TWI602811B - Diamine compound, polymer, insulating film and electronic device - Google Patents

Description

Diamine compounds, polymers, insulating films and electronic equipment Set

The present invention relates to a diamine compound, a polymer produced using the same, an insulating film and an electronic device, and particularly to a diamine compound which is advantageous for enhancing metal adhesion and which is prepared by using the same. Objects, insulating films and electronic devices.

Diamine compounds have good reactivity, and can be used as monomers for synthesizing polymers. For example, diamine compounds have been widely used in the synthesis of polyamide (PA), polyamide acid (PAA), and poly Polymers such as polyimide (PI) have become more and more important as the application of the above polymers has expanded.

Taking the development of today's display technology as an example, the main demands of the new generation of displays are light, thin and flexible. The conventional glass substrates are not suitable. The use of plastic materials made of organic materials instead of glass substrates has been developed in recent years. One of the focuses, polyimine is seen as having the potential to be applied to next-generation displays. And other transparent materials such as polyethylene terephthalate (PET) and triacetate Compared with Triacetyl Cellulose (TAC), polyimine has a high glass transition temperature (Tg), excellent thermal properties, and good chemical resistance, and can withstand acid-base and solvent processes. An ideal material to replace glass substrates.

However, the use of the plastic substrate is often followed by other materials, for example, the plastic substrate and the metal layer are laminated or covered on the metal foil, and the adhesion of the polyimide to the metal is not good, so it is disadvantageously applied to the plastic substrate. Alternatively, it needs to be improved by surface chemical treatment or by using a bonding glue, which increases the complexity of the process and the manufacturing cost.

SUMMARY OF THE INVENTION One object of the present invention is to provide a diamine compound which can be used as a monomer for a synthetic polymer, for example, polyamine, polylysine, polyimine or a copolymer thereof.

Another object of the present invention is to provide a polymer which has good metal adhesion and which is advantageous for expanding its application range, for example, for manufacturing various molding materials such as plastic substrates.

It is still another object of the present invention to provide an insulating film which has good metal adhesion, which is advantageous for simplifying the process and reducing the manufacturing cost.

It is still another object of the present invention to provide an electronic device including an insulating film.

According to an embodiment of the present invention, there is provided a diamine compound having a structure as shown in formula (i): Wherein X is -O-, -COO-, -NH-, -CONH- or -NHCO-, Y is a single bond or a divalent aliphatic hydrocarbon group, and Z is an aromatic heterocyclic ring containing at least three nitrogens.

According to another embodiment of the present invention, there is provided a polymer produced by a polymerization reaction of a diamine compound as described in paragraph [0009], wherein the polymer comprises formula (I) and/or formula (II) and/or Or one of the structures shown in formula (III): Wherein A ¹ is a divalent organic group, and each of A ² and A ³ is independently a tetravalent organic group, and each of E ¹ , E ² and E ³ is independently a residue of the diamine compound described in paragraph [0009].

According to still another embodiment of the present invention, there is provided an insulating film which is made of a polymer as described in paragraph [0010].

According to still another embodiment of the present invention, there is provided an electronic device comprising an insulating film made of a polymer as described in paragraph [0010].

The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Gas chromatography-mass spectrometry, GC-MS) results.

<Diamine compound>

The present invention provides a diamine compound having a structure as shown in formula (i): Wherein X is -O-, -COO-, -NH-, -CONH- or -NHCO-, Y is a single bond or a divalent aliphatic hydrocarbon group, and Z is an aromatic heterocyclic ring containing at least three nitrogens.

Specifically, the above divalent aliphatic hydrocarbon group may be, but not limited to, a divalent alkane group, a divalent alkene group (a hydrocarbon group containing a carbon-carbon double bond) or a divalent alkyne group (containing a carbon-carbon triple bond) The hydrocarbon group), or the above-mentioned divalent aliphatic hydrocarbon group may be, but not limited to, a hydrocarbon group having 1 to 4 carbon atoms. Z may be a group of the formula (z-1), the formula (z-2) or the formula (z-3): Wherein R is each independently -H or a hydrocarbon group having 1 to 4 carbon atoms, and for example, R may be a methyl group, an ethyl group, a propyl group or a butyl group.

More specifically, the diamine compound of the above formula (i) may be, but not limited to, one of the structures shown in any one of the formulae (i-1) to (i-6):

The diamine compound of the formula (i) can be used as a monomer of a synthetic polymer, that is, the diamine compound of the above formula (i) can be polymerized to form a poly The composition, whereby the polymer synthesized can have good metal adhesion. The polymer will be described in detail below.

In the present invention, the "diamine compound of the formula (i)" can be expressed as "diamine compound (i)", and the expression of other compounds is the same, and will not be described below.

<Other diamine compounds>

In the above polymerization reaction using the diamine compound (i) as a monomer, other diamine compounds may be simultaneously used, that is, the polymer may simultaneously contain the residue of the diamine compound (i) and the residues of other diamine compounds. The properties of the polymer can be adapted to the actual needs. For example, in the above polymerization, other diamine compounds containing a hydroxyl group can be used at the same time, and the polymer is a copolymer comprising a polyhydroxyguanamine and/or a polybenzoxazole fragment. In the present invention, the "residue" means that a part of the structure of the monomer becomes a part of the polymer structure after the monomer participates in the polymerization reaction, and a part of the structure of the monomer is a residue. In the present invention, the "other diamine compound" means a diamine compound other than the diamine compound of the formula (i). The other diamine compound may be, but not limited to, the structure represented by formula (ii-1), formula (ii-2), formula (ii-3), formula (ii-4) or formula (ii-5) or such Structural isomers:

When it is a monomer of a synthetic polymer, the above other diamine compounds may be used singly or in combination.

<other monomer>

In the above polymerization reaction using the diamine compound (i) as a monomer, the other monomer is contained at the same time, and the other monomer contains at least one reactive functional group, and can react with the amine group of the diamine compound to form a polymer. For example, the other monomer may be, but not limited to, a dianhydride compound, a dioxonium chloride compound or a mixture thereof, and when the other monomer is a dianhydride compound, a polyamine acid may be formed by polymerization with the diamine compound (i), when other The monomer is a diterpene chlorine compound, which can be polymerized with a diamine compound (i) to form a polydecylamine. When the other monomer is a mixture of a dianhydride compound and a dioxonium compound, it can be polymerized with the diamine compound (i). The reaction produces a polyamine-poly-proline copolymer, and the poly-polyamine or polyamine-poly-proline copolymer can be subjected to partial or complete dehydration ring-closure reaction to form polyimine, poly-proline- Polyimine copolymer, polyamine-polyimine copolymer or polyamine-polyamine-polyimine copolymer.

The dianhydride compound may be, but is not limited to, the structure represented by formula (iii-1), formula (iii-2), formula (iii-3) or formula (iii-4) or an isomer of such structure: (iii-1), (iii-2),

When used as a monomer of a synthetic polymer, the above dianhydride compounds may be used singly or in combination.

The dioxonium compound may be, but is not limited to, a structure represented by formula (iv-1), formula (iv-2) or formula (iv-3) or an isomer of such a structure:

When used as a monomer of a synthetic polymer, the above dichloro chloro compounds may be used singly or in combination.

<polymer>

The present invention provides a polymer which is produced by a polymerization reaction of a diamine compound (i).

Specifically, the polymer is produced by a polymerization reaction of a diamine compound (i) with another monomer. The reactants of the polymerization reaction may further comprise other diamine compounds to provide polymerization of the amine groups with other monomers. Selection of monomers (diamine compounds of formula (i), other diamine compounds, other monomers) Alternatively, different polymers can be obtained. For example, the polymer can be, but not limited to, polyglycolic acid, polyamidamine, polyamine-poly-proline copolymer, poly-proline-polyhydroxyphthalamide copolymer, Polyamine-polyhydroxyguanamine copolymer, polyamine-poly-proline-polyhydroxyphthalamide copolymer, polyimine, polyamine-polyimine copolymer, polyamine-polyamide Amine-polyproline copolymer, polyimide-polybenzoxazole copolymer, polyimine-poly-proline-polybenzoxazole-polyhydroxyguanamine copolymer, polyamine-polyphenylene Oxazole copolymer, polyamine-polybenzoxazole-polyhydroxyguanamine copolymer, polyamine-polyimine-polyamine-polybenzoxazole-polyhydroxyphthalamide copolymer.

More specifically, the polymer may comprise a structure of formula (I) and/or formula (II) and/or formula (III): Wherein A ¹ is a divalent organic group, and each of A ² and A ³ is independently a tetravalent organic group, and each of E ¹ , E ² and E ³ is independently a residue of the diamine compound of formula (i).

The polymer may further comprise one of the structures shown in formula (IV) and/or formula (V): Wherein the T ¹ and T ² systems are each independently a divalent organic group, and the M ¹ and M ² systems are each independently a tetravalent organic group.

Depending on the polymer described above, the sum of the contents of formula (I), formula (II) and formula (III) may be greater than or equal to 5 mole percent based on the polymer being 100 mole percent.

Depending on the polymer described above, the polymer may further comprise saturated terminal functional groups. Thereby, the developability can be further improved. The saturated terminal functional group may be, but not limited to, a residue of alkyl hydrazine chloride, aromatic hydrazine chloride, aliphatic aromatic hydrazine chloride, aromatic monoamine, aliphatic monoamine, aliphatic aromatic monoamine or the like.

According to the aforementioned polymer, A ² and A ³ may each independently be a residue of an aromatic dianhydride compound. Thereby, the heat resistance and mechanical properties can be further improved.

<Method for preparing polymer>

The preparation method of the polymer comprises the steps of: providing a diamine compound (i), another monomer, and optionally providing a monomer such as another diamine compound as a reactant, and performing polymerization in an organic solvent to obtain a polymer comprising the polymer. The reaction solution. And the dehydration ring closure reaction can be selectively performed. In addition, the polymer end may be blocked with a monofunctional monomer such as alkyl hydrazine chloride, aromatic hydrazine chloride, aliphatic aromatic hydrazine chloride, aromatic monoamine, aliphatic monoamine, aliphatic aromatic Monoamine, etc., and forming a terminal functional group on the polymer, the content of the other monomer is 100% by mole, and the monomer content of the terminal functional group is 1 to 60 mole percentage, and the preferred content is 20-40. Percent of moles. When the total content of all diamine compounds is 100 mole percent, the terminal functional group monomer content is from 1 to 60 mole percent, preferably from 20 to 40 mole percent.

The organic solvent is used to dissolve a monomer and a product polymer as a reactant, and can be distinguished into an organic solvent having a good solubility and an organic solvent having a poor solubility depending on the solubility of the organic solvent to the polymer.

The organic solvent having a better solubility may be, but not limited to, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylcaprolactam. , dimethyl hydrazine, tetramethyl urea, hexamethyl phosphoniumamine, gamma-butyl lactone (GBL) or pyridine, the above organic solvents may be used alone or in combination of two or more. .

The organic solvent having a poor solubility may also be used in combination with the above-mentioned organic solvent having a better solubility, provided that the polymer is not precipitated. Poorly soluble organic solvents include, but are not limited to, methanol, ethanol, isopropanol, n-butanol, cyclohexanol, ethylene glycol, ethylene glycol methyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethyl ether, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, tetrahydrofuran, dichloromethane, three Methyl chloride, 1,2-dichloroethane, benzene, toluene, xylene, n-hexane, n-heptane, n-octane.

In addition to the organic solvents listed above, an organic solvent which can dissolve a monomer and a polymer can be used as an organic solvent for the polymerization reaction.

The polymer can be purified, the purification step is as follows, and the polymerization will be included. The reaction solution of the substance is poured into a large amount of solvent having a poor solubility to obtain a precipitate, which is dried under reduced pressure to obtain a preliminary purified polymer. The preliminary purified polymer is continuously dissolved in an organic solvent and precipitated with a solvent having a poor solubility. This step is carried out one or more times to obtain a purified polymer.

When the polymerization reaction is carried out, the ratio of the diamine compound (i) to all the diamine compounds (diamine compound (i) plus other diamine compounds) is such that the diamine compound (i) accounts for more than or equal to the content of all the diamine compounds. The percentage of 5 moles is preferably from 10 to 90 mole percent, preferably from 20 to 80 mole percent.

Hereinafter, the preparation method of the polymer will be described in detail by taking the polymer as a poly-proline, a polyimine, and a polyimine-polyamide copolymer.

A monomer such as a diamine compound (i), another diamine compound, and a dianhydride compound is used as a reactant, and polymerization is carried out in an organic solvent at a temperature of 0 ° C to 70 ° C for 1 to 24 hours to obtain a poly-containing polymer. The reaction solution of valine acid, the temperature and time of the above polymerization reaction can be elastically adjusted according to the amount of the reactants. Thereafter, the polymer is purified to obtain purified polylysine. Please refer to the above for the organic solvent and purification steps, and no further details are given here.

When the polymerization reaction is carried out, the ratio of the diamine compound (i), the other diamine compound, and the dianhydride compound is 1 equivalent of the anhydride group content of the dianhydride compound, and the amine group of all the diamine compounds is preferably 0.5 to 2 equivalents. , 0.7 to 1.5 equivalents is more preferred.

If a polythenimine or a polyimine-polyamide copolymer is to be formed, the reaction solution containing the poly-proline may be subjected to a complete or partial dehydration ring-closing reaction to obtain a polyimine or polyfluorene. Imine-polyamide copolymer The reaction solution is subjected to a purification step to obtain a purified polyimine or polyimine-polyamide copolymer.

The dehydration ring closure reaction can be carried out by direct heating or by adding a dehydrating agent and a catalyst. The direct heating temperature may be from 50 ° C to 300 ° C, and preferably from 100 ° C to 250 ° C. The temperature of the dehydrating agent and the catalyst may be -20 ° C to 150 ° C, and preferably 0 ° C to 120 ° C. The dehydrating agent may use an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride, and the amount of the dehydrating agent may depend on the desired ring closure ratio (imidization ratio), and the catalyst may use a tertiary amine such as triethylamine or pyridine. Or lutidine. The dehydration ring closure reaction is conventional, and other details are not described again.

Hereinafter, the polymer is a polyamine-polyhydroxyguanamine copolymer as an example, and the preparation method of the polymer will be described in detail.

The polymer is a reaction product of a diamine compound (i), another diamine compound containing a hydroxyl group, and a dioxonium chloride compound, and is subjected to polymerization in an organic solvent, and is carried out at a temperature of -10 ° C to 40 ° C for 1 to 24 In an hour, to obtain a reaction solution containing a polyamine-polyhydroxyguanamine copolymer, the temperature and time of the above polymerization reaction can be elastically adjusted depending on the amount of the reactants. Thereafter, the polymer was purified to obtain a purified polyamine-polyhydroxyguanamine copolymer. Please refer to the above for the organic solvent and purification steps, and no further details are given here.

When the polymerization reaction is carried out, the ratio of the diamine compound (i), the other diamine compound containing a hydroxyl group, and the diterpene chlorine compound is 1 equivalent of the chloro group content of the dichloro chloro compound, and the amine group of all the diamine compounds is 0.5 to 2 equivalents are preferred, and 0.7 to 1.5 equivalents are more preferred.

The weight average molecular weight of the polymer may preferably be from 18,000 to 26,000, depending on the aforementioned polymer. Thereby, the mechanical properties can be further improved.

If the polyamine-polybenzoxazole copolymer or the polyamine-polybenzoxazole-polyhydroxyguanamine copolymer is to be formed, the reaction solution containing the polyamine-polyhydroxyguanamine copolymer described above may be completely or Partial dehydration ring closure reaction to obtain a reaction solution comprising a polyamine-polybenzoxazole copolymer or a polyamido-polybenzoxazole-polyhydroxyguanamine copolymer, and then performing a purification step to obtain a purified Polyamine-polybenzoxazole copolymer or polyamine-polybenzoxazole-polyhydroxyguanamine copolymer.

The dehydration ring closure reaction can be carried out by direct heating or by adding a dehydrating agent and a catalyst. The direct heating temperature may be from 50 ° C to 450 ° C, and preferably from 150 ° C to 350 ° C. The temperature of the dehydrating agent and the catalyst may be from 50 ° C to 450 ° C, and preferably from 100 ° C to 250 ° C. The catalyst may use a sulfonic acid catalyst such as p-toluenesulfonic acid or methyl p-toluenesulfonate. The catalyst may be added in an amount of from 0.01 to 20 mol per 1 mol of the polyamine-polyhydroxyguanamine copolymer.

<Resin varnish>

The resin varnish of the present invention dissolves the above-mentioned synthesized polymer in an organic solvent, and optionally other additives such as an organic oxime compound, an epoxy compound, a photoinitiator, a photosensitive compound, and a sealant. Promoters, catalysts, thermal initiators, and the like. Thereby, it is advantageous for the subsequent application of the polymer, for example, it can be applied to the manufacture of a plastic substrate in a display, as a photosensitive resin, or as a protective layer for electronic components.

The viscosity (η _ln ) of the resin varnish of the present invention is obtained from the following formula (1) by dissolving the polymer in a solvent of N-methyl-2-pyrrolidone to prepare a solution having a concentration of 0.5 g/100 ml. And measure the viscosity of the solution at 30 ° C:

The resin varnish may have a solid content of, but not limited to, 5 wt% to 30 wt%, depending on viscosity and volatility. When the solid content is low, the film thickness is easily thinned, and when the solid content is high, the coating quality is easily affected.

The temperature at which the resin varnish is prepared is preferably from 0 ° C to 150 ° C, more preferably from 20 ° C to 50 ° C.

The organic solvent of the resin varnish of the present invention may be, but not limited to, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylhexene. Indamine, dimethyl hydrazine, γ-butyrolactone, γ-butyrolactam, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol For the monobutyl ether or the like, the above organic solvents may be used singly or in combination of two or more. In addition to the organic solvents listed above, any organic solvent which can dissolve the polymer can be used.

The resin varnish of the present invention may optionally be added with an organic sulfonium (oxy) alkane compound, which may be, but not limited to, aminopropyltrimethoxydecane, aminopropyltriethyldecane, vinyl Methyl decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane , vinyl triethoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-glycidoxy propyl trimethoxy decane, 3-glycidoxy propyl methyl 2 Methoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N- Ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3- Aminopropyltriethoxyamine decane, N-triethoxycarbenylpropyltriethylamine, N-trimethoxycarbamidopropyltriethylamine, N-bis ( Oxyethyl)-3-aminopropyltrimethoxydecane, N-bis(oxyethylidene)-3-aminopropyltriethyldecane, and the like. The content of the organic bismuth (oxy) alkane compound in the resin varnish is based on the principle that the adhesion of the resin varnish to the surface of the substrate and the leveling property can be improved without affecting the properties required of the original resin varnish. When the content of the oxyalkylene compound is too large, the formed film tends to be less likely to be released. If the content of the organic sulfonium (oxy) alkane compound in the resin varnish is too small, the formed film is liable to cause a leveling failure. Therefore, in the resin varnish of the present invention, the content of the organic oxime (oxy) alkane compound is preferably from 0.01 to 5 parts by weight, more preferably from 0.1 to 3 parts by weight, based on 100 parts by weight based on the total mass of the polymer.

The resin varnish of the present invention may optionally be added with an epoxy compound, which may be, but not limited to, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl Ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2, 4-hexanediol, N,N,N ' ,N ' -tetraglycidyl-m-phenylene, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N ' ,N ' -tetraglycidyl-4,4 ' -diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxy Decane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, 9,9-bis[(2,3-epoxypropoxy)phenyl]anthracene. The content of the epoxy compound in the resin varnish is based on the premise that the properties of the original resin varnish are not affected, and the adhesion of the resin varnish to the surface of the substrate can be improved. If the content of the epoxy compound is too large, the formed film tends to be less likely to be released. If the epoxy compound content is too small, the resulting resin varnish tends to be poorly adhered. Therefore, the resin varnish of the present invention contains 100 parts by weight of the total weight of the resin varnish, and the content of the epoxy compound is preferably 0.01 to 3 parts by weight, more preferably 0.1 to 2 parts by weight.

The resin varnish of the present invention may optionally be added with a photosensitive compound, and specifically, but not limited to, a compound represented by the following formula (vi-1) or formula (vi-2): Where R is hydrogen, NAC4 or NAC5, and the structures of NAC4 and NAC5 are as follows:

The resin varnish of the present invention may optionally be added with a catalyst, specifically but not limited to the following compounds: p-toluenesulfonic acid or methyl p-toluenesulfonate.

<insulation film>

The present invention provides an insulating film which is made of the aforementioned polymer.

Specifically, the method of forming an insulating film comprises the steps of: first, preparing a polymer as a resin varnish, and applying the resin varnish to a glass substrate by a roll coating method, a spin coating method, or a printing method to form a coating. Floor. Secondly, the coating layer is heated and baked to form a film, and the purpose of heating baking is to move In addition to the organic solvent in the resin varnish, in addition, when the polymer contains a fragment such as polyglycolic acid or polyhydroxyguanamine, the heat baking can promote the dehydration ring closure reaction. In general, the temperature of the heating bake can be from 80 ° C to 300 ° C, or from 100 ° C to 240 ° C. The thickness of the formed film can be, but is not limited to, 0.005 micrometers to 50 micrometers. Thereafter, the baked film is further baked by heating at 100 ° C to 200 ° C to eliminate thermal stress, and the insulating film of the present invention can be obtained by gently scraping the film around the blade and removing it.

Thereby, the insulating film has good metal adhesion, is advantageous as a plastic substrate for a display, or can be used as an insulating member in an electronic device, such as a protective layer, and has a wide range of applications.

<electronic device>

The present invention provides an electronic device comprising an insulating film made of the aforementioned polymer. Please refer to the above for details of the insulating film, and will not be described here.

The electronic device may be a display device. For example, the electronic device may be a flexible Organic Light Emitting Diode (OLED) display or an electronic paper display, and the insulating film serves as a flexible plastic substrate.

Alternatively, the electronic device may be a semiconductor device, and the insulating film may be a flexible circuit substrate, various wiring coating protectors, a heat resistant adhesive, a wire or cable insulating film, or the like.

The embodiments are described in detail below based on the above embodiments, but the invention is not limited to the specific embodiments disclosed.

<Synthesis of diamine compounds>

Synthesis of Diamine Compound (i-1): The synthesis method of the diamine compound (i-1) is as shown in the following reaction equation 1:

The specific steps are as follows: 23.5 g of 3,5-dinitrophenylphosphonium chloride is dissolved in N,N-dimethylacetamide (DMAc), and 2 equivalents of pyridine are added, followed by 8.48 g of 3 -Amino-1,2,4-triazole, slowly added dropwise at 0 ° C, the reaction temperature should not exceed 3 ° C. After reacting for 6 hours, water was added to precipitate a solid, and the solid was collected and washed twice with 0.1 N hydrochloric acid, and then washed with a saturated aqueous solution of potassium carbonate, and then washed twice with pure water, and finally washed with ethanol. Product S-1. Next, 20 g of the intermediate product S-1 was dissolved in N-methyl-2-pyrrolidone, 5 wt% of palladium metal activated carbon was added, and 20 g of 80% hydrazine hydrate was slowly added dropwise at 25 ° C. After the hour, the filtrate was collected by filtration, and the product was obtained after extraction. The product was analyzed by gas chromatography mass spectrometry. Please refer to Fig. 1, which is the result of gas chromatography mass spectrometry of diamine compound (i-1). As can be seen from Fig. 1, the extract having a residence time of 27.14 minutes is the diamine compound (i-1) having a molecular weight of 283 and the product being the diamine compound (i-1).

<Synthesis of Polymer>

Synthesis Examples 1 to 11: A diamine compound, another diamine compound, and a dianhydride compound were sequentially added to N-methyl-2-pyrrolidone according to the type and ratio of Table 1, to prepare a solution having a solid content of 15% by weight. After reacting at 40 ° C for 5 to 6 hours, a reaction solution containing polylysine can be obtained. If imidization is required, the reaction solution containing polylysine is diluted, and then an appropriate ratio of pyridine and acetic anhydride is added, and the dehydration ring-closing reaction is carried out at 100 ° C to 110 ° C for 3 to 4 hours to obtain a polybendimimine. Or a reaction solution of polyimine-polyamide. Thereafter, the reaction solution was poured into ethanol to be precipitated, and washed and purified with ethanol, and finally, the solid was collected and dried under reduced pressure to obtain a polymer. The weight average molecular weight (Mw) of the polymer was measured by Gel Permeation Chromatography (GPC) and recorded in Table 1.

In Table 1, the structure of the other diamine compound (v-1) is as follows:

Synthesis Examples 12 to 16: A diamine compound, another diamine compound, a dioxonium chloride compound, and a blocking agent were sequentially added to N-methyl-2-pyrrolidone according to the type and ratio of Table 2 to prepare a solid content. A 15 wt% solution was reacted at 0 ° C for 5-6 hours to obtain a reaction solution containing polyamine-polyhydroxyguanamine. Then, the reaction solution was poured into a mixed solution of methanol/water in a volume ratio of 1:1, and washed with a mixed solution of methanol/water in a volume ratio of 1:1, and finally the solid was collected and dried under reduced pressure. A polymer is available. The weight average molecular weight (Mw) of the polymer was measured by GPC and recorded in Table 2.

Examples 1 to 14 and Comparative Examples 1' to 4': The polymer was dissolved in γ-butyrolactone or N-methyl-2-pyrrolidone according to the mixing ratio shown in Table 3 to prepare a solid content of A 15 wt% solution was filtered through a filter having a diameter of 1 μm, and the collected filtrates were resin varnishes of Examples 1 to 14 and Comparative Examples 1 to 4'. The resin varnishes of Examples 1 to 14 and Comparative Examples 1' to 4' were each applied to a glass substrate by a spin coater, and dried on a hot plate at 250 ° C for 20 minutes to obtain a film having a thickness of 10 μm. That is, the insulating films of Examples 1 to 14 and Comparative Examples 1' to 4'. Examples 1 to 14 and Comparative Examples 1' to 4' were evaluated for metal adhesion, heat resistance and mechanical properties, and the evaluation results are shown in Table 3. For the evaluation method, refer to the following.

As can be seen from Table 3, in Examples 1 to 14 of the present invention, the metal adhesion was good or excellent, and the comparative examples 1' to 4' did not use the diamine compound of the formula (i) as a monomer for forming a polymer. The metal adhesion is inferior. It is apparent that the present invention can provide a good metal adhesion by using the diamine compound of the formula (i) as a monomer for forming a polymer. Further, from Examples 1, 2, or Examples 3, 4, and 5, it is understood that when the amount of the diamine compound (i) used is increased, the metal adhesion can be improved. From Examples 1 to 11 and Examples 12 to 13, it is understood that the mechanical properties can be further improved by increasing the molecular weight of the polymer. It is understood from Examples 1 to 11 and Example 14 that when the dianhydride compound to be used is an aromatic dianhydride compound, it contributes to improvement in heat resistance and mechanical properties.

Examples 15 to 17 and Comparative Examples 5' to 7': according to Table 4 Mixing ratio of polymer, diamine compound (i-1), photosensitive compound (PAC), epoxy compound, catalyst, etc. in γ-butyrolactone (GBL), propylene glycol methyl ether acetate (propylene glycol) The monomethyl ether acetate (PGMEA) was filtered through a filter having a diameter of 1 μm, and the collected filtrates were the resin varnishes of Examples 15 to 17 and Comparative Examples 5' to 7'. The resin varnishes of Examples 15 to 17 and Comparative Examples 5' to 7' were each applied to a glass substrate by a spin coater, and dried on a hot plate at 250 ° C for 20 minutes to obtain a film having a thickness of 10 μm. That is, the insulating films of Examples 15 to 17 and Comparative Examples 5' to 7'. Examples 15 to 17 and Comparative Examples 5' to 7' were evaluated for metal adhesion and developability, and the evaluation results are shown in Table 4, and the evaluation method is as follows.

In Table 4, PAC is TPD423, purchased from MIWON, epoxy The compound is 9,9-bis[(2,3-epoxypropoxy)phenyl]anthracene, and the catalyst is methyl p-toluenesulfonate.

As can be seen from Table 4, in Examples 15 to 17 of the present invention, the metal adhesion was good or excellent, and the comparative examples 5' to 6' did not use the diamine compound of the formula (i) as a monomer for forming a polymer. The metal adhesion is poor, and it is apparent that the present invention can impart good metal adhesion by using the diamine compound (i) as a monomer for forming a polymer. From Examples 15 to 16 and Example 17, it is understood that when the terminal functional group of the polymer is a saturated terminal functional group, the developability can be further improved. It can be seen from Examples 15 to 17 and Comparative Example 7' that when the diamine compound of the formula (i) is added, not as a monomer for forming a polymer (that is, the polymer does not contain the diamine compound of the formula (i) Residue) is not conducive to improving metal adhesion.

<Evaluation method of embodiment>

The qualitative mass measurement methods of Examples 1 to 17 and Comparative Examples 1' to 7' are as follows.

Metal adhesion: The resin varnishes of Examples 1 to 17 and Comparative Examples 1' to 7' were applied to a molybdenum/aluminum (Mo/Al) alloy film glass, and after soaking for 10 minutes at room temperature through 2.38% TMAH, It is cleaned and dried, and tested by the Baige test method (ASTM M3359). The test results are represented by 0B-5B, where 0B stands for inferior, 1B-2B stands for difference, 3B is medium, 4B is better, and 5B is excellent.

Heat resistance: The insulating films of Examples 1 to 17 and Comparative Examples 1' to 7' were analyzed by Thermogravimetric analysis (TGA; model TA-TAQ500), and were measured from room temperature to 800 under nitrogen. °C, and increase the temperature by 10 °C per minute, measure the thermal cracking temperature (Td), with Td _5% 550 ° C is excellent, 450 ° C Td _5% <550 ° C is better, Td _5% <450 ° C is worse.

Mechanical characteristics: The insulating films of Examples 1 to 17 and Comparative Examples 1' to 7' were measured with a universal tensile machine (model SHIMADZU EZ-L) to break elongation (Eb) 20% is excellent, 10% Eb <20% is better, 5% Eb < 10% is poor, and Eb < 5% is bad.

Developability: The method of measuring the minimum exposure amount (Eth) is to apply the resin varnishes of Examples 15 to 17 and Comparative Examples 5' to 7' to a glass substrate to form a coating layer of 2 μm to 4 μm, and the glass substrate can be used. The coating layer was heated and baked by using 0.5 mm thick EXG glass produced by Corning Inc. or 0.5 mm thick OA-10 glass produced by Nippon Electric Glass Co., Ltd. After baking to obtain a photosensitive resin, I-Line exposure and development were carried out, wherein the development was carried out with tetramethylammonium hydroxide (TMAH) as a developer for 60 seconds, and then, at which energy, no residual film was observed, and the obtained The energy is Eth. Eth 120 mJ/cm ^{2 is} preferred, and >120 mJ/cm ² is poor.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.

Claims (10)

A diamine compound having a structure as shown in formula (i): Wherein X is -O-, -COO-, -NH-, -CONH- or -NHCO-, and Y is a single bond or a divalent aliphatic hydrocarbon group, and Z is an aromatic heterocyclic ring containing at least three nitrogens. A polymer produced by a polymerization reaction of a diamine compound according to claim 1 wherein the polymer comprises the formula (I) and/or formula (II) and/or formula (III) Show one structure: Wherein the A ¹ is a divalent organic group, and the A ² and the A ³ are each independently a tetravalent organic group, and the E ¹ , the E ² and the E ³ are each independently described in claim 1 The residue of the diamine compound. The polymer of claim 2, wherein the polymer further comprises a structure represented by formula (IV) and/or formula (V): Wherein the T ¹ and the T ² are each independently a divalent organic group, and the M ¹ and the M ² are each independently a tetravalent organic group. The polymer of claim 2, wherein the polymer is polyamine, polylysine, polyimine or a copolymer thereof. The polymer of claim 4, wherein the reactant of the polymerization further comprises other diamine compounds. The polymer of claim 2, wherein the total content of the formula (I), the formula (II) and the formula (III) is greater than or equal to 5 mol based on the polymer being 100 mol%. percentage. The polymer of claim 2, wherein the polymer further comprises a saturated terminal functional group. The polymer of claim 2, wherein the A ² and A ³ are each independently a residue of an aromatic dianhydride compound. An insulating film made of the polymer according to any one of claims 2 to 8. An electronic device comprising: an insulating film made of the polymer according to any one of claims 2 to 8.