisting of (i) the diamine of formula (1a) or (ii) 4,4'-oxydianiline (4,4'-ODA), phenylmethyldiamine, 3,4'-oxydianiline 3,4'-ODA), 1,4-phenylene diamine (1,4-PDA), 4,4'-sulfonyl dianiline (4,4'- DDS), 2,2'- Amino-4-hydroxyphenyl) -hexafluoropropane (AHHFP), 2,2'-bis (4-aminophenyl) -hexafluoropropane (BAPFP), 4,4'-diaminodiphenylmethane (MDA), bis (4-aminophenoxy) phenylsulfone, bis [4- (3-aminophenoxy) phenyl] sulfone and bis A mixture of a first diamine and a second diamine of the general formula (1a).

At this time, the dianhydride and the diamine are reacted at almost the same molar equivalents.

Another aspect of the present invention relates to a method for preparing polyamic acid, comprising the steps of: (A) reacting dianhydride with diamine to obtain a polyamic acid according to claim 3; (A ') reacting said polyamic acid with an endcapping agent to obtain an end- To obtain a polyamic acid of Formula 1b.

The dianhydride and the diamine are mentioned above.

The end capping agent is at least one selected from 3-aminophenylacetylene, 3-aminophenylcyclobutene, maleic anhydride and norbornene-2,3-dicarboxylic anhydride.

At this time, 1 mole of the mixture of diamine and end capping agent per mole of dianhydride is used, and the diamine and end capping agent are used in a molar ratio of 0.1-0.4 mole and 0.6-0.9 mole, respectively.

In one embodiment, the diamine is in the case of stomach (ii), i.e. a mixture of a first diamine and a second diamine wherein the weight ratio of the first diamine to the second diamine is preferably 5-15: 1 And if it is outside the above range, the mechanical properties of the membrane may be reduced.

Another aspect of the present invention relates to (B) a process for producing a polyimide represented by the above formula (1c), comprising the step of curing a polyamic acid according to various embodiments of the present invention to obtain a polyimide.

According to one embodiment, in the step (B), a low-temperature curing catalyst and an inorganic filler are used.

The low temperature curing catalyst may be selected from the group consisting of 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undec-7- Or more.

The inorganic filler may be selected from the group consisting of silica, alumina, titania, manganese oxide, zirconium oxide, tetraethoxysilane, montmorillonite martensitic, zirconium phosphate (ZrP), phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, And multiple acids (HPA).

According to another embodiment, in the step (B), the low temperature curing catalyst is first added to the polyamic acid reaction product obtained in step (A) or step (A '), .

According to another embodiment, the low temperature curing catalyst is selected from the group consisting of 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undec- Hydroxypyridine in a weight ratio of 1: 1.5-2.5: 4.5-5.5.

According to another embodiment, the step (B) is carried out by spin-coating the polyamic acid of the step (A) or (A ') and then curing at 200-250 ° C for 30-120 minutes.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the scope and content of the present invention can not be construed to be limited or limited by the following Examples. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the present invention as set forth in the following claims. It is natural that it belongs to the claims. In addition, the experimental results presented below only show representative experimental results of the embodiments and the comparative examples, and the respective effects of various embodiments of the present invention which are not explicitly described below will be specifically described in the corresponding part.

Example

Comparative Example  One

0.003 mol of 4,4'-oxydianiline was completely dissolved in N-methylpyrrolidinone in a 50-mL Erlenmeyer flask equipped with a mechanical stirrer and a nitrogen inlet tube at 25 ° C under a nitrogen atmosphere, Hexafluoroisopropylidene) diphthalic dianhydride was further added thereto, and an ice bath was further placed thereon. The mixture was stirred at a temperature of 0 ° C for 24 hours to prepare a viscous polyamic acid. Then, 100 parts by weight of the polyamic acid 1 part by weight of 1,4-diazabicyclo [2,2,2] octane as a low-temperature curing catalyst was added and the mixture was cured at low temperature by spin coating on a glass plate to prepare a polyimide thin film.

Comparative Example  2

A polyimide thin film was prepared in the same manner as in Comparative Example 1, except that 5 parts by weight of the low temperature curing catalyst was used instead of 1 part by weight.

Comparative Example  3

4,4'- (hexafluoroisopropylidene) diphthalic acid Polyimide thin films were prepared in the same manner as in Comparative Example 1, except that 4,4'-oxydiphthalic dianhydride was used instead of anhydride.

Example  One

4,4'-oxy-dimethyl aniline rather than 0.003 mol diamine of the formula 1a below (where A = CH ₂₎ after the use of 0.003 mol, and the addition of the inorganic filler, silica 5 parts by weight of the polyamic acid to 100 parts by weight based on the A polyimide thin film was prepared in the same manner as in Comparative Example 1, except that 1 part by weight of 1,4-diazabicyclo [2,2,2] octane was further added.

[Formula 1a]

Example  2

Except that 0.003 mol of diamine of the above formula (1a) was used instead of 0.0003 mol of diamine of the above formula (1a) and 0.0027 mol of 4,4'-oxydianiline was used, the same procedure as in Example 1 To prepare a polyimide thin film.

Example  3

Instead of adding 1 part by weight of 1,4-diazabicyclo [2,2,2] octane after 5 parts by weight of silica was added, 1,4-diazabicyclo [2,2,2] A polyimide thin film was prepared in the same manner as in Example 1, except that 5 parts by weight of silica was further added.

Example  4

Instead of using 1 wt% of the 1,4-diazabicyclo [2,2,2] octane, 1,4-diazabicyclo [2,2,2] octane: 1,8-diazabicyclo [ , 0] undec-7-ene: 4-hydroxypyridine in a weight ratio of 1: 2: 5 was used instead of the polyimide thin film.

Example  5

Diazabicyclo [2,2,2] octane: 1,8-diazabicyclo [5.4] diazabicyclo [2.2.2] octane instead of using 1 wt% , 0] undec-7-ene: 4-hydroxypyridine in a weight ratio of 5: 2: 3 was used instead of the polyimide thin film.

Experimental Example  One

Structural analysis for the novel diamine prepared according to Example 3 was carried out using hydrogen-resonance spectroscopy ( ¹ H-NMR), and the results are shown in FIG.

Experimental Example  2

The decomposition initiation temperature (T _{d, 5%} ) and the thermal stability of the polyimide thin films prepared according to the comparative examples and the examples were analyzed by a thermogravimetric analyzer (TGA, TA Instrument Co., USA, Q50) . Under the analysis conditions, the temperature raising rate was raised from room temperature to 600 ° C at 10 ° C / min.

Experimental Example  3

The glass transition temperature (T _g ) of the polyimide thin films prepared according to the comparative examples and the examples was measured using Differential scanning calorimetry (DSC, TA Instrument Co., USA, Q10). The results are shown in Table 1 below.

Experimental Example  4

The transmittance of the polyimide thin film prepared according to the comparative examples and the examples was measured by ultraviolet light and visible light spectrophotometer (UV-visible spectrometer). The results are shown in Table 1 below.

Experiment result

As shown in Table 1 below, the polyimide exhibited improved decomposition initiation temperature, glass transition temperature and maximum transmittance in the case of using the diamine of formula 1 in comparison with the comparative example, and further improved thermal stability And excellent transmittance.

division Decomposition initiation temperature Glass transition temperature Maximum permeability Comparative Example 1 532.3 DEG C 285.6 DEG C 73.2% Comparative Example 2 530.2 DEG C 289.6 DEG C 81.8% Comparative Example 3 548.8 DEG C 293.2 DEG C 86.1% Example 1 557.5 DEG C 297.4 DEG C 89.3% Example 2 559.1 DEG C 299.2 DEG C 90.5% Example 3 560.8 DEG C 301.2 DEG C 91.6% Example 4 565.2 DEG C 304.7 ℃ 93.4% Example 5 562.1 DEG C 302.5 ° C 92.1%

Particularly, it has been confirmed that it is advantageous in terms of thermal stability and transparency to be used in combination with existing monomers such as 4,4'-oxydianiline, rather than using only diamines of the above formula (1a). In addition, It was also confirmed that the order of introduction of the catalyst is important in terms of thermal stability and permeability.

Further, it is also possible to use 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undec-7-ene or 4-hydroxypyridine as low- In contrast, the use of a mixture of these three compounds showed a greater improvement in thermal stability and permeability, especially when 1,4-diazabicyclo [2,2,2] octane: 1,8 - diazabicyclo [5,4,0] undec-7-ene: 4-hydroxypyridine in the range of 1: 1.5-2.5: 4.5-6.5. In particular, it has been confirmed that the maximum permeability is maintained without deterioration even after 1,000 hours or more of use by adjusting the mixing ratio at such a weight ratio.

Claims (14)

delete delete delete delete delete delete delete delete delete (B) A process for producing a polyimide represented by the following formula (1c), comprising the step of curing a polyamic acid represented by the following formula (1b) to obtain a polyimide;
[Chemical Formula 1b]

[Chemical Formula 1c]

remind

Has a structure represented by the following formula (2e)
Wherein -Ar ₂ - has the structure of the following formula (1d)
Wherein -Ar ₃ - has the structure of formula (3a)
Wherein -X ₁ and -X ₂ are the same or different and independently represent a structure of any one of the following formulas (4a) to (4d)
N is 0 or 1, m1 is a number of 5 to 1,000 or less, m2 is a number of 0 to 10,000 or less,
[Formula 2e]

≪ RTI ID = 0.0 &

[Chemical Formula 3]

[Chemical Formula 4a]

(4b)

[Chemical Formula 4c]

[Chemical formula 4d]

In the step (B), a low temperature curing catalyst and an inorganic filler are used,
The low temperature curing catalyst may be selected from the group consisting of 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undec-7-ene, 4- 1.5-2.5: a mixture of 4.5-5.5. 11. The method of claim 10, wherein the inorganic filler is selected from the group consisting of silica, alumina, titania, manganese oxide, zirconium oxide, tetraethoxysilane, montmorillonite matenenite, zirconium phosphate (ZrP), phosphotungstic acid, silicotungstic acid, Polyphosphoric acid, phosphomolybdic acid, and heteropoly acid (HPA). 12. The method according to claim 11, wherein, in the step (B) , the low-temperature curing catalyst is first charged, and then the inorganic filler is introduced. The process for producing a polyamic acid according to claim 10, wherein the polyamic acid is prepared by the following step (A) when n is 0, and sequentially performing the following steps (A) and (A ') when n is 1 Wherein the polyimide is a polyimide.
(A) reacting dianhydride with diamine to obtain a polyamic acid of formula (1b) wherein n is 0,
(A ') reacting the polyamic acid of formula (1b), wherein n is 0, with an end capping agent to obtain a polyamic acid of formula (1b) wherein n is 1, wherein the n is 1, the dianhydride is pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3'4,4'-benzo (6HPA), 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride (BTDA), 4,4'- (hexafluoroisopropylidene) diphthalic acid dianhydride One or two species selected from water (DSDA)
The diamine may be a diamine of the formula (I) or a 4,4'-oxydianiline (4,4'-ODA), phenylmethyldiamine, 3,4'-oxydianiline ), 1,4-phenylene diamine (1,4-PDA), 4,4'-sulfonyl dianiline (4,4'-DDS), 2,2'- Phenyl) -hexafluoropropane (AHHFP), 2,2'-bis (4-aminophenyl) -hexafluoropropane (BAPFP), 4,4'-diaminodiphenylmethane (MDA), bis At least one first diamine selected from the group consisting of bis (4-aminophenyl) sulfone (BAPS), bis [4- (4-aminophenoxy) phenyl] sulfone and bis [4- Lt; RTI ID = 0.0 > (IIa) < / RTI > [14] The method of claim 12, wherein the step (B) is performed by spin-coating the polyamic acid of the step (A) or (A ') and then curing the mixture at 200-250 [deg.] C for 30-120 minutes Gt; polyimide < / RTI >

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