WO2023068121A1 - ポリアミドフィルム積層体 - Google Patents

ポリアミドフィルム積層体 Download PDF

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Publication number
WO2023068121A1
WO2023068121A1 PCT/JP2022/037978 JP2022037978W WO2023068121A1 WO 2023068121 A1 WO2023068121 A1 WO 2023068121A1 JP 2022037978 W JP2022037978 W JP 2022037978W WO 2023068121 A1 WO2023068121 A1 WO 2023068121A1
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Prior art keywords
polyamide
polyamide film
carbon atoms
film
film laminate
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PCT/JP2022/037978
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English (en)
French (fr)
Japanese (ja)
Inventor
直樹 高石
剛史 丸尾
吉朗 服部
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Unitika Ltd
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Unitika Ltd
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Priority to CN202280067900.0A priority Critical patent/CN118076481A/zh
Priority to KR1020247009112A priority patent/KR20240087700A/ko
Priority to JP2023512795A priority patent/JP7274246B1/ja
Publication of WO2023068121A1 publication Critical patent/WO2023068121A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • 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
    • 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
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
    • H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Definitions

  • the present invention relates to polyamide film laminates.
  • Polyamide films are widely used in electric and electronic parts due to their excellent heat resistance and mechanical properties.
  • reflow soldering is often performed at a high temperature of 250 ° C. or higher during circuit formation, so a semi-aromatic polyamide film with high heat resistance such as a melting point exceeding 300 ° C. is used (for example, Patent Documents 1 and 2).
  • the semi-aromatic polyamide film has high rigidity and insufficient flexibility.
  • Patent Document 3 discloses a film made of polyamide composed of terephthalic acid, 1,10-decanediamine, dimer acid, and dimer diamine. Further, for example, low dielectric materials such as liquid crystal polymer, low dielectric polyimide and polyarylene ether ketone are known as film materials (Patent Documents 4 and 5).
  • the inventors of the present invention have found that the conventional technology has the following problems. For example, in recent years, as the performance and speed of electronic devices have increased, it has become necessary for flexible printed circuit boards to cope with high-speed signal transmission, and reduction in transmission loss is required for use in such devices. However, the film of Patent Document 3 cannot sufficiently reduce the transmission loss in some cases.
  • Signal transmission loss mainly includes loss derived from the dielectric and loss derived from the conductor (copper foil), and the loss increases depending on the frequency. Since the loss derived from the dielectric depends on the dielectric properties (relative dielectric constant, dielectric loss tangent) of the film substrate and adhesive, materials with excellent dielectric properties are required to suppress loss in the high-frequency range. Become. However, since low-dielectric materials with excellent dielectric properties generally have low adhesion to conductors (eg, copper foil), adhesion to conductors is ensured by an anchor effect that utilizes the unevenness of the conductor surface.
  • the loss derived from a conductor is caused by the resistance component of the conductor, but the current distribution is concentrated on the conductor surface depending on the frequency (skin effect), so the surface roughness of the conductor has a greater effect in the high frequency range. In order to suppress the loss in the high frequency region, a conductor with small surface roughness is required.
  • Copper-clad laminates for flexible printed circuit boards are made by laminating insulating films and copper foils.
  • a method for laminating such a copper-clad laminate when the insulating film is polyimide, for example, there are a method of bonding with an adhesive such as an epoxy resin or an acrylic resin, and a method of applying varnish on a copper foil and heat-treating it. be.
  • Copper foil with a rough surface is used to obtain adhesion, but in order to suppress transmission loss in the high-frequency range, it is necessary to use copper foil with a small surface roughness and use a low-dielectric base film. It is desirable to use materials and laminate without the use of adhesives.
  • low-dielectric materials such as liquid crystal polymers and low-dielectric polyimides are difficult to adhere to copper foil, so a method for increasing adhesion to copper foil is required (Patent Document 4).
  • Polyarylene ether ketone is also known as another low dielectric material, but it has poor processing dimensional stability, and when metal layers are laminated, the laminate curls or deforms. In order to improve processing dimensional stability, it is necessary to add a fluororesin or mica, which significantly reduces the flexibility. Moreover, although a metal layer can be formed only by thermal fusion bonding, a high heating temperature of 345° C. is required (Patent Document 5).
  • the present invention is intended to solve the above problems, and is sufficiently excellent in heat resistance, flexibility, adhesion between the metal layer and the polyamide film, and transmission characteristics, and after heat treatment (for example, reflow treatment)
  • Another object of the present invention is to provide a polyamide film laminate in which warpage is sufficiently reduced.
  • the gist of the present invention is as follows. ⁇ 1> A unit consisting of an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms, a unit consisting of an aliphatic diamine (B) having 18 or more carbon atoms, and an aromatic dicarboxylic acid (C) having 12 or less carbon atoms unit and a polyamide (E) containing a unit consisting of an aliphatic diamine (D) having 12 or less carbon atoms, a melting point of 240 ° C.
  • a unit consisting of an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms a unit consisting of an aliphatic diamine (B) having 18 or more carbon atoms, and an aromatic dicarboxylic acid (C) having 12 or less carbon atoms unit and a polyamide (E) containing a unit consisting of an aliphatic diamine (D) having 12 or less carbon atoms, a melting point of 240
  • the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms is a dimer acid
  • the aliphatic diamine (B) having 18 or more carbon atoms is a dimer diamine
  • the aromatic dicarboxylic acid (C) having 12 or less carbon atoms is The polyamide film laminate according to ⁇ 1> or ⁇ 2>, wherein the terephthalic acid and the aliphatic diamine (D) having 12 or less carbon atoms is 1,10-decanediamine.
  • ⁇ 4> The total content of the unit consisting of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and the unit consisting of the aliphatic diamine (B) having 18 or more carbon atoms constitutes the polyamide (E)
  • ⁇ 5> The polyamide film laminate according to any one of ⁇ 1> to ⁇ 4>, wherein the peel strength between the polyamide film (F) and the metal layer is 0.1 [N/mm] or more.
  • ⁇ 6> ⁇ 1> to ⁇ 5> wherein the absolute value of the transmission loss of the microstrip line having a characteristic impedance of 50 ⁇ , which is produced from the polyamide film laminate, is 1.80 [dB/100 mm] or less at 5 GHz.
  • a polyamide film laminate according to any one of the above. ⁇ 7> The polyamide film laminate according to any one of ⁇ 1> to ⁇ 6>, wherein the metal layer is in direct contact with the polyamide film (F).
  • the metal layer is made of a metal selected from the group consisting of copper, aluminum, iron, nickel, tin, gold, silver, alloy steel, and alloy plating.
  • the polyamide film laminate has the metal layer on one or both sides of the polyamide film (F), and further has a resin layer on the metal layer, any of ⁇ 1> to ⁇ 8>
  • the content of the unit composed of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms is 3 to 45% by mass with respect to the total monomer components constituting the polyamide
  • the content of units composed of the aliphatic diamine (B) having 18 or more carbon atoms is 3 to 45% by mass with respect to the total monomer components constituting the polyamide
  • the content of units composed of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms is 3 to 45% by mass with respect to the total monomer components constituting the polyamide, Any one of ⁇ 1> to ⁇ 9>, wherein the content of the unit composed of the aliphatic diamine (D) having 12 or less carbon atoms is 3 to 52% by mass with respect to the total mono
  • Polyamide film laminate according to. ⁇ 11> The polyamide film laminate according to any one of ⁇ 1> to ⁇ 10>, wherein the polyamide film (F) has a crystal melting enthalpy of 25 J/g or more.
  • Polyamide film laminate according to any one of. ⁇ 13> The polyamide film (F) has a thickness of 1 ⁇ m to 2 mm, The polyamide film laminate according to any one of ⁇ 1> to ⁇ 12>, wherein the metal layer has a thickness of 1 to 500 ⁇ m.
  • ⁇ 14> A method for producing a polyamide film laminate according to any one of ⁇ 1> to ⁇ 13>, A method for producing a polyamide film laminate, comprising laminating the polyamide film (F) and the metal layer by heating and pressing.
  • the polyamide film (F) and the metal layer are laminated by heating and pressing at “the melting point of the polyamide film (F) ⁇ 100° C.” to “the melting point of the polyamide film (F) ⁇ 5° C.” , the method for producing a polyamide film laminate according to ⁇ 14>.
  • a method for producing a polyamide film laminate according to any one of ⁇ 1> to ⁇ 13> A method for producing a polyamide film laminate, wherein the metal layer is provided on the polyamide film (F) by a method selected from the group consisting of a plating method, an inkjet method, a physical vapor deposition method, and a chemical vapor deposition method.
  • the heat resistance, flexibility, adhesion between the metal layer and the polyamide film, and transmission characteristics are sufficiently excellent, and even after heat treatment (for example, reflow treatment), warpage is sufficiently reduced.
  • a polyamide film laminate can be provided.
  • the polyamide film laminate of the present invention is laminated with a conductor (copper foil), it has a good appearance with respect to deformation of the laminate, surface unevenness and film bleeding, and is also good after heat treatment (for example, reflow treatment). is.
  • the polyamide film laminate of the present invention can be suitably used for flexible printed circuit boards and flexible antenna substrates, for example.
  • FIG. 4 is a schematic diagram showing a hysteresis curve for explaining a method of calculating a hysteresis loss rate
  • the polyamide film laminate of the present invention comprises a unit comprising an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms (hereinafter sometimes referred to as component (A)) and an aliphatic diamine (B) having 18 or more carbon atoms. (hereinafter sometimes referred to as component (B)), a unit composed of an aromatic dicarboxylic acid (C) having 12 or less carbon atoms (hereinafter sometimes referred to as component (C)), and the number of carbon atoms
  • a metal layer is provided on a polyamide film (F) containing a polyamide (E) containing units consisting of 12 or less aliphatic diamines (D) (hereinafter sometimes referred to as component (D)).
  • Components (A) to (D) are contained as monomer components (or monomer residues) in the polyamide. Therefore, "a unit comprising an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms” may simply be expressed as "a monomer of an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms” or a residue thereof.
  • a "unit consisting of an aliphatic diamine (B) having 18 or more carbon atoms” may simply be expressed as "a monomer of an aliphatic diamine (B) having 18 or more carbon atoms" or a residue thereof.
  • a "unit consisting of an aromatic dicarboxylic acid (C) having 12 or less carbon atoms” may simply be expressed as "a monomer of an aromatic dicarboxylic acid (C) having 12 or less carbon atoms” or a residue thereof.
  • a “unit consisting of an aliphatic diamine (D) having 12 or less carbon atoms” may simply be expressed as an "aliphatic diamine (D) monomer having 12 or less carbon atoms" or a residue thereof.
  • an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms that constitutes the polyamide (E) used in the film laminate of the present invention an aliphatic dicarboxylic acid consisting entirely of hydrocarbons other than the carboxyl group is preferable.
  • dimer acid 36 carbon atoms.
  • an aliphatic dicarboxylic acid having 20 or more carbon atoms is preferred, and a dimer acid is more preferred, because of its high flexibility.
  • the dimer acid may be an addition reaction of two molecules selected from unsaturated fatty acids such as oleic acid and linoleic acid.
  • the two molecules may be the same type of molecule, or they may be heterologous molecules to each other.
  • the dimer acid may be a dicarboxylic acid having an unsaturated bond, but is preferably a dicarboxylic acid in which all the bonds are saturated by hydrogenation because it is less likely to be colored.
  • Component (A) may be used alone or in combination of two or more of the above.
  • the number of carbon atoms in component (A) is preferably 20 to 40, more preferably 30 to 40, and still more preferably 30 to 40, from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity, and further reducing warpage. is 34-38.
  • heat resistance refers to heat resistance of a film and its laminate with a metal layer. is a property that can be reduced more fully. Heat resistance preferably also includes the property that the appearance of the film laminate is sufficiently good even after heat treatment. Flexibility refers to the flexibility of a film and its laminate with a metal layer, and more specifically, the property that the film has a sufficiently high elongational recovery rate and a sufficiently low tensile modulus of the film. Adhesion is the adhesion of a laminate of a film and a metal layer, and more specifically, it is a property in which the peel strength between the film and the metal layer is sufficiently high.
  • the transmission characteristic is the transmission characteristic of the laminate of the film and the metal layer, and more specifically, the characteristic that can sufficiently reduce the transmission loss when the laminate is used as the substrate of the electronic component.
  • Rubber elasticity refers to the rubber elasticity of a film, and more specifically, the property that the crystal melting enthalpy of the film is sufficiently high.
  • Elastomeric properties preferably also include the property that the hysteresis loss of the film is much lower.
  • the content of component (A) is preferably 3 to 45% by mass, more preferably 5 to 45% by mass, from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity and further reducing warpage. %, more preferably 10 to 45% by mass, particularly preferably 10 to 40% by mass, fully preferably 13 to 40% by mass, and 13 to 33% by mass. is more fully preferred.
  • the content is the content of the residue of component (A) and is the ratio to all the monomer components (or the total amount of those residues) constituting the polyamide. When the polyamide contains two or more components (A), the total amount thereof should be within the above range.
  • an aliphatic dicarboxylic acid consisting entirely of hydrocarbons other than amino groups is preferable. 18 carbon atoms), eicosane diamine (20 carbon atoms), and dimer diamine (36 carbon atoms). Among them, dimer diamine is preferred. By using dimer diamine, the flexibility of the entire polymer can be effectively improved even with a resin composition having a relatively smaller amount than other monomers. Dimer diamines are usually prepared by reacting a dimer acid with ammonia followed by dehydration, nitrile and reduction.
  • the dimer diamine may be a diamine having an unsaturated bond, but is preferably a diamine in which all bonds are saturated by hydrogenation because it is less likely to be colored.
  • Component (B) may be used alone or in combination of two or more of the above.
  • the number of carbon atoms in component (B) is preferably 20 to 40, more preferably 30 to 40, and still more preferably 30 to 40, from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity, and further reducing warpage. is 34-38.
  • the content of component (B) is preferably 3 to 45% by mass, more preferably 5 to 45% by mass, from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity and further reducing warpage. %, more preferably 10 to 45% by mass, particularly preferably 10 to 40% by mass, and fully preferably 12 to 27.3% by mass.
  • the content is the content of the residue of component (B) and is the ratio to all the monomer components (or the total amount of those residues) constituting the polyamide. When the polyamide contains two or more components (B), the total amount thereof should be within the above range.
  • aromatic dicarboxylic acid (C) having 12 or less carbon atoms constituting the polyamide (E) used in the film laminate of the present invention examples include terephthalic acid (8 carbon atoms), isophthalic acid (8 carbon atoms), and orthophthalic acid. (carbon number 8). Among them, aromatic dicarboxylic acids having 8 or more carbon atoms are preferred, and terephthalic acid is more preferred, because they tend to further improve heat resistance, flexibility and rubber elasticity.
  • Component (C) may be used alone or in combination of two or more of the above.
  • the number of carbon atoms in component (C) is preferably 4 to 12, more preferably 6 to 12, and even more preferably 6 to 12, from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity, and further reducing warpage. is 6-10.
  • the content of component (C) is preferably 3 to 45% by mass, more preferably 5 to 45% by mass, from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity and further reducing warpage. %, more preferably 5 to 40% by mass, particularly preferably 8 to 35% by mass, fully preferably 8 to 33% by mass, and 15 to 33% by mass. is more fully preferred.
  • the content is the content of the residue of component (C) and is the ratio to all the monomer components (or the total amount of those residues) constituting the polyamide. When the polyamide contains two or more components (C), the total amount thereof should be within the above range.
  • Examples of the aliphatic diamine (D) having 12 or less carbon atoms constituting the polyamide (E) used in the film laminate of the present invention include 1,12-dodecanediamine (12 carbon atoms), 1,10-decanediamine ( 10 carbon atoms), 1,9-nonanediamine (9 carbon atoms), 1,8-octanediamine (8 carbon atoms), and 1,6-hexanediamine (6 carbon atoms).
  • diamines having 6 or more carbon atoms are preferred, diamines having 8 or more carbon atoms are more preferred, and 1,10-decanediamine is even more preferred, since they tend to further improve heat resistance, flexibility and rubber elasticity.
  • (D) may be used alone among the above, or may be used in combination of two or more.
  • the number of carbon atoms in component (D) is preferably 4 to 12, more preferably 6 to 12, and still more preferably 6 to 12, from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity and further reducing warpage. is 8-12.
  • the content of component (D) is preferably 3 to 52% by mass, more preferably 5 to 50% by mass, from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity and further reducing warpage. %, more preferably 5 to 40% by mass, particularly preferably 10 to 40% by mass, fully preferably 20 to 40% by mass, and 25 to 40% by mass. is more fully preferred.
  • the content is the content of the residue of component (D) and is the ratio to all the monomer components (or the total amount of those residues) constituting the polyamide. When the polyamide contains two or more components (D), the total amount thereof should be within the above range.
  • the polyamide (E) may be a random polyamide in which components (A) to (D) are randomly arranged and polymerized, or a hard segment and component consisting of components (C) and (D) It may be a block-type polyamide containing a soft segment consisting of (A) and (B).
  • Polyamide (E) is preferably a block-type polyamide from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission properties and rubber elasticity and further reducing warpage.
  • the block-type structure a phase-separated structure of hard segments and soft segments is formed, the hard segments play the role of cross-linking points of rubber, and the soft segments can expand and contract freely. Therefore, the polyamide (E) can have sufficiently superior flexibility (and rubber elasticity) while having sufficiently superior heat resistance. As a result, it is believed that further improvements in heat resistance, flexibility, adhesion, transmission properties and rubber elasticity and further reduction in warpage are achieved in films and laminates.
  • Combinations of components (C) and (D) include, for example, terephthalic acid and butanediamine, terephthalic acid and 1,9-nonanediamine, terephthalic acid and 1,10-decanediamine, and terephthalic acid and 1,12-dodecanediamine.
  • terephthalic acid and 1,10-decanediamine are preferred.
  • the hard segment tends to be a highly crystalline segment, so the formation of a phase separation structure between the hard segment and the soft segment is promoted, and sufficiently excellent flexibility and It expresses rubber elasticity.
  • "Rubber” is used as a concept of a substance that exhibits the characteristic of being locally deformed by an external force, but returning to its original shape when the force is removed.
  • Total content of units consisting of aliphatic dicarboxylic acid (A) having 18 or more carbon atoms in polyamide (E) used in the present invention and units consisting of aliphatic diamine (B) having 18 or more carbon atoms is 10 to 90% by mass from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity and further reducing warpage.
  • it is 15 to 80% by mass, more preferably 20 to 80% by mass, particularly preferably 30 to 75% by mass, and fully preferably 30 to 60% by mass. .
  • the total content is the total content of the residues of the component (A) and the residues of the component (B), and all the monomer components (or the total amount of their residues) constituting the polyamide (E) is the ratio to When the polyamide (E) contains two or more polyamides as described later, the total content of the component (A) and the component (B) in the total polyamide (E) should be within the above range.
  • the total content of component (A) and component (B) in each polyamide (E) is It is preferably within the above range, and at this time, it is more preferable that the content of component (A) and the content of component (B) in each polyamide (E) be within the ranges described above.
  • the polyamide (E) used in the present invention does not contain a polyether component or a polyester component that easily decomposes during polymerization.
  • polyether components include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and polyoxyethylene/polyoxypropylene glycol.
  • Polyester components include, for example, polyethylene adipate, polytetramethylene adipate, and polyethylene sebacate. When a polyether component or polyester component is used, decomposition may occur if the polymerization temperature is high.
  • the total content of the polyether component and the polyester component is preferably 2% by mass or less from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity and further reducing warpage, and 1 mass % or less, more preferably 0.1 mass % or less.
  • the lower limit of the total content range is usually 0% by mass.
  • the total content is the content of the residues of the polyether component and the polyester component, and is the ratio to all the monomer components (or the total amount of their residues) constituting the polyamide (E).
  • the polyether component and the polyester component are components that form a part of the polyamide through covalent bonding with the polyamide, and are not simply blended with the polyamide.
  • the polyamide (E) used in the present invention may contain an end-blocking agent for adjusting the degree of polymerization and suppressing decomposition and coloring of the product.
  • terminal blocking agents include monocarboxylic acids such as acetic acid, lauric acid, benzoic acid and stearic acid, and monoamines such as octylamine, cyclohexylamine, aniline and stearylamine.
  • One of the above terminal blocking agents may be used alone, or two or more thereof may be used in combination.
  • the content of the terminal blocking agent is not particularly limited, but is usually 0 to 10 mol % relative to the total molar amount of dicarboxylic acid and diamine.
  • the method for producing the polyamide (E) used in the present invention is not particularly limited.
  • a method of collectively reacting a group dicarboxylic acid (C) and an aliphatic diamine having 12 or less carbon atoms (D) (hereinafter sometimes referred to as a "batch polymerization method” or a “one-step method”), or component (C) and component (D) separately from component (A) and component (B) (hereinafter sometimes referred to as “split polymerization method” or “two-step method”).
  • the polyamide (E) used in the present invention is preferably produced by a split polymerization method from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission properties and rubber elasticity and further reducing warpage.
  • the polyamide By producing the polyamide by a split polymerization method, the polyamide has a more preferable crystal melting enthalpy (especially 25 J / g or more), heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity are further improved and This is because a further reduction in warpage is achieved.
  • the polymerization method is not particularly limited, but includes, for example, a method of heating to a temperature below the melting point of the polyamide to be obtained, and polymerizing by maintaining the temperature under a nitrogen stream while removing condensation water out of the system.
  • a polyamide polymerized by a batch polymerization method can be called a "random type polyamide” from the viewpoint that all components are arranged randomly.
  • the "melting point of the resulting polyamide” is the "melting point of the target polyamide", and may be, for example, the "melting point of the hard segment polymer” described in the division polymerization method described below.
  • a hard segment polymer is obtained by the production method explained in the split polymerization method described later.
  • the melting point of the resulting hard segment polymer is measured.
  • a method for measuring the melting point is not particularly limited, and for example, it can be measured by a differential scanning calorimeter.
  • the polyamide can be produced by subjecting the mixture containing the monomer (or prepolymer) to a polymerization reaction at a temperature below the "melting point" (particularly below the melting point).
  • the melting point of the "target polyamide” (for example, the “melting point of the hard segment polymer") is 315° C.
  • the polymerization temperature in batch polymerization may be 220 to 300° C. (especially 240 to 280° C.).
  • the polymerization time in the batch polymerization method is not particularly limited as long as sufficient polymerization is performed, and may be, for example, 1 to 10 hours (especially 3 to 7 hours).
  • component (C) and component (D) are reacted separately from component (A) and component (B) to polymerize.
  • the reaction product is further reacted with component (A) and component (B) to polymerize.
  • component (A) and component (B) may be used in an unreacted state with each other or in a mutually reacted state (i.e., in the form of their reaction products).
  • the polyamide (E) used in the present invention is a reaction product of the component (A) and the component (B) obtained by reacting the component (A) and the component (B) in advance, and the component (C ) and the component (D) by reacting and polymerizing.
  • the polyamide (E) used in the present invention is polymerized by reacting the reaction product of the component (A) and the component (B) with the reaction product of the component (C) and the component (D).
  • Component (A) and component (B) are in a mutually reacted state (that is, their reaction products are form) is preferably used.
  • the polyamide polymerized by the split polymerization method is a polyamide composed of a hard segment composed of components (C) and (D) and a soft segment composed of components (A) and (B). is obtained as Therefore, the polyamide polymerized by the batch polymerization method is called "random type polyamide", whereas the polyamide polymerized by the division polymerization method is called "block type polyamide” from the viewpoint of containing hard segments and soft segments. can be done.
  • the chain length of the resulting reaction product can be controlled and, as a result, the flexibility and rubber elasticity of the resulting polyamide can be controlled.
  • the molar ratio [(C)/(D)] is preferably 45/55 to 60/40, more preferably 45/55 to 55/45, because flexibility and rubber elasticity are more sufficiently improved. is more preferred.
  • reaction product manufacturing method X a method for producing a reaction product containing an aromatic dicarboxylic acid (C) having 12 carbon atoms or less and an aliphatic diamine (D) having 12 carbon atoms or less
  • reaction product manufacturing method X a method for producing a reaction product containing an aromatic dicarboxylic acid (C) having 12 carbon atoms or less and an aliphatic diamine (D) having 12 carbon atoms or less
  • reaction product manufacturing method X a method for producing a reaction product containing an aromatic dicarboxylic acid (C) having 12 carbon atoms or less and an aliphatic diamine (D) having 12 carbon atoms or less
  • reaction product manufacturing method X a method for producing a reaction product containing an aromatic dicarboxylic acid (C) having 12 carbon atoms or less and an aliphatic diamine (D) having 12 carbon atoms or less
  • the component A method of adding (D) can be mentioned.
  • the heating temperature may be 100 to 240°C
  • the reaction product of component (C) and component (D) may be in the form of salts of component (C) and component (D), or condensates (or oligomers or prepolymers) thereof. or a composite form thereof.
  • the method of reacting the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms with the aliphatic diamine (B) having 18 or more carbon atoms is not particularly limited.
  • a method of reacting at a temperature of 80 to 150° C. (especially 100 to 150° C.) for 0.5 to 3 hours can be mentioned.
  • reaction product of component (A) and component (B), like the reaction product of component (C) and component (D), may also be in the form of a salt, or may be in the form of condensation. It may have the form of a substance (or oligomer or prepolymer), or it may have a composite form thereof.
  • the polymerization method is not particularly limited. and a method of polymerizing at a temperature of less than Specifically, the hard segment polymer (for example, a polyamide composed only of components (C) and (D) constituting the hard segment) is heated to a temperature below the melting point, and condensed water is removed from the system under a nitrogen stream. , polymerize by maintaining the temperature. By polymerizing in this manner, the hard segments are not melted, and only the soft segments can be polymerized in a melted state.
  • the method of polymerizing at a temperature below the melting point of the hard segment polymer is particularly effective in the polymerization of polyamide having a high melting point of 280° C. or higher, which tends to decompose due to the high polymerization temperature.
  • the “melting point of the hard segment polymer” is the melting point of the polyamide obtained by sufficiently polymerizing only the components (C) and (D) that constitute the hard segment as monomer components.
  • the “melting point of the hard segment polymer” is, for example, the method described in WO 2013/042541 pamphlet, even if it is the melting point of a polyamide obtained by sufficiently polymerizing only the components (C) and (D) as monomer components. good.
  • the “melting point of the hard segment polymer” is obtained by a method comprising step (i) of obtaining a reaction product from components (C) and (D) and step (ii) of polymerizing the resulting reaction product. is the melting point of polyamide (hard segment polymer).
  • step (i) components (C) and (D) are heated to a temperature equal to or higher than the melting point of component (D) and equal to or lower than the melting point of component (C),
  • the reaction product can be obtained by adding component (D) so as to maintain the powdery state of .
  • step (i) for example, when terephthalic acid and 1,10-decanediamine are used as components (C) and (D), respectively, the heating temperature is 100 to 240°C (preferably 140 to 200°C, especially 170°C).
  • Addition of component (D) is preferably carried out continuously, for example, preferably over 1 to 10 hours (preferably 1 to 5 hours, particularly 2.5 hours).
  • step (ii) the reaction product in a solid state obtained in step (i) is sufficiently heated so as to maintain the solid state to polymerize (i.e. solid phase polymerization).
  • the heating temperature that is, polymerization temperature
  • the heating time that is, polymerization time
  • Steps (i) and (ii) are preferably carried out in a stream of nitrogen inert gas or the like.
  • the melting point of the "hard segment polymer" is usually 315°C.
  • the following method can be adopted.
  • the reaction product is obtained by reacting the component (C) and the component (D) by the above-described reaction product manufacturing method X, and then the reaction product is heated to a temperature below the “melting point of the hard segment polymer”.
  • Polyamide can be produced by further reacting and polymerizing with component (A) and component (B).
  • dimer acid, dimer diamine, terephthalic acid and 1,10-decanediamine are used as components (A) to (D) respectively
  • the polymerization temperature in the split polymerization method is 220 to 300° C. (preferably 240 to 280° C., particularly 260° C. °C).
  • the polymerization time in the split polymerization method is not particularly limited as long as sufficient polymerization is performed, and may be, for example, 1 to 10 hours (preferably 3 to 7 hours, particularly 5 hours).
  • a catalyst may be used, if necessary, in the batch polymerization method and the divisional polymerization method (hereinafter sometimes simply referred to as the "method for producing the polyamide (E) used in the present invention").
  • Catalysts include, for example, phosphoric acid, phosphorous acid, hypophosphorous acid, or salts thereof.
  • the content of the catalyst is not particularly limited, but is usually 0 to 2 mol % relative to the total molar amount of dicarboxylic acid and diamine.
  • an organic solvent or water may be added as necessary.
  • polymerization may be performed in a closed system or under normal pressure.
  • the pressure may be increased due to volatilization of the monomers, generation of condensed water, etc. Therefore, it is preferable to appropriately control the pressure.
  • the monomer to be used has a high boiling point and does not flow out of the system without pressurization, the polymerization can be carried out under normal pressure.
  • a combination of dimer acid, dimer diamine, terephthalic acid and decanediamine can be polymerized under normal pressure.
  • the method for producing the polyamide (E) used in the present invention it is preferable to carry out polymerization under a nitrogen atmosphere or under vacuum in order to prevent oxidative deterioration.
  • the polymerized polyamide may be extruded into strands into pellets, or may be hot-cut or underwater-cut into pellets.
  • solid-phase polymerization may be performed after polymerization in order to further increase the molecular weight.
  • Solid phase polymerization is particularly effective when the viscosity during polymerization is high and operation becomes difficult.
  • the solid phase polymerization is preferably carried out by heating at a temperature below the melting point of the resin composition for 30 minutes or longer, more preferably for 1 hour or longer, under inert gas flow or under reduced pressure.
  • the melting point of the resin composition may be the same temperature as the "melting point of the hard segment polymer" described above.
  • the polyamide (E) may contain two or more polyamides having different monomer compositions (types), monomer sequences, and/or molecular weights (especially melting points).
  • the two or more polyamides may be two or more polyamides selected from the polyamide (E) described above.
  • the two or more types of polyamides having different monomer sequences are the above-described random type polyamide and the above-described block type polyamide. From the viewpoint of further improving heat resistance, flexibility, adhesion, transmission properties and rubber elasticity, and further reducing warpage, the polyamide (E) preferably has a higher block-type polyamide content.
  • the content of the block-type polyamide is preferably 10% by mass or more relative to the total amount of the polyamide (E), from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity and further reducing warpage. More preferably 30% by mass or more, still more preferably 45% by mass or more, particularly preferably 70% by mass or more, fully preferably 80% by mass or more, more preferably 90% by mass or more, most preferably 100% by mass be.
  • the content of components (A) to (D) described herein is the content of components (A) to (D) in the total polyamide (E) It can be the amount.
  • the polyamide (E) may be used by pre-melting and mixing part or all of the two or more polyamides, or each polyamide ( Pellets) may be used by dry-blending them, or they may be used in a composite form.
  • the polyamide (E) used in the present invention contains two types of polyamides, a random type polyamide and a block type polyamide
  • the polyamide obtained by the batch polymerization method and the division polymerization method may be produced by performing melt-mixing in any combination of two or more.
  • melt-mixing can be performed by combining a random type polyamide and a random type polyamide, a combination of a random type polyamide and a block type polyamide, or a combination of a block type polyamide and a block type polyamide.
  • a combination of block-type polyamide and block-type polyamide or a combination of random-type polyamide and block-type polyamide is preferable, and a combination of block-type polyamide and block-type polyamide is preferable. is more preferred.
  • the melt-mixing is preferably performed at a temperature equal to or higher than the melting point of the polyamide used for melt-mixing.
  • the polyamides used for melt-mixing have different melting points, it is preferable to perform melt-mixing at a temperature equal to or higher than the melting point of the polyamide having the highest melting point.
  • the monomer composition of each polyamide e.g., the contents of components (A), (B), (C) and (D) are mutually the same. may be different.
  • the polyamide (E) contains two or more types of polyamides
  • the component (A) and the component (B) described above can be obtained. can be arbitrarily adjusted.
  • the polyamide film (F) used in the present invention is obtained by melting and mixing the polyamide (E) at 240 to 340 ° C. for 3 to 15 minutes, extruding it into a sheet through a T-die, and extruding the extruded product from -10 to 80.
  • An unstretched film can be produced by contacting and cooling on a drum whose temperature is adjusted to °C.
  • the polyamide film (F) may further contain other polymers in addition to the polyamide (E).
  • the other polymer is usually 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 0% by mass, based on the total amount of the film. %.
  • the polyamide film (F) may be in an unstretched state or in a stretched state. From the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity and further reducing warpage, especially after heat treatment, the warpage of the film laminate is more sufficiently reduced, and the appearance of the film laminate is improved. From the viewpoint of making it more satisfactory, it is preferable that the polyamide film (F) is in a stretched state.
  • the stretching is preferably uniaxial or biaxial stretching to further improve heat resistance, flexibility, adhesion, transmission properties and rubber elasticity, and From the viewpoint of further reducing warpage, stretching in the biaxial stretching direction is more preferable.
  • the stretching method includes a simultaneous stretching method and a sequential stretching method.
  • the stretching method is preferably a simultaneous stretching method from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission properties and rubber elasticity and further reducing warpage.
  • An example of the simultaneous biaxial stretching method is a method in which an unstretched film is simultaneously biaxially stretched and then heat-set. Stretching is performed at 30 to 150° C., for example, 1.2 to 8 times in both the width direction (hereinafter sometimes abbreviated as “TD”) and the longitudinal direction (hereinafter sometimes abbreviated as “MD”). It is preferable to perform The draw ratio is preferably 1.3 to 5 times, more preferably 1.3 to 5 times in both the TD and MD directions, from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission properties and rubber elasticity, and further reducing warpage. is 1.4 to 4 times, more preferably 1.8 to 2.5 times, particularly preferably 2 to 2.5 times.
  • the heat setting treatment is preferably performed at 150 to 300° C. for several seconds with a TD relaxation treatment of several percent. Prior to the simultaneous biaxial stretching, the film may be subjected to preliminary longitudinal stretching of more than 1 to 1.2 times or less.
  • An example of the sequential biaxial stretching method is a method in which an unstretched film is subjected to heat treatment such as roll heating or infrared heating, and then stretched in the longitudinal direction, followed by continuous lateral stretching and heat setting.
  • the longitudinal stretching (in the MD direction) is preferably carried out at 30 to 150° C. at a stretching ratio within the same range as the stretching ratio in the MD direction in the simultaneous biaxial stretching method.
  • the transverse stretching (TD direction) is preferably carried out at a temperature of 30 to 150° C., which is the same as in the longitudinal stretching, and at a stretching ratio within the same range as the stretching ratio in the TD direction in the simultaneous biaxial stretching method.
  • the heat setting treatment is preferably carried out at 150 to 300° C. for several seconds with TD relaxation set to several percent.
  • the surfaces of cylinders, melting parts of barrels, weighing parts, tubes, filters, T-dies, etc. are treated to reduce surface roughness in order to prevent resin from stagnation. preferably.
  • a method of reducing surface roughness for example, a method of modifying with a substance having low polarity can be mentioned.
  • a method of vapor-depositing silicon nitride or diamond-like carbon on the surface for example, a method of vapor-depositing silicon nitride or diamond-like carbon on the surface.
  • Examples of methods for stretching a film include a flat sequential biaxial stretching method, a flat simultaneous biaxial stretching method, and a tubular method. Among them, it is preferable to adopt the flat simultaneous biaxial stretching method from the viewpoint of improving the thickness accuracy of the film and making the MD properties of the film uniform.
  • Examples of the heat treatment method after stretching include known methods such as a method of blowing hot air, a method of irradiating with infrared rays, and a method of irradiating with microwaves.
  • the method of blowing hot air is preferable because it enables uniform and accurate heating.
  • the film used in the present invention has a heat-stabilizing agent in order to increase the thermal stability during film formation, prevent deterioration of the strength and elongation of the film, and prevent deterioration of the film due to oxidation and decomposition during use. It is preferred to include an agent.
  • heat stabilizers include hindered phenol-based heat stabilizers, hindered amine-based heat stabilizers, phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and bifunctional heat stabilizers.
  • hindered phenol-based heat stabilizers examples include Irganox 1010 (registered trademark) (manufactured by BASF Japan, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) and Irganox 1076.
  • hindered amine heat stabilizers examples include Nylostab S-EED (registered trademark) (manufactured by Clariant Japan, N,N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3- benzenedicarboxamide).
  • Examples of phosphorus-based heat stabilizers include Irgafos168 (registered trademark) (manufactured by BASF Japan, tris(2,4-di-tert-butylphenyl) phosphite), Irgafos12 (registered trademark) (manufactured by BASF Japan, 6 ,6′,6′′-[nitrilotris(ethyleneoxy)]tris(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin)) , Irgafos38 (registered trademark) (manufactured by BASF Japan, bis (2,4-di-tert-butyl)-6-methylphenyl) ethyl phosphite), ADKSTAB329K (registered trademark) (manufactured by ADEKA, tris (mono-di nonylphenyl)
  • sulfur-based heat stabilizers examples include DSTP "Yoshitomi” (registered trademark) (manufactured by Mitsubishi Chemical Corporation, chemical formula name: distearyl thiodipropionate), Seenox 412S (registered trademark) (manufactured by Cipro Kasei Co., Ltd., pentaerythritol tetrakis -(3-dodecylthiopropionate)).
  • Bifunctional heat stabilizers include, for example, Sumilizer GM (registered trademark) (manufactured by Sumitomo Chemical Co., Ltd., 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4 -methylphenyl acrylate), Sumilizer GS (registered trademark) (manufactured by Sumitomo Chemical Co., Ltd., 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert- pentylphenyl acrylate).
  • the thermal decomposition temperature of the hindered phenol heat stabilizer is preferably 320°C or higher, more preferably 350°C or higher.
  • a hindered phenol heat stabilizer having a thermal decomposition temperature of 320° C. or higher there is Sumilizer GA-80.
  • the hindered phenol-based heat stabilizer has an amide bond, deterioration of film strength can be prevented.
  • Hindered phenolic heat stabilizers having an amide bond include, for example, Irganox 1098.
  • a hindered phenol-based heat stabilizer together with a bifunctional heat stabilizer deterioration of film strength can be further reduced.
  • heat stabilizers may be used alone or in combination of two or more.
  • a hindered phenol-based heat stabilizer and a phosphorus-based heat stabilizer are used in combination, it is possible to prevent pressure build-up in the filter for filtering raw materials during film formation, and to prevent deterioration of film strength.
  • a hindered phenol-based heat stabilizer, a phosphorus-based heat stabilizer, and a bifunctional heat stabilizer are used in combination, it is possible to prevent pressure build-up in the filter for filtering raw materials during film formation, and to improve film strength. Degradation can be further reduced.
  • a combination of the hindered phenol heat stabilizer and the phosphorus heat stabilizer a combination of Sumilizer GA-80 or Irganox 1098 and Hostanox P-EPQ or GSY-P101 is preferable.
  • a combination of a hindered phenol-based heat stabilizer, a phosphorus-based heat stabilizer, and a bifunctional heat stabilizer a combination of Sumilizer GA-80 or Irganox 1098, HostanoxP-EPQ or GSY-P101, and Sumilizer GS is preferable.
  • Sumilizer GA-80, GSY-P101 and Sumilizer GS are more preferred.
  • the content of the heat stabilizer in the polyamide film (F) used in the present invention is preferably 0.01 to 2 parts by weight, preferably 0.04 to 1 part by weight, with respect to 100 parts by weight of the polyamide (A). Part is more preferable.
  • the content of the heat stabilizer is preferably 0.01 to 2 parts by mass, thermal decomposition can be suppressed more efficiently.
  • both the individual content of each heat stabilizer and the total content of the heat stabilizers are preferably within the above range.
  • the polyamide film (F) used in the present invention may contain lubricant particles in order to improve slipperiness.
  • lubricant particles include inorganic particles such as silica, alumina, titanium dioxide, calcium carbonate, kaolin, and barium sulfate, and organic fine particles such as acrylic resin particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene particles. be done.
  • the polyamide film (F) used in the present invention may contain various additives as necessary within a range that does not impair the effects of the present invention.
  • Additives include, for example, coloring agents such as pigments and dyes, coloring inhibitors, antioxidants different from the above heat stabilizers, weather resistance improvers, flame retardants, plasticizers, release agents, reinforcing agents, modifiers agents, antistatic agents, ultraviolet absorbers, antifogging agents, and various polymers.
  • Pigments include titanium oxide and the like.
  • weather resistance improvers include benzotriazole compounds.
  • flame retardants include brominated flame retardants and phosphorus flame retardants.
  • reinforcing agents include talc and the like.
  • the various additives described above may be added at any stage during film production.
  • the additives may be independently pre-kneaded with the polyamide (E), or may be added just before melt-mixing during extrusion into a sheet. good.
  • the polyamide film (F) used in the present invention contains heat stabilizers, lubricant particles, and various additives, it is preferable to knead the polyamide (E) and the additives in advance.
  • the kneader used for kneading with the polyamide (E) is not particularly limited, and examples thereof include known melt kneaders such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll.
  • the melt-kneading temperature is usually at least the melting point of the polyamide (E).
  • the polyamide film (F) used in the present invention can be treated to improve the adhesion of its surface.
  • methods for improving adhesion include corona treatment, plasma treatment, acid treatment, and flame treatment.
  • Various coating agents may be applied to the surface of the polyamide film (F) used in the present invention in order to impart functions such as easy adhesion, antistatic properties, releasability, and gas barrier properties.
  • the thickness of the polyamide film (F) used in the present invention is usually 1 ⁇ m to 2 mm, and from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity and further reducing warpage, preferably 10 ⁇ m to 10 ⁇ m. 500 ⁇ m, more preferably 25-100 ⁇ m.
  • the stretched polyamide film (F) has the above thickness.
  • the polyamide film (F) used in the present invention has excellent heat resistance, and the melting point, which is an index of heat resistance, must be 240° C. or higher, preferably 250° C. or higher, and 270° C. It is more preferably 300° C. or higher, and more preferably 300° C. or higher. If the melting point is too low, the heat resistance will be lowered.
  • the melting point of the polyamide film (F) is determined by the molecular weight of the polyamide (E), the content of the reaction product (hard segment polymer) composed of the aromatic dicarboxylic acid (C) and the aliphatic diamine having 12 or less carbon atoms (D), ( It can be controlled by adjusting one or more factors selected from the C)/(D) content ratio. For example, increasing the molecular weight of polyamide (E) raises its melting point. Also, for example, if the molecular weight of polyamide (E) is reduced, the melting point will be lowered. Further, for example, increasing the content of the reaction product consisting of the aromatic dicarboxylic acid (C) and the aliphatic diamine having 12 or less carbon atoms (D) tends to increase the melting point.
  • the melting point is the temperature based on the endothermic peak when the temperature is raised at a temperature elevation rate of 20°C/min with a differential scanning calorimeter.
  • the polyamide film (F) used in the present invention is excellent in flexibility, and the elongation recovery rate, which is one indicator of flexibility, is usually 30% or more, and the heat resistance, flexibility, adhesion, and transmission characteristics And from the viewpoint of further improvement of rubber elasticity and further reduction of warpage, it is preferably 40% or more, more preferably 50% or more, and even more preferably 55% or more. If the elongation recovery rate is too low, the flexibility will decrease. The elongation recovery rate is usually 100% or less (especially 90% or less).
  • the polyamide (E) that constitutes the polyamide film (F) has a block-type structure, so that an elongation recovery rate of 50% or more (especially 55% or more) can be achieved.
  • the elongation recovery rate of the polyamide film (F) depends on the polymer structure of the polyamide (E), the draw ratio, the content of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and the aliphatic diamine (B) having 18 or more carbon atoms. can be controlled by adjusting one or more factors selected from For example, when the polymer structure of polyamide (E) is adjusted from a random type structure to a block type structure, the elongation recovery rate tends to increase. Further, for example, when the draw ratio is increased, the elongation recovery rate is decreased. On the other hand, when the draw ratio is reduced, the elongation recovery rate increases.
  • the elongation recovery rate is the value obtained when a tensile test is performed under the conditions of a chuck-to-chuck distance of 70 mm and a tensile test speed of 5 mm/min in an environment of 23°C.
  • the tensile modulus (MD) which is one indicator of the flexibility of the polyamide film (F) used in the present invention, is usually 2500 MPa or less, and the heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity are further improved and From the viewpoint of further reducing warpage, it is preferably 2000 MPa or less, more preferably 1500 MPa or less, even more preferably 1000 MPa or less, particularly preferably 500 MPa or less, and 310 MPa or less is sufficient. preferred. Too high a tensile modulus reduces flexibility.
  • the tensile modulus is usually 10 MPa or more.
  • the tensile modulus of the polyamide film (F) depends on the polymer structure of the polyamide (E), the draw ratio, the content of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and the aliphatic diamine (B) having 18 or more carbon atoms. can be controlled by adjusting one or more factors selected from For example, when the polymer structure of polyamide (E) is adjusted from a random type structure to a block type structure, the tensile modulus tends to decrease. Further, for example, when the draw ratio is increased, the tensile elastic modulus increases. On the other hand, reducing the draw ratio reduces the tensile modulus.
  • the tensile modulus uses values measured in an environment with a temperature of 20°C and a humidity of 65% according to JIS K 7127.
  • the crystalline melting enthalpy of the polyamide film (F) used in the present invention is usually 15 J / g or more, and from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity and further reducing warpage, 18 J /g or more, more preferably 20 J/g or more, even more preferably 23 J/g or more, particularly preferably 25 J/g or more, and 30 J/g or more. Fully preferred, 40 J/g or greater is more preferred, and 50 J/g or greater is most preferred. The higher the crystallinity of the hard segment, the more the formation of a phase separation structure between the hard segment and the soft segment is promoted, and the flexibility and rubber elasticity are improved.
  • the crystal melting enthalpy is usually 120 J/g or less (especially 90 J/g or less).
  • a crystalline melting enthalpy of 23 J/g or more is achieved because the polyamide (E) constituting the polyamide film (F) has a block type structure. can do.
  • the crystal melting enthalpy of the polyamide film (F) is determined by the polymer structure of the polyamide (E), the reaction product (hard segment polymer) composed of the aromatic dicarboxylic acid (C) and the aliphatic diamine (D) having 12 or less carbon atoms. It can be controlled by adjusting one or more factors selected from the content. For example, when the polymer structure of polyamide (E) is adjusted from a random type structure to a block type structure, the crystal melting enthalpy tends to increase. Further, for example, when the content of the reaction product composed of the aromatic dicarboxylic acid (C) and the aliphatic diamine having 12 or less carbon atoms (D) is increased, the crystal melting enthalpy is increased.
  • the crystal melting enthalpy uses the value of the calorie of the endothermic peak measured by the same method as the melting point.
  • the hysteresis loss rate is 90% or less (from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission characteristics and rubber elasticity and further reducing warpage.
  • the hysteresis loss rate is preferably 85% or less, more preferably 80% or less, and is usually 10% or more (especially 30% or more).
  • the hysteresis loss rate of the polyamide film (F) is determined by the polymer structure of the polyamide (E), the draw ratio, the content of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and the aliphatic diamine (B) having 18 or more carbon atoms.
  • the hysteresis loss rate tends to decrease.
  • the draw ratio is increased, the hysteresis loss rate increases.
  • the draw ratio is reduced, the hysteresis loss rate is reduced.
  • the hysteresis loss rate uses the value obtained when a tensile test is performed in the same manner as the elongation recovery rate.
  • the polyamide film (F) used in the present invention has sufficiently low dielectric loss tangent and relative dielectric constant, is excellent in dielectric properties, and is also excellent in insulating properties.
  • the polyamide film (F) used in the present invention has sufficiently reduced heat shrinkage and water absorption.
  • the obtained film may be in the form of a sheet, or may be in the form of a film roll by being wound up on a take-up roll. From the viewpoint of productivity when used for various purposes, it is preferable to use the form of a film roll. When a film roll is used, it may be slit to a desired width.
  • the metal layer is provided on at least one side of the polyamide film (F), for example, it may be provided on only one side, or may be provided on both sides. Also, the metal layer may be provided entirely or partially on one side or both sides of the polyamide film (F).
  • the thickness of the metal layer is not particularly limited as long as the flexibility of the laminate (especially the film) is not hindered, and may be, for example, 1 to 500 ⁇ m. From the viewpoint of further improvement of the resistance and further reduction of warpage, the thickness is preferably 1 to 105 ⁇ m, more preferably 9 to 35 ⁇ m.
  • a resin layer may be further provided in the laminate of the present invention.
  • the resin layer may be provided on the metal layer, or the side of the polyamide film (F) not provided with the metal layer (opposite side) may be provided in A resin layer is usually provided on the metal layer.
  • the resin layer may be provided on one metal layer, or may be provided on both metal layers.
  • the resin constituting the resin layer is not particularly limited, and examples thereof include polyimide, polyamideimide, polyetherimide, polyarylene ether ketone, polyarylene sulfide, fluorocarbon polymer, polyamide, polyester, polyether, polyolefin, polystyrene, polycarbonate, and polyurethane. , ethylene/vinyl acetate copolymers, ethylene/ ⁇ -olefin copolymers, ethylene/acrylate copolymers, maleic anhydride-modified polyolefins, and ionomers.
  • the resin constituting the resin layer is polyamide
  • the polyamide may be polyamide (E) or other polyamide.
  • the metal layer provided on one side may be made of the same metal as the metal layer provided on the other side, or may be made of a different metal. may be configured.
  • the metal layer may be provided on the polyamide film (F) via a third member such as an adhesive layer. is preferably provided in direct contact with the This is because the transmission loss can be sufficiently reduced by not interposing a third member such as an adhesive layer between the metal layer and the polyamide film (F).
  • Examples of the method for producing the polyamide laminate used in the present invention include (1) a method of bonding a film and a metal by heating and pressing, (2) plating; inkjet method; vapor deposition (PVD); or a method of forming a metal layer by a chemical vapor deposition (CVD) method using heat, plasma, or light as an energy form; (3) forming a seed layer by plating, inkjet, PVD, or CVD; A method of forming a metal layer by plating after coating is exemplified. Among them, a method of laminating a film and a metal by heating and pressing is preferable from the viewpoint of productivity and further reduction of transmission loss.
  • a method of laminating a film and a metal by heating and pressurizing for example, a method of applying an adhesive to a film and then superimposing a metal and laminating by heating and pressurizing, or a method of laminating an adhesive sheet between a film and a metal.
  • a method of sandwiching and laminating by heating and pressurizing, and a method of directly laminating a film and metal and laminating by heating and pressurizing can be used.
  • heating and pressing methods include a method using a vacuum press and a method using a roll laminator.
  • the heating temperature should be "film melting point (°C) -100°C” to "film melting point (°C) -5°C”
  • the pressure should be 10 MPa or less
  • the processing time should be within 2 hours. preferable.
  • the heating temperature is preferably from “film melting point (°C) -100°C” to "film melting point (°C ) ⁇ 50° C.”, more preferably “melting point (° C.) of film ⁇ 90° C.” to “melting point (° C.) of film ⁇ 50° C.”.
  • the pressure is preferably 0.1 to 5 MPa, more preferably 0.5 to 2 MPa, from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission properties and rubber elasticity and further reducing warpage.
  • the treatment time is preferably 1 to 60 minutes, more preferably 1 to 10 minutes, from the viewpoint of further improving heat resistance, flexibility, adhesion, transmission properties and rubber elasticity and further reducing warpage.
  • the film surface is coated with a solution in which an adhesive component is dispersed, dried to form an adhesive layer, and then the metal is applied.
  • a method of stacking and laminating by heating and pressurizing may be mentioned.
  • the drying temperature after coating is preferably 100° C. or less.
  • a method of sandwiching an adhesive sheet between a film and a metal and laminating them by heating and pressurizing includes, for example, a method of superimposing an adhesive sheet on a film and laminating a metal by heating and pressurizing.
  • the peel strength between the polyamide film and the metal layer of the polyamide film laminate of the present invention is preferably 0.1 [N/mm] or more, more preferably 0.3 [N/mm] or more, More preferably, it is 0.5 [N/mm] or more.
  • the peel strength is usually 2 [N/mm] or less.
  • the peel strength uses the value measured according to JIS C 6471 (Method A).
  • the absolute value of transmission loss in a microstrip line having a characteristic impedance of 50 ⁇ , which is produced from the polyamide laminate of the present invention, is preferably 1.80 [dB/100 mm] or less at 5 GHz, and preferably 1.70 or less. is more preferable, and 1.65 or less is even more preferable.
  • the absolute value of transmission loss is usually 1 [dB/100 mm] or more at 5 GHz.
  • the transmission loss uses the value at 5 GHz of a microstrip line made from a polyamide film laminate so that the characteristic impedance is 50 ⁇ .
  • the polyamide film laminate of the present invention is excellent in heat resistance and flexibility, has good adhesion to metals and resins, and has reduced warpage when formed into a laminate.
  • the polyamide film laminate of the present invention has good appearance and reduced warpage even after heat treatment (for example, reflow treatment).
  • the polyamide film laminate of the present invention also has reduced transmission loss when used as a flexible printed circuit board.
  • the polyamide film laminate of the present invention is suitably used for, for example, flexible printed circuit boards, flexible printed circuit boards for high-speed communication, antenna substrates for high-speed communication, coverlays, flexible antenna substrates, bonding sheets, electromagnetic shielding materials, and the like. be able to.
  • the polyamide film laminate of the present invention can be used by etching the metal layer of the polyamide film laminate to form metal wiring.
  • the polyamide film laminate of the present invention can be formed by a method selected from the group consisting of a plating method, an ink jet method, a physical vapor deposition method, and a chemical vapor deposition method, the polyamide of the present invention
  • a film laminate can also be used as a flexible printed circuit board.
  • the polyamide film laminate of the present invention When used for a flexible antenna substrate, it can be used by etching the metal layer of the polyamide film laminate to form metal wiring. Alternatively, by forming a metal layer as a metal wiring on the polyamide film (F) by a method selected from the group consisting of a plating method, an ink jet method, a physical vapor deposition method, and a chemical vapor deposition method, the polyamide of the present invention A film laminate can also be used as a flexible antenna substrate.
  • Resin Composition of Film A few mg of the obtained film was sampled and subjected to 1 H-NMR analysis using a high-resolution nuclear magnetic resonance spectrometer (ECA-500NMR manufactured by JEOL Ltd.) to determine the composition of each copolymer component. It was determined from the peak intensity (resolution: 500 MHz, solvent: mixed solvent of deuterated trifluoroacetic acid and deuterated chloroform at a volume ratio of 4/5, temperature: 23°C). In Table 1, the resin composition is shown in mass ratio as the final composition.
  • Crystal melting enthalpy is obtained from the peak area in the temperature range from the start to the end of melting.
  • the average value of the values measured at arbitrary 10 points was used. Melting points were evaluated according to the following criteria. ⁇ : 300 ° C. or higher (excellent); ⁇ : 270°C or higher and lower than 300°C (good); ⁇ : 240° C. or more and less than 270° C. (practically no problem); x: Less than 240°C (problem in practice).
  • Elongation recovery rate (%) (14-A) / 14 x 100 Furthermore, it was calculated by the following formula from the obtained hysteresis curve.
  • Hysteresis loss rate (%) area (Oabcd) / area (OabeO) x 100
  • the area (Oabcd) is the area of the region indicated by the broken line (vertical broken line)
  • the area (OabeO) is the area of the region indicated by the solid line (horizontal solid line).
  • FIG. 1 is a schematic diagram showing a hysteresis curve for explaining a method of calculating a hysteresis loss rate.
  • Deformation of the laminate is a state in which wrinkles are generated on the surface of the peripheral portion of the laminate, or the peripheral portion is deformed in a wavy manner. This is a phenomenon that occurs.
  • the unevenness of the surface is a state in which the surface of the laminate is deformed due to poor air evacuation, and is a phenomenon caused by the crystal melting enthalpy, the elongation recovery rate, and the tensile elastic modulus.
  • Film exudation is a state in which the film protrudes from the gaps in the laminate, and is a phenomenon that occurs due to the heating temperature and pressure at the time of laminate production, the melting point of the film, the crystalline melting enthalpy, the elongation recovery rate, and the tensile modulus. is.
  • the case where the warp was concave was given a positive value, and the case where the warp was a convex shape was given a negative value.
  • the average value (absolute value) X of the measured values of the four corners was evaluated according to the following criteria. If the average value X is 0 mm or more and less than 5 mm, “ ⁇ (best)", if it is 5 mm or more and less than 10 mm, “ ⁇ (excellent)", if it is 10 mm or more and less than 20 mm, " ⁇ (good)", 20 mm or more and 25 mm A case of less than 25 mm was evaluated as " ⁇ (practically no problem)", and a case of 25 mm or more was evaluated as "x (practically problematic)”.
  • ⁇ There was no change in the appearance of the film, and the average warpage value X was 0 mm or more and less than 5 mm (best); A: No change in film appearance, no change in film appearance, average warpage value X of 5 mm or more and less than 10 mm (excellent); ⁇ : No change in appearance of the film, and the average warpage value X was 10 mm or more and less than 20 mm (good); ⁇ : There was no change in the appearance of the film, and the average warpage value X was 20 mm or more and less than 25 mm (practically no problem); x: The appearance of the film deteriorated, or even if the appearance of the film did not change, the average warpage value X was 25 mm or more (problematic in practice).
  • ⁇ absolute value Y was 1.65 [dB / 100 mm] or less (excellent); ⁇ : the absolute value Y was more than 1.65 [dB / 100 mm] and 1.75 [dB / 100 mm] or less (good); ⁇ : Absolute value Y was more than 1.75 [dB / 100 mm] and 1.80 [dB / 100 mm] or less (no practical problem); x: Absolute value Y was over 1.80 [dB/100 mm] (problem in practice).
  • Elongation recovery rate ⁇ 50% or more (excellent); ⁇ : 40% or more and less than 50% (good); ⁇ : 30% or more and less than 40% (practically no problem); x: Less than 30% (practically problematic).
  • the molten polymer was filtered using a metal fiber sintered filter (“NF-13” manufactured by Nippon Seisen Co., Ltd., nominal filtration diameter: 60 ⁇ m). After that, the molten polymer was extruded in the form of a film from a T-die set at 330° C. to obtain a film-shaped melt. The melt was brought into close contact with a cooling roll set at 0° C. by an electrostatic application method and cooled to obtain a substantially non-oriented, unstretched polyamide film M1. When the resin composition of the polyamide component of the obtained unstretched polyamide film M1 was determined, it was the same as the resin composition of the polyamide used.
  • NF-13 metal fiber sintered filter
  • the obtained unstretched polyamide film M1 was biaxially stretched by a flat simultaneous biaxial stretching machine while holding both ends with clips.
  • the drawing conditions were as follows: temperature of the preheating section was 80°C, temperature of the drawing section was 80°C, MD drawing strain rate was 2400%/min, TD drawing strain rate was 2400%/min, and MD draw ratio was 2.3. times, and the draw ratio in TD was 2.3 times.
  • heat setting was performed at 270° C. in the same tenter of the biaxial stretching machine, and the film was subjected to a relaxation treatment of 6% in the width direction to obtain a simultaneously biaxially stretched polyamide film S1.
  • Examples 2-9 Polyamides P2 to P9 were obtained in the same manner as in Example 1, except that the amounts of monomers introduced into the reaction vessel were changed as shown in Table 1. Further, using the obtained pellets, the same operations as in Example 1 were performed to perform melt kneading, production of unstretched films M2 to M9, and simultaneous biaxial stretching, to simultaneously biaxially stretch polyamide films S2 to S9. Obtained.
  • a polyamide film laminate having copper foil layers on both sides was obtained by performing the same operation as in Example 1 except that the heating and pressing conditions were changed as shown in Table 2. When the resin composition of the polyamide component of the obtained unstretched polyamide film was determined, it was the same as the resin composition of the polyamide used.
  • Example 10 A reaction vessel equipped with a heating mechanism and a stirring mechanism was charged with 26.7 parts by mass of dimer acid, 25.3 parts by mass of dimer diamine, 23.5 parts by mass of terephthalic acid, 24.4 parts by mass of 1,10-decanediamine, and sodium hypochlorite. 0.1 part by mass of sodium phosphate monohydrate was added. Thereafter, the mixture was heated to 260° C. with stirring, and polymerization was carried out at 260° C. under normal pressure for 5 hours under a nitrogen stream while condensed water was removed from the system. The system was in suspension during the polymerization. After the polymerization was completed, it was discharged, cut, and dried to obtain polyamide P10 in the form of pellets.
  • Example 2 Using the obtained pellets, the same operations as in Example 1 were performed to melt-knead, prepare an unstretched film M10, and perform simultaneous biaxial stretching to obtain a simultaneous biaxially stretched polyamide film S10.
  • the resin composition of the polyamide component of the obtained unstretched polyamide film M10 was determined, it was the same as the resin composition of the polyamide used.
  • the same operation as in Example 1 was performed to obtain a polyamide film laminate having copper foil layers on both sides.
  • Examples 11 and 12 Polyamides P11 and 12 were obtained in the same manner as in Example 10, except that the amounts of dimer acid, dimer diamine, terephthalic acid and 1,10-decanediamine added were changed to those shown in Table 1. Further, using the obtained pellets, the same operations as in Example 1 were performed to perform melt kneading, production of unstretched films M11 and M12, and simultaneous biaxial stretching, to simultaneously biaxially stretch polyamide films S11 and S12. Obtained. A polyamide film laminate having copper foil layers on both sides was obtained by performing the same operation as in Example 1 except that the heating and pressing conditions were changed as shown in Table 2. When the resin composition of the polyamide component of the obtained unstretched film was determined, it was the same as the resin composition of the polyamide used.
  • Comparative example 1 In a reaction vessel equipped with a heating mechanism and a stirring mechanism, 44.0 parts by mass of dimer acid, 41.7 parts by mass of dimer diamine, 6.9 parts by mass of terephthalic acid, 7.3 parts by mass of 1,10-decanediamine, sodium hypochlorite 0.1 part by mass of sodium phosphate monohydrate was added. Thereafter, the mixture was heated to 260° C. with stirring, and polymerization was carried out at 260° C. under normal pressure for 5 hours under a nitrogen stream while condensed water was removed from the system. The system was in suspension during the polymerization. After the polymerization was completed, it was discharged, cut, and dried to obtain polyamide P13 in the form of pellets.
  • Example 2 Using the obtained pellets, the same operations as in Example 1 were performed to melt-knead, prepare an unstretched film M13, and perform simultaneous biaxial stretching to obtain a simultaneous biaxially stretched polyamide film S13. Using the obtained simultaneous biaxially stretched polyamide film S13, the same operation as in Example 1 was performed to obtain a polyamide film laminate having copper foil layers on both sides.
  • Comparative example 2 Polyamide P14 was obtained in the same manner as in Example 10, except that the amounts of dimer acid, dimer diamine, terephthalic acid and 1,10-decanediamine added were changed to those shown in Table 1. Using the obtained pellets, the same operations as in Example 1 were performed to melt-knead, prepare an unstretched film M14, and perform simultaneous biaxial stretching to obtain a simultaneous biaxially stretched polyamide film S14. A polyamide film laminate having copper foil layers on both sides was obtained by performing the same operation as in Example 1 except that the heating and pressing conditions were changed as shown in Table 2. When the resin composition of the polyamide component of the obtained unstretched film was determined, it was the same as the resin composition of the polyamide used.
  • Comparative example 3 49.0 parts by mass of terephthalic acid and 0.1 parts by mass of sodium hypophosphite monohydrate were charged into a powder stirring device equipped with a heating mechanism. While heating at 170° C. and stirring, 50.9 parts by mass of 1,10-decanediamine was added little by little over 3 hours to obtain a reaction product. After that, the reaction product was heated to 250° C. with stirring, and polymerization was carried out at 250° C. for 7 hours under normal pressure under a nitrogen stream while removing condensed water out of the system. The system was in powder form during the polymerization. After the polymerization was completed, it was discharged to obtain polyamide P15 in powder form.
  • Example 2 Using the obtained powder, the same operations as in Example 1 were performed to melt-knead, prepare an unstretched film M15, and perform simultaneous biaxial stretching to obtain a simultaneous biaxially stretched polyamide film S15. Using the obtained simultaneous biaxially stretched polyamide film, the same operation as in Example 1 was performed to obtain a polyamide film laminate having copper foil layers on both sides.
  • Comparative example 4 A reactor equipped with a heating mechanism and a stirring mechanism was charged with 51.3 parts by mass of dimer acid, 48.6 parts by mass of dimer diamine, and 0.1 part by mass of sodium hypophosphite monohydrate. Thereafter, the mixture was heated to 260° C. with stirring, and polymerization was carried out at 260° C. under normal pressure for 5 hours under a nitrogen stream while condensed water was removed from the system. The system was in a homogeneous molten state during the polymerization. After the polymerization was completed, it was discharged, cut and dried to obtain polyamide P16 in the form of pellets. Using the obtained pellets, the same operations as in Example 1 were performed to perform melt-kneading, preparation of unstretched film M16, and simultaneous biaxial stretching, but a stretched film could not be obtained.
  • Comparative example 5 In a reaction vessel equipped with a heating mechanism and a stirring mechanism, 51.0 parts by mass of polyoxytetramethylene glycol (PTMG1000) having a number average molecular weight of 1000 and having amino groups instead of hydroxyl groups at both ends, 28.3 parts by mass of terephthalic acid, 20.6 parts by mass of 1,10-decanediamine and 0.1 part by mass of sodium hypophosphite monohydrate were added. Thereafter, the mixture was heated to 250° C. with stirring, and polymerization was carried out at 250° C. under normal pressure for 5 hours under a nitrogen stream while removing condensed water out of the system. The system was in a suspended solution during the polymerization. After the polymerization was completed, it was discharged, cut and dried to obtain polyamide P17 in the form of pellets, which were brittle and not suitable for practical use.
  • PTMG1000 polyoxytetramethylene glycol
  • Example 13 Polyamide P18 50 parts by mass of polyamide P8 pellets obtained in Example 8, 50 parts by mass of polyamide P9 pellets obtained in Example 9, and 0.4 parts by mass of Sumilizer GA-80 are dry blended, and the cylinder temperature is 330 ° C. The mixture was put into a twin-screw extruder having a screw diameter of 26 mm and was melt-kneaded, and extruded into a strand. It was then cooled and cut to obtain polyamide P18 in the form of pellets.
  • the obtained unstretched polyamide film M18 was biaxially stretched by a flat simultaneous biaxial stretching machine while holding both ends with clips.
  • the drawing conditions were as follows: temperature of the preheating section was 80°C, temperature of the drawing section was 80°C, MD drawing strain rate was 2400%/min, TD drawing strain rate was 2400%/min, and MD draw ratio was 2.3. times, and the draw ratio in TD was 2.3 times.
  • the film was continuously heat-set at 270° C. in the same tenter of the biaxial stretching machine, and subjected to a relaxation treatment of 6% in the width direction of the film to obtain a simultaneously biaxially stretched polyamide film S18.
  • Examples 14-22 Polyamides P19 to P27 were obtained in the same manner as in Example 13 except that the type of polyamide used and the amount to be dry-blended were changed as shown in Table 3. Further, using the obtained pellets, the same operation as in Example 13 was performed to prepare unstretched films M19 to M27, and simultaneous biaxial stretching was performed to obtain simultaneous biaxially stretched polyamide films S19 to S27. A polyamide film laminate having copper foil layers on both sides was obtained by performing the same operation as in Example 13 except that the heating and pressing conditions were changed as shown in Table 4.
  • Comparative example 6 Polyamide P28 was obtained in the same manner as in Example 13 except that the type of polyamide used and the amount to be dry-blended were changed as shown in Table 3. Using the obtained pellets, the same operations as in Example 13 were performed to prepare an unstretched film M28 and to perform simultaneous biaxial stretching, but a stretched film could not be obtained.
  • Example 23 The substantially non-oriented unstretched polyamide film M1 obtained in Example 1 was heat-treated at 270°C. Using the obtained heat-treated polyamide film, the same operation as in Example 1 was performed except that the heating and pressing conditions were changed as shown in Table 5 to obtain a polyamide film laminate having copper foil layers on both sides. rice field.
  • Examples 25, 26 and 29-34 A polyamide film laminate having copper foil layers on both sides was obtained in the same manner as in Example 1, except that the unstretched polyamide film, the stretching conditions, and the heating and pressing conditions were changed as shown in Table 5.
  • Example 27 Provide of sequentially biaxially stretched polyamide film
  • the substantially non-oriented unstretched polyamide film M1 obtained in Example 1 was biaxially stretched by a flat type sequential axial stretching machine.
  • the unstretched polyamide film M1 was heated to 80° C. by roll heating, infrared heating, or the like, and stretched 4.0 times in the MD at a stretching strain rate of 2400%/min to obtain a longitudinally stretched film.
  • both ends of the film in the width direction were held by clips of a transverse stretching machine, and the film was transversely stretched.
  • the temperature of the preheating section for TD stretching was 85° C.
  • the temperature of the stretching section was 85° C.
  • the stretching strain rate was 2400%/min
  • the TD stretching ratio was 4.0 times.
  • heat setting was performed at 270° C.
  • the film was subjected to a relaxation treatment of 6% in the width direction to obtain successively biaxially stretched polyamide films.
  • the same operation as in Example 1 was performed except that the heating and pressing conditions were changed as shown in Table 5 to obtain a polyamide film laminate having copper foil layers on both sides. got
  • Example 28 The substantially non-oriented unstretched polyamide film M3 obtained in Example 3 was heat-treated at 270°C. Using the obtained heat-treated film, the same operation as in Example 3 was performed except that the heating and pressing conditions were changed as shown in Table 5 to obtain a polyamide film laminate having copper foil layers on both sides. .
  • Comparative Examples 7-9 A polyamide film laminate having copper foil layers on both sides was obtained in the same manner as in Example 1, except that the unstretched polyamide film, the stretching conditions, and the heating and pressing conditions were changed as shown in Table 5.
  • Comparative Example 7 a heat-treated film obtained by heat-treating a substantially non-oriented unstretched polyamide film M15 at 270° C. without stretching was used.
  • Examples 36 and 37 Polyamide film lamination having a copper foil layer on one side and a polyimide layer or polyamide film S15 on the other side was performed in the same manner as in Example 35 except that the counterpart material of the laminate was changed as shown in Table 6. got a body
  • a commercially available aluminum foil (25 ⁇ m) is superimposed on the opposite side, set in a vacuum press, and heat-pressed at 230 ° C. and 1 MPa for 5 minutes to obtain a copper foil layer on one side and an aluminum foil layer on the other side.
  • Examples 39, 40, 42, 43, 45, 46 Polyamide film lamination having a copper foil layer on one side and a polyimide layer or polyamide film S15 on the other side was performed in the same manner as in Example 35 except that the counterpart material of the laminate was changed as shown in Table 6. got a body
  • Table 1 shows the production conditions and evaluation of the polyamides obtained in Examples 1-12 and Comparative Examples 1-5.
  • A fatty acid dicarboxylic acid with 18 or more carbon atoms
  • C aromatic dicarboxylic acid having 12 or less carbon atoms
  • C terephthalic acid
  • B aliphatic diamine
  • D aliphatic diamine
  • D having 12 or less carbon atoms (decane diamine)
  • E PTMG1000 with amino groups at both ends
  • F sodium hypophosphite monohydrate
  • the melting point is usually 240°C or higher, preferably 270°C or higher, more preferably 300°C or higher.
  • Table 2 shows the polyamides used for the polyamide films obtained in Examples 1 to 12 and Comparative Examples 1 to 5, the stretching conditions, their evaluation, and the heating and pressurizing conditions and evaluation of the obtained polyamide film laminates.
  • Table 3 shows the production conditions and evaluation of the polyamides obtained in Examples 13-22 and Comparative Example 6
  • the melting point is usually 240°C or higher, preferably 270°C or higher, more preferably 300°C or higher.
  • Table 4 shows the polyamides used for the polyamide films obtained in Examples 13 to 22 and Comparative Example 6, the stretching conditions, their evaluation, and the heating and pressurizing conditions and evaluation of the obtained polyamide film laminates.
  • Table 5 shows the unstretched films used for the polyamide films obtained in Examples 23 to 34 and Comparative Examples 7 to 9, the stretching conditions, the thickness, and the pressure heating conditions and evaluation of the obtained polyamide laminates.
  • Table 6 shows the stretched films and thicknesses used for the polyamide films obtained in Examples 35-46 and Comparative Examples 10-12, and the pressurization and heating conditions and evaluation of the obtained polyamide laminates.
  • the polyamide film used has a melting point of 240° C. or higher, which is an index of heat resistance, and an elongation recovery rate of 30% or more in a hysteresis test, which is an index of flexibility. , excellent in heat resistance and flexibility.
  • the film laminates of Examples 1 to 22 had excellent rubber elasticity because the polyamide films used had a crystal melting enthalpy of 15 J/g or more, which is an index of crystallinity.
  • the film laminates of Examples 1 to 22 all had excellent adhesion, good appearance, little warpage, and good appearance after the heat resistance test.
  • the polyamide film laminates of Examples 1 to 9 were obtained by a split polymerization method in which a hard segment reaction product was prepared and then added to the soft segment reaction product and polymerized. Polyamide films made of polyamide were used. .
  • polyamide films made of polyamide obtained by a batch polymerization method in which raw materials are put together and polymerized were used.
  • the former polyamide film had higher elongation recovery rate and crystal melting enthalpy than the latter polyamide film, and had higher flexibility and rubber elasticity.
  • the polyamide film laminates of Examples 1 to 9 had better flexibility and adhesion than the polyamide film laminates of Examples 10 to 12, had a good appearance, had less warpage, and after the heat resistance test Appearance was also good.
  • polyamide films composed of two types of polyamide obtained by a split polymerization method were used.
  • polyamide films composed of one type of polyamide obtained by a split polymerization method and one type of polyamide obtained by a batch polymerization method were used.
  • polyamide films composed of two types of polyamide obtained by batch polymerization were used. Comparing Examples 13, 16 and 19 of the same monomer composition to each other; Examples 14, 18 and 20 of the same monomer composition to each other; and Examples 15, 17 and 21 of the same monomer composition to each other.
  • ⁇ A polyamide film containing more polyamide obtained by the split polymerization method has a higher elongation recovery rate and crystalline melting enthalpy, and a higher tensile modulus than a polyamide film containing less polyamide obtained by the split polymerization method. It was smaller and had higher flexibility and rubber elasticity.
  • the polyamide film laminates of Examples 13 to 15 had better flexibility and adhesion than the polyamide film laminates of Examples 16 to 21, had a good appearance, had a small warp, and after the heat resistance test The appearance was also good.
  • the polyamide film laminates of Examples 16 to 18 have better flexibility and adhesion than the polyamide film laminates of Examples 19 to 21, and have good appearance, less warpage, and good appearance after the heat resistance test. Met.
  • polyamide film laminates of Examples 35 to 37 one of the counterpart materials to be laminated to the film was a different material, but after preparing the reaction product of the hard segment, it was added to the reaction product of the soft segment and polymerized. Since a polyamide film made of polyamide obtained by the division polymerization method was used, all of them had excellent adhesion, good appearance, little warpage, and good appearance after the heat resistance test.
  • polyamide film laminates of Examples 41 to 43 and 44 to 46 one of the counterpart materials to be laminated to the film was a different material, but a polyamide film containing polyamide obtained by a split polymerization method was used. , the adhesiveness was excellent, the appearance was good, the warp was small, and the appearance after the heat resistance test was good.
  • the polyamide film laminate of Comparative Example 1 is made of a polyamide that does not contain the components (A) and (B) that form the soft segments, and since a polyamide film with a low elongation recovery rate is used, the adhesion is low and the appearance is poor. there were.
  • the polyamide film laminates of Comparative Examples 8 and 9 consist of a polyamide that does not contain the components (A) and (B) that form the soft segment, and use a polyamide film with a low elongation recovery rate. was raised to (melting point -5°C), but the adhesion was only slightly increased and the appearance was poor.
  • the polyamide film laminate of the present invention is sufficiently excellent in heat resistance, flexibility, adhesion to metals and resins, appearance characteristics, warpage resistance characteristics and transmission loss reduction characteristics, among these characteristics, It is useful in applications where at least one property is required (and preferably where all of these properties are required).
  • the polyamide film laminate of the present invention is suitably used for flexible printed circuit boards, flexible printed circuit boards for high-speed communication, antenna substrates for high-speed communication, coverlays, flexible antenna substrates, bonding sheets, electromagnetic shielding materials, and the like. be able to.

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PCT/JP2022/037978 2021-10-19 2022-10-12 ポリアミドフィルム積層体 Ceased WO2023068121A1 (ja)

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JP2012234849A (ja) * 2011-04-28 2012-11-29 Unitika Ltd フレキシブルプリント配線板用の銅張積層板およびフレキシブルプリント配線板
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JP2020514139A (ja) * 2017-03-20 2020-05-21 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 金属及びポリアミド組成物を含有する積層体
WO2021106541A1 (ja) * 2019-11-27 2021-06-03 ユニチカ株式会社 柔軟性ポリアミドフィルム
JP2021154650A (ja) * 2020-03-27 2021-10-07 三井化学株式会社 金属／樹脂複合構造体、金属／樹脂複合構造体の製造方法およびエンジンマウント部材
WO2022054944A1 (ja) * 2020-09-14 2022-03-17 ユニチカ株式会社 ポリアミドおよびそれからなる成形体およびフィルムならびに該ポリアミドの製造方法

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JP2000186141A (ja) 1998-12-22 2000-07-04 Kuraray Co Ltd ポリアミドおよびそれからなるポリアミドフィルム
JP6000084B2 (ja) 2011-11-17 2016-09-28 ユニチカ株式会社 半芳香族ポリアミド樹脂組成物
JP6585273B1 (ja) 2018-12-28 2019-10-02 住友化学株式会社 発光素子用組成物及び発光素子の製造方法

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JPS6274641A (ja) * 1985-09-30 1987-04-06 東レ株式会社 ポリアミドエラストマ含有積層構造体
JP2012234849A (ja) * 2011-04-28 2012-11-29 Unitika Ltd フレキシブルプリント配線板用の銅張積層板およびフレキシブルプリント配線板
JP2020514139A (ja) * 2017-03-20 2020-05-21 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 金属及びポリアミド組成物を含有する積層体
WO2020085360A1 (ja) * 2018-10-25 2020-04-30 ユニチカ株式会社 柔軟性ポリアミド
WO2021106541A1 (ja) * 2019-11-27 2021-06-03 ユニチカ株式会社 柔軟性ポリアミドフィルム
JP2021154650A (ja) * 2020-03-27 2021-10-07 三井化学株式会社 金属／樹脂複合構造体、金属／樹脂複合構造体の製造方法およびエンジンマウント部材
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