KR20240079802A - Diamine compound, heat-resistant resin, resin composition, cured film and display device - Google Patents

Abstract

The present invention relates to a novel diamine compound, a heat-resistant resin polymerized including the same, a resin composition containing the heat-resistant resin, a cured film manufactured using the same, and an image display device including the cured film. When synthesizing the resin, it relates to health and It has excellent solubility in solvents to replace N-methylpyrrolidone (NMP), which causes environmental problems, and has a heat-resistant resin containing the diamine compound of the present invention, a resin composition, a cured film using the same, and a film containing the same. The image display device has excellent heat resistance and moisture absorption, resulting in improved reliability.

Description

Diamine compound, heat-resistant resin, resin composition, cured film and image display device {DIAMINE COMPOUND, HEAT-RESISTANT RESIN, RESIN COMPOSITION, CURED FILM AND DISPLAY DEVICE}

The present invention relates to a novel diamine compound, a heat-resistant resin polymerized including the same, a resin composition containing the heat-resistant resin, a cured film manufactured using the resin composition, and an image display device including the cured film.

Recently, in the field of electronic devices such as displays, weight reduction and miniaturization have become important, and polymer materials that are light, flexible, and have excellent processability are being applied. In general, polymer materials are light, have excellent moldability, and have excellent physical properties, but have the problem of poor heat resistance. Among polymer materials, polymer resins such as polyimide and polybenzoxazole, which have excellent mechanical properties and heat resistance, are used in various fields. there is.

Polymer resins such as polyimide and polybenzoxazole are polymers characterized by having a rigid main chain, and have excellent properties such as heat resistance, chemical resistance, mechanical properties, and low dielectric constant, and are widely used in coating materials, molding materials, composite materials, etc. It is applied for a wide range of purposes. However, resins such as polyimide and polybenzoxazole have the problem of being very difficult to process because they do not dissolve in most solvents due to rigidity due to the imide ring, benzoxazole ring, etc. in the main chain.

Accordingly, after processing their precursors, polyamic acid and polyhydroxyamide, resins such as polyimide and polybenzoxazole were obtained through thermal cyclization reaction. This process requires curing at a high temperature, but due to concerns about damage when applied to electronic devices that are vulnerable to high temperatures, there was a problem that the heat resistance of the polymer resin deteriorated when curing was required at a low temperature.

Until now, polyimides with improved solubility in solvents (e.g., Japanese Patent Laid-open No. 2005-41936) or polyimide precursors (e.g., Japanese Patent Laid-Open Nos. 2011-42701 and Japanese Patent Laid-Open Nos. No. 2011-202059) has been proposed, but these resins also have insufficient solubility and insufficient hygroscopicity, so their use is limited.

Meanwhile, in order to facilitate the dissolution of polymer resins with such a rigid ring structure, solvents such as N-methylpyrrolidone (NMP) and N,N-dimethylformamide (DMF) are used as solvents when synthesizing polymer resins. have been using it However, the European Union (EU) has adopted separate regulations for the management and restriction of high-risk chemicals that cause health and environmental problems, and according to the EU, N-methylpyrrolidone (NMP), N, N - Solvents such as dimethylformamide (DMF) cannot be manufactured or used, so there are limits to the use of these solvents.

Therefore, there is a need for the development of heat-resistant resins with excellent solubility in solvents to replace N-methylpyrrolidone (NMP) and new diamine compounds for producing the heat-resistant resins.

Japanese Patent Publication No. 2005-41936 Japanese Patent Publication No. 2011-42701 Japanese Patent Publication No. 2011-202059

The present invention is intended to improve the conventional technical problems described above, and provides a heat-resistant resin with excellent solubility in solvents and excellent heat resistance and hygroscopicity to replace N-methylpyrrolidone (NMP), which causes health and environmental problems. The purpose is to provide a diamine compound that can be obtained as a resin composition.

Additionally, the present invention aims to provide a heat-resistant resin polymerized with the diamine compound and a resin composition containing the same.

Additionally, the present invention aims to provide a cured film manufactured using the above resin composition and an image display device including the same.

However, the problem to be solved by the present application is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

To achieve the above object, the present invention provides a diamine compound represented by Formula 1.

[Formula 1]

(In Formula 1,

X and Y each independently represent a substituted or unsubstituted divalent aliphatic group or a substituted or unsubstituted divalent aromatic group.

A represents -O-, -CO-, -SO ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -.)

Additionally, the present invention provides a heat-resistant resin polymerized including the diamine compound.

Additionally, the present invention provides a resin composition containing the heat-resistant resin.

Additionally, the present invention provides a cured film manufactured using the above resin composition.

Additionally, the present invention provides an image display device including the cured film.

The diamine compound of the present invention is gammabutyrolactin (GBL), which has less impact on health and the environment, replacing N-methylpyrrolidone (NMP), which was used in the synthesis of polymer resins with a rigid ring structure. The heat-resistant resin polymerized with the diamine compound of the present invention, the resin composition containing the same, and the cured film manufactured using the same have excellent solubility in solvents such as heat resistance and hygroscopicity, and are an image display device with improved reliability. It has the effect of providing.

The present invention relates to a diamine compound represented by Formula 1, a heat-resistant resin polymerized including the diamine compound, a resin composition including the same, a cured film manufactured using the same, and an image display device including the same, and has no effect on health and the environment. The present invention was completed by experimentally confirming that it has excellent solubility in relatively small solvents such as gamma butyrolactone (GBL) and excellent heat resistance and hygroscopicity, thereby improving reliability.

Hereinafter, the present invention will be described in detail. However, the present invention is not limited to these components.

<Diamine compound>

The present invention provides a diamine compound represented by Formula 1.

[Formula 1]

(In Formula 1,

X and Y each independently represent a substituted or unsubstituted divalent aliphatic group or a substituted or unsubstituted divalent aromatic group.

A represents -O-, -CO-, -SO ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -.)

The diamine compound represented by Formula 1 of the present invention is characterized by having a more linear structure including -S- between The reliability of heat resistance and hygroscopicity of the polymer resin can be improved. In particular, if only -O- rather than -S- is included between X and Y, there may be a problem with hygroscopicity.

The X and Y may be the same or different. Additionally, the two Xs may be the same or different, and the two Ys may also be the same or different.

In the present invention, the “divalent” group may mean that two hydrogen atoms are removed from any position of the compound.

Specifically, the divalent aliphatic group for

Examples of the saturated hydrocarbon group include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl groups; Branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group; and alicyclic alkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group. Additionally, substituents that the aliphatic group may have include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; Hydrocarbon groups with 1 to 12 carbon atoms, such as methyl and ethyl groups; Alkoxy groups having 1 to 6 carbon atoms, such as methoxy group and ethoxy group; -OH; -SO ₃ H; -SO ₃ -; Alkylsulfonyl groups having 1 to 6 carbon atoms, such as methylsulfonyl groups; Alkoxycarbonyl groups having 1 to 6 carbon atoms, such as methoxycarbonyl group and ethoxycarbonyl group; etc. can be mentioned.

-CH ₂ - constituting the saturated hydrocarbon group may be substituted with -O-, -CO-, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH-, or -NHCO-. However, adjacent -CH ₂ - cannot be substituted with the same group at the same time, and -CH ₂ - at the terminal cannot be substituted.

The divalent aromatic group for

Examples of the aromatic hydrocarbon group include phenyl group, tolyl group, xylyl group, mesityl group, propylphenyl group, butylphenyl group, and naphthyl group. Additionally, substituents that the aromatic group may have include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; Saturated hydrocarbon groups having 1 to 12 carbon atoms, such as methyl and ethyl groups; Alkoxy groups having 1 to 6 carbon atoms, such as methoxy group and ethoxy group; -OH; -SO ₃ H; -SO ₃ -; Alkylsulfonyl groups having 1 to 6 carbon atoms, such as methylsulfonyl groups; Alkoxycarbonyl groups having 1 to 6 carbon atoms, such as methoxycarbonyl group and ethoxycarbonyl group; and the like, and may preferably be a saturated hydrocarbon group having 1 to 12 carbon atoms. -CH ₂ - constituting the saturated hydrocarbon group may be substituted with -O-, -CO-, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH-, or -NHCO-.

The A represents -O-, -CO-, -SO ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -, and from the viewpoint of solubility, -O-, -SO ₂ - or -C(CF ₃ ) ₂ - is preferred.

The method for producing the diamine compound of the present invention is not particularly limited, and may be produced by methods known to those skilled in the art.

Examples of the diamine compounds include bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), bis(3-amino-4-hydroxyphenyl)sulfone, and bis(3-amino-4-hydroxyphenyl). ) Propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino) Diamines containing hydroxyl groups such as -4-hydroxyphenyl)fluorene, diamines containing carboxyl groups such as 3,5-diaminobenzoic acid and 3-carboxy-4,4'-diaminodiphenyl ether, 3-sulfonic acid-4 , 4'-diaminodiphenyl ether, diamine containing sulfonic acid, dithiohydroxyphenylenediamine, etc.

Examples of reaction solvents include ketones such as methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methyl ethyl ketone, and acetone, esters such as ethyl acetate, butyl acetate, and isobutyl acetate, tetrahydrofuran, and dimethoxy. Ethers such as ethane, diethoxyethane, dibutyl ether, and diethylene glycol dimethyl ether can be mentioned. Among these, from the viewpoint of solubility and versatility, it is more preferable to use acetone. These may be used individually or in mixture of two or more types. The amount of the reaction solvent used is preferably in the range of 100 to 5000 parts by mass from the viewpoint of solubility with respect to 100 parts by mass of the diamine compound.

<Heat-resistant resin>

The heat-resistant resin of the present invention includes, without limitation, a resin polymerized including the diamine compound described in the above <diamine compound> section. Specifically, the heat-resistant resin of the present invention may be polymerized including a diamine compound represented by Formula 1 above. In addition, it may be polymerized by further including a diamine compound other than the diamine compound represented by Formula 1, and may be polymerized by further including at least one type selected from acid dianhydride and acid chloride.

Specifically, the heat-resistant resin of the present invention includes a precursor resin obtained by polymerizing one or more of the above diamine compounds and one or more selected from acid dianhydrides and acid chlorides, and a polymer resin obtained by heating and/or dehydrating the precursor resin. As such, it may include one or more types selected from the group consisting of polyimide, polybenzoxazole, polybenzimidazole, polybenzothiazole, precursors thereof, and polymers thereof.

As the acid dianhydride, tetracarboxylic dianhydride may be used, for example, aromatic, alicyclic, or a structure in which two or more of them are connected by a single bond or functional group in the molecule, or aromatic, alicyclic It may include a ring structure such as a single ring structure, a fused heterocyclic ring structure, or a structure in which two or more of them are connected by a single bond.

The acid dianhydride is, for example, 4,4'-oxydiphthalic anhydride, pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4 '-Biphenyl-tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 5-(2 ,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride or 1,2,4,5-cyclohexanetetracarboxylic dianhydride, but is limited thereto. Not necessarily, and preferably 4,4'-Oxydiphthalic Anhydride (ODPA).

Examples of the acid chloride include 4,4'-oxybis(benzoyl chloride), terephthaloyl chloride, isophthaloyl chloride, 3,4'-oxybis(benzoyl chloride), 2,2-bis(4) -benzoyl chloride) hexafluoropropane, 2,2-bis (4-benzoyl chloride) propane, biphenyl-4,4'-dicarboxylic acid chloride, or 4,4'-methane-bis (benzoyl chloride). However, it is not limited to this, and is preferably 4,4'-Oxybis(benzoyl Chloride) (OBC).

According to one embodiment of the present invention, the heat-resistant resin of the present invention may be polymerized by containing the diamine compound represented by Formula 1 above and at least one selected from acid dianhydride and acid chloride as monomers, and additional monomers may be added as necessary. It may be polymerized further.

The diamine compound represented by Formula 1 may be included in an amount of 1 to 80 mol%, preferably 10 to 70 mol%, based on 100 mol% of all monomers used in the polymerization of the heat-resistant resin. When the diamine compound represented by Formula 1 is included in the above range relative to a total of 100 mol% of all monomers, the heat-resistant resin or heat-resistant resin precursor obtained from the diamine compound in which the hydroxyl group and amino group are adjacent to each other is formed by forming an amide group and a hydroxyl group during heat treatment. Since the actual group forms an oxazole ring through a dehydration reaction, there is an advantage in that the heat resistance and hygroscopicity of the resulting resin are improved.

According to one embodiment of the present invention, the diamine compound represented by Chemical Formula 1 of the present invention and at least one selected from acid dianhydride and acid chloride may be included in a molar ratio of 1:0.5 to 0.5:1, improving reactivity and processability. Considering this, it may be preferable to react at a molar ratio of 1:0.6 to 0.6:1.

According to one embodiment of the present invention, the heat-resistant resin of the present invention may be polymerized by further including other diamine compounds as monomers in addition to the diamine compound represented by Formula 1 above.

Other diamine compounds include, for example, 4,4'-oxydianiline, p-phenylene diamine, m-phenylene diamine, 2,2-bis(4-4[aminophenoxy]-phenyl)propane , 2,2'-dimethyl-4,4'-diamino biphenyl, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis(4-[3-aminophenoxy]phenyl)sulfone , 4,4'-diamino benzanilide or 4,4'-bis (4-aminophenoxy) biphenyl or 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropanyl. However, it is not limited to this, and is preferably 4,4'-oxydianiline (ODA).

When the heat-resistant resin of the present invention is polymerized by further including a diamine compound other than the diamine compound represented by Formula 1 above as a monomer, the diamine compound represented by Formula 1 of the present invention is present in an amount of 1 to 100 mol% based on 100 mol% of all diamine compounds. It may be included at 100 mol%, preferably 10 to 100 mol%. When the diamine compound represented by Formula 1 is included in the above range relative to 100 mol% of all diamine compounds, a cured film having the above-mentioned structure as a main component can be obtained, which has excellent solubility in organic solvents and heat resistance when the resin composition is cured. There are benefits to this.

The heat-resistant resin of the present invention may have a weight average molecular weight ranging from 2,000 to 200,000 g/mol, preferably 3,000 to 50,000 g/mol. In this case, since appropriate solubility in an alkaline developer is obtained, a desired pattern can be formed with high contrast between exposed and unexposed areas. In terms of solubility in an alkaline developer, the weight average molecular weight of the heat-resistant resin is more preferably 100,000 or less, and even more preferably 50,000 or less. Also, in terms of improving elongation, it is preferable that it is 3,000 or more. The weight average molecular weight can be measured by gel permeation chromatography (GPC) and obtained by conversion from a standard polystyrene calibration curve.

In order to improve storage stability, the heat-resistant resin of the present invention may further include other end capping agents such as monoamines, monocarboxylic acids, active ester compounds, and acid anhydrides at the main chain ends.

The introduction rate of the end capping agent is preferably 0.1 mol% or more relative to the total diamine, acid dianhydride or acid chloride components in order to prevent the heat-resistant resin of the present invention from increasing its weight average molecular weight and reducing its solubility in alkaline solutions. More preferably, it is 5 mol% or more. Moreover, in order to suppress a decrease in the mechanical properties of the cured film obtained due to a decrease in the weight average molecular weight of the polyamide resin, it is preferably 60 mol% or less, more preferably 50 mol% or less. Additionally, a plurality of end capping agents can be reacted to introduce a plurality of different end groups.

Monoamines as end capping agents specifically include M-600, M-1000, M-2005, M-2070 (trade names above, manufactured by HUNTSMAN Co., Ltd.), aniline, 2-ethynylaniline, and 3-ethynylaniline. , 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy Roxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy- 6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid , 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxy Pyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. can be used, and two or more types of these can be used.

The monocarboxylic acid, active ester compound, and acid anhydride as the end capping agent are 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1 -Hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3 - Monocarboxylic acids such as carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid; Active ester compounds whose carboxyl groups are esterified; Phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride (5-Norbonene-2,3- Acid anhydrides such as dicarboxylic Anhydride (NA); The dicarboxylic acids phthalic acid, maleic acid, nadic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, or the tricarboxylic acids trimellitic acid and trimes. Acid, diphenyl ether tricarboxylic acid, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2, By reaction of the carboxyl group on one side of dicarboxylic acids such as 6-dicarboxynaphthalene with N-hydroxybenzotriazole, imidazole, or N-hydroxy-5-norbornene-2,3-dicarboximide. The resulting active ester compound; Compounds in which some of the hydrogen atoms of these aromatic rings or hydrocarbons are replaced with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, etc.; etc. can be used, and two or more types of these can be used.

In addition, the resin terminal or resin side chain of the heat-resistant resin in the present invention preferably has a structure in which the resin terminal or resin side chain is sealed with an imide precursor or imide such as amic acid or amidic acid ester. Since the resin terminal has more sites in contact with other components or the substrate than the main chain of the resin, adhesion can be improved and the storage stability of the resin composition can be improved. For this reason, it is preferable to have an imide precursor structure or an imide structure, and it is more preferable to exist near the end of the polyimide precursor structure or polyimide structure. Thereby, adhesion can be improved and the storage stability of the alkali-soluble resin can also be improved. For this purpose, it is preferable to polymerize the polyamide structure and then copolymerize it with at least one of the polyimide precursor structure and the polyimide structure.

The structure in which the resin terminal or resin side chain of the heat-resistant resin of the present invention is sealed with an imide precursor or imide such as amidic acid or amidic acid ester includes phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, Acid anhydrides such as 3-hydroxyphthalic anhydride; Dicarboxylic acids such as phthalic acid, maleic acid, nadic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, and 5-norbornene-2,3-dicarboxylic acid; Tricarboxylic acid, trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene , a carboxyl group on one side of dicarboxylic acids such as 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, N-hydroxybenzotriazole, imidazole, N-hydroxy-5-norbornene-2 , Active ester compounds obtained by reaction with 3-dicarboximide, and compounds obtained by substituting part of the aromatic ring or hydrogen atom of the hydrocarbon with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, etc. However, it is not limited to these.

The end cap agent that can be used in the present invention can be easily detected by the following method. For example, an alkali-soluble resin into which an end capping agent has been introduced is dissolved in an acidic solution, decomposed into the amine component and acid anhydride component as structural units, and used in the present invention by gas chromatography (GC) or NMR. The end sealant can be easily detected. Separately from this, the alkali-soluble resin component into which the end capping agent has been introduced can be easily detected by directly measuring it with a thermal decomposition gas chromatograph (PGC) or an infrared spectrum and a ¹³ C-NMR spectrum.

The heat-resistant resin of the present invention is polymerized by, for example, the following method, but is not limited thereto.

First, at least one selected from acid dianhydride and acid chloride and a diamine compound represented by Formula 1 are dissolved in a solvent and then polymerized by heating. From the viewpoint of solution stability during reaction, it is preferable to dissolve the highly soluble diamine compound first. Thereafter, in some cases, other copolymerization components are added, and an acid or acid anhydride serving as an end capping agent is added and polymerized.

When introducing a diamine other than the diamine compound represented by Formula 1, the reaction is preferably performed at 0 to 200°C.

The polyimide precursor structure is a structure derived from an acid anhydride in the above polymerization method, and in the case of an amidic acid ester, it is obtained by reacting carboxylic acid with an esterifying agent after the above polymerization.

The heat-resistant resin of the present invention includes polyimide, and the polyimide has already been prepared using a known imidization reaction method, for example, obtaining an imide precursor and polymerizing it at 70 to 200°C. A method of ring-closing all of the imide rings of the imide precursor, a method of stopping the imidization reaction midway and introducing a portion of the imide structure, and furthermore, an imide polymer of a closed ring in which all of the imide rings of the imide precursor are ring-closed, and the above-mentioned imide polymer. It can be synthesized using a method of introducing some of the imide structure by mixing polyimide precursors.

The benzoxazole used in the present invention can be synthesized, for example, by obtaining polyamide and polymerizing it at 150 to 250°C, or by adding an acidic catalyst to ring-close it.

Solvents used in the polymerization reaction of the heat-resistant resin include, for example, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ. -Cyclic esters such as butyrolactone; esters such as ethyl acetate, propylene glycol monomethyl ether acetate, and ethyl lactate; ethers such as tetrahydrofuran, dioxane, diethylene glycol ethyl methyl ether, and propylene glycol monomethyl ether; Ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, and diacetone alcohol; Carbonates such as ethylene carbonate and propylene carbonate; Glycols such as propylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and triethylene glycol; Aromatic hydrocarbons such as toluene and xylene can be used, and γ-butyrolactone (GBL) can be preferably used from the viewpoint of high solubility and low hygroscopicity.

The heat-resistant resin of the present invention is preferably polymerized by the above method, then added to a large amount of water or a mixture of methanol and water, precipitated, filtered, dried, and isolated. The drying temperature is preferably 40 to 100°C, more preferably 50 to 80°C. At this time, oligomer components such as unreacted monomers, dimers, and trimers are removed, and film properties after heat curing can be improved.

The imidation rate in the heat-resistant resin of the present invention can be easily determined, for example, by the following method. First, the infrared absorption spectrum of the polymer is measured, and the presence of imide structure absorption peaks (around 1780 cm ^-1 and 1377 cm ^-1 ) resulting from polyimide is confirmed. Next, the infrared absorption spectrum was measured using a sample of the polymer heat-treated at 300°C for 1 hour with an imidization rate of 100%, and the peak intensity around 1377 cm ^-1 was compared for the resin before and after heat treatment. Calculate the content of imide groups and determine the imidization rate. Since the change in the rate of closure during thermal curing is suppressed and the effect of lowering stress is obtained, the imidization rate is preferably 50% or more, and more preferably 80% or more.

<Resin composition>

The resin composition of the present invention includes the above heat-resistant resin.

The resin composition may be used as a photosensitive resin composition, for example, and may include one or more of a photosensitive compound, a photopolymerizable compound, a photopolymerization initiator, and a solvent in addition to a heat-resistant resin.

In this case, the heat-resistant resin is preferably contained in an amount of 10% by weight or more and 100% by weight or less, and is particularly preferably contained in an amount of 20% by weight or more and 95% by weight or less, based on the total composition constituting the resin composition. If the heat-resistant resin is less than the above range, there is a problem that the heat resistance of the resin cured film is lowered because the resin ratio is too small.

The photosensitive compound is a photoacid generator and includes quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. By containing a photo acid generator, acid is generated in the light irradiated area, solubility of the light irradiated area in an aqueous alkaline solution is increased, and a positive relief pattern in which the light irradiated area is dissolved can be obtained.

Specific examples of the quinonediazide compound include a polyhydroxy compound in which the sulfonic acid of quinonediazide is bonded to an ester, a polyamizo compound in which the sulfonic acid of quinonediazide is bonded to a sulfonamide, and a polyhydroxypolyamino compound in which quinonediazide is bonded. The sulfonic acid of azide may be bound to an ester bond and/or a sulfonamide bond, but is not limited thereto. It is preferable that 50 mol% or more of the total functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinonediazide. Additionally, it is preferable to contain two or more types of photoacid generators, and a highly sensitive photosensitive resin composition can be obtained.

The photopolymerizable compound is a compound that can be polymerized by the action of the following photopolymerization initiator, and may be a monofunctional monomer, a difunctional monomer, or a polyfunctional monomer, and it is preferable to use a polyfunctional monomer having two or more functions.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, or N-vinylpy. Lolidon, etc., but is not limited thereto.

Specific examples of the bifunctional monomer include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. , bis(acryloyloxyethyl)ether of bisphenol A, or 3-methylpentanediol di(meth)acrylate, etc., but is not limited thereto.

Specific examples of the multifunctional monomer include trimethylol propane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and pentaerythritol tri. (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexaacrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated Dipentaerythritol hexa(meth)acrylate or dipentaerythritol hexa(meth)acrylate, etc., but are not limited thereto.

In addition, the photopolymerizable compound may be included in an amount of 5 to 50% by weight, preferably 7 to 45% by weight, and more preferably 10 to 20% by weight, based on the total weight of the resin composition in consideration of strength and smoothness. there is.

The photopolymerization initiator is a compound that generates radicals that can initiate polymerization of the photopolymerizable compound upon exposure to radiation such as visible light, ultraviolet rays, deep ultraviolet rays, electron beams, or X-rays.

The photopolymerization initiator contains an oxime ester-based photopolymerization initiator as an essential component.

The oxime ester-based compounds include 2-O-benzoyloxime-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-[9-ethyl-6-(2-methylbenzyl)-9H -Carbazol-3-yl]ethanone 1-(O-acetyloxime) (1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) ), etc., and commercially available oxime ester photopolymerization initiators include BASF's Irgacure® OXE 01, Irgacure® OXE 02, and Irgacure® OXE 03. Since the absorbance and radical species generated are diverse, two or more types are used together. It is desirable to do so.

In addition, photopolymerization initiators other than the oxime ester-based photopolymerization initiator can also be used in combination. Typically, it is preferable to use at least one compound selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, and thioxanthone-based compounds.

Specific examples of the acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2-hydroxy Roxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1 -one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc.

Examples of the benzophenone-based compounds include benzophenone, 0-benzoylmethylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra ( tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

Specific examples of the triazine-based compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2- yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro) Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole , 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4, 4',5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4',5,5' position is substituted by a carboalkoxy group. Among these, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4' ,5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole are preferred. It is used.

Examples of the thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc. There is.

Additionally, the photopolymerization initiator may further include a photopolymerization initiation auxiliary agent to improve the sensitivity of the resin composition. By containing a photopolymerization initiation aid, the resin composition according to the present invention can further increase sensitivity and improve productivity.

As the photopolymerization initiation aid, for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and polyfunctional thiol compounds having a thiol group may be preferably used.

As the amine compound, it is preferable to use an aromatic amine compound, specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone) ), 4,4'-bis(diethylamino)benzophenone, etc. can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, and dimethoxyphenylthioacetic acid. Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

Examples of the polyfunctional thiol compound having the thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mer Captobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mergaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) cypionate), etc.

Additionally, the photopolymerization initiator may further include a photopolymerization initiation auxiliary agent to improve the sensitivity of the resin composition. By containing a photopolymerization initiation aid, the resin composition can further increase sensitivity and improve productivity.

The photopolymerization initiation aid may preferably be, for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and polyfunctional thiol compounds.

As the amine compound, it is preferable to use an aromatic amine compound, specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone) ), 4,4'-bis(diethylamino)benzophenone, etc. can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, and dimethoxyphenylthioacetic acid. Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

The polyfunctional thiol compounds include Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, Trimethylolpropane tris -3-mercaptopropionate), Pentaerythritol tetrakis-3-mercaptopropionate), and Dipentaerythritol hexa-3-mercaptopropionate).

The photopolymerization initiator may be included in an amount of 1 to 20% by weight, preferably 1 to 10% by weight, based on the total weight of the resin composition. If the photopolymerization initiator is within the above-mentioned range, the resin composition becomes highly sensitive and the exposure time is shortened, so productivity can be improved, which is desirable in terms of smoothness. In addition, in the case of the oxime ester-based photopolymerization initiator, it should contain 10 to 100% by weight, preferably 20 to 100% by weight, of the total photopolymerization initiator. If the ratio of the oxime ester-based photopolymerization initiator to the total photopolymerization initiator is less than 10% by weight, the decrease in sensitivity caused by the dye cannot be overcome and short circuiting of the pattern is likely to occur during the development process.

In addition, when the photopolymerization initiation aid is further used, the photopolymerization initiation aid may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on the total of 100 parts by weight of the heat-resistant resin and the photopolymerizable compound based on solid content. there is. When the amount of the photopolymerization initiation aid used is within the range of 0.1 to 40 parts by weight, the sensitivity of the resin composition is higher and productivity is improved.

The solvent can be used as long as it is effective in dissolving other components included in the resin composition, and an organic solvent with a boiling point of 80°C to 250°C is preferred in terms of applicability and drying properties. More preferably, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene Glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl Acetates such as formate, propyl formate, methyl lactate, ethyl lactate, butyl lactate and propyl lactate, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptane Ketones such as thananone, alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol, Aromatic hydrocarbons such as toluene and xylene, as well as dimethyl sulfoxide and γ-butyrolactone, are included.

Particularly preferred ones include, specifically, cyclopentanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, methyl lactate, ethyl lactate, diacetone alcohol, and 3-methyl-3-methoxy. Butanol and γ-butyrolactone can be mentioned.

The above solvents can be used alone or in a mixture of two or more types.

In addition to the above solvent, a solvent used in a typical photosensitive resin composition that is effective in dissolving other components included in the photosensitive resin composition may be used in combination. In particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters, or amides are preferable.

Specifically, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic esters, such as γ-butyrolactone, etc. are mentioned.

The amount of the solvent is preferably 50 parts by weight or more and 2,000 parts by weight or less, and more preferably 100 parts by weight or more and 1,500 parts by weight or less, based on 100 parts by weight of solid content of the resin composition.

If the solvent is within the above-mentioned range, it provides the effect of improving applicability when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes called a die coater), or inkjet.

In addition to the above components, the resin composition of the present invention may also contain additives such as antioxidants, fillers, other polymer compounds, curing agents, adhesion promoters, ultraviolet absorbers, and aggregation inhibitors, as required by those skilled in the art, as long as they do not impair the purpose of the present invention. do.

< Cured film and image display device >

The present invention includes a cured film manufactured using the heat-resistant resin or a resin composition containing the same. Additionally, the present invention includes an image display device including the cured film.

The cured film may be in the form of a film or film, and a pattern may be formed as needed.

The method of producing the cured film is not particularly limited, and can be obtained, for example, by applying or coating the heat-resistant resin or a resin composition containing it and heat treatment.

The heat-resistant resin or a resin composition containing the same is applied or coated on a substrate. Application or coating methods at this time include spray coating, screen printing, blade coater, die coater, bar coater, roll coater, gravure coater, and slit die coater. It can be applied or coated by a known method using, etc. The film thickness at this time may vary depending on the application method, viscosity, etc., but after drying, the film thickness can be 0.1㎛ to 150㎛.

The heat treatment may be performed at 50°C to 400°C, and may be performed by gradually increasing the temperature within the above temperature range or continuously increasing the temperature to a specific temperature. For example, heat treatment can be performed continuously and stepwise by heat treating at 50 to 150°C for 20 to 40 minutes, followed by heat treatment at 150 to 250°C for 20 to 40 minutes, and then heat treating at 250 to 400°C for 20 to 40 minutes. Alternatively, heat treatment can be performed by continuously raising the temperature from room temperature to 400°C over 2 hours.

Heat treatment can use ovens, hot plates, infrared rays, etc.

The cured film obtained in this way may have a weight loss temperature (T _d ) of 400°C or higher, preferably 400°C or higher and 600°C or lower. The weight loss temperature (T _d ) means that when the cured film is heated from 0°C to 800°C at a temperature increase rate of 10°C/min, it is specified as the temperature at which the weight of the cured film decreases by 10% compared to the initial value.

In addition, the cured film may have a coefficient of thermal expansion (CTE) of 50 ppm/℃ or less, preferably 1 ppm/℃ or more and 50 ppm/℃ or less. The coefficient of thermal expansion (CTE) was determined by hanging the sample on a quartz hook, applying a force of 0.010 N, and heating it at a rate of 10°C/min from 30°C to 400°C under a nitrogen atmosphere, within the range of 50°C to 200°C. Measured.

It is preferable that the cured film of the present invention satisfies the above weight loss temperature (T _d ) and coefficient of thermal expansion (CTE) ranges because it can secure excellent heat resistance properties.

The cured film of the present invention may have a hygroscopicity of 1.0% or less, and satisfying the above range is preferable in terms of adhesion and stability.

Hereinafter, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are merely examples and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and further includes all changes within the scope and meaning equivalent to the record of the claims. In addition, in the following examples and comparative examples, “%” and “part” indicating content are based on mass unless otherwise specified.

<Example>

Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-2: Synthesis of diamine compounds

Example 1-1: Synthesis of diamine compound (A-1)

18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15°C. A solution of 14.0 g (0.11 mole) of 3-chloropropionyl chloride dissolved in 100 mL of acetone was added dropwise here. After the dropwise addition was completed, the mixture was stirred at -15°C for 4 hours and then returned to room temperature. Additionally, a solution of 8.5 g (0.11 mol) of 2-aminoethanethiol dissolved in 100 mL of acetone was added dropwise, and stirred at room temperature for 2 hours. The precipitated white solid was filtered and dried under vacuum at 50°C.

30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Here, hydrogen was introduced using a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, it was confirmed that the balloon was no longer deflated and the reaction was terminated. After completion of the reaction, the catalyst palladium compound was removed by filtration and concentrated using a rotary evaporator to obtain diamine compound (A-1) represented by the following formula (2).

[Formula 2]

Example 1-2: Synthesis of diamine compound (A-2)

18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15°C. A solution of 22.3 g (0.11 mole) of phthaloyl chloride dissolved in 100 mL of acetone was added dropwise here. After the dropwise addition was completed, the mixture was stirred at -15°C for 4 hours and then returned to room temperature. Next, 16.8 g (0.11 mol) of 2-hydroxyethyl 2-chloropropanate was added dropwise, and the mixture was stirred at room temperature for 2 hours. Additionally, a solution of 8.5 g (0.11 mol) of 2-aminoethanethiol dissolved in 100 mL of acetone was added dropwise, and stirred at room temperature for 2 hours. The precipitated white solid was filtered and dried under vacuum at 50°C.

30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Here, hydrogen was introduced using a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, it was confirmed that the balloon was no longer deflated and the reaction was terminated. After completion of the reaction, the catalyst palladium compound was removed by filtration and concentrated using a rotary evaporator to obtain diamine compound (A-2) represented by the following formula (3).

[Formula 3]

Example 1-3: Synthesis of diamine compound (A-3)

A diamine compound (A- 3) was obtained.

[Formula 4]

Comparative Example 1-1: Synthesis of diamine compound (A-4)

18.3 g (0.05 mol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15°C. A solution of 26.1 g (0.11 mol) of 3-(1,3-dioxoisoindolin-2-yl)propanoyl chloride dissolved in 100 ml of acetone was added dropwise here. After the dropwise addition was completed, the reaction was performed at -15°C for 4 hours and then returned to room temperature. The solution was concentrated in a rotary evaporator, and the obtained solid was recrystallized from a solution of tetrahydrofuran and ethanol.

The solid collected after recrystallization was dissolved in 400 ml of ethanol and refluxed under a nitrogen atmosphere. To this suspension, a 10 ml solution of 3.76 g (0.06 mmol) of 80% hydrazine monohydrate in ethanol was added dropwise over 15 minutes, followed by refluxing for 4 hours. The reaction solution was cooled to room temperature, filtered, and the filtrate (white powder, mainly containing phthalic acid hydrazide) was rinsed once with 25 ml of ethanol and twice with 50 ml, and the filtrate and rinse solution were combined. Since this solution showed some turbidity, it was filtered to obtain a clear solution. This filtrate was concentrated in a rotary evaporator to obtain diamine compound (A-4) represented by the following formula (5).

[Formula 5]

Comparative Example 1-2: Synthesis of diamine compound (A-5)

18.3 g (0.05 mol) of bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15°C. Here, 40.6 g (0.11 mol) of 3-(2-(2-(2-(1,3-dioxoisoindolin-2-yl)ethoxy)ethoxy)ethoxy)propyl chloride was dissolved in 100 ml of acetone. The solution was added dropwise. After the dropwise addition was completed, the reaction was performed at -15°C for 4 hours and then returned to room temperature. The solution was concentrated in a rotary evaporator, and the obtained solid was recrystallized from a solution of tetrahydrofuran and ethanol.

The solid collected after recrystallization was dissolved in 400 ml of ethanol and refluxed under a nitrogen atmosphere. To this suspension, a 10 ml solution of 3.76 g (0.06 mmol) of 80% hydrazine monohydrate in ethanol was added dropwise over 15 minutes, followed by refluxing for 4 hours. The reaction solution was cooled to room temperature, filtered, and the filtrate (white powder, mainly containing phthalic acid hydrazide) was rinsed once with 25 ml of ethanol and twice with 50 ml, and the filtrate and rinse solution were combined. Since this solution showed some turbidity, it was filtered to obtain a clear solution. This filtrate was concentrated in a rotary evaporator to obtain diamine compound (A-5) represented by the following formula (6).

[Formula 6]

Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-5: Synthesis of heat-resistant resin

Example 2-1

Under a dry nitrogen stream, 31.43 g (0.05 mol) of diamine compound (A-1) obtained in Example 1-1 was dissolved in 100 g of gammabutyrolactone (GBL). To this, 13.95 g (0.045 mol) of 4,4'-oxydiphthalic anhydride (ODPA) was added along with 10 g of GBL, and reacted at 40°C for 1 hour. Afterwards, 14.8 g (0.01 mol) of 5-norbornene-2,3-dicarboxylic anhydride (NA) was added as an end capping agent, and the reaction was completed after stirring at 40° C. for 1 hour to synthesize a heat-resistant resin. did.

Examples 2-2 to 2-6 and Comparative Examples 2-1 to 2-5

A heat-resistant resin was synthesized in the same manner as in Example 2-1, except that the contents of acid dianhydride, acid chloride, diamine compound, and acid anhydride were adjusted to have the molar ratio shown in Table 1 below.

- A-1 to A-5: diamine compounds according to Examples 1-1 to 1-3 and Comparative Examples 1-1 and 1-2

- ODPA: 4,4'-Oxydiphthalic Anhydride

- OBC: 4,4'-Oxybis(benzoyl Chloride)

- ODA: 4,4'-Oxydianiline

- PEG Diamine 2000: Poly(ethylene glycol) diamine

- NA: 5-Norbornene-2,3-dicarboxylic Anhydride

Examples 3-1 to 3-6 and Comparative Examples 3-1 to 3-5: Preparation of resin composition

The heat-resistant resin obtained through Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-5 was dissolved in gammabutyrolactone (GBL) to obtain an appropriate solid content by weight in Example 3-1. Resin compositions of to 3-6 and Comparative Examples 3-1 to 3-5 were prepared.

Experiment example

1. Preparation of cured film

The resin compositions (solids content: 15% by weight) according to Examples 3-1 to 3-6 and Comparative Examples 3-1 to 3-5 were coated on a glass plate using a bar coater, and then heat-treated in a high-temperature convection oven. . Heat treatment was performed in a nitrogen atmosphere by continuously raising the temperature to 100°C for 30 minutes, 220°C for 30 minutes, and 300°C for 60 minutes to obtain a cured film with a thickness of 10 μm. Regarding this, the physical properties were measured in the following manner, and the results are shown in Table 2 below.

2. Solubility evaluation

The heat-resistant resin obtained through Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-5 was powdered and added to gammabutyrolactone (GBL) to have a solid concentration of 30% by weight at room temperature. After stirring for 1 hour, the state was observed with the naked eye to confirm the presence or absence of insoluble resin. Resins in which insoluble resin was not observed were judged to be dissolved, and resins in which insoluble resin was observed were judged to be insoluble.

3. Weight loss temperature (T _d ) measurement

The weight loss temperature (T _d ) of the cured film obtained above was measured using TA Discovery TGA5500. The weight loss temperature (T _d ) was measured at a temperature increase of 10°C/min from 0°C to 800°C in an air atmosphere when the weight of the cured film decreased by 10% compared to the initial level.

4. Coefficient of thermal expansion (CTE) measurement

The coefficient of thermal expansion (CTE) of the cured film obtained above was measured using TA Q800. The sample was hung on a quartz hook, a force of 0.010 N was applied, and the sample was heated from 30°C to 400°C at a rate of 10°C/min in a nitrogen atmosphere. The thermal expansion coefficient was obtained within the range of 50℃ to 200℃.

5. Hygroscopicity evaluation

The cured film obtained above was heated from room temperature to 150°C for 5 minutes using a moisture trap equipment (WDS-400), and then heat-treated at 150°C for 10 minutes to measure the amount of moisture generated. After completing the measurement, the cured film was maintained at 121°C and 2 atm for 24 hours using pressure cooking treatment (PCT) equipment, vacuum dried at room temperature for 2 hours, and then the amount of moisture was measured again using moisture trap equipment. Measurements were made, and the moisture absorbed amount of the cured film was calculated.

Referring to the results in Table 2, it can be seen that Examples 3-1 to 3-6, which contain heat-resistant resins polymerized with the diamine compound represented by Formula 1 of the present application as a monomer, are excellent in solubility, heat resistance, and hygroscopicity. You can check it.

On the other hand, in the case of Comparative Examples 3-1 to 3-3 containing a heat-resistant resin polymerized without containing the diamine compound represented by Formula 1 of the present application as a monomer, the solubility and/or heat resistance were significantly reduced compared to the Examples. , it can be confirmed that in the case of Comparative Examples 3-4 and 3-5, which contain a heat-resistant resin polymerized with a compound outside the range of the diamine compound represented by Formula 1, there is a problem with hygroscopicity and thus defects may occur. there is.

Claims (13)

A diamine compound represented by formula (1).
[Formula 1]

(In Formula 1,
X and Y each independently represent a substituted or unsubstituted divalent aliphatic group or a substituted or unsubstituted divalent aromatic group.
A represents -O-, -CO-, -SO ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -.)
In claim 1,
The diamine compound wherein X and Y represent a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.
A heat-resistant resin polymerized comprising the diamine compound according to claim 1.
In claim 3,
A heat-resistant resin polymerized further comprising at least one selected from acid dianhydride and acid chloride.
In claim 3,
A heat-resistant resin polymerized by containing the diamine compound according to claim 1 in an amount of 1 to 80 mol% based on 100 mol% of all monomers.
In claim 3,
A heat-resistant resin having a weight average molecular weight of 2,000 to 200,000 g/mol.
A resin composition comprising the heat-resistant resin according to claim 3.
In claim 7,
A resin composition further comprising one or more of a photosensitive compound, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
A cured film manufactured using the resin composition according to claim 7.
In claim 9,
The cured film has a 10% weight loss temperature (T _d ) of 400°C or higher.
In claim 9,
The cured film has a coefficient of thermal expansion (CTE) of 50ppm/℃ or less.
In claim 9,
The cured film has a hygroscopicity of 1.0% or less.
An image display device comprising the cured film according to claim 9.