JP6868883B2 - Polyamideimide, polyamide-imide raw material salt, their production method, and polyamide-imide resin composition - Google Patents

Description

The present invention relates to a polyamide-imide, a polyamide-imide raw material salt, a method for producing the same, and a polyamide-imide resin composition.

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

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

The isocyanate method is a method of reacting an imide dicarboxylic acid synthesized from an aromatic tricarboxylic acid anhydride or an aromatic tricarboxylic acid anhydride / aromatic diamine (molar ratio 2/1) 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 is reacted with an aromatic diamine 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).

Special Publication No. 44-19274 Tokukousho No. 45-2397 Tokukousho 50-33120 Gazette Special Publication No. 42-15637 Special 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 the amide bond and the imide bond at the initial stage of the reaction, and a high-purity polyamide-imide cannot be obtained or a branched structure is generated. As a result, there is a problem that a gelation phenomenon derived from the branched structure occurs and a linear polymer having a high degree of polymerization cannot be obtained. Further, in the isocyanate method, when an amide-based solvent such as N-methylpyrrolidone is used as the solvent, there is a problem that the amide-based solvent reacts with diisocyanate.

On the other hand, the acid chloride method can obtain a highly linear polyamide-imide with relatively few side reactions and few crosslinked structures, but has a problem that highly corrosive hydrogen chloride is produced as a by-product and remains in the polyamide-imide. It was. Further, in the acid chloride method, since the amine terminal of the diamine reacts with both the chloride terminal and the anhydrous group of the aromatic tricarboxylic acid anhydride chloride, there is a problem that the regularity in the molecular chain is low. As a result, when the obtained polyamide-imide was used in a molded product, the physical properties of the molded product were not sufficient, and the use of the molded product was limited.

Further, since the direct polymerization method does not use diisocyanate or acid chloride, there is no problem of gelation or generation of hydrogen chloride, but 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 anhydrous group, there is a problem that the regularity in the molecular chain is low. As a result, when the obtained polyamide-imide was used in a molded product, the physical properties of the molded product were not sufficient, and the use of the molded product was limited.

Since all of the above three methods for producing polyamide-imide are performed in a solution, it is necessary to separate and purify the obtained polyamide-imide solution in order to use the polyamide-imide as a molded product.

The present invention solves the above problems, and has high regularity of molecular structure, few branched structures, does not contain hydrogen halide, and does not need to be separated and purified in a subsequent step. Various molding materials and compositions. It is an object of the present invention to provide a polyamide-imide which can be suitably used as a material material.

As a result of diligent studies on the above-mentioned problems, the present inventors have carried out the above-mentioned problems by synthesizing a polyamide-imide from a bisimide dicarboxylic acid composed of a diamine and a tricarboxylic acid anhydride and a diamine same or different from the diamine. We have found that we can solve the problem and arrived at the present invention.

（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):

(In the formula, 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 an aromatic ring or. It represents a trivalent residue having an aliphatic ring, and the hydrogen atom bonded to each ring may be replaced with another atom or atomic group).
(2) A method for producing a polyamide-imide having a repeating unit represented by the above general formula (1), which comprises polymerizing a polyamide-imide from a bisimide dicarboxylic acid and a diamine.
(3) A method for producing a polyamide-imide having a repeating unit represented by the above general formula (1), which comprises polymerizing a polyamide-imide raw material salt composed of a bisimide dicarboxylic acid and a diamine.
(4) A polyamide-imide raw material salt comprising a bisimide dicarboxylic acid and a diamine, which constitute the polyamide-imide represented by the above formula (1).
(5) The above, wherein 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 method for producing a polyamide-imide raw material salt according to the above.
(6) A polyamide-imide resin composition containing the above-mentioned polyamide-imide.

According to the present invention, it can be suitably used as various molding materials and composition materials having high regularity of molecular structure, few branched structures, no hydrogen halide, and no need for separation and purification in a subsequent step. A possible polyamide-imide can be provided.

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

In the above formula (1), R ¹ is centered on 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 benzene ring. Diamine selected from the following chemical formula (3) having a heterocycle, the following chemical formula (4) containing a heterocycle, the chemical formula (5) having a cyclohexane ring at the center, and the diamine represented by the 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 form an aromatic ring or an aliphatic ring. It represents a trivalent residue having, and the hydrogen atom bonded to each ring may be replaced with another atom or atomic group. The number of repeating units is 1 or more, preferably 4 to 1000, and more preferably 20 to 1000.

In formula (2), R ⁶ and R ⁷ independently represent an arylene group or an alkylene group, respectively. It is preferably 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 an alkane divalent group having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, more preferably a methylene group. Is.

n ₁ and n ₂ represent 0 or 1, preferably 0, which are independent and preferably the same, respectively. n ₁ and n ₂ are more preferably 0 for both. 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), the bond at the para position is preferable, and in the case of the following formula (2-3), the bond at the ortho position is preferable.

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

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

R ⁹ and R ¹⁰ independently represent an arylene group or an alkylene group, respectively. It is preferably an arylene group. R ⁹ and R ¹⁰ are preferably the same divalent group. The arylene group is benzene or 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 represent 0 or 1, preferably 1, which are independent and preferably the same, respectively. 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 equation (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 independently represent an arylene group or an arylene alkylene group, respectively. It is preferably an arylene group. R ¹¹ and R ¹² are preferably the same divalent group. The arylene group is benzene or 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 represent 0 or 1, preferably 0, which are independent and preferably the same, respectively. n ₅ and n ₆ are preferably 0 for both. 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 the formula (3), R ¹³ and R ¹⁴ each independently have 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 represent 0 or 1, preferably 0, which are independent and preferably the same, respectively. 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 the positional relationship of the para position, the meta position, and more preferably the meta position.

Wherein ^{(3), R 15} is 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, more preferably an alkyl group having one carbon atom.

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

R ¹⁵ is ^{bonded to the benzene ring with respect to R 13} or R ¹⁴ , preferably 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 formula (3-2).

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

In the formula (5), R ¹⁷ and R ¹⁸ are independently each of an alkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms, and even more preferably a methylene group. Is.

R ¹⁷ and R ¹⁸ are bonded to the cyclohexane ring in the positional relationship of the para-position or the meta-position.

n ₁₁ and n ₁₂ are independent of each other and represent 0 or 1. When n ₁₁ or n ₁₂ is 0, it indicates that the amino group is directly attached to the cyclohexane ring.

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

n ₁₃ represents 1 to 10, preferably 1 to 5, more preferably 1 to 3, and even more preferably 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.

A preferable specific example represented by the formula (5) is a diamine represented by the following chemical formulas (5-1) and (5-2).

In the formula (6), R ²⁰ and R ²¹ are independent, preferably the same, having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms, and even more preferably. Is a methylene group.

n ₁₄ and n ₁₅ represent 0 or 1, preferably 0, which are independent and preferably the same, respectively. When n ₁₄ and n ₁₅ are 0, it indicates that the amino group is directly attached 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 even more preferably a methylene group.

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

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

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

Tricarboxylic acids also include those in which a hydrogen atom bonded to a 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, and 3,4,4'-biphenyltricarboxylic acid. An anhydride, 1,2,4-cyclohexanetricarboxylic acid anhydride, etc., preferably a trimellitic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 3,4,4'-biphenyltricarboxylic acid anhydride, Examples thereof include 1,2,4-cyclohexanetricarboxylic acid anhydride, more preferably trimellitic acid anhydride, or 1,2,4-cyclohexanetricarboxylic acid anhydride, and even more preferably trimellitic acid anhydride. The tricarboxylic acid anhydride may be used alone or in combination of two or more.

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

n ₁₆ represents 1 or 2, preferably 1.

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

When n ₁₆ is 2, it is preferable that the two phenylene groups are 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.

Wherein ^{(7), R 25} is 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, more preferably an alkyl group having one carbon atom.

n ₁₉ represents 0 to 4, preferably 0 to 2, more preferably 0 to 1, and even more preferably 0.

R ²³ and R ²⁴ are independent, preferably the same, methylene groups having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, and more preferably 1 carbon number.

n ₁₇ and n ₁₈ represent 0 or 1, preferably 0, which are independent and preferably the same, respectively. When n ₁₇ and n ₁₈ are 0, it indicates that the amino group is directly bonded to the benzene ring.

Specific examples represented by the formula (7) are m-phenylenediamine, p-phenylenediamine, m-xylenediamine, p-xylylenediamine, benzidine, 4,4'-diaminodiphenylpropane, 4,4'-diamino. It is an aromatic diamine selected from diphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, and 4,4'-diaminodiphenyl ether. Preferably, it is an aromatic diamine selected from m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 4,4'-diaminodiphenyl ether and benzidine. More preferably, it is an aromatic diamine selected from m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, and 4,4'-diaminodiphenyl ether. Even more preferably, it is an aromatic diamine selected from m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine. Of these, m-xylylenediamine and p-xylylenediamine are preferable, and m-xylylenediamine is most preferable.

In the present invention, aromatic diamines containing a fused ring, for example, 1,5-diaminonaphthalene, 3,3-diaminonaphthalene and the like can also be used.

Specific examples of the aliphatic hydrocarbon diamine containing R ² include hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,4-diaminocyclohexane, 1,10-diamino-1, Examples include 10-dimethyldecane.

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

The diamine residue may be used alone or in combination of two or more.

The polyamide-imide (1) of the present invention is synthesized by once synthesizing a polyamide-imide raw material salt composed of a bisimide dicarboxylic acid and a 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 (2) direct reaction of bisimide dicarboxylic acid and diamine.
First, the two-step synthesis method will be described.

(Two-step synthesis method)
In the two-step synthesis method, the polyamide-imide of the present invention can be produced by once synthesizing a polyamide-imide raw material salt composed of a bisimide dicarboxylic acid and a 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 for example, one synthesized from tricarboxylic acid anhydride and diamine may be used.

When bisimide-dicarboxylic acid is synthesized, the reaction between the tricarboxylic acid anhydride and the diamine may be carried out in a solution state or a molten state, or in a solid (powder) state, but may be carried out in a solvent drying step or in a solvent drying step. The solid state is preferable from the viewpoint that it can be used for the synthesis of the polyamide-imide raw material salt powder without requiring a crushing step or the like.

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

The method for obtaining the polyamide-imide raw material salt by the reaction of the bisimide dicarboxylic acid and the diamine may be carried out in a solution state, a melted state, or a solid state. The solid state is preferable from the viewpoint that the polyamide-imide raw material salt powder can be synthesized without requiring a solvent drying step or a pulverization step.

Hereinafter, a method for obtaining a polyamide-imide raw material salt by reacting a bisimide dicarboxylic acid with a 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. This can be achieved by heating above the melting point and adding a diamine.

In order to maintain the solid state of the bisimide dicarboxylic acid and the obtained polyamide-imide raw material salt during the process, the amount of diamine added, the rate of addition, the method of addition, 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 agitated.

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

In the present invention, as described above, the bisimide dicarboxylic acid maintains its solid state. The average particle size of the bisimide dicarboxylic acid is preferably 5 μm to 1 mm, 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 polyamide-imide raw material salt can be accelerated.

The average particle size can be measured by the sedimentation method or the laser diffraction / scattering method, and in the present invention, the value measured by the laser diffraction / scattering method is used.

The diamine is not particularly limited as long as it is in a liquid state during the reaction with the solid bisimide dicarboxylic acid, and may be added as a solid or may be added after being heated and melted to form a liquid. From the viewpoint of reducing the particle size of the obtained polyamide-imide raw material salt, it is preferable to add it after heating and melting it into a liquid.
The shorter the heating time, the more preferable the diamine. Therefore, from this viewpoint, the diamine is preferably added in a solid form such as a powder or a granular material which is not heated by itself.

When the diamine is added as a solid, for example, a pollinator equipped with a double damper mechanism can be mentioned. On the other hand, when diamine is added as a liquid, the diamine is heated and melted in a container different from the reaction vessel to make it a liquid, and then the liquid is sent to the reaction vessel, and the liquid diamine is added dropwise 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 carried out after the addition of the diamine or before the addition of the diamine, but the latter is more preferable.

When the bisimide dicarboxylic acid is preheated before the addition of the diamine, the heating temperature is preferably equal to or higher than the melting point of the diamine and lower than the melting point of the bisimide dicarboxylic acid, and is more than (melting point of diamine + 10 ° C.) and (bisimide). It is more preferable that the melting point of the dicarboxylic acid is −5 ° C.) or lower. When the heating temperature exceeds the melting point of the bisimide dicarboxylic acid, the entire reaction system may become liquid and the whole may be agglomerated with the formation of the polyamide-imide raw material salt. On the other hand, when the heating temperature is equal to or lower than the melting point of the diamine, both the bisimide dicarboxylic acid and the diamine may be in a solid state, and the formation reaction of the polyamide-imide raw material salt may hardly proceed.

Within the above range, 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, and more preferably 120 ° C. or higher and 200 ° C. or lower. When the heating temperature exceeds 210 ° C., a polymerization reaction occurs during the reaction for producing the polyamide-imide raw material salt, so that water is generated, and as a result, the obtained polyamide-imide raw material salt is produced due to the generated water. It may be partially melted and fused, or the reaction system may become high pressure. On the other hand, if the heating temperature is less than 100 ° C., the reaction for producing the polyamide-imide raw material salt may be insufficient.

The heating temperature for preheating the bisimide dicarboxylic acid and the reaction temperature for producing the polyamide-imide raw material salt may be the same temperature or different temperatures.

The method of 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 obtained polyamide-imide raw material salt from becoming lumpy and efficiently performing the production reaction, a method of continuously adding diamines or a method of dividing the diamines in appropriate amounts (for example, the total amount of diamines to be added). A method of intermittently adding 1/10 to 1/100 of the amount) is preferable. The addition rate of the diamine is preferably 0.005 to 2.00% by mass / min, preferably 0.01 to 1.00% by mass / min, from the viewpoint of stably maintaining the solid state of the bisimide dicarboxylic acid. Is more preferable. Here, "mass% / min" is the ratio of the low melting point component added in 1 minute to the total amount of the low melting point component finally added. Further, a method in which the above methods are combined, such as a method in which an appropriate amount of diamine is added intermittently and then a diamine is continuously added, may be used.

If 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 diluting 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 size of the obtained polyamide-imide raw material salt is preferably 2 mm or less, more preferably 500 μm or less. By setting the average particle size of the polyamide-imide raw material salt to 2 mm or less, for example, even if water is generated when the polyamide-imide raw material salt is solid-phase polymerized to obtain a polyamide-imide, the water content inside the polyamide-imide raw material salt remains. Since it is easy to come off, there is an advantage that the speed of the polymerization reaction can be increased.

In the method for producing a polyamide-imide raw material salt of the present invention, in order to completely carry out the reaction for producing the polyamide-imide raw material salt, it is preferable to sufficiently stir during the addition of the diamine and after the addition of the diamine is completed. The stirring mechanism provided in the reaction device for reacting the bisimide dicarboxylic acid with the diamine may be appropriately selected according to the type and production amount of the polyamide-imide raw material salt to be produced, such as paddle type, tumbler type, ribbon type and the like. Blenders, mixers, etc. Further, a combination of these may be used.

The reaction device for reacting the bisimide dicarboxylic acid with the diamine is not particularly limited as long as the bisimide dicarboxylic acid and the diamine can be sufficiently stirred, and a known reaction device 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 a heat medium such as steam, a heater or the like is used. A method of heating can be mentioned.

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

By the above method of obtaining a polyamide-imide raw material salt by a reaction of a bisimide dicarboxylic acid and a diamine in a 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. It is possible to provide a granular polyamide-imide raw material salt capable of obtaining a polyamide-imide.

Here, (1) a polyamide-imide raw material salt characterized by being composed of 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. The method for producing a polyamide-imide raw material salt according to (1); and (3) Production of the polyamide-imide raw material salt according to (2) above, wherein the diamine is dissolved in a diluting solvent and added to the bisimide dicarboxylic acid. The invention relating to the method is provided.

The polymerization method of the polyamide-imide raw material salt may be either a melt polymerization method or a solid phase polymerization method. However, since the flow start temperature and the thermal decomposition temperature of the polyamide-imide are often close to each other, the solid phase polymerization method is used. preferable.

In the solid phase polymerization method, the reaction temperature is not particularly limited as long as it is lower than the melting point of the produced polyamide-imide or lower 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, preferably in the range of 0.5 to 8 hours, from the viewpoint of the balance between the molecular weight finally reached and the productivity. Is more preferable. The solid-phase polymerization may be carried out in an inert gas stream such as nitrogen, or may be carried out under reduced pressure. Further, it may be carried out by standing still or while stirring.

In the present invention, the melting point and glass transition temperature of polyamide-imide 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 the temperature up to the measurement limit of 350 ° C., it was regarded as undetected. If the polyamide-imide to be measured is amorphous, the melting point is not measured.

In the solid phase polymerization method, from the viewpoint of omitting the pulverization step after the polymerization, the polyamide-imide raw material salt is heated at a temperature lower than the melting point of the bisimide dicarboxylic acid and higher than 200 ° C., and the polymerization is carried out so as to maintain the solid state thereof. It is preferable to do so. It is more preferably set to (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.

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 polyamide-imide. From the viewpoint of the balance between the molecular weight finally reached and the productivity, the reaction time is preferably in the range of 0.5 to 36 hours after reaching the reaction temperature, and more preferably in the range of 1 to 16 hours. preferable. The melt polymerization may be carried out in an inert gas stream such as nitrogen, or may be carried out under pressure.

In the method for producing polyamide-imide of the present invention, when the raw material is supplied to the reaction vessel, a terminal sequestering agent, a polymerization catalyst, and other additives are added in addition to the polyamide-imide raw material salt as long as the effects of the present invention are not impaired. You may.

The terminal sequestering agent seals the terminal functional group of the polymer. Specific examples of the terminal blocker include acetic acid, lauric acid, benzoic acid, octylamine, cyclohexylamine, and aniline. The amount of the terminal sequestering agent used is preferably 5 mol% or less based on the total number of moles of the polyamide-imide raw material salt.

Specific examples of the polymerization catalyst include phosphoric acid, phosphorous acid, hypophosphorous acid and salts thereof. The amount of the polymerization catalyst used is preferably 2 mol% or less with respect to the total number of moles of the polyamide-imide raw material salt because it causes deterioration of product performance and processability.

Examples of other additives include the following various additives, for example, various fillers and stabilizers. The amount of the additive used is preferably 30% by mass or less based on the total mass of the polyamide-imide raw material salt from the viewpoint of the reactivity of the bisimide dicarboxylic acid salt.

Next, the one-step synthesis method will be described.
(One-step synthesis method)
The polyamide-imide of the present invention can be produced by heating a bisimide dicarboxylic acid at a temperature below its melting point, exceeding 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 carried out after the addition of the diamine or before the addition of the diamine, but the latter is more preferable.

It is more preferable that the heating temperature when the bisimide dicarboxylic acid is preheated before the addition of the diamine is (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 the bisimide dicarboxylic acid is appropriately set within the above temperature range according to the bisimide carboxylic acid, the diamine, and a combination thereof.

Other conditions (conditions and methods for maintaining the solid state of bisimide dicarboxylic acid, addition amount of diamine, addition rate, addition method, etc.) can be carried out 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 polyamide-imide raw material salt. By using the polyamide-imide raw material salt, it is possible to obtain a polyamide-imide having a higher regularity of the molecular structure and a smaller number of branched structures.

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

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

The degree of polymerization can generally be measured by estimation by gel permission chromatography, nuclear magnetic resonance (NMR), solution viscosity method, or melt viscosity method.

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

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

Further, the polyamide-imide obtained by the present invention has a melting point of at least 150 ° C., higher at least 250 ° C., higher at least 300 ° C., and even higher at least 350 ° C. when crystalline. be able to.

In addition, the polyamide-imide obtained according to the present invention can have a 5% weight loss temperature of at least 300 ° C., higher at least 350 ° C., higher at least 380 ° C., and even higher at at least 480 ° C.

If necessary, various additives may be added to the polyamide-imide of the present invention to prepare a polyamide-imide resin composition. Specific examples of the additive include fibrous reinforcing material, plate-like reinforcing material, impact-resistant improving material, antistatic agent, conductivity-imparting agent, heat-conductive filler, aliphatic polyamide, semi-aromatic polyamide, and amorphous polyamide. , Other resin components, heat stabilizers, light stabilizers, slidability improvers, flame retardants, flame retardants, pigments and the like. The additives may be used alone or in combination.

Specific examples of the fibrous reinforcing material include carbon fiber, glass fiber, boron fiber, asbestos fiber, polyvinyl alcohol fiber, polyester fiber, acrylic fiber, total aromatic polyamide fiber, polybenzoxazole fiber, polytetrafluoroethylene fiber, and Kenaf. Examples thereof include fibers, bamboo fibers, hemp fibers, bagas fibers, high-strength polyethylene fibers, alumina fibers, silicon carbide fibers, potassium titanate fibers, brass fibers, stainless steel fibers, steel fibers, ceramics fibers, genbuiwa fibers, sepiolite, and parigol skit. By adding the fibrous reinforcing material, the mechanical strength can be improved. Of these, glass fiber, carbon fiber, and metal fiber are preferable because they have high heat resistance and are easily available. 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 vinylsilane-based, acrylicsilane-based, epoxysilane-based, and aminosilane-based, and aminosilane-based coupling agents are preferable because they have high adhesion to polyamide-imide.

The average fiber length of the fibrous reinforcing material is preferably 0.1 to 7 mm, 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 polyamide-imide can be improved without adversely affecting the moldability. The average fiber diameter is preferably 3 to 20 μm, more preferably 5 to 13 μm. When the average fiber diameter is 3 to 20 μm, the mechanical properties of the polyamide-imide can be improved while reducing breakage during melt-kneading. The cross-sectional shape is preferably a circular cross-section, but may be rectangular, elliptical (flat), or other irregular cross-section, if necessary.

When a fibrous reinforcing material is used, its content is preferably 5 to 200 parts by mass, more preferably 10 to 180 parts by mass, and 20 to 150 parts by mass with respect to 100 parts by mass of polyamide-imide. It is more preferable to use 30 to 130 parts by mass, and most preferably 30 to 130 parts by mass.

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

When a plate-shaped reinforcing material is used, its content is preferably 40 parts by mass or less, and more preferably 20 parts by mass or less, based on 100 parts by mass of polyamide-imide.

Specific examples of the impact resistance improving material include (ethylene and / or propylene) / α-olefin polymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid). Examples thereof include olefin-based polymers such as and / or unsaturated carboxylic acid ester) -based copolymers, and elastomers such as styrene-based elastomers. By adding the impact resistance improving material, the impact resistance and the weld strength can be improved.

Specific examples of antistatic agents include anionic antistatic agents, cationic antistatic materials, and nonionic antistatic agents, and specific examples of conductivity-imparting agents include carbon black, carbon fibers, and metal fibers. Be done. By adding an antistatic agent or a conductivity-imparting agent, the surface resistivity value and the volume resistivity value can be lowered.

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

Specific examples of the aliphatic polyamide include polyamide 6, polyamide 66, polyamide 610, polyamide 11, and polyamide 12. By adding the aliphatic polyamide, the 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 are a polycondensate of isophthalic acid / terephthalic acid / 1,6-hexanediamine / bis (3-methyl-4-aminocyclohexyl) methane, and terephthalic acid / 2,2,4-trimethyl. Polycondensation of -1,6-hexanediamine / 2,4,4-trimethyl-1,6-hexanediamine, polycondensation of isophthalic acid / bis (3-methyl-4-aminocyclohexyl) methane / ω-laurolactum Body, 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-hexanediamine polycondensate, isophthalic acid / bis Examples thereof include a polycondensate of (3-methyl-4-aminocyclohexyl) methane / ω-laurolactum and a polycondensate of isophthalic acid / terephthalic acid / other diamine components. The amorphous polyamide refers to a polyamide having a heat of fusion of 1 cal / g or less measured at a heating rate of 16 ° C./min in a nitrogen atmosphere using a differential scanning calorimeter (DSC). By adding amorphous polyamide, surface gloss and the like can be improved.

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

Specific examples of other resin components include polyimide resins, polyetherimide resins, polyurea resins, epoxy resins, polyester resins, polyesterimide resins, polyurethane resins, polyarylate resins, and polycarbonate resins. Polyether ether ketone, polyphenylene sulfide, polyphenyl sulfone, polysulfone, polyether sulfone, 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, silicone resin and the like. By adding other resin components, heat resistance, strength, flexibility and the like can be improved.

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

When a heat stabilizer is used, its content is preferably 6 parts by mass or less, and more preferably 3 parts by mass or less, based on 100 parts by mass of polyamide-imide.

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

When a light stabilizer is used, its content is preferably 6 parts by mass or less, and more preferably 3 parts by mass or less, based on 100 parts by mass of polyamide-imide.

Specific examples of the slidability improving material include fluororesins such as polytetrafluoroethylene and silicones such as polydimethylsiloxane and fluorine-modified polydimethylsiloxane.

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

Specific examples of the brominated flame retardant include brominated polystyrene, polybrominated styrene, and brominated polyphenylene ether. Among them, those containing 40 to 80% by mass of bromine are preferable, and those containing 50 to 70% by mass of bromine are more preferable, because the effect of improving flame retardancy is high. These brominated flame retardants are used in combination with flame retardants such as antimony trioxide, antimony tetroxide, antimony tetroxide, sodium antimonate, tin oxide (IV), iron (III) oxide, zinc oxide, and zinc borate. It is preferable to do so.

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

Specific examples of the phosphorus-containing flame retardant include phosphate ester compounds, phosphinates and diphosphinates.

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 the 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 metal hydrated flame retardant include aluminum hydroxide, boehmite, magnesium hydroxide, calcium hydroxide, and calcium aluminates.

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

When a flame retardant is used, its content is preferably 5 to 100 parts by mass, more preferably 7.5 to 40 parts by mass, and 10 to 30 parts by mass with respect to 100 parts by mass of polyamide-imide. Is more preferable.

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

When a pigment is used, its content is preferably 10 to 60 parts by mass, more preferably 15 to 50 parts by mass, and 20 to 40 parts by mass with respect to 100 parts by mass of polyamide-imide. More preferred.

When the above-mentioned various additives are contained at the time of polymerization, the amount including those amounts is the amount of the additives in the resin composition.

The polyamide-imide of the present invention and its resin composition can be made into a molded product by injection molding, compression molding or extrusion molding. Above all, injection molding is preferable. The injection molding machine used for injection molding is not particularly limited, and examples thereof include a screw in-line type injection molding machine and a plunger type injection molding machine. Polyamide-imide, which is heated and melted in the cylinder of an injection molding machine, is weighed for each shot, injected into a 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 polyamide-imide, and more preferably lower than the weight reduction start temperature. Even more preferably, the temperature is (glass transition temperature + 50 ° C.) or higher and (5% weight loss temperature −10 ° C.) or lower.

The polyamide-imide used for injection molding is preferably sufficiently dried. Polyamide-imide, which has a high water content, foams in the cylinder of an injection molding machine, and it may be difficult to obtain an optimum molded product. The water content of the polyamide-imide used for injection molding is preferably less than 0.3% by mass, more preferably less than 0.1% by mass.

The polyamide-imide of the present invention is excellent in heat resistance, chemical resistance, mechanical strength, and moldability. Therefore, a wide range of parts such as automobile parts, electrical and electronic parts, sliding parts, tube-related parts, household products, metal coating agents, 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. Further, the polyamide-imide or its resin composition of the present invention can be used as a resin solution by dissolving or dispersing it in a solution, and can be suitably applied to applications such as paints, varnishes and prepregs.

Specific examples of automobile parts include base plates used for pedestals 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 rears. 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 retainer, gear, wire harness, relay block, sensor housing, encapsulation, ignition coil, distributor, water pump renlet, water pump outlet , Thermostat housing, cooling fan, fan shroud, oil pan, oil filter housing, oil filter cap, oil level gauge, timing belt cover, engine cover, fuel tank, fuel tube, fuel cutoff valve, quick connector, canister, fuel delivery Examples include pipes, fuel filler necks, fuel piping joints, lamp reflectors, lamp housings, lamp extensions, lamp sockets, and the like.

Specific examples of electrical and electronic components include connectors, HDD lamp rails, board reinforcement plates, LED reflectors, switches, sensors, sockets, capacitors, jacks, fuse holders, relays, coil bobbins, resistors, ICs, LED housings, and lithium batteries. Examples include a binder for an electrode of a next battery or the like.

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

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

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

Specific examples of the metal coating agent include metal coating agents for water-related parts such as liquid metal pipes and water tanks.

Specific examples of industrial material supplies include tire cords, belts, bulletproof clothing, protective clothing, flameproof clothing, work clothing, concrete reinforcements, asbestos substitutes, ropes, shoe members, fishing threads, fishing nets, sail cloth, cushioning materials, etc. Examples include blades for wind power generation, felts for papermaking, copying machine 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 substrate, a seamless belt, a speaker diaphragm, and a film capacitor.

The paint and varnish contain the polyamide-imide of the present invention as a binder resin. As the paint, other materials used for the varnish, and the amount used, ordinary known materials can be applied. Solvents include water, methanol, ethanol, propanol, isopropanol, 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, etc. or a solvent containing these may be used.

The polyamide-imide resin solution of the present invention can also be used in the production of prepregs. The prepreg can be obtained by impregnating or coating a reinforcing fiber cloth with a resin solution in which a solvent-soluble polyamide-imide of the present invention and a compound that further reacts and polymerizes with the resin are dissolved in an organic solvent, and then dried. it can. Specific examples of the compound that further reacts and polymerizes with the polyamide-imide resin include the polyamide-imide 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 thereof include compounds, polyurethane-based resin compounds, polyarylate-based 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, and aliphatic chain. Epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol diglycidyl etherified product, naphthalenediol diglycidyl etherified product, phenol diglycidyl etherified product, alcohol diglycidyl etherified product Examples include glycidyl etherified products, their alkyl substituents, epoxies or hydrogenated products. 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 diisocyanate. Examples thereof include aromatic diisocyanates such as isocyanate and 2,4-tolylene dimer, hexamethylene diisocyanate, aliphatic diisocyanates such as 4,4-methylenebis (cyclohexylisocyanate) 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 and dimethylacetamide (DMAc). , Dimethylformamide (DMF), dimethylsulfoxide, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, sulfolane, cyclohexanone and the like, or solvents containing these.

For application to prepregs, the polyamideimide of the present invention can be applied to known prepregs such as polyethylene resin, polypropylene resin, polyether ether ketone resin, polyether sulfone resin, polyphenyl sulfone resin, epoxy resin, polyimide resin, and polyamide resin. , Polycarbonate resin, polyethylene terephthalate resin, polyurethane resin, polyester resin, fluoropolymer, etc. may be used as an additive to the prepreg, and may be used so as to impart the characteristics of the polyamideimide of the present invention.

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited thereto.

Identification of bisimide dicarboxylic acid The molecular weight of the principal component was determined by measurement under the following conditions using a high performance liquid chromatograph mass spectrometer (LC / MS).
Sample: Bisimidedicarboxylic acid / DMSO solution (200 μg / mL)
Equipment: Bruker Daltonix microTOF2-kp
Column: Cadenza CD-C18 3 μm 2 mm × 150 mm
Mobile phase: (Mobile phase A) 0.1% aqueous formic acid 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: Perkin Elmer System 2000 infrared spectroscope Method: KBr method Accumulation number: 64 scans (resolution 4 cm ^-1 )

The general formula of the bisimide dicarboxylic acid used in the preparation of the polyamide-imide raw material salt is shown below.

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

Diamine name and structure used in R ¹ of the bisimide dicarboxylic acid

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

It was confirmed by IR measurement and mass spectrometry by GC / MS that the bisimide dicarboxylic acid having the above structure could be synthesized. It 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 weights of the main components are 760 (m / z) (structure 1), 642 (m / z) (structure 2), 562 (m / z) (structure 4), 472 (m / m /. z) (Structure 5), 472 (m / z) (Structure 6), 492 (m / z) (Structure 8), 560 (m / z) (Structure 9).

Structures 3 and 7
To a mixing tank equipped with a double helical type stirring blade, 33.4 mol% of a diamine having a granular structure 3 or 7 was added, and the mixture was heated to 175 ° C. under a nitrogen atmosphere while stirring. While confirming that the diamine of structure 3 or 7 maintains its shape there, a pollinator equipped with a double damper mechanism is used to add 66.6 mol% of solid trimellitic anhydride (melting point: 168 ° C.). Used at a rate of 0.4% by weight / min) to give a mixture. The contents were granular during and after the addition.
Then, the mixture was heated to 300 ° C. with stirring, and heated at 300 ° C. for 2 hours.

It was confirmed by IR measurement and mass spectrometry by GC / MS that the bisimide dicarboxylic acid having the above structure could be synthesized. It 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. Further, from the result of mass spectrometry, the molecular weight of the principal component was estimated to be 778 (m / z) (structure 3) and 537 (m / z) (structure 7).

Structure 10
To a mixing tank equipped with a double helical type stirring blade, 66.6 mol% of granular trimellitic anhydride (melting point: 168 ° C.) was added, and the mixture was heated to 80 ° C. under a nitrogen atmosphere while stirring. While confirming that the trimellitic anhydride maintains its shape there, 33.4 mol% of the diamine of the structure 10 heated to 80 ° C. was added to 0.28% by mass / min using a liquid feeder. Addition at a rate gave a mixture. The contents were granular during and after the addition.
Then, the mixture was heated to 300 ° C. with stirring, and heated at 300 ° C. for 2 hours.

It was confirmed by IR measurement and mass spectrometry by GC / MS that the bisimide dicarboxylic acid having the above structure could be synthesized. When IR measurement was performed ^{, absorption was confirmed near 1778 cm -1 and} around 1714 cm ^-1 , confirming the formation of an imide bond. Moreover, from the result of mass spectrometry, the molecular weight of the principal component was estimated to be 520 (m / z).

Synthesis of Polyamide-imide Raw Material Salt Example 1
Ribbon blender type reactor with a mixture consisting of 728 parts by mass of bisimide dicarboxylic acid (melting point: undetected 300 ° C. or higher) (average particle size: 450 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite shown in Structure 1. And heated to 170 ° C. with stirring at a rotation speed of 70 rpm under nitrogen flow. Then, 139 parts by mass of m-xylylene diamine (melting point: 14 ° C.) heated to 25 ° C. was added 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-xylylene diamine = 47: 50 (molar ratio)]. The obtained polyamide-imide raw material salt was granular (average particle size: 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 It was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Example 2
A ribbon blender-type reactor containing a mixture of 614 parts by mass of bisimide dicarboxylic acid (melting point: undetected 300 ° C. or higher) (average particle size: 452 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite shown in Structure 2. And heated to 170 ° C. with stirring at a rotation speed of 70 rpm under nitrogen flow. Then, 139 parts by mass of m-xylylene diamine (melting point: 14 ° C.) heated to 25 ° C. was added 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-xylylene diamine = 47: 50 (molar ratio)]. The obtained polyamide-imide raw material salt was granular (average particle size: 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 It was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Example 3
A ribbon blender-type reactor containing a mixture consisting of 745 parts by mass of bisimide dicarboxylic acid (melting point: undetected 300 ° C. or higher) (average particle size: 478 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite shown in Structure 3. And heated to 170 ° C. with stirring at a rotation speed of 70 rpm under nitrogen flow. Then, 139 parts by mass of m-xylylene diamine (melting point: 14 ° C.) heated to 25 ° C. was added 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-xylylene diamine = 47: 50 (molar ratio)]. The obtained polyamide-imide raw material salt was granular (average particle size: 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 It was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Example 4
A ribbon blender-type reactor in which a mixture consisting of 538 parts by mass of bisimide dicarboxylic acid (melting point: undetected 300 ° C. or higher) (average particle size: 355 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite shown in Structure 4 is used. And heated to 170 ° C. with stirring at a rotation speed of 70 rpm under nitrogen flow. Then, 139 parts by mass of m-xylylene diamine (melting point: 14 ° C.) heated to 25 ° C. was added 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-xylylene diamine = 47: 50 (molar ratio)]. The obtained polyamide-imide 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 It 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 with a mixture consisting of 451 parts by mass of bisimide dicarboxylic acid (melting point: undetected 300 ° C. or higher) (average particle size: 394 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite shown in structure 5. And heated to 170 ° C. with stirring at a rotation speed of 70 rpm under nitrogen flow. Then, 139 parts by mass of m-xylylene diamine (melting point: 14 ° C.) heated to 25 ° C. was added 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-xylylene diamine = 47: 50 (molar ratio)]. The obtained polyamide-imide raw material salt was granular (average particle size: 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 It 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 with a mixture consisting of 451 parts by mass of bisimide dicarboxylic acid (melting point: undetected 300 ° C. or higher) (average particle size: 479 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite shown in structure 6. And heated to 170 ° C. with stirring at a rotation speed of 70 rpm under nitrogen flow. Then, 139 parts by mass of m-xylylene diamine (melting point: 14 ° C.) heated to 25 ° C. was added 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-xylylene diamine = 47: 50 (molar ratio)]. The obtained polyamide-imide raw material salt was granular (average particle size: 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 It 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 with a mixture consisting of 514 parts by mass of bisimide dicarboxylic acid (melting point: undetected 300 ° C. or higher) (average particle size: 364 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite shown in structure 7. And heated to 170 ° C. with stirring at a rotation speed of 70 rpm under nitrogen flow. Then, 139 parts by mass of m-xylylene diamine (melting point: 14 ° C.) heated to 25 ° C. was added 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-xylylene diamine = 47: 50 (molar ratio)]. The obtained polyamide-imide raw material salt was granular (average particle size: 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 It was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Example 8
A ribbon blender-type reactor in which a mixture consisting of 471 parts by mass of bisimide dicarboxylic acid (melting point: undetected 300 ° C. or higher) (average particle size: 454 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite shown in Structure 8 is used. And heated to 170 ° C. with stirring at a rotation speed of 70 rpm under nitrogen flow. Then, 139 parts by mass of m-xylylene diamine (melting point: 14 ° C.) heated to 25 ° C. was added 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-xylylene diamine = 47: 50 (molar ratio)]. The obtained polyamide-imide raw material salt was granular (average particle size: 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 It 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 with a mixture consisting of 536 parts by mass of bisimide dicarboxylic acid (melting point: undetected 300 ° C. or higher) (average particle size: 463 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite shown in structure 9. And heated to 170 ° C. with stirring at a rotation speed of 70 rpm under nitrogen flow. Then, 139 parts by mass of m-xylylene diamine (melting point: 14 ° C.) heated to 25 ° C. was added 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-xylylene diamine = 47: 50 (molar ratio)]. The obtained polyamide-imide raw material salt was granular (average particle size: 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 It 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 with a mixture consisting of 497 parts by mass of bisimide dicarboxylic acid (melting point: undetected 300 ° C. or higher) (average particle size: 477 μm) and 0.593 parts by mass of anhydrous sodium hypophosphite shown in structure 10. And heated to 170 ° C. with stirring at a rotation speed of 70 rpm under nitrogen flow. Then, 139 parts by mass of m-xylylene diamine (melting point: 14 ° C.) heated to 25 ° C. was added 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-xylylene diamine = 47: 50 (molar ratio)]. The obtained polyamide-imide raw material salt was granular (average particle size: 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 It was confirmed by the disappearance of the peak derived from the melting point of m-xylylenediamine by differential scanning calorimetry (DSC).

Synthesis of polyamide-imide

1. 1. Analytical method (1) Melting point and glass transition temperature 5 mg of polyamide-imide is heated at 20 ° C / min from 25 ° C to 350 ° C in a nitrogen atmosphere using a differential scanning calorimeter (“DSC8500” manufactured by PerkinElmer). (1st Scan) and held at 350 ° C. for 5 minutes. Then, the temperature was lowered to 25 ° C. at 500 ° C./min, held at 25 ° C. for 5 minutes, and then further heated to 350 ° C. at 20 ° C./min (2nd Scan). Then, the peak top temperature of the crystal melting peak observed in the 1st Scan was defined as the melting point, and the midpoint between the temperatures of the two bending points derived from the glass transition observed in the 2nd Scan was defined as the glass transition temperature.

(2) 5% weight loss temperature Using a differential thermogravimetric simultaneous measuring device (TG / DTA "TG / DTA7200" manufactured by Hitachi High-Tech Science Co., Ltd.), 10 from 30 ° C to 800 ° C under a nitrogen atmosphere of 200 mL / min. The temperature was raised at ° C / min. The temperature at which the temperature decreased by 5% by weight with respect to the weight before the temperature rise was defined as the thermal decomposition temperature.

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

The glass transition temperature of the obtained polyamide-imide was 230 ° C., and the 5% weight loss temperature was 390 ° C.

In addition, in the measurement of nuclear magnetic resonance (NMR), when 10 mg of the 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-that 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 in the presence of m-xylylene diamine between the amide bond and the imide bond. ^{Since no peak derived from 13} C at the 2-position of xylylene diamine was observed, the obtained polyamide-imide has a structure in which the repeating units represented by the formula (1) are linearly connected. It was confirmed that.

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

The glass transition temperature of the obtained polyamide-imide was 220 ° C., and the 5% weight loss temperature was 390 ° C.

In addition, in the measurement of nuclear magnetic resonance (NMR), when 10 mg of the 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 that 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 in the presence of m-xylylene diamine between the amide bond and the imide bond. ^{Since no peak derived from 13} C at the 2-position of −xylylene diamine was observed, the obtained polyamide-imide had a structure in which the repeating units represented by the formula (1) were linearly connected. It was confirmed that there was.

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

The glass transition temperature of the obtained polyamide-imide was 226 ° C., and the 5% weight loss temperature was 390 ° C.

In addition, in the measurement of nuclear magnetic resonance (NMR), when 10 mg of the 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 that 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 in the presence of m-xylylene diamine between the amide bond and the imide bond. ^{Since no peak derived from 13} C at the 2-position of −xylylene diamine was observed, the obtained polyamide-imide had a structure in which the repeating units represented by the formula (1) were linearly connected. It was confirmed that there was.

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

The glass transition temperature of the obtained polyamide-imide was 220 ° C., and the 5% weight loss temperature was 390 ° C.

In addition, in the measurement of nuclear magnetic resonance (NMR), when 10 mg of the 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 that 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 in the presence of m-xylylene diamine between the amide bond and the imide bond. ^{Since no peak derived from 13} C at the 2-position of −xylylene diamine was observed, the obtained polyamide-imide had a structure in which the repeating units represented by the formula (1) were linearly connected. It was confirmed that there was.

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

The glass transition temperature of the obtained polyamide-imide was 205 ° C., and the 5% weight loss temperature was 390 ° C.

In addition, in the measurement of nuclear magnetic resonance (NMR), when 10 mg of the 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 that 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 in the presence of m-xylylene diamine between the amide bond and the imide bond. ^{Since no peak derived from 13} C at the 2-position of −xylylene diamine was observed, the obtained polyamide-imide had a structure in which the repeating units represented by the formula (1) were linearly connected. It was confirmed that there was.

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

The glass transition temperature of the obtained polyamide-imide was 200 ° C., and the 5% weight loss temperature was 390 ° C.

In addition, in the measurement of nuclear magnetic resonance (NMR), when 10 mg of the 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 that 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 in the presence of m-xylylene diamine between the amide bond and the imide bond. ^{Since no peak derived from 13} C at the 2-position of −xylylene diamine was observed, the obtained polyamide-imide had a structure in which the repeating units represented by the formula (1) were linearly connected. It was confirmed that there was.

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

The glass transition temperature of the obtained polyamide-imide was 230 ° C., and the 5% weight loss temperature was 390 ° C.

In addition, in the measurement of nuclear magnetic resonance (NMR), when 10 mg of the 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 that 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 in the presence of m-xylylene diamine between the amide bond and the imide bond. ^{Since no peak derived from 13} C at the 2-position of −xylylene diamine was observed, the obtained polyamide-imide had a structure in which the repeating units represented by the formula (1) were linearly connected. It was confirmed that there was.

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

The glass transition temperature of the obtained polyamide-imide was 185 ° C., and the 5% weight loss temperature was 360 ° C.

In addition, in the measurement of nuclear magnetic resonance (NMR), when 10 mg of the 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 that 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 in the presence of m-xylylene diamine between the amide bond and the imide bond. ^{Since no peak derived from 13} C at the 2-position of −xylylene diamine was observed, the obtained polyamide-imide had a structure in which the repeating units represented by the formula (1) were linearly connected. It was confirmed that there was.

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

The glass transition temperature of the obtained polyamide-imide was 190 ° C., and the 5% weight loss temperature was 360 ° C.

In addition, in the measurement of nuclear magnetic resonance (NMR), when 10 mg of the 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 that 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 in the presence of m-xylylene diamine between the amide bond and the imide bond. ^{Since no peak derived from 13} C at the 2-position of −xylylene diamine was observed, the obtained polyamide-imide had a structure in which the repeating units represented by the formula (1) were linearly connected. It was confirmed that there was.

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

The glass transition temperature of the obtained polyamide-imide was 175 ° C., and the 5% weight loss temperature was 365 ° C.

In addition, in the measurement of nuclear magnetic resonance (NMR), when 10 mg of the 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 that 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 in the presence of m-xylylene diamine between the amide bond and the imide bond. ^{Since no peak derived from 13} C at the 2-position of −xylylene diamine was observed, the obtained polyamide-imide had a structure in which the repeating units represented by the formula (1) were linearly connected. It was confirmed that there was.

Claims (8)

Method of making a polyamide-imide having a repeating unit represented by the following general formula (1), characterized in that polymerizing a polyamide-imide material salt comprising bisimide dicarboxylic acid and diamine:

(In the formula (1), R ¹ is centered on the following chemical formula (2) having at least two benzene rings, the following chemical formula (3) having a benzene ring at the center, the following chemical formula (4) containing a heterocycle, and a cyclohexane ring. Represents a divalent residue given by a diamine selected from the chemical formula (5) having the chemical formula (5) and the chemical formula (6) having at least two cyclohexane rings;
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 the hydrogen atom bonded to each ring may be replaced with another atom or atomic group;

In formula (2), R ⁶ and R ⁷ independently represent an arylene group or an alkylene group; n ₁ and n ₂ independently represent 0 or 1, respectively; R ⁵ represents the following formula ( It is a divalent group represented by 2-1) to (2-3).

In formula (2-1), R ⁸ represents an arylene group or an arylene alkylene arylene group;
In formula (2-2), R ⁹ and R ¹⁰ independently represent an arylene group or an alkylene group; n ₃ and n ₄ independently represent 0 or 1, respectively;
In formula (2-3), R ¹¹ and R ¹² independently represent an arylene group or an arylene alkylene group; n ₅ and n ₆ independently represent 0 or 1, respectively;
In formula (3), R ¹³ and R ¹⁴ each independently represent an alkylene group; n ₇ and n ₈ independently represent 0 or 1, respectively; R ¹⁵ has 1-3 carbon atoms. Represents an alkyl group; n ₉ represents 1-4;
In formula (4), R ¹⁶ represents an alkyl or aryl group; n ₁₀ represents 0 or 1;
In formula (5), R ¹⁷ and R ¹⁸ independently represent 1 to 5 alkylene groups having 1 to 5 carbon atoms; n ₁₁ and n ₁₂ independently represent 0 or 1, respectively; R ¹⁹ represents carbon. Represents an alkyl group of numbers 1 to 3; n ₁₃ represents 1 to 10;
In formula (6), R ²⁰ and R ²¹ each independently represent an alkylene group having 1 to 5 carbon atoms; n ₁₄ and n ₁₅ independently represent 0 or 1, respectively; R ²² represents carbon. Represents an alkylene group of numbers 1-3. ) . The method for producing a polyamide-imide according to claim 1, wherein the number of repeating units is 4 to 1000. The method for producing a polyamide-imide according to claim 1 or 2, which has a glass transition temperature of at least 100 ° C. A polyamide-imide raw material salt comprising a bisimide dicarboxylic acid and a diamine, which constitute the polyamide-imide represented by the formula (1) according to claim 1. The fourth aspect of claim 4, wherein 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 polyamide-imide raw material salt. A polyamide-imide resin composition containing a polyamide-imide and a fibrous reinforcing material produced by the method according to any one of claims 1 to 3. The polyamide-imide resin composition according to claim 6 , further containing an antioxidant. The repeating unit represented by the general formula (1) according to any one of claims 1 to 3, wherein the bisimide dicarboxylic acid and the diamine are polymerized at a temperature lower than the melting point of the bisimide dicarboxylic acid and at 200 ° C. or higher. A method for producing a polyamide-imide having.