JP2018058965A - Polyamide imide, polyamide imide raw material salt and method for producing them, and polyamide imide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polyamide imide which has high regularity of a molecular structure, has few branch structures, contains no hydrogen halide, and does not need to separate and purity in a post process; polyamide imide raw material salt; a method for producing them; and a polyamide imide resin composition.SOLUTION: Polyamide imide has repeating units represented by formula (1). In formula (1), Ris a divalent residue given by specific diamine having a benzene ring, diamine containing a heterocycle or specific diamine having a cyclohexane ring; Ris a divalent residue having an aromatic ring, an aliphatic ring or aliphatic hydrocarbon; Rand Reach are independently a trivalent residue having an aromatic ring or an aliphatic ring; and hydrogen atoms bonded to each ring may be substituted with other atoms or atomic groups.SELECTED DRAWING: None

Description

  The present invention relates to a polyamideimide, a polyamideimide raw material salt, a production method thereof, and a polyamideimide resin composition.

  Polyamideimide is widely used for applications such as films, wire coating materials, molding materials, adhesives and the like because of its high heat resistance and chemical resistance.

  As a method for producing polyamideimide, three methods are known: an isocyanate method, an acid chloride method, and a direct polymerization method.

  The isocyanate method is a method in which an aromatic dicarboxylic acid or an imide dicarboxylic acid synthesized from an aromatic tricarboxylic anhydride / aromatic diamine (molar ratio 2/1) is reacted with an aromatic diisocyanate (for example, Patent Documents 1 to 3).

  The acid chloride method is a method in which a substantially equimolar amount of an aromatic tricarboxylic acid anhydride chloride and an aromatic diamine are reacted in an organic polar solvent (for example, Patent Document 4).

  The direct polymerization method is a method in which an aromatic tricarboxylic acid or a derivative thereof (excluding an acid chloride derivative) and an aromatic diamine are directly reacted in the presence of a dehydration catalyst (for example, Patent Document 5).

Japanese Patent Publication No. 44-19274 Japanese Patent Publication No. 45-2397 Japanese Patent Publication No. 50-33120 Japanese Patent Publication No.42-15637 Japanese Patent Publication No.49-4077

  However, in the isocyanate method, since diisocyanate is used as a raw material, a urea bond is generated by a side reaction in addition to an amide bond or an imide bond at the initial stage of the reaction, and a high-purity polyamideimide cannot be obtained, or a branched structure is generated. As a result, there is a problem that a gelation phenomenon derived from a branched structure occurs and a linear polymer having a high degree of polymerization cannot be obtained. Further, in the isocyanate method, when an amide solvent such as N-methylpyrrolidone is used as a solvent, there is a problem that the amide solvent reacts with diisocyanate.

  On the other hand, the acid chloride method has a relatively low side reaction and a low-crosslinking structure and a highly linear polyamideimide, but has a problem in that highly corrosive hydrogen chloride is by-produced and remains in the polyamideimide. It was. Further, the acid chloride method has a problem that the regularity in the molecular chain is low because the amine terminal of the diamine reacts with both the chloride terminal and the anhydride group of the aromatic tricarboxylic acid anhydride chloride. As a result, when the obtained polyamideimide was used for a molded article, the physical properties of the molded article were not sufficient, and the usage to be used was limited.

  In addition, since the direct polymerization method does not use diisocyanate or acid chloride, there is no problem of gelation or generation of hydrogen chloride. However, like the acid chloride method, the amine terminal of the diamine is an aromatic tricarboxylic acid anhydride. Since it reacts with both the carboxyl terminal and the anhydride group, there is a problem that the regularity in the molecular chain is low. As a result, when the obtained polyamideimide was used for a molded article, the physical properties of the molded article were not sufficient, and the usage to be used was limited.

  Since the above three methods for producing polyamideimide are all carried out in solution, it was necessary to separate and purify the obtained polyamideimide solution in order to use polyamideimide as a molded product.

  The present invention solves the above-mentioned problems, and has various types of molding materials and compositions that have high molecular structure regularity, few branch structures, no hydrogen halide, and do not need to be separated and purified in subsequent steps. An object of the present invention is to provide a polyamideimide that can be suitably used as a material.

  As a result of intensive studies on the above problems, the present inventors have synthesized a polyamideimide from a bisimide dicarboxylic acid composed of a diamine and a tricarboxylic acid anhydride and a diamine that is the same as or different from the diamine, thereby producing the above-mentioned problem. The present invention has been found.

（式中、Ｒ^１、Ｒ^２は、独立して、芳香環、脂肪族環または脂肪族炭化水素を有する二価の残基を表し、Ｒ^３、Ｒ^４は、独立して、芳香環または脂肪族環を有する三価の残基を表し、それぞれの環に結合した水素原子は他の原子または原子団に置換されていてもよい。）。
（２）ビスイミドジカルボン酸とジアミンからポリアミドイミドを重合せしめることを特徴とする上記一般式（１）で表される繰り返し単位を有するポリアミドイミドの製造方法。
（３）ビスイミドジカルボン酸とジアミンからなるポリアミドイミド原料塩を重合せしめることを特徴とする上記一般式（１）で表される繰り返し単位を有するポリアミドイミドの製造方法。
（４）上記式（１）で表されるポリアミドイミドを構成する、ビスイミドジカルボン酸とジアミンとからなることを特徴とするポリアミドイミド原料塩。
（５）ビスイミドジカルボン酸を、ビスイミドジカルボン酸の融点未満、ジアミンの融点以上で加熱し、ビスイミドジカルボン酸が、その固体状態を保つように、前記ジアミンを添加することを特徴とする上記（５）記載のポリアミドイミド原料塩の製造方法。
（６）上記ポリアミドイミドを含有するポリアミドイミド樹脂組成物。 That is, the gist of the present invention is as follows.
(1) Polyamideimide having a repeating unit represented by the general formula (1):

(Wherein R ¹ and R ² independently represent a divalent residue having an aromatic ring, an aliphatic ring or an aliphatic hydrocarbon, and R ³ and R ⁴ independently represent an aromatic ring or It represents a trivalent residue having an aliphatic ring, and the hydrogen atom bonded to each ring may be substituted with another atom or atomic group.
(2) A method for producing a polyamideimide having a repeating unit represented by the general formula (1), wherein a polyamideimide is polymerized from a bisimide dicarboxylic acid and a diamine.
(3) A method for producing a polyamideimide having a repeating unit represented by the above general formula (1), wherein a polyamideimide raw material salt composed of bisimidedicarboxylic acid and diamine is polymerized.
(4) Polyamideimide raw material salt comprising bisimidedicarboxylic acid and diamine constituting the polyamideimide represented by the above formula (1).
(5) The bisimide dicarboxylic acid is heated below the melting point of the bisimide dicarboxylic acid and above the melting point of the diamine, and the diamine is added so that the bisimide dicarboxylic acid maintains its solid state. (5) The manufacturing method of the polyamidoimide raw material salt of description.
(6) A polyamideimide resin composition containing the polyamideimide.

  According to the present invention, it can be suitably used as various molding materials and composition materials having a high molecular structure regularity, a small branched structure, no hydrogen halide, and no need for separation and purification in subsequent steps. Can be provided.

The polyamideimide of the present invention is a polyamideimide having a repeating unit represented by the general formula (1) composed of bisimide dicarboxylic acid and diamine.

In the above formula (1), R ¹ is a divalent residue having an aromatic ring, an aliphatic ring or an aliphatic hydrocarbon, preferably the following chemical formula (2) having at least two benzene rings, A diamine selected from the following chemical formula (3) having, a chemical formula (4) containing a heterocyclic ring, a chemical formula (5) having a cyclohexane ring as a center, and a diamine represented by a chemical formula (6) having at least two cyclohexane rings Represents a divalent residue given by

In the above formula (1), R ² represents a divalent residue having an aromatic ring, an aliphatic ring or an aliphatic hydrocarbon, and R ³ and R ⁴ independently represent an aromatic ring or an aliphatic ring. The hydrogen atom bonded to each ring may be substituted with another atom or atomic group. The number of repeating units is 1 or more, preferably 4 to 1000, more preferably 20 to 1000.

In formula (2), R ⁶ and R ⁷ each independently represents an arylene group or an alkylene group. Preferably, it is an alkylene group. R ⁶ and R ⁷ are preferably the same divalent group. The arylene group is benzene, naphthalene, preferably a divalent group of benzene, and the alkylene group is a divalent group of an alkane having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, more preferably a methylene group. It is.

n ₁ and n ₂ each independently represent 0 or 1, preferably 0, which are preferably the same. n ₁ and n ₂ are more preferably 0. When n ₁ and n ₂ are 0, it indicates that the N atom in the formula (2) and the benzene ring are directly bonded.

In the above formula (2), R ⁵ is a divalent group represented by the following formulas (2-1) to (2-3).

R ⁵ , R ⁶ , and R ⁷ are bonded to the benzene ring at the para or ortho position. In the case of the following formulas (2-1) and (2-2), a bond at the para position is preferable, and in the case of the following formula (2-3), a bond at the ortho position is preferable.

In formula (2-1), R ⁸ represents an arylene group or an arylene alkylenearylene group (hereinafter referred to as “alkylene diarylene group”), and the arylene group includes benzene, naphthalene, preferably divalent benzene. The group or alkylene group is an alkylene group having 1 to 4 carbon atoms, preferably 2 to 4 carbon atoms, and more preferably a dimethylmethylene group.

Preferable specific examples represented by the formula (2-1) are divalent groups represented by the following chemical formulas (2-1-1) and (2-1-2).

R ⁹ and R ¹⁰ each independently represents an arylene group or an alkylene group. An arylene group is preferable. R ⁹ and R ¹⁰ are preferably the same divalent group. The arylene group is benzene, naphthalene, preferably a divalent group of benzene, and the alkylene group is an alkylene group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, and more preferably a methylene group.

n ₃ and n ₄ each independently represents 0 or 1, preferably 1, which is the same. n ₃ and n ₄ are preferably both 1. When n ₃ and n ₄ are 0, it indicates that the S atom and the O atom in the formula (2-2) are directly bonded.

  A preferred specific example represented by the formula (2-2) is a divalent group represented by the following chemical formula (2-2-1).

R ¹¹ and R ¹² each independently represents an arylene group or an arylene alkylene group. An arylene group is preferable. R ¹¹ and R ¹² are preferably the same divalent group. The arylene group is benzene, naphthalene, preferably a divalent group of benzene, and the alkylene group is an alkylene group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, and more preferably a methylene group.

n ₅ and n ₆ each independently represent 0 or 1, preferably 0, which is preferably the same. n ₅ and n ₆ are preferably both 0. When n ₅ and n ₆ are 0, it indicates that the C atom in the formula (2-3) and the benzene ring are directly bonded.

A preferred specific example represented by the formula (2-3) is a divalent group represented by the following chemical formula (2-3-1).

In formula (3), R ¹³ and R ¹⁴ are each independently an alkylene group, preferably an alkylene group having 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms, and even more preferably an alkylene group having 1 carbon atom. is there.

n ₇ and n ₈ each independently represent 0 or 1, preferably 0, which is preferably the same. n ₇ and n ₈ are more preferably 0 for both. When n ₇ and n ₈ are 0, it indicates that the amino group and the benzene ring are directly bonded in the formula (3).

R ¹³ and R ¹⁴ are preferably bonded to the benzene ring in a positional relationship of para position, meta position, more preferably meta position.

In the formula (3), R ¹⁵ is an alkyl group having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, more preferably 1 carbon atom.

n ₉ represents 1 to 4, preferably 1 to 3, more preferably 1 to 2, more preferably 1.

R ¹⁵ is preferably bonded to the benzene ring with respect to R ¹³ or R ^{14 in} an ortho-position or para-position.

A preferred specific example represented by the formula (3) is a divalent group represented by the following formula (3-1) or the formula (3-2).

In the formula (4), R ¹⁶ represents an alkyl group, an aryl group, preferably an aryl group. The alkyl group is an alkyl group having 1 to 3 carbon atoms. The aryl group is a phenyl group, a naphthyl group, preferably a phenyl group.

In the formula (4), n ₁₀ represents 0 or 1, preferably 1. When n ₁₀ is 0, it indicates that a hydrogen atom is bonded to the triazine ring.

A preferred specific example represented by the formula (4) is a triazine compound represented by the following chemical formula (4-1).

In formula (5), R <^17> , R <^18> is respectively independently C1-C5, Preferably it is C1-C3, More preferably, it is C1-C2 alkylene group, More preferably, it is a methylene group. It is.

R ¹⁷ and R ¹⁸ are bonded to the cyclohexane ring in a para or meta position.

n ₁₁ and n ₁₂ are each independently 0 or 1; When n ₁₁ or n ₁₂ is 0, it indicates that the amino group is directly bonded to the cyclohexane ring.

R ¹⁹ represents an alkyl group having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, more preferably a methyl group.

n ₁₃ is 1 to 10, preferably 1 to 5, more preferably 1 to 3, even more preferably a 3. If n ₁₃ is an integer of 2 or ^{more, a} portion ^{R 19} is bonded to the cyclohexane ring is not particularly limited, ^preferably, the same portions as ^{R 17} and ^{R 18,} or the relationship of ^{R 17, R 18} and ortho It is a certain part.

Preferable specific examples represented by the formula (5) are diamines represented by the following chemical formulas (5-1) and (5-2).

In formula (6), R ²⁰ and R ²¹ are each independently, preferably the same, C 1-5, preferably C 1-3, more preferably C 1-2 alkylene, and even more preferably. Is a methylene group.

n ₁₄ and n ₁₅ each independently represent 0 or 1, preferably 0, which is the same. When n ₁₄ and n ₁₅ are 0, the amino group is directly bonded to the cyclohexane ring.

In the formula (6), R ²² is an alkylene group having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, and more preferably a methylene group.

R ²² and R ²⁰ and R ²¹ are bonded to each other on cyclohexane in the ortho-position or para-position, preferably para-position.

A preferred specific example represented by the formula (6) is a compound represented by the following chemical formula (6-1).

  The tricarboxylic anhydride used for the bisimide dicarboxylic acid is an aromatic or alicyclic tricarboxylic anhydride. Specific examples of the tricarboxylic acid ring include benzene ring, naphthalene ring, anthracene ring, biphenyl ring, cyclohexane ring, preferably benzene ring, naphthalene ring, biphenyl ring, cyclohexane ring, more preferably benzene ring, cyclohexane ring, More preferably, a benzene ring is mentioned.

  Tricarboxylic acids also include those in which a hydrogen atom bonded to the ring is replaced with another atom or atomic group.

  Specific examples of the tricarboxylic acid anhydride include trimellitic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 2,3,6-anthracentricarboxylic acid anhydride, 3,4,4′-biphenyltricarboxylic acid Anhydride, 1,2,4-cyclohexanetricarboxylic acid anhydride, preferably trimellitic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 3,4,4′-biphenyltricarboxylic acid anhydride, 1,2,4-cyclohexanetricarboxylic acid anhydride, more preferably trimellitic acid anhydride, or 1,2,4-cyclohexanetricarboxylic acid anhydride, and still more preferably trimellitic acid anhydride. A tricarboxylic acid anhydride may be used independently and may use 2 or more types together.

R ² represents a divalent residue having an aromatic ring, an aliphatic ring or an aliphatic hydrocarbon. Preferably, it is a divalent residue derived from an aromatic diamine, aliphatic diamine or aliphatic hydrocarbon diamine, more preferably a divalent residue derived from an aromatic diamine or aliphatic diamine. Even more preferably, it is an aromatic diamine represented by the following formula (7). The diamine may include —O— and —S—, one or more hydrogen atoms may be substituted with halogen, and may have a side chain.

n ₁₆ represents 1 or 2, preferably 1.

When n ₁₆ is 1, R ²³ and R ²⁴ are bonded in a para-position or a meta-position, preferably a meta-position.

When n ₁₆ is 2, the two phenylene groups are preferably bonded in a p-position relationship. An alkylene group having 1 to 3 carbon atoms, a sulfide group or an ether group may be present between the two phenylene groups.

In Formula (7), R ²⁵ is an alkyl group having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, and more preferably 1 carbon atom.

n ₁₉ is 0-4, preferably 0-2, more preferably 0-1, even more preferably represents 0.

R ²³ and R ²⁴ are each independently, preferably the same, a methylene group having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, more preferably 1 carbon atom.

n ₁₇ and n ₁₈ each independently represent 0 or 1, preferably 0, which is preferably the same. When n ₁₇ and n ₁₈ are 0, the amino group is directly bonded to the benzene ring.

  Specific examples represented by formula (7) are m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, benzidine, 4,4′-diaminodiphenylpropane, 4,4′-diamino. An aromatic diamine selected from diphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfone, and 4,4′-diaminodiphenyl ether. An aromatic diamine selected from m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 4,4'-diaminodiphenyl ether, and benzidine is preferable. More preferred is an aromatic diamine selected from m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, and 4,4'-diaminodiphenyl ether. Even more preferable is an aromatic diamine selected from m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine. Among these, m-xylylenediamine and p-xylylenediamine are preferable, and m-xylylenediamine is most preferable.

  In the present invention, aromatic diamines containing a condensed ring such as 1,5-diaminonaphthalene and 3,3-diaminonaphthalene can also be used.

Specific examples of the aliphatic hydrocarbon diamine containing R ² include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 1,4-diaminocyclohexane, 1,10-diamino-1, An example is 10-dimethyldecane.

Specific examples of the aliphatic diamine containing R ² include 1,4-diaminocyclohexane and 1,4-bis (aminomethyl) cyclohexane.

  The said diamine residue may be used independently and may use 2 or more types together.

The polyamide-imide (1) of the present invention is synthesized by once synthesizing a polyamide-imide raw material salt comprising bisimide dicarboxylic acid and diamine, and then polymerizing the polyamide-imide raw material salt (hereinafter, “ It can be synthesized in one step (hereinafter referred to as “one-step synthesis method”) by directly reacting bisimide dicarboxylic acid and diamine.
First, the two-stage synthesis method will be described.

(Two-step synthesis method)
In the two-step synthesis method, the polyamideimide of the present invention can be produced by once synthesizing a polyamideimide raw material salt composed of bisimide dicarboxylic acid and diamine, and heating and polymerizing the raw material salt.

  As the bisimide dicarboxylic acid, a known one (for example, a commercially available product) may be used, or one synthesized from a tricarboxylic acid anhydride and a diamine may be used, for example.

  When synthesizing bisimide dicarboxylic acid, the reaction between tricarboxylic acid anhydride and diamine may be performed in a solution state or a molten state, or may be performed in a solid (powder) state. The solid state is preferred from the viewpoint that it can be used for the synthesis of polyamideimide raw material salt powder without requiring a pulverization step or the like.

  The polyamideimide raw material salt can be obtained by neutralizing a bisimide dicarboxylic acid synthesized from a tricarboxylic acid anhydride and a diamine with a diamine that is the same as or different from the diamine.

  The method of obtaining the polyamideimide raw material salt by the reaction of bisimide dicarboxylic acid and diamine may be performed in a solution state or a molten state, or may be performed in a solid state. The solid state is preferable from the viewpoint that the polyamideimide raw material salt powder can be synthesized without requiring a solvent drying step, a pulverizing step, or the like.

  Hereinafter, a method for obtaining a polyamideimide raw material salt by a reaction between bisimide dicarboxylic acid and diamine in a solid state will be described.

  The polyamide-imide raw material salt of the present invention can be achieved by reacting a solid bisimide dicarboxylic acid with a liquid diamine. Specifically, the bisimide dicarboxylic acid has a melting point of less than that of the diamine. This can be achieved by heating above the melting point and adding diamine.

  In order to maintain the solid state of the bisimide dicarboxylic acid and the resulting polyamideimide salt during the process, the amount of diamine added, the addition rate, the addition method, the heating temperature of the bisimide dicarboxylic acid, the reaction time, etc. It is preferable that the conditions are set appropriately and the contents are sufficiently stirred.

  The “melting point” is also referred to as “melting point” and is used in the general sense of a temperature at which a solid melts. The melting point can be obtained by filling a sample in a capillary and heating it, and visually observing the melting point, or by a measuring device such as differential scanning calorimetry (DSC).

  In the present invention, as described above, bisimide dicarboxylic acid maintains its solid state. The average particle diameter of the bisimide dicarboxylic acid is preferably 5 μm to 1 mm, and more preferably 20 to 200 μm. By setting the particle size of the imide dicarboxylic acid to 5 μm to 1 mm, the progress of the reaction of the polyamideimide raw material salt can be accelerated.

  The average particle diameter can be measured by a sedimentation method or a laser diffraction / scattering method. In the present invention, a value measured by a laser diffraction / scattering method is used.

The diamine is not particularly limited as long as it is in a liquid state at the time of reaction with the solid bisimide dicarboxylic acid, and may be added as a solid, or may be added after being heated and melted to be a liquid. From the viewpoint of reducing the particle size of the resulting polyamideimide raw material salt, it is preferable to add it after heating and melting to form a liquid.
Since the time for heating the diamine is shorter, it is preferable that the diamine is added in a solid form such as a powder or a granule that is not heated by itself.

  When adding diamine with solid, the powder-feeding apparatus provided with the double damper mechanism is mentioned, for example. On the other hand, when the diamine is added as a liquid, the diamine is heated and melted in a container different from the reaction container to form a liquid, and then sent to the reaction container, and the liquid diamine is dropped or added to the bisimide dicarboxylic acid. It is preferable to spray in the form of a spray.

  In the present invention, the heating of the bisimide dicarboxylic acid may be performed after adding the diamine or may be performed before adding the diamine, but the latter is more preferable.

  The heating temperature when the bisimide dicarboxylic acid is heated in advance before the addition of the diamine is preferably set to be equal to or higher than the melting point of the diamine and lower than the melting point of the bisimide dicarboxylic acid. The melting point of dicarboxylic acid is more preferably −5 ° C. or less. When the said heating temperature exceeds melting | fusing point of bisimide dicarboxylic acid, the whole reaction system will become liquid, and the whole may agglomerate with the production | generation of a polyamideimide raw material salt. On the other hand, when the said heating temperature is below the melting point of diamine, both bisimide dicarboxylic acid and diamine will be in a solid state, and the production | generation reaction of a polyamideimide raw material salt may hardly advance.

  Among the above ranges, the heating temperature of the bisimide dicarboxylic acid is 100 ° C. or higher and 210 ° C. or lower, preferably 100 ° C. or higher and 200 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower. When the heating temperature exceeds 210 ° C., water is generated because a polymerization reaction occurs during the formation reaction of the polyamideimide raw material salt. As a result, the resulting polyamideimide raw material salt is caused by the generated water. There is a case where a part is melted and fused, or the reaction system becomes a high pressure. On the other hand, when the heating temperature is less than 100 ° C., the formation reaction of the polyamideimide raw material salt may be insufficient.

  In addition, the same temperature may be sufficient as the heating temperature at the time of heating bisimide dicarboxylic acid previously, and the production | generation temperature of a polyamideimide raw material salt may be different.

  The method for adding the diamine is not particularly limited as long as the bisimide dicarboxylic acid can maintain its solid state during the reaction. Among them, from the viewpoint of suppressing the resulting polyamideimide raw material salt from being agglomerated and performing a production reaction efficiently, a method of continuously adding diamines, or divided into appropriate amounts (for example, total amount of diamine added) Among these, the method of intermittently adding 1/10 to 1/100 of each) is preferred. The addition rate of the diamine is preferably 0.005 to 2.00% by mass / min from the viewpoint of stably maintaining the solid state of the bisimide dicarboxylic acid, and 0.01 to 1.00% by mass / min. It is more preferable that Here, “mass% / min” is the ratio of the low melting point component added per minute to the total amount of the low melting point component finally added. Moreover, after adding a suitable amount of diamine intermittently, a method combining the above methods such as a method of continuously adding diamine may be used.

  When the reaction between the diamine and the bisimide dicarboxylic acid is difficult to proceed uniformly, the diamine may be dissolved in a diluting solvent and added to the bisimide dicarboxylic acid. Specific examples of the dilution solvent include water, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and diethylene glycol, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylacetamide.

  The average particle diameter of the resulting polyamideimide raw material salt is preferably 2 mm or less, and more preferably 500 μm or less. By setting the average particle size of the polyamideimide raw material salt to 2 mm or less, for example, even when water is generated when the polyamideimide raw material salt is solid-phase polymerized to obtain the polyamideimide, the water inside the polyamideimide raw material salt is reduced. Since it can be easily removed, there is an advantage that the speed of the polymerization reaction can be increased.

  In the method for producing the polyamideimide raw material salt of the present invention, it is preferable to sufficiently stir during the addition of the diamine or after the completion of the addition of the diamine in order to complete the formation reaction of the polyamideimide raw material salt. The stirring mechanism provided in the reaction apparatus for reacting bisimide dicarboxylic acid and diamine may be appropriately selected according to the type and production amount of the polyamideimide raw material salt to be produced, such as paddle type, tumbler type, ribbon type, etc. And blenders and mixers. A combination of these may also be used.

  The reaction apparatus for reacting bisimide dicarboxylic acid and diamine is not particularly limited as long as bisimide dicarboxylic acid and diamine can be sufficiently stirred, and a known reaction apparatus can be used.

  In the above reaction apparatus, the method of heating the bisimide dicarboxylic acid before the reaction or heating the reaction system during the production reaction is not particularly limited, and using a heat medium such as steam, a heater or the like. The method of heating is mentioned.

  In the present invention, the reaction between the bisimide dicarboxylic acid and the diamine may be carried out in any atmosphere under an air atmosphere or an inert gas atmosphere such as nitrogen, in order to suppress side reactions and coloring. Is preferably performed in an inert gas atmosphere. In addition, the reaction may be performed in a sealed state or under an inert gas flow.

  By the above method of obtaining a polyamideimide raw material salt by the reaction of bisimide dicarboxylic acid and diamine in the solid state, it is not necessary to remove the solvent after the reaction, and it is easy and low-cost without using a poor solvent or a cleaning solution. A granular polyamideimide raw material salt from which polyamideimide can be obtained can be provided.

Here, (1) a polyamideimide raw material salt characterized by comprising a bisimide dicarboxylic acid and a diamine;
(2) The bisimide dicarboxylic acid is heated below the melting point of the bisimide dicarboxylic acid and above the melting point of the diamine, and the diamine is added so that the bisimide dicarboxylic acid maintains its solid state. (1) Production method of polyamideimide raw material salt; and (3) Production of polyamideimide raw material salt according to (2), wherein diamine is dissolved in a diluting solvent and added to bisimide dicarboxylic acid. An invention relating to a method is provided.

  The polymerization method of the polyamideimide raw material salt may be either a melt polymerization method or a solid phase polymerization method, but since the polyamideimide is often close to the flow initiation temperature and the thermal decomposition temperature, the solid phase polymerization method is preferable.

  In the solid phase polymerization method, the reaction temperature is not particularly limited as long as it is less than the melting point of the polyamideimide to be produced, or less than the decomposition temperature, but is usually 160 to 350 ° C. The reaction time is preferably in the range of 0.5 to 24 hours after reaching the reaction temperature, and in the range of 0.5 to 8 hours from the viewpoint of the balance between the finally reached molecular weight and productivity. Is more preferable. The solid phase polymerization may be performed in an inert gas stream such as nitrogen, or may be performed under reduced pressure. Moreover, you may carry out still and may carry out stirring.

  In the present invention, the melting point and glass transition temperature of polyamideimide refer to the melting point and glass transition temperature measured by the following “analysis method (1) melting point and glass transition temperature”. When the melting point could not be measured at a temperature up to 350 ° C., the measurement limit, it was not detected. In addition, when the polyamideimide to be measured is amorphous, the melting point is not measured.

  In the solid-state polymerization method, from the viewpoint of omitting the pulverization step after polymerization, the polyamideimide raw material salt is heated at a temperature lower than the melting point of bisimide dicarboxylic acid and higher than 200 ° C., and polymerization is performed so as to maintain the solid state. Preferably it is done. More preferably, the melting point of the bisimide dicarboxylic acid is −5 ° C. or less. This is because the solid state of the bisimide dicarboxylic acid can be reliably maintained.

  In the melt polymerization method, the reaction temperature is not particularly limited as long as it is equal to or higher than the glass transition temperature of the produced polyamideimide. The reaction time is preferably in the range of 0.5 to 36 hours and more preferably in the range of 1 to 16 hours after reaching the reaction temperature from the viewpoint of the balance between the finally reached molecular weight and productivity. preferable. The melt polymerization may be carried out in an inert gas stream such as nitrogen or under pressure.

  In the method for producing the polyamideimide of the present invention, when the raw material is supplied to the reaction vessel, in addition to the polyamideimide raw material salt, a terminal blocking agent, a polymerization catalyst, and other additives are added within a range that does not impair the effects of the present invention. May be.

  The terminal blocking agent seals the terminal functional group of the polymer. Specific examples of the terminal blocking agent include acetic acid, lauric acid, benzoic acid, octylamine, cyclohexylamine, and aniline. It is preferable that the usage-amount of terminal blocker is 5 mol% or less with respect to the total mol number of a polyamideimide raw material salt.

  Specific examples of the polymerization catalyst include phosphoric acid, phosphorous acid, hypophosphorous acid and salts thereof. Since the usage-amount of a polymerization catalyst causes the performance of a product and workability fall, it is preferable that it is 2 mol% or less with respect to the total mol number of a polyamideimide raw material salt.

  Examples of other additives include various additives described below, for example, various fillers and stabilizers. From the viewpoint of the reactivity of the bisimide dicarboxylate, the amount of the additive used is preferably 30% by mass or less based on the total mass of the polyamideimide raw material salt.

Next, the one-step synthesis method will be described.
(One-step synthesis method)
The polyamideimide of the present invention can be produced by heating the bisimide dicarboxylic acid at a temperature below its melting point and above 200 ° C. and adding the diamine so as to maintain its solid state.

  In this synthesis, the heating of the bisimide dicarboxylic acid may be performed after adding the diamine or may be performed before adding the diamine, but the latter is more preferable.

  The heating temperature when the bisimide dicarboxylic acid is heated in advance before the addition of the diamine is more preferably (melting point of bisimide dicarboxylic acid −5 ° C.) or less. This is because the solid state of the bisimide dicarboxylic acid can be reliably maintained.

  The specific heating temperature of bisimide dicarboxylic acid is suitably set by the bisimide carboxylic acid, diamine, and combinations thereof within the above temperature range.

  Other conditions (conditions, method for maintaining the solid state of bisimide dicarboxylic acid, addition amount of diamine, addition rate, addition method, etc.) can be performed with reference to the conditions described in the above two-step synthesis method.

  In the polymerization method of the present invention, it is preferable to use a polyamideimide raw material salt. By using the polyamideimide raw material salt, a polyamideimide having a higher molecular structure regularity and fewer branched structures can be obtained.

  Polyamideimide having a degree of polymerization (n) (number of repeating units) of about 4 to 1000, preferably about 10 to 1000, and more preferably about 20 to 500 can be synthesized by the above production method.

  The degree of polymerization can be adjusted by changing the blending ratio of bisimide dicarboxylic acid and diamine, the amount of end-capping agent added, the polymerization temperature, the polymerization time, etc., for example, the degree of polymerization is the addition of end-capping agent It can be increased by reducing the amount.

  In general, the degree of polymerization can be measured by estimation by gel permeation chromatography, nuclear magnetic resonance (NMR), solution viscosity method, or melt viscosity method.

  The polyamideimide of the present invention has a structure in which the repeating units represented by the general formula (1) are regularly connected linearly, and has few branched and crosslinked structures.

  The polyamideimides obtained according to the invention can have a glass transition temperature of at least 100 ° C., higher, at least 150 ° C., even higher, at least 250 ° C., even higher, at least 270 ° C.

  Also, the polyamideimide obtained by the present invention, when having crystallinity, has a melting point of at least 150 ° C, higher, at least 250 ° C, even higher, at least 300 ° C, and even higher, at least 350 ° C. be able to.

  Also, the polyamideimides obtained according to the present invention can have a 5% weight loss temperature of at least 300 ° C., higher, at least 350 ° C., even higher, at least 380 ° C., even higher, at least 480 ° C.

  If necessary, various additives may be added to the polyamideimide of the present invention to form a polyamideimide resin composition. Specific examples of additives include fibrous reinforcing materials, plate-like reinforcing materials, impact resistance improving materials, antistatic agents, conductive agents, thermally conductive fillers, aliphatic polyamides, semi-aromatic polyamides, and amorphous polyamides. , Other resin components, heat stabilizers, light stabilizers, slidability improvers, flame retardants, flame retardant aids, and pigments. Additives may be used alone or in combination.

  Specific examples of the fibrous reinforcement include carbon fiber, glass fiber, boron fiber, asbestos fiber, polyvinyl alcohol fiber, polyester fiber, acrylic fiber, wholly aromatic polyamide fiber, polybenzoxazole fiber, polytetrafluoroethylene fiber, kenaf. Examples include fiber, bamboo fiber, hemp fiber, bagasse fiber, high-strength polyethylene fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, basalt fiber, sepiolite, and palygorskite. By adding a fibrous reinforcing material, the mechanical strength can be improved. Among them, glass fiber, carbon fiber, and metal fiber are preferable because of high heat resistance and easy availability. Two or more kinds of fibrous reinforcing materials may be used in combination. The fibrous reinforcing material may be surface-treated with a silane coupling agent. Specific examples of the silane coupling agent include vinyl silanes, acrylic silanes, epoxy silanes, and amino silanes, and aminosilane coupling agents are preferred because of their high adhesion to polyamideimide.

  The average fiber length of the fibrous reinforcing material is preferably 0.1 to 7 mm, and more preferably 0.5 to 6 mm. When the average fiber length of the fibrous reinforcing material is 0.1 to 7 mm, the mechanical properties of the polyamideimide can be improved without adversely affecting the moldability. Moreover, it is preferable that an average fiber diameter is 3-20 micrometers, and it is more preferable that it is 5-13 micrometers. When the average fiber diameter is 3 to 20 μm, the mechanical properties of the polyamideimide can be improved while reducing breakage during melt-kneading. The cross-sectional shape is preferably a circular cross-section, but may be a rectangle, an ellipse (flat), or any other irregular cross-section as necessary.

  When using a fibrous reinforcement, the content is preferably 5 to 200 parts by mass, more preferably 10 to 180 parts by mass, and more preferably 20 to 150 parts by mass with respect to 100 parts by mass of polyamideimide. More preferably, it is most preferable to set it as 30-130 mass parts.

  Specific examples of the plate reinforcing material include talc, mica, sericite, glass flake, plate calcium carbonate, plate aluminum hydroxide, graphite, kaolin, and swellable layered silicate. Dimensional stability can be improved by adding a plate-like reinforcing material.

  When using a plate-shaped reinforcing material, the content is preferably 40 parts by mass or less, and more preferably 20 parts by mass or less, with respect to 100 parts by mass of polyamideimide.

  Specific examples of the impact resistance improver include (ethylene and / or propylene) · α-olefin copolymer, (ethylene and / or propylene) · (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid. And / or unsaturated carboxylic acid ester) -based copolymers and the like, and styrene-based elastomers and the like. By adding an impact resistance improving material, impact resistance and weld strength can be improved.

  Specific examples of the antistatic agent include an anionic antistatic agent, a cationic antistatic material, and a nonionic antistatic agent, and specific examples of the conductivity imparting agent include carbon black, carbon fiber, and metal fiber. It is done. By adding an antistatic agent or a conductivity-imparting agent, the surface resistivity or volume resistivity can be lowered.

  Specific examples of the thermally conductive filler include talc, aluminum oxide, magnesium oxide, zinc oxide, magnesium carbonate, silicon carbide, aluminum nitride, boron nitride, silicon nitride, carbon, and graphite. By adding a thermally conductive filler, the thermal conductivity can be improved.

  Specific examples of the aliphatic polyamide include polyamide 6, polyamide 66, polyamide 610, polyamide 11, and polyamide 12. By adding aliphatic polyamide, vibration fatigue strength can be improved.

  Specific examples of the semi-aromatic polyamide include polyamide 6T, polyamide 9T, polyamide 10T, polyamide 11T, polyamide 12T, and polyamide 6T / 6I.

  Specific examples of the amorphous polyamide include polycondensates of isophthalic acid / terephthalic acid / 1,6-hexanediamine / bis (3-methyl-4-aminocyclohexyl) methane, terephthalic acid / 2,2,4-trimethyl. -1,6-hexanediamine / 2,4,4-trimethyl-1,6-hexanediamine polycondensate, isophthalic acid / bis (3-methyl-4-aminocyclohexyl) methane / ω-laurolactam polycondensation , Polycondensate of isophthalic acid / terephthalic acid / 1,6-hexanediamine, isophthalic acid / 2,2,4-trimethyl-1,6-hexanediamine / 2,4,4-trimethyl-1,6-hexane Polycondensate of diamine, isophthalic acid / terephthalic acid / 2,2,4-trimethyl-1,6-hexanediamine / 2,4,4-trimethyl-1,6 Polycondensate hexanediamine, polycondensates of isophthalic acid / bis (3-methyl-4-aminocyclohexyl) methane / .omega. laurolactam include polycondensates of isophthalic acid / terephthalic acid / other diamine component. The amorphous polyamide refers to a polyamide having a heat of fusion of 1 cal / g or less measured by a differential scanning calorimeter (DSC) at a heating rate of 16 ° C./min in a nitrogen atmosphere. By adding amorphous polyamide, surface glossiness and the like can be improved.

  When amorphous polyamide is used, the content thereof is preferably 10 to 100 parts by mass and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of polyamideimide.

  Specific examples of other resin components include polyimide resins, polyetherimide resins, polyurea resins, epoxy resins, polyester resins, polyesterimide resins, polyurethane resins, polyarylate resins, polycarbonate resins, Polyetheretherketone, polyphenylene sulfide, polyphenylsulfone, polysulfone, polyethersulfone, liquid crystal polymer, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyacetal, polyphenylene ether, polyethylene, polypropylene, polyvinyl chloride, polystyrene , ABS resin, AS resin, acrylic resin, phenol resin, melamine resin, and silicone resin. By adding other resin components, heat resistance, strength, flexibility, and the like can be improved.

  Specific examples of the heat stabilizer include hindered phenol compounds, phosphite compounds, hindered amine compounds, triazine compounds, and sulfur compounds. By adding a heat stabilizer, it is possible to suppress a decrease in the molecular weight and color degradation of the polyamideimide.

  When using a heat stabilizer, the content is preferably 6 parts by mass or less, and more preferably 3 parts by mass or less with respect to 100 parts by mass of polyamideimide.

  Specific examples of the light stabilizer include benzophenone compounds, benzotriazole compounds, salicylate compounds, hindered amine compounds, and hindered phenol compounds. By adding the light stabilizer, it is possible to suppress a decrease in the molecular weight of the polyamideimide due to ultraviolet rays.

  When using a light stabilizer, the content is preferably 6 parts by mass or less, and more preferably 3 parts by mass or less with respect to 100 parts by mass of polyamideimide.

  Specific examples of the sliding property improving material include fluorine resins such as polytetrafluoroethylene, and silicones such as polydimethylsiloxane and fluorine-modified polydimethylsiloxane.

   Specific examples of the flame retardant include bromine-containing flame retardant, nitrogen-containing flame retardant, phosphorus-containing flame retardant, nitrogen-phosphorus-containing flame retardant, hydrated metal flame retardant, and inorganic flame retardant.

  Specific examples of the bromine-containing flame retardant include brominated polystyrene, polybrominated styrene, and brominated polyphenylene ether. Especially, what contains 40-80 mass% of bromine is preferable at a point with the high flame-retardant improvement effect, and what contains 50-70 mass% is more preferable. These bromine-containing flame retardants are used in combination with flame retardant aids such as antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, tin (IV) oxide, iron (III) oxide, zinc oxide and zinc borate. It is preferable to do.

  Specific examples of the nitrogen-containing flame retardant include melamine compounds, salts of cyanuric acid or isocyanuric acid and melamine compounds, salts of phosphoric acid or polyphosphoric acids and ammonia or melamine compounds.

  Specific examples of phosphorus-containing flame retardants include phosphate ester compounds, phosphinic acid salts and diphosphinic acid salts.

  Specific examples of the nitrogen-phosphorus-containing flame retardant include an adduct (melamine adduct) formed from melamine or a condensation product thereof and phosphoric acid. Examples of phosphoric acid constituting this melamine adduct include orthophosphoric acid, phosphonic acid, phosphinic acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid.

  Specific examples of the hydrated metal flame retardant include aluminum hydroxide, boehmite, magnesium hydroxide, calcium hydroxide, and calcium aluminate.

  Examples of the inorganic flame retardant include zinc borate and a mixture of zinc borate and other zinc salts.

  When using a flame retardant, the content is preferably 5 to 100 parts by mass, more preferably 7.5 to 40 parts by mass, and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of polyamideimide. More preferably.

  Specific examples of the pigment include titanium oxide, zinc oxide, zinc sulfide, zinc sulfate, barium sulfate, calcium carbonate, and alumina oxide.

  When using a pigment, the content is preferably 10 to 60 parts by mass, more preferably 15 to 50 parts by mass, and more preferably 20 to 40 parts by mass with respect to 100 parts by mass of polyamideimide. Further preferred.

  In addition, when it contains the said various additives at the time of superposition | polymerization, the quantity including those quantities is the quantity of the additive in a resin composition.

  The polyamideimide and the resin composition of the present invention can be formed into a molded body by injection molding, compression molding or extrusion molding. Of these, injection molding is preferred. Although it does not specifically limit as an injection molding machine used for injection molding, For example, a screw in-line type injection molding machine and a plunger type injection molding machine are mentioned. The polyamideimide heated and melted in the cylinder of the injection molding machine is weighed for each shot, injected into the mold in a molten state, cooled and solidified in a predetermined shape, and then taken out from the mold as a molded body. . The resin temperature at the time of injection molding is preferably equal to or higher than the glass transition temperature of polyamideimide, and more preferably less than the weight reduction start temperature. Even more preferably, the temperature is (glass transition temperature + 50 ° C.) or more and (5% weight loss temperature−10 ° C.) or less.

  In addition, it is preferable that the polyamideimide used for injection molding is sufficiently dried. Polyamideimide having a high moisture content may foam in the cylinder of an injection molding machine, making it difficult to obtain an optimal molded body. The moisture content of the polyamideimide used for injection molding is preferably less than 0.3% by mass, and more preferably less than 0.1% by mass.

  The polyamideimide of the present invention is excellent in heat resistance, chemical resistance, mechanical strength, and moldability. Therefore, automotive parts, electrical and electronic parts, sliding parts, tube-related parts, household goods, metal coatings, industrial material supplies, computer and related equipment parts, optical equipment parts, information / communication equipment parts, precision equipment parts, etc. Can be used for various purposes. Moreover, the polyamideimide of the present invention or the resin composition thereof can be used as a resin solution by dissolving or dispersing in the solution, and can be suitably applied to coatings, varnishes, prepregs and the like.

  Specific examples of automotive parts include base plates for cylinders such as shift levers and gearboxes, cylinder head covers, engine mounts, air intake manifolds, throttle bodies, air intake pipes, radiator tanks, radiator supports, radiator hoses, radiator grills, and rear Spoiler, wheel cover, wheel cap, cowl vent grill, 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 rear -Inner, 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 cut-off valve, Quick connector, Canister, Fuel delivery pipe, Fuel filler neck, Fuel pipe fitting, Lamp reflector, Lamp housing, Lamp Examples include extensions and lamp sockets.

  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 batteries Examples include binders for electrodes such as secondary batteries.

  Specific examples of the sliding parts include gears, gears, washers, actuators, bearing retainers, bearings, switches, pistons, packings, rollers, belts for copying machines, 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, tubes for window washer fluid, cooler tubes for cooling water and refrigerant, air conditioners, etc. Tubes for refrigerants, tubes for floor heating, tubes for fire extinguishers and fire extinguishing equipment, tubes for medical cooling equipment, tubes for spraying paints, tubes for transporting chemicals, tubes for fuel transport, tubes for diesel gasoline, tubes for oil drilling, etc. Examples include alcohol gasoline tubes, engine coolant (LLC) tubes, reservoir tank tubes, load heating tubes, floor heating tubes, infrastructure supply tubes, and gas tubes.

  Specific examples of household items include baby bottles, eyeglass frames, sports shoes, and ski board surface materials.

  Specific examples of the metal coating include metal coatings for water-circulating parts such as liquid metal pipes and water tanks.

  Specific examples of industrial materials include tire cords, belts, bulletproof clothing, protective clothing, flameproof clothing, work clothing, concrete reinforcements, asbestos substitutes, ropes, shoe materials, fishing lines, fishing nets, sail cloths, cushion materials, Examples include wind power blades, papermaking felts, copier cleaners, filters, and hollow fiber membranes.

  The polyamide-imide of the present invention can be used as a film, and specific examples of such a film include a flexible printed board, a seamless belt, a speaker diaphragm, and a film capacitor.

  As the paint and varnish, the polyamideimide of the present invention is contained as a binder resin. Other known materials and amounts used for paints and varnishes can be used. Solvents include water, methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, triethylamine, triethanolamine, dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylsulfoxide, N-methyl-2 -Pyrrolidone (NMP), γ-butyrolactone, sulfolane, cyclohexanone or the like or a solvent containing these may be used.

  The polyamideimide resin solution of the present invention can also be used for the production of prepreg. The prepreg can be obtained by impregnating or coating a reinforcing fiber cloth with a resin solution obtained by dissolving a polyamideimide of the present invention soluble in a solvent and a compound further reactively polymerized with the resin in an organic solvent, and then drying. it can. Specific examples of the compound further reactively polymerized with the polyamideimide resin include the polyamideimide raw material salt of the present invention, a polyimide resin compound, a polyetherimide resin compound, a polyurea resin compound, a polyester resin compound, and a polyesterimide resin. Examples include compounds, polyurethane resin compounds, polyarylate resin compounds, epoxy compounds, and isocyanate compounds. The epoxy compound is a compound having at least one glycidyl group in the molecule, and preferably a compound having two or more glycidyl groups. Specific examples of the epoxy compound include bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain Epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalenediol, diglycidyl etherified product of phenol, diester of alcohol Examples thereof include glycidyl etherified products and alkyl-substituted products, halides or hydrogenated products thereof. Specific examples of the isocyanate compound include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, and m-xylylene diene. Aromatic diisocyanates such as isocyanate and 2,4-tolylene dimer, aliphatic diisocyanates such as hexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the organic solvent include water, methanol, ethanol, propanol, isopropanol, benzene, toluene, xylene, trimethylbenzene, cresol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, triethylamine, triethanolamine, dimethylacetamide (DMAc). , Dimethylformamide (DMF), dimethyl sulfoxide, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, sulfolane, cyclohexanone and the like, or a solvent containing them.

  As an application to a prepreg, the polyamideimide of the present invention is used as a known prepreg, for example, polyethylene resin, polypropylene resin, polyetheretherketone resin, polyethersulfone resin, polyphenylsulfone resin, epoxy resin, polyimide resin, polyamide resin. It may be used as an additive to a prepreg such as a polycarbonate resin, a polyethylene terephthalate resin, a polyurethane resin, a polyester resin, and a fluoropolymer so as to impart the properties of the polyamideimide of the present invention.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited by these.

Identification of Bisimide Dicarboxylic Acid Using a high performance liquid chromatograph mass spectrometer (LC / MS), the molecular weight of the main component was determined by measurement under the following conditions.
Sample: Bisimide dicarboxylic acid / DMSO solution (200 μg / mL)
Equipment: microTOF2-kp manufactured by Bruker Daltonics
Column: Cadenza CD-C18 3μm 2mm × 150mm
Mobile phase: (Mobile phase A) 0.1% formic acid aqueous solution, (Mobile phase B) Methanol gradient (B Conc.): 0min (50%)-5,7min (60%)-14.2min (60%)-17min (100 %)-21.6min (100%)-27.2min (50%)-34min (50%)
Ionization method: ESI
Detection condition: Negative mode

Infrared spectroscopy (IR)
Equipment: System 2000 infrared spectrometer manufactured by Perkin Elmer Method: KBr method Number of integrations: 64 scans (4 cm ^-1 resolution)

  The general formula of the bisimide dicarboxylic acid used for the preparation of the polyamideimide raw material salt is shown below.

The structure of R ¹ is shown in Table 1 below.

Name and structure of diamine used for R ^{1 of} bisimide dicarboxylic acid

Synthesis of bisimide dicarboxylic acid (structures 1-10) Structures 1-2, 4-6, 8-9
66.6 mol% of granular trimellitic anhydride (melting point: 168 ° C) was added to a mixing tank equipped with a double helical stirring blade, and heated to 160 ° C under a nitrogen atmosphere while stirring. While confirming that the trimellitic anhydride maintains its shape, 33.4 mol% of the diamine of the solid structure 1-2, 4-6, 8-9 is fed with a double damper mechanism. Using the apparatus, it was added at a rate of 0.5% by mass / min to obtain a mixture. During and after the addition, the contents were granular.
Thereafter, the mixture was heated to 300 ° C. while stirring and heated at 300 ° C. for 2 hours.

The synthesis of the bisimide dicarboxylic acid having the above structure was confirmed by IR measurement and mass spectrometry by GC / MS. Was subjected to IR measurement, absorption in the vicinity of 1778cm ^-1 and near 1714 cm ^-1 was confirmed the formation of imide bonds because it can be confirmed for all compounds. From the results of mass spectrometry, the molecular weight of the main component is 760 (m / z) (Structure 1), 642 (m / z) (Structure 2), 562 (m / z) (Structure 4), 472 (m / z). z) (Structure 5), 472 (m / z) (Structure 6), 492 (m / z) (Structure 8), 560 (m / z) (Structure 9).

Structure 3, 7
To a mixing vessel equipped with a double helical stirring blade, 33.4 mol% of the diamine having a granular structure 3 or 7 was added and heated to 175 ° C. in a nitrogen atmosphere while stirring. While confirming that the diamine of structure 3 or 7 maintains the shape, 66.6 mol% of solid trimellitic anhydride (melting point: 168 ° C.) is added to a powder feeding device equipped with a double damper mechanism. And a mixture was obtained at a rate of 0.4% by mass / min). During and after the addition, the contents were granular.
Thereafter, the mixture was heated to 300 ° C. while stirring and heated at 300 ° C. for 2 hours.

The synthesis of the bisimide dicarboxylic acid having the above structure was confirmed by IR measurement and mass spectrometry by GC / MS. Was subjected to IR measurement, absorption in the vicinity of 1778cm ^-1 and near 1714 cm ^-1 was confirmed the formation of imide bonds because it can be confirmed for all compounds. From the results of mass spectrometry, the molecular weight of the main component was estimated to be 778 (m / z) (structure 3) and 537 (m / z) (structure 7).

Structure 10
66.6 mol% of granular trimellitic anhydride (melting point: 168 ° C) was added to a mixing vessel equipped with a double helical stirring blade, and heated to 80 ° C under a nitrogen atmosphere while stirring. While confirming that the trimellitic anhydride maintained its shape, 33.4 mol% of the diamine having the structure 10 heated to 80 ° C. was 0.28% by mass / min using a liquid feeder. Added at a rate to give a mixture. During and after the addition, the contents were granular.
Thereafter, the mixture was heated to 300 ° C. while stirring and heated at 300 ° C. for 2 hours.

The synthesis of the bisimide dicarboxylic acid having the above structure was confirmed by IR measurement and mass spectrometry by GC / MS. When IR measurement was performed, absorption was confirmed in the vicinity of 1778 cm ⁻¹ and 1714 cm ⁻¹ , thereby confirming the formation of imide bonds. The molecular weight of the main component was estimated to be 520 (m / z) from the results of mass spectrometry.

Example 1 Synthesis of polyamideimide raw material salt
Ribbon blender type reactor comprising a mixture of 728 parts by mass of bisimide dicarboxylic acid shown in structure 1 (melting point: not detected at 300 ° C. or higher) (average particle size: 450 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 139 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 0.695 parts by mass / minute (0.50% by mass / minute) using a liquid feeder. It was added to the bisimide dicarboxylic acid of structure 1 kept at 170 ° C. over time [bisimide dicarboxylic acid: m-xylylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle diameter: 430 μm).

The polyamide-imide raw material salt is generated by infrared spectroscopy ^{(IR), 164cm -1, 1559cm} -1, an increase of absorption derived from a salt of a carboxylic acid and an amine which is detected in the vicinity of 1374cm ^-1 and This was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Example 2
Ribbon blender type reactor comprising a mixture of 614 parts by mass of bisimide dicarboxylic acid shown in structure 2 (melting point: not detected 300 ° C. or higher) (average particle size: 452 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 139 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 0.695 parts by mass / minute (0.50% by mass / minute) using a liquid feeder. It was added to the bisimide dicarboxylic acid of structure 1 kept at 170 ° C. over time [bisimide dicarboxylic acid: m-xylylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle diameter: 396 μm).

The polyamide-imide raw material salt is generated by infrared spectroscopy ^{(IR), 164cm -1, 1559cm} -1, an increase of absorption derived from a salt of a carboxylic acid and an amine which is detected in the vicinity of 1374cm ^-1 and This was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Example 3
Ribbon blender type reactor comprising a mixture of 745 parts by mass of bisimide dicarboxylic acid shown in structure 3 (melting point: not detected 300 ° C. or higher) (average particle size: 478 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 139 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 0.695 parts by mass / minute (0.50% by mass / minute) using a liquid feeder. It was added to the bisimide dicarboxylic acid of structure 1 kept at 170 ° C. over time [bisimide dicarboxylic acid: m-xylylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle diameter: 445 μm).

The polyamide-imide raw material salt is generated by infrared spectroscopy ^{(IR), 164cm -1, 1559cm} -1, an increase of absorption derived from a salt of a carboxylic acid and an amine which is detected in the vicinity of 1374cm ^-1 and This was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Example 4
Ribbon blender type reactor comprising a mixture of 538 parts by mass of bisimide dicarboxylic acid shown in structure 4 (melting point: not detected 300 ° C. or higher) (average particle size: 355 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 139 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 0.695 parts by mass / minute (0.50% by mass / minute) using a liquid feeder. It was added to the bisimide dicarboxylic acid of structure 1 kept at 170 ° C. over time [bisimide dicarboxylic acid: m-xylylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle size: 343 μm).

The polyamide-imide raw material salt is generated by infrared spectroscopy ^{(IR), 164cm -1, 1559cm} -1, an increase of absorption derived from a salt of a carboxylic acid and an amine which is detected in the vicinity of 1374cm ^-1 and This was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Example 5
Ribbon blender type reactor comprising a mixture of 451 parts by mass of bisimide dicarboxylic acid shown in structure 5 (melting point: not detected 300 ° C. or higher) (average particle size: 394 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 139 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 0.695 parts by mass / minute (0.50% by mass / minute) using a liquid feeder. It was added to the bisimide dicarboxylic acid of structure 1 kept at 170 ° C. over time [bisimide dicarboxylic acid: m-xylylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle diameter: 360 μm).

The polyamide-imide raw material salt is generated by infrared spectroscopy ^{(IR), 164cm -1, 1559cm} -1, an increase of absorption derived from a salt of a carboxylic acid and an amine which is detected in the vicinity of 1374cm ^-1 and This was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Example 6
Ribbon blender type reactor comprising a mixture of 451 parts by weight of bisimide dicarboxylic acid shown in structure 6 (melting point: not detected 300 ° C. or higher) (average particle size: 479 μm) and 0.593 parts by weight of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 139 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 0.695 parts by mass / minute (0.50% by mass / minute) using a liquid feeder. It was added to the bisimide dicarboxylic acid of structure 1 kept at 170 ° C. over time [bisimide dicarboxylic acid: m-xylylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle diameter: 382 μm).

The polyamide-imide raw material salt is generated by infrared spectroscopy ^{(IR), 164cm -1, 1559cm} -1, an increase of absorption derived from a salt of a carboxylic acid and an amine which is detected in the vicinity of 1374cm ^-1 and This was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Example 7
Ribbon blender type reactor comprising a mixture of 514 parts by mass of bisimide dicarboxylic acid shown in structure 7 (melting point: not detected 300 ° C. or higher) (average particle size: 364 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 139 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 0.695 parts by mass / minute (0.50% by mass / minute) using a liquid feeder. It was added to the bisimide dicarboxylic acid of structure 1 kept at 170 ° C. over time [bisimide dicarboxylic acid: m-xylylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle diameter: 329 μm).

The polyamide-imide raw material salt is generated by infrared spectroscopy ^{(IR), 164cm -1, 1559cm} -1, an increase of absorption derived from a salt of a carboxylic acid and an amine which is detected in the vicinity of 1374cm ^-1 and This was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Example 8
Ribbon blender type reactor comprising a mixture of 471 parts by weight of bisimide dicarboxylic acid shown in structure 8 (melting point: not detected 300 ° C. or higher) (average particle size: 454 μm) and 0.593 parts by weight of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 139 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 0.695 parts by mass / minute (0.50% by mass / minute) using a liquid feeder. It was added to the bisimide dicarboxylic acid of structure 1 kept at 170 ° C. over time [bisimide dicarboxylic acid: m-xylylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle diameter: 433 μm).

The polyamide-imide raw material salt is generated by infrared spectroscopy ^{(IR), 164cm -1, 1559cm} -1, an increase of absorption derived from a salt of a carboxylic acid and an amine which is detected in the vicinity of 1374cm ^-1 and This was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Example 9
Ribbon blender-type reactor comprising a mixture of 536 parts by weight of bisimide dicarboxylic acid shown in structure 9 (melting point: not detected at 300 ° C. or higher) (average particle size: 463 μm) and 0.593 parts by weight of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 139 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 0.695 parts by mass / minute (0.50% by mass / minute) using a liquid feeder. It was added to the bisimide dicarboxylic acid of structure 1 kept at 170 ° C. over time [bisimide dicarboxylic acid: m-xylylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle diameter: 450 μm).

The polyamide-imide raw material salt is generated by infrared spectroscopy ^{(IR), 164cm -1, 1559cm} -1, an increase of absorption derived from a salt of a carboxylic acid and an amine which is detected in the vicinity of 1374cm ^-1 and This was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Example 10
Ribbon blender type reactor comprising a mixture of 497 parts by mass of bisimide dicarboxylic acid shown in structure 10 (melting point: not detected 300 ° C. or higher) (average particle size: 477 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 139 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 0.695 parts by mass / minute (0.50% by mass / minute) using a liquid feeder. It was added to the bisimide dicarboxylic acid of structure 1 kept at 170 ° C. over time [bisimide dicarboxylic acid: m-xylylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle diameter: 442 μm).

The polyamide-imide raw material salt is generated by infrared spectroscopy ^{(IR), 164cm -1, 1559cm} -1, an increase of absorption derived from a salt of a carboxylic acid and an amine which is detected in the vicinity of 1374cm ^-1 and This was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

  Synthesis of polyamideimide

1. Analysis Method (1) Melting Point and Glass Transition Temperature Polyamideimide 5 mg was heated at 20 ° C./min from 25 ° C. to 350 ° C. under a nitrogen atmosphere using a differential scanning calorimeter (“DSC8500” manufactured by Perkin Elmer). (1st Scan) and held at 350 ° C. for 5 minutes. Thereafter, the temperature was lowered to 25 ° C. at 500 ° C./minute, held at 25 ° C. for 5 minutes, and further heated to 350 ° C. at 20 ° C./minute (2nd Scan). The peak top temperature of the crystal melting peak observed at 1st Scan was the melting point, and the intermediate point between the temperatures of the two bending points derived from the glass transition observed at 2nd Scan was the glass transition temperature.

(2) 5% weight reduction temperature 10 from 30 ° C. to 800 ° C. under a nitrogen atmosphere of 200 mL / min using a differential thermothermal gravimetric simultaneous measurement device (TG / DTA “TG / DTA7200” manufactured by Hitachi High-Tech Science Co., Ltd.) The temperature was raised at 0 ° C / min. The temperature at which the weight decreased by 5% by weight with respect to the weight before the temperature increase was taken as the thermal decomposition temperature.

Synthesis of Polyamideimide Example P-1
The polyamideimide raw material salt obtained in Example 1 was again added to the ribbon blender reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C., and further heated at 200 ° C. for 6 hours to obtain granular (average particle size: 280 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 230 ° C. and a 5% weight loss temperature of 390 ° C.

Further, in the measurement of nuclear magnetic resonance (NMR), 10 mg of sample was dissolved in 1 mL of DMSO-d6, and HMBC-two-dimensional NMR measurement was performed at 120 ° C., no peak derived from the side reaction was detected, M- correlates with both ¹ H of the methylene group adjacent to the amide bond and ¹ H of the methylene group adjacent to the imide bond, which is detected when m-xylylenediamine is present between the amide bond and the imide bond. Since the peak derived from ¹³ C at the 2-position of xylylenediamine was not observed, the obtained polyamide-imide has a structure in which the repeating units represented by the formula (1) are connected in a linear form. It was confirmed.

Example P-2
The polyamideimide raw material salt obtained in Example 2 was again added to the ribbon blender reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C., and further heated at 200 ° C. for 6 hours to obtain granular (average particle size: 263 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 220 ° C. and a 5% weight loss temperature of 390 ° C.

Further, in the measurement of nuclear magnetic resonance (NMR), 10 mg of sample was dissolved in 1 mL of DMSO-d6, and HMBC-two-dimensional NMR measurement was performed at 120 ° C., no peak derived from the side reaction was detected, M which correlates with both ¹ H of the methylene group adjacent to the amide bond and ¹ H of the methylene group adjacent to the imide bond, which is detected when m-xylylenediamine is present between the amide bond and the imide bond. -From the fact that no peak derived from ^{13C at} the 2-position of xylylenediamine was not observed, the obtained polyamideimide had a structure in which the repeating units represented by the formula (1) were connected in a straight chain. It was confirmed that

Example P-3
The polyamideimide raw material salt obtained in Example 3 was again added to the ribbon blender reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C., and further heated at 200 ° C. for 6 hours to obtain granular (average particle size: 241 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 226 ° C. and a 5% weight loss temperature of 390 ° C.

Further, in the measurement of nuclear magnetic resonance (NMR), 10 mg of sample was dissolved in 1 mL of DMSO-d6, and HMBC-two-dimensional NMR measurement was performed at 120 ° C., no peak derived from the side reaction was detected, M which correlates with both ¹ H of the methylene group adjacent to the amide bond and ¹ H of the methylene group adjacent to the imide bond, which is detected when m-xylylenediamine is present between the amide bond and the imide bond. -From the fact that no peak derived from ^{13C at} the 2-position of xylylenediamine was not observed, the obtained polyamideimide had a structure in which the repeating units represented by the formula (1) were connected in a straight chain. It was confirmed that

Example P-4
The polyamideimide raw material salt obtained in Example 4 was again added to the ribbon blender reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C., and further heated at 200 ° C. for 6 hours to obtain granular (average particle size: 242 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 220 ° C. and a 5% weight loss temperature of 390 ° C.

Further, in the measurement of nuclear magnetic resonance (NMR), 10 mg of sample was dissolved in 1 mL of DMSO-d6, and HMBC-two-dimensional NMR measurement was performed at 120 ° C., no peak derived from the side reaction was detected, M which correlates with both ¹ H of the methylene group adjacent to the amide bond and ¹ H of the methylene group adjacent to the imide bond, which is detected when m-xylylenediamine is present between the amide bond and the imide bond. -From the fact that no peak derived from ^{13C at} the 2-position of xylylenediamine was not observed, the obtained polyamideimide had a structure in which the repeating units represented by the formula (1) were connected in a straight chain. It was confirmed that

Example P-5
The polyamideimide raw material salt obtained in Example 5 was again added to the ribbon blender reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C., and further heated at 200 ° C. for 6 hours to obtain granular (average particle size: 220 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 205 ° C. and a 5% weight loss temperature of 390 ° C.

Further, in the measurement of nuclear magnetic resonance (NMR), 10 mg of sample was dissolved in 1 mL of DMSO-d6, and HMBC-two-dimensional NMR measurement was performed at 120 ° C., no peak derived from the side reaction was detected, M which correlates with both ¹ H of the methylene group adjacent to the amide bond and ¹ H of the methylene group adjacent to the imide bond, which is detected when m-xylylenediamine is present between the amide bond and the imide bond. -From the fact that no peak derived from ^{13C at} the 2-position of xylylenediamine was not observed, the obtained polyamideimide had a structure in which the repeating units represented by the formula (1) were connected in a straight chain. It was confirmed that

Example P-6
The polyamideimide raw material salt obtained in Example 6 was again added to the ribbon blender reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C., and further heated at 200 ° C. for 6 hours to obtain granular (average particle size: 218 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 200 ° C. and a 5% weight loss temperature of 390 ° C.

Further, in the measurement of nuclear magnetic resonance (NMR), 10 mg of sample was dissolved in 1 mL of DMSO-d6, and HMBC-two-dimensional NMR measurement was performed at 120 ° C., no peak derived from the side reaction was detected, M which correlates with both ¹ H of the methylene group adjacent to the amide bond and ¹ H of the methylene group adjacent to the imide bond, which is detected when m-xylylenediamine is present between the amide bond and the imide bond. -From the fact that no peak derived from ^{13C at} the 2-position of xylylenediamine was not observed, the obtained polyamideimide had a structure in which the repeating units represented by the formula (1) were connected in a straight chain. It was confirmed that

Example P-7
The polyamideimide raw material salt obtained in Example 7 was again added to the ribbon blender reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C., and further heated at 200 ° C. for 6 hours to obtain granular (average particle size: 227 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 230 ° C. and a 5% weight loss temperature of 390 ° C.

Further, in the measurement of nuclear magnetic resonance (NMR), 10 mg of sample was dissolved in 1 mL of DMSO-d6, and HMBC-two-dimensional NMR measurement was performed at 120 ° C., no peak derived from the side reaction was detected, M which correlates with both ¹ H of the methylene group adjacent to the amide bond and ¹ H of the methylene group adjacent to the imide bond, which is detected when m-xylylenediamine is present between the amide bond and the imide bond. -From the fact that no peak derived from ^{13C at} the 2-position of xylylenediamine was not observed, the obtained polyamideimide had a structure in which the repeating units represented by the formula (1) were connected in a straight chain. It was confirmed that

Example P-8
The polyamideimide raw material salt obtained in Example 8 was again added to the ribbon blender reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C., and further heated at 200 ° C. for 6 hours to obtain granular (average particle size: 231 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 185 ° C. and a 5% weight loss temperature of 360 ° C.

Further, in the measurement of nuclear magnetic resonance (NMR), 10 mg of sample was dissolved in 1 mL of DMSO-d6, and HMBC-two-dimensional NMR measurement was performed at 120 ° C., no peak derived from the side reaction was detected, M which correlates with both ¹ H of the methylene group adjacent to the amide bond and ¹ H of the methylene group adjacent to the imide bond, which is detected when m-xylylenediamine is present between the amide bond and the imide bond. -From the fact that no peak derived from ^{13C at} the 2-position of xylylenediamine was not observed, the obtained polyamideimide had a structure in which the repeating units represented by the formula (1) were connected in a straight chain. It was confirmed that

Example P-9
The polyamideimide raw material salt obtained in Example 9 was again added to the ribbon blender reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C., and further heated at 200 ° C. for 6 hours to obtain granular (average particle size: 263 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 190 ° C. and a 5% weight loss temperature of 360 ° C.

Further, in the measurement of nuclear magnetic resonance (NMR), 10 mg of sample was dissolved in 1 mL of DMSO-d6, and HMBC-two-dimensional NMR measurement was performed at 120 ° C., no peak derived from the side reaction was detected, M which correlates with both ¹ H of the methylene group adjacent to the amide bond and ¹ H of the methylene group adjacent to the imide bond, which is detected when m-xylylenediamine is present between the amide bond and the imide bond. -From the fact that no peak derived from ^{13C at} the 2-position of xylylenediamine was not observed, the obtained polyamideimide had a structure in which the repeating units represented by the formula (1) were connected in a straight chain. It was confirmed that

Example P-10
The polyamideimide raw material salt obtained in Example 10 was again added to the ribbon blender reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C., and further heated at 200 ° C. for 6 hours to obtain granular (average particle size: 284 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 175 ° C. and a 5% weight loss temperature of 365 ° C.

Further, in the measurement of nuclear magnetic resonance (NMR), 10 mg of sample was dissolved in 1 mL of DMSO-d6, and HMBC-two-dimensional NMR measurement was performed at 120 ° C., no peak derived from the side reaction was detected, M which correlates with both ¹ H of the methylene group adjacent to the amide bond and ¹ H of the methylene group adjacent to the imide bond, which is detected when m-xylylenediamine is present between the amide bond and the imide bond. -From the fact that no peak derived from ^{13C at} the 2-position of xylylenediamine was not observed, the obtained polyamideimide had a structure in which the repeating units represented by the formula (1) were connected in a straight chain. It was confirmed that

Claims (9)

Polyamideimide having a repeating unit represented by the general formula (1):

(In the formula (1), R ¹ is the following chemical formula (2) having at least two benzene rings, the following chemical formula (3) having a benzene ring as the center, the following chemical formula (4) including a heterocyclic ring, and the cyclohexane ring being the center And represents a divalent residue provided by a diamine selected from the diamine represented by the chemical formula (5) having at least two cyclohexane rings and
R ² represents a divalent residue having an aromatic ring, an aliphatic ring or an aliphatic hydrocarbon;
R ³ and R ⁴ independently represent a trivalent residue having an aromatic ring or an aliphatic ring, and a hydrogen atom bonded to each ring may be substituted with another atom or atomic group;

In formula (2), R ⁶ and R ⁷ each independently represent an arylene group or an alkylene group; n ₁ and n ₂ each independently represent 0 or 1; R ⁵ represents the following formula ( 2-1) to (2-3).

In formula (2-1), R ⁸ represents an arylene group or an arylene alkylenearylene group;
In formula (2-2), R ⁹ and R ¹⁰ each independently represent an arylene group or an alkylene group; n ₃ and n ₄ each independently represent 0 or 1;
In formula (2-3), R ¹¹ and R ¹² each independently represent an arylene group or an arylene alkylene group; n ₅ and n ₆ each independently represent 0 or 1;
In the formula (3), R ¹³ and R ¹⁴ each independently represents an alkylene group; n ₇ and n ₈ each independently represent 0 or 1; R ¹⁵ represents 1 to 3 carbon atoms. Represents an alkyl group; n ₉ represents 1 to 4;
In the formula (4), R ¹⁶ represents an alkyl group or an aryl group; n ₁₀ represents 0 or 1;
In formula (5), R ¹⁷ and R ¹⁸ each independently represents an alkylene group having 1 to 5 carbon atoms; n ₁₁ and n ₁₂ each independently represents 0 or 1; and R ¹⁹ represents carbon. Represents an alkyl group of 1 to 3; n ₁₃ represents 1 to 10;
In formula (6), R ²⁰ and R ²¹ each independently represents an alkylene group having 1 to 5 carbon atoms; n ₁₄ and n ₁₅ each independently represents 0 or 1; R ²² represents carbon Represents an alkylene group of 1 to 3; ).   The polyamideimide according to claim 1, wherein the number of repeating units is 4 to 1000.   Polyamideimide according to claim 1 or 2, having a glass transition temperature of at least 100 ° C.   The method for producing a polyamideimide according to any one of claims 1 to 3, wherein a polyamideimide raw material salt composed of bisimidedicarboxylic acid and diamine is polymerized.   A polyamideimide raw material salt comprising a bisimidedicarboxylic acid and a diamine constituting the polyamideimide represented by the formula (1) according to claim 1.   6. The bisimide dicarboxylic acid is heated below the melting point of the bisimide dicarboxylic acid and above the melting point of the diamine, and the diamine is added so that the bisimide dicarboxylic acid maintains its solid state. A method for producing a polyamideimide raw material salt.   A polyamideimide resin composition comprising the polyamideimide according to any one of claims 1 to 3 and a fibrous reinforcing material.   Furthermore, the polyamideimide resin composition of Claim 7 containing antioxidant.   The method for producing a polyamideimide according to any one of claims 1 to 3, wherein the bisimide dicarboxylic acid and the diamine are subjected to a polymerization reaction at 200 ° C or higher below the melting point of the bisimide dicarboxylic acid.