JP2019048948A - Compound, cured product and bond magnet - Google Patents

Abstract

To provide a compound capable of manufacturing a molded product having high mechanical strength and excellent heat resistance, to provide a cured product of the compound and to provide a bond magnet including the cured product.SOLUTION: The compound comprises a polyamide-imide having a siloxane structure, an epoxy resin and a metal element-containing powder.SELECTED DRAWING: None

Description

  The present invention relates to a compound, a cured product, and a bonded magnet.

  A compound containing a metal powder and a resin composition is used as a raw material of various industrial products such as an inductor, an electromagnetic wave shield, or a bonded magnet according to various physical properties of the metal powder (see Patent Documents 1 to 4 below) ).

JP-A-8-273916 JP 2001-214054 A Unexamined-Japanese-Patent No. 2004-31786 JP, 2012-209484, A

  When a molded body produced from a compound is used as an industrial product, the molded body is required to have mechanical strength and heat resistance.

  The present invention has been made in view of the above circumstances, and provides a compound capable of producing a molded article having high mechanical strength and excellent heat resistance, a cured product of the compound, and a bonded magnet including the cured product. With the goal.

  The compound according to one aspect of the present invention comprises a polyamideimide having a siloxane structure, an epoxy resin, and a metal element-containing powder.

  In the compound according to one aspect of the present invention, the polyamideimide may have two or more carboxy groups at at least one end of both ends of the molecular chain of the polyamideimide.

  In the compound according to one aspect of the present invention, the metal element-containing powder may be a powder of a rare earth magnet.

  The compound according to one aspect of the present invention may be for a bonded magnet.

  The cured product according to one aspect of the present invention is a cured product of the above compound.

  In the cured product according to one aspect of the present invention, the polyamideimide may have two or more carboxy groups at at least one end of both ends of the molecular chain of the polyamideimide, and the cured product is It may contain a reaction site of the above-mentioned carboxy group and the epoxy group which the above-mentioned epoxy resin has.

  The cured product according to one aspect of the present invention may include the cured polyamideimide and the epoxy resin, and the metal element-containing powder bonded to each other by the cured polyamideimide and the epoxy resin.

  A bonded magnet according to one aspect of the present invention includes the above-mentioned cured product.

  ADVANTAGE OF THE INVENTION According to this invention, the mechanical strength is high and the compound which can produce the molded object which is excellent in heat resistance, the hardened | cured material of the said compound, and the bonded magnet containing the said hardened | cured material are provided.

  Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited to the following embodiment.

<Compound>
The compound according to the present embodiment includes a polyamideimide having a siloxane structure, an epoxy resin, and a metal element-containing powder. Polyamideimide having a siloxane structure may be rephrased as siloxane modified polyamideimide. The siloxane structure may be reworded as a chain structure of polysiloxane or a chain structure of silicone. Polyamideimide having a siloxane structure may be described as "SPAI" (Siloxane-modified PolyAmide Imide). The compound according to this embodiment may contain, in addition to SPAI, a polyamideimide not having a siloxane structure. The metal element-containing powder may be, for example, at least one powder selected from the group consisting of elemental metals, alloys, and metal compounds. The compound may comprise a curing agent. The compound may comprise a cure accelerator. The compound may comprise an additive. It is a component including SPAI, an epoxy resin, a curing agent, a curing accelerator and an additive, and the remaining components (non-volatile components) excluding the organic solvent and the metal element-containing powder are described as “resin composition” May be The compound may be restated as a composition containing a resin composition and a metal element-containing powder. The resin contained in the resin composition may be only SPAI and epoxy resin. The resin composition may further contain another resin in addition to the SPAI and the epoxy resin. The additive is a component of the resin composition except the resin, the curing agent and the curing accelerator. The additive is, for example, a coupling agent, a flow aid, a flame retardant, or a lubricant.

  By curing the compound according to the present embodiment, a cured product of the compound is obtained. The mechanical strength of the molded object comprised from the said hardened | cured material is high, and the said molded object is excellent in heat resistance. It is considered that the heat resistance of the SPAI included in the compound contributes to the improvement of the heat resistance of the molded body. The reason why the mechanical strength of the molded body is high is not always clear. When the compound cures, the amide structure of SPAI reacts with the epoxy resin. It is inferred that the action of the amide structure and the epoxy resin contributes to the improvement of the mechanical strength of the molded body. However, the effects according to the present invention are not limited to the above.

  The compound may include a metal element-containing powder and a resin composition attached to the surface of individual particles constituting the metal element-containing powder. The resin composition may be attached to the entire surface of the particle or may be attached to only a part of the surface of the particle. The compound may contain an uncured resin composition and a metal element-containing powder. The compound may include a semi-cured resin composition (eg, a B-stage resin composition) and a metal-element-containing powder.

  The mass of the SPAI contained in the compound is not limited, but may be, for example, 80 to 99 parts by mass, or 85 to 95 parts by mass with respect to 100 parts by mass in total of the mass of the SPAI and epoxy resin contained in the compound. . Although the mass of the epoxy resin contained in the compound is not limited, it is, for example, 1 to 20 parts by mass, or 5 to 15 parts by mass with respect to 100 parts by mass in total of the mass of SPAI and epoxy resin contained in the compound Good.

  Although the mass of the resin composition contained in the compound is not limited, for example, 0.2 to 17 parts by mass, 0.2 parts by mass with respect to 100 parts by mass in total of the mass of the resin composition and the metal element-containing powder contained in the compound. 2 to 10 parts by mass, 0.2 to 5 parts by mass, 0.2 to 2 parts by mass, 0.4 to 17 parts by mass, 0.4 to 10 parts by mass, 0.4 to 5 parts by mass, or 0.4 -2 mass parts may be sufficient. When the mass of the resin composition is in the above-mentioned range, a molded article having sufficient mechanical strength, heat resistance and physical properties derived from the metal element-containing powder can be easily obtained.

  When the mass of the resin composition is represented as M and the mass of the metal element-containing powder is represented as m, m / (m + M) is, for example, 0.830 or more and 0.998 or less, 0.830 or more 0.996 or less, 0.900 to 0.998, 0.900 to 0.996, 0.950 to 0.998, 0.950 to 0.996, 0.980 to 0.998, Or you may be 0.980 or more and 0.996 or less. When m / (m + M) is in the above range, a molded product having mechanical strength, heat resistance, and physical properties derived from metal element-containing powder can be easily obtained. m / (m + M) · 100 can be said to be the space factor of the metal element-containing powder in the compound.

(Details of metal-containing powder)
As described above, the metal-element-containing powder may be, for example, at least one powder selected from the group consisting of elemental metals, alloys, and metal compounds. The alloy may include at least one selected from the group consisting of solid solution, eutectic and intermetallic compounds. The alloy may be, for example, stainless steel (Fe-Cr based alloy, Fe-Ni-Cr based alloy, etc.). The metal compound may be, for example, an oxide such as ferrite. The metal element-containing powder may contain one metal element or a plurality of metal elements. The metal element contained in the metal element-containing powder may be, for example, a base metal element, a noble metal element, a transition metal element, or a rare earth element. The metal element contained in the metal element-containing powder is, for example, iron (Fe), copper (Cu), titanium (Ti), manganese (Mn), cobalt (Co), nickel (Ni), zinc (Zn), aluminum ( Al), tin (Sn), chromium (Cr), barium (Ba), strontium (Sr), lead (Pb), silver (Ag), praseodymium (Pr), neodymium (Nd), samarium (Sm) and dysprosium ( It may be at least one selected from the group consisting of Dy). The metal element-containing powder may contain an element other than the metal element. The metal element-containing powder may contain, for example, oxygen (O), beryllium (Be), phosphorus (P), boron (B), or silicon (Si). The metal element-containing powder may be magnetic powder. The metal element-containing powder may be a soft magnetic alloy or a ferromagnetic alloy. The metal element-containing powder may be a powder of a rare earth magnet. Metallic element-containing powders include, for example, neodymium magnets (Nd-Fe-B alloys), samarium cobalt magnets (Sm-Co alloys), samarium-iron-nitrogen magnets (Sm-Fe-N alloys), and praseodymium magnets. It may be a powder of at least one rare earth magnet selected from the group consisting of (Pr-Co based alloy). The metal element-containing powder may be powder of a magnet other than the rare earth magnet. The metal element-containing powder may be, for example, a powder of an alnico magnet (Al-Ni-Co alloy). Metallic element-containing powders include, for example, Fe-Si alloys, Fe-Si-Al alloys (Sendust), Fe-Ni alloys (Permalloy), Fe-Cu-Ni alloys (Permalloy), Fe-Co alloys The magnetic powder may be at least one selected from the group consisting of (permendur), Fe-Cr-Si alloy (magnetic stainless steel) and ferrite. The ferrite may be, for example, spinel ferrite, hexagonal ferrite, or garnet ferrite. The metal element-containing powder may be a copper alloy such as a Cu-Sn alloy, a Cu-Sn-P alloy, a Cu-Ni alloy, or a Cu-Be alloy. The metal-element-containing powder may contain one of the above-described elements and compositions, and may contain two or more of the above-described elements and compositions.

  The shape of the individual particles constituting the metal element-containing powder is not particularly limited. The individual particles may, for example, be flat. The flat shape may be, for example, a shape having a shape aspect ratio of 0.3 or less. The shape aspect ratio is a value (short diameter / long diameter) obtained by dividing the short diameter of particles by the long diameter of particles. When the shape of the individual particles constituting the metal element-containing powder is a flat shape, the individual particles tend to be laminated when forming a compact from a compound by compression molding. Therefore, it is difficult for voids and resin accumulation to occur between particles, and the space factor of the metal element-containing powder in the molded body tends to be high. As a result, the density of the shaped body tends to be high, and the mechanical strength of the shaped body tends to be high. The average particle size of the metal element-containing powder may be, for example, preferably 20 to 300 μm, more preferably 40 to 250 μm. The particle size distribution of the metal element-containing powder is calculated based on, for example, mass measurement by sieving or analysis using a measuring instrument such as a laser diffraction / scattering device.

(Details of SPAI)
SPAI is a polymer having a siloxane structure, an amido group, and an imide group in one molecule. In other words, the minimum structural unit of SPAI may include a siloxane structure, a structure having an imide bond, and a structure having an amide bond. In the structural unit, for example, silicon belonging to a siloxane structure may be bonded to nitrogen forming an imide bond through an organic group, and an element (for example, carbon) belonging to an imide group is carbon forming an amide bond You may combine. For example, SPAI may include at least a structural unit represented by the following chemical formula (21) in one molecule. One SPAI molecule may contain multiple types of structural units.

In the above chemical formula (21), each of R ₃₁ , R ₃₂ and R ₃₅ independently represents a hydrogen atom or an organic group (for example, a monovalent organic group). Each of R ₃₃ and R ₃₆ independently represents an organic group (eg, a divalent organic group). R ₃₄ represents an organic group (trivalent organic group).

Each of R ₃₁ , R ₃₂ and R ₃₅ may be independently a hydrogen atom, a monovalent aliphatic group, or a monovalent aromatic group. Each of R ₃₁ , R ₃₂ and R ₃₅ may be independently a hydrogen atom, an alkyl group or an aryl group. R ₃₁ and R ₃₂ may both be methyl groups. R ₃₅ may be a hydrogen atom.

Each of R ₃₃ and R ₃₆ may be independently a divalent aliphatic group or a divalent aromatic group. Each of R ₃₃ and R ₃₆ may be independently an alkylene group or an arylene group. R ₃₃ may be a propylene group.

R ₃₄ may be a trivalent aliphatic group or a trivalent aromatic group. R ₃₄ may be a ring structure. R ₃₄ may be an alicyclic structure or an aromatic ring. R ₃₄ may be a benzene ring.

  SPAI may contain at least a repeating unit represented by the following chemical formula (22) in one molecule.

In the above chemical formula (22), each of R ₄₁ , R ₄₄ , R ₄₅ and R ₄₈ independently represents a hydrogen atom or an organic group (for example, a monovalent organic group). Each of R ₄₃ , R ₄₆ and R ₄₉ independently represents an organic group (for example, a divalent organic group). Each of R ₄₂ and R ₄₇ independently represents a trivalent organic group. n3 represents an integer of 1 or more. The plurality of R ₄₄ present in the chemical formula (22) may be the same as or different from each other. The plurality of R ₄₅ present in the chemical formula (22) may be the same as or different from one another.

Each of R ₄₁ , R ₄₄ , R ₄₅ and R ₄₈ may be independently a hydrogen atom, a monovalent aliphatic group, or a monovalent aromatic group. Each of R ₄₁ , R ₄₄ , R ₄₅ and R ₄₈ may be independently a hydrogen atom, an alkyl group or an aryl group. Each of R ₄₁ and R ₄₈ may independently be a hydrogen atom. R ₄₄ and R ₄₅ may both be methyl groups. R ₄₁ and R ₄₈ may both be hydrogen atoms.

Each of R ₄₃ , R ₄₆ and R ₄₉ may be independently a divalent aliphatic group or a divalent aromatic group. Each of R ₄₃ , R ₄₆ and R ₄₉ may be independently an alkylene group or an arylene group. Each of R ₄₃ and R ₄₆ may independently be a propylene group. R ₄₃ and R ₄₆ may both be a propylene group.

  n3 may be, for example, an integer of 1 or more and 50 or less.

  SPAI may contain at least a repeating unit represented by the following chemical formula (23) in one molecule.

In the above chemical formula (23), each of R ₅₁ , R ₅₃ , R ₅₄ and R ₅₆ independently represents a hydrogen atom or an organic group (for example, a monovalent organic group). Each of R ₅₂ , R ₅₅ and R ₅₇ independently represents an organic group (for example, a divalent organic group). n4 represents an integer of 1 or more. The plurality of R ₅₃ present in the chemical formula (23) may be the same as or different from each other. The plurality of R ₅₄ present in the chemical formula (23) may be the same as or different from each other.

Each of R ₅₁ , R ₅₃ , R ₅₄ and R ₅₆ independently may be a hydrogen atom, a monovalent aliphatic group, or a monovalent aromatic group. Each of R ₅₁ , R ₅₃ , R ₅₄ and R ₅₆ independently may be a hydrogen atom, an alkyl group or an aryl group. Each of R ₅₃ and R ₅₄ may be independently a methyl group. Each of R ₅₃ and R ₅₄ may be a methyl group. Each of R ₅₁ and R ₅₆ independently may be a hydrogen atom. R ₅₁ and R ₅₆ may both be hydrogen atoms.

Each of R ₅₂ , R ₅₅ and R ₅₇ may be independently a divalent aliphatic group or a divalent aromatic group. Each of R ₅₂ , R ₅₅ and R ₅₇ may be independently an alkylene group or an arylene group. Each of R ₅₂ and R ₅₅ may independently be a propylene group. R ₅₂ and R ₅₅ may both be a propylene group.

  n4 may be, for example, an integer of 1 or more and 50 or less.

SPAI may be, for example, a compound represented by the following chemical formula (24).
_{R 61 -R 62 - (X 3} ) n5 -R 63 (24)

In the above chemical formula (24), each of R ₆₁ and R ₆₃ independently represents an organic group (for example, a monovalent organic group). R ₆₂ represents an organic group (eg, a divalent organic group). X ₃ represents a structural unit represented by the above chemical formula (22) or a structural unit represented by the above chemical formula (23). n5 represents an integer of 1 or more. When n5 is an integer of 2 or more, a plurality of X ₃ present in the chemical formula (24) may be the same as or different from one another.

Each of R ₆₁ and R ₆₃ may be independently an isocyanate group or a group represented by the following chemical formula (25). R ₆₂ may be a divalent aliphatic group or a divalent aromatic group. R ₆₂ may be an alkylene group or an arylene group. n5 may be an integer of 1 or more and 80 or less.

In the above chemical formula (25), R ₆₄ represents a hydrogen atom or an organic group (for example, a monovalent organic group). R ₆₅ represents an organic group (for example, a monovalent organic group).

R ₆₄ may be a hydrogen atom, a monovalent aliphatic group, or a monovalent aromatic group. R ₆₄ may be a hydrogen atom.

R ₆₅ may be a monovalent organic group having two or more carboxy groups. R ₆₅ may be a monovalent organic group having two carboxy groups.

  SPAI may have two or more carboxy groups at at least one end of both ends of the molecular chain of SPAI. SPAI may have two or more carboxy groups at each end of the molecular chain of SPAI. When SPAI having two or more carboxy groups at both ends is used, the toughness of the molded article tends to be greater.

  When the above-mentioned SPAI having two or more carboxy groups is used, the toughness of the cured product of the compound is likely to be increased, and the toughness of the molded product composed of the cured product is also likely to be increased. The reason why the toughness of the cured product of the compound tends to increase is presumed to be as follows. When SPAI having no two or more carboxy groups is used, the epoxy group possessed by the epoxy resin tends to react with the amide group possessed by SPAI when the compound is cured. When SPAI and an epoxy resin are bonded by the reaction of an epoxy group and an amido group, the amido group possessed by SPAI is distributed over the entire molecular chain of SPAI, so SPAI and epoxy resin form a cross-linked structure Easy to do. As a result, the cured product tends to be hard, and the toughness of the cured product tends to be reduced. On the other hand, when the above-mentioned SPAI having two or more carboxy groups is used, when the compound is cured, the epoxy group possessed by the epoxy resin is likely to react with the carboxyl group among the amide group and the carboxy group possessed by SPAI. When the SPAI and the epoxy resin are bonded by the reaction of the epoxy group and the carboxy group, the carboxy group is present at the end of the molecular chain of the SPAI, so that the SPAI and the epoxy resin tend to form a chain-like crosslinked structure. As a result, the cured product does not become excessively hard, and the toughness of the cured product tends to increase. However, the reason why the toughness of the cured product tends to increase is not limited to the above.

  Hereinafter, specific examples of the SPAI will be described in detail. For convenience of explanation, the SPAI is classified into "first SPAI" and "second SPAI". The compound according to the present embodiment may include only the first SPAI as the SPAI. The compound according to the present embodiment may include only the second SPAI as the SPAI. The compound according to the present embodiment may include both the first SPAI and the second SPAI. First, the details of the first SPAI will be described.

[Details of the first SPAI]
The first SPAI may be manufactured, for example, by the following method. A mixture of diamine (A) and siloxane diamine (B) having three or more aromatic rings is reacted with trimellitic anhydride to obtain a mixture containing diimide dicarboxylic acid. The diimide dicarboxylic acid may be represented by the following chemical formula (11) and chemical formula (12). When the number of moles of diamine (A) is A, the number of moles of siloxane diamine (B) is B, and the number of moles of trimellitic anhydride is TMA, the molar ratio A / B is 99.9 / 0. It may be adjusted to 1 to 0.1 / 99.9, and the molar ratio (A + B) / TMA may be adjusted to 1 / 2.05 to 1 / 2.20. Subsequently, a mixture containing the above diimide dicarboxylic acid is reacted with an aromatic diisocyanate represented by the following chemical formula (13) to obtain a siloxane-containing polyamideimide. This siloxane-containing polyamideimide may be described as "SPAI-1a" below. When the number of moles of aromatic diisocyanate is ADI, the molar ratio (A + B) / ADI may be adjusted to 1 / 1.05 to 1 / 1.50.

R ₂₁ in the chemical formula (11) may be represented by the above chemical formula (11-a).

X ₂ in the above chemical formula (11-a) is the above (11-b), (11-c), (11-d), (11-e), (11-f), (11-g), It may be represented by a kind of chemical formula selected from the group consisting of (11-h) and (11-i).

R ₂₂ in the chemical formula (12) may be represented by the above chemical formula (12-a).
Each of R ₂₃ and R ₂₄ in the chemical formula (12) independently represents a divalent organic group. Each of R ₂₅ , R ₂₆ , R ₂₇ and R _{28 in the} chemical formula (12) independently represents an alkyl group, a phenyl group or a substituted phenyl group. n2 represents an integer of 1 to 50;

R ₂₉ in the above chemical formula (13) is a kind of chemical formula selected from the group consisting of the above (13-a), (13-b), (13-c), (13-d) and (13-e) May be represented by

  From the viewpoint of improving the synthesis efficiency of the first SPAI, the molar ratio A / B is preferably 50/50 to 90/10, more preferably 60/40 to 80/20. It is particularly preferable to be / 35 to 75/25.

  The molar ratio (A + B) / ADI described above is preferably 1 / 1.10 to 1 / 1.50 from the viewpoint of easily synthesizing a high molecular weight siloxane-containing polyamideimide without adding a catalyst or the like, and 1 It is more preferable that it is /1.20 to 1 / 1.30.

  In the production method of SPAI-1a, the mixture (mixture 1) of the above diamine (A) and siloxane diamine (B) and trimellitic anhydride are reacted at 50 to 90 ° C. in an aprotic polar solvent. You may Subsequently, after the aromatic hydrocarbon is charged into the aprotic polar solvent, the reaction in the aprotic polar solvent may further proceed at 120 to 180 ° C. By these reactions, a solution of a mixture (mixture 2) containing aromatic diimide dicarboxylic acid and siloxane diimide dicarboxylic acid is obtained. Reaction of the mixture 2 with the aromatic diisocyanate may give a siloxane-containing polyamideimide (SPAI-1a). The aromatic diimide dicarboxylic acid in the mixture 2 is represented, for example, by the above chemical formula (11). The siloxane diimide dicarboxylic acid in the mixture 2 is represented, for example, by the above chemical formula (12).

  After distilling off the aromatic hydrocarbon from the solution of the mixture 2, the reaction of the mixture 2 with the aromatic diisocyanate may be carried out.

  The aprotic polar solvent used for producing the first SPAI is, for example, at least one selected from the group consisting of dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 4-butyrolactone, sulfolane and cyclohexanone. May be there. Since the imidation reaction requires high temperature, N-methyl-2-pyrrolidone having a high boiling point is particularly preferable. The amount of water contained in the aprotic polar solvent is preferably controlled to 0.2% by mass or less. As the water content in the aprotic polar solvent increases, the reaction does not proceed sufficiently due to trimellitic acid generated by hydration of trimellitic anhydride, and the molecular weight of the first SPAI tends to decrease. The content of diamine (A), siloxane diamine (B) and trimellitic anhydride in the aprotic polar solvent may be 10 to 70% by mass.

  The aromatic hydrocarbon introduced into the aprotic polar solvent may be an aromatic hydrocarbon which can azeotrope with water. The aromatic hydrocarbon which can be azeotroped with water may be, for example, at least one selected from the group consisting of toluene, benzene, xylene and ethylbenzene. In particular, toluene having a relatively low boiling point and less harmfulness is preferable. During the reaction, the aromatic hydrocarbon flows out of the reaction system by azeotropic distillation with water at 120 to 180 ° C. Therefore, aromatic hydrocarbons in the aprotic polar solvent tend to decrease gradually. In order to maintain the amount of aromatic hydrocarbon present in the reaction system at a constant rate, for example, the solvent which has flowed out of the system is separated from the water using a cocked water quantitative receiver or the like, and then returned to the system. Alternatively, aromatic hydrocarbons may be replenished into the reaction system. The above reaction at 120 to 180 ° C. is performed until water is not by-produced in the reaction system.

  The mass of the aromatic hydrocarbon introduced into the aprotic polar solvent may be adjusted to 0.1 to 0.5 times (10 to 50 mass%) the mass of the aprotic polar solvent. The removal effect of water by azeotropic distillation falls that the usage-amount of aromatic hydrocarbon is less than said range, and it is hard to produce | generate a diimide dicarboxylic acid. When the amount of aromatic hydrocarbon used exceeds the above range, there is a possibility that the aromatic amidocarboxylic acid of the reaction intermediate or the produced aromatic diimide dicarboxylic acid may be precipitated.

  The first SPAI is a diimide dicarboxylic acid such as 2,2-bis [4- {4- (5-hydroxycarbonyl-1,3-dione-isoindolino) phenoxy} phenyl] propane (C) and bis (5-hydroxy carbonyl) as diimide dicarboxylic acid It may be a siloxane-containing polyamideimide obtained by reacting a mixture (mixture 3) of (1,3-dione isoindolinino) propylpolydimethylsiloxane (D) with an aromatic diisocyanate. The number of moles of 2,2-bis [4- {4- (5-hydroxycarbonyl-1,3-dione-isoindolino) phenoxy} phenyl] propane (C) is C, and bis (5-hydroxycarbonyl-1, When the number of moles of 3-dione isoindolino) propylpolydimethylsiloxane (D) is D and the number of moles of aromatic diisocyanate is ADI, the molar ratio C / D is 99.9 / 0.1-0. It may be adjusted to 1 / 99.9, and the molar ratio (C + D) / ADI may be adjusted to 1 / 1.05 to 1 / 1.50.

  The mixture 3 described above is, for example, a mixture of 2,2-bis [4- (4-aminophenoxy) phenyl] propane which is an aromatic diamine (A) and diaminopolydimethylsiloxane which is a siloxane diamine; It is obtained by reacting with a mellitic acid.

  The first SPAI may be a siloxane-containing polyamideimide obtained by reacting SPAI-1a obtained by the above method, the above mixture 3 and aromatic diisocyanate.

  The above diamine (A) which is a raw material of the first SPAI is, for example, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone, Bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4, 4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) And the like, and at least one selected from the group consisting of benzene and 1,4-bis (4-aminophenoxy) benzene. The above diamines (A) may be used alone or in combination. 2,2-bis [4- (4-aminophenoxy) phenyl] propane is particularly preferred from the viewpoint of the balance of the properties of polyamideimide and the cost.

  As said siloxane diamine (B) which is a raw material of 1st SPAI, what is represented by Chemical formula (14) may be used, for example.

Each of R ₂₃ and R ₂₄ in the chemical formula (14) independently represents a divalent organic group. Each of R ₂₅ , R ₂₆ , R ₂₇ and R _{28 in the} chemical formula (14) independently represents an alkyl group, a phenyl group or a substituted phenyl group. N2 in Chemical Formula (14) represents an integer of 1 to 50.

  Specific examples of the siloxane diamine (B) represented by the chemical formula (14) are represented, for example, by a kind of chemical formula selected from the group consisting of the following (15-a), (15-b) and (15-c) You may

N2 in the chemical formulas (15-a), (15-b) and (15-c) represents an integer of 1 to 50.

  The siloxane diamine (B) may be, for example, an amino-modified reactive silicone oil (a dimethylsiloxane having an amino group at both ends). Commercially available products of such siloxane diamines (B) are, for example, X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1,500), BY16-853 (amine equivalent 650) or BY16-853B (amine equivalent 2,200). X-22-161AS, X-22-161A and X-22-161B are all trade names manufactured by Shin-Etsu Chemical Co., Ltd. Both BY16-853 and BY16-853B are trade names manufactured by Toray Dow Corning Silicone Co., Ltd. (current company name: Toray Dow Corning Co., Ltd.).

  The above-mentioned siloxane diamines (B) may be used alone or in combination.

  The aromatic diisocyanate which is the raw material of the first SPAI is, for example, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate and 2,4'-diisocyanate. -At least one selected from the group consisting of tolylene diisocyanate dimers. The above aromatic diisocyanates may be used alone or in combination. In view of the fact that isocyanate groups are separated from each other in the molecular structure, and the concentration of amide groups and imide groups in the molecules of the first SPAI is relatively low and the solubility is excellent, 4,4'-diphenylmethane diisocyanate is particularly preferred. preferable. A reaction of a mixture of an aromatic diimide dicarboxylic acid and a siloxane diimide dicarboxylic acid with an aromatic diisocyanate at 100 to 200 ° C. from the viewpoint of generating the first SPAI in a short time while suppressing the reaction between isocyanates. preferable.

[Details of the second SPAI]
The second SPAI may have two or more carboxy groups at at least one end of both ends of the molecular chain of the second SPAI.

  The second SPAI may have a polysiloxane imide structure in the molecular chain of the second SPAI, and the polysiloxane imide structure may have an unsaturated bond-containing group in the side chain.

  The second SPAI may further include a polyoxypropyleneimide structure in the molecular chain of the second SPAI.

  At least one end of both ends of the molecular chain of the second SPAI may be an aromatic amide group having two or more carboxy groups.

  The second SPAI is a compound having three or more carboxy groups after reacting a dicarboxylic acid having a siloxane structure with a diisocyanate in a ratio of 1.05 to 1.45 moles of diisocyanate with respect to 1 mole of dicarboxylic acid. Can be obtained by further reacting them.

  The compound having three or more carboxy groups may be an aromatic tricarboxylic acid which is not subjected to dehydration ring closure.

  The second SPAI may comprise an organopolysiloxane structure.

  The second SPAI is preferably obtained by the reaction of a dicarboxylic acid compound and a diisocyanate. Specifically, at least one of the two ends of the molecular chain of the reaction product obtained by reacting in a ratio of 1.05 to 1.45 moles of diisocyanate to 1 mole of dicarboxylic acid is at least one carboxy group. It is preferable that it is obtained by introduce | transducing. When a dicarboxylic acid compound having a polysiloxane structure having an unsaturated bond-containing group in a side chain is used, a second SPAI including a siloxane imide structure having an unsaturated bond-containing group in a side chain can be produced. . In addition, the preparation method of the dicarboxylic acid compound which has unsaturated bond containing group in a side chain is mentioned later.

  As described above, when an excess of diisocyanate is reacted with the dicarboxylic acid compound, it is possible to form SPAI in which the molecular chain end is an isocyanate group. Then, only one of the above-mentioned carboxy groups is reacted with isocyanate by reacting a predetermined amount of, for example, a compound having three or more carboxy groups that do not close a ring with SPAI in which the molecular chain end is an isocyanate group. Can. This makes it possible to leave more than one carboxy group. Thus, a second SPAI having two or more carboxy groups at at least one end of both ends of the molecular chain can be produced. In the reaction of SPAI in which the molecular chain end is an isocyanate group and the compound having three or more carboxy groups which do not ring-close, gelation can be suppressed by selecting an amount ratio of the above-mentioned compounds. In addition, the carboxy group which does not ring-close here means the thing which does not carry out dehydration ring-closing under reaction temperature conditions of 100 degreeC or more. For example, in the case of a compound in which three carboxy groups are bonded to an aromatic ring or a fused ring, the positional relationship between the two nearest carboxy groups is such that carbon atoms to which the carboxy groups are bound separate at least one carbon atom. It refers to something in a connected relationship. That is, of the two or more carboxy groups (the three carboxy groups mentioned above) located at the end of the molecular chain of the second SPAI, one carboxy group is represented as carboxy group 1 and is located closest to carboxy group 1 When another carboxy group present is represented as carboxy group 2, the carbon to which carboxy group 1 is attached is represented as carbon 1, and the carbon to which carboxy group 2 is attached is represented as carbon 2, carbon 1 And carbon 2 may be bonded via at least one carbon atom. It is preferable to use such a compound because the carboxy groups are separated from each other and the ring closure does not occur to form an imide ring.

  The compound having three or more carboxy groups which do not undergo ring closure is preferably an aromatic polybasic acid, and is preferably one which does not undergo dehydration ring closure by heat. When the compound having three or more carboxy groups not subjected to ring closure is an aromatic polybasic acid, at least one end of both ends of the molecular chain of the second SPAI is an aromatic having two or more carboxy groups. It can be an amide group. Thereby, the heat resistance and hydrolysis resistance of the compound can be improved, and a cured product capable of forming a film without a support when the compound is thermally cured can be obtained. As such an aromatic polybasic acid, for example, 1,3,5-benzenetricarboxylic acid (trimesic acid), 1,3,5-naphthalenetricarboxylic acid, 1,3,7-naphthalenetricarboxylic acid, 1,5 And aromatic tricarboxylic acids such as 7-naphthalene tricarboxylic acid. Among these, 1,3,5-benzenetricarboxylic acid (trimesic acid) is particularly preferable from the viewpoint of easy availability and the formability of polyamideimide.

  Also, by reacting a predetermined amount of SPAI having an isocyanate group at the molecular chain end with a compound having two or more non-closed carboxy groups and a hydroxyl group, at least one of the two ends of the molecular chain may also be reacted It is possible to make a second SPAI having the above carboxy group. Examples of the compound having two or more non-cyclized carboxy groups and hydroxyl groups include phenolic hydroxyl group-containing aromatic polybasic acids such as hydroxyisophthalic acid and 2-hydroxy-3,6-carboxynaphthalene.

  The hydroxyl group contained in the phenolic hydroxyl group-containing aromatic polybasic acid is preferable in that it can be reacted at a lower temperature since it is more likely to react with an isocyanate than a carboxy group.

  In the reaction of an aromatic carboxy group in which a carboxy group is bonded to an aromatic ring with an isocyanate, an amide bond is formed, and in the reaction of a phenolic hydroxyl group and an isocyanate, a urethane bond is formed. From these differences in reactivity, for example, when an aromatic polybasic acid having one or more hydroxyl groups and two or more carboxy groups is used, two or more aromatic carboxys are formed at the molecular chain end via a urethane bond. A second SPAI can be made with remaining groups. Examples of the aromatic polybasic acid having one or more hydroxyl groups and two or more carboxy groups include hydroxyisophthalic acid, 2-hydroxy-3,6-carboxynaphthalene and the like. However, the second SPAI via the urethane bond may be inferior in heat resistance or hygroscopicity to the second SPAI via the amide bond.

  When an aromatic tricarboxylic acid that does not undergo ring closure is used as the aromatic polybasic acid, the amount added is the molecular weight (MW) of the aromatic tricarboxylic acid that does not undergo ring closure, and the mass (A) of SPAI whose molecular chain terminal is an isocyanate group And 0.3 to 1.2 times the amount determined by “2 × A × MW / Mn” from the number average molecular weight Mn of the SPAI, and preferably 0.5 to 1.0 times It is more preferable to do. If this amount is less than 0.3, the effect of introduction of two or more carboxy groups to the molecular terminal of SPAI tends to be small, and when the resin composition is made into a varnish, the microgel in the varnish is May generate. In addition, when this amount exceeds 1.2, unreacted tricyclic acid without reaction closure may precipitate in the varnish, and the film property may decrease. Thus, aromatic tricarboxylic acid without reaction closure without ring closure A filtration step is required to filter out the

  The number average molecular weight of the second SPAI is preferably 10,000 to 40,000, more preferably 15,000 to 30,000, and 18,000 to 25,000. More preferable. If the number average molecular weight exceeds 40,000, the moldability tends to be insufficient when formed into a film, and if less than 10,000, film formation becomes difficult and the strength of the film after heat curing is not good. It tends to be enough.

  The number average molecular weight of the second SPAI can be determined by converting a chromatogram of molecular weight distribution measured (at 25 ° C.) by GPC (gel permeation chromatography) using standard polystyrene.

  Moreover, it is preferable that it is 140-190 degreeC, and, as for the reaction temperature of SPAI in which a molecular chain terminal is an isocyanate group, and aromatic polybasic acid, it is more preferable that it is 160-180 degreeC.

  Next, the dicarboxylic acid and diisocyanate used for the formation of SPAI in which the molecular chain end is an isocyanate group will be described in detail.

  The dicarboxylic acid compound is preferably a diimide dicarboxylic acid obtained by reacting diamine and trimellitic anhydride. By selecting the structure of the diamine used for the reaction, it becomes possible to control the flexibility, heat resistance, strength and the like of the second SPAI.

  The diamine may be a diamine having an organopolysiloxane structure represented by the following chemical formula (1). By including a diamine having an organopolysiloxane structure in the above diamine, a second SPAI having an organopolysiloxane structure is obtained. The flexibility of the second SPAI containing the organopolysiloxane structure is improved over that of the polyamideimide not having the organopolysiloxane structure. Moreover, when the resin composition is used as a film, the film can be made to have a low modulus of elasticity in addition to the increase in the drying property of the film to facilitate the low volatilization differentiation of the film.

In Chemical Formula (1), each of R ₁ and R ₂ independently represents a divalent organic group, R ₃ , R ₄ , R _5, and R ₆ each independently represent a monovalent organic group, and n is Indicates an integer of 1 or more. Further, _{if R 3} and _{R 5} there are a plurality, the plurality of _{R 3} and _{R 5} may be different from each other.

  As the divalent organic group, an alkylene group, a phenylene group or a substituted phenylene group is preferable. Moreover, it is preferable that carbon number of the said bivalent organic group is 1-6. As said bivalent organic group, a C1-C3 alkylene group is still more preferable.

  The monovalent organic group is preferably an alkyl group, a phenyl group or a substituted phenyl group. Moreover, it is preferable that carbon number of the said monovalent organic group is 1-6. As said monovalent organic group, a C1-C3 alkyl group is still more preferable.

  In addition, n is preferably an integer of 1 to 50.

In the present embodiment, it is particularly preferable that R ₁ and R ₂ are all propylene groups, and all of R ₃ , R ₄ , R ₅ and R ₆ are methyl groups.

  As a diamine which has the organopolysiloxane structure shown by said Formula (1), the siloxane diamine of following Chemical formula (3) and (4) is mentioned, for example.

  N in the chemical formula (3) is as defined above. Further, in the chemical formula (4), m represents an integer of 1 or more, q represents an integer of 0 or more, and m + q is preferably 1 to 50.

  As siloxane diamine represented by the said Chemical formula (3), X-22-161AS (the present name: KF8010) (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent), for example Amine equivalent 1500) (above, Shin-Etsu Chemical Co., Ltd. product name), BY16-853 (amine equivalent 650), BY16-853 B (amine equivalent 2200), (above, Toray Dow Corning Silicone Co., Ltd. (current name: Toray Dow Corning Co., Ltd. product names) and the like. Examples of the siloxane diamine represented by the above formula (4) include X-22-9409 (amine equivalent of 700), X-22-1660B-3 (amine equivalent of 2200) (all manufactured by Shin-Etsu Chemical Co., Ltd., products) Name) etc.

The main chain of the second SPAI may contain an alkylene group and / or an oxyalkylene group in addition to the organopolysiloxane structure described above. That is, the main chain of the second SPAI may contain the following (I), (II) and (III).
(I) organopolysiloxane structure and alkylene group,
(II) organopolysiloxane structure and oxyalkylene group,
(III) organopolysiloxane structure, alkylene group and oxyalkylene group.

  Here, as an alkylene group of (I) and (III), a linear or branched alkylene group is preferable, and it is preferable that carbon number of the said alkylene group is 1-12. Moreover, it is preferable that carbon number of the oxyalkylene group of (II) and (III) is 1-6, and it is more preferable that it is 2-4. Two or more of the oxyalkylene groups may be repeated to form a polyoxyalkylene structure.

  The second SPAI containing the above (I), (II) and (III) is, for example, using, as the above diamine, a diamine having an alkylene group and / or an oxyalkylene group and a diamine having an organopolysiloxane structure Can be produced by

  Examples of the diamine containing an alkylene group and / or an oxyalkylene group include low molecular weight diamines such as hexamethylene diamine, nona methylene diamine and diaminodiethyl ether; both ends aminated polyethylene, both ends aminated polypropylene and so on Oligomers; or both-end aminated polymers can be exemplified. As a diamine which contains an alkylene group, carbon number of an alkylene group is four or more, and 6-18 are more preferable. In the present embodiment, it is particularly preferable to use a diamine having an alkylene group and an oxyalkylene group. As this diamine, diamines, such as following Chemical formula (6a), (6b), (6c) and (6d), are mentioned.

  In Chemical Formula (6a), a represents an integer of 2 to 70.

  In the chemical formula (6b), b, c and d each represent an integer of 1 or more. In addition, it is preferable that b + c + d is 5-40.

  As the diamines of (6a), (6b), (6c) and (6d), Jeffamine D 2000, Jeffamine D 230, Jeffamine D 400, Jeffamine D 4000, etc. Jeffamine D series, Jeffamine ED 600, Jeffamine respectively. Jeffamine ED series, such as ED900 and Jeffamine ED2003, Jeffamine XTJ-511, Jeffamine XTJ-512 (above, Huntsman company make, product name), etc. are mentioned.

  The molecular weight of the diamine having an alkylene group and / or an oxyalkylene group is preferably 30 to 20,000, more preferably 50 to 5,000, and still more preferably 100 to 3,000. When the molecular weight of the diamine having an alkylene group and / or an oxyalkylene group is within such a range, the occurrence of wrinkles and warpage after drying can be effectively reduced when the obtained fiber substrate is impregnated. It will be possible to Among them, Jeffamine is particularly preferable because it has an appropriate molecular weight and is excellent in the elastic modulus and the dielectric constant of the second SPAI to be obtained.

  It is particularly preferable that the main chain of the second SPAI contains the above (III). Moreover, it is particularly preferable that the alkylene group and the oxyalkylene group in this case have one or more of the structures of the following chemical formulas (4a), (4b), (4c) and (4d).

  In the chemical formula (4a), a is as defined in the chemical formula (6a).

  In chemical formula (4b), b, c and d are as defined in chemical formula (6b).

  The second SPAI containing a polysiloxane imide structure having an unsaturated bond-containing group in the side chain can be obtained, for example, by using, as the dicarboxylic acid compound, one containing a polysiloxane structure having an unsaturated bond-containing group in the side chain. It can be made. And the dicarboxylic acid compound which has unsaturated bond containing group in a side chain can be manufactured, for example by using the diamine which contains the polysiloxane structure which has unsaturated bond containing group in a side chain as said diamine. In addition, as a unsaturated bond containing group, a vinyl group, a phenyl group, etc. are mentioned, for example.

  Examples of the diamine containing a polysiloxane structure having an unsaturated bond-containing group in a side chain include polysiloxane diamine containing silicon to which a vinyl group is bonded. As such a polysiloxane diamine, the diamine etc. which are represented by following Chemical formula (1a) are mentioned, for example.

In the chemical formula (1a), R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R _{17 each} represent CH ₃ , C ₂ H ₅ or C ₃ H ₇ . In addition, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ may be identical to or different from each other. Each of R ₁₈ and R ₁₉ independently represents a divalent organic group. In addition, each of R ₁₈ and R ₁₉ is preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. n1 is an integer of 0 or more, m1 is an integer of 1 or more, and n1 + m1 is 1 to 50.

  As polysiloxane diamine represented by Chemical formula (1a), X-22-9412 (The Shin-Etsu Chemical Co., Ltd. make, product name) is commercially available.

  When the said diamine contains the diamine represented by Chemical formula (1a), it is preferable that it is 30-70 mass parts with respect to 100 mass parts of total amounts of the diamine to be used, and it is more preferable that it is 35-65 mass parts. Preferably, it is 40 to 60 parts by mass.

  Moreover, as polysiloxane diamine containing silicon which the phenyl group couple | bonded as an unsaturated bond, X-22-9409, X-22-1660-B3 (above, Shin-Etsu Chemical Co., Ltd. product name) etc. are mentioned. Can be mentioned.

  Here, when a mixture of a diamine having a polysiloxane structure having an unsaturated bond-containing group in the side chain and a terminal aminated polypropylene glycol is used as the diamine, a polysiloxane structure having an unsaturated bond-containing group in the side chain and A dicarboxylic acid compound having a polyoxypropylene structure can be produced. That is, when such a diamine is used as a diamine, it is possible to produce a second SPAI having a polysiloxane imide structure having an unsaturated bond-containing group in a side chain and a polyoxypropylene imide structure. According to such a second SPAI, the compound is further reduced in elastic modulus and elongation is improved.

  In this case, the terminal aminated polypropylene glycol is preferably 70 to 130 parts by mass and 80 to 120 parts by mass with respect to 100 parts by mass of the diamine containing a polysiloxane structure having an unsaturated bond-containing group in the side chain. It is more preferable that it is 90-110 mass parts.

  In the step of producing diimide dicarboxylic acid from diamine and trimellitic anhydride, it is preferable to use an aprotic polar solvent as a solvent. Examples of the aprotic polar solvent include dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 4-butyrolactone, sulfolane and the like. Among them, it is particularly preferable to use N-methyl-2-pyrrolidone which has a high boiling point and good solubility of the raw material and the obtained polymer, since the step of producing diimide dicarboxylic acid requires a high reaction temperature.

  The combined mass of the diamine and trimellitic anhydride is preferably an amount corresponding to 10 to 70% by mass with respect to the mass of the solvent. If it is less than 10% by mass, the solvent is consumed in large quantities, the efficiency is poor, and if it exceeds 70% by mass, the diamine and trimellitic anhydride can not be dissolved completely, which tends to make it difficult to perform a sufficient reaction. is there.

  The trimellitic anhydride is preferably used in a molar amount of 2.00 to 2.20 times the total number of moles of diamine. By using the amount of trimellitic anhydride of 2.00 to 2.20 times the molar amount of the amine mixture, it is possible to obtain a reaction product (diimidic dicarboxylic acid) in which both ends become a carboxy group more reliably, in a high yield. . As a result, since it is possible to increase the reactive activity point with diisocyanate, it becomes easy to obtain a high molecular weight second SPAI, and it is possible to further improve the mechanical strength of the obtained second SPAI.

  Moreover, it is preferable that it is 50-150 degreeC, and, as for the reaction temperature in reaction of diamine and trimellitic anhydride, it is more preferable that it is 50-90 degreeC. If the temperature is lower than 50 ° C., the reaction is slow and tends to be industrially disadvantageous, and if the temperature is higher than 150 ° C., the reaction with the non-cyclized carboxy group proceeds to inhibit the reaction to form imide Tend.

  In the diimide dicarboxylic acid production step, it is considered that the anhydride portion of trimellitic anhydride is once ring-opened and then subjected to dehydration ring closure to form an imide bond by the reaction of diamine and trimellitic anhydride. The dehydration ring closure reaction is preferably carried out by adding an aromatic hydrocarbon capable of azeotroping with water to the reaction mixture obtained at the end of the diimide dicarboxylic acid production step, and raising the temperature. Water generated by the dehydration ring closure reaction can be efficiently removed by adding water and an aromatic hydrocarbon capable of azeotroping to the reaction mixture.

  It is preferable to carry out the above-mentioned dehydration ring closure reaction until generation of water disappears. The completion of the dehydration ring closure reaction can be performed, for example, by confirming that the theoretical amount of water has been distilled off using a water content measuring receiver or the like.

  Examples of aromatic hydrocarbons that can be azeotroped with water include benzene, xylene, ethylbenzene, toluene and the like. Toluene is preferred because it is easy to distill off because of its low boiling point and its relatively low harmfulness.

  It is preferable to add an amount corresponding to 10 to 50% by mass with respect to the mass of the aprotic polar solvent, for the aromatic hydrocarbon which can be azeotroped with water. If the amount of aromatic hydrocarbon that can be azeotroped with water is less than 10% by mass with respect to the amount of aprotic polar solvent, the removal effect of water tends to decrease, and if it is 50% by mass or more, the product There is a tendency for certain diimide dicarboxylic acids to precipitate.

  The dehydration ring closure reaction is preferably carried out at a reaction temperature of 120 to 180 ° C. Temperatures below 120 ° C. may not be sufficient to remove water, and temperatures above 180 ° C. may not prevent aromatic hydrocarbon dissipation.

  Furthermore, it is preferable to remove the aromatic hydrocarbon which can be azeotroped with water before reacting the diimide dicarboxylic acid with the diisocyanate. In the state containing an aromatic hydrocarbon, there may be a case where a product, that is, a polyamideimide having an isocyanate group at the molecular chain end may be precipitated during the reaction. Although there is no restriction | limiting in particular in the method of removing an aromatic hydrocarbon, For example, the method of distilling off an aromatic hydrocarbon by raising temperature further after dehydration ring-closing reaction is mentioned.

  Examples of the diisocyanate to be reacted with the above-mentioned diimidodicarboxylic acid include 4,4'-diphenylmethane diisocyanate (hereinafter referred to as MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5- Aromatic diisocyanates such as diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, 2,4-tolylene dimer, and aliphatic diisocyanates such as hexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, etc. It can be mentioned. From the viewpoint of improving the heat resistance of polyamideimide, aromatic diisocyanate is preferable.

  The diisocyanate is preferably used in a molar amount of 1.05 to 1.45 times the total number of moles of the diimide dicarboxylic acid. By using a diisocyanate within the above range, the molecular weight of the second SPAI obtained can be made into a molecular weight range that allows melt molding. This makes it possible to suppress gelation in the subsequent reaction of SPAI in which the molecular chain end is an isocyanate group with a compound having three or more carboxy groups, and finally cures a compound containing a polyfunctional glycidyl compound. Growth can be made sufficient.

  Both terminal dicarboxylic acid modified polyamideimide (γ) and its preparation scheme are shown below.

  In the above scheme, the diamine having a siloxane structure X can be optionally selected from the diamines described above. Moreover, also about the diisocyanate which has Y, it can select arbitrarily from the diisocyanate mentioned above. Also, k is an integer of 1 or more. K is preferably 10 to 80, more preferably 20 to 50, and still more preferably 30 to 40. According to such a scheme, it is possible to prepare a both-terminal dicarboxylic acid modified second SPAI (γ) having an aromatic amide group having two or more carboxy groups at both ends. The above-described SPAI (β) having no carboxy group at both ends of the molecular chain may also be used in the compound according to the present embodiment.

  According to such a method, it is preferable to proceed efficiently without taking out the reaction product in all steps from the reaction of diamine and trimellitic anhydride to the formation of the second SPAI.

  Here, in the case where the both terminal dicarboxylic acid modified second SPAI (γ) is to be a both terminal dicarboxylic acid modified second SPAI including a polysiloxane imide structure having an unsaturated bond-containing group in the side chain, Let the diamine which has X be a diamine containing the polysiloxane structure which has unsaturated bond containing group in a side chain. According to such a scheme, both terminal dicarboxylic acid-modified second including a polysiloxane imide structure having an aromatic amide group having two or more carboxy groups at both ends and an unsaturated bond-containing group at a side chain It is possible to make SPAI.

  The diamine used to make the second SPAI may contain further diamines in addition to the above diamines. For example, the diamine may contain at least one of aliphatic diamine and aromatic diamine.

  Examples of aliphatic diamines include linear aliphatic diamines such as hexamethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine and octadecamethylene diamine, and terminal aminated polypropylene glycols. The aliphatic diamine preferably contains an ether group from the viewpoint of achieving both of a low elastic modulus and a high Tg, and is preferably a terminal aminated polypropylene glycol. Jeffamine D-230, D-400, D-2000, D-4000 (manufactured by Huntsman, product name) having different molecular weights can be obtained as the terminal aminated polypropylene glycol.

  As an aromatic diamine, for example, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4- (4-amino)] Aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4'-bis (4- Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis (trifluoro) (Methyl) biphenyl-4,4'-diamine, 2,6,2 ', 6'-tetramethyl-4,4'-diamine, 5,5'-dimethyl-2,2'-sulfonyl-biphenyl-4,4 '-Diamine, 3,3'-dihydroxybiphenyl-4,4'-diamine, (4,4'-diamino) diphenyl ether, (4,4'-diamino) diphenyl sulfone, (4,4'-diamino) benzophenone, Examples include (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether and the like.

(Details of epoxy resin)
The epoxy resin may be, for example, a resin having two or more epoxy groups in one molecule. The epoxy resin may have two or more glycidyl groups in one molecule. The epoxy resin may be cured at a temperature of 180 ° C. or less. The epoxy resin is, for example, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom containing type epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy resin, salicylaldehyde type epoxy resin, naphthols and phenol Copolymerized epoxy resin, epoxy compound of aralkyl type phenol resin, bisphenol type epoxy resin, glycidyl ether type epoxy resin of alcohols, glycidyl ether type epoxy resin of paraxylylene and / or metaxylylene modified phenolic resin, terpene modified phenolic resin Of glycidyl ether type epoxy resin, cyclopentadiene type epoxy resin, glycidyl ether type epoxy resin of polycyclic aromatic ring modified phenolic resin, naphthalene Containing phenolic resin glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl type or methyl glycidyl type epoxy resin, alicyclic type epoxy resin, halogenated phenol novolac type epoxy resin, hydroquinone type epoxy resin, trimethylolpropane type epoxy It may be at least one selected from the group consisting of a resin and a linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid. The epoxy resin may be liquid or semi-solid. The compound may include one of the above epoxy resins, and the compound may include one or more of the above epoxy resins.

(Reaction of second SPAI with epoxy resin)
In a compound containing SPAI and an epoxy resin which does not have two or more carboxy groups at at least one end of both ends of the molecular chain, the amide group in SPAI is a crosslinking point. Therefore, the resin in the C-stage state after heat curing tends to have a high crosslinking density. On the other hand, in the case of SPAI having two or more carboxy groups at at least one end of both ends of the molecular chain, the glycidyl group of the epoxy resin reacts with the carboxy group of SPAI preferentially over the amide group of SPAI. Do. Therefore, at the time of heat curing, chain elongation and crosslinking occur preferentially at the end of SPAI, and it becomes difficult for the amide group to form a crosslinking point. This makes it possible to achieve sufficient crosslinking of the entire resin composition contained in the compound while maintaining the crosslinking density of the soft component low. As a result, the present inventors believe that both mechanical strength and heat resistance can be achieved. However, the effects according to the present invention are not limited to the above.

  As a specific example for explaining the above-mentioned action and effect, a reaction (i) as a reaction (i) is exemplified as a reaction which is a reaction between the both-terminal dicarboxylic acid-modified SPAI and an epoxy resin (hereinafter sometimes referred to as “EP”). Show.

  In the above reaction (i), the reaction in the case of dicarboxylic acid-modified SPAI is shown schematically, but even if it is SPAI modified with dicarboxylic acid at one end, the epoxy resin is the molecular chain terminal of SPAI The reaction with the carboxy group or the isocyanate group of the above causes chain elongation and crosslinking, so that the same effect as described above can be exhibited.

  When SPAI has an unsaturated bond-containing group in the side chain, the side chain unsaturated bond-containing group improves the compatibility of SPAI with a curing agent such as an epoxy resin and a phenol resin, thereby reacting the epoxy resins with each other or The reaction between the epoxy resin and the curing agent is suppressed from occurring preferentially to the reaction between the epoxy resin and the SPAI. As a result, it is considered that the elastic modulus of the cured resin tends to be low. Such a presumption is based on the findings of the present inventors that the unsaturated bond-containing group remains unreactive at the time of heat curing. However, the above-mentioned effect concerning the present invention is not limited to the above-mentioned matter.

  As a specific example for explaining the above-mentioned function and effect, both-terminal dicarboxylic acid modified SPAI containing a polysiloxane imide structure having an unsaturated bond-containing group in a side chain, and an epoxy resin (hereinafter sometimes referred to as "EP") What represented the reaction with and is shown below as reaction (ii).

  In the above reaction (ii), the reaction in the case of the both terminal dicarboxylic acid modified SPAI is shown schematically, but even if it is SPAI in which the carboxylic acid is modified at one end, the epoxy resin is the molecular chain terminal of SPAI The reaction with the carboxy group or the isocyanate group of the above causes chain elongation and crosslinking, so that the same effect as described above can be exhibited.

(Details of curing agent)
The curing agent is classified into a curing agent which cures an epoxy resin in a range from low temperature to room temperature, and a heat curing type curing agent which cures an epoxy resin with heating. Examples of curing agents that cure epoxy resins in the range from low temperature to room temperature include aliphatic polyamines, polyaminoamides, polymercaptans and the like. The heat-curable curing agent is, for example, an aromatic polyamine, an acid anhydride, a phenol novolac resin, and dicyandiamide (DICY).

  When a curing agent for curing the epoxy resin in the range from low temperature to room temperature is used, the glass transition point of the cured product of the epoxy resin is low, and the cured product of the epoxy resin tends to be soft. As a result, the molded body composed of the cured product of the compound also tends to be soft. On the other hand, from the viewpoint of improving the heat resistance of the molded product, the curing agent may preferably be a heat-curing type curing agent, more preferably a phenol resin, and still more preferably a phenol novolac resin. In particular, by using a phenol novolac resin as a curing agent, a cured product of an epoxy resin having a high glass transition temperature can be easily obtained. As a result, the heat resistance and mechanical strength of the molded body can be easily improved.

  The phenolic resin is, for example, an aralkyl type phenolic resin, a dicyclopentadiene type phenolic resin, a salicylaldehyde type phenolic resin, a novolak type phenolic resin, a copolymer type phenolic resin of benzaldehyde type phenol and an aralkyl type phenol, paraxylylene and / or metaxylylene modified From the group consisting of phenolic resin, melamine modified phenolic resin, terpene modified phenolic resin, dicyclopentadiene type naphthol resin, cyclopentadiene modified phenolic resin, polycyclic aromatic ring modified phenolic resin, biphenyl type phenolic resin, and triphenylmethane type phenolic resin It may be at least one selected. The phenolic resin may be a copolymer composed of two or more of the above. As a commercially available phenol resin, for example, Tamanor 758 manufactured by Arakawa Chemical Industries, Ltd., HP-850N manufactured by Hitachi Chemical Co., Ltd., or the like may be used.

  The phenol novolac resin may be, for example, a resin obtained by condensation or cocondensation of phenols and / or naphthols with aldehydes under an acidic catalyst. The phenols constituting the phenol novolac resin may be, for example, at least one selected from the group consisting of phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol and aminophenol. The naphthols constituting the phenol novolac resin may be, for example, at least one selected from the group consisting of α-naphthol, β-naphthol and dihydroxynaphthalene. The aldehydes constituting the phenol novolac resin may be, for example, at least one selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde.

  The curing agent may be, for example, a compound having two phenolic hydroxyl groups in one molecule. The compound having two phenolic hydroxyl groups in one molecule may be, for example, at least one selected from the group consisting of resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenol.

  The curing agent may be at least one selected from the group consisting of amines, polyfunctional phenols, and acid anhydrides. For example, when the curing agent is an amine, the content of the curing agent is preferably such that the equivalent of active hydrogen in the amine and the epoxy equivalent in the epoxy resin are approximately equal. Here, it is preferable that the epoxy equivalent of an epoxy resin is a value which also considered reaction with the amide group of polyamidoimide. When the curing agent is a polyfunctional phenol or acid anhydride, it is preferable that the phenolic hydroxyl group or carboxy group is 0.6 to 1.2 equivalents to 1 equivalent of the epoxy resin. If the content of the curing agent is too low, uncured epoxy resin tends to remain in the cured product of the compound, and the glass transition point Tg of the cured product of the compound tends to be low. When the content of the curing agent is too large, unreacted curing agent tends to remain in the cured product of the compound, and the insulating property of the cured product of the compound tends to be reduced. However, even if the content of the curing agent is out of the above range, the effects according to the present invention can be obtained.

  The compound may comprise one of the above phenolic resins, and the compound may comprise more than one of the above phenolic resins. The compound may comprise one of the above mentioned curing agents, and the compound may comprise more than one of the above curing agents.

  The ratio of the active group (phenolic OH group) in the curing agent that reacts with the epoxy group in the epoxy resin is preferably 0.5 to 1.5 equivalents, more preferably one equivalent to the epoxy group in the epoxy resin. May be 0.9 to 1.4 equivalents, more preferably 1.0 to 1.2 equivalents. When the ratio of active groups in the curing agent is less than 0.5 equivalent, the amount of OH per unit mass of the epoxy resin after curing decreases, and the curing rate of the resin composition (epoxy resin) decreases. If the ratio of active groups in the curing agent is less than 0.5 equivalent, the glass transition temperature of the resulting cured product may be lowered, or a sufficient elastic modulus of the cured product may not be obtained. On the other hand, when the ratio of active groups in the curing agent exceeds 1.5 equivalents, the mechanical strength of the molded article after curing tends to decrease. However, even if the ratio of the active group in the curing agent is outside the above range, the effect according to the present invention can be obtained.

(Details of curing accelerator)
The curing accelerator is not limited as long as it is, for example, a composition that reacts with the epoxy resin to accelerate the curing of the epoxy resin. The curing accelerator may be, for example, an alkyl group-substituted imidazole or an imidazole such as benzimidazole. The compound may comprise one type of cure accelerator, and may comprise multiple cure accelerators.

  When the curing accelerator is an imidazole, the content of the curing accelerator is not set based on the equivalent of active hydrogen in imidazole, but empirically, 0.001 to 100 parts by mass of epoxy resin. It is preferably 10 parts by mass. If the content of the curing accelerator is too low, the uncured epoxy resin tends to remain in the cured product of the compound, and the glass transition point Tg of the cured product of the compound tends to be low. When the content of the curing accelerator is too large, unreacted curing accelerator tends to remain in the cured product of the compound, and the insulating property of the cured product of the compound tends to be reduced. However, even if the content of the curing accelerator is outside the above range, the effects according to the present invention can be obtained.

(Details of coupling agent)
The coupling agent improves the adhesion between the resin composition and the metal element-containing powder, and improves the mechanical strength of a molded body composed of a cured product of the compound. The coupling agent may be, for example, at least one selected from the group consisting of silane compounds (silane coupling agents), titanium compounds, aluminum compounds (aluminum chelates), and aluminum / zirconium compounds. The silane coupling agent may be, for example, at least one selected from the group consisting of epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, acid anhydride silane and vinylsilane. In particular, aminophenyl-based silane coupling agents are preferred. The compound may include one of the above coupling agents, and may include more than one of the above coupling agents.

(Details of fluidization aid)
The compound may contain a flow aid to improve the flowability of the compound. The flow aid may be, for example, inorganic fine particles. The inorganic fine particles may be, for example, at least one selected from the group consisting of silica, alumina, calcium carbonate, kaolin clay, titanium oxide, barium sulfate, zinc oxide, aluminum hydroxide, magnesium hydroxide, talc and mica. Among these, silica is preferable because it is inexpensive. The silica may be, for example, Aerosil®. When the compound contains alumina, the thermal conductivity of the resulting molded body is likely to be improved. The compound may include one of the flow aids described above, and may include a plurality of flow aids of the above. The average particle size (D ₅₀ ) of the flow aid may be 100 nm or less, or 10 nm or less. When the average particle size (D ₅₀ ) of the flow aid is within the above range, the mechanical strength of the molded article is likely to be improved.

  The compounds may contain flame retardants because of their environmental safety, recyclability, moldability and low cost. The flame retardant is, for example, at least one selected from the group consisting of bromine flame retardants, stalk flame retardants, hydrated metal compound flame retardants, silicone flame retardants, nitrogen containing compounds, hindered amine compounds, organic metal compounds and aromatic engineering plastics It may be. The compound may include one of the above-described flame retardants, and may include more than one of the above-described flame retardants.

  The compound may comprise further resins in addition to the SPAI and the epoxy resin. The compound may contain, for example, at least one selected from the group consisting of silicone resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyethylene terephthalate. The resin contained in the compound may be only SPAI and epoxy resin.

(Method of manufacturing compound)
Although the manufacturing method of the compound which concerns on this embodiment is not limited, For example, you may be as follows. First, a resin solution is prepared by uniformly stirring and mixing SPAI, an epoxy resin, metal element-containing powder, and an organic solvent. In other words, the resin solution, the metal element-containing powder and the organic solvent are mixed to prepare a resin solution. The resin solution may contain a curing agent. The resin solution may contain a curing accelerator. The resin solution may contain additives such as coupling agents, flow aids, flame retardants, and lubricants. The resin solution is prepared by preparing in advance a varnish containing components (SPAI, epoxy resin and organic solvent) excluding metal element-containing powder and additives, and uniformly stirring and mixing the varnish, metal element-containing powder and additives, It may be prepared. The additive may be contained in the resin solution or may not be contained in the resin solution, but may be added to the coarse powder described later according to the type. The organic solvent is not particularly limited as long as it is a liquid that dissolves the resin composition. The organic solvent is, for example, at least one selected from the group consisting of N-methyl pyrrolidinone (N-methyl-2-pyrrolidone), γ-butyrolactone, dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, methyl isobutyl ketone, toluene and xylene. Good. The organic solvent may be a low boiling point solvent or a high boiling point solvent. The low boiling point solvent may be, for example, at least one selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, toluene and xylene. The high boiling point solvent may be, for example, at least one selected from the group consisting of N-methyl pyrrolidinone, γ-butyrolactone, dimethylformamide, and dimethyl sulfoxide. The organic solvent may be only a low boiling point solvent. The organic solvent may be only a high boiling point solvent. The organic solvent may be a mixed solvent of a high boiling point solvent and a low boiling point solvent. The resin solution may include one of the above-described organic solvents, and may include a plurality of the above-described organic solvents.

  Subsequently, aggregates are obtained by sufficiently removing the organic solvent from the above resin solution. Here, along with the removal of the organic solvent, the resin composition adheres to the surfaces of the individual particles constituting the metal element-containing powder. The resin composition may be attached to the entire surface of the particle or may be attached to only a part of the surface of the particle. The method for removing the organic solvent from the resin solution is not particularly limited. For example, when the organic solvent is a low boiling point solvent, the low boiling point solvent is easy to dry. Therefore, the organic solvent can be removed from the resin solution by drying the resin solution. The method of drying the resin solution may be, for example, vacuum drying. When the organic solvent is a high boiling point solvent, the organic solvent may be removed from the resin solution by, for example, the following method. First, the resin solution is poured into the poor solvent, and the resin solution is brought into contact with the poor solvent to obtain a precipitate. The poor solvent is a solvent in which the resin composition is difficult to dissolve. The poor solvent may be, for example, methanol. The precipitate may be further washed with a poor solvent. Subsequently, the precipitate is dried to obtain aggregates. The method of drying the precipitate may, for example, be vacuum drying. When SPAI has two or more carboxy groups at at least one end of both ends of the molecular chain of SPAI, the SPAI is easily soluble in a low boiling point solvent. Therefore, when using the above-mentioned SPAI having two or more carboxy groups, a low boiling point solvent can be used as the organic solvent, and the resin composition can be easily attached to the metal element-containing powder by drying the resin solution. Can.

  Subsequently, the above aggregate is coarsely crushed to obtain a coarse powder. The particle size of the coarse powder may be adjusted to increase the density of the shaped body. The particle size of the coarse powder may be adjusted, for example, by removing the coarse powder from the coarse powder using a sieve.

  A lubricant may be added to the crude powder obtained above in order to reduce damage to the mold in the second step described later. The lubricant is not particularly limited. The lubricant may be, for example, at least one selected from the group consisting of metal soaps and wax-based lubricants. The metal soap may be, for example, at least one selected from the group consisting of zinc stearate, magnesium stearate, lithium stearate, and calcium stearate. The wax-based lubricant may be, for example, at least one selected from the group consisting of long chain hydrocarbon, EBS (ethylene bis-stearic acid amide), and polyethylene. Also, in order to reduce damage to the mold in the second step, a lubricant is dispersed in a suitable dispersion medium to prepare a dispersion, and the dispersion is used as a wall in the mold die (wall in contact with the punch) And the applied dispersion may be dried. A powdery compound is obtained by the above method.

(Application of compound)
Depending on the composition or combination of the metal element-containing powder contained in the compound, various properties such as electromagnetic properties or thermal conductivity of the molded article composed of the cured product of the compound can be freely controlled, and the molded article can be variously It can be used for industrial products or their raw materials. Industrial products manufactured using the compound may be, for example, automobiles, medical devices, electronic devices, electric devices, information communication devices, home appliances, audio devices, and general industrial devices. For example, when the compound contains a powder of permanent magnet as a metal element-containing powder, the compound may be used as a raw material of a bonded magnet. When the compound contains a magnetic powder such as an Fe-Si-Cr alloy or ferrite as a metal element-containing powder, a molded body (for example, a sheet) produced from the compound is used as a raw material (for example, core) of an inductor such as an EMI filter May be done. When the compound contains iron powder and copper powder as the metal element-containing powder, a formed body (for example, a sheet) produced from the compound may be used as an electromagnetic wave shield. The molded object comprised from the hardened | cured material of the compound which concerns on this embodiment has high mechanical strength, and is excellent in heat resistance. Therefore, even if the molded body is used in an on-vehicle environment exposed to a high temperature of, for example, 200 ° C. or higher, or exposed to a high temperature in refrigerator oil for a long time, the mechanical strength of the molded body does not easily decrease. It is difficult to change the dimensions of the molded body.

<Cured product of compound>
The cured product according to the present embodiment is a cured product of the above compound. The cured product may comprise cured SPAI and epoxy resin, and metal element-containing powder bound to each other by the cured SPAI and epoxy resin. In other words, the cured product may include the cured resin composition and the metal element-containing powder bound to each other by the cured resin composition. The "cured resin composition" may be described as "cured resin". The SPAI included in the compound may have two or more carboxy groups at at least one end of both ends of the molecular chain of the SPAI, and the cured product includes the carboxy group and the epoxy group of the epoxy resin. It may contain a reaction site. The reactive site is a site formed by the reaction of a carboxy group and an epoxy group. When the cured product contains a reaction site of a carboxy group and an epoxy group, the toughness of a molded article composed of the cured product tends to be large.

  The glass transition temperature is a temperature at which tan δ peaks (maximum) in dynamic viscoelasticity measurement. The resin cured product may have a glass transition point derived from dimethylsiloxane at around -50 ° C. Above this temperature range, the stress relaxation function of the siloxane structure works, and the stress is dispersed when an external impact is applied to the molded body. As a result, the mechanical strength of the molded body tends to be high. The resin cured product may have a glass transition temperature derived from a crosslinked structure formed by the reaction of an epoxy group possessed by the epoxy resin and an amide group possessed by the polyamideimide. The glass transition temperature derived from the crosslinked structure may be, for example, 150 ° C. or more, preferably 180 ° C. or more, and more preferably 200 ° C. or more. When the resin cured product has a glass transition temperature of 150 ° C. or more, the mechanical strength of a molded article composed of the cured product of the compound is unlikely to decrease even under a high temperature environment.

  The thermal decomposition temperature is a 5% thermal weight loss temperature. The thermal decomposition temperature of the resin cured product may be, for example, 350 ° C. or higher. When the thermal decomposition temperature of the resin cured product is within the above range, the wettability and adhesion between the resin cured product and the metal element-containing powder are likely to be improved. As a result, the heat resistance and the mechanical strength of the molded article composed of the cured product of the compound can be easily improved, and the mechanical strength of the molded article can not be easily reduced. Therefore, when the thermal decomposition temperature of the resin cured product is within the above range, the molded product is suitable for industrial products in the automotive field.

(Method of manufacturing molded body)
The manufacturing method of the molded object comprised from the hardened | cured material of the compound which concerns on this embodiment may be equipped with a 1st process, a 2nd process, and a 3rd process. Below, the detail of each process is demonstrated.

  In the first step, the resin composition is attached to the surfaces of the individual particles constituting the metal element-containing powder to produce a compound. The method of making the compound may be as described above.

  In the second step, the compound is pressurized in a mold to obtain a molded body (a molded body of B-stage). Here, the resin composition is filled between the individual particles constituting the metal element-containing powder. And a resin composition functions as a binding material (binder), and mutually binds the individual particles which constitute metal element content powder. The higher the pressure exerted on the compound, the higher the density of the molded body, and the higher the mechanical strength of the molded body. When manufacturing a bonded magnet, the higher the pressure exerted on the compound, the higher the magnetic flux density of the bonded magnet tends to be, and the higher the mechanical strength of the bonded magnet. The pressure exerted on the compound may be, for example, preferably 500 MPa or more and 2500 MPa or less, more preferably 1400 MPa or more and 2000 MPa or less. When the pressure exerted on the compound is within the above range, the mass productivity of the molded product is likely to be improved and the life of the mold is likely to be extended. The relative density of the shaped body to the true density of the metal element-containing powder may be, for example, preferably 75% to 86%, and more preferably 80% to 86%. If the relative density of the shaped body is within the above range, a shaped body having sufficient mechanical strength, heat resistance, and physical properties derived from the metal element-containing powder can be easily obtained.

  In the third step, the compact is cured by heat treatment to obtain a C-staged compact. The temperature of the heat treatment may be a temperature at which the resin composition in the molded body is sufficiently cured. The temperature of the heat treatment may be, for example, preferably 150 ° C. or more and 300 ° C. or less, more preferably 175 ° C. or more and 250 ° C. or less. In order to suppress the oxidation of the metal element-containing powder in the molded body, the heat treatment is preferably performed in an inert atmosphere. When the heat treatment temperature exceeds 300 ° C., the metal element-containing powder is oxidized or the cured resin product is degraded by a trace amount of oxygen inevitably contained in the atmosphere of the heat treatment. In order to cure the resin composition sufficiently while suppressing the oxidation of the metal element-containing powder and the deterioration of the cured resin, the holding time of the heat treatment temperature is preferably several minutes to 4 hours, more preferably 5 minutes. It may be one hour or less.

<Bond magnet>
The bonded magnet according to the present embodiment includes a cured product of the above compound. The bonded magnet may consist only of the cured product of the compound, and may contain other components in addition to the cured product.

  The magnetic flux density of Nd-Fe-B based magnets is high, and Nd-Fe-B based magnets have very strong magnetic force. Therefore, when producing a bonded magnet using a compound, it is preferable to use a powder of Nd-Fe-B based magnet (Nd-Fe-B based alloy) as the metal element-containing powder. When the space factor of powder of Nd-Fe-B based magnet in bonded magnet is 83% or more, sufficient magnetic characteristics can be obtained even if the bonded magnet is used as a rotor of a motor having a shaft member, etc. easy. The cured resin composition is excellent in wettability and adhesiveness with the metal element-containing powder. Therefore, the space factor of the powder of the Nd-Fe-B based magnet in the bonded magnet can be, for example, 95% or more or 98% or more. The higher the space factor of the powder of the Nd-Fe-B magnet, the higher the magnetic force of the bond magnet, the higher the density of the bond magnet, and the higher the mechanical strength of the bond magnet.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited by these examples.

<Synthesis of Polyamideimide>
Synthesis Example 1
A 1-liter separable flask equipped with a 25 ml water content receiver with a faucet, a thermometer and a stirrer was prepared. A reflux condenser was connected to the moisture determination receiver. In this separable flask, 65.7 g (0.16 mol) of diamine having three or more aromatic rings, 33.3 g (0.04 mol) of siloxane diamine, 80.7 g (0.42 mol) of trimellitic anhydride (TMA), And 560 g of aprotic polar solvent.

  As a diamine having three or more aromatic rings, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) was used. As siloxane diamine, the reactive silicone oil "X-22-161AS" made from Shin-Etsu Chemical Co., Ltd. was used. The amine equivalent of siloxane diamine was 416. N-methyl-2-pyrrolidone (NMP) was used as an aprotic polar solvent.

  The raw material in the separable flask was stirred at 80 ° C. for 30 minutes. Subsequently, 100 ml of an aromatic hydrocarbon which can be azeotroped with water was placed in a separable flask. Toluene was used as an aromatic hydrocarbon capable of azeotroping with water.

  The material in the separable flask was refluxed by heating at about 160 ° C. for 2 hours. It was confirmed that about 7.2 ml or more of water was accumulated in the water content measuring receiver and that distillation of water was not observed. The toluene in the separable flask was removed from the raw material by heating the raw material in the separable flask to about 190 ° C. while removing the distillate accumulated in the water quantitative receiver. After the raw material was returned to room temperature, 60.1 g (0.24 mol) of aromatic diisocyanate was charged in a separable flask. As aromatic diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI) was used.

  The raw material in the separable flask was heated at 190 ° C. for 2 hours to obtain an NMP solution of polyamideimide of Synthesis Example 1. The polyamideimide of Synthesis Example 1 had a siloxane structure.

(Composition example 2)
A 1-liter separable flask equipped with a 25 ml water content receiver with a faucet, a thermometer and a stirrer was prepared. A reflux condenser was connected to the moisture determination receiver. In this separable flask, 52.4 g (0.06 mol) of siloxane diamine, 80.0 g (0.04 mol) of aliphatic diamine, 2.1 g (0.01 mol) of "Wandamine WHM" manufactured by Shin Nippon Rika Co., Ltd., anhydrous 40.3 g (0.21 mol) of trimellitic acid (TMA) and 357 g of an aprotic polar solvent were contained.

  As the siloxane diamine, a reactive silicone oil “X-22-9412” manufactured by Shin-Etsu Chemical Co., Ltd. was used. The amine equivalent of siloxane diamine was 437. As aliphatic diamine, "D2000" manufactured by Mitsui Chemicals Fine Inc. was used. The amine equivalent of aliphatic diamine was 1000. N-methyl-2-pyrrolidone (NMP) was used as an aprotic polar solvent.

  The raw material in the separable flask was stirred at 80 ° C. for 30 minutes. Subsequently, 120 ml of an aromatic hydrocarbon which can be azeotroped with water was placed in a separable flask. Toluene was used as an aromatic hydrocarbon capable of azeotroping with water.

  The material in the separable flask was refluxed by heating at about 160 ° C. for 2 hours. It was confirmed that about 3.8 ml or more of water was accumulated in the water content measuring receiver and that distillation of water was not observed. The toluene in the separable flask was removed from the raw material by heating the raw material in the separable flask to about 190 ° C. while removing the distillate accumulated in the water quantitative receiver. After this raw material was cooled to 50 ° C., 32.5 g (0.13 mol) of aromatic diisocyanate was charged in a separable flask. As aromatic diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI) was used.

  The material in the separable flask was heated at 180 ° C. for 2 hours. After this raw material was cooled to 50 ° C., 2.6 g (0.0122 mol) of trimesic acid (1,3,5-benzenetricarboxylic acid) was placed in a separable flask. The raw material in the separable flask was heated at 160 ° C. for 1 hour to obtain an NMP solution of polyamideimide of Synthesis Example 2. The polyamideimide of Synthesis Example 2 had a siloxane structure. The end of the molecular chain of the polyamideimide of Synthesis Example 2 had two carboxy groups. The number average molecular weight of the polyamideimide of Synthesis Example 2 was 30,500. The non volatile matter content of the NMP solution of polyamide imide of synthesis example 2 was 34 mass%.

(Comparative Example 1)
A 1-liter separable flask equipped with a 25 ml water content receiver with a faucet, a thermometer and a stirrer was prepared. A reflux condenser was connected to the moisture determination receiver. In this separable flask, 82.13 g (0.20 mol) of diamine having three or more aromatic rings, 33.3 g (0.04 mol) of siloxane diamine, 80.7 g (0.42 mol) of trimellitic anhydride (TMA), And 560 g of aprotic polar solvent.

  As a diamine having three or more aromatic rings, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) was used. N-methyl-2-pyrrolidone (NMP) was used as an aprotic polar solvent.

  The raw material in the separable flask was stirred at 80 ° C. for 30 minutes. Subsequently, 100 ml of an aromatic hydrocarbon which can be azeotroped with water was placed in a separable flask. Toluene was used as an aromatic hydrocarbon capable of azeotroping with water.

  The material in the separable flask was refluxed by heating at about 160 ° C. for 2 hours. It was confirmed that about 7.2 ml or more of water was accumulated in the water content measuring receiver and that distillation of water was not observed. The toluene in the separable flask was removed from the raw material by heating the raw material in the separable flask to about 190 ° C. while removing the distillate accumulated in the water quantitative receiver. After the raw material was returned to room temperature, 60.1 g (0.24 mol) of aromatic diisocyanate was charged in a separable flask. As aromatic diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI) was used.

  The raw material in the separable flask was heated at 190 ° C. for 2 hours to obtain an NMP solution of polyamideimide of Comparative Synthesis Example 1. The polyamideimide of Comparative Synthesis Example 1 did not have a siloxane structure.

Preparation of Varnish
(Varnish 1)
The NMP solution of polyamideimide of Synthesis Example 1, an epoxy resin, a curing accelerator, and a dilution solvent were placed in a plastic container. The content of each of the NMP solution of the polyamideimide of Synthesis Example 1 in the raw material in the plastic container, the epoxy resin, and the curing accelerator was adjusted to the value shown in Table 1 below (unit: mass part). In Table 1, "SPAI" means an NMP solution of polyamideimide having a siloxane structure. "PAI" means an NMP solution of polyamideimide without a siloxane structure.

  As the epoxy resin, "NC3000H" manufactured by Nippon Kayaku Co., Ltd. was used. As a solvent, a mixed solution of γ-butyrolactone (GBL) and methyl ethyl ketone (MEK) was used. In Table 1, "GBL / MEK" means a mixture of GBL and MEK. As a curing accelerator, "2E4MZ" manufactured by Shikoku Kasei Kogyo Co., Ltd. was used.

  Varnish 1 was obtained by stirring and mixing the raw materials in the plastic container at a rotation number of 40 rpm for 1 hour using a mix rotor. Content of the non volatile matter (solid content) of the varnish 1 was a value (unit: mass%) shown by Table 1.

[Calculation of glass transition point]
Varnish 1 was applied to the surface of the copper foil. As copper foil, "F2-WS-12" made by Furukawa Circuit Foil Co., Ltd. was used. The thickness of the copper foil was 12 μm. The sheet was formed on the surface of the copper foil by drying the varnish 1 applied to the copper foil at 140 ° C. for 15 minutes. The thickness of the dried sheet was 50 μm. Two sheets formed on the surface of copper foil were produced by the above-mentioned method. A laminate was formed by superposing the surfaces of the two sheets. The laminate was vacuum pressed. In a vacuum press, the laminate was heated at 200 ° C. for 1 hour while being pressurized at 2 MPa. Subsequently, the copper foil was removed from the laminate by etching treatment to obtain a resin film. The dynamic viscoelasticity of the resin film was measured using a dynamic viscoelasticity measuring device. As a dynamic viscoelasticity measuring device, REO-GEL E-4000 made by UBM Corporation was used. In the measurement of dynamic viscoelasticity, the resin film was heated from 30 ° C. to 350 ° C. at a heating rate of 5 ° C./min. As dynamic viscoelasticity, storage elastic modulus E ′ and loss elastic modulus E ′ ′ were measured. Tan δ was calculated from E ′ and E ′ ′. tan δ is defined as the ratio of loss modulus E ′ ′ to storage modulus E ′ (E ′ ′ / E ′). In the measurement of the above-mentioned dynamic viscoelasticity, the temperature at which tan δ shows a maximum was calculated as the glass transition point Tg (unit: ° C.). The Tg of the resin film produced from Varnish 1 is shown in Table 1.

[Measurement of thermal decomposition temperature]
The resin film was produced from the varnish 1 by the method similar to calculation of said glass transition point. The thermal weight loss temperature of 5% was measured as the thermal decomposition temperature using TG-DTA manufactured by Bruker Co., Ltd. In the measurement of the thermal decomposition temperature, the resin film was heated at a temperature rising rate of 10 ° C./minute in an air atmosphere. The thermal decomposition temperature of the resin film produced from the varnish 1 is shown in Table 1.

(Varnish 2 to 5)
In preparation of each varnish 2-5, each raw material was filled in the plastic container so that it might become the composition shown in Table 1 of the composition of each varnish. Varnishes 2 to 5 were prepared in the same manner as Varnish 1 except for the above points.

  The resin film was produced from each of varnish 2-5 by the method similar to varnish 1, and Tg of each resin film was computed. Each Tg is shown in Table 1. By the method similar to the varnish 1, the resin film was produced from each of varnish 2-5, and the thermal decomposition temperature of each resin film was measured. Each thermal decomposition temperature is shown in Table 1.

<Production of Bonded Magnet>
Example 1
The above varnish 1, magnetic powder, and silane coupling agent were placed in a 650 ml ointment container. The content of each of the varnish 1, the magnetic powder, and the silane coupling agent in the raw material in the ointment container was adjusted to the value (unit: mass part) shown in Table 2 below.

  A neodymium-iron-boron alloy was used as the magnetic powder. As the neodymium-iron-boron alloy, "MQP-B" manufactured by Moricorp Magnench Co., Ltd. was used. The average particle size of the magnetic powder was 100 μm. As a silane coupling agent, "KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd. was used.

  The raw material in the ointment container was stirred at a revolution speed of 1000 rpm and a rotation speed of 500 rpm for 40 seconds using a revolution stirrer, and then cooled to room temperature. This operation was repeated three times. Subsequently, the whole of the raw material in the ointment container was poured into 500 ml of methanol. The precipitate formed in methanol was further washed with methanol. The precipitate was vacuum dried at room temperature for 24 hours to obtain aggregates. The aggregate was coarsely crushed to obtain a coarse powder. The particle size of the coarse powder was adjusted by removing the coarse powder from the coarse powder using a 100 mesh sieve. 0.3 parts by mass of a lubricant was added to 100 parts by mass of the coarse powder whose particle size was adjusted. Calcium stearate was used as a lubricant. The compound of Example 1 was obtained by mixing this coarse powder and a lubricant using a V-type mixer for about 1.0 hour. In Table 2, a "coating method" means the method of making a resin composition adhere on the surface of metal element containing powder (magnetic powder). "Poor solvent contact" means that the raw material in the ointment container was brought into contact with a poor solvent (methanol).

By pressing the compound of Example 1 at 2000 MPa using a hydraulic press, a cylindrical compression-molded article was obtained. The dimensions of the compression molded article were outer diameter 11.3 mm × height 8 mm. The compression molded product was heated at 200 ° C. for 10 minutes in a nitrogen gas (N ₂ ) atmosphere to cure the compression molded product, thereby obtaining a bonded magnet (cured product of compound) of Example 1.

[Crushing strength test]
Using a universal compression tester, compressive pressure was applied to the virgin bonded magnet of Example 1 from the height direction. As a universal compression tester, "AG-10TBR" manufactured by Shimadzu Corporation was used. The maximum value of the compression pressure when the bond magnet was broken by the compression pressure was calculated as the crush strength (unit: MPa). The crushing strength of the unused bonded magnet of Example 1 is shown in Table 2.

Thermal degradation test
A thermal deterioration test was performed on the bonded magnet of Example 1 not used. In the thermal degradation test, an unused bonded magnet was heated at 200 ° C. for 1000 hours in an air atmosphere in a dryer.

  The crush strength of the bonded magnet after the thermal degradation test was calculated by the same method as the crush strength test described above. The crush strength of the bonded magnet of Example 1 after the thermal deterioration test is shown in Table 2.

(Example 2)
In Example 2, the compound of Example 2 was obtained by the same method as in Example 1 except that the above-mentioned varnish 2 was used instead of varnish 1.

  A bonded magnet of Example 2 was obtained in the same manner as Example 1, except that the compound of Example 2 was used instead of the compound of Example 1.

  The crushing strength of the unused bonded magnet of Example 2 and the crushing strength of the bonded magnet of Example 2 after the thermal deterioration test were respectively calculated by the same method as in Example 1. Each result is shown in Table 2.

(Example 3)
The above varnish 3, magnetic powder, and silane coupling agent were placed in a 300 ml eggplant type flask. The content of each of the varnish 3, the magnetic powder and the silane coupling agent in the raw material in the eggplant-type flask was adjusted to the value shown in Table 2 (unit: mass part).

  A neodymium-iron-boron alloy was used as the magnetic powder. As the neodymium-iron-boron alloy, "MQP-B" manufactured by Moricorp Magnench Co., Ltd. was used. The average particle size of the magnetic powder was 100 μm. As a silane coupling agent, "KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd. was used.

  The raw material in the eggplant-type flask was stirred at 25 ° C. for about 30 minutes in an evaporator. The pressure in the evaporator was reduced, and the raw material was removed from the eggplant type flask. The inside of the evaporator was depressurized to 0.1 MPa or less, and the raw material was vacuum dried to sufficiently remove the solvent from the raw material to obtain an aggregate. The aggregate was coarsely crushed to obtain a coarse powder. The particle size of the coarse powder was adjusted by removing the coarse powder from the coarse powder using a 100 mesh sieve. 0.3 parts by mass of a lubricant was added to 100 parts by mass of the coarse powder whose particle size was adjusted. Calcium stearate was used as a lubricant. The compound of Example 3 was obtained by mixing this coarse powder and a lubricant using a V-type mixer for about 1.0 hour. In Table 2, "vacuum drying" means that the raw material in the eggplant-type flask was vacuum-dried.

  A bonded magnet of Example 3 was obtained in the same manner as Example 1, except that the compound of Example 3 was used instead of the compound of Example 1.

  By the same method as in Example 1, the crushing strength of the unused bonded magnet of Example 3 and the crushing strength of the bonded magnet of Example 3 after the thermal deterioration test were respectively calculated. Each result is shown in Table 2.

(Example 4)
In Example 4, the compound of Example 4 was obtained in the same manner as in Example 3 except that the varnish 4 was used instead of the varnish 3.

  The bonded magnet of Example 4 was obtained in the same manner as in Example 1 except that the compound of Example 4 was used instead of the compound of Example 1.

  The crushing strength of the unused bonded magnet of Example 4 and the crushing strength of the bonded magnet of Example 4 after the thermal deterioration test were respectively calculated by the same method as in Example 1. Each result is shown in Table 2.

(Comparative example 1)
13.0 g of an epoxy resin, 7.0 g of a curing agent, 0.13 g of a curing accelerator, a magnetic powder, and a silane coupling agent were placed in a 300 ml eggplant-type flask. Of the raw materials in the eggplant-type flask, the remaining part excluding the magnetic powder and the silane coupling agent corresponds to the varnish of Comparative Example 1. The content of each of the varnish, the magnetic powder, and the silane coupling agent of Comparative Example 1 in the raw material in the eggplant type flask was adjusted to the value (unit: mass part) shown in Table 2.

  As the epoxy resin, "EPPN 502H" manufactured by Nippon Kayaku Co., Ltd. was used. As a curing agent, "HP850N" manufactured by Hitachi Chemical Co., Ltd. was used. As a curing accelerator, "2PZ-CN" manufactured by Shikoku Kasei Kogyo Co., Ltd. was used. A neodymium-iron-boron alloy was used as the magnetic powder. As the neodymium-iron-boron alloy, "MQP-B" manufactured by Moricorp Magnench Co., Ltd. was used. The average particle size of the magnetic powder was 100 μm. As a silane coupling agent, "KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd. was used.

  The raw material in the eggplant-type flask was stirred at 25 ° C. for about 30 minutes in an evaporator. The pressure in the evaporator was reduced, and the raw material was removed from the eggplant type flask. The inside of the evaporator was decompressed to 0.1 MPa or less, and the solvent was sufficiently removed from the raw material to obtain an aggregate. The aggregate was coarsely crushed to obtain a coarse powder. The particle size of the coarse powder was adjusted by removing the coarse powder from the coarse powder using a 100 mesh sieve. 0.3 parts by mass of a lubricant was added to 100 parts by mass of the coarse powder whose particle size was adjusted. Calcium stearate was used as a lubricant. The compound of Comparative Example 1 was obtained by mixing this coarse powder and a lubricant using a V-type mixer for about 1.0 hour. The compound of Comparative Example 1 did not contain SPAI.

  A bonded magnet of Comparative Example 1 was obtained by the same method as that of Example 1, except that the compound of Comparative Example 1 was used instead of the compound of Example 1.

  By the method similar to Example 1, the crushing strength of the bonded magnet of Comparative Example 1 of unused and the crushing strength of the bonded magnet of Comparative Example 1 after the thermal deterioration test were respectively calculated. Each result is shown in Table 2.

(Comparative example 2)
In Comparative Example 2, a compound of Comparative Example 2 was obtained by the same method as Example 1 except that the above-mentioned varnish 5 was used instead of varnish 1.

  A bonded magnet of Comparative Example 2 was obtained by the same method as that of Example 1, except that the compound of Comparative Example 2 was used instead of the compound of Example 1.

  The crushing strength of the bonded magnet of Comparative Example 2 not in use and the crushing strength of the bonded magnet of Comparative Example 2 after the thermal deterioration test were respectively calculated by the same method as Example 1. Each result is shown in Table 2.

  As shown in Table 2, the crush strength of the bonded magnets of each of the unused Examples 1 to 4 was higher than the crush strength of each of the bonded magnets of the unused Comparative Examples 1 and 2. The crushing strength of the bonded magnet of each of Examples 1 to 4 after the thermal deterioration test was higher than the crushing strength of each of the bonded magnets of Comparative Examples 1 and 2 after the thermal deterioration test. In Examples 1 to 4, compared with Comparative Examples 1 and 2, the value obtained by subtracting the crushing strength of the bonded magnet after the thermal deterioration test from the crushing strength of the unused bonded magnet was smaller. That is, in Examples 1 to 4, compared to Comparative Examples 1 and 2, the decrease in the crush strength of the bonded magnet in the thermal deterioration test was suppressed. According to the present invention, it has been confirmed that a compound capable of producing a molded article having high mechanical strength and excellent heat resistance, a cured product of the compound, and a bonded magnet including the cured product are provided.

  The compound according to the present invention is used, for example, as a material of a bonded magnet.

Claims (8)

A polyamideimide having a siloxane structure,
Epoxy resin,
Powder containing metal element,
Equipped with
compound. The polyamideimide has two or more carboxy groups at at least one end of both ends of a molecular chain of the polyamideimide.
A compound according to claim 1. The metal element-containing powder is a powder of a rare earth magnet,
A compound according to claim 1 or 2. For bonded magnets,
The compound as described in any one of Claims 1-3.   The hardened | cured material of the compound as described in any one of Claims 1-4. The polyamideimide has two or more carboxy groups at at least one end of both ends of the molecular chain of the polyamideimide,
The cured product includes a reaction site of the carboxy group and an epoxy group of the epoxy resin.
The cured product according to claim 5. The cured polyamideimide and the epoxy resin;
The cured polyamidoimide and the metal element-containing powder mutually bound by the epoxy resin;
Equipped with
The hardened | cured material of Claim 5 or 6.   A bonded magnet comprising the cured product according to any one of claims 5 to 7.