JP7232521B2 - Method for producing polyamideimide resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polyamideimide resin.

Polyamideimides are usually synthesized by the isocyanate method by reacting trimellitic anhydride and aromatic diisocyanate, or synthesized by the acid chloride method by reacting aromatic diamine and trimellitic acid chloride.

However, in the isocyanate method, the types of industrially produced and commercially available aromatic diisocyanates are limited, which limits the types of polyamideimides that can be produced, making it difficult to provide a wide range of properties. On the other hand, the acid chloride method requires a process for desorbing hydrogen chloride, which is a by-product.

Therefore, a method for producing polyamideimide has been proposed, which is characterized by a two-step method in which trimellitic anhydride and diamine are reacted in a solvent in a state in which the acid component is excessive, and then diisocyanate is reacted (Patent Document 1). . In this method, a diimidedicarboxylic acid is produced in the first step, and then a polyamideimide is produced by a decarboxylation reaction between the diimidedicarboxylic acid and a diisocyanate in the second step.

Alternatively, trimellitic anhydride and diamine are reacted in a solvent, then an aromatic hydrocarbon capable of azeotroping with water is added, the reaction is carried out at 120° C. to 180° C. to produce a diimidedicarboxylic acid, and the solution is A method has been proposed for producing a polyamide-imide by removing an aromatic hydrocarbon and reacting it with an aromatic diisocyanate (Patent Document 2). This method also belongs to the two-step method.

By using such a two-step method, polyamideimide can be modified by using a wide variety of diamines as they are, and a polyamideimide resin solution can be produced without the by-production of hydrogen chloride as in the acid chloride method. be able to.

However, these two-step methods have problems in that the imidization reaction of diimidodicarboxylic acid takes a long time and the imidization rate is low in the first step of the process for producing diimidodicarboxylic acid. Normally, a temperature of 300° C. or higher is required to quantitatively advance the imidization reaction by heating. and the imidization rate becomes low. Due to the low imidization rate, the amount of carboxylic acid residues increases, and when reacting with diisocyanate in a later step, a branched structure is formed, and a polyamideimide resin with a low molecular weight due to the deviation of the molar balance. can only be obtained.

Furthermore, in the two-step method, it is necessary to remove water generated by the imidization reaction in the first step of the diimidedicarboxylic acid production process by adding an azeotropic solvent and selectively vaporizing the water. However, in this method, it is difficult to completely remove water, and in addition, an azeotropic solvent removal step is required, which increases the number of steps and complicates the process. In particular, if the removal of water is incomplete, the isocyanate group of the diisocyanate is hydrolyzed in a subsequent step to produce an amino group. As a result, the elongation reaction during polymerization is inhibited, and not only is it impossible to obtain a polyamideimide with a high molecular weight, but also the reaction between the amino group and the isocyanate group produces a urea bond as a by-product, lowering the purity of the polyamideimide resin. .

In addition, in the two-step method, it is generally necessary to add an azeotropic solvent, which is a poor solvent, to the diimidodicarboxylic acid, and since the diimidodicarboxylic acid cannot be dissolved in the solvent at a high concentration, the solid content concentration cannot produce varnishes with high Furthermore, since a diimidedicarboxylic acid with low solubility in a solvent cannot be used, there is a problem that the raw material monomers to be used are limited.

JP-A-03-181511 Japanese Patent No. 09-268214

An object of the present invention is to provide a novel production method for obtaining a polyamide-imide resin.
Specifically, the present invention provides polyamideimide resins of various compositions having sufficiently high molecular weights at low cost and in a simple manner without the need for a complicated imidization step in a solvent or a step for removing water from the solvent. An object is to provide a novel manufacturing method for manufacturing.

The present invention also provides a low-cost, easy-to-use polymer that does not contain branched structures and urea bonds in its structure and has a sufficient molecular weight without requiring a complicated imidization step in a solvent or a step of removing water from a solvent. An object of the present invention is to provide a novel production method for producing polyamide-imide resins having various compositions and having a high viscosity.

As a result of intensive studies to solve such problems, the present inventors have found that the above object can be achieved by using a specific raw material and utilizing the mechanochemical effect, and have reached the present invention. bottom.

That is, the gist of the present invention is as follows.
[1] Using a mechanochemical effect, a tricarboxylic anhydride-based compound and a diamine-based compound or a monoaminomonocarboxylic acid-based compound are reacted, or a tetracarboxylic anhydride-based compound and a monoaminomonocarboxylic acid-based compound are reacted. a step of reacting with a compound and imidizing by heating to produce an imidedicarboxylic acid; and a step of reacting the imidedicarboxylic acid with a diisocyanate in an organic solvent;
A method for producing a polyamideimide resin, comprising:
[2] The diimidedicarboxylic acid precursor is produced by reacting the tricarboxylic anhydride-based compound with the diamine-based compound in an amount of 0.3 to 0.7 times the molar amount of the compound, according to [1]. A method for producing a polyamide-imide resin.
[3] Producing a diimidedicarboxylic acid precursor by reacting the tetracarboxylic anhydride-based compound with the monoaminomonocarboxylic acid-based compound in an amount 1.8 to 2.2 times the molar amount of the compound, [1] A method for producing a polyamide-imide resin according to [1].
[4] Producing a monoimide dicarboxylic acid precursor by reacting the tricarboxylic anhydride-based compound with the monoaminomonocarboxylic acid-based compound in an amount 0.8 to 1.2 times the molar amount of the compound, [1] A method for producing a polyamide-imide resin according to [1].
[5] The method for producing a polyamide-imide resin according to any one of [1] to [4], wherein the reaction utilizing the mechanochemical effect and the imidization by heating are solventless reactions.
[6] The method for producing a polyamide-imide resin according to any one of [1] to [5], wherein the reaction utilizing the mechanochemical effect is carried out until the average particle size of the raw material compound becomes 500 μm or less.
[7] The method for producing a polyamide-imide resin according to any one of [1] to [6], wherein the imidization by heating is performed during and/or after the reaction utilizing the mechanochemical effect.
[8] The method for producing a polyamideimide resin according to any one of [1] to [7], wherein the imidization is performed by heating at a temperature of 100 to 450°C for 10 minutes to 16 hours.
[9] The method for producing a polyamideimide resin according to any one of [1] to [8], wherein the imidodicarboxylic acid has an imidization rate of 95.0% or more.
[10] The method for producing a polyamideimide resin according to any one of [1] to [9], wherein the imidodicarboxylic acid has a water content of 10 to 10000 ppm.
[11] Production of the polyamideimide resin according to any one of [1] to [10], wherein the reaction of the imidodicarboxylic acid and the diisocyanate is performed by stirring at a temperature of 80 to 250° C. for 1 to 16 hours. Method.
[12] The method for producing a polyamideimide resin according to any one of [1] to [11], wherein the diisocyanate is reacted in two or more steps.
[13] The method for producing a polyamideimide resin according to any one of [1] to [12], wherein the polyamideimide resin has an average molecular weight of 2,000 to 300,000.

The production method of the present invention does not require a complicated imidization step in a solvent or a water removal step from a solvent, so it is possible to easily produce polyamideimide resins of various compositions with sufficiently high molecular weights at low cost. can do.
Since the polyamideimide resin obtained by the production method of the present invention does not contain branched structures and urea bonds in its structure, the purity of the linear polyamideimide is high.

[Method for producing polyamideimide resin]
A method for producing a polyamideimide resin according to the present invention includes a step of producing an imidedicarboxylic acid and a step of producing a polyamideimide resin.

<Manufacturing process of imidodicarboxylic acid>
This step includes an imidodicarboxylic acid precursor manufacturing step and an imidization step. Both the imidodicarboxylic acid precursor manufacturing process and the imidization process are solvent-free reaction processes, which do not require a complicated imidization process in a solvent or a process for removing water from the solvent, resulting in low cost and simplicity. In addition, a polyamideimide resin can be produced. A solventless reaction is a reaction carried out in a dry manner without using a solvent.

As used herein, imidodicarboxylic acid refers to a compound having one or more imide bonds and two carboxyl groups in one molecule. Imidodicarboxylic acids typically include monoimidodicarboxylic acids and diimidodicarboxylic acids.

(Manufacturing process of imidodicarboxylic acid precursor)
In the process for producing an imidodicarboxylic acid precursor, an imidodicarboxylic acid precursor is produced by reacting raw material compounds using mechanochemical effects. Specifically, the imide dicarboxylic acid precursor is obtained by expressing a mechanochemical effect by utilizing the mechanical energy generated when the raw material compound is pulverized.

In the present invention, the mechanochemical effect refers to the application of mechanical energy (compressive force, shear force, impact force, grinding force, etc.) to a raw material compound in a solid state under a reaction environment to pulverize the raw material compound. , is the effect (or phenomenon) that activates the grinding interface that is formed. This causes a reaction between the functional groups of the raw material compound. Reactions between functional groups usually occur between two or more starting compound molecules. For example, the reaction between functional groups may occur between two starting compound molecules with different chemical structures, or between two starting compound molecules with the same chemical structure. Reaction between functional groups does not occur only between a limited set of two starting compound molecules, but usually occurs between another set of two starting compound molecules. A new reaction between the functional groups may occur between the compound molecule generated by the reaction between the functional groups and the raw material compound molecule. The reaction between functional groups is usually a chemical reaction whereby a linking group (particularly a covalent bond) is formed to yield another compound molecule. Reaction between functional groups may or may not produce small molecules such as water, carbon dioxide, and/or alcohol.

The reaction environment means an environment in which the raw material compounds are placed for the reaction, that is, an environment to which mechanical energy is applied, and may be, for example, an environment within an apparatus. Being in a solid state under a reaction environment means being in a solid state under an environment in which mechanical energy is imparted (eg, under temperature and pressure within an apparatus). The raw material compound that is in a solid state under the reaction environment is generally in a solid state under normal temperature (25° C.) and normal pressure (101.325 kPa). A raw material compound that is in a solid state under the reaction environment may be in a solid state at the start of application of mechanical energy. According to the present invention, a raw material compound in a solid state under a reaction environment is brought into a liquid state (for example, a molten state) during reaction (or processing) due to an increase in temperature and/or pressure accompanying continuous application of mechanical energy. ), but from the viewpoint of improving the reaction rate, it is preferably in a solid state continuously during the reaction (or during the treatment).

Although the details of the mechanochemical effect are not clear, it is believed to follow the principle below. When mechanical energy is applied to one or more solid state source compounds to cause pulverization, the absorption of the mechanical energy activates the pulverization interface. It is believed that such surface activation energy at the pulverized interface causes a chemical reaction between two raw material compound molecules. Pulverization means that when mechanical energy is applied to raw material compound particles, the particles absorb the mechanical energy, causing cracks in the particles and renewing the surface. Renewing the surface means forming a pulverized interface as a new surface. In the mechanochemical effect, the new surface state formed by surface renewal is not particularly limited as long as activation of the grinding interface by grinding occurs, and it may be in a dry state or in a wet state. good too. The new wet state of the surface due to surface renewal results from the source compound in a liquid state separate from the source compound in the solid state.

Mechanical energy is imparted to a feedstock mixture containing one or more feedstock compounds in a solid state under the reaction environment. The state of the raw material mixture is not particularly limited as long as the raw material compound in a solid state is pulverized by the application of mechanical energy. For example, the raw material mixture may be in a dry state due to all raw material compounds contained in the raw material mixture being in a solid state. Further, for example, the raw material mixture may be in a wet state because at least one raw material compound contained in the raw material mixture is in a solid state and the rest of the raw material compounds are in a liquid state. Specifically, for example, when the raw material mixture contains only one raw material compound, the one raw material compound is in a solid state. Further, for example, when the raw material mixture contains two raw material compounds, the two raw material compounds may both be in a solid state, or one raw material compound may be in a solid state and the other raw material compound may be in a liquid state. may be in a state

The production of the imidodicarboxylic acid precursor by the mechanochemical effect is achieved by subjecting a raw material mixture containing at least one raw material compound in a solid state as described above to a pulverization treatment. The comminution process can be accomplished by any device (e.g. so-called comminution, mixing or agitating devices) capable of transferring mechanical energy to the raw compounds, such as by compression, impact, shearing and/or grinding. may For example, crushing processes include jaw crushers, gyratory crushers, cone crushers, impact (hammer) crushers, roll crushers, cutter mills, autogenous crushers, stamp mills, stone mills, mortars, mortar mills, Muller mills, Eirich Mill, Ring Mill, Roller Mill, Jet Mill, High Speed Bottom Stirring Mixer, High Speed Rotary Pulverizer (Hammer Mill, Pin Mill), Vessel Driven Mill (Rotary Mill, Vibration Mill, Planetary Mill), Media Stirring Mill (, bead mill), a high-speed fluidized mixer, a Henschel mixer, or the like. Among such apparatuses, representative apparatuses include, for example, a high-speed bottom agitating mixer, a high-speed rotary pulverizer, a vessel-driven mill, and a medium-agitation mill.

A high-speed bottom agitating mixer generally has a structure in which large, high-speed rotating blades are arranged at the bottom of a cylindrical container, and the rotating blades are arranged in two stages, upper and lower.
A high-speed rotary pulverizer is a device that pulverizes a sample by colliding it with impactors such as hammers, pins, and bars on a rotating rotor.
Vessel-driven mills (rotary mills, vibrating mills, planetary mills) are devices that grind raw materials by putting media such as balls in a rotating vessel and rotating the vessel.
A medium agitating mill is a device that uses balls or beads as grinding media and collides them to grind a sample between them.

The reaction conditions (that is, mixing/stirring/pulverizing conditions) are not particularly limited as long as the mechanochemical effect is exhibited and the desired imidodicarboxylic acid precursor powder is obtained. For example, the speed of rotation depends on the equipment used and should be chosen to provide sufficient energy. Also, for example, the treatment time varies depending on the device used, and it is necessary to select a time that provides sufficient energy.

Specifically, for example, using a high-speed rotary grinder, the capacity of the grinding tank (or tank) for grinding treatment is 75 to 200 mL (especially 150 mL), and the weight of the raw material mixture is 50 to 250 g (especially 100 g ), the rotation speed is usually 3000 rpm or more, especially 14000 rpm, and the grinding time is usually 1 minute or more, especially 2 to 10 minutes.

The raw material compound to be pulverized includes one or more raw material compounds that are in a solid state under the reaction environment as described above. When a raw material compound that is in a liquid state under the reaction environment is used as the raw material compound, the liquid raw material compound is at least one solid raw material compound contained in the raw material mixture from the viewpoint of further improving the reaction rate. is preferably mixed or added before or during grinding. At this time, from the viewpoint of further improving the reaction rate, the raw material compound in a liquid state is preferably added in multiple portions, more preferably in drops, in an amount obtained by dividing a predetermined addition amount into two or more portions. is preferred.

Such pulverization treatment and subsequent cooling treatment of the pulverized material (for example, standing cooling treatment) may be repeated two or more times, for example, 2 to 10 times. Thereby, the mechanochemical effect is exhibited more effectively, and the reaction rate is further improved.

The raw material compound (especially the raw material compound in a solid state under the reaction environment) usually has a particle shape with a maximum length of 0.001 to 20.0 mm, particularly 0.01 to 10.0 mm. The cumulative 50% diameter was used as the maximum length. Specifically, the maximum length is a value measured as a cumulative 50% particle size from the particle size distribution by the sieving test described in JISZ8815 in accordance with JISZ8815 when particles with a particle size of 0.5 mm or more are included. bottom. When particles with a diameter of 0.5 mm or more are not included, the cumulative 50% diameter determined by a particle size distribution measuring device based on a laser diffraction/scattering method was taken as the maximum length.

Although the molecular weight of the raw material compound is not particularly limited, it is preferably 2,000 or less, particularly 1,500 to 30, more preferably 1,000 to 30, from the viewpoint of further improving the reaction rate. If a compound having a molecular weight larger than the above range is used as a raw material compound, the reaction rate is lowered, which is not preferable. Although the details of the reason for this are not clear, the activation of the pulverization interface in the mechanochemical effect is based on the activity of the molecule of the raw material compound. be done. Alternatively, when the molecular weight is large, the density of the functional groups per molecule is low, so that the probability of contact between activated functional groups is reduced.

The reaction due to the mechanochemical effect (that is, the application of mechanical energy) may be carried out in one step or in multiple steps of two or more steps. A method of applying mechanical energy in one step can be referred to as a one-step mechanochemical method. A method of applying mechanical energy in two or more steps can be called a multistep mechanochemical method. For example, in the one-step mechanochemical method, the raw material compounds are put into the above-described apparatus (for example, a pulverizing device, a mixing device, or a stirring device) at a desired composition ratio, and then a mechanochemical reaction is performed in a one-step pulverization process. terminate. Further, for example, in the two-stage mechanochemical method, after the raw material compound is put into the above-described apparatus at the desired composition ratio, the first-stage pulverization process is performed to coarsely pulverize, and then the second-stage pulverization process is performed to further finely pulverize. I do.

From the viewpoint of further improving the reaction rate and workability, it is preferable to employ a multi-stage mechanochemical method (especially a two-stage mechanochemical method). Specifically, if the pulverization process is suddenly performed in the first stage, the sample will adhere or adhere to the equipment, resulting in a decrease in the yield of the product obtained or an operability problem such as the equipment stopping during processing. There is also Therefore, it is preferable to employ a multi-stage mechanochemical method from the viewpoint of further improving the reaction rate and workability.

In the multi-step mechanochemical process, the equipment used in each step may be independently selected from the equipment detailed above. Particularly in the two-stage mechanochemical method, it is preferable that the apparatus used in the first-stage coarse pulverization treatment and the apparatus used in the second-stage fine pulverization treatment are different. Where there is an appropriate target particle size (recommended target particle size after pulverization) in the apparatus, efficiency can be improved by using an apparatus with different appropriate target particle sizes at each stage in the multi-stage mechanochemical process. Since it is possible to perform effective pulverization, the reaction rate is further improved as a result. From the viewpoint of further improving the reaction rate based on such efficient pulverization (that is, reducing the particle size), in the multi-stage mechanochemical method, the equipment used immediately after the appropriate target particle size is used immediately before. It is preferable to use a device that is smaller than the appropriate target particle size for the device being used. From the same point of view, for example, in the two-stage mechanochemical method, it is preferable to perform pulverization using a high-speed bottom-stirring mixer in the first stage, and to perform pulverization using a medium-stirring mill in the second stage.

In the present invention, the type (structure) of the imide dicarboxylic acid precursor to be produced can be controlled by adjusting or selecting the types and ratios of the raw material compounds.

Specifically, the imidedicarboxylic acid precursor can be produced by reacting the following combinations of compounds as raw material compounds:
(Combination A) reacting a tricarboxylic anhydride-based compound with a diamine-based compound;
(Combination B) reacting a tricarboxylic anhydride-based compound with a monoaminomonocarboxylic acid-based compound; or (combination C) reacting a tetracarboxylic anhydride-based compound with a monoaminomonocarboxylic acid-based compound.

・Combination A
In the above combination A, usually about 0.5-fold molar amount, for example, 0.3-0.7-fold molar amount, preferably 0.4-0.6-fold molar amount relative to the tricarboxylic anhydride-based compound and the compound A diimide dicarboxylic acid precursor is produced by reaction with a diamine compound in an amount, more preferably 0.45 to 0.55 times the molar amount. In combination A, the diimide dicarboxylic acid precursor is obtained by binding two molecules of a tricarboxylic anhydride compound to one molecule of a diamine compound by forming two amide groups based on ring opening of the acid anhydride group. An organic compound that is The product obtained by such a reaction is not only the diimidedicarboxylic acid precursor, but also one molecule of tricarboxylic acid anhydride compound per molecule of diamine compound based on ring opening of the acid anhydride group. It may also be a mixture containing an organic substance obtained by bonding through formation of an amide group, an unreacted tricarboxylic anhydride-based compound, and an unreacted diamine-based compound.

In combination A, the tricarboxylic anhydride-based compound that can constitute the diimide dicarboxylic acid precursor is an organic compound having three carboxyl groups in one molecule, two of which form an acid anhydride group with the carboxyl groups. It's about. The tricarboxylic anhydride-based compound includes an aromatic tricarboxylic anhydride containing an aromatic ring, an alicyclic tricarboxylic anhydride containing an aliphatic ring but not an aromatic ring, and an aromatic ring that is also an alicyclic It includes aliphatic tricarboxylic acid anhydrides that also do not contain rings. The tricarboxylic acid anhydrides may contain ether groups and/or thioether groups and/or one or more of the hydrogen atoms are replaced by other atoms such as halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms). Alternatively, it may be substituted by an atomic group. As used herein, an ether group is an "--O--" group present between carbon atoms. A thioether group is a "-S-" group that exists between carbon atoms. Examples of aromatic rings include benzene ring, naphthalene ring, anthracene ring, biphenyl ring and the like. Examples of the aliphatic ring include cyclohexane ring and the like. Tricarboxylic anhydrides may be used alone or in combination of two or more.

Specific examples of aromatic tricarboxylic anhydrides include trimellitic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 2,3,6-anthracentric tricarboxylic anhydride, and 3,4,4′. -biphenyltricarboxylic anhydride, hemimellitic anhydride, 1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, 3, 4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenylethertricarboxylic anhydride, 2,3,2'-biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride and 3,4,4′-biphenylsulfonetricarboxylic acid anhydride. Aromatic tricarboxylic acid anhydrides may be used alone or in combination of two or more.

Specific examples of the alicyclic tricarboxylic anhydride include 1,2,4-cyclohexanetricarboxylic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, and 1,2,3-cyclohexanetricarboxylic anhydride. and 1,3,5-cyclohexanetricarboxylic anhydride. The alicyclic tricarboxylic acid anhydrides may be used alone, or two or more of them may be used in combination.

Specific examples of aliphatic tricarboxylic acid anhydrides include 3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3- and tricarboxylic acid-1,2-anhydride. Aliphatic tricarboxylic acid anhydrides may be used alone or in combination of two or more.

The tricarboxylic acid anhydride of the imidedicarboxylic acid precursor in combination A contains an aromatic tricarboxylic acid anhydride and/or an alicyclic tricarboxylic acid anhydride from the viewpoint of improving the heat resistance of the finally obtained polyamide-imide resin. is preferred. In the case of using a tricarboxylic acid anhydride that is preferable from the viewpoint of "improving the heat resistance of the polyamide-imide resin", it is more preferable from the same viewpoint to use a diamine that is preferable from the same viewpoint, which will be described later.
The tricarboxylic acid anhydride of the imidedicarboxylic acid precursor in combination A is only an aromatic tricarboxylic acid anhydride and/or an alicyclic tricarboxylic acid anhydride from the viewpoint of further improving the heat resistance of the finally obtained polyamide-imide resin. is preferably included. In the case of using a tricarboxylic acid anhydride that is preferable from the viewpoint of "further improving the heat resistance of the polyamide-imide resin", it is more preferable from the same viewpoint to use a diamine that is preferable from the same viewpoint, which will be described later.

From the viewpoint of improving the non-coloring property of the finally obtained polyamide-imide resin, the tricarboxylic acid anhydride of the imidedicarboxylic acid precursor in combination A is, among the above tricarboxylic acid anhydrides, an alicyclic tricarboxylic acid anhydride and / Or it is preferable to use an aliphatic tricarboxylic acid anhydride. In the case of using a preferable tricarboxylic acid anhydride from the viewpoint of "improving the non-coloring property of the polyamideimide resin", it is more preferable from the same viewpoint to use a preferable diamine described later from the same viewpoint.
The tricarboxylic anhydride of the imidedicarboxylic acid precursor in combination A is an alicyclic tricarboxylic anhydride among the above tricarboxylic anhydrides from the viewpoint of further improving the non-coloring property of the finally obtained polyamide-imide resin. and/or it is preferred to use only aliphatic tricarboxylic acid anhydrides. In the case of using a tricarboxylic acid anhydride that is preferable from the viewpoint of "further improving the non-coloring property of the polyamide-imide resin", it is more preferable from the same viewpoint to use a diamine that is preferable from the same viewpoint, which will be described later.

The tricarboxylic acid anhydride of the imidedicarboxylic acid precursor in combination A is, from the viewpoint of improving the solubility and non-coloring property of the finally obtained polyamide-imide resin, among the above tricarboxylic acid anhydrides, alicyclic anhydride tricarboxylic acid It preferably contains an acid component and/or an aliphatic tricarboxylic anhydride component.
From the viewpoint of further improving the solubility and non-coloring property of the finally obtained polyamide-imide resin, the tricarboxylic anhydride of the imidodicarboxylic acid precursor in combination A is an alicyclic anhydride among the above tricarboxylic anhydrides. It preferably contains only a tricarboxylic acid component and/or an aliphatic tricarboxylic anhydride component.

From the viewpoint of versatility, the tricarboxylic anhydride of the imidodicarboxylic acid precursor in combination A is a group consisting of trimellitic anhydride and 1,2,4-cyclohexanetricarboxylic anhydride among the above tricarboxylic anhydrides. (hereinafter referred to as group P1). In the case of using a tricarboxylic acid anhydride that is preferable from the viewpoint of such versatility, it is more preferable from the same viewpoint to use a diamine that is preferable from the same viewpoint, which will be described later.
From the viewpoint of further improving versatility, the tricarboxylic anhydride of the imidodicarboxylic acid precursor in combination A may contain only one or more compounds selected from the above group P1 among the above tricarboxylic anhydrides. preferable. In the case of using a tricarboxylic acid anhydride that is preferable from the viewpoint of further improving versatility, it is more preferable from the same viewpoint to use a diamine that is preferable from the same viewpoint, which will be described later.

The diamine-based compound that can constitute the diimidedicarboxylic acid precursor in combination A is an organic compound having two amino groups in one molecule. Diamine-based compounds include aromatic diamines containing an aromatic ring, alicyclic diamines containing an aliphatic ring but no aromatic ring, and aliphatic diamines containing neither an aromatic ring nor an alicyclic ring. do. The diamine-based compound may contain an ether group and/or a thioether group, and/or one or more of the hydrogen atoms are other atoms such as halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms), or It may be substituted by an atomic group. As used herein, an ether group is an "--O--" group present between carbon atoms. A thioether group is a "-S-" group that exists between carbon atoms. The diamine-based compound may have side chains. A side chain is a residue having a methyl group, a methylene group, a methoxy group, an ethoxy group, an acetyl group, an ether group, a thioether group, a sulfonyl group, a hydroxyl group, a phenyl group, a sulfonic acid group, etc., and a hydrogen atom. may be substituted with another atom or atomic group such as a halogen atom (eg, fluorine atom, chlorine atom, bromine atom). A diamine compound may be used independently and may use two or more types together.

Examples of aromatic diamines in combination A include m-xylylenediamine, p-xylylenediamine, benzidine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-toluenediamine, 2,6 -toluenediamine, m-aminobenzylamine, p-aminobenzylamine, bis(3-aminophenyl)sulfide, (3-aminophenyl)(4-aminophenyl)sulfide, bis(4-aminophenyl)sulfide, bis( 3-aminophenyl)sulfoxide, (3-aminophenyl)(4-aminophenyl)sulfoxide, bis(3-aminophenyl)sulfone, (3-aminophenyl)(4-aminophenyl)sulfone, bis(4-aminophenyl) ) sulfone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane , 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminobenzanilide, 3,3′-dimethyl-3,4′-diaminobiphenyl, 2 , 2′-dimethyl-3,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, bis[4-(3-aminophenoxy)phenyl]methane, bis[ 4-(4-aminophenoxy)phenyl]methane, 1,1-bis[4-(3-aminophenoxy)phenyl]ethane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1 , 2-bis[4-(3-aminophenoxy)phenyl]ethane, 1,2-bis[4-(4-aminophenoxy)phenyl]ethane, 2,2-bis[4-(3-aminophenoxy)phenyl ] Propane, 2,2-bis[4-(3-aminophenoxy)phenyl]butane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3- hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-amino nophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis(4-aminophenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, 1,4'- Bis(4-aminophenoxy)benzene, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]ketone , bis[4-(4-aminophenoxy)phenyl]ketone, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[4-(3- aminophenoxy)phenyl]sulfoxide, bis[4-(aminophenoxy)phenyl]sulfoxide, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4 -(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, 1,4-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,3-bis[4 -(3-aminophenoxy)benzoyl]benzene, 4,4'-bis[3-(4-aminophenoxy)benzoyl]diphenyl ether, 4,4'-bis[3-(3-aminophenoxy)benzoyl]diphenyl ether, 4 , 4′-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4′-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfone, bis[4-{4-(4-aminophenoxy)phenoxy}phenyl]sulfone, 1,4-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4 -(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis(3-(4-aminophenoxy)phenoxy)benzene, 1,3-bis(3-(2-aminophenoxy)phenoxy ) benzene, 1,3-bis(4-(2-aminophenoxy)phenoxy)benzene, 1,3-bis(2-(2-aminophenoxy)phenoxy)benzene, 1,3-bis(2-(3- aminophenoxy)phenoxy)benzene, 1,3-bis(2-(4-aminophenoxy)phenoxy)benzene, 1,4-bis(3-(3-aminophenoxy)phenoxy)benzene, 1,4-bis(3-(4-aminophenoxy)phenoxy)benzene, 1,4-bis(3-(2-aminophenoxy)phenoxy)benzene, 1,4-bis(4-(2-aminophenoxy) phenoxy)benzene, 1,4-bis(2-(2-aminophenoxy)phenoxy)benzene, 1,4-bis(2-(3-aminophenoxy)phenoxy)benzene, 1,4-bis(2-(4 -aminophenoxy)phenoxy)benzene, 1,2-bis(3-(3-aminophenoxy)phenoxy)benzene, 1,2-bis(3-(4-aminophenoxy)phenoxy)benzene, 1,2-bis( 3-(2-aminophenoxy)phenoxy)benzene, 1,2-bis(4-(4-aminophenoxy)phenoxy)benzene, 1,2-bis(4-(3-aminophenoxy)phenoxy)benzene, 1, 2-bis(4-(2-aminophenoxy)phenoxy)benzene, 1,2-bis(2-(2-aminophenoxy)phenoxy)benzene, 1,2-bis(2-(3-aminophenoxy)phenoxy) Benzene, 1,2-bis(2-(4-aminophenoxy)phenoxy)benzene, 1,3-bis(3-(3-aminophenoxy)phenoxy)-2-methylbenzene, 1,3-bis(3- (4-aminophenoxy)phenoxy)-4-methylbenzene, 1,3-bis(4-(3-aminophenoxy)phenoxy)-2-ethylbenzene, 1,3-bis(3-(2-aminophenoxy)phenoxy )-5-sec-butylbenzene, 1,3-bis(4-(3-aminophenoxy)phenoxy)-2,5-dimethylbenzene, 1,3-bis(4-(2-amino-6-methylphenoxy ) phenoxy)benzene, 1,3-bis(2-(2-amino-6-ethylphenoxy)phenoxy)benzene, 1,3-bis(2-(3-aminophenoxy)-4-methylphenoxy)benzene, 1 , 3-bis(2-(4-aminophenoxy)-4-tert-butylphenoxy)benzene, 1,4-bis(3-(3-aminophenoxy)phenoxy)-2,5-di-tert-butylbenzene , 1,4-bis(3-(4-aminophenoxy)phenoxy)-2,3-dimethylbenzene, 1,4-bis(3-(2-amino-3-propylphenoxy)phenoxy)benzene, 1,2 -bis(3-(3-aminophenoxy)phenoxy)-4-methylbenzene, 1 , 2-bis(3-(4-aminophenoxy)phenoxy)-3-n-butylbenzene, 1,2-bis(3-(2-amino-3-propylphenoxy)phenoxy)benzenebis(3-aminopropyl ) tetramethyldisiloxane, bis(3-aminophenoxymethyl)tetramethyldisiloxane, α,ω-bis(3-aminopropyl)poly(dimethylsiloxane-diphenylsiloxane) copolymers, and analogs of the above diamines. These may be used individually by 1 type, and can also be used as a mixture of 2 or more types.

Alicyclic diamines in combination A include, for example, trans-1,4-cyclohexanediamine, cis-1,4-cyclohexanediamine, 4,4′-methylenebis(cyclohexylamine)), 1,4-bis(aminomethyl ) cyclohexane, isophorone diamine. These may be used individually by 1 type, and can also be used as a mixture of 2 or more types.

Aliphatic diamines in Combination A include, for example, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 1,10-diamino-1 , 10-dimethyldecane, bis(10-aminodecamethylene)tetramethyldisiloxane, α,ω-bisaminopolydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, 1,3-bis( 3-aminopropyl)tetramethyldisiloxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, bis(10-aminodecamethylene)tetramethyldisiloxane, dimer diamine is mentioned. These may be used individually by 1 type, and can also be used as a mixture of 2 or more types. A dimer diamine is a compound obtained by polymerizing an unsaturated fatty acid such as oleic acid or linoleic acid to form a dimer acid, and then reducing and aminating it (reductive amination). Depending on the purpose of use, it may be hydrogenated to lower the degree of unsaturation. Commercial products such as "Priamine 1074 and 1075" (manufactured by Croda Japan) and "Versamin 551 and 552" (manufactured by Cognis Japan) can be used as the dimer diamine.

The diamine of the imidedicarboxylic acid precursor in combination A preferably contains an aromatic diamine and/or an alicyclic diamine, more preferably an aromatic diamine, from the viewpoint of improving the heat resistance of the finally obtained polyamideimide resin. Contains diamine.
The diamine of the imidedicarboxylic acid precursor in combination A preferably contains only an aromatic diamine and/or an alicyclic diamine, more preferably, from the viewpoint of further improving the heat resistance of the finally obtained polyamideimide resin. Contains only aromatic diamines.

From the viewpoint of the solubility of the finally obtained polyamide-imide resin, the diamine of the imidedicarboxylic acid precursor in combination A is an ether group, a ketone group, a sulfonyl group, a thioether group, a methyl group, and a methylene group among the above diamines. , an isopropylidene group, a phenyl group, a fluorene structure, a fluorine atom (or a substituent containing a fluorine atom), or a diamine having a siloxane bond is preferably used.
From the viewpoint of further improving the solubility of the finally obtained polyamide-imide resin, the diamine of the imidodicarboxylic acid precursor in combination A is an ether group, a ketone group, a sulfonyl group, a thioether group, and a methyl group among the above diamines. , a methylene group, an isopropylidene group, a phenyl group, a fluorene structure, a fluorine atom (or a substituent containing a fluorine atom), or a diamine having a siloxane bond.

The diamine of the imidedicarboxylic acid precursor in combination A has a fluorine atom (or a substituent containing a fluorine atom) among the above diamines, from the viewpoint of improving the non-coloring property of the finally obtained polyamideimide resin. It preferably contains aromatic diamine, cycloaliphatic diamine, and/or aliphatic diamine components. The alicyclic diamines and aliphatic diamines exemplified herein, unlike aromatic diamines, are not intended to have fluorine atoms (or substituents containing fluorine atoms).
From the viewpoint of further improving the non-coloring property of the finally obtained polyamide-imide resin, the diamine of the imidodicarboxylic acid precursor in combination A includes a fluorine atom (or a substituent containing a fluorine atom) among the above diamines. It is preferred that only aromatic diamine, cycloaliphatic diamine, and/or aliphatic diamine components are included. The alicyclic diamines and aliphatic diamines exemplified herein are also not intended to have fluorine atoms (or substituents containing fluorine atoms), unlike aromatic diamines.

From the viewpoint of versatility, the diamine of the imidodicarboxylic acid precursor in combination A is m-xylylenediamine, p-xylylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, p-phenylenediamine, m-phenylenediamine, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-amino phenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis(4-aminophenyl)sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4′- Diaminobenzanilide, 3,3'-dimethyl-3,4'-diaminobiphenyl, 2,2'-dimethyl-3,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2 '-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,2-bis(3-(2-amino-3-propylphenoxy)phenoxy)benzenebis(3-aminopropyl)tetramethyldisiloxane, α,ω-bis(3-aminopropyl)polymethylphenylsiloxane, α ,ω-bis(3-aminopropyl)poly(dimethylsiloxane-diphenylsiloxane) copolymer, trans-1,4-cyclohexanediamine, 4,4′-methylenebis(cyclohexylamine), cis-1,4-cyclohexanediamine, 1 ,4-bis(aminomethyl)cyclohexane, isophoronediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, 1,10-diaminodecane, 1,12-diaminododecane, bis(10-aminodecamethylene)tetramethyldiamine siloxane, α,ω-bisaminopolydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(3 -aminopropyl)-1,1,3,3 -tetramethyldisiloxane, bis(10-aminodecamethylene)tetramethyldisiloxane, and dimer diamine (hereinafter referred to as group P2).
From the viewpoint of further improving versatility, the diamine of the imidodicarboxylic acid precursor in combination A preferably contains only one or more compounds selected from the above group P2 among the above diamines.

・Combination B
In the above combination B, usually about 1-fold molar amount, for example, 0.8-1.2-fold molar amount, preferably 0.9-1.1-fold molar amount relative to the tricarboxylic anhydride-based compound and the compound, More preferably, a monoimidedicarboxylic acid precursor is produced by reacting with a monoaminomonocarboxylic acid compound in a molar amount of 0.95 to 1.05 times. In combination B, the monoimide dicarboxylic acid precursor is such that one molecule of the tricarboxylic anhydride compound per molecule of the monoaminomonocarboxylic acid compound generates one amide group based on the ring opening of the acid anhydride group. It is an organic compound obtained by combining with The product obtained by such a reaction may be a mixture containing not only the monoimide dicarboxylic acid precursor, but also an unreacted tricarboxylic anhydride-based compound and an unreacted monoaminomonocarboxylic acid-based compound. .

The tricarboxylic anhydride-based compound that can constitute the monoimidedicarboxylic acid precursor in combination B is the same tricarboxylic anhydride-based compound as the tricarboxylic anhydride-based compound that can constitute the diimidedicarboxylic acid precursor in combination A. More specifically, it includes aromatic tricarboxylic anhydrides, alicyclic tricarboxylic anhydrides, and aliphatic tricarboxylic anhydrides similar to the tricarboxylic anhydride compounds that can constitute the diimide dicarboxylic acid precursors described above.

The tricarboxylic acid anhydride of the monoimide dicarboxylic acid precursor in combination B is an aromatic tricarboxylic acid anhydride and/or an alicyclic tricarboxylic acid anhydride from the viewpoint of improving the heat resistance of the finally obtained polyamideimide resin. It preferably contains an aromatic tricarboxylic acid anhydride. In the case of using a tricarboxylic acid anhydride that is preferable from the viewpoint of "improving the heat resistance of the polyamideimide resin", it is more preferable from the same viewpoint to use a monoaminomonocarboxylic acid that is preferable from the viewpoint described later.
The tricarboxylic acid anhydride of the monoimide dicarboxylic acid precursor in combination B is an aromatic tricarboxylic acid anhydride and/or an alicyclic tricarboxylic acid anhydride from the viewpoint of further improving the heat resistance of the finally obtained polyamideimide resin. It preferably contains only aromatic tricarboxylic anhydrides, more preferably contains only aromatic tricarboxylic acid anhydrides. In the case of using a tricarboxylic acid anhydride that is preferable from the viewpoint of "further improving the heat resistance of the polyamideimide resin", it is more preferable from the same viewpoint to use a monoaminomonocarboxylic acid that is preferable from the viewpoint described later.

The tricarboxylic acid anhydride of the monoimide dicarboxylic acid precursor in combination B is an alicyclic tricarboxylic acid anhydride among the above tricarboxylic acid anhydrides from the viewpoint of improving the non-coloring property of the finally obtained polyamideimide resin. and/or aliphatic tricarboxylic acid anhydrides are preferably used. In the case of using a tricarboxylic acid anhydride that is preferable from the viewpoint of "improving the non-coloring property of the polyamide-imide resin", it is more preferable from the same viewpoint to use a monoaminomonocarboxylic acid that is preferable from the same viewpoint, which will be described later.
The tricarboxylic acid anhydride of the monoimidedicarboxylic acid precursor in combination B is an alicyclic tricarboxylic acid anhydride among the above tricarboxylic acid anhydrides, from the viewpoint of further improving the non-coloring property of the finally obtained polyamideimide resin. It is preferred to use only mono and/or aliphatic tricarboxylic acid anhydrides. In the case of using a tricarboxylic acid anhydride that is preferable from the viewpoint of such "further improvement in the non-coloring property of the polyamideimide resin", it is more preferable from the same viewpoint to use a monoaminomonocarboxylic acid that is preferable from the same viewpoint, which will be described later.

The tricarboxylic acid anhydride of the monoimide dicarboxylic acid precursor in combination B is, from the viewpoint of improving the solubility and non-coloring property of the finally obtained polyamideimide resin, among the above tricarboxylic acid anhydrides, alicyclic tricarboxylic acid It preferably contains an acid anhydride and/or an aliphatic tricarboxylic anhydride component. When using a tricarboxylic acid anhydride that is preferable from the viewpoint of such "improving the solubility and non-coloring property of the polyamideimide resin", it is more preferable from the same viewpoint to use a monoaminomonocarboxylic acid that is preferable from the same viewpoint described later. preferable.
The tricarboxylic acid anhydride of the monoimide dicarboxylic acid precursor in combination B is, from the viewpoint of further improving the solubility and non-coloring property of the finally obtained polyamideimide resin, among the above tricarboxylic acid anhydrides, alicyclic It preferably contains only tricarboxylic anhydride and/or aliphatic tricarboxylic anhydride components. When using a tricarboxylic acid anhydride that is preferable from the viewpoint of such "further improvement in the solubility and non-coloring property of the polyamideimide resin", it is more preferable from the same viewpoint to use a monoaminomonocarboxylic acid that is preferable from the same viewpoint described later. More preferred.

From the viewpoint of versatility, the tricarboxylic anhydride of the monoimidedicarboxylic acid precursor in combination B is a group consisting of trimellitic anhydride and 1,2,4-cyclohexanetricarboxylic anhydride among the above tricarboxylic anhydrides. (hereinafter referred to as group P3). In the case of using a tricarboxylic acid anhydride that is preferable from the viewpoint of versatility, it is more preferable from the same viewpoint to use a monoaminomonocarboxylic acid that is preferable from the viewpoint described later.
From the viewpoint of further improving versatility, the tricarboxylic anhydride of the monoimide dicarboxylic acid precursor in Combination B contains only one or more compounds selected from the above group P3 among the above tricarboxylic anhydrides. is preferred. In the case of using a tricarboxylic acid anhydride that is preferable from the viewpoint of further improving such versatility, it is more preferable from the same viewpoint to use a monoaminomonocarboxylic acid that is preferable from the viewpoint described later.

The monoaminomonocarboxylic acid compound that can constitute the monoimide dicarboxylic acid precursor in combination B is an organic compound having one amino group and one carboxyl group in one molecule. Monoaminomonocarboxylic acid compounds include aromatic monoaminomonocarboxylic acids containing an aromatic ring, alicyclic monoaminomonocarboxylic acids containing an aliphatic ring but not an aromatic ring, and aromatic rings. It includes aliphatic monoaminomonocarboxylic acids that also do not contain an alicyclic ring. The monoaminomonocarboxylic acid may contain an ether group and/or a thioether group and/or one or more of the hydrogen atoms are replaced with halogen atoms (e.g., fluorine, chlorine, bromine atoms). may

Examples of aromatic monoaminomonocarboxylic acids in combination B include phenylalanine, tryptophan, thyroxine, tyrosine, diiodotyrosine, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-amino-3 -methylbenzoic acid, 2-amino-4-methylbenzoic acid, 2-amino-5-methylbenzoic acid, 2-amino-6-methylbenzoic acid, 3-amino-2-methylbenzoic acid, 3-amino-4 -methylbenzoic acid, 4-amino-2-methylbenzoic acid, 4-amino-3-methylbenzoic acid, 5-amino-2-methylbenzoic acid, 2-amino-3,4-dimethylbenzoic acid, 2-amino -3,5-dimethylbenzoic acid, 2-amino-4,5-dimethylbenzoic acid, 2-amino-4-methoxybenzoic acid, 3-amino-4-methoxybenzoic acid, 4-amino-2-methoxybenzoic acid , 4-(aminomethyl)benzoic acid, 6-amino-2-naphthalenecarboxylic acid, 3-amino-2-naphthoic acid and the like. These may be used individually by 1 type, and can also be used as a mixture of 2 or more types.

Examples of alicyclic monoaminomonocarboxylic acids in combination B include 4-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 2-aminocyclohexanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-(aminomethyl) cyclohexanecarboxylic acid, gabapentin, 2-cyclohexylglycine, 3-cyclohexylalanine, 1-aminocyclopentanecarboxylic acid, 1-aminocyclobutanecarboxylic acid and the like. These may be used individually by 1 type, and can also be used as a mixture of 2 or more types.

Examples of aliphatic monoaminomonocarboxylic acids in combination B include glycine, α-alanine, β-alanine, serine, glycine, valine, norvaline, threonine, leucine, norleucine, isoleucine, proline, hydroxyproline, methionine, cystine, Cysteine, oxamic acid, glycylglycine, α-aminobutyric acid, γ-aminobutyric acid, 5-aminopentanoic acid, 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10- aminodecanoic acid, 11-aminoundecanoic acid, 12-aminolauric acid, 17-aminoheptadecanoic acid and the like. These may be used individually by 1 type, and can also be used as a mixture of 2 or more types.

In the combination B, the monoaminomonocarboxylic acid-based compound of the monoimidedicarboxylic acid precursor is an aromatic monoaminomonocarboxylic acid and/or an alicyclic monocarboxylic acid from the viewpoint of improving the heat resistance of the finally obtained polyamideimide resin. It preferably contains an aminomonocarboxylic acid, more preferably an aromatic monoaminomonocarboxylic acid.
In combination B, the monoaminomonocarboxylic acid-based compound of the monoimidedicarboxylic acid precursor is an aromatic monoaminomonocarboxylic acid and/or an alicyclic from the viewpoint of further improving the heat resistance of the finally obtained polyamideimide resin. It preferably contains only aromatic monoaminomonocarboxylic acids, more preferably only aromatic monoaminomonocarboxylic acids.

The monoaminomonocarboxylic acid-based compound of the monoimidedicarboxylic acid precursor in combination B is, from the viewpoint of improving the non-coloring property of the finally obtained polyamideimide resin, among the above monoaminomonocarboxylic acids, alicyclic It is preferable to use a monoaminomonocarboxylic acid-based compound and/or an aliphatic monoaminomonocarboxylic acid-based compound.
From the viewpoint of further improving the non-coloring property of the finally obtained polyamideimide resin, the monoaminomonocarboxylic acid-based compound of the monoimidedicarboxylic acid precursor in combination B is, among the above monoaminomonocarboxylic acids, an alicyclic It is preferable to use only monoaminomonocarboxylic acid-based compounds and/or aliphatic monoaminomonocarboxylic acids.

The monoaminomonocarboxylic acid-based compound of the monoimidedicarboxylic acid precursor in combination B is, from the viewpoint of improving the solubility and non-coloring property of the finally obtained polyamideimide resin, among the above monoaminomonocarboxylic acids, It preferably contains an alicyclic monoaminomonocarboxylic acid and/or an aliphatic monoaminomonocarboxylic acid.
The monoaminomonocarboxylic acid-based compound of the monoimidedicarboxylic acid precursor in combination B is selected from the above monoaminomonocarboxylic acids from the viewpoint of further improving the solubility and non-coloring property of the finally obtained polyamideimide resin. , cycloaliphatic monoaminomonocarboxylic acids and/or aliphatic monoaminomonocarboxylic acids.

From the viewpoint of versatility, the monoaminomonocarboxylic acid-based compound of the monoimide dicarboxylic acid precursor in combination B is glycine, α-alanine, β-alanine, valine, norvaline, α among the above monoaminomonocarboxylic acids. -aminobutyric acid, γ-aminobutyric acid, serine, leucine, isoleucine, threonine, proline, hydroxyproline, methionine, cysteine, 5-aminopentanoic acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 9-nonanoic acid, 11- aminoundecanoic acid, 12-aminolauric acid, 17-aminoheptadecanoic acid, phenylalanine, tryptophan, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-amino-3-methylbenzoic acid, 2-amino-4-methylbenzoic acid, 2-amino-5-methylbenzoic acid, 2-amino-6-methylbenzoic acid, 3-amino-2-methylbenzoic acid, 3-amino-4-methylbenzoic acid, 4-amino-2-methylbenzoic acid, 4-amino-3-methylbenzoic acid, 5-amino-2-methylbenzoic acid, 2-amino-3,4-dimethylbenzoic acid, 2-amino-4,5- dimethylbenzoic acid, 2-amino-4-methoxybenzoic acid, 3-amino-4-methoxybenzoic acid, 4-amino-2-methoxybenzoic acid, 6-amino-2-naphthalenecarboxylic acid, 3-amino-2- It preferably contains one or more compounds selected from the group consisting of naphthalenecarboxylic acids (hereinafter referred to as group P4).
From the viewpoint of further improving versatility, the monoaminomonocarboxylic acid-based compound of the monoimidedicarboxylic acid precursor in combination B is one or more compounds selected from the above group P4 among the above monoaminomonocarboxylic acids. It preferably contains only

・Combination C
In the above combination C, the tetracarboxylic acid anhydride compound and about 2 times the molar amount of the compound, for example, 1.8 to 2.2 times the molar amount, preferably 1.9 to 2.1 times the molar amount , more preferably 1.95 to 2.05 times the molar amount of a monoaminomonocarboxylic acid compound to produce a diimidedicarboxylic acid precursor. In combination C, the diimidedicarboxylic acid precursor is a tetracarboxylic anhydride-based compound, and two molecules of a monoaminomonocarboxylic acid-based compound generate two amide groups based on ring-opening of the acid anhydride group. It is an organic compound obtained by combining with The product obtained by such a reaction includes not only the diimidedicarboxylic acid precursor, but also one molecule of the monoaminomonocarboxylic acid compound per molecule of the tetracarboxylic anhydride compound. It may also be a mixture containing an organic compound obtained by bonding through the formation of one amide group based on ring opening, an unreacted tetracarboxylic anhydride-based compound, and an unreacted monoaminomonocarboxylic acid-based compound.

In combination C, the tetracarboxylic anhydride-based compound that can constitute the diimidodicarboxylic acid precursor is usually a tetracarboxylic dianhydride, has four carboxyl groups in one molecule, and those carboxyl groups An organic compound in which two acid anhydride groups are formed by Such tetracarboxylic dianhydrides include aromatic tetracarboxylic dianhydrides containing an aromatic ring, alicyclic tetracarboxylic dianhydrides containing an aliphatic ring but not an aromatic ring, and It includes aliphatic tetracarboxylic dianhydrides that contain neither aromatic nor alicyclic rings. The tetracarboxylic dianhydride may contain ether groups, ketone groups, sulfonyl groups and/or thioether groups, and/or one or more of the hydrogen atoms are halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atom). As used herein, an ether group is an "--O--" group present between carbon atoms. A ketone group is a "-C(=O)-" group present between carbon atoms. A sulfonyl group is a "-S(=O)2-" group present between carbon atoms. A thioether group is a "-S-" group that exists between carbon atoms.

Examples of aromatic tetracarboxylic dianhydrides in combination C include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4' -biphenyltetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, 4,4′-(hexafluoroisopropylidene)diphthalic acid anhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3,6-bis(trifluoromethyl)pyromellitic dianhydride, 3,3′,4,4 '-diphenylmethanetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4 ,4′-ethylene glycol dibenzoate tetracarboxylic dianhydride, 3,3″,4,4″-terphenyltetracarboxylic dianhydride, 3,3′,4,4′-quaterphenyltetracarboxylic dianhydride Carboxylic dianhydride, 3,3′,4,4′-kinkphenyltetracarboxylic dianhydride, 2,2′,3,3′-biphenyltetracarboxylic dianhydride, methylene-4,4′- Diphthalic dianhydride, 1,1-ethynylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4' -diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4 ,4′-diphthalic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, difluoromethylene-4, 4'-diphthalic dianhydride, 1,1,2,2-tetrafluoro-1,2-ethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3-hexa Fluoro-1,3-trimethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3,4,4-octafluoro-1,4-tetramethylene-4,4'- Diphthalic dianhydride, 1,1,2,2,3,3,4,4,5,5-decafluoro-1,5-pentamethylene-4,4'-diphthalic dianhydride, oxy-4 ,4'-diphthalic dianhydride, thio-4,4'-diphthalic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethylsiloxane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene anhydride, 1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4 -Dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4- Dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane Dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride product, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis[4-( 3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)-1,1, 3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 2,2'-difluoro-3 ,3′,4,4′-biphenyltetracarboxylic dianhydride, 5,5′-difluoro-3,3′,4,4′-biphenyltetracarboxylic dianhydride, 6,6′-difluoro-3 ,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2′,5,5′,6,6′-hexafluoro-3,3′,4,4′-biphenyltetracarboxylic dianhydride anhydride, 2,2′-bis(trifluoromethyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride, 5,5′-bis(trifluoromethyl)-3,3′, 4,4′-biphenyltetracarboxylic dianhydride, 6,6′-bis(trifluoro methyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2′,5,5′-tetrakis(trifluoromethyl)-3,3′,4,4′-biphenyltetra Carboxylic dianhydride, 2,2',6,6'-tetrakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 5,5',6,6' -tetrakis(trifluoromethyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',5,5',6,6'-hexakis(trifluoromethyl)-3, 3',4,4'-biphenyltetracarboxylic dianhydride, 3,3'-difluorooxy-4,4'-diphthalic dianhydride, 5,5'-difluorooxy-4,4'-diphthalic acid dianhydride, 6,6'-difluorooxy-4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexafluorooxy-4,4'-diphthalic acid dianhydride anhydride, 3,3'-bis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 5,5'-bis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride , 6,6′-bis(trifluoromethyl)oxy-4,4′-diphthalic dianhydride, 3,3′,5,5′-tetrakis(trifluoromethyl)oxy-4,4′-diphthalic acid dianhydride, 3,3′,6,6′-tetrakis(trifluoromethyl)oxy-4,4′-diphthalic dianhydride, 5,5′,6,6′-tetrakis(trifluoromethyl)oxy -4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexakis(trifluoromethyl)oxy-4,4'-diphthalic dianhydride, 3,3' -difluorosulfonyl-4,4'-diphthalic dianhydride, 5,5'-difluorosulfonyl-4,4'-diphthalic dianhydride, 6,6'-difluorosulfonyl-4,4'-diphthalic dianhydride anhydride, 3,3′,5,5′,6,6′-hexafluorosulfonyl-4,4′-diphthalic dianhydride, 3,3′-bis(trifluoromethyl)sulfonyl-4,4′ -diphthalic dianhydride, 5,5'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 6,6'-bis(trifluoromethyl)sulfonyl-4,4'-diphthalic acid dianhydride, 3,3′,5,5′-tetrakis(trifluoromethyl)sulfonyl-4,4′-diphthalic dianhydride, 3,3′,6,6′-tetrakis(trifluoromethyl)sulfonyl-4,4′-diphthalic dianhydride, trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)sulfonyl-4,4'-diphthalic dianhydride, 3,3' ,5,5′,6,6′-hexakis(trifluoromethyl)sulfonyl-4,4′-diphthalic dianhydride, 3,3′-difluoro-2,2-perfluoropropylidene-4,4′ -diphthalic dianhydride, 5,5'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 6,6'-difluoro-2,2-perfluoropropylidene- 4,4'-diphthalic dianhydride, 3,3',5,5',6,6'-hexafluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3 ,3′-bis(trifluoromethyl)-2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 5,5′-bis(trifluoromethyl)-2,2-perfluoropropyl Lidene-4,4'-diphthalic dianhydride, 6,6'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',5,5'- Tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3',6,6'-tetrakis(trifluoromethyl)-2,2-perfluoro Propylidene-4,4'-diphthalic dianhydride, 5,5',6,6'-tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride , 3,3′,5,5′,6,6′-hexakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 9-phenyl-9-( trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic dianhydride, 4, 4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 9,9-bis[4-(3,4-dicarboxy)phenyl]fluorene dianhydride, 9,9-bis[4- (2,3-dicarboxy)phenyl]fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 1,2 ,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-tetracarboxyperylene dianhydride things are mentioned. These may be used individually by 1 type, and can also be used as a mixture of 2 or more types.

Examples of the alicyclic tetracarboxylic dianhydride in combination C include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3, 4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3′,4,4′-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4 '-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'- Bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethynylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4 '-Bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-bis(cyclohexane-1,2 -dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid di anhydride, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid-2,6: 3,5-dianhydride, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid 1,4: 2,3-dianhydrides are mentioned. These may be used individually by 1 type, and can also be used as a mixture of 2 or more types.

Examples of the aliphatic tetracarboxylic dianhydride in combination C include 1,2,3,4-butanetetracarboxylic dianhydride and 1,1,2,2-ethanetetracarboxylic dianhydride. . These may be used individually by 1 type, and can also be used as a mixture of 2 or more types.

The tetracarboxylic dianhydride of the imidodicarboxylic acid precursor in combination C is an aromatic tetracarboxylic dianhydride and/or an alicyclic acid dianhydride from the viewpoint of improving the heat resistance of the finally obtained polyamideimide resin. It preferably contains an anhydride. In the case of using a tetracarboxylic dianhydride that is preferable from the viewpoint of "improving the heat resistance of the polyamideimide resin", it is more preferable from the same viewpoint to use a monoaminomonocarboxylic acid that is preferable from the viewpoint described later.
The tetracarboxylic dianhydride of the imidodicarboxylic acid precursor in the combination C is an aromatic tetracarboxylic dianhydride and/or an alicyclic acid from the viewpoint of further improving the heat resistance of the finally obtained polyamideimide resin. It preferably contains only dianhydrides. When using a preferable tetracarboxylic dianhydride from the viewpoint of such "further improvement in the heat resistance of the polyamideimide resin", it is more preferable from the same viewpoint to use a preferable monoaminomonocarboxylic acid from the same viewpoint described later. .

From the viewpoint of the solubility of the finally obtained polyamideimide resin, the tetracarboxylic dianhydride of the imidodicarboxylic acid precursor in the combination C is, among the above tetracarboxylic dianhydrides, an ether group, a ketone group, a sulfonyl group, a thioether group, a methyl group, a methylene group, an isopropylidene group, a phenyl group, a fluorene structure, a biphenyl structure, or a tetracarboxylic acid dianhydride having a fluorine atom (or a substituent containing a fluorine atom). .
From the viewpoint of further improving the solubility of the finally obtained polyamideimide resin, the tetracarboxylic dianhydride of the imidodicarboxylic acid precursor in the combination C is an ether group, a ketone among the above tetracarboxylic dianhydrides. group, sulfonyl group, thioether group, methyl group, methylene group, isopropylidene group, phenyl group, fluorene structure, biphenyl structure, or only tetracarboxylic dianhydrides having fluorine atoms (or substituents containing fluorine atoms) It is preferable to use

The tetracarboxylic dianhydride of the imidodicarboxylic acid precursor in the combination C has a fluorine atom (or It preferably contains an aromatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride component, or an aliphatic tetracarboxylic dianhydride component having a fluorine atom-containing substituent. When using a preferable tetracarboxylic dianhydride from the viewpoint of such "improvement of the non-coloring property of the polyamideimide resin", it is more preferable from the same viewpoint to use a preferable monoaminomonocarboxylic acid from the same viewpoint described later. . The alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides exemplified here contain fluorine atoms (or substituents containing fluorine atoms), unlike aromatic tetracarboxylic dianhydrides. It is not intended to have
The tetracarboxylic dianhydride of the imidodicarboxylic acid precursor in combination C contains a fluorine atom ( or a substituent containing a fluorine atom), an alicyclic tetracarboxylic dianhydride component, or an aliphatic tetracarboxylic dianhydride component alone. When using a preferable tetracarboxylic dianhydride from the viewpoint of such "further improvement of the non-coloring property of the polyamideimide resin", it is more preferable from the same viewpoint to use a preferable monoaminomonocarboxylic acid from the same viewpoint described later. preferable. The alicyclic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides exemplified here contain fluorine atoms (or substituents containing fluorine atoms), unlike aromatic tetracarboxylic dianhydrides. It is not intended to have

From the viewpoint of versatility, the tetracarboxylic dianhydride of the imidodicarboxylic acid precursor in combination C is pyromellitic dianhydride, 3,3′,4,4′ among the above tetracarboxylic dianhydrides. -biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride 4,4'-(4,4'-isopropyl reddenediphenoxy)diphthalic anhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclohexane-1,2, 3,4-tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride) (hereinafter referred to as group P5). preferable. In the case of using a tetracarboxylic dianhydride that is preferable from the viewpoint of versatility, it is more preferable from the same viewpoint to use a monoaminomonocarboxylic acid that is preferable from the viewpoint described later.
From the viewpoint of further improving versatility, the tetracarboxylic dianhydride of the imidodicarboxylic acid precursor in the combination C is only one or more compounds selected from the above group P5 among the above tetracarboxylic dianhydrides. is preferably included. In the case of using a tetracarboxylic dianhydride that is preferable from the viewpoint of further improving versatility, it is more preferable from the same viewpoint to use a monoaminomonocarboxylic acid that is preferable from the viewpoint described later.

The monoaminomonocarboxylic acid compound that can constitute the diimidedicarboxylic acid precursor in combination C is the same monoaminomonocarboxylic acid compound that can constitute the monoimidedicarboxylic acid precursor in combination B. aromatic monoaminomonocarboxylic acids, alicyclic monoaminomonocarboxylic acids, and aliphatic monocarboxylic acids similar to the monoaminomonocarboxylic acid-based compounds that can constitute the monoimidedicarboxylic acid precursors described above. It includes aminomonocarboxylic acids.

The monoaminomonocarboxylic acid of the diimide dicarboxylic acid precursor in combination C is aromatic monoaminomonocarboxylic acid and/or alicyclic monoaminomonocarboxylic acid from the viewpoint of improving the heat resistance of the finally obtained polyamideimide resin. It preferably contains an acid, more preferably an aromatic monoaminomonocarboxylic acid.
The monoaminomonocarboxylic acid of the diimidedicarboxylic acid precursor in combination C is an aromatic monoaminomonocarboxylic acid and/or an alicyclic monoaminomonocarboxylic acid from the viewpoint of further improving the heat resistance of the finally obtained polyamideimide resin. It preferably contains only carboxylic acids, more preferably only aromatic monoaminomonocarboxylic acids.

The monoaminomonocarboxylic acid of the diimide dicarboxylic acid precursor in combination C is, from the viewpoint of improving the non-coloring property of the finally obtained polyamideimide resin, among the above monoaminomonocarboxylic acids, alicyclic monoaminomono Preference is given to using carboxylic acids and/or aliphatic monoaminomonocarboxylic acids.
From the viewpoint of further improving the non-coloring property of the finally obtained polyamideimide resin, the monoaminomonocarboxylic acid of the diimidedicarboxylic acid precursor in the combination C is, among the above monoaminomonocarboxylic acids, an alicyclic monoamino It is preferred to use only monocarboxylic acids and/or aliphatic monoaminomonocarboxylic acids.

The monoaminomonocarboxylic acid of the diimide dicarboxylic acid precursor in combination C is, from the viewpoint of improving the solubility and non-coloring property of the finally obtained polyamideimide resin, among the above monoaminomonocarboxylic acids, alicyclic It preferably contains a monoaminomonocarboxylic acid and/or an aliphatic monoaminomonocarboxylic acid.
The monoaminomonocarboxylic acid of the diimide dicarboxylic acid precursor in combination C is, from the viewpoint of further improving the solubility and non-coloring property of the finally obtained polyamideimide resin, among the above monoaminomonocarboxylic acids, an alicyclic It preferably contains only aliphatic monoaminomonocarboxylic acids and/or aliphatic monoaminomonocarboxylic acids.

From the viewpoint of versatility, the monoaminomonocarboxylic acid of the diimidodicarboxylic acid precursor in combination C is glycine, α-alanine, β-alanine, valine, norvaline, α-aminobutyric acid among the above monoaminomonocarboxylic acids. , γ-aminobutyric acid, serine, leucine, isoleucine, threonine, proline, hydroxyproline, methionine, cysteine, 5-aminopentanoic acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 9-nonanoic acid, 11-aminoundecanoic acid , 12-aminolauric acid, 17-aminoheptadecanoic acid, phenylalanine, tryptophan, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-amino-3-methylbenzoic acid, 2-amino -4-methylbenzoic acid, 2-amino-5-methylbenzoic acid, 2-amino-6-methylbenzoic acid, 3-amino-2-methylbenzoic acid, 3-amino-4-methylbenzoic acid, 4-amino -2-methylbenzoic acid, 4-amino-3-methylbenzoic acid, 5-amino-2-methylbenzoic acid, 2-amino-3,4-dimethylbenzoic acid, 2-amino-4,5-dimethylbenzoic acid , 2-amino-4-methoxybenzoic acid, 3-amino-4-methoxybenzoic acid, 4-amino-2-methoxybenzoic acid, 6-amino-2-naphthalenecarboxylic acid, 3-amino-2-naphthalenecarboxylic acid It preferably contains one or more compounds selected from the group consisting of (hereinafter referred to as group P6).
From the viewpoint of further improving versatility, the monoaminomonocarboxylic acid of the diimidedicarboxylic acid precursor in Combination C contains only one or more compounds selected from the above group P6 among the above tricarboxylic anhydrides. is preferred.

Common to Combinations A to C The timing of completion of this step (that is, the reaction utilizing the mechanochemical effect) is not particularly limited as long as the imidodicarboxylic acid precursor can be obtained. In this step, the average particle size of the imidodicarboxylic acid precursor (reaction product) (that is, the average particle size of the raw material compound in terms of appearance) is usually 500 μm or less, preferably 0.01 to 300 μm, more preferably 0.1 to 0.1 μm. It is performed until it becomes 100 micrometers. For example, when the maximum length of the starting compound having a particle shape (particularly the starting compound in a solid state in the reaction environment) is Rm (μm), the average particle diameter is 0.5×Rm or less, particularly 0.1. The pulverization process is performed until it becomes xRm or less. When the precursor powder has the above average particle size, in this step, a higher reaction rate is obtained when the mechanochemical reaction is performed, and when obtaining a polyamideimide resin in the process for producing a polyamideimide resin described later, a high molecular weight It is easy to obtain a modified linear polyamideimide. The above average particle size may have been achieved at the end of the production process of the imide dicarboxylic acid.

In the present invention, in order to suppress the adhesion of particles to the inner walls of the mixing tank, stirring tank and pulverizing tank, to increase the pulverization efficiency of the particles, and to increase the efficiency of energy transfer to the particles, the raw material mixture is made to contain an auxiliary agent. may As the auxiliary agent, water, alcohol, water-soluble polymer, synthetic polymer, inorganic particles, surfactants, waxes and the like can be used. For example, water, methanol, ethanol, triethylamine, triethanolamine, hexane solution of cetyl alcohol; lower alcohols such as propyl alcohol; ethylene glycol, propylene glycol, neopentyl glycol, 1,3-butylene glycol, dipropylene glycol, 1 , 2-pentanediol, glycols such as polyethylene glycol; glycerols such as glycerin, diglycerin, polyglycerin; cellulose derivatives such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose; alginic acid Natural polymers such as soda, carrageenan, quince seed gum, agar, gelatin, xanthan gum, locust bean gum, pectin, gellan gum; polyvinyl alcohol, carboxyvinyl polymer, alkyl-added carboxyvinyl polymer, sodium polyacrylate, polymethacryl Carbon black, titanium oxide, black titanium oxide, cerium oxide, konjo, ultramarine, red iron oxide, iron oxide, yellow iron oxide, black iron oxide, black iron oxide, zinc oxide , aluminum oxide, silicic anhydride, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, calcium sulfate, chromium oxide, chromium hydroxide, carbon black, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica, synthetic mica , sericite, talc, kaolin, silicon carbide, barium sulfate, bentonite, smectite, inorganic powders such as boron nitride; bismuth oxychloride, titanium oxide-coated mica, iron oxide-coated mica, iron oxide-coated mica titanium, organic pigment-coated Bright powders such as mica titanium and aluminum powder; nylon powder, polymethyl methacrylate powder, acrylonitrile-methacrylic acid copolymer powder, vinylidene chloride-methacrylic acid copolymer powder, polyethylene powder, polystyrene powder, (dimethicone/vinyl Dimethicone) Crosspolymer Powder, (Vinyl Dimethicone/Methicone Silsesquioxane) Crosspolymer Powder, (Diphenyl Dimethicone/Vinyldiphenyl Dimethicone/Silsesquioxane) Crosspolymer Powder, Polymethylsilses Organic powders such as quioxane powder, polyurethane powder, wool powder, silk powder, N-acyl lysine; dye powders such as organic tar pigments and organic dye lake pigments; fine particle titanium oxide coated mica titanium, fine particle zinc oxide Composite powders such as coated mica titanium, barium sulfate-coated mica titanium, titanium oxide-containing silica, zinc oxide-containing silica; glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, propylene glycol fatty acid esters and their alkylene glycol adducts, sorbitan fatty acid esters and their alkylene glycol adducts, sorbitol fatty acid esters and their alkylene glycol adducts, polyalkylene glycol fatty acid esters, polyoxyalkylene-modified silicones, polyoxyalkylenealkyl co-modified silicones, etc. Nonionic surfactants; fatty acids such as stearic acid, lauric acid and inorganic or organic salts thereof; alkylbenzene sulfates, alkylsulfonates, α-olefinsulfonates, dialkylsulfosuccinates, α-sulfonation Fatty acid salts, acyl methyl taurate salts, N-methyl-N-alkyl taurate salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene Anionic surfactants such as alkylphenyl ether phosphates, N-acyl-N-alkylamino acid salts; cationic surfactants such as alkylamine salts, polyamines and alkanoylamine fatty acid derivatives, alkylammonium salts, alicyclic ammonium salts Surfactants; amphoteric surfactants such as phospholipids, N,N-dimethyl-N-alkyl-N-carboxymethylammonium betaine; paraffin wax, ceresin wax, ozokerite, microcrystalline wax, montan wax, fishatropus wax , polyethylene wax, liquid paraffin, squalane, petrolatum, polyisobutylene, polybutene, and other hydrocarbons; carnauba wax, beeswax, lanolin wax, candelilla, and other natural waxes; glyceryl 2-ethylhexanoate, pentaerythritol rosinate, cetyl isooctanoate, isopropyl myristate, diglyceryl triisostearate, Dipentaerythritol fatty acid ester, diisostearyl malate, esters such as dimer dilinoleic acid (phytosteryl/isostearyl/cetyl/stearyl/behenyl); fatty acids such as stearic acid, behenic acid, 12-hydroxystearic acid higher alcohols such as cetanol, stearyl alcohol and behenyl alcohol; lanolin derivatives such as lanolin fatty acid isopropyl and lanolin alcohol; amino acid derivatives such as N-lauroyl L-glutamic acid di(cholesteryl/behenyl/octyldodecyl); perfluoropolyether , perfluorodecane, and perfluorooctane. 1 type, or 2 or more types can be used for these.

The amount of auxiliary agent used is usually 10.0 parts by mass or less, particularly 0.01 to 5.0 parts by mass, per 100 parts by mass of the total amount of the starting compounds.

The process for producing the imidodicarboxylic acid precursor is carried out in the absence of a solvent, and can be carried out, for example, in an air atmosphere, an inert gas atmosphere, or under vacuum. This step is preferably carried out under an atmosphere of dry air or an inert gas such as nitrogen.

(Imidation step)
In this step, the imidodicarboxylic acid precursor is imidized by heating to obtain the imidodicarboxylic acid. This step is also carried out in the absence of a solvent, for example, in an air atmosphere, an inert gas atmosphere, or under vacuum, as in the production step of the imidodicarboxylic acid precursor. This step is preferably carried out in an inert gas atmosphere such as nitrogen.

The heating temperature for imidization must be lower than the decomposition temperature of the resulting imidodicarboxylic acid. The heating temperature may be, for example, 100-450°C, particularly 150-450°C, preferably 150-350°C. The heating time is not particularly limited, and may be, for example, 10 minutes to 16 hours, particularly 10 minutes to 8 hours, preferably 0.5 to 8 hours. The heating may be carried out while standing still, or may be carried out while stirring.

The imidization step may be performed in one step or in multiple steps. Performing the imidization step in multiple stages means that the imidization step with different heating temperatures is performed continuously two or more times, for example, two to three times. When the imidization process is performed in multiple stages, the heating temperature in the imidization process after the second imidization process is preferably higher than the heating temperature in the imidization process immediately before, from the viewpoint of further improving the imidization rate. For example, the heating temperature in the second imidization step is preferably higher than the heating temperature in the first imidization step. Further, for example, the heating temperature in the third imidization step is preferably higher than the heating temperature in the second imidization step. When imidization is carried out in multiple steps, the total heating time should be within the above range.

The imidization rate of the obtained imidodicarboxylic acid is preferably 95.0% or more, more preferably 98.0% or more, and even more preferably 99.0% or more. The imidization rate of imidodicarboxylic acid is not particularly limited, and may be, for example, 100%.

The water content (i.e., water content) of the resulting diimidedicarboxylic acid is preferably 10 to 10,000 ppm, more preferably 50 to 5,000 ppm, even more preferably 50 to 1,000 ppm, and 50 to 500 ppm. is more preferred.

Imidization may be performed during and/or after the mechanochemical reaction. In other words, the imidization step may be performed simultaneously with the step of producing the imide dicarboxylic acid precursor and/or after the step of producing the imide dicarboxylic acid precursor. Performing this imidization step at the same time as the step of producing an imidodicarboxylic acid precursor means that imidization is performed by heating while producing an imidodicarboxylic acid precursor using a mechanochemical effect to obtain an imidodicarboxylic acid. That's what it means. From the viewpoint of further increasing the molecular weight of the finally obtained polyamideimide resin and further increasing the purity of the linear polyamideimide, the imidization step is preferably performed after the step of producing the imidedicarboxylic acid precursor.

<Manufacturing process of polyamideimide resin>
In this step, an imidodicarboxylic acid and a diisocyanate are reacted in an organic solvent to obtain a polyamide-imide resin. For example, a polyamidoimide resin can be obtained in the form of a solution by adding a diisocyanate or a solution thereof to a heated imidedicarboxylic acid solution and reacting them by heating.

The imidodicarboxylic acid solution is a solution obtained by dissolving imidodicarboxylic acid in an organic solvent. The concentration of imidedicarboxylic acid in the solution is not particularly limited, and is, for example, 1 to 70% by mass. It is preferably 5 to 45% by mass. Dissolution may be accelerated by heating during preparation of the imidodicarboxylic acid solution. The heating temperature may be independently selected from within the same range as the reaction temperature described below. The above concentration may be the concentration of imide dicarboxylic acid in the reaction solution (reaction system). The concentration in the reaction solution (reaction system) means the concentration in the solution after addition of the diisocyanate.

A diisocyanate component is an organic compound having two isocyanate groups in one molecule. Diisocyanate components include aromatic diisocyanates containing aromatic rings, cycloaliphatic diisocyanates containing aliphatic rings but no aromatic rings, and aliphatic diisocyanates containing neither aromatic rings nor cycloaliphatic rings. . These may be used individually by 1 type, and can also be used as a mixture of 2 or more types.

Examples of aromatic diisocyanates include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, meta-xylylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2 ,6-tolylene diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate, 3,3′-dimethoxybiphenyl-4,4′-diisocyanate, 1,5-naphthalene diisocyanate, tetramethylxylylene diisocyanate, Examples include polymethylene polyphenyl polyisocyanate.

Examples of alicyclic diisocyanates include isophorone diisocyanate, dicyclohexylmethane diisocyanate, 2,4′-diisocyanatodicyclohexylmethane, 2,2′-diisocyanatodicyclohexylmethane, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane. diisocyanate, 1-methylcyclohexane-2,4-diyl diisocyanate, 1-methylcyclohexane-2,6-diyl diisocyanate, cyclohexane-1,4-diyl bis(methylene) diisocyanate, 1,3-bis( isocyanatomethyl)cyclohexane and the like.

Examples of aliphatic diisocyanates include hexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,5-diisocyanato-2-methylpentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4 -trimethyl-1,6-diisocyanatohexane, 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane and the like.

The diisocyanate preferably contains an aromatic diisocyanate and/or an alicyclic diisocyanate from the viewpoint of improving the heat resistance of the finally obtained polyamide-imide resin.
The diisocyanate preferably contains only an aromatic diisocyanate and/or an alicyclic diisocyanate from the viewpoint of further improving the heat resistance of the finally obtained polyamide-imide resin.

Among the diisocyanates described above, it is preferable to use an alicyclic diisocyanate and/or an alicyclic diisocyanate from the viewpoint of improving the non-coloring property of the finally obtained polyamide-imide resin.
Among the above diisocyanates, it is preferable to use only alicyclic diisocyanates and/or alicyclic diisocyanates, from the viewpoint of further improving the non-coloring property of the finally obtained polyamide-imide resin.

Among the above diisocyanates, the diisocyanate preferably contains an aromatic diisocyanate and/or an alicyclic diisocyanate from the viewpoint of improving the mechanical strength of the finally obtained polyamide-imide resin.
The diisocyanate preferably contains only aromatic diisocyanate and/or alicyclic diisocyanate among the above diisocyanates, from the viewpoint of further improving the mechanical strength of the finally obtained polyamide-imide resin.

Diisocyanate, from the viewpoint of versatility, among the above diisocyanates, 4,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, meta-xylylene diisocyanate, 2,4-tolylene diisocyanate , 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate) (hereinafter referred to as group P7). preferably contains a compound of )
From the viewpoint of further improving versatility, the diisocyanate preferably contains only one or more compounds selected from the above group P7 among the above diisocyanates.

A diisocyanate solution is a solution in which diisocyanate is dissolved in an organic solvent. The diisocyanate concentration in the solution is not particularly limited, and is, for example, 5 to 95% by mass. From the viewpoint of further increasing the molecular weight of the finally obtained polyamideimide resin and further increasing the purity of the linear polyamideimide, it is preferably 30 to 90% by mass. Dissolution may be accelerated by heating during preparation of the diisocyanate solution. The heating temperature may be independently selected from within the same range as the reaction temperature described below.

Diisocyanate is preferably reacted in two or more steps. That is, from the viewpoint of further increasing the molecular weight of the finally obtained polyamide-imide resin, the diisocyanate solution is preferably added in multiple portions, with the predetermined addition amount being divided into two or more times. Dropping is preferred. When the diisocyanate solution is added dropwise, the dropping rate is usually 0.1 to 10% by mass/minute, preferably 0.2 to 5% by mass/minute. This unit "% by mass/minute" is the amount added per minute, and the amount added is the value with respect to the total amount of the diisocyanate solution finally added.

Various organic solvents can be independently used for the imidedicarboxylic acid solution and the diisocyanate solution. For example, alcohol solvents such as methanol, ethanol, propanol and isopropanol; hydrocarbon solvents such as cyclohexane, benzene, toluene, xylene and trimethylbenzene; amine solvents such as triethylamine and triethanolamine; dimethylacetamide (DMAc) and dimethyl amide solvents such as formamide (DMF) and N-methyl-2-pyrrolidone (NMP); urea solvents such as N,N-dimethylethylene urea, N,N-dimethylpropylene urea and tetramethylurea; γ-butyrolactone, Lactone solvents such as γ-caprolactone; Carbonate solvents such as propylene carbonate; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Methyl acetate, ethyl acetate, n-butyl acetate, butyl cellosolve acetate, butyl carbitol acetate , ethyl cellosolve acetate, ethyl carbitol acetate; ester solvents such as diglyme, triglyme, tetraglyme; phenolic solvents such as cresol, phenol, halogenated phenol; sulfone solvents such as sulfolane; DMSO) and the like. The above solvents may be used alone, or two or more of them may be used in combination. Further, it may be used by mixing with a solvent other than the above.

The temperature at which the imidodicarboxylic acid and the diisocyanate are reacted is preferably 80 to 250°C, more preferably 120 to 220°C. The reaction temperature is the temperature of the diimidecarboxylic acid solution when mixing the imidodicarboxylic acid and the diisocyanate is started, and/or the temperature when the mixture is stirred after the total amount of both is mixed.

The reaction time of imidodicarboxylic acid and diisocyanate is preferably 0.5 to 36 hours, more preferably 1 to 16 hours, and more preferably 2 to 16 hours. The reaction time is the stirring time from the start of mixing the imidodicarboxylic acid and the diisocyanate to the end of the reaction.

The molecular weight of the resulting polyamide-imide resin is preferably 2000 to 300000, particularly preferably 2000 to 200000, more preferably 5000 to 200000, further preferably 6500 to 180000, further preferably 8000 to 150000. Most preferred. The molecular weight of the polyamideimide resin is preferably 9,000 to 150,000, particularly preferably 10,000 to 150,000, more preferably 15,000 to 100,000, from the viewpoint of differentiation from the molecular weight of the polyamideimide resin obtained by a conventional method. It is preferably 20,000 to 80,000.

In this step, a terminal blocking agent may be used to adjust the molecular weight. End-blocking agents include aliphatic monocarboxylic acids such as acetic acid, lauric acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid; phthalic anhydride, 2 ,3-benzophenonedicarboxylic anhydride, 3,4-benzophenonedicarboxylic anhydride, 2,3-dicarboxyphenylphenyl ether anhydride, 2,3-biphenyldicarboxylic anhydride, 3,4-biphenyldicarboxylic anhydride , 2,3-dicarboxyphenylphenyl sulfone anhydride, 3,4-dicarboxyphenyl phenyl sulfone anhydride, 2,3-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3 - Monofunctional compounds such as naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2,3-anthracenedicarboxylic anhydride, and 1,9-anthracenedicarboxylic anhydride acid anhydrides.

The polyamide-imide obtained by the production method of the present invention is used for automobile parts, electrical and electronic parts, sliding parts, tube-related parts, household goods, metal coating agents, industrial materials, computer and related equipment parts, optical equipment parts, information・It can be used for a wide range of applications such as communication equipment parts and precision equipment parts.

Specific examples of automotive parts include shift levers, base plates for gear boxes, cylinder head covers, engine mounts, air intake manifolds, throttle bodies, air intake pipes, radiator tanks, radiator supports, radiator hoses, radiator grills, rear Spoiler, wheel cover, wheel cap, cowl vent grille, air outlet louver, air scoop, hood bulge, fender, back door, fuel sender module, shift lever housing, propeller shaft, stabilizer bar linkage rod, window regulator, door lock, Door handle, outside door mirror stay, accelerator pedal, pedal module, seal ring, bearing retainer, gear, wire harness, relay block, sensor housing, encapsulation, ignition coil, distributor, water pump renlet, water pump outlet , thermostat housing, cooling fan, fan shroud, oil pan, oil filter housing, oil filter cap, oil level gauge, timing belt cover, engine cover, fuel tank, fuel tube, fuel cutoff valve, quick connector, canister, fuel delivery Pipes, fuel filler necks, fuel line joints, lamp reflectors, lamp housings, lamp extensions, lamp sockets and the like.

Specific examples of electrical and electronic components include connectors, HDD lamp rails, board reinforcing plates, LED reflectors, switches, sensors, sockets, capacitors, jacks, fuse holders, relays, coil bobbins, resistors, ICs, LED housings, lithium secondary Binders for electrodes of secondary batteries and the like can be mentioned.

Specific examples of sliding parts include gears, gears, washers, actuators, bearing retainers, bearings, switches, pistons, packings, rollers, copier belts, and belts.

Specific examples of tube-related parts include feed tubes, return tubes, evaporation tubes, fuel filler tubes, reserve tubes, vent tubes, oil tubes, brake tubes, windshield washer fluid tubes, cooler tubes for cooling water and refrigerant, and air conditioners. Refrigerant tubes, floor heating tubes, fire extinguisher and fire extinguisher tubes, medical cooling equipment tubes, paint spraying tubes, chemical transport tubes, fuel transport tubes, diesel gasoline tubes, oil drilling tubes, etc. Alcohol gasoline tubes, engine coolant (LLC) tubes, reservoir tank tubes, road heating tubes, floor heating tubes, infrastructure supply tubes, gas tubes.

Specific examples of household goods include baby bottles, spectacle frames, sports shoes, and surface materials for skis.

Specific examples of metal coating agents include metal coating agents for plumbing parts such as liquid metal pipes and water tank tanks.

Specific examples of industrial materials include tire cords, belts, bulletproof clothing, protective clothing, fireproof clothing, work clothing, concrete reinforcing materials, asbestos alternative materials, ropes, shoe members, fishing lines, fishing nets, sail cloths, cushion materials, Blades for wind power generation, felt for papermaking, copier cleaners, filters, and hollow fiber membranes.

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these. In addition, evaluation in each example was performed by the following methods.

1. Reaction rate 1-1. Reaction Rate of Tricarboxylic Anhydride and Diamine The reaction rate of the imidodicarboxylic acid precursor powder obtained in each example was determined by ¹ H-NMR measurement. Approximately 10 mg of the imidodicarboxylic acid precursor powder was dissolved in approximately 1 mL of a mixed solution of deuterated dimethyl sulfoxide/heavy water/deuterated trifluoroacetic acid (=91.5/5.0/3.5 wt%) for 30 minutes. After ultrasonic treatment, ¹ H-NMR measurement was performed.
In the resulting ¹ H-NMR spectrum, among the diamine-derived peaks, A1 is the sum of the integrated values of the peaks derived from structure a1 in which both amino groups are amidated, and one amino group is derived from structure a2 in which the amino group is amidated. The reaction rate of the diamine was obtained by the following formula, where A2 is the sum of the integrated values of the peaks, and A3 is the sum of the integrated values of the peaks derived from the structure a3 in which both amino groups are not amidated. For example, in the case of the compound obtained in Example 1-1, the peaks derived from structure a1 are at 6.90 to 7.00 ppm and 7.63 to 7.67 ppm, and the peaks derived from structure a2 are from 7.02 to At 7.10 ppm, 7.34-7.36 ppm and 7.63-7.67 ppm, with peaks from structure a3 at 7.12-7.16 ppm and 7.36-7.41 ppm.
Diamine reaction rate (%) = (A1 + A2/2) / (A1 + A2 + A3) x 100

In addition, when each peak cannot be attributed to the above three structures due to overlap of peaks, etc., the sum of the integrated values of the peaks derived from the proton b1 adjacent to the amide bond generated by the reaction in the structure of the diamine is B1, The reaction rate of diamine was determined by the following formula, where B2 is the sum of the integral values of the peaks derived from protons b2 adjacent to unreacted amino groups. For example, in the case of the compound obtained in Example 1-15, the peak derived from proton b1 is at 3.10-3.12 ppm and the peak derived from proton b2 is at 2.70-2.74 ppm.
Diamine reaction rate (%) = B1/(B1+B2) x 100

The reaction rate was also measured after heat treatment (imidization) of the imidodicarboxylic acid precursor powder in the same manner as described above, except that the NMR solvent was changed to deuterated dimethylsulfoxide.

1-2. Reaction Rate of Tricarboxylic Anhydride and Monoaminomonocarboxylic Acid The reaction rate of the imidodicarboxylic acid precursor powder obtained in each example was determined by ¹ H-NMR measurement. Approximately 10 mg of the imidodicarboxylic acid precursor powder was dissolved in approximately 1 mL of a mixed solution of deuterated dimethyl sulfoxide/heavy water/deuterated trifluoroacetic acid (=91.5/5.0/3.5 wt%) for 30 minutes. After ultrasonic treatment, ¹ H-NMR measurement was performed.
In the obtained ¹ H-NMR spectrum, the sum of the integrated values of the peaks derived from the structure c1 in which the amino group is amidated among the peaks derived from the monoaminomonocarboxylic acid is C1, and the structure c2 in which the amino group is not amidated The reaction rate of amine was obtained by the following formula, where C2 is the sum of the integrated values of the peaks derived from .
Amine reaction rate (%) = C1/(C1+C2) x 100
The reaction rate was also measured after heat treatment (imidization) of the imidodicarboxylic acid precursor powder in the same manner as described above, except that the NMR solvent was changed to deuterated dimethylsulfoxide.

1-3. Reaction rate of acid dianhydride and monoaminomonocarboxylic acid 1-2. The reaction rate of amine was determined in the same manner as the reaction rate of tricarboxylic anhydride and monoaminomonocarboxylic acid. The reaction rate was also measured by the same method after the heat treatment (imidation) of the imidodicarboxylic acid precursor powder.

2. Measurement of Imidization Rate The imide dicarboxylic acid obtained in each example was subjected to transmission infrared absorption spectrum (IR) measurement to determine the absorbance ratio of the imide group.
Absorption originating from imide groups is usually detected in the wavenumber region of 1750-1800 cm ⁻¹ or 1350-1400 cm ⁻¹ . The line connecting the bases on both sides of the absorption peaks detected at these wavenumbers is taken as the baseline, and the line from the top of the peak perpendicular to the baseline is drawn from the intersection point to the top of the peak. Absorbance was calculated from the length.

Infrared spectroscopy (IR)
Apparatus: System 2000 infrared spectrometer manufactured by Perkin Elmer Method: KBr method Accumulation times: 64 scans (resolution 4 cm ^-1 )

Next, the details of the method for calculating the imidization rate will be described. First, the imidodicarboxylic acid obtained in each example was mixed with KBr powder to prepare a sample for IR measurement, and the measurement was performed. It was confirmed that the intensity of the peak showing the highest absorbance in the obtained spectrum fell within the absorbance range of 0.8 to 1.0, and the absorbance α of the imide group was determined. Next, this sample was heat-treated in an oven at a temperature of 350° C. for 2 hours under a stream of nitrogen to allow 100% imidization. This 100% imidized sample was subjected to IR measurement by the same method, and the absorbance α' of the wave number due to the imide groups was obtained. At this time, the imidization rate of the sample was obtained by the following formula.
Imidation rate (%) = α/α' × 100

3. Measurement of Moisture Percentage Moisture content was determined by the Karl Fischer moisture measurement method.

4. Measurement of Average Particle Size The average particle size was measured by a laser diffraction method, and the value of the particle size (median size) with respect to cumulative 50% of the obtained cumulative distribution. Specifically, 0.1 to 1.0 g of the imidodicarboxylic acid precursor powder was measured with a laser diffraction particle size distribution analyzer (Mastersizer 3000 manufactured by Malvern) to obtain a particle size distribution. The value of the particle size (median size) for cumulative 50% of the obtained cumulative distribution was defined as the average particle size.

5. Measurement of Molecular Weight of Polyamideimide Resin The number average molecular weight was obtained by the following method by gel permeation chromatography (GPC). First, GPC of standard polystyrene was measured under the following conditions to create a calibration curve. Subsequently, the GPC of the sample was measured under the same conditions to determine the average molecular weight in terms of polystyrene.
(GPC measurement conditions)
Column: 3 Shodex AD-80M/S manufactured by Showa Denko Co., Ltd. Pre-column: 1 Shodex KD-G manufactured by Showa Denko Co., Ltd. Solvent: N,N-dimethylformamide (containing LiBr 50 mmol/L)
Flow rate: 1.0 mL/min
Temperature: Column 35°C
Sample concentration: 0.5% by mass
Detector: UV detector Calibration sample: Monodisperse standard polystyrene

6. Confirmation of branched structure and urea bond The presence or absence of branched structure and urea bond was confirmed by ¹ H-NMR measurement for the polyamideimide resin solution obtained in each example. About 50 mg of the polyamideimide resin solution was dissolved in about 1 mL of deuterated dimethyl sulfoxide, subjected to ultrasonic treatment for 10 minutes, and subjected to ¹ H-NMR measurement under the following conditions.
Device: JNM-ECA500 made by JEOL
Measurement nuclide: proton Solvent: deuterated dimethyl sulfoxide Temperature: 25°C
Number of times of accumulation: 128 times In the obtained ¹ H-NMR spectrum, when the integral value of the peak derived from the amide group detected at 9.0 to 10.5 ppm is set to 100, the integral value is 5.5 to 7.0 ppm. When a peak of 0.2 or more was detected as a value, it was determined that urea binding was occurring.
Regarding the branched structure, it is presumed that the higher the imidization rate of the imidodicarboxylic acid, the less branched structure is produced in the resulting polyamide-imide resin. More specifically, when the imidization rate of the imidodicarboxylic acid is 99.8% or more, particularly 99.9% or more, the resulting polyamide-imide resin hardly has a branched structure. In particular, when the imidization rate of imidodicarboxylic acid is 100%, no branched structure is generated in the resulting polyamide-imide resin.

[Method for producing imidodicarboxylic acid]
(Diimidodicarboxylic acid)
Example 1-1
A total of 100 g of 657 parts by mass of trimellitic anhydride and 343 parts by mass of 4,4'-diaminodiphenyl ether were added to the grinding tank of a high-speed rotary grinder (capacity: 150 mL). The mixture was stirred at 14,000 rpm for 5 minutes in an air atmosphere to cause a mechanochemical reaction to obtain a diimidedicarboxylic acid precursor powder.
From the NMR measurement of the obtained diimidodicarboxylic acid precursor powder, a peak derived from a reactant in which both amino groups were amidated near 6.98 ppm (doublet) in the ¹ H-NMR spectrum, 7.00 ppm (doublet). , 7.07 ppm (doublet), peaks derived from reactants in which one amino group was amidated near 7.35 ppm (doublet), 7.13 ppm (doublet), and unreacted amine near 4.49 ppm (doublet). Derived peaks were detected. From this result, the reaction rate of trimellitic anhydride and 4,4'-diaminodiphenyl ether was 57.0%.
The obtained pulverized material was heated at 300° C. for 2 hours in a nitrogen atmosphere to carry out an imidization reaction. The resulting diimidedicarboxylic acid had an imidization rate of 100% and a water content of 330 ppm.
NMR chart for calculating the reaction rate and the reaction rate, IR chart for calculating the imidization rate and the imidization rate, and a high molecular weight polyamideimide resin in Example 2-1 etc. described later. From the results, it was identified that a predetermined diimide dicarboxylic acid was produced.

Examples 1-2 to 1-16
A diimidedicarboxylic acid was obtained in the same manner as in Example 1-1, except that the amine composition was changed.
In the NMR measurement of each example, as in Example 1-1, in the ¹ H-NMR spectrum, peaks derived from a reactant in which both amino groups were amidated, and a reaction in which one amino group was amidated A peak derived from a substance and a peak derived from an unreacted amine were respectively detected.
The imidization reaction was carried out by heating the pulverized material obtained in each example at 300° C. for 2 hours in a nitrogen atmosphere. The imidization rate and water content of the resulting diimidedicarboxylic acid were measured.
By a method similar to the identification method in Example 1-1, it was identified that a predetermined diimidedicarboxylic acid was produced.

Examples 1-17
738 parts by mass of trimellitic anhydride was added to a mixing vessel equipped with a double helical stirring blade and stirred at 40°C. 262 parts by mass of m-xylylenediamine was added at a rate of 2.13 parts by mass/minute using a tube pump to obtain a mixed powder of two components.
A total of 100 g of the mixed powder was added to the grinding tank of a high-speed rotary grinder (capacity: 150 mL). The mixture was stirred at 14,000 rpm for 5 minutes in an air atmosphere to cause a mechanochemical reaction to obtain a diimidedicarboxylic acid precursor powder.
In the NMR measurement of this example, as in Example 1-1, in the ¹ H-NMR spectrum, peaks derived from a reactant in which both amino groups were amidated, and a reaction in which one amino group was amidated A peak derived from a substance and a peak derived from an unreacted amine were respectively detected.
The obtained pulverized material was heated at 300° C. for 2 hours in a nitrogen atmosphere to carry out an imidization reaction. The resulting diimidedicarboxylic acid had an imidization rate of 99.9% and a water content of 350 ppm.
By a method similar to the identification method in Example 1-1, it was identified that a predetermined diimidedicarboxylic acid was produced.

Examples 1-18 to 1-19
A diimidedicarboxylic acid was obtained in the same manner as in Example 1-17, except for changing the amine composition.
In the NMR measurement of each example, as in Example 1-1, in the ¹ H-NMR spectrum, peaks derived from a reactant in which both amino groups were amidated, and a reaction in which one amino group was amidated A peak derived from a substance and a peak derived from an unreacted amine were respectively detected.
The imidization reaction was carried out by heating the pulverized material obtained in each example at 300° C. for 2 hours in a nitrogen atmosphere. The imidization rate and water content of the resulting diimidedicarboxylic acid were measured.
By a method similar to the identification method in Example 1-1, it was identified that a predetermined diimidedicarboxylic acid was produced.

Example 1-20
A total of 100 g of 444 parts by mass of pyromellitic dianhydride and 556 parts by mass of 4-aminobenzoic acid was added to the grinding tank of a high-speed rotary grinder (capacity: 150 mL). The mixture was stirred at 14,000 rpm for 5 minutes in an air atmosphere to cause a mechanochemical reaction to obtain a diimidedicarboxylic acid precursor powder.
In the NMR measurement of this example, as in Example 1-1, in the ¹ H-NMR spectrum, peaks derived from a reactant in which both amino groups were amidated, and a reaction in which one amino group was amidated A peak derived from a substance and a peak derived from an unreacted amine were respectively detected.
The obtained pulverized material was heated at 300° C. for 2 hours in a nitrogen atmosphere to carry out an imidization reaction. The resulting diimidedicarboxylic acid had an imidization rate of 99.8% and a water content of 300 ppm.
By a method similar to the identification method in Example 1-1, it was identified that a predetermined diimidedicarboxylic acid was produced.

Examples 1-21 to 1-43
A diimide dicarboxylic acid was obtained in the same manner as in Example 1-20, except that the tricarboxylic dianhydride composition and the amine composition were changed.
In the NMR measurement of each example, as in Example 1-1, in the ¹ H-NMR spectrum, peaks derived from a reactant in which both amino groups were amidated, and a reaction in which one amino group was amidated A peak derived from the substance and a peak derived from unreacted amine were respectively detected.
The imidization reaction was carried out by heating the pulverized material obtained in each example at 300° C. for 2 hours in a nitrogen atmosphere. The imidization rate and water content of the resulting diimidedicarboxylic acid were measured.
By a method similar to the identification method in Example 1-1, it was identified that a predetermined diimidedicarboxylic acid was produced.

(monoimidodicarboxylic acid)
Example 1-44
A total of 100 g of 584 parts by mass of trimellitic anhydride and 416 parts by mass of 2-aminobenzoic acid were added to the grinding tank of a high-speed rotary grinder (capacity: 150 mL). The mixture was stirred at 14,000 rpm for 5 minutes in an air atmosphere, and a mechanochemical reaction was performed to obtain a monoimide dicarboxylic acid precursor powder.
In the NMR measurement of this example, as in Example 1-1, in the ¹ H-NMR spectrum, peaks derived from a reactant in which both amino groups were amidated, and a reaction in which one amino group was amidated A peak derived from the substance and a peak derived from unreacted amine were respectively detected.
The obtained pulverized material was heated at 300° C. for 2 hours in a nitrogen atmosphere to carry out an imidization reaction. The obtained monoimide dicarboxylic acid had an imidization rate of 100% and a water content of 320 ppm.
NMR chart for calculating the reaction rate and the reaction rate, IR chart for calculating the imidization rate and the imidization rate, and a high molecular weight polyamideimide resin in Example 2-57 etc. described later. From the results, it was identified that a given monoimide dicarboxylic acid was produced.

Examples 1-45 to 1-60
Except for changing the amine composition, the same operation as in Example 1-44 was performed to obtain a monoimide dicarboxylic acid.
In the NMR measurement of each example, as in Example 1-1, in the ¹ H-NMR spectrum, peaks derived from a reactant in which both amino groups were amidated, and a reaction in which one amino group was amidated A peak derived from the substance and a peak derived from unreacted amine were respectively detected.
The imidization reaction was carried out by heating the pulverized material obtained in each example at 300° C. for 2 hours in a nitrogen atmosphere. The imidization rate and water content of the obtained monoimidodicarboxylic acid were measured.
By the same identification method as in Example 1-44, it was identified that the predetermined monoimide dicarboxylic acid was produced.

[Preparation of imidedicarboxylic acid solution and polyamideimide resin solution]
Example 2-1
687 parts by mass of the imidodicarboxylic acid obtained in Example 1-1 was added to a separable flask equipped with a thermometer, a reflux condenser and a stirrer, and N-methyl-2-pyrrolidone was heated to 200°C under a nitrogen atmosphere. It was dissolved in 2933 parts by mass to obtain an imide dicarboxylic acid solution.
On the other hand, a diisocyanate solution was prepared by dissolving 313 parts by mass of diphenylmethane diisocyanate in 627 parts by mass of N-methyl-2-pyrrolidone at room temperature.
The diisocyanate solution was added dropwise at a rate of 0.83 mass %/min to the imidodicarboxylic acid solution maintained at 200° C. under a nitrogen atmosphere while stirring. After completion of dropping, the mixture was stirred for 2 hours while maintaining the temperature at 200° C., and then cooled to obtain a polyamide-imide resin solution. The resulting polyamide-imide resin contained no urea bond and had a molecular weight of 32,500.

Examples 2-2 to 2-64
A polyamideimide resin solution was obtained in the same manner as in Example 2-1, except that the composition of imidodicarboxylic acid and diisocyanate and the mixing ratio with N-methyl-2-pyrrolidone were changed. The polyamideimide resin obtained in each example contained no urea bond.

Example 2-65
703 parts by mass of the imidodicarboxylic acid obtained in Example 1-1 was added to a separable flask equipped with a thermometer, a reflux condenser and a stirrer, and N-methyl-2-pyrrolidone was heated to 200°C under a nitrogen atmosphere. It was dissolved in 3045 parts by mass to obtain an imide dicarboxylic acid solution.
On the other hand, a diisocyanate solution was prepared by dissolving 241 parts by mass of diphenylmethane diisocyanate and 56 parts by mass of 2,4′-tolylenediisocyanate in 593 parts by mass of N-methyl-2-pyrrolidone at room temperature.
The diisocyanate solution was added dropwise at a rate of 0.83 mass %/min to the imidodicarboxylic acid solution maintained at 200° C. under a nitrogen atmosphere while stirring. After completion of dropping, the mixture was stirred for 2 hours while maintaining the temperature at 200° C., and then cooled to obtain a polyamide-imide resin solution. The resulting polyamide-imide resin contained no urea bond and had a molecular weight of 34,300.

Examples 2-66 to 2-80
A polyamideimide resin solution was obtained in the same manner as in Example 2-65, except that the composition of imidodicarboxylic acid and diisocyanate and the mixing ratio with N-methyl-2-pyrrolidone were changed. The polyamideimide resin obtained in each example contained no urea bond.

Example 2-81
530 parts by mass of the imidedicarboxylic acid obtained in Example 1-1 and 147 parts by mass of the imidedicarboxylic acid obtained in Example 1-3 were added to a separable flask equipped with a thermometer, a reflux condenser and a stirrer, It was dissolved in 3074 parts by mass of N-methyl-2-pyrrolidone heated to 200° C. under a nitrogen atmosphere to obtain an imide dicarboxylic acid solution.
On the other hand, a diisocyanate solution was prepared by dissolving 323 parts by mass of diphenylmethane diisocyanate in 645 parts by mass of N-methyl-2-pyrrolidone at room temperature.
The diisocyanate solution was added dropwise at a rate of 0.83 mass %/min to the imidodicarboxylic acid solution maintained at 200° C. under a nitrogen atmosphere while stirring. After completion of dropping, the mixture was stirred for 2 hours while maintaining the temperature at 200° C., and then cooled to obtain a polyamide-imide resin solution. The resulting polyamide-imide resin contained no urea bond and had a molecular weight of 36,300.

Examples 2-82 to 2-88
A polyamideimide resin solution was obtained in the same manner as in Example 2-81 except that the composition of imidodicarboxylic acid and diisocyanate and the mixing ratio with N-methyl-2-pyrrolidone were changed. The polyamideimide resin obtained in each example contained no urea bond.

Comparative example 1
A polyamide-imide resin was prepared according to Example 1 of Japanese Patent No. 02829354. Details are as follows.

[Preparation of imidodicarboxylic acid]
34.3 g (0.5 mol) of 4,4'-diaminodiphenyl ether as a diamine and anhydrous 65.7 g (1.0 mol) of trimellitic acid and 486.4 g of NMP (N-methyl-2-pyrrolidone) as an aprotic solvent were added and stirred at 80° C. for 30 minutes. After adding 81.0 g of toluene as an aromatic hydrocarbon capable of azeotroping with water, the temperature was raised and refluxed at about 160° C. for 2 hours while removing water.
At this time, as the imidization reaction proceeded, a solid content precipitated, resulting in an opaque solution state. After that, the temperature was raised to 190° C. to remove the toluene, resulting in a homogeneous solution.
The obtained solution was measured for imidization rate of imidodicarboxylic acid, and the imidization rate was 89.7%.

[Production of polyamideimide resin]
The resulting imide dicarboxylic acid solution was returned to room temperature, 42.8 g (0.5 mol) of diphenylmethane diisocyanate was added as an aromatic diisocyanate, and reacted at 190° C. for 2 hours to obtain a polyamideimide resin solution. The resulting polyamide-imide resin solution contained gel-like undissolved matter, and when the soluble matter was subjected to NMR measurement, a peak derived from urea bond was detected. The molecular weight was 8410.

The production method of the present invention does not require a complicated imidization step in a solvent or a water removal step from a solvent, so it is possible to easily produce polyamideimide resins of various compositions with sufficiently high molecular weights at low cost. can do. Therefore, the method of the present invention is useful in the field of producing polyamideimide resins from the viewpoint of environmental load, work environment, purity of linear polyamideimide, increase in molecular weight, and the like.

Claims (13)

Using the mechanochemical effect, a tricarboxylic anhydride-based compound and a diamine-based compound or a monoaminomonocarboxylic acid-based compound are reacted, or a tetracarboxylic anhydride-based compound and a monoaminomonocarboxylic acid-based compound are reacted. a step of reacting and imidizing by heating to produce an imidodicarboxylic acid; and a step of reacting the imidodicarboxylic acid with a diisocyanate in an organic solvent;
including
The mechanochemical effect is obtained by applying mechanical energy to a raw material mixture containing one or more raw material compounds in a solid state in a reaction environment, thereby pulverizing the raw material compounds and activating the pulverized interface formed. A method for producing a polyamide-imide resin, characterized in that it is an effect of causing a reaction between functional groups of the raw material compound . Polyamideimide according to claim 1, wherein a diimidedicarboxylic acid precursor is produced by reacting the tricarboxylic anhydride-based compound with the diamine-based compound in an amount of 0.3 to 0.7 times the molar amount of the compound. A method for producing resin. Claim 1, wherein a diimidedicarboxylic acid precursor is produced by reacting the tetracarboxylic anhydride-based compound with the monoaminomonocarboxylic acid-based compound in an amount 1.8 to 2.2 times the molar amount of the compound. A method for producing a polyamide-imide resin according to . Claim 1, wherein a monoimidedicarboxylic acid precursor is produced by reacting the tricarboxylic anhydride-based compound with the monoaminomonocarboxylic acid-based compound in an amount 0.8 to 1.2 times the molar amount of the compound. A method for producing a polyamide-imide resin according to . The method for producing a polyamide-imide resin according to any one of claims 1 to 4, wherein the reaction utilizing the mechanochemical effect and the imidization by heating are solventless reactions. The method for producing a polyamideimide resin according to any one of claims 1 to 5, wherein the reaction utilizing the mechanochemical effect is performed until the average particle size of the imidedicarboxylic acid precursor produced by the reaction is 500 µm or less. . The method for producing a polyamide-imide resin according to any one of claims 1 to 6, wherein the imidization by heating is performed after the reaction utilizing the mechanochemical effect. The method for producing a polyamideimide resin according to any one of claims 1 to 7, wherein the imidization is performed by heating at a temperature of 100 to 450°C for 10 minutes to 16 hours. The method for producing a polyamideimide resin according to any one of claims 1 to 8, wherein the imidodicarboxylic acid has an imidization rate of 95.0% or more. The method for producing a polyamideimide resin according to any one of claims 1 to 9, wherein the imide dicarboxylic acid has a water content of 10 to 10000 ppm. The method for producing a polyamideimide resin according to any one of claims 1 to 10, wherein the reaction of the imidodicarboxylic acid and the diisocyanate is performed by stirring at a temperature of 80 to 250°C for 1 to 16 hours. The method for producing a polyamideimide resin according to any one of claims 1 to 11, wherein the diisocyanate is reacted in two or more steps. The method for producing a polyamideimide resin according to any one of claims 1 to 12, wherein the polyamideimide resin has an average molecular weight of 2,000 to 300,000.