JP2018058969A - Polyamide imide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide imide resin composition having more excellent mechanical characteristics than those of a polyamide resin composition using conventional polyamide imide.SOLUTION: A polyamide imide resin composition contains polyamide imide having repeating units represented by formula (1), and a reinforcement material. In formula (1), Rand Reach independently represent a divalent residue having an aromatic ring, an aliphatic ring or aliphatic hydrocarbon ring; and Rand Reach independently represent a trivalent residue having an aromatic ring, an aliphatic ring or aliphatic hydrocarbon.SELECTED DRAWING: None

Description

  The present invention relates to a polyamideimide resin composition having excellent mechanical properties.

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

  Conventionally, as a method for producing polyamideimide, three methods of an isocyanate method, an acid chloride method, and a direct polymerization method are known.

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

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

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

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

  In the isocyanate method, since diisocyanate is used as a raw material, in the initial stage of the reaction, in addition to the amide bond and the imide bond, a urea bond is generated by a side reaction, and a high-purity polyamideimide cannot be obtained, or a branched structure is generated. As a result, there was a problem that a gelation phenomenon derived from a branched structure occurred and a linear polymer having a high degree of polymerization could not be obtained.

  In addition, the acid chloride method yields a polyamideimide having a relatively low side reaction and a low cross-linking structure and a high linearity, but has a problem that a highly corrosive hydrogen chloride is by-produced and remains in the polyamideimide. It was. Further, the acid chloride method has a problem that the regularity in the molecular chain is low because the amine terminal of the diamine reacts with both the chloride terminal and the anhydride group of the aromatic tricarboxylic acid anhydride chloride.

  In addition, since the direct polymerization method does not use diisocyanate or acid chloride, there is no problem of gelation or generation of hydrogen chloride. However, like the acid chloride method, the amine terminal of the diamine is an aromatic tricarboxylic acid anhydride. Since it reacts with both the carboxyl terminal and the anhydride group, there is a problem that the regularity in the molecular chain is low.

  From the above problems, when a conventional polyamideimide is used for a molded product, the strength of the molded product is not sufficient, and the application to be used is limited.

  This invention solves the said subject, Comprising: It aims at providing the polyamideimide resin composition which has a mechanical characteristic superior to the polyamideimide resin composition using the conventional polyamideimide. It is.

  As a result of intensive studies, the present inventors use a polyamideimide obtained from a bisimide dicarboxylic acid composed of a diamine and a tricarboxylic acid anhydride and a diamine that is the same as or different from the diamine. As a result, the inventors have found that the above problems can be solved, and have reached the present invention.

That is, the gist of the present invention is as follows.
(1) Polyamideimide resin composition containing a polyamideimide having a repeating unit represented by the general formula (1) and a reinforcing material:
(Wherein R ¹ and R ² independently represent a divalent residue having an aromatic ring, an aliphatic ring or an aliphatic hydrocarbon, and R ³ and R ⁴ independently represent an aromatic ring or A trivalent residue having an aliphatic ring is shown, and a hydrogen atom bonded to each ring may be substituted with another atom or atomic group.
(2) The polyamideimide resin composition according to (1), wherein the reinforcing material is at least one fibrous reinforcing material selected from the group consisting of glass fiber, carbon fiber, and stainless steel fiber.
(3) The polyamideimide resin composition according to (1) or (2), further containing an antioxidant.
(4) The polyamideimide resin composition according to any one of (1) to (3), wherein the number of repeating units of polyamideimide is 4 to 1000.
(5) The polyamideimide resin composition according to any one of (1) to (4), wherein the polyamideimide has a glass transition temperature of at least 100 ° C.
(6) A molded article obtained by molding the polyamideimide resin composition according to any one of (1) to (5).

  ADVANTAGE OF THE INVENTION According to this invention, the polyamide-imide resin composition which has the outstanding mechanical characteristic can be provided rather than the polyamide-imide resin composition using the conventional polyamide-imide.

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

In the above formula, 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 This represents a trivalent residue having an aliphatic ring, and the hydrogen atom bonded to each ring may be substituted with another atom or atomic group. The number of repeating units is shown as an average value obtained from the number average molecular weight, and is 2 or more, preferably 3 to 1000, more preferably 3 to 500, even more preferably 3 to 30, most preferably 3 to 25. .

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

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

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

In formula (1), R ¹ and R ² may be the same or different and each represents a divalent residue having an aromatic ring, an aliphatic ring or an aliphatic hydrocarbon.

R ¹ is preferably a divalent residue derived from an aromatic diamine, aromatic amine ether, aliphatic cyclic diamine or aliphatic hydrocarbon diamine, more preferably derived from an aromatic diamine, aromatic amine ether or aliphatic diamine. It is a divalent residue. R ¹ is still more preferably a divalent residue derived from an aromatic diamine represented by the following formula (2) and an aromatic amine ether represented by the following formula (3). The diamine may include —O— and —S—, one or more hydrogen atoms may be substituted with halogen, and may have a side chain.

In the formula (2), n ₁ represents 1 or 2, preferably 1.

When n ₁ is 1, R ⁵ and R ⁶ are bonded in the ortho-position, meta-position, or para-position, preferably in the meta-position or para-position.

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

R ⁷ is an alkyl group having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, more preferably 1 carbon atom.

n ₄ represents 0 to 4, preferably 0 to 3, more preferably 0 to 2, even more preferably 0 to 1, and most preferably 0.

R ⁵ and R ⁶ are each independently, preferably the same, an alkylene group having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, more preferably 1 carbon atom.

n ₂ and n ₃ each independently represents 0 or 1, preferably the same. When n ₂ and n ₃ are 0, the amino group is directly bonded to the benzene ring.

  Specific examples of the diamine represented by the general formula (2) include m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, benzidine, 4,4′-diaminodiphenylpropane, 4, An aromatic diamine selected from 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 2,4-tolylenediamine, and 2,6-tolylenediamine. An aromatic diamine selected from m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, and benzidine is preferable. More preferred is an aromatic diamine selected from m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine. Even more preferably, an aromatic selected from m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, especially m-xylylenediamine, p-xylylenediamine, p-phenylenediamine. Diamine.

Wherein (3), _{n 5} is 1 to 4, preferably 1 to 3, more preferably 1 to 2, even more preferably 1 integer.

R ⁸ and R ⁹ may be the same or different and are alkyl groups having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, and more preferably 1 carbon atom.

n ₆ and n ₇ may be the same or different, and are preferably the same, 0 to 4, preferably 0 to 3, more preferably 0 to 2, even more preferably 0 to 1, Most preferably 0 is represented.

  In formula (3), the amino groups at both ends are bonded to the oxygen atom of the ether at the ortho position, meta position, or para position, preferably para position or meta position, more preferably para position.

  Specific examples of the aromatic amine ether diamine represented by the general formula (3) include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,3′-bis (4-aminophenoxy) benzene, 1 4,4′-bis (4-aminophenoxy) benzene, preferably 4,4′-diaminodiphenyl ether.

In general formula (1), R ² is preferably a divalent residue derived from aromatic diamine, aromatic amine ether, aliphatic cyclic diamine or aliphatic hydrocarbon diamine, more preferably aromatic diamine or aromatic amine. It is a divalent residue derived from an ether or an aliphatic diamine. R ² is still more preferably a divalent residue derived from an aromatic diamine represented by the following formula (4) and an aromatic amine ether represented by the above formula (3). The diamine may include —O— and —S—, one or more hydrogen atoms may be substituted with halogen, and may have a side chain.

In formula (4), n ₈ represents 1 or 2, preferably 1.

When n ₈ is 1, R ¹⁰ and R ¹¹ are bonded in a relationship of ortho position, meta position, or para position, preferably meta position or para position, more preferably meta position.

When n ₈ is 2, the two phenylene groups are preferably bonded in a para-position. An alkylene group having 1 to 3 carbon atoms or a sulfide group may be present between the two phenylene groups.

R ¹² is an alkyl group having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, and more preferably 1 carbon atom.

n ₁₁ is 0-4, preferably 0-3, more preferably 0-2, even more preferably 0-1, and most preferably represents 0.

R ¹⁰ and R ¹¹ are each independently, preferably the same, an alkylene group having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, more preferably 1 carbon atom.

n ₉ and n ₁₀ each independently represents 0 or 1, preferably the same. When n ₉ and n ₁₀ are 0, it means that the amino group is directly bonded to the benzene ring.

  Specific examples of the diamine represented by the general formula (4) include m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, benzidine, 4,4′-diaminodiphenylpropane, 4, 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,3-diaminobenzophenone, 4,4-diaminobenzophenone, 2,4-tolylenediamine, 2,6- An aromatic diamine selected from tolylenediamine. An aromatic diamine selected from m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, and benzidine is preferable. More preferred is an aromatic diamine selected from m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine. Even more preferable is an aromatic diamine selected from m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine. Among these, m-xylylenediamine and p-xylylenediamine are preferable, and m-xylylenediamine is most preferable.

In the present invention, an aromatic diamine containing a condensed ring such as 1,5-diaminonaphthalene, 3,3-diaminonaphthalene, etc. can be used as the aromatic diamine containing R ¹ or R ² .

In the present invention, specific examples of the aliphatic hydrocarbon diamine containing R ¹ or R ² include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 1,4-diaminocyclohexane, 1 , 10-diamino-1,10-dimethyldecane.

In the present invention, specific examples of the aliphatic ring diamine containing R ¹ or R ² include 1,4-diaminocyclohexane, 4,4-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane. 4,4′-methylenebis (cyclohexylamine) and isophoronediamine.

Specific examples of other diamines comprising R ¹ or R ² include diaminosiloxanes such as α, ω-bisaminopolydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, bis (10-aminodecamethylene) tetra Methyldisiloxane, bis (3-aminophenoxymethyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polymethylphenylsiloxane, α, ω-bis (3-aminopropyl) poly (dimethylsiloxane-diphenyl) Siloxane) copolymers.

Further, specific examples of diamines comprising other R ¹ or R ² include diamines having at least two benzene rings and an ether bond, such as 2,2-bis [4- (4-aminophenoxy). It is also possible to apply phenyl] propane, 1,3-bis (4-aminophenoxy) benzene.

Furthermore, as a specific example of the diamine containing R ¹ or R ² , a diamine containing a heterocyclic ring, for example, benzoguanamine can be applied.

As diamine compounds other than those represented by formula (2) and formula (3), diamines comprising R ¹ include 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis. (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 3,3-diaminobenzophenone, 2,4-tolylenediamine (2,4-diaminotoluene), 2,6-tri Range amine (2,6-diaminotoluene), benzoguanamine, 1,4-bis (aminomethyl) cyclohexane, 4,4′-methylenebis (cyclohexylamine), isophorone diamine, and isophorone diamine can be preferably used.

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

  As the diamine constituting the polyamideimide, the same or different diamine used for the bisimide carboxylic acid can be used.

  The polyamideimide used in the present invention is synthesized by (1) once synthesizing a polyamideimide raw material salt composed of bisimide dicarboxylic acid and diamine, and then polymerizing the polyamideimide raw material salt (hereinafter referred to as “two-step synthesis method”). Or (2) can be synthesized in one step (hereinafter referred to as “one-step synthesis method”) by directly reacting bisimide dicarboxylic acid and diamine.

  First, the two-stage synthesis method will be described.

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

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

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

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

  The method of obtaining the polyamideimide raw material salt by the reaction of bisimide dicarboxylic acid and diamine may be performed in a solution state or a molten state, or may be performed in a solid state.

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

  The polyamideimide raw material salt used in the present invention can be achieved by reacting a solid bisimide dicarboxylic acid with a liquid diamine. Specifically, the bisimide dicarboxylic acid is dissolved in a diamine having a melting point lower than its melting point. It can be achieved by heating above the melting point and adding diamine.

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

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

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

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

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

  Since the time for heating the diamine is shorter, it is preferable that the diamine is added in a solid form such as a powder or a granule that is not heated by itself.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The glass transition temperature of the polyamideimide used in the present invention refers to the glass transition temperature measured by the following “analysis method (1) glass transition temperature”.

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

  In the melt polymerization method, the reaction temperature is not particularly limited as long as it is equal to or higher than the glass transition temperature of the produced polyamideimide. The reaction time is preferably in the range of 0.5 to 36 hours, more preferably in the range of 1 to 8 hours after reaching the reaction temperature, from the viewpoint of the balance between the finally reached molecular weight and productivity. preferable. The melt polymerization may be carried out in an inert gas stream such as nitrogen or under pressure.

  In the method for producing the polyamideimide used in the present invention, when the raw material is supplied to the reaction vessel, a polymerization catalyst and other additives may be added in addition to the polyamideimide raw material salt as long as the effects of the present invention are not impaired. .

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

  Specific examples of other additives include stabilizers such as antioxidants. From the viewpoint of the reactivity of the bisimide dicarboxylate, the amount of the additive used is preferably 30% by mass or less based on the total mass of the polyamideimide raw material salt.

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

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

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

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

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

  In the polyamideimide polymerization method used in the present invention, a polyamideimide raw material salt is preferably used. By using the polyamideimide raw material salt, a polyamideimide having a higher molecular structure regularity and fewer branched structures can be obtained.

  Polyamideimide having a degree of polymerization (n) (number of repeating units) of up to about 1000 can be synthesized by the above production method.

  The degree of polymerization can be adjusted in the range of 2 to 1000 by changing conditions such as the mixing ratio of bisimide dicarboxylic acid and diamine, polymerization temperature, and polymerization time.

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

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

  The polyamideimides used in the present invention can have a glass transition temperature of at least 100 ° C, higher, at least 150 ° C, even higher, at least 250 ° C, and even higher, at least 270 ° C.

  Also, the polyamideimide used in the present invention, when having crystallinity, has a melting point of at least 150 ° C., higher, at least 250 ° C., even higher, at least 300 ° C., and even higher, at least 350 ° C. Can do.

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

  The polyamide-imide resin composition of the present invention needs to contain a reinforcing material in order to improve mechanical properties. Examples of the reinforcing material include a fibrous reinforcing material and a plate-like reinforcing material, among which a fibrous reinforcing material is preferable.

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

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

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

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

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

  In addition to the reinforcing material, other additives may be added to the polyamideimide resin composition of the present invention as necessary. Specific examples of other additives include impact resistance improvers, antistatic agents, conductivity-imparting agents, thermally conductive fillers, aliphatic polyamides, semi-aromatic polyamides, amorphous polyamides, other resin components, thermal stability Agents, light stabilizers, slidability improvers, flame retardants, flame retardant aids, and pigments. Two or more other additives may be used in combination.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The polyamideimide resin composition of the present invention is excellent in heat resistance, chemical resistance, mechanical strength, and moldability. Therefore, automotive parts, electrical and electronic parts, sliding parts, tube-related parts, household goods, metal coatings, industrial material supplies, computer and related equipment parts, optical equipment parts, information / communication equipment parts, precision equipment parts, etc. Can be used for a wide range of applications.

  Specific examples of automotive parts include base plates for cylinders such as shift levers and gearboxes, cylinder head covers, engine mounts, air intake manifolds, throttle bodies, air intake pipes, radiator tanks, radiator supports, radiator hoses, radiator grills, and rear Spoiler, wheel cover, wheel cap, cowl vent grill, air outlet louver, air scoop, hood bulge, fender, back door, fuel sender module, shift lever housing, propeller shaft, stabilizer bar linkage rod, window regulator, door lock, Door handle, outside door mirror stay, accelerator pedal, pedal module, seal ring, bearing rear -Inner, gear, wire harness, relay block, sensor housing, encapsulation, ignition coil, distributor, water pump renlet, water pump outlet, thermostat housing, cooling fan, fan shroud, oil pan, oil filter housing, oil Filter cap, Oil level gauge, Timing belt cover, Engine cover, Fuel tank, Fuel tube, Fuel cut-off valve, Quick connector, Canister, Fuel delivery pipe, Fuel filler neck, Fuel pipe fitting, Lamp reflector, Lamp housing, Lamp Extensions and lamp sockets.

  Specific examples of electrical and electronic components include connectors, HDD lamp rails, board reinforcing plates, LED reflectors, switches, sensors, sockets, capacitors, jacks, fuse holders, relays, coil bobbins, resistors, ICs, LED housings, lithium batteries Examples include binders for electrodes such as secondary batteries.

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

  Specific examples of tube-related parts include feed tubes, return tubes, evaporation tubes, fuel filler tubes, reserve tubes, vent tubes, oil tubes, brake tubes, tubes for window washer fluid, cooler tubes for cooling water and refrigerant, air conditioners, etc. Tubes for refrigerants, tubes for floor heating, tubes for fire extinguishers and fire extinguishing equipment, tubes for medical cooling equipment, tubes for spraying paints, tubes for transporting chemicals, tubes for fuel transport, tubes for diesel gasoline, tubes for oil drilling, etc. Examples include alcohol gasoline tubes, engine coolant (LLC) tubes, reservoir tank tubes, load heating tubes, floor heating tubes, infrastructure supply tubes, and gas tubes.

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

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

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

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

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

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

(3) Melt flow rate (MFR) of polyamideimide resin composition
Using polyamideimide resin composition pellets, by a flow tester (CFT-500D manufactured by Shimadzu Corporation), 330 ° C. in Examples 1-11 and 17-22, 200 kgf, 355 ° C. in Examples 12-16 and 23-28 , And measured with a load of 300 kgf. The unit is g / 10 minutes.

(4) Flexural strength and flexural modulus of polyamideimide resin composition Using the obtained test piece, measurement was performed according to ISO178.

2. Raw material (1) Reinforcement material GF-1: Glass fiber (trade name “03JAFT692” manufactured by Asahi Fiber Glass Co., Ltd.), average fiber diameter 10 μm, average fiber length 3 mm
GF-2: glass fiber (manufactured by Nittobo, trade name “CS3G225S”), average fiber diameter 9.5 μm, average fiber length 3 mm
Flat GF: Flat glass fiber (manufactured by Nittobo, trade name “CSG3PA820S”), major axis 28 μm × minor axis 7 μm, average fiber length 3 mm
CF: carbon fiber (manufactured by Toho Tenax Co., Ltd., trade name “HTA-C6-NR”), average fiber diameter 7 μm, average fiber length 6 mm
MF: Stainless steel fiber (manufactured by Nippon Seisen Co., Ltd., trade name “Naslon SUS304”), average fiber diameter 8 μm, average fiber length 6 mm

(2) Antioxidant PA-1: Phosphorous antioxidant, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylylene phosphite (manufactured by Clariant Japan, trade name “Hosta” Knox P-EPQ ")
PA-2: Phosphorous antioxidant, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name “Adeka Stab PEP-36” manufactured by Adeka)
PA-3: Phosphorous antioxidant, bis (nonylphenyl) pentaerythritol diphosphite (manufactured by Adeka, trade name “Adekastab PEP-4C”)
HPA: hindered phenol antioxidant, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide] (manufactured by Ciba Specialty Chemicals) , Trade name "Irganox 1098")

(3) Polyamideimide The general formula of bisimide dicarboxylic acid used for the preparation of polyamideimide is shown below.

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

Production Example 1
Ribbon blender type reactor comprising a mixture of 668 parts by mass of bisimide dicarboxylic acid shown in structure 1 (melting point: not detected 300 ° C. or higher) (average particle size: 310 μm) and 1.02 parts by mass of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 200 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 1.00 parts by mass / min (0.50% by mass / min) 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-xylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle size: 283 μm). The obtained polyamideimide raw material salt was again added to a ribbon blender type reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C. and heated for 4 hours, and further heated to 220 ° C. and heated for 4 hours to obtain granular (average particle size: 300 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 196 ° C. and a 5% weight loss temperature of 359 ° C. The number average molecular weight was 12270 (degree of polymerization: 20.4). The solution viscosity was 8.2 Pa · s.

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

Production Example 2
Ribbon blender type reactor comprising a mixture of 668 parts by mass of bisimide dicarboxylic acid shown in structure 2 (melting point: not detected 300 ° C. or higher) (average particle size: 371 μm) and 1.02 parts by mass of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 200 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 1.00 parts by mass / min (0.50% by mass / min) 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-xylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle diameter: 362 μm). The obtained polyamideimide raw material salt was again added to a ribbon blender type reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C. and heated for 4 hours, and further heated to 220 ° C. and heated for 4 hours to obtain granular (average particle size: 331 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 195 ° C. and a 5% weight loss temperature of 360 ° C. The number average molecular weight was 11320 (degree of polymerization: 18.8). The solution viscosity was 7.9 Pa · s.

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

Production Example 3
Ribbon blender type reactor comprising a mixture of 630 parts by mass of bisimide dicarboxylic acid shown in structure 3 (melting point: not detected at 300 ° C. or higher) (average particle size: 397 μm) and 1.02 parts by mass of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 200 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 1.00 parts by mass / min (0.50% by mass / min) 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-xylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle diameter: 389 μm). The obtained polyamideimide raw material salt was again added to a ribbon blender type reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C. and heated for 4 hours, and further heated to 240 ° C. and heated for 4 hours to obtain granular (average particle size: 361 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 227 ° C. and a 5% weight loss temperature of 396 ° C. The number average molecular weight was 11000 (degree of polymerization: 19.1). The solution viscosity was 8.0 Pa · s.

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

Production Example 4
Ribbon blender type reactor comprising a mixture of 757 parts by mass of bisimide dicarboxylic acid shown in structure 4 (melting point: not detected 300 ° C. or higher) (average particle size: 353 μm) and 1.02 parts by mass of anhydrous sodium hypophosphite And heated to 170 ° C. with stirring at a rotational speed of 70 rpm under a nitrogen flow. Thereafter, 200 parts by mass of m-xylylenediamine (melting point: 14 ° C.) heated to 25 ° C. was used at a rate of 1.00 parts by mass / min (0.50% by mass / min) using a liquid feeder. It added to the bisimide dicarboxylic acid of the structure 1 kept at 120 degreeC over time [Bismimido dicarboxylic acid: m-xylenediamine = 47: 50 (molar ratio)]. The obtained polyamideimide raw material salt was granular (average particle size: 337 μm). The obtained polyamideimide raw material salt was again added to a ribbon blender type reactor. Then, it heated at 180 degreeC for 2 hours, stirring with rotation speed 50rpm under nitrogen circulation. Thereafter, the temperature was raised to 200 ° C. and heated for 4 hours, and further heated to 240 ° C. and heated for 4 hours to obtain granular (average particle size: 301 μm) polyamideimide.

  The obtained polyamideimide had a glass transition temperature of 231 ° C. and a 5% weight loss temperature of 397 ° C. The number average molecular weight was 12400 (degree of polymerization: 18.6). The solution viscosity was 8.3 Pa · s.

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

Production Example 5
515 parts by mass of 4,4-bis (N-trimellitimidophenyl) ether was added to a ribbon blender reactor. Thereafter, 0.69 parts by mass of anhydrous sodium hypophosphite was added, and the mixture was heated to 250 ° C. under a nitrogen flow. While confirming that the shape of 4,4-bis (N-trimellitimidophenyl) ether is maintained, 200 parts by mass of solid 4,4′-diaminodiphenyl ether (melting point: 188 ° C.) It added at the speed | rate (0.333 mass% / min) of 0.67 mass part / min using the powder feeder provided with the damper mechanism. After completion of the addition, heating was performed at 250 ° C. for 4 hours to obtain a granular (average particle size: 380 μm) polyamideimide.

  The resulting polyamideimide had a glass transition temperature of 267 ° C. and a 5% weight loss temperature of 487 ° C. The number average molecular weight was 10900 (degree of polymerization: 14.9). The solution viscosity was 8.7 Pa · s.

  Moreover, in the measurement of nuclear magnetic resonance (NMR), 10 mg of a sample was dissolved in 1 mL of DMSO-d6, and 1H-NMR measurement was performed at 120 ° C., no peak derived from a side reaction was detected, and an amide bond -No peaks were found near 7.86 ppm (doublet), 7.55 ppm (doublet), or 7.15 ppm (doublet + doublet) detected when 4,4'-diaminodiphenyl ether was present between the imide bonds. From the above, it was confirmed that the obtained polyamideimide had a structure in which the repeating units represented by the formula (1) were connected in a linear form.

Production Example 6
192 parts by weight of trimellitic anhydride, 188 parts by weight of m-xylene diisocyanate, and 887 parts by weight of N-methyl-2-pyrrolidone were placed in a reactor equipped with a stirring blade and a heating medium jacket, and stirred under a nitrogen stream. The mixture was heated to 200 ° C. and reacted for 6 hours. The reaction solution was reprecipitated with 3801 parts by mass of methanol. After filtration, it was further washed with water and dried to obtain polyamideimide.

  The resulting polyamideimide had a glass transition temperature of 188 ° C. and a 5% weight loss temperature of 340 ° C. The number average molecular weight and degree of polymerization could not be measured due to the large amount of gelled product in the resin.

Example 1
100 parts by mass of the polyamideimide (P-1) obtained in Production Example 1 was weighed using a Kubota loss-in-weight continuous quantitative supply device CE-W-1, and the screw diameter was 37 mm and L / D40 was in the same direction biaxial. It supplied to the main supply port of the extruder (Toshiba machine company TEM37BS). The extruder was set at a barrel temperature of 300 ° C. to 340 ° C., screw rotation speed 250 rpm, discharge rate 35 kg / hour, melt-kneaded, and 30 parts by mass of (GF-1) was supplied from the side feeder and further kneaded. Finally, the strand was taken out from the die into a strand shape, and then cooled and solidified by passing through a water tank, which was cut with a pelletizer to obtain a polyamideimide resin composition pellet.
After sufficiently drying the obtained polyamide-imide resin composition, using an injection molding machine (EC100 manufactured by Toshiba Machine Co., Ltd.), a test piece in accordance with ISO 178 was prepared under conditions of a cylinder temperature of 330 ° C. and a mold temperature of 110 ° C. Produced.

Examples 2-28
Except for changing the resin composition and molding conditions of the polyamideimide resin composition, the same operation as in Example 1 was performed to obtain a polyamideimide resin composition pellet, which was injection-molded to produce a test piece.

Comparative Example 1
Except for changing the resin composition and molding conditions of the polyamideimide resin composition, the same operation as in Example 1 was performed to obtain a polyamideimide resin composition pellet and injection molding was performed, but the melt viscosity was too high. Thus, injection molding could not be performed.

  Tables 2 and 3 show the resin composition, molding conditions, and characteristic values of the obtained test pieces of the polyamideimide resin compositions obtained in the examples.

  The polyamideimide resin compositions obtained in Examples 1 to 28 were excellent in bending strength and bending elastic modulus.

Claims (6)

Polyamideimide resin composition comprising a polyamideimide having a repeating unit represented by the general formula (1) and a reinforcing material:
(Wherein R ¹ and R ² independently represent a divalent residue having an aromatic ring, an aliphatic ring or an aliphatic hydrocarbon, and R ³ and R ⁴ independently represent an aromatic ring or A trivalent residue having an aliphatic ring is shown, and a hydrogen atom bonded to each ring may be substituted with another atom or atomic group. The polyamide-imide resin composition according to claim 1, wherein the reinforcing material is at least one fibrous reinforcing material selected from the group consisting of glass fiber, carbon fiber and stainless steel fiber. Furthermore, the polyamideimide resin composition of Claim 1 or 2 containing antioxidant. The polyamideimide resin composition according to any one of claims 1 to 3, wherein the number of repeating units of polyamideimide is 4 to 1,000. The polyamideimide resin composition according to any one of claims 1 to 4, wherein the polyamideimide has a glass transition temperature of at least 100 ° C. The molded object formed by shape | molding the polyamideimide resin composition in any one of Claims 1-5.