Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
  • H01B3/305—Polyamides or polyesteramides

Definitions

• the present invention relates to high-voltage insulating materials, high-voltage insulating molded products, and their applications.
• Polyamide resins have excellent mechanical properties, surface appearance, and heat resistance, making them ideal for use in automobiles and electrical/electronic parts.
• polyamide resins are used in engine peripheral parts due to their excellent mechanical properties and heat resistance, but in recent years, as engine peripheral parts have become denser and engine power has increased, the environmental conditions around the engine have become increasingly severe, and there is a demand for mechanical properties and surface appearances that can withstand higher temperatures and humidity.
• weight reduction, space saving, and increased capacity are also progressing, and there is a growing demand for improved properties for resin molded products that make up part of the parts.
• polyamide resin materials with high insulating properties.
• Patent Document 1 discloses a polyamide resin composition containing, per 100 parts by weight of (A) polyamide resin, (B) 0.5 to 10 parts by weight of a compound represented by the following general formula (1), and (C) 0.005 to 0.5 parts by weight of a fatty acid metal salt, in which the weight ratio of metal elements contained in component (C) relative to component (B) is 100 ppm or more and 5000 ppm or less.
• X is one bond selected from amine, ketone, ether and sulfonyl.
• R 1 to R 10 may be the same or different and are any one selected from hydrogen, a halogen atom, a hydroxyl group, an amino group, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.
• the present invention has an object to solve the above problems, and to provide an insulating material having excellent mechanical strength and high withstand voltage, and an insulating molded article having high withstand voltage.
• A represents the content (mass %) of the ring (a) in the polyamide resin (A) based on the molecular weight
• B represents the average number of bonds between the ring (a) and the amide bond closest to the ring (a) in each structural unit
• C represents the average number of bonds between the positions at which groups linked from
• ⁇ 2> The high-voltage insulating material according to ⁇ 1>, wherein the content of the ring (a) in the polyamide resin (A) is 10 to 40 mass% based on the molecular weight.
• ⁇ 3> The high-voltage insulating material according to ⁇ 1> or ⁇ 2>, wherein the value of B in formula (A) is 0.8 to 3.2.
• ⁇ 4> The high-voltage insulating material according to any one of ⁇ 1> to ⁇ 3>, wherein the value of C in formula (A) is 1.0 to 3.0.
• the high-voltage insulating material according to any one of ⁇ 1> to ⁇ 4>, in which the structural unit including the front ring (a) includes a structural unit represented by formula (X).
• Formula (X) (In formula (X), R 1 to R 8 each independently represent a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms. Cy represents a benzene ring, a naphthalene ring, or a cyclohexane ring. Each n1 independently represents an integer of 0 to 2, and each n2 independently represents 0 or 1.
• the polyamide resin (A) contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, ⁇ 5>
• the polyamide resin (A) contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, ⁇ 5>
• the polyamide resin (A) contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit,
• the high-voltage insulating material according to any one of ⁇ 1> to ⁇ 7>, wherein the diamine-derived structural unit includes a diamine-derived structural unit represented by formula (Y): Formula (Y) (In formula (Y), R 1 to R 8 each independently represent a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms.
• the polyamide resin (A) contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, ⁇ 9> The high-voltage insulating material according to any one of ⁇ 1> to ⁇ 8>, wherein the diamine-derived structural unit includes a xylylenediamine-derived structural unit.
• the polyamide resin (A) contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, 30 mol % or more of the dicarboxylic acid-derived structural units contain aliphatic dicarboxylic acid-derived structural units having 4 to 20 carbon atoms.
• the polyamide resin (A) contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, 70 mol % or more of the dicarboxylic acid-derived structural units contain structural units derived from an aliphatic dicarboxylic acid having 4 to 20 carbon atoms.
• the polyamide resin (A) contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit,
• the high-voltage insulating material according to any one of ⁇ 1> to ⁇ 11>, wherein the dicarboxylic acid-derived structural unit includes at least one of adipic acid, sebacic acid, and dodecanedioic acid.
• the polyamide resin (A) contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, 70 mol % or more of the diamine-derived structural units contain xylylenediamine-derived structural units, ⁇ 13>
• ⁇ 15> The high withstand voltage insulating material according to any one of ⁇ 1> to ⁇ 14>, wherein the insulating material has a time to breakdown at a voltage of 2000 V according to JIS-C2136 constant voltage tracking method of 30 minutes or more.
• ⁇ 16> A high-voltage insulating molded product formed from the high-voltage insulating material according to any one of ⁇ 1> to ⁇ 15>.
• the content ratio of the ring (a) in the polyamide resin (A) based on the molecular weight is 10 to 60 mass % and the polyamide resin (A) satisfies formula (A), and is used in a high-voltage insulating material.
• A represents the content (mass %) of the ring (a) in the polyamide resin (A) based on the molecular weight
• B represents the average number of bonds between the ring (a) and the amide bond closest to the ring (a) in each structural unit
• C represents the average number of bonds between the positions at which groups linked from amide bonds are bonded to the ring (a) in each structural unit.
• the polyamide resin (A) has a content ratio of the ring (a) based on the molecular weight of 10 to 60 mass% and satisfies formula (A), and the polyamide resin (A) is melt-kneaded with other components and then molded.
• A represents the content (mass %) of the ring (a) in the polyamide resin (A) based on the molecular weight
• B represents the average number of bonds between the ring (a) and the amide bond closest to the ring (a) in each structural unit
• C represents the average number of bonds between the positions at which groups linked from amide bonds are bonded to the ring (a) in each structural unit.
• the present invention provides a high-voltage insulating material with excellent mechanical strength, and a high-voltage insulating molded product.
• FIG. 1 is a diagram showing the relationship between formula (A) and anti-tracking time for each of the examples and comparative examples.
• the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.
• the use of "to” means that the numerical values before and after it are included as the lower limit and upper limit.
• various physical properties and characteristic values are those at 23° C. unless otherwise specified.
• groups (atomic groups) in this specification the notation that does not indicate whether it is substituted or unsubstituted includes both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents.
• alkyl group includes not only alkyl groups that have no substituents (unsubstituted alkyl groups), but also alkyl groups that have substituents (substituted alkyl groups).
• the notation that does not indicate whether it is substituted or unsubstituted is preferably unsubstituted. If the measurement methods, etc. described in the standards shown in this specification vary from year to year, they will be based on the standards as of January 1, 2022, unless otherwise specified.
• the high-voltage insulating material of the present embodiment is characterized in that it contains a polyamide resin (A) including a structural unit containing a ring (a) selected from the group consisting of a benzene ring, a naphthalene ring, and a cyclohexane ring, and the content ratio of the ring (a) in the polyamide resin (A) based on the molecular weight is 10 to 60 mass %, and the material satisfies formula (A).
• a polyamide resin (A) including a structural unit containing a ring (a) selected from the group consisting of a benzene ring, a naphthalene ring, and a cyclohexane ring, and the content ratio of the ring (a) in the polyamide resin (A) based on the molecular weight is 10 to 60 mass %, and the material satisfies formula (A).
• A represents the content (mass %) of the ring (a) in the polyamide resin (A) based on the molecular weight
• B represents the average number of bonds between the ring (a) and the amide bond closest to the ring (a) in each structural unit
• C represents the average number of bonds between the positions at which groups linked from amide bonds are bonded to the ring (a) in each structural unit.
• resins with many ring structures such as aromatic rings tend to have poorer insulation (e.g., tracking resistance). Specifically, the more ring structures there are, the more likely a carbonized conductive path is formed in the resin, and the insulation tends to deteriorate. Among ring structures, this tendency is particularly noticeable when the resin has an aromatic ring. In this embodiment, despite the use of a polyamide resin containing a ring structure such as an aromatic ring, the insulation, particularly the tracking resistance under high voltage, is not deteriorated.
• A the content (mass%) of the ring (a) in the polyamide resin (A) based on the molecular weight
• B the average number of bonds between the ring (a) and the amide bond closest to the ring (a) in each structural unit
• C By precisely adjusting the average number of bonds between the positions in each structural unit where the groups connected from the amide bonds are bonded to the ring (a), it is possible to adjust the proportion of the ring (a) in the structural unit and the size of the structural unit, and provide an insulating material with excellent mechanical strength and high voltage resistance.
• the polyamide resin (A) in this embodiment contains a ring (a) selected from the group consisting of a benzene ring, a naphthalene ring, and a cyclohexane ring.
• a a ring selected from the group consisting of a benzene ring, a naphthalene ring, and a cyclohexane ring.
• the number of rings (a) per one structural unit of the polyamide resin (A) is not particularly limited as long as the content ratio of the ring (a) in the polyamide resin (A) based on the molecular weight standard is satisfied, and may be one or two or more.
• the number (average value) of rings (a) per one structural unit is preferably 0.9 to 2.5, more preferably 0.9 to 2.0, even more preferably 0.9 to 1.7, even more preferably 0.9 to 1.4, and even more preferably 0.9 to 1.1.
• the benzene ring, naphthalene ring and cyclohexane ring may have a substituent, but it is preferable that they have no substituent.
• examples of the substituent include a hydrocarbon group having 1 to 3 carbon atoms and a halogen atom.
• examples of the substituent include those that do not have a phenolic hydroxyl group.
• the ring (a) preferably contains a benzene ring or a naphthalene ring, and more preferably contains a benzene ring.
• a benzene ring or a naphthalene ring particularly a benzene ring, there is a tendency that the mechanical strength is further improved and the deterioration of the insulating properties at a high withstand voltage can be more effectively suppressed.
• the content ratio of the ring (a) in the polyamide resin (A) based on the molecular weight is 10 to 60% by mass.
• the content ratio based on the molecular weight means the formula weight of the ring structure relative to the formula weight of each structural unit (the molecular weight when the structural unit is assumed to be a molecule).
• the structural unit has a composition formula in which the part derived from adipic acid is C 6 H 8 O 2 , the part derived from metaxylylenediamine is C 8 H 10 N 2 , the formula weight of the structural unit is 246.3, and the composition formula derived from the ring (a) (benzene ring) is C 6 H 4 , which is 76.1, so that (76.1/246.3) x 100 ⁇ 30.9% by mass.
• the ring structure has a substituent, the molecular weight of the ring structure does not include the substituent.
• the dicarboxylic acid structural unit is derived from 5-hydroxyisophthalic acid
• the composition formula derived from 5-hydroxyisophthalic acid is C 8 H 4 O 3
• the composition formula derived from ring (a) (benzene ring) not including the substituent is C 6 H 3 , which is 75.1.
• the content ratio of the ring (a) in the polyamide resin (A) based on the molecular weight (i.e., A in formula (A) described in detail later) is 10% by mass or more, preferably 14% by mass or more, more preferably 16% by mass or more, even more preferably 18% by mass or more, even more preferably 20% by mass or more, even more preferably 22% by mass or more, and may be 24% by mass or more or 26% by mass or more depending on the application. By making it equal to or more than the lower limit, the mechanical strength of the obtained molded product tends to be further improved.
• the content ratio of the ring (a) in the polyamide resin (A) based on the molecular weight is 60% by mass or less, preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 33% by mass or less, and may be 32% by mass or less or less than 32% by mass depending on the application.
• the high voltage insulating material of the present embodiment may contain only one type of polyamide resin (A) or may contain two or more types. When two or more types are contained, the total content is the sum of the values obtained by multiplying the content ratio of the ring (a) of each polyamide resin (A) based on the molecular weight by the mass fraction.
• the polyamide resin (A) in this embodiment satisfies formula (A).
• A represents the content (mass %) of the ring (a) in the polyamide resin (A) based on the molecular weight
• B represents the average number of bonds between the ring (a) and the amide bond closest to the ring (a) in each structural unit
• C represents the average number of bonds between the positions at which groups linked from amide bonds are bonded to the ring (a) in each structural unit.
• the value of [B/(A ⁇ C)] ⁇ 100 is preferably 1.0 or more, more preferably 1.7 or more, even more preferably 2.3 or more, even more preferably 2.7 or more, and even more preferably 3.1 or more. By making it equal to or more than the lower limit, the tracking resistance time under high voltage conditions tends to be improved.
• the value of [B/(A ⁇ C)] ⁇ 100 is preferably 5.0 or less, more preferably 4.1 or less, even more preferably 3.9 or less, even more preferably 3.6 or less, and even more preferably 3.4 or less. By making it equal to or less than the upper limit, the bending elastic modulus per tracking resistance time represented by formula (B) tends to be improved.
• the higher the flexural modulus per tracking resistance time the higher the flexural modulus value and the better the mechanical properties.
• the higher the flexural modulus per tracking resistance time the better the performance of the mechanical properties in terms of tracking resistance.
• the polyamide resin (A) satisfying the formula (A) exhibits both high levels of tracking resistance and mechanical properties under high voltage.
• A is the content ratio of the ring (a) in the polyamide resin (A) based on the molecular weight, and the larger this value is, the higher the ratio of the ring (a) is, and the more likely it is that a carbonized conductive path will be formed.
• B represents the average number of bonds between the ring (a) in each structural unit and the amide bond closest to the ring (a).
• the number of bonds between the ring (a) and the amide bond closest to the ring (a) is 2.
• the value of B is the number of bonds between Cy (corresponding to ring (a)) and ad (amide bond) in the part enclosed in a square shown below, so when n1 and n2 are 1, it is 4.
• R 1 to R 8 each independently represent a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms.
• Cy represents a benzene ring, a naphthalene ring, or a cyclohexane ring.
• Each n1 independently represents an integer of 0 to 2, and each n2 independently represents 0 or 1.
• ad represents an amide bond.
• the value of B is usually 0.5 or more, preferably 0.8 or more, more preferably 1.0 or more, even more preferably 1.1 or more, even more preferably 1.5 or more, and even more preferably 1.8 or more. By making it equal to or more than the lower limit, the tracking resistance time under high voltage conditions tends to be improved. Although it is only a guess, when the value of B is small, the amide bond and the ring (a) in which electrons are delocalized tend to interact with each other in the molecule under high voltage, and the carbonized conductive path is easily formed. In other words, the value of B is larger, the better.
• the value of B is preferably 4.0 or less, more preferably 3.5 or less, even more preferably 3.0 or less, still more preferably 2.5 or less, and even more preferably 2.2 or less.
• C represents the average number of bonds between the positions where the groups linked from the amide bonds are bonded to the ring (a) in each structural unit.
• the group linked from the amide bond means the amide bond -CH 2 - portion.
• the number of bonds between the two amide bonds -CH 2 - is 1 and 2 as shown below, so C is 2.
• the value of C (average value) is 3.0 or less, preferably less than 3.0, more preferably 2.5 or less, even more preferably 2.3 or less, and even more preferably 2.1 or less.
• the lower limit of the value of C is preferably 1.0 or more, more preferably 1.3 or more, even more preferably 1.5 or more, and even more preferably 1.8 or more.
• the structural unit containing the ring (a) preferably contains a structural unit represented by formula (X).
• the structural unit represented by formula (X) may contain only one type, or may contain two or more types.
• Formula (X) (In formula (X), R 1 to R 8 each independently represent a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms. Cy represents a benzene ring, a naphthalene ring, or a cyclohexane ring. Each n1 independently represents an integer of 0 to 2, and each n2 independently represents 0 or 1. ad represents an amide bond.)
• R 1 to R 8 each independently represent a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms, and each independently is preferably a hydrogen atom or a methyl group.
• Cy represents a benzene ring, a naphthalene ring, or a cyclohexane ring, preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.
• n1 each independently represents an integer of 0 to 2.
• the first example of n1 is that n1 is 0.
• a second example of n1 is that n1 is 1.
• a third example of n1 is that n1 is 2.
• the first to third examples of n1 are appropriately selected depending on the application, etc.
• n2 is 0 or 1.
• the first example of n2 is that n2 is 0.
• a second example of n2 is when n2 is 1.
• the first and second examples of n2 are appropriately selected depending on the application, etc.
• n1 is 0 and n2 is 1, and/or that n1 is 1 and 2 is 1.
• Cy is preferably linked to the para or meta position.
• the polyamide resin (A) contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and it is preferable that 30 mol% or more of the diamine-derived structural units contain structural units containing the ring (a) (for example, a diamine-derived structural unit represented by formula (Y), and furthermore, a xylylenediamine-derived structural unit), it is more preferable that 70 mol% or more of the diamine-derived structural units contain structural units containing the ring (a), it is even more preferable that 80 mol% or more of the diamine-derived structural units contain structural units containing the ring (a), it is even more preferable that 90 mol% or more of the diamine-derived structural units contain structural units containing the ring (a), and it is even more preferable that 95 mol% or more of the diamine-derived structural units contain structural units containing the ring (a).
• a for example, a diamine-derived structural unit represented by formula (Y), and furthermore, a
• the polyamide resin (A) contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and the diamine-derived structural unit preferably contains a diamine-derived structural unit represented by formula (Y).
• Formula (Y) (In formula (Y), R 1 to R 8 each independently represent a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms. Each n independently represents an integer of 0 to 2.)
• R 1 to R 8 have the same meaning as R 1 to R 8 in formula (X), and the preferred ranges are also the same.
• each n is independently an integer of 0 to 2.
• the first example of n is that n is 0.
• a second example of n is that n is 1.
• a third example of n is that n is 2.
• the first to third examples of n are appropriately selected depending on the application, etc.
• the benzene ring is preferably a ring having the above-mentioned substituent (aminoalkyl group) at the para or meta position.
• the diamine constituting the structural unit derived from the diamine is exemplified by xylylenediamine, benzenediethaneamine, benzenedipropaneamine, and bisaminomethylcyclohexane, preferably xylylenediamine and/or benzenediethaneamine, and more preferably xylylenediamine.
• the preferred ratio of these diamines in the structural unit derived from the diamine is as described above.
• the xylylenediamine metaxylylenediamine and/or paraxylylenediamine is more preferred.
• the molar ratio (m/p) of metaxylylenediamine to paraxylylene in the xylylenediamine is preferably 100-10/0-90, more preferably 100-30/0-70, even more preferably 100-60/0-40, and even more preferably 100-90/0-10.
• the benzenediethaneamine is preferably m-benzenediethaneamine and/or p-benzenediethaneamine, and more preferably p-benzenediethaneamine.
• the benzenedipropaneamine is preferably m-benzenedipropaneamine and/or p-benzenedipropaneamine, and more preferably p-benzenedipropaneamine.
• the bisaminomethylcyclohexane is preferably 1,3-bisaminomethylcyclohexane and/or 1,4-bisaminomethylcyclohexane, more preferably 1,3-bisaminomethylcyclohexane.
• the diamine constituting the structural unit other than the structural unit containing the ring (a) can be a wide variety of known chain aliphatic diamines, and aliphatic diamines having 6 to 12 carbon atoms are preferred, such as 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, and the like.
• Examples include linear aliphatic diamines such as 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine, and branched aliphatic diamines such as 2-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine, 2,2,4-/2,4,4-trimethylhexamethylenediamine, 2-methyl-1,5-pentanediamine, 2-methyl-1,6-hexanediamine, and 2-methyl-1,7-heptanediamine.
• linear aliphatic diamines such as 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine
• branched aliphatic diamines such as 2-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine, 2,2,4-/2,4,4-trimethylhexamethylened
• the dicarboxylic acid-derived structural unit may be a structural unit that does not contain the ring (a) or a structural unit that contains the ring (a).
• the polyamide resin (A) contains diamine-derived structural units and dicarboxylic acid-derived structural units, and it is preferable that 30 mol% or more of the dicarboxylic acid-derived structural units contain structural units derived from aliphatic dicarboxylic acids having 4 to 20 carbon atoms, it is more preferable that 70 mol% or more of the dicarboxylic acid-derived structural units contain structural units derived from aliphatic dicarboxylic acids having 4 to 20 carbon atoms, it is even more preferable that 80 mol% or more of the dicarboxylic acid-derived structural units contain structural units derived from aliphatic dicarboxylic acids having 4 to 20 carbon atoms, it is even more preferable that 90 mol% or more of the dicarboxylic acid-derived structural units contain structural units derived from aliphatic dicarboxylic acids having 4 to 20 carbon atoms, and it is even more preferable that 95 mol% or more of the dicarboxylic acid-derived structural units contain
• Examples of aliphatic dicarboxylic acids having 4 to 20 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and it is more preferable to include at least one of adipic acid, sebacic acid, and dodecanedioic acid, and it is even more preferable to include adipic acid and/or sebacic acid (preferably adipic acid).
• the polyamide resin (A) contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 30 mol% or more of the dicarboxylic acid-derived structural unit contains an aromatic dicarboxylic acid-derived structural unit containing a ring (A).
• the polyamide resin (A) contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and it is more preferred that 70 mol% or more of the dicarboxylic acid-derived structural unit contains an aromatic dicarboxylic acid-derived structural unit containing a ring (A), it is even more preferred that 80 mol% or more of the dicarboxylic acid-derived structural unit contains an aromatic dicarboxylic acid-derived structural unit containing a ring (A), it is even more preferred that 90 mol% or more of the dicarboxylic acid-derived structural unit contains an aromatic dicarboxylic acid-derived structural unit containing a ring (A), and it is even more preferred that 95 mol% or more of the dicarboxylic acid-derived structural unit contains an aromatic dicarboxylic acid-derived structural unit containing a ring (A).
• aromatic dicarboxylic acids containing a ring (A) include isophthalic acid, terephthalic acid, orthophthalic acid, phenylene diacetic acid (o-phenylene diacetic acid, p-phenylene diacetic acid, m-phenylene diacetic acid), and naphthalene dicarboxylic acids (1,2-naphthalene dicarboxylic acid, 1,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and 2,7-naphthalene dicarboxylic acid).
• polyamide resin (A) contains diamine-derived structural units and dicarboxylic acid-derived structural units, and 30 mol % or more of the dicarboxylic acid-derived structural units contain aromatic dicarboxylic acid-derived structural units containing ring (A), the diamine-derived structural units may or may not contain aromatic dicarboxylic acid-derived structural units containing ring (A).
• the polyamide resin (A) used in this embodiment preferably contains a dicarboxylic acid-derived structural unit and a diamine-derived structural unit, but may contain structural units other than the dicarboxylic acid-derived structural unit and the diamine-derived structural unit, or other moieties such as terminal groups.
• Examples of other structural units include, but are not limited to, structural units derived from lactams such as ⁇ -caprolactam, valerolactam, laurolactam, and undecalactam, and aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid.
• the polyamide resin (A) used in this embodiment may contain trace components such as additives used in the synthesis.
• the polyamide resin (A) used in the present embodiment is preferably composed of 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 98% by mass or more of dicarboxylic acid-derived structural units and diamine-derived structural units.
• the polyamide resin (A) used in this embodiment preferably has an amino group (-NH 2 ) or a carboxylic acid group (-COOH) as a terminal group.
• the polyamide resin (A) may be capped with a terminal capping agent, and the terminal capping agent preferably has 8 or less carbon atoms.
• a first embodiment of the polyamide resin (A) used in the present embodiment contains diamine-derived structural units and dicarboxylic acid-derived structural units, in which 70 mol % or more of the diamine-derived structural units contain diamine-derived structural units represented by formula (Y), and 70 mol % or more of the dicarboxylic acid-derived structural units contain at least one of adipic acid, sebacic acid, and dodecanedioic acid.
• a second embodiment of the polyamide resin (A) used in the present embodiment contains diamine-derived structural units and dicarboxylic acid-derived structural units, in which 70 mol % or more of the diamine-derived structural units contain diamine-derived structural units represented by formula (Y), and 70 mol % or more of the dicarboxylic acid-derived structural units contain adipic acid and/or sebacic acid.
• the diamine represented by formula (Y) is preferably metaxylylenediamine, paraxylylenediamine, parabenzenediethaneamine, or 1,3-bisaminomethylcyclohexane, and more preferably metaxylylenediamine and/or paraxylylenediamine.
• the polyamide resin (A) used in this embodiment preferably does not have an imide group. In other words, it is preferably not a polyamideimide.
• the polyamide resin (A) in the high voltage insulating material of this embodiment preferably has a moisture content (hereinafter sometimes referred to as "humidity-conditioned moisture content") of 1 mass% or more when measured according to the moisture evaporation method of JIS K 7251 after storing the polyamide resin (A) in an environment of 85°C/85% RH for 300 hours.
• a moisture content hereinafter sometimes referred to as "humidity-conditioned moisture content”
• the moisture content of the polyamide resin (A) in the high voltage insulating material of this embodiment is also preferably 8 mass% or less. By making the moisture content equal to or less than the upper limit, resistance to acids and alkalis tends to be improved.
• the formula weight (average value) of the constituent units of the polyamide resin (A) used in this embodiment is preferably 200 or more, and more preferably 220 or more. This tends to improve the stability of the melt viscosity during molding processing. It is also preferably 500 or less, more preferably 350 or less, and even more preferably 280 or less. This tends to improve the mechanical strength. It is also preferable that the constituent units having a formula weight within the above range account for 95% by mass or more of all the constituent units, more preferably 98% by mass or more, and even more preferably 99% by mass or more.
• the number average molecular weight (Mn) of the polyamide resin used in the present embodiment is preferably 8,000 or more, and is preferably 50,000 or less, and more preferably 30,000 or less.
• the number average molecular weight (Mn) of the polyamide resin can be measured by gel permeation chromatography (GPC) measurement in terms of standard polymethyl methacrylate (PMMA).
• hexafluoroisopropanol hexafluoroisopropanol (HFIP) with a sodium trifluoroacetate concentration of 2 mmol/L is used as the solvent, and the resin concentration is 0.02 mass%, the column temperature is 40°C, the flow rate is 0.3 mL/min, and the refractive index detector (RI) is used.
• the calibration curve is measured by dissolving six levels of PMMA in HFIP.
• the glass transition temperature of the polyamide resin (A) used in the present embodiment is preferably 30° C. or higher and 100° C. or lower.
• the polyamide resin (A) used in this embodiment may be a crystalline resin or a non-crystalline resin, but is preferably a crystalline resin.
• the melting point of the polyamide resin (A) used in this embodiment is preferably 180° C. or higher and 350° C. or lower.
• the melting point (Tm) and the glass transition temperature (Tg) are values measured by differential scanning calorimetry (DSC) in accordance with JIS K7121 and K7122. Specifically, a differential scanning calorimeter is used, the synthesized polyamide resin is crushed and placed in the measurement pan of the differential scanning calorimeter, the temperature is raised in a nitrogen atmosphere at a heating rate of 10°C/min to the melting point + 20°C shown in Table 1, and immediately after the heating is completed, the measurement pan is removed and pressed against dry ice for rapid cooling, and then the measurement is performed.
• DSC differential scanning calorimetry
• the measurement conditions are heating at a heating rate of 10°C/min to the melting point + 20°C and held for 5 minutes, and then measuring is performed at a cooling rate of -5°C/min to 100°C to determine the melting point (Tm) and glass transition temperature (Tg).
• Tm melting point
• Tg glass transition temperature
• a differential scanning calorimeter a "DSC-60" manufactured by Shimadzu Corporation can be used.
• the value is the sum of the values obtained by multiplying each of the above physical property values by the mass fraction of the polyamide resin (A).
• the content of polyamide resin (A) in the high voltage insulating material of this embodiment is not particularly specified.
• One example of the high voltage insulating material of this embodiment is one in which the proportion of polyamide resin (A) in the high voltage insulating material is 90 mass% or more, preferably 95 mass% or more.
• Another example of the high voltage insulating material of this embodiment is one in which the total proportion of polyamide resin (A) and filler in the high voltage insulating material is 90 mass% or more, preferably 95 mass% or more.
• the high voltage insulating material of the present embodiment may or may not contain a polyamide resin other than the polyamide resin (A).
• the high voltage insulating material of the present embodiment contains a polyamide resin other than the polyamide resin (A)
• the other polyamide resin that the high voltage insulating material of the present embodiment may contain may be an aliphatic polyamide resin or a semi-aromatic polyamide resin.
• aliphatic polyamide resins examples include polyamide 6, polyamide 66, polyamide 46, polyamide 6/66 (a copolymer consisting of a polyamide 6 component and a polyamide 66 component), polyamide 610, polyamide 612, polyamide 410, polyamide 1010, polyamide 11, polyamide 12, and polyamide 9C (a polyamide consisting of a mixed diamine consisting of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 1,4-cyclohexanedicarboxylic acid).
• the high withstand voltage insulating material of the present embodiment contains a polyamide resin other than the polyamide resin (A), the content thereof is preferably 1 to 10 mass% relative to 100 mass% of the polyamide resin (A).
• the polyamide resin other than the polyamide resin (A) may be contained in one type or in two or more types.
• the high-voltage insulating material of the present embodiment preferably does not substantially contain any polyamide resin other than the polyamide resin (A).
• “Substantially does not contain” means that the content of polyamide resins other than the polyamide resin (A) is less than 1 mass%, preferably less than 0.1 mass%, and more preferably less than 0.01 mass%, relative to 100 mass% of the polyamide resin (A).
• the high-voltage insulating material of the present embodiment may contain components other than the polyamide resin.
• An example of the other component is a stabilizer.
• the stabilizer include a heat stabilizer, an antioxidant, and a component derived from a phosphorus atom-containing compound or a polymerization rate regulator that can be added during the synthesis of a polyamide resin.
• the total amount of the stabilizer is preferably 0.001 to 3 parts by mass per 100 parts by mass of the polyamide resin (A).
• antioxidants examples include phenol-based antioxidants (preferably hindered phenol-based antioxidants), amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. These antioxidants can be used alone or in combination of two or more.
• the amount of the antioxidant added is preferably 0.001 to 3.0 parts by mass per 100 parts by mass of the polyamide resin (A).
• the phosphorus atom-containing compound include phosphinic acid compounds such as dimethylphosphinic acid and phenylmethylphosphinic acid; hypophosphorous acid compounds such as hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, magnesium hypophosphite, calcium hypophosphite, and ethyl hypophosphite; and phosphonic acid compounds such as phosphonic acid, sodium phosphonate, lithium phosphonate, potassium phosphonate, magnesium phosphonate, calcium phosphonate, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, diethyl phenylphosphonate, sodium ethylphosphonate, and potassium ethylphosphonate.
• phosphinic acid compounds such as dimethylphosphinic acid and phenylmethylphosphinic acid
• phosphonous acid compounds such as phosphonous acid, sodium phosphonite, lithium phosphonite, potassium phosphonite, magnesium phosphonite, calcium phosphonite, phenylphosphonous acid, sodium phenylphosphonite, potassium phenylphosphonite, lithium phenylphosphonite, and ethyl phenylphosphonite
• phosphorous acid compounds such as phosphorous acid, sodium hydrogen phosphite, sodium phosphite, lithium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, triethyl phosphite, triphenyl phosphite, and pyrophosphorous acid, among which sodium diphosphite and calcium diphosphite are preferred, and calcium hypophosphite is more preferred.
• the amount of the phosphorus atom-containing compound added is preferably an amount that gives a phosphorus atom concentration in the polyamide resin (A) of 0.01 to 0.1% by mass.
• components other than the stabilizer include thermoplastic resins other than polyamide resins, fillers, hydrolysis resistance improvers, matting agents, plasticizers, dispersants, antistatic agents, coloring inhibitors, antigelling agents, colorants, etc.
• thermoplastic resins other than polyamide resins fillers, hydrolysis resistance improvers, matting agents, plasticizers, dispersants, antistatic agents, coloring inhibitors, antigelling agents, colorants, etc.
• the total amount of the other components is preferably 20.0 mass % or less, more preferably 10.0 mass % or less, even more preferably 5.0 mass % or less, and even more preferably 1.0 mass % or less of the high voltage insulating material of this embodiment. Only one type of the other components may be used, or two or more types may be used in combination. In the present embodiment, it is preferable to melt-knead the polyamide resin (A) and other components and then mold the mixture.
• the high voltage insulating material of this embodiment preferably has excellent tracking resistance under conditions where a high voltage is applied.
• the time until the insulating material breaks down at a voltage of 2000V according to the JIS-C2136 constant voltage tracking method is preferably 30 minutes or more, more preferably 34 minutes or more, even more preferably 35 minutes or more, even more preferably 39 minutes or more, even more preferably 41 minutes or more, even more preferably 46 minutes or more, and even more preferably 50 minutes or more, 55 minutes or more, 58 minutes or more, 60 minutes or more, 65 minutes or more, 66 minutes or more, 70 minutes or more, 75 minutes or more, 80 minutes or more, 85 minutes or more, 89 minutes or more, 93 minutes or more, or 95 minutes or more.
• the high voltage insulating material of the present embodiment is preferably used in applications where high voltage is applied, for example, in electric and electronic components such as chargers and connectors for high-speed charging. It is also preferably used as a covering material for cords and bus bars, and as a circuit board material. In addition to the above, the high voltage insulating material of this embodiment can also be used for the applications described in paragraph 0049 of JP 2020-076023 A, the contents of which are incorporated herein by reference.
• the high-voltage insulating molded product of this embodiment is formed from the high-voltage insulating material of this embodiment.
• the method for forming the molded product is not particularly limited, and a conventionally known molding method can be adopted, for example, injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, hollow molding, gas-assisted hollow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding), rotational molding, multi-layer molding, two-color molding, insert molding, sandwich molding, foam molding, pressure molding, stretching, vacuum molding, etc.
• the high-voltage insulating material of this embodiment is preferably molded by injection molding.
• Examples of insulating molded products formed from the high voltage insulating material of this embodiment include injection molded products, thin-walled molded products, hollow molded products, films (including plate-shaped and sheet-shaped products), cylindrical shapes (hoses, tubes, etc.), annular shapes, circular shapes, elliptical shapes, gear shapes, polygonal shapes, irregular shapes, hollow products, frame-shaped, box-shaped, panel-shaped extrusion molded products, fibers, and the like, and injection molded products are preferred.
• the high voltage insulating material of this embodiment can also be used as a surface layer material. For example, it can be attached to the surface of a conductive or weakly insulating film or sheet.
• the high voltage insulating material of this embodiment can also be molded with other materials by insert molding.
• the resulting polyamide resin had a moisture content of 4.6%, a number average molecular weight of 15,000, a glass transition temperature of 85°C and a melting point of 237°C.
• ⁇ Tracking resistance time>> The polyamide resin obtained in Example 1 was dried, and then injection molded at a cylinder temperature of melting point + 20°C to obtain a plate with a thickness of 6 mm.
• the obtained plate was cut into a size of 120 mm in length and 50 mm in width, sandwiched between glass plates, and held at 150°C for 1 hour under a nitrogen gas atmosphere to perform a crystallization treatment.
• ⁇ Flexural modulus>> The polyamide resin material obtained in Example 1 was dried and then injection molded at a cylinder temperature of melting point + 20°C to obtain a test piece having a thickness of 4 mm. The obtained rectangular piece was sandwiched between glass plates and held at 150°C for 1 hour in a nitrogen gas atmosphere to perform a crystallization treatment. The obtained test piece was stored at 23°C and 50% RH (relative humidity) for 7 days, and then the flexural modulus (GPa) was determined according to JIS K 7171. The measurement was performed using a Bendograph Type B (manufactured by Toyo Seiki Co., Ltd.) at a measurement temperature of 23° C. and a measurement humidity of 50% RH.
• adipic acid manufactured by BASF
• 11.7 g sodium acetate/sodium hypophosphite monohydrate
• the internal temperature was increased, and when it reached 270° C., the pressure inside the reaction vessel was reduced, and the internal temperature was further increased to continue the melt polycondensation reaction for 20 minutes at 280° C. Thereafter, the system was pressurized with nitrogen, and the obtained polymer was taken out of the strand die and pelletized to obtain a polyamide resin material.
• the resulting polyamide resin material had a moisture content of 4.5%, a number average molecular weight of 15,000, a glass transition temperature of 89°C and a melting point of 257°C.
• the tracking resistance time and the flexural modulus were measured.
• Example 3 PXD10 In a jacketed reactor equipped with a stirrer, a partial condenser, a cooler, a thermometer, a dropping tank and a nitrogen gas inlet tube, 10,000g (49.4mol) of sebacic acid (manufactured by CASDA), 0.8g of sodium acetate and 1.2g of calcium hypophosphite were charged, and the contents were fully replaced with nitrogen, and after heating and melting at 170°C, 6667g (48.9mol) of paraxylylenediamine (manufactured by Showa Denko) was dropped into the melt in the reactor while stirring the contents, and the internal temperature was continuously raised to 290°C over 2.5 hours while discharging the generated condensed water out of the system.
• sebacic acid manufactured by CASDA
• the resulting polyamide resin material had a moisture content of 2.1%, a number average molecular weight of 15,000, a glass transition temperature of 73°C and a melting point of 290°C.
• the tracking resistance time and the flexural modulus were measured.
• the polyamide resin material did not have a clear melting point and was an amorphous resin.
• the resulting polyamide resin material had a moisture content of 7.2%, a number average molecular weight of 15,000 and a glass transition temperature of 127°C.
• the tracking resistance time and the flexural modulus were measured.
• Example 5 p-BDE10> ⁇ Example of p-BDEA (p-benzenediethaneamine)>> p-Xylylene dicyanide (Tokyo Chemical Industry Co., Ltd.) was reduced under a hydrogen atmosphere, and the resulting product was purified by distillation to obtain p-benzenediethaneamine. Analysis by gas chromatography revealed that the purity was 99.7%.
• the resulting polyamide resin material had a moisture content of 1.9%, a number average molecular weight of 15,000 and a melting point of 295°C.
• the tracking resistance time and the flexural modulus were measured.
• PA10T > 5500 g (33.1 mol) of terephthalic acid, 5648 g (32.8 mol, manufactured by Kokura Synthetic Industries), 0.8 g of calcium hypophosphite, 0.5 g of sodium acetate, and 5743 g of water were placed in a reactor having an internal volume of 50 L, and the inside of the reactor was replaced with nitrogen, and heating was started with stirring, and the internal temperature was raised to 160° C. over one hour. At this time, stirring was performed using a double helical ribbon type stirring blade, and the gap between the shaft of the stirring blade and the top plate of the reactor was sealed with pure water as a sealing liquid.
• the internal temperature was raised to 200° C., and 3600 g of water was distilled off over 3 hours.
• the internal temperature was then raised to 210° C., and maintained at that temperature for 1.5 hours.
• a primary polycondensate was obtained by flashing from the outlet at the bottom of the reaction vessel.
• the obtained primary polycondensate was then polymerized to a high degree by solid-state polymerization.
• the solid-state polymerization was carried out by heating in an inert oven under a nitrogen atmosphere at 260° C. for 2 hours.
• the sample after the solid-state polymerization was dry-blended with 0.02% by mass of copper iodide and 0.06% by mass of potassium iodide, extruded by a twin-screw extruder, and pelletized to obtain a polyamide resin material.
• the resulting polyamide resin material had a moisture content of 2.1%, a number average molecular weight of 11,000 and a melting point of 304°C.
• the tracking resistance time and the flexural modulus were measured.
• Example 7 p-BIC 4552 g (27.4 mol) of isophthalic acid, 524 g (3.0 mol) of 1,4-cyclohexanedicarboxylic acid (manufactured by Nikko Spain), 5000 g (30.4 mol) of p-BDEA, 1.5 g of calcium hypophosphite, 1.0 g of sodium acetate, and 5240 g of water were placed in a reactor having an internal volume of 50 L, and the reactor was purged with nitrogen, and heating was started with stirring, and the internal temperature was raised to 160° C. over 1 hour.
• stirring was performed using a double helical ribbon type stirring blade, and the gap between the stirring blade shaft and the top plate of the reactor was sealed with pure water as a sealing liquid. Thereafter, the internal temperature was raised to 200° C., and 3600 g of water was distilled off over 3 hours. The internal temperature was then raised to 210° C., and maintained at that temperature for 1.5 hours. Thereafter, a primary polycondensate was obtained by flashing from the outlet at the bottom of the reaction vessel. Subsequently, the obtained primary polycondensate was polymerized to a high degree by solid-state polymerization. At this time, the solid-state polymerization was carried out by heating in an inert oven under a nitrogen atmosphere at 260° C. for 2 hours.
• the sample after the solid-state polymerization was extruded with a twin-screw extruder and pelletized to obtain a polyamide resin material.
• the resulting polyamide resin material had a moisture content of 4.9%, a number average molecular weight of 11,000, a glass transition temperature of 155°C and a melting point of 304°C.
• the tracking resistance time and the flexural modulus were measured.
• Example 8 1,3-BAC6>
• 7220g 49.4mol
• adipic acid manufactured by BASF
• the resulting polyamide resin material had a moisture content of 7.0%, a number average molecular weight of 15,000, a glass transition temperature of 105°C and a melting point of 232°C.
• the tracking resistance time and the flexural modulus were measured.
• Comparative Example 1 Meta-aramid An aramid M plate material (manufactured by Oiles Corporation) was cut into a size of 120 mm in length, 50 mm in width, and 6 mm in thickness. The tracking resistance time of the obtained plate was measured in the same manner as in Example 1. The conditioned moisture content of the aramid M plate material was 3.1%.
• A represents the content (mass%) of ring (a) in polyamide resin (A) based on molecular weight
• B represents the average number of bonds between ring (a) and the amide bond closest to said ring (a) in each structural unit
• C represents the average number of bonds between the positions where groups linked from amide bonds are bonded to said ring (a) in each structural unit.
• [B/(A ⁇ C)] ⁇ 100 is the calculated value of formula (A).
• the insulating material of the present embodiment was excellent in high voltage resistance and also in mechanical strength.
• the data for Examples 1 to 11 and Comparative Example 1 are shown in Figure 1.
• the vertical axis indicates the tracking resistance time under a voltage of 2000 V
• the horizontal axis indicates the value of [B/(A x C)] x 100.

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