KR20230134981A - Novel diamine compounds and polyimide polymer derived therefrom - Google Patents

Abstract

The present invention relates to a novel diamine compound and a polyimide-based polymer derived therefrom, and the diamine compound is represented by the following formula (1):
[Formula 1]

In Formula 1, L is a direct bond or a divalent organic group,
X ₁ and X ₂ are the same or different from each other and are each independently fluorine or a fluorine-substituted alkyl group,
n means the number of X ₁ substituted in the benzene ring, n' means the number of X ₂ substituted in the benzene ring, and n and n' are natural numbers from 1 to 4.

Description

Novel diamine compounds and polyimide polymer derived therefrom}

The present invention relates to a novel diamine compound and a polyimide-based polymer derived therefrom, and more specifically, to a novel diamine compound, a method for producing the same, and a method for producing the same, and the flexibility and heat resistance obtained by polymerizing the novel diamine compound as a monomer. It relates to a polyimide-based polymer capable of producing this excellent film.

Polyimide is easy to synthesize, can make thin films, and has the advantage of not requiring a cross-linker for curing. Recently, with the phenomenon of lighter and more precise electronic products, it has been used as a semiconductor material such as liquid crystal displays (LCDs) and plasma display panels (PDPs). It is widely applied as an integration material. In addition, much research is being conducted to use polyimide in flexible plastic display boards that are light and flexible.

Polyimide film is manufactured by turning the polyimide into a film. In general, polyimide is prepared by solution polymerizing aromatic dianhydride and aromatic diamine or aromatic diisocyanate to prepare a polyamic acid derivative solution, It is manufactured by coating it on a silicon wafer or glass, followed by heat treatment and hardening.

These polyimide-based polymers are manufactured by dissolving in an organic solvent with a high boiling point and applying it to a substrate in the form of polyamic acid, a precursor of polyimide, followed by heat treatment at a temperature of 300°C or higher for a long time to dehydrate and imidize.

However, the dehydration and imidization reactions of the polyamic acid are heated at high temperatures for a long time, causing deterioration. In addition, if heating is insufficient, polyamic acid remains in the structure of the produced polyimide polymer, causing a decrease in moisture resistance, corrosion resistance, etc.

Accordingly, a method of manufacturing a polyimide polymer film by applying a polyimide polymer solution dissolved in an organic solvent to a substrate and then heating to volatilize the solvent was proposed [Japanese Patent Publication Hei 2-36232]. However, the polyimide-based polymer film produced by the above method had the disadvantage of low solvent resistance.

In addition, a thermosetting polyimide-based polymer composition [Japanese Patent Application Laid-Open No. 10-195278], which produces a polyimide-based polymer film with excellent adhesion and solvent resistance by heat treatment at low temperature for a short time, was proposed. However, the thermosetting resin has the disadvantage of not showing sufficient heat resistance or having low transparency, which limits its field of use.

Republic of Korea Publication No. 10-2013-0094738 A

In order to solve the above-mentioned problems,

One object of the present invention is to provide a novel diamine compound.

One object of the present invention is to provide a polyimide-based polymer derived from the novel diamine compound.

One object of the present invention is to provide a polyimide film manufactured from the novel diamine compound, which has excellent flexibility and heat resistance.

The diamine compound according to one embodiment is represented by the following formula (1).

[Formula 1]

_In Formula 1, L _is a direct bond or a divalent organic group, X ₁ and means the number, n' means the number of X ₂ substituted on the benzene ring, and n and n' are natural numbers from 1 to 4.

The diamine compound according to one aspect may be a diamine compound represented by the following Chemical Formula 1-A.

[Formula 1-A]

In Formula 1-A, L is as defined in Formula 1 above.

The diamine compound according to one embodiment may be any one of the compounds represented by the following formulas 1-A-1 to 1-A-7.

[Formula 1-A-1]

[Formula 1-A-2]

[Formula 1-A-3]

[Formula 1-A-4]

[Formula 1-A-5]

[Formula 1-A-6]

[Formula 1-A-7]

The diamine compound according to one aspect may be a monomer derived from a polyimide-based polymer.

The polyimide-based polymer according to one aspect may include a repeating unit represented by the following formula (2).

[Formula 2]

In Formula 2, L, X ₁ , X ₂ , n, and n' are as defined in Formula 1, and Y is a tetravalent organic group.

The polyimide-based polymer according to one aspect may include a repeating unit represented by the following Chemical Formula 2-A.

[Formula 2-A]

In Formula 2-A, L and Y are as defined in Formula 2.

The polyimide film according to one aspect may include the polyimide-based polymer.

A device according to one aspect may include the polyimide film.

When the diamine compound of the novel structure according to the present invention is used as a monomer, there is an advantage in producing a polyimide film with excellent flexibility and heat resistance.

Therefore, the polyimide film according to the present invention is useful in color filters in semiconductor devices, protective films for light emitting diodes, laser diodes, liquid crystal alignment films, liquid crystal displays, flexible substrates for optical devices, and other electronics and optical fields.

Expressions such as “comprising” used herein should be understood as open-ended terms that imply the possibility of including other elements.

As used herein, “preferred” and “preferably” refer to embodiments of the invention that may provide certain advantages under certain circumstances. However, other embodiments may also be preferred, under the same or different circumstances, and are not intended to exclude other embodiments from the scope of the present invention.

As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly dictates otherwise.

The diamine compound according to one embodiment is represented by the following formula (1).

[Formula 1]

In Formula 1, L is a direct bond or a divalent organic group.

Here, the divalent organic group for L means a substituent having two bonding positions and includes all general organic functional groups.

In addition, in this specification, direct bonding means that the portion indicated by L is connected without a separate atom.

As an example, L is a direct bond, an organic group substituted or unsubstituted, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an aralkenyl group, an alkylaryl group, -CO-, -O-, -S- , -S0-, -SO ₂ -.

Here, ‘substituted or unsubstituted’ means deuterium; halogen; Nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; Amine group; amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkylthioxy group; Arylthioxy group; Alkyl sulphoxy group; Aryl sulfoxy group; silyl group; boron group; Alkyl group; Cycloalkyl group; alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups, or substituted or unsubstituted with two or more substituents among the above-exemplified substituents linked. As an example, the substituent may include fluorine.

In Formula 1, X ₁ and X ₂ are the same as or different from each other, and each independently represents a fluorine or a fluorine-substituted alkyl group. As an example, the fluorine-substituted alkyl group may be a fluoromethyl group.

In Formula 1, n means the number of X ₁ substituted in the benzene ring, n' means the number of X ₂ substituted in the benzene ring, and n and n' are natural numbers from 1 to 4.

For understanding, for example, when n is 4, it means that 4 X1 are substituted on the benzene ring.

In one embodiment, the diamine compound may be represented by the following Chemical Formula 1-1 or Chemical Formula 1-2.

[Formula 1-1]

[Formula 1-2]

In Formula 1-1 or Formula 1-2, L, X ₁ , X ₂ , n, and n' are as defined in Formula 1.

In one embodiment, the amine (-NH ₂ ) group may be independently substituted at the ortho, meta, or para position in each benzene ring.

In one embodiment, X ₁ or X ₂ may be independently substituted at one or more of the ortho, meta, or para positions in each benzene ring.

In one aspect, the diamine compound may be represented by the following formula 1-3.

[Formula 1-3]

In Formula 1-3, L, X ₁ , X ₂ , n, and n' are as defined in Formula 1.

In one embodiment, the diamine compound may be represented by the following formula 1-3-1. In this case, both X ₁ and X ₂ are fluorine groups.

[Formula 1-3-1]

In Formula 1-3-1, L, n, and n' are as defined in Formula 1.

The diamine compound according to one aspect may be a diamine compound represented by the following Chemical Formula 1-A.

[Formula 1-A]

In Formula 1-A, L is as defined in Formula 1 above.

The diamine compound according to one embodiment may be any one of the compounds represented by the following formulas 1-A-1 to 1-A-7.

[Formula 1-A-1]

[Formula 1-A-2]

[Formula 1-A-3]

[Formula 1-A-4]

[Formula 1-A-5]

[Formula 1-A-6]

[Formula 1-A-7]

The novel diamine compound according to one aspect can be produced by various production methods.

As an example, the diamine compound of Chemical Formula 1-A-1 can be prepared according to Scheme 1 below.

The diamine compound according to one aspect may be a monomer derived from a polyimide-based polymer.

At this time, the meaning of monomer derived from polyimide-based polymer means that the diamine compound is used as a monomer for synthesizing polyimide-based polymer.

Here, polyimide-based polymer means that it includes both polyimide and polyimide precursor (i.e., polyamic acid or polyamic acid ester).

Additionally, the diamine compound may be used to produce polyimide film. The diamine compound is used as a monomer to synthesize a polyimide-based polymer, and can be used to manufacture a polyimide film containing the synthesized polyimide-based polymer.

Additionally, in a more preferred embodiment, the polyimide-based polymer may be produced through a polymerization reaction of a diamine compound and acid dianhydride.

In this case, the polyimide-based polymer may further include a repeating unit derived from acid dianhydride in addition to the repeating unit derived from the diamine compound.

As a more preferred example, tetracarboxylic dianhydride may be used as the acid dianhydride polymerized with the diamine compound.

The tetracarboxylic dianhydride polymerized with the diamine compound is preferably uncolored or difficult to form a charge transfer complex, which is known to cause coloration. In addition, aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride is preferred in that it has excellent transparency, but aromatic tetracarboxylic dianhydride with better heat resistance can also be used as long as it is not colored.

For example, aliphatic tetracarboxylic dianhydride includes butane-1,2,3,4-tetracarboxylic dianhydride or pentane-1,2,4,5-tetracarboxylic dianhydride. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutane tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, and dianhydride. Cyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride, 2,3,4, 5-tetrahydrofuran tetracarboxylic dianhydride, etc. are mentioned.

For example, aromatic tetracarboxylic dianhydride includes pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-diphenyl ether. Tetracarboxylic dianhydride, 4,4'-hexafluoropropylidenebisphthalic dianhydride, and 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride.

In addition, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3 -Dione,1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c] An aliphatic tetracarboxylic dianhydride having an aromatic ring such as furan-1,3-dione can also be used.

In one aspect, these tetracarboxylic dianhydrides can be used individually or in combination of two or more types.

The polyimide-based polymer according to one aspect may include a repeating unit represented by the following formula (2).

[Formula 2]

In Formula 2, L, X ₁ , X ₂ , n, and n' are as defined in Formula 1, and Y is a tetravalent organic group.

In Formula 2, the organic group of Y refers to a substituent having four bonding positions and includes all general organic functional groups.

As an example, the Y is , , or It can be.

The Y may be derived from an acid dianhydride that polymerizes with the diamine compound.

In one embodiment, when there are n repeating units represented by Formula 2, n may be a natural number selected from 10 to 1000, but is not limited thereto.

In one aspect, the polyimide-based polymer may include a repeating unit represented by the following Chemical Formula 2-1 or Chemical Formula 2-2.

[Formula 2-1]

[Formula 2-2]

In Formula 2-1 or Formula 2-2, L, X ₁ , X ₂ , n, n', and Y are as defined in Formula 2.

In one aspect, the polyimide-based polymer may include a repeating unit represented by the following formula 2-3.

[Formula 2-3]

In Formula 2-3, L, X ₁ , X ₂ , n, n', and Y are as defined in Formula 2.

In one aspect, the polyimide-based polymer may include a repeating unit represented by the following formula 2-3-1. In this case, both X1 and X2 are fluorine groups.

[Formula 2-3-1]

In Formula 2-3-1, L, n, n', and Y are as defined in Formula 2.

The polyimide-based polymer according to one aspect may include a repeating unit represented by the following Chemical Formula 2-A.

[Formula 2-A]

In Formula 2-A, L and Y are as defined in Formula 2.

In one aspect, the polyimide-based polymer may include one or more repeating units represented by the following formulas 2-A-1 to 2-A-6.

[Formula 2-A-1]

[Formula 2-A-2]

[Formula 2-A-3]

[Formula 2-A-4]

[Formula 2-A-5]

[Formula 2-A-6]

[Formula 2-A-7]

According to one embodiment of the present invention, when polymerizing a polyimide precursor, one or more additional diamine compounds may be mixed and used in addition to the diamine compound, for example, a monocyclic or polycyclic aromatic divalent oil having 6 to 24 carbon atoms. A diamine compound containing a group, a monocyclic or polycyclic alicyclic divalent organic group having 6 to 18 carbon atoms, or a structure in which two or more of these are connected by a single bond or functional group can be additionally used. Alternatively, a diamine compound containing a single or fused heterocyclic ring structure such as aromatic or alicyclic ring structure, or a structure in which two or more of these are connected by a single bond can be additionally used.

In this case, the polyimide-based polymer may further include repeating units derived from diamine compounds that are mixed together, in addition to repeating units derived from the diamine compounds.

In addition, even if not exemplified in this specification, various monomers, additives, etc. required for polyimide resin synthesis can be applied without limitation as needed.

Meanwhile, before the polyimide is formed, polyamic acid or polyamic acid ester may be formed as a precursor compound. In this case, the polyimide precursor may include a repeating unit derived from the diamine compound.

Additionally, in one aspect, the polyimide precursor may further include a repeating unit derived from acid dianhydride.

Additionally, in one aspect, the polyimide precursor may further include a repeating unit derived from another diamine compound in addition to the repeating unit derived from the diamine compound.

In addition, even if not exemplified in this specification, various monomers, additives, etc. required for polyimide precursor synthesis can be applied without limitation as needed.

A method for producing a polyimide polymer resin according to one aspect of the present invention is a one-stage polymerization method in which the diamine and tetracarboxylic dianhydride are used in approximately equimolar amounts in the presence of a solvent and polymerized only at high temperature, or first at low temperature. You may use any of the two-stage polymerization methods of synthesizing amic acid and then imidizing it at high temperature.

In one aspect, the ratio of diamine to tetracarboxylic dianhydride can be appropriately adjusted depending on the molecular weight of the polyimide-based polymer resin. According to one embodiment, the diamine is preferably used in a molar ratio of 0.95 to 1.05, and preferably in a molar ratio of 0.98 to 1.02.

Additionally, in order to adjust the molecular weight of the polyimide polymer resin, monofunctional raw materials such as phthalic anhydride and aniline may be added. In this case, the amount of the added raw material is preferably 2 mol% or less relative to the polyimide polymer resin.

In the case of a one-stage polymerization method, the reaction temperature is 150 to 300 ℃, and the reaction time can be performed for 1 to 15 hours. In addition, in the case of a two-stage polymerization method, polyamic acid synthesis can be performed at a temperature of 0 to 120 ℃ for 1 to 100 hours, and imidization can be performed at a temperature of 0 to 300 ℃ for 1 to 15 hours.

According to one embodiment, the solvent that can be used during synthesis is preferably compatible with the diamine and tetracarboxylic dianhydride as raw materials and the polyimide-based polymer resin as the product. Specifically, phenols such as phenol, 4-methoxyphenol-4-methoxyphenol, 2,6-dimethylphenol, and m-cresol; ethers such as tetrahydrofuran and anisole; Ketones such as cyclohexanone, 2-butanone, methyl isobutyl ketone, 2-heptanone, 2-octanone, and acetophenone; esters such as butyl acetate, methyl benzoate, and ã-butyrolactone; Cellosolves such as butyl cellosolve acetate and propylene glycol monomethyl ether acetate; Amides such as N,N-dimethylformamide, N,N-dimethylacetoamide, and N-methyl-2-pyrrolidone may be used.

In addition, when aromatic hydrocarbons such as toluene and xylene are used together, water generated during imidization can be easily removed by azeotrope. These solvents may be used alone or in combination of two or more types.

In one embodiment, when using at least one of the diamine and tetracarboxylic dianhydride, a method of mixing all the raw materials in advance and then polycondensing them together, or two or more types of aromatic diamine or tetracarboxylic acid used A method of sequentially adding dianhydrides while reacting them individually may be used.

Additionally, in the imidization process, a dehydrating agent and an imidization catalyst may be added and, if necessary, heated to imidize the imidization method. The dehydrating agent may be, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride. This dehydrating agent is preferably used in an amount of 1 to 10 moles per mole of diamine.

The imidization catalyst may be, for example, a tertiary amine such as pyridine, collidine, lutidine, or triethylamine. This imidization catalyst is preferably used in an amount of 0.5 to 10 mol per 1 mol of dehydrating agent.

Since the polyimide-based polymer resin according to the present invention has excellent solubility, it is possible to adjust the viscosity to an appropriate level by dissolving it in an organic solvent so that it can be easily coated on various substrates.

Organic solvents capable of dissolving the polyimide-based polymer resin include, for example, general organic solvents used in polyimide-based polymer resin synthesis, aromatic hydrocarbon-based solvents different from those used during synthesis, ketone-based solvents, etc. Among these, in the case of dissolving in low boiling point aromatic hydrocarbon-based solvents or ketone-based solvents, it can be used to re-dissolve the purified polyimide resin by a method such as adding a poor solvent to the prepared polyimide resin solution and reprecipitating it. .

In one aspect, the substrate that can be coated with the polyimide polymer resin includes, for example, metals such as iron, copper, nickel, and aluminum; inorganic substances such as glass; It may be an organic resin such as epoxy resin or acrylic resin.

Additionally, in one aspect, thermosetting properties can be further improved by adding a material that reacts with a phenol group in the polyimide-based polymer resin prepared above. Examples of substances that react with the phenol group include polyfunctional organic compounds such as resins and oligomers containing two or more functional groups capable of reacting with phenol groups such as carboxyl groups, amino groups, and epoxy groups.

The present invention also provides a polyimide film with excellent flexibility and heat resistance manufactured by curing the polyimide-based polymer resin.

The curing may be performed under normal conditions, and is specifically preferably performed at a temperature of 80 to 300°C, preferably 100 to 250°C. If the curing temperature is less than 80°C, the curing time is long, making it less practical, and problems with storage stability may occur when selecting a device used at low temperatures. In addition, unlike conventional polyamic acid solutions, it does not require long-term heating at a temperature higher than 300°C after application, thereby suppressing heat-induced deterioration of the substrate.

When the film thickness is 10 ㎛, the polyimide film has a transmittance of 80% or more (at a film thickness of 10 ㎛) in the 400 to 700 ㎚ region (visible light), and the temperature at which the weight of the film is reduced by 5% is 300 ℃ or more. , the thermal decomposition start temperature may be 300°C or higher.

The present invention provides a device, particularly a flexible device, including the polyimide film as a substrate. The flexible device may be, for example, a thin film transistor, liquid crystal display (LCD), electronic paper, organic EL display, plasma display panel (PDP), IC card, etc., but is not limited thereto.

The structure and manufacturing method of the device are in accordance with known information.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention more practically, and it will be obvious to those skilled in the art that the scope of the present invention is not limited by these examples according to the gist of the present invention.

Examples and Comparative Examples

Polyimide-based polymer production

Into a flask equipped with a stirrer, thermometer, dropping device, and nitrogen substitution device, 0.2 mol of tetracarboxylic dianhydride and 200 g of dimethylacetylamide (DMA) as shown in Table 1 below were added and dissolved by heating to 50°C and stirring. Afterwards, 0.2 mol of the following aromatic diamine was dissolved in 200 g of dimethylacetylamide (DMA) at room temperature, and then added dropwise over 1 hour using a dropping funnel, followed by stirring at 50°C for 5 hours.

A portion of the reaction mixture was dissolved in DMSO-d6 solvent and NMR was measured to confirm that diamine was not present in the reaction product. On the other hand, it was confirmed that polyamic acid was produced through IR measurement.

Specifically, the reacted diamine compound and tetracarboxylic dianhydride are summarized in Table 1 below.

[Table 1]

Polyimide film manufacturing

The polyimide polymer solutions according to the examples and comparative examples prepared above were applied on a glass substrate and dried in a hot air dryer at 100°C for 10 minutes to prepare a film with a thickness of 10 ㎛. To imidize the amic acid remaining in the film, it was further heated in an oven at 300°C for 3 hours. Afterwards, the film prepared from the glass substrate was peeled to prepare a polyimide film.

Experiment example

Characterization evaluation of polyimide film

The physical properties of the polyimide films prepared in Examples and Comparative Examples were measured in the following manner, and the results are shown in Table 2 below.

1. Flexibility

The breaking angle was measured while bending the polyimide films prepared in Examples and Comparative Examples.

[Evaluation standard]

◎: Does not break even when bent 180 degrees

Ｏ: Broken at 150 to 180 degrees

×: Broken below 150 degrees

2. Heat resistance

The temperature at which the weight of the polyimide films of Examples and Comparative Examples manufactured using TA Instruments' Q50 equipment is reduced by 5% and the thermal decomposition initiation temperature were measured and classified as follows.

[Evaluation standard]

◎: The temperature at which the weight is reduced by 5% and the thermal decomposition start temperature is 320℃ or higher.

Ｏ: The temperature at which the weight is reduced by 5% and the thermal decomposition start temperature is 300℃ or more and less than 320℃.

×: Temperature at which weight is reduced by 5% and thermal decomposition start temperature is less than 300℃

[Table 2]

As can be seen in Table 2, the polyimide films according to the examples of the present invention (Examples 1 to 3) were different from the polyimide films according to the comparative example (Comparative Examples 1 and 2) even though the same acid anhydride was used. In comparison, it can be seen that it is superior in both flexibility and heat resistance.

As described above, specific parts of the present invention have been described in detail through various embodiments. For those skilled in the art, these specific techniques are merely preferred embodiments, thereby limiting the scope of the present invention. It will be clear that this is not the case. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (8)

Represented by the formula 1 below,
Diamine compounds:
[Formula 1]

In Formula 1, L is a direct bond or a divalent organic group,
X ₁ and X ₂ are the same or different from each other and are each independently fluorine or a fluorine-substituted alkyl group,
n means the number of X ₁ substituted in the benzene ring, n' means the number of X ₂ substituted in the benzene ring, and n and n' are natural numbers from 1 to 4.
According to claim 1,
A diamine compound represented by the following formula 1-A:
[Formula 1-A]

In Formula 1-A, L is as defined in Formula 1 above.
According to claim 1,
Any one of the compounds represented by the following formulas 1-A-1 to 1-A-7,
Diamine compounds:
[Formula 1-A-1]

[Formula 1-A-2]

[Formula 1-A-3]

[Formula 1-A-4]

[Formula 1-A-5]

[Formula 1-A-6]

[Formula 1-A-7]

According to claim 1,
The diamine compound represented by Formula 1 is a monomer derived from a polyimide polymer,
Diamine compounds.
Containing a repeating unit represented by Formula 2 below,
Polyimide-based polymer:
[Formula 2]

In Formula 2, L, X ₁ , X ₂ , n, and n' are as defined in Formula 1,
The Y is a tetravalent organic group.
According to claim 5,
Containing a repeating unit represented by the following formula 2-A,
Polyimide-based polymer:
[Formula 2-A]

In Formula 2-A, L and Y are as defined in Formula 2.
Containing the polyimide-based polymer of claim 5,
Polyimide film.
Comprising the polyimide film of claim 7,
device.