WO2023171521A1

WO2023171521A1 - Polyamide film and method for producing same

Info

Publication number: WO2023171521A1
Application number: PCT/JP2023/007760
Authority: WO
Inventors: 直樹高石; 剛史丸尾; 吉朗服部
Original assignee: ユニチカ株式会社
Priority date: 2022-03-10
Filing date: 2023-03-02
Publication date: 2023-09-14
Also published as: TW202346417A; JPWO2023171521A1; JP7445356B2

Abstract

The present invention provides a polyamide film which has excellent heat resistance and excellent flexibility, and which is not only capable of being uniformly stretched both before and after a heat treatment, but also capable of maintaining the uniform state after the uniform stretching by means of the heat treatment and restoring the state before the application of a tension by means of release after the application of the tension. The present invention relates to a polyamide film which contains a polyamide (E) that contains a unit derived from an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms, a unit derived from an aliphatic diamine (B) having 18 or more carbon atoms, a unit derived from an aromatic dicarboxylic acid (C) having 12 or less carbon atoms, and a unit derived from an aliphatic diamine (D) having 12 or less carbon atoms, and which has a melting point of 240°C or higher, an elongation recovery ratio of 30% or more in a hysteresis test, a tensile modulus of 1,500 MPa or less, a 10% elongation strength of 70 MPa or less and a crystal melting enthalpy of 15 J/g or more.

Description

Polyamide film and its manufacturing method

The present invention relates to a polyamide film and a method for producing the same.

Highly flexible films that can be stretched under low loads at room temperature can be used in a wide range of applications, including base materials for adhesive tapes, transfer base materials for decoration or molding, cushioning materials for pressing, and manufacturing process applications for circuits and semiconductors. It is utilized in the field (Patent Document 1).

For example, a dicing film is used in the process of dividing a semiconductor wafer into chips (dicing), and is often also used in the next expanding process. In the expanding process, in order to uniformly widen the gaps between chips, the dicing film is required to have the property of expanding evenly (Patent Document 2). If the film cannot be expanded evenly, there is a problem in that chips are divided incorrectly and the yield is reduced.

In the expanding process, the dicing film is stretched radially, and is heated to remove slack. For this reason, even if the slack is removed by heat treatment, it is necessary to maintain equal intervals between the divided chips. Therefore, the dicing film is also required to have uniformity after heat treatment. If the film does not have uniformity after heat treatment, there is a problem that the distance between the divided chips cannot be maintained. If the chip spacing cannot be maintained, it may cause pick-up failure in subsequent processes.

After the expansion step, there is a step of hooking up each divided chip, in which tension is applied by pushing up with a needle or the like. For this reason, it is required that no distortion occurs to the film even when pushed up, and that residual distortion is reduced even when the film is picked up many times (Patent Document 3). Therefore, the dicing film also needs to have restorability. If the film cannot be restored sufficiently, distortion may accumulate and the chip may become misaligned or tilted, resulting in pick-up failure.

As another example, easy-to-form films such as release films are stretched along the surface of a mold, etc., and are in close contact with the surface, so the film has flexibility, can be stretched evenly, and has the ability to follow deformation to the mold. is required. In particular, when used as a release film, it must withstand molding temperatures. From the viewpoint of surface protection after molding, it is preferable that the film has restorability.

As a film with high heat resistance and high flexibility, for example, Patent Document 4 discloses a film made of polyamide made of terephthalic acid, 1,10-decanediamine, dimer acid, and dimer diamine.

Japanese Patent Application Publication No. 2021-116351 JP 2021-14557 Publication Japanese Patent Application Publication No. 2021-174841 International Publication 2021/106541 pamphlet

The inventors of the present invention found that the following problems occur with the conventional technology.
For example, the film of Patent Document 4 had at least one of the following problems:
・Unable to expand uniformly at least before and after heat treatment;
・Even if it could be expanded evenly, the uniform state could not be maintained due to heat treatment;
・It was not possible to fully restore the state before tension was applied by releasing the tension after applying it.

The present invention aims to solve the above-mentioned problems, and is capable of not only expanding uniformly both before and after heat treatment, but also maintaining the uniform state even after heat treatment after uniform expansion, as well as being able to maintain the uniform state even after applying tension. An object of the present invention is to provide a polyamide film with excellent heat resistance and flexibility that can be restored to its pre-applying state even when released.

The gist of the 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 unit consisting of an aliphatic diamine (D) having 12 or less carbon atoms, the melting point is 240°C or higher, the elongation recovery rate in the hysteresis test is 30% or higher, and the tensile modulus is 1500 MPa. Hereinafter, a polyamide film having a 10% elongation strength of 70 MPa or less and a crystal melting enthalpy of 15 J/g or more.
<2> The aliphatic dicarboxylic acid having 18 or more carbon atoms (A) is a dimer acid, the aliphatic diamine having 18 or more carbon atoms (B) is a dimer diamine, and the aromatic dicarboxylic acid having 12 or less carbon atoms (C) is The polyamide film according to <1>, wherein terephthalic acid and the aliphatic diamine (D) having 12 or less carbon atoms are 1,10-decanediamine.
<3> 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). The polyamide film according to <1> or <2>, which is 10 to 90% by mass based on all monomer components.
<4> The content of the unit consisting of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms is 3 to 45% by mass based on the total monomer components constituting the polyamide (E),
The content of the unit consisting of the aliphatic diamine (B) having 18 or more carbon atoms is 3 to 45% by mass based on the total monomer components constituting the polyamide (E),
The content of the unit consisting of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms is 3 to 45% by mass based on the total monomer components constituting the polyamide (E),
<1> to <3>, wherein the content of the unit consisting of the aliphatic diamine (D) having 12 or less carbon atoms is 3 to 52% by mass based on the total monomer components constituting the polyamide (E). The polyamide film according to any one of the above.
<5> The polyamide film according to any one of <1> to <4>, wherein the crystal melting enthalpy is 25 J/g or more.
<6> The content of the unit consisting of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms is 8 to 35% by mass based on the total monomer components constituting the polyamide (E), <5> Polyamide film described in.
<7> The polyamide (E) includes a hard segment consisting of a unit consisting of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms, a unit consisting of the aliphatic diamine (D) having 12 or less carbon atoms, and the <1> to <6> containing a block polyamide containing a soft segment consisting of a unit consisting of an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and a unit consisting of an aliphatic diamine (B) having 18 or more carbon atoms. The polyamide film according to any one of the above.
<8> The polyamide film according to <7>, wherein the content of the block polyamide is 10% by mass or more based on the total amount of the polyamide (E).
<9> The polyamide film according to <7>, wherein the content of the block polyamide is 40% by mass or more based on the total amount of the polyamide (E).
<10> A method for producing the polyamide film according to any one of <1> to <9>, comprising:
An aromatic dicarboxylic acid (C) having 12 or more carbon atoms and an aliphatic diamine (D) having 12 or less carbon atoms are combined with an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and an aliphatic diamine having 18 or more carbon atoms (B). ) A method for producing a polyamide film, which comprises reacting separately with polyamide (E) to obtain polyamide (E).
<11> The polyamide film according to any one of <1> to <9> and at least one layer provided on the polyamide film selected from the group consisting of a resin layer, a metal layer, and an inorganic material layer. , polyamide film laminate.
<12> A decorative molding film comprising the polyamide film according to any one of <1> to <9> or the polyamide film laminate according to <11>.
<13> A dicing film comprising the polyamide film according to any one of <1> to <9> or the polyamide film laminate according to <11>.
<14> A flat or curved printed circuit board comprising the polyamide film according to any one of <1> to <9> or the polyamide film laminate according to <11>.
<15> A planar or curved antenna substrate comprising the polyamide film according to any one of <1> to <9> or the polyamide film laminate according to <11>.

The polyamide film of the present invention can expand more fully and evenly both before and after heat treatment.
After the polyamide film of the present invention has been uniformly expanded, the uniform state can be more fully maintained even by heat treatment, and even when tension is applied and then released, it can be more fully restored to the state before application.

FIG. 2 is a schematic diagram showing a hysteresis curve for explaining a method of calculating a hysteresis loss rate.

The polyamide film of the present invention comprises a unit consisting of 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 referred to as component (A)). , a unit consisting of an aromatic dicarboxylic acid (C) having 12 or less carbon atoms (hereinafter sometimes referred to as component (C)), and a unit consisting of an aromatic dicarboxylic acid (C) having 12 or less carbon atoms (hereinafter sometimes referred to as component (C)); This is a polyamide film containing a polyamide (E) containing a unit consisting of an aliphatic diamine (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 consisting of an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms" may simply be expressed as "an aliphatic dicarboxylic acid (A) monomer 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 be simply expressed as "an aliphatic diamine (B) monomer 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 be simply expressed as "an aromatic dicarboxylic acid (C) monomer 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 be simply expressed as "an aliphatic diamine (D) monomer having 12 or less carbon atoms" or a residue thereof.

The aliphatic dicarboxylic acid (A) having 18 or more carbon atoms constituting the polyamide (E) used in the polyamide film of the present invention is preferably an aliphatic dicarboxylic acid consisting of hydrocarbons except for carboxyl groups, such as hexadecanedicarboxylic acid. (18 carbon atoms), octadecanedicarboxylic acid (20 carbon atoms), and dimer acid (36 carbon atoms). Among these, aliphatic dicarboxylic acids having 20 or more carbon atoms are preferred, and dimer acids are more preferred because of their increased 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 molecules or may be mutually different types of molecules. The dimer acid may be a dicarboxylic acid having an unsaturated bond, but a dicarboxylic acid in which all bonds are saturated by hydrogenation is preferred 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, even more preferably 34 to 40, from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability. It is 38.

As used herein, heat resistance refers to a film property that has a sufficiently high melting point.
Flexibility is a property in which the elongation recovery rate of the film is sufficiently high and the tensile modulus of the film is sufficiently low.
Uniform expandability refers to a film characteristic that allows it to expand more uniformly from the center to the edges both before and after heat treatment.
Heat-resistant uniformity refers to a film characteristic that can sufficiently maintain a uniform state even after heat treatment after uniform expansion.
Restorability refers to the property of a film that, after being expanded evenly, can be more fully restored to the state before tension is applied even after tension is applied and then released.

The content of component (A) is preferably 3 to 45% by mass, and preferably 5 to 45% by mass, from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability. more preferably 10 to 45% by weight, even more preferably 10 to 40% by weight, fully preferably 13 to 40% by weight, and 16 to 33% by weight. is more fully preferred. The content is the content of the residues of component (A), and is the ratio to all the monomer components (or the total amount of those residues) constituting the polyamide (E). When the polyamide contains two or more types of components (A), the total amount thereof may be within the above range.

The aliphatic diamine (B) having 18 or more carbon atoms constituting the polyamide (E) used in the polyamide film of the present invention is preferably an aliphatic dicarboxylic acid consisting of all hydrocarbons except for the amino group. For example, octadecanediamine (carbon 18), eicosandiamine (carbon number 20), and dimer diamine (carbon number 36). Among them, dimer diamine is preferred. By using dimer diamine, the flexibility of the entire polymer can be effectively improved even if the resin composition is relatively small compared to other monomers. Generally, dimer diamine is produced by reacting dimer acid with ammonia, followed by dehydration, nitrification, and reduction. The dimer diamine may be a diamine having an unsaturated bond, but a diamine in which all bonds are saturated by hydrogenation is preferred 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, still more preferably 34 to 40, from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability. It is 38.

The content of component (B) is preferably 3 to 45% by mass, and preferably 5 to 45% by mass, from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability. It is more preferably 10 to 45% by weight, even more preferably 10 to 40% by weight, and fully preferably 20 to 34% by weight. The content is the content of the residues of component (B), and is the ratio to all the monomer components (or the total amount of those residues) constituting the polyamide (E). When the polyamide contains two or more types of components (B), the total amount thereof may be within the above range.

Examples of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms constituting the polyamide (E) used in the polyamide film of the present invention include terephthalic acid (8 carbon atoms), isophthalic acid (8 carbon atoms), orthophthalic acid ( carbon number 8). Among these, aromatic dicarboxylic acids having 8 or more carbon atoms are preferred, and terephthalic acid is more preferred, since heat resistance, flexibility, and rubber elasticity can be further improved. 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, even more preferably 6 to 12, from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability. It is 10.

The content of component (C) is preferably 3 to 45% by mass, and preferably 5 to 45% by mass, from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability. It is more preferably 5 to 40% by weight, even more preferably 8 to 35% by weight, and fully preferably 15 to 30% by weight. The content is the content of the residues of component (C), and is the ratio to all the monomer components (or the total amount of those residues) constituting the polyamide (E). When the polyamide contains two or more types of components (C), the total amount thereof may be within the above range.

Examples of the aliphatic diamine (D) having 12 or less carbon atoms constituting the polyamide (E) used in the polyamide film of the present invention include 1,12-dodecanediamine (12 carbon atoms), 1,10-decanediamine (carbon 10), 1,9-nonanediamine (9 carbon atoms), 1,8-octanediamine (8 carbon atoms), and 1,6-hexanediamine (6 carbon atoms). Among these, 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 heat resistance, flexibility, and rubber elasticity can be further improved. (D) may be used alone or in combination of two or more of the above.

The number of carbon atoms in component (D) is preferably 4 to 12, more preferably 6 to 12, even more preferably 8 to 12, from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability. It is 12.

The content of component (D) is preferably 3 to 52% by mass, and 5 to 50% by mass from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability. The content is more preferably 5 to 40% by weight, even more preferably 10 to 40% by weight, and fully preferably 20 to 30% by weight. The content is the content of the residues of component (D), and is the ratio to all the monomer components (or the total amount of those residues) constituting the polyamide (E). When the polyamide contains two or more types of components (D), the total amount thereof may be within the above range.

In the present invention, the polyamide (E) may be a random polyamide in which the components (A) to (D) are randomly arranged and polymerized, or a hard segment and a component consisting of the components (C) and (D). It may be a block-type polyamide containing a soft segment consisting of (A) and (B), or a polyamide containing both a random-type polyamide and a block-type polyamide. The polyamide (E) preferably contains block-type polyamide, and preferably contains only block-type polyamide, from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, restorability, and rubber elasticity. . Although the details of the mechanism by which block-type polyamides are preferred are not clear, it is thought to be based on the following phenomenon. In the block type structure, a phase-separated structure of hard segments and soft segments is formed, the hard segments play the role of crosslinking points of the rubber, and the soft segments can freely expand and contract. Therefore, the polyamide (E) can have sufficiently excellent heat resistance and also sufficiently excellent flexibility (and rubber elasticity). As a result, it is thought that further improvements in heat resistance, flexibility, uniform expandability, heat resistance uniformity, restorability, and rubber elasticity are achieved in films and laminates. Examples of combinations of components (C) and (D) include terephthalic acid and butanediamine, terephthalic acid and 1,9-nonanediamine, terephthalic acid and 1,10-decanediamine, and terephthalic acid and 1,12-dodecanediamine. Among them, terephthalic acid and 1,10-decanediamine are preferred. By using terephthalic acid and 1,10-decanediamine, the hard segment tends to become a highly crystalline segment, which promotes the formation of a phase-separated structure between the hard segment and the soft segment, resulting in more excellent flexibility and Demonstrates rubber elasticity. ``Rubber'' is used in the concept of a material that is locally deformed by external force, but returns to its original shape when the force is removed.

The total content of units consisting of aliphatic dicarboxylic acids (A) having 18 or more carbon atoms and units consisting of aliphatic diamines having 18 or more carbon atoms (B) in the polyamide (E) used in the present invention is determined by the heat resistance , from the viewpoint of further improving flexibility, uniform expandability, heat resistance uniformity, and restorability, preferably from 10 to 90% by mass, more preferably from 15 to 80% by mass, and from 20 to 80% by mass. More preferably, the amount is from 30 to 75% by weight, particularly preferably from 40 to 65% by weight. The total content is the total content of the residues of component (A) and the residues of component (B), and is the total content of all monomer components (or the total amount of those residues) constituting the polyamide (E). It is a percentage of

The polyamide (E) used in the present invention preferably does not contain polyether components or polyester components that are easily decomposed during polymerization. Examples of such polyether components include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and polyoxyethylene/polyoxypropylene glycol. Examples of the polyester component include polyethylene adipate, polytetramethylene adipate, and polyethylene sebacate. When a polyether component or a 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, and 1% by mass or less from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability. It is more preferable that the amount is 0.1% by mass or less, and even more preferably 0.1% by 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 those residues) constituting the polyamide (E). The polyether component and the polyester component are components that form a part of the polyamide through covalent bonds with the polyamide, and are not simply blended into the polyamide.

The polyamide (E) used in the present invention may contain an end-capping agent in order to adjust the degree of polymerization, inhibit product decomposition, inhibit coloring, and the like. Examples of the terminal capping agent include monocarboxylic acids such as acetic acid, lauric acid, benzoic acid, and stearic acid, and monoamines such as octylamine, cyclohexylamine, aniline, and stearylamine. Among the terminal blocking agents, one of the above may be used alone, or two or more thereof may be used in combination. The content of the terminal capping agent is not particularly limited, but is usually 0 to 10 mol% based on 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, and includes, for example, an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms, an aliphatic diamine (B) having 18 or more carbon atoms, and an aromatic acid having 12 or less carbon atoms. A method in which a group dicarboxylic acid (C) and an aliphatic diamine having 12 or less carbon atoms (D) are reacted together (hereinafter sometimes referred to as "bulk polymerization method"), or a method in which component (C) and component (D) are reacted together. can be obtained by a method in which component (A) and component (B) are reacted separately (hereinafter sometimes referred to as "split polymerization method"). The polyamide (E) used in the present invention is prepared by split polymerization from the viewpoint of further improving the heat resistance, flexibility, rubber elasticity, uniform expansibility, heat resistance uniformity, restorability, and adhesion to metal of the polyamide film of the present invention. Preferably, it is produced by a method. By producing polyamide by a split polymerization method, the polyamide has a more preferable enthalpy of crystal fusion, especially 25 J/g or more, and the polyamide film of the present invention has good heat resistance, flexibility, rubber elasticity, uniform extensibility, This is because heat resistance uniformity, restorability, and adhesion to metal are further improved.

In the batch polymerization method, all predetermined components are mixed and polymerized. The polymerization method is not particularly limited, but examples include a method in which the polyamide is heated to a temperature below the melting point of the resulting polyamide, and polymerized by maintaining the temperature under a nitrogen stream while removing condensed water from the system. A polyamide polymerized by a batch polymerization method can be referred to as a "random type polyamide" from the viewpoint that all components are arranged randomly. The "melting point of the obtained polyamide" refers to the "melting point of the target polyamide", and may be, for example, the "melting point of the hard segment polymer" explained in the divisional polymerization method described below.

Therefore, when producing polyamide by the batch polymerization method, first, for example, a hard segment polymer is obtained by the production method described below in the divisional polymerization method. Next, the melting point of the obtained hard segment polymer is measured. The method for measuring the melting point is not particularly limited, and for example, the melting point can be measured using a differential scanning calorimeter. Thereafter, polyamide can be produced by subjecting the mixture containing the monomer (or prepolymer) to a polymerization reaction at a temperature below the "melting point" (especially at a temperature below the melting point). For example, when using dimer acid, dimer diamine, terephthalic acid, and 1,10-decanediamine as components (A) to (D), the melting point of the "target polyamide" (for example, the "melting point of the hard segment polymer") is The polymerization temperature in the batch polymerization method may be 220 to 300°C (particularly 240 to 280°C). In this case, the polymerization time in the batch polymerization method is not particularly limited as long as sufficient polymerization is carried out, and may be, for example, 1 to 10 hours (particularly 3 to 7 hours).

In the split polymerization method, component (C) and component (D) are reacted separately from component (A) and component (B) to perform polymerization. For example, component (C) and component (D) are reacted to obtain a reaction product, and then the reaction product is further reacted with component (A) and component (B) to polymerize. For more information,
Ingredient (A) and
Ingredient (B) and
A reaction product of component (C) and component (D),
react and polymerize.

In such a split polymerization method, component (A) and component (B) may be used in a non-reacted state or in a mutually reacted state (i.e., the form of their reaction products). ) may be used. For example, the polyamide (E) used in the present invention can be prepared by reacting component (A) and component (B) in advance, and then combining the obtained reaction product of component (A) and component (B) with component (C ) and component (D) may be reacted and polymerized. Specifically, the polyamide (E) used in the present invention is polymerized by reacting a reaction product of component (A) and component (B) with a reaction product of component (C) and component (D). It may be obtained by doing so. Component (A) and component (B) reacted with each other from the viewpoint of further improving the heat resistance, flexibility, rubber elasticity, uniform extensibility, heat resistance uniformity, restorability, and adhesion to metal of the polyamide film. Preferably, they are used in the form (ie in the form of their reaction products).

Polyamide polymerized by the split polymerization method is different from polyamide polymerized by the batch polymerization method, and is a polyamide composed of a hard segment consisting of components (C) and (D) and a soft segment consisting of components (A) and (B). obtained as. Therefore, polyamide polymerized by bulk polymerization is called "random polyamide," whereas polyamide polymerized by split polymerization is called "block polyamide" from the viewpoint of containing hard segments and soft segments. I can do it.

In the split polymerization method, the monomer ratio [(C)/(D)] of aromatic dicarboxylic acid (C) having 12 or less carbon atoms and aliphatic diamine (D) having 12 or less carbon atoms to be used can be adjusted. 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 from 45/55 to 60/40, and preferably from 45/55 to 55/45, since flexibility and rubber elasticity are more sufficiently improved. is more preferable.

In the split polymerization method, a method for producing a reaction product containing an aromatic dicarboxylic acid (C) having 12 or less carbon atoms and an aliphatic diamine (D) having 12 or less carbon atoms (hereinafter simply referred to as "method for producing a reaction product X") '') is not particularly limited, but for example, the component (C) may be heated to a temperature above the melting point of the component (D) and below the melting point of the component (C) to maintain the powder state of the component (C). An example is a method of adding (D). For example, when using terephthalic acid and 1,10-decanediamine as components (C) and (D), the heating temperature may be 100 to 240°C (particularly 140 to 200°C). The addition of component (D) is preferably carried out continuously, for example over a period of 1 to 10 hours (especially 1 to 5 hours).

The reaction product of component (C) and component (D) may have the form of a salt of component (C) and component (D), or a condensate (or oligomer or prepolymer) thereof. or a combination thereof.

When reacting component (A) and component (B) in advance, 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, but For example, a method of reacting at a temperature of 80 to 150°C (particularly 100 to 150°C) for 0.5 to 3 hours can be mentioned.

The reaction product of component (A) and component (B) may also be in the form of a salt, similar to the reaction product of component (C) and component (D), or may be in the form of a salt, or may be formed by condensation thereof. It may have the form of a substance (or oligomer or prepolymer), or it may have a composite form of these.

In the split polymerization method, the polymerization method is not particularly limited; Examples include a method of polymerizing at a temperature below Specifically, it is heated to a temperature below the melting point of the hard segment polymer (for example, a polyamide composed only of components (C) and (D) that constitute the hard segment), and is heated under a nitrogen stream while removing condensed water from the system. , polymerization occurs by maintaining the temperature. By polymerizing in this manner, the hard segments can be polymerized without melting, and only the soft segments are molten. The method of polymerizing at a temperature below the melting point of the hard segment polymer is particularly effective in the polymerization of polyamides having a high melting point of 280° C. or higher, which tend to be decomposed due to high polymerization temperatures.

"Melting point of hard segment polymer" refers to the melting point of a polyamide obtained by sufficiently polymerizing only components (C) and (D) constituting the hard segment as monomer components. The "melting point of a hard segment polymer" may be the melting point of a polyamide obtained by sufficiently polymerizing only components (C) and (D) as monomer components, for example, by the method described in International Publication No. 2013/042541 pamphlet. good. Specifically, 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 obtained reaction product. This is the melting point of polyamide (hard segment polymer). In the process of producing a hard segment polymer, in step (i), components (C) and (D) are heated to a temperature above the melting point of component (D) and below the melting point of component (C), and component (C) The reaction product can be obtained by adding component (D) so as to maintain the powder state. In step (i), for example, when using terephthalic acid and 1,10-decanediamine as components (C) and (D), the heating temperature is 100 to 240°C (preferably 140 to 200°C, particularly 170°C). It may be. The addition of component (D) is preferably carried out continuously, for example over a period of 1 to 10 hours (preferably 1 to 5 hours, particularly 2.5 hours). In the process of producing a hard segment polymer, in step (ii), the reaction product in the solid phase obtained in step (i) is sufficiently heated to maintain the solid phase to undergo polymerization (i.e., solidification). phase polymerization). In step (ii), for example, when using terephthalic acid and 1,10-decanediamine as components (C) and (D), the heating temperature (i.e., polymerization temperature) is 220 to 300°C (preferably 240 to 280°C). , especially 260° C.), and the heating time (ie, polymerization time) may be 1 to 10 hours (preferably 3 to 7 hours, especially 5 hours). Steps (i) and (ii) are preferably carried out in a stream of nitrogen inert gas or the like. For example, when terephthalic acid and 1,10-decanediamine are used as components (C) and (D), the "melting point of the hard segment polymer" is usually 315°C.

Therefore, when producing polyamide by the split polymerization method, for example, the following method can be adopted. First, using only the components (C) and (D) constituting the polyamide, sufficient polymerization is carried out in the steps (i) and (ii) described above to obtain a polyamide (ie, hard segment polymer). Next, the melting point of the obtained polyamide is measured. The method for measuring the melting point is the same as in the batch polymerization method. Thereafter, component (C) and component (D) are reacted to obtain a reaction product according to the reaction product manufacturing method By further reacting and polymerizing component (A) and component (B), polyamide can be produced. When using dimer acid, dimer diamine, terephthalic acid and 1,10-decanediamine as components (A) to (D), the polymerization temperature in the split polymerization method is 220 to 300°C (preferably 240 to 280°C, especially 260°C). ℃). In this case, the polymerization time in the split polymerization method is not particularly limited as long as sufficient polymerization is carried out, and may be, for example, 1 to 10 hours (preferably 3 to 7 hours, particularly 5 hours).

In the batch polymerization method and the split polymerization method (hereinafter sometimes simply referred to as "method for producing polyamide (E) used in the present invention"), a catalyst may be used as necessary. Examples of the catalyst include phosphoric acid, phosphorous acid, hypophosphorous acid, or salts thereof. The content of the catalyst is not particularly limited, but is usually 0 to 2% by mole based on the total mole amount of dicarboxylic acid and diamine.

In the method for producing polyamide (E) used in the present invention, an organic solvent or water may be added as necessary.

In the method for producing polyamide (E) used in the present invention, polymerization may be carried out in a closed system or at normal pressure. When carrying out in a closed system, the pressure may increase due to volatilization of monomers, generation of condensed water, etc., so it is preferable to control the pressure appropriately. On the other hand, if the monomer used has a high boiling point and does not flow out of the system even without pressurization, polymerization can be carried out at normal pressure. For example, in the case of a combination of dimer acid, dimer diamine, terephthalic acid, and decanediamine, polymerization can be carried out at normal pressure.

In the method for producing polyamide (E) used in the present invention, in order to prevent oxidative deterioration, it is preferable to carry out the polymerization under a nitrogen atmosphere or under vacuum.

The polymerized polyamide may be extruded into strands and made into pellets, or may be hot-cut or underwater-cut to make pellets.

In the method for producing polyamide (E) used in the present invention, solid phase polymerization may be performed after polymerization 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 more, more preferably for 1 hour or more, under an inert gas flow or under reduced pressure. The melting point of the resin composition may be the same temperature as the above-mentioned "melting point of the hard segment polymer."

The polyamide (E) may include two or more types of polyamides (E) that differ in monomer composition (type), monomer arrangement, and/or molecular weight (especially melting point). The two or more types of polyamides (E) may be two or more types of polyamides (E) selected from the range of the polyamides (E) described above. Therefore, two or more types of polyamides (E) may each contain components (A) to (D). The two or more types of polyamides (E) having different monomer sequences are one or more types (especially one type) of the above-mentioned random type polyamides and one or more types (especially one type) of the above-described block type polyamides. From the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability, the polyamide (E) preferably contains block polyamide, and the content of block polyamide is higher. is more preferable. The content of the block polyamide is preferably 10% by mass or more based on the total amount of polyamide (E), more preferably 30% by weight or more, more preferably 40% by weight or more, particularly preferably 45% by weight or more, sufficiently preferably 70% by weight or more, even more preferably 80% by weight or more, still more preferably 90% by weight or more, Most preferably it is 100% by mass. When the polyamide (E) contains two or more types of polyamides (E), the contents of the components (A) to (D) described herein are the same as those of the components (A) to (D) in the total polyamide (E), respectively. The content may be D).

When the polyamide (E) contains two or more types of polyamides (E), the polyamide (E) may be used by melt-mixing some or all of the two or more types of polyamides (E) in advance. Alternatively, each polyamide (pellet) may be used as a dry blend, or a composite form of these may be used.

For example, when the polyamide (E) used in the present invention contains two types of polyamides, a random type polyamide and a block type polyamide, in the method for producing the polyamide (E), polyamides obtained by a batch polymerization method and a split polymerization method are used. The two types may be melt-mixed in advance, or the respective polyamides (pellets) may be dry blended.
For example, when the polyamide (E) used in the present invention contains two types of random polyamides, in the method for producing the polyamide (E), two types of random polyamides obtained by a batch polymerization method are melt-mixed in advance. Alternatively, each polyamide (pellet) may be dry blended.
For example, when the polyamide (E) used in the present invention contains two types of block polyamides, in the method for producing the polyamide (E), two types of block polyamides obtained by a split polymerization method are melt-mixed in advance. Alternatively, each polyamide (pellet) may be dry blended.
From the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability, the polyamide (E) used in the present invention should include at least block polyamide (for example, block polyamide and block polyamide). or a combination of a random polyamide and a block polyamide), and preferably contains two types of block polyamides (for example, two types of block polyamides and no random polyamide). ) is more preferable.

The content of the random polyamide in the polyamide (E) is preferably as low as possible from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability. , preferably 90% by weight or less, more preferably 70% by weight or less, even more preferably 60% by weight or less, particularly preferably 55% by weight or less, fully preferably 30% by weight or less, even more preferably 20% by weight or less. , even more preferably 10% by weight or less, and most preferably 0% by weight.

When the polyamide (E) used in the present invention is obtained by melt-mixing, the melt-mixing is preferably performed at a temperature equal to or higher than the melting point of the polyamide used for melt-mixing. When the polyamides used for melt-mixing have different melting points, it is preferable to perform the melt-mixing at a temperature equal to or higher than the melting point of the polyamide with the highest melting point.

When the polyamide (E) contains two or more types of polyamides (E), the monomer composition of each polyamide (E) (for example, the content of components (A), (B), (C) and (D)) is They may be the same or different.

When polyamide (E) contains two or more types of polyamide (E), the content of each component and The total content of component (A) and component (B) described above can be adjusted as desired.

The polyamide film of the present invention is produced by melt-mixing the above polyamide (E) at 240 to 340°C for 3 to 15 minutes, extruding it into a sheet through a T-die, and controlling the temperature of the extruded product to -10 to 80°C. It can be produced as an unstretched film by placing the film in close contact with a stretched drum and cooling it. The content of polyamide (E) in the polyamide film is not particularly limited, and is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and It is preferably 95% by mass or more, particularly preferably 100% by mass.

The polyamide film may further contain other polymers. Other polymers include polyamides other than polyamide (E), polyimides, polyamideimides, polyetherimides, polyarylene ether ketones, polyarylene sulfides, fluorocarbon polymers, polyesters, polyethers, polyolefins, polystyrene, polycarbonates, polyurethanes, and ethylene/acetic acid. Examples include vinyl copolymers, ethylene/α-olefin copolymers, ethylene/acrylic acid ester copolymers, maleic anhydride-modified polyolefins, and ionomers. The amount of other polymers is usually 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, particularly preferably 0% by mass, based on the total amount of the film. %.

The polyamide film of the present invention may be in an unstretched state or may be in a stretched state. From the perspective of further improving heat resistance, flexibility, uniform extensibility, heat resistance uniformity, resilience, and rubber elasticity, polyamide films can be used in an unstretched state or, if stretched, at a relatively low stretching ratio. It is preferable that

When the polyamide film of the present invention is used in a stretched state, the stretching is preferably uniaxial or biaxial stretching, which improves heat resistance, flexibility, uniform extensibility, heat resistance uniformity, resilience, and elasticity. From the viewpoint of further improving elasticity, stretching in the biaxial stretching direction is more preferable. Examples of the stretching method include 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, uniform expandability, heat resistance uniformity, restorability, and rubber elasticity, and further reducing warpage.

An example of a simultaneous biaxial stretching method includes a method in which an unstretched film is simultaneously biaxially stretched and then subjected to heat setting treatment. Stretching is carried out at 30 to 150°C, and 1.01 to 5 times in both the width direction (hereinafter sometimes abbreviated as "TD") and longitudinal direction (hereinafter sometimes abbreviated as "MD"). It is preferable to increase the amount, and more preferably 1.1 to 3 times. The stretching ratio is preferably 3.5 times or less in both the TD direction and the MD direction (for example, 1.01 to 3.5 times, especially 1.1 to 3.5 times), more preferably 2.5 times or less (for example, 1.01 to 2.5 times, especially 1.1 to 2.5 times), even more preferably is 2 times or less (for example, 1.01 to 2 times, especially 1.1 to 2 times). The heat setting treatment is preferably performed at 150 to 300° C. for several seconds with a few percent of TD relaxation treatment. Before simultaneous biaxial stretching, the film may be subjected to preliminary longitudinal stretching of more than 1 and 1.2 times or less.

An example of a 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 transverse stretching and heat setting treatment. can be mentioned. It is preferable to carry out the stretching at a stretching ratio within the same range as the MD direction stretching ratio in the simultaneous biaxial stretching method. The transverse stretching (TD direction) is preferably carried out at the same temperature as the longitudinal stretching, from 30 to 150° C., and at a stretching ratio within the same range as the TD direction stretching ratio 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 of several percent.

In film manufacturing equipment, the surfaces of cylinders, barrel melting and metering parts, single tubes, filters, T-dies, etc. are treated to reduce surface roughness to prevent resin from stagnation. It is preferable that An example of a method for reducing surface roughness is a method of modifying the surface with a less polar substance. Alternatively, a method may be used in which silicon nitride or diamond-like carbon is deposited on the surface.

Examples of the method for stretching the film include a flat sequential biaxial stretching method, a flat simultaneous biaxial stretching method, and a tubular method. Among these, it is preferable to employ 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 stretching apparatus for employing the flat simultaneous biaxial stretching method include a screw type tenter, a pantograph type tenter, and a linear motor-driven clip type tenter.

Examples of the heat treatment method after stretching include known methods such as blowing hot air, infrared ray irradiation, and microwave irradiation. Among these, the method of blowing hot air is preferable because it allows uniform and accurate heating.

The polyamide film of the present invention has a thermal stability that increases thermal stability during film formation, prevents deterioration of film strength and elongation, and prevents film deterioration caused by oxidation and decomposition during use. It is preferable to include an agent. Examples of the heat stabilizer include hindered phenol heat stabilizers, hindered amine heat stabilizers, phosphorus heat stabilizers, sulfur heat stabilizers, and bifunctional heat stabilizers.

Examples of the hindered phenol heat stabilizer include Irganox1010 (registered trademark) (manufactured by BASF Japan, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), Irganox1076 (registered trademark) (manufactured by BASF Japan, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), Cyanox1790 (registered trademark) (manufactured by Solvay, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid), Irganox1098 (registered trademark) (manufactured by BASF Japan, N,N'-(hexane-1,6-diyl)bis[3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide]), SumilizerGA-80 (registered trademark) (manufactured by Sumitomo Chemical Co., Ltd., 3,9-bis[2-{3-(3-tert -butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane).

Examples of hindered amine heat stabilizers 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 the phosphorus-based heat stabilizer include Irgafos168 (registered trademark) (manufactured by BASF Japan, tris(2,4-di-tert-butylphenyl) phosphite), Irgafos12 (registered trademark) (manufactured by BASF Japan, tris(2,4-di-tert-butylphenyl) phosphite), (2-((2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy)ethyl)amine), 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-dinonylphenyl) phosphite) Fit), ADKSTAB PEP36 (registered trademark) (manufactured by ADEKA, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-di-phosphite), Hostanox P-EPQ (registered trademark) (Clariant) Tetrakis (2,4-di-tert-butylphenyl)-4,4'-biphenyldiphosphonite), GSY-P101 (registered trademark) (manufactured by Sakai Chemical Industry Co., Ltd., Tetrakis (2,4-di-tert-butylphenyl)-4,4'-biphenyldiphosphonite), tert-butyl-5-methylphenyl)-4,4'-biphenylene diphosphonite), Sumilizer GP (registered trademark) (manufactured by Sumitomo Chemical Co., Ltd., 6-[3-(3-tert-butyl-4-hydroxy-5) -methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]-dioxaphosphepine).

Examples of the sulfur-based heat stabilizer 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)).

Examples of the bifunctional heat stabilizer include Sumilizer GM (registered trademark), 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4 (manufactured by Sumitomo Chemical Co., Ltd.) -methylphenylacrylate), 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).

From the viewpoint of preventing deterioration of film strength, hindered phenol heat stabilizers are preferred. The thermal decomposition temperature of the hindered phenol thermal stabilizer is preferably 320°C or higher, more preferably 350°C or higher. Examples of the hindered phenol heat stabilizer having a thermal decomposition temperature of 320° C. or higher include Sumilizer GA-80. Furthermore, if the hindered phenol heat stabilizer has an amide bond, it can prevent deterioration of film strength. An example of the hindered phenol heat stabilizer having an amide bond is Irganox 1098. Further, by using a difunctional type heat stabilizer in combination with the hindered phenol type heat stabilizer, deterioration in film strength can be further reduced.

These heat stabilizers may be used alone or in combination of two or more. For example, if a hindered phenol-based heat stabilizer and a phosphorus-based heat stabilizer are used together, it is possible to prevent pressure increase in the raw material filtration filter during film formation, and also prevent deterioration of film strength. . In addition, by using a hindered phenol-based heat stabilizer, a phosphorus-based heat stabilizer, and a bifunctional heat stabilizer together, it is possible to prevent pressure increase in the raw material filtration filter during film formation, and to improve film strength. Deterioration can be further reduced.

As a combination of a hindered phenol heat stabilizer and a phosphorus heat stabilizer, a combination of Sumilizer GA-80 or Irganox 1098 and Hostanox P-EPQ or GSY-P101 is preferred. As a combination of a hindered phenol heat stabilizer, a phosphorus heat stabilizer, and a bifunctional heat stabilizer, a combination of Sumilizer GA-80 or Irganox 1098, Hostanox P-EPQ or GSY-P101, and Sumilizer GS is preferred. , Sumilizer GA-80, and combinations of GSY-P101 and Sumilizer GS are more preferred.

The content of the heat stabilizer in the polyamide film of the present invention is preferably 0.01 to 2 parts by mass, and preferably 0.04 to 1 part by mass, based on 100 parts by mass of polyamide (E). is more preferable. By setting the content of the heat stabilizer to 0.01 to 2 parts by mass, thermal decomposition can be suppressed more efficiently. In addition, when using two or more types of heat stabilizers in combination, it is preferable that both the individual content of each heat stabilizer and the total content of the heat stabilizers fall within the above range.

The polyamide film of the present invention may contain lubricant particles in order to improve slipperiness. Examples of 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. It will be done.

The polyamide film of the present invention may contain various additives as necessary, within a range that does not impair the effects of the present invention. Examples of additives include coloring agents such as pigments and dyes, coloring inhibitors, antioxidants different from the above heat stabilizers, weather resistance improvers, flame retardants, plasticizers, mold release agents, reinforcing agents, and modifiers. agents, antistatic agents, ultraviolet absorbers, antifogging agents, and various polymers. Examples of pigments include titanium oxide and the like. Examples of weather resistance improvers include benzotriazole compounds and the like. Examples of the flame retardant include brominated flame retardants and phosphorus flame retardants. Examples of the reinforcing agent include talc and the like. The various additives mentioned above may be added at any stage during film production.

When the polyamide film contains the other polymers and/or additives described above, the other polymers and additives may be individually kneaded with the polyamide (E) in advance, or when extruded into a sheet. may be added (or dry blended) immediately before melt mixing.

When the polyamide film used in the present invention contains a heat stabilizer, lubricant particles, and various additives, it is preferable to knead the polyamide (E) and the additives in advance. The kneader used for kneading is not particularly limited, and examples thereof include known melt-kneading machines 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 higher than the melting point of polyamide (E).

The polyamide film of the present invention can be subjected to a treatment to improve its surface adhesion, if necessary. Examples of 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 of the present invention in order to impart functions such as easy adhesion, antistatic properties, mold release properties, and gas barrier properties.

The thickness of the polyamide film of the present invention is usually 1 μm to 2 mm, preferably 10 μm to 1 mm, more preferably from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, restorability, and rubber elasticity. is 50 to 200 μm. When the polyamide film is stretched, the stretched polyamide film has the above thickness.

The polyamide film of 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 preferably 270°C or higher. is more preferable, and even more preferably 300°C or higher. If the melting point is too low, heat resistance will decrease.

The melting point of a polyamide film is determined by the molecular weight of polyamide (E), the content of a reaction product (hard segment polymer) consisting of aromatic dicarboxylic acid (C) and aliphatic diamine having 12 or less carbon atoms (D), (C)/ (D) It can be controlled by adjusting one or more factors selected from the content ratio. For example, increasing the molecular weight of polyamide (E) increases its melting point. For example, if the molecular weight of polyamide (E) is reduced, the melting point will be lowered.
Further, for example, when the content of the reaction product consisting of the aromatic dicarboxylic acid (C) and the aliphatic diamine having 12 or less carbon atoms (D) is increased, the melting point tends to increase.

In this specification, the melting point is the temperature based on the endothermic peak when the temperature is increased at a temperature increase rate of 20° C./min using a differential scanning calorimeter.

The polyamide film of the present invention has excellent flexibility, and the elongation recovery rate, which is an index of flexibility, is usually 30% or more, and has good heat resistance, flexibility, uniform extensibility, heat resistance uniformity, restorability, and From the viewpoint of further improving rubber elasticity, 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, flexibility will decrease. The elongation recovery rate is usually 100% or less (particularly 90% or less). In the present invention, since the polyamide (E) constituting the polyamide film has a block structure, an elongation recovery rate of 50% or more (particularly 55% or more) can be achieved.

The stretch recovery rate of the polyamide film is selected from the polymer structure of the polyamide (E), the stretching ratio, and 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. It can be controlled by adjusting one or more factors.
For example, when the polymer structure of polyamide (E) is adjusted from a random structure to a block structure, the elongation recovery rate tends to increase.
For example, when the stretching ratio is increased, the stretching recovery rate decreases. On the other hand, when the stretching ratio is reduced, the stretching recovery rate increases.
Further, for example, if 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 is increased, or if the content of (B) is increased, the elongation recovery can be improved. rates tend to increase.

In this specification, the elongation recovery rate is the value obtained when a tensile test was performed under the conditions of a 23° C. environment, a distance between chucks of 70 mm, and a tensile test speed of 5 mm/min.

The polyamide film of the present invention usually has a tensile modulus (MD), which is one index of flexibility, of 1500 MPa or less, and has excellent heat resistance, flexibility, uniform extensibility, heat resistance uniformity, resilience, and rubber elasticity. From the viewpoint of improvement, it is preferably 1300 MPa or less, more preferably 1000 MPa or less, even more preferably 600 MPa or less, and particularly preferably 500 MPa or less. If the tensile modulus is too high, flexibility will decrease. The tensile modulus is usually 10 MPa or more.

The tensile modulus of the polyamide film is selected from the polymer structure of the polyamide (E), the stretching ratio, and 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. It can be controlled by adjusting one or more factors.
For example, when the polymer structure of polyamide (E) is adjusted from a random structure to a block structure, the tensile modulus tends to decrease.
For example, when the stretching ratio is increased, the tensile modulus is increased. On the other hand, when the stretching ratio is reduced, the tensile modulus is reduced.
Furthermore, for example, when the content of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and the aliphatic diamine having 18 or more carbon atoms (B) is increased, the elastic modulus tends to decrease; As the modulus of elasticity decreases, the modulus of elasticity tends to increase.

In this specification, the tensile modulus uses a value measured in an environment of a temperature of 20° C. and a humidity of 65% according to JIS K 7127.

The polyamide film of the present invention usually has a 10% elongation strength (MD), which is an index of flexibility and uniform extensibility, of 70 MPa or less, and has excellent heat resistance, flexibility, uniform expansibility, heat resistance uniformity, restorability, and rubber. From the viewpoint of further improving elasticity, it is preferably 50 MPa or less, more preferably 35 MPa or less, and even more preferably 25 MPa or less. If the 10% elongation strength is too high, flexibility and uniform extensibility will decrease. The 10% elongation strength is usually 1 MPa or more.

The 10% elongation strength of the polyamide film is selected from the polymer structure of the polyamide (E), the stretching ratio, and 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.
For example, when the polymer structure of polyamide (E) is adjusted from a random structure to a block structure, the 10% elongation strength tends to decrease.
For example, when the stretching ratio is increased, the tensile modulus is increased. On the other hand, when the stretching ratio is reduced, the tensile modulus is reduced.
Furthermore, for example, when the content of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and the aliphatic diamine having 18 or more carbon atoms (B) is increased, the 10% elongation strength tends to decrease; When the content is increased, the 10% elongation strength tends to increase.

In this specification, the 10% elongation strength uses a value measured in an environment of a temperature of 20° C. and a humidity of 65% according to JIS K 7127.

In the polyamide film of the present invention, the smaller the hysteresis loss rate, the higher the rubber elasticity. In the polyamide film, the hysteresis loss rate is preferably 90% or less, and preferably 85% or less, from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, restorability, and rubber elasticity. is more preferable, and even more preferably 80% or less. The hysteresis loss rate is usually 10% or more (particularly 30% or more).

The hysteresis loss rate of the polyamide film is selected from the polymer structure of the polyamide (E), the stretching ratio, and 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. It can be controlled by adjusting one or more factors.
For example, when the polymer structure of polyamide (E) is adjusted from a random structure to a block structure, the hysteresis loss rate tends to decrease.
For example, when the stretching ratio is increased, the hysteresis loss rate increases. On the other hand, when the stretching ratio is reduced, the hysteresis loss rate is reduced.
Furthermore, for example, if 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 is increased, or if the content of (B) is increased, the hysteresis loss rates tend to decrease.

In this specification, the hysteresis loss rate uses a value obtained when a tensile test is performed in the same manner as the elongation recovery rate.

The polyamide film of the present invention preferably has a crystal melting enthalpy of 15 J/g or more, preferably 18 J/g, from the viewpoint of further improving heat resistance, flexibility, uniform expandability, heat resistance uniformity, restorability, and rubber elasticity. It is more preferably at least 20 J/g, even more preferably at least 23 J/g, sufficiently preferably at least 25 J/g, and preferably at least 40 J/g. Much more preferred. The higher the crystallinity of the hard segment, the more the formation of a phase-separated structure between the hard segment and the soft segment is promoted, and the flexibility and rubber elasticity are improved. If the crystal melting enthalpy is too low, flexibility and/or rubber elasticity will decrease. The crystal melting enthalpy is usually 120 J/g or less (particularly 90 J/g or less). In the present invention, since the polyamide (E) constituting the polyamide film has a block structure, a crystal melting enthalpy of 25 J/g or more can be achieved.

The crystal melting enthalpy of a polyamide film is determined from the polymer structure of polyamide (E) and the content of a reaction product (hard segment polymer) consisting of an aromatic dicarboxylic acid (C) and an aliphatic diamine having 12 or less carbon atoms (D). It can be controlled by adjusting one or more selected factors.
For example, when the polymer structure of polyamide (E) is adjusted from a random structure to a block structure, the enthalpy of crystal fusion tends to increase.
For example, when the content of the reaction product consisting of the aromatic dicarboxylic acid (C) and the aliphatic diamine having 12 or less carbon atoms (D) is increased, the enthalpy of crystal fusion increases.

In this specification, the enthalpy of crystal fusion uses the value of the amount of heat of an endothermic peak measured in the same manner as the melting point.

The polyamide film of the present invention has sufficiently low dielectric loss tangent and dielectric constant, and has excellent dielectric properties, and also has excellent insulation properties.

The polyamide film of the present invention may be in the form of a single sheet, or may be wound into a film roll by being wound around a take-up roll. From the viewpoint of productivity when used for various purposes, it is preferable to take the form of a film roll. When made into a film roll, it may be slit to a desired width.

The polyamide film of the present invention may be used as it is or in the form of a laminate.

When the polyamide film of the present invention is used in the form of a laminate, the polyamide film laminate is composed of the polyamide film of the present invention described above and a resin layer, a metal layer, and an inorganic material layer provided on the polyamide film. at least one layer selected from the group consisting of:

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/α-olefin copolymers, ethylene/acrylic acid ester copolymers, maleic anhydride-modified polyolefins, and ionomers. When the resin constituting the resin layer is polyamide, the polyamide may be polyamide (E) or another polyamide.
Examples of the metal constituting the metal layer include copper, aluminum, iron, nickel, tin, gold, silver, alloy steel (for example, stainless steel), and alloy plating.
Examples of inorganic materials constituting the inorganic material layer include nonmetals such as diamond and silicon, inorganic compounds (oxides) such as silicon dioxide, alumina, zirconia, titanium oxide, barium titanate, silicon carbide, aluminum nitride, and gallium nitride. , carbide, nitride), sapphire glass, and silicate glass.

The polyamide film and polyamide film laminate of the present invention are sufficiently superior in heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability, so at least one of these properties is required. (preferably applications requiring all of these properties). For example, the polyamide film and polyamide film laminate of the present invention can be used as decorative molding materials (particularly decorative molding films) such as in-mold molding, film insert molding, vacuum molding, pressure molding, and press molding; curved circuit boards; Films for substrates such as flexible printed circuit boards, curved antenna boards, and flexible antenna boards; dicing tape, die attach film integrated with dicing tape (i.e., dicing/die attach film), die bonding film integrated with dicing tape (i.e., dicing/die bonding) Semiconductor process films (especially dicing films) such as dicing tape-integrated wafer back protection film, back gliding film; Shock absorbing materials such as tube covering films, wire covering films, shock absorbing films, and sealing films. It can be suitably used for.

When the polyamide film of the present invention is used as a decorative molding film, the polyamide film of the present invention is used alone or in the form of a laminate.
A polyamide film used as a decorative molding film can protect or seal the surface of an object by, for example, cold molding or hot molding.
A polyamide film laminate used as a decorative molding film is made by forming a resin layer or a metal layer on the above-mentioned polyamide film, and can be used to impart designs or functionality to the surface of a molded product, for example, by in-mold molding or film insert molding. It is now possible to do so.
When forming a metal layer on the polyamide film laminate, there are, for example, a method of forming a conductive circuit on the surface of the polyamide film, or a method of etching the metal layer of the polyamide film laminate to form metal wiring.

When the polyamide film of the present invention is used as a dicing film, the polyamide film of the present invention is used in the form of a polyamide film laminate.
A polyamide film laminate used as a dicing film has a resin layer (particularly an adhesive layer) formed on the polyamide film described above, and is capable of holding, for example, a semiconductor wafer.
A dicing film is a film that collectively holds a plurality of divided semiconductor wafers in a semiconductor manufacturing process (particularly a dicing process). In the expansion process, the dicing film is radially stretched (expansion process) and heat-treated to remove slack. After the expanding process, the dicing film is given tension by being pushed up with a needle or the like in the process of picking up each divided chip.

When manufacturing a semiconductor using the polyamide film of the present invention as a dicing film, heat treatment (for example, a sealing process or a reflow process) may be performed before and/or after the dicing process. This is because the polyamide film of the present invention is excellent in heat resistance, flexibility, uniform expandability, heat resistance uniformity, and restorability, and can exhibit these excellent properties even after such heat treatment. The heat treatment in the sealing step may involve heating at 150° C. or higher, for example. The heat treatment in the reflow process may involve heating at 200° C. or higher, for example.

When the polyamide film and polyamide film laminate of the present invention are used for a flat or curved printed circuit board, the polyamide film and polyamide film laminate of the present invention may be used to form a conductive circuit on the surface of the polyamide film, or to form a polyamide film laminate on the surface of the polyamide film. It can be used by etching the metal layer of the body and forming metal wiring.
A flat or curved printed circuit board is a printed circuit board that may have a planar shape or a curved shape.

When the polyamide film and polyamide film laminate of the present invention are used for a flat or curved antenna substrate, the polyamide film and polyamide film laminate of the present invention may be used to form a conductive circuit on the surface of the polyamide film, or to form a polyamide film laminate on the surface of the polyamide film. It can be used by etching a metal layer and forming a metal wiring.
A planar or curved antenna substrate is an antenna substrate that may have a planar shape or a curved shape.

Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

A. Evaluation method The polyamide film was evaluated by the following method.

(1) Resin composition of the film A few mg of the obtained film was taken and analyzed by ¹ H-NMR using a high-resolution nuclear magnetic resonance apparatus (ECA-500NMR manufactured by JEOL Ltd.) to determine the respective copolymer components. It was determined from the peak intensity (resolution: 500 MHz, solvent: mixed solvent of deuterated trifluoroacetic acid and deuterated chloroform in a volume ratio of 4/5, temperature: 23° C.). In Table 1, the resin composition is shown as the final composition in terms of mass ratio.

(2) Melting point and enthalpy of crystal fusion of the film Several mg of the obtained film was taken and heated to 350°C at a heating rate of 20°C/min using a differential scanning calorimeter DSC-7 model (manufactured by PerkinElmer). Thereafter, the temperature was held at 350°C for 5 minutes, the temperature was lowered to 25°C at a temperature decreasing rate of 20°C/min, and after further holding at 25°C for 5 minutes, the temperature was raised again at a temperature increasing rate of 20°C/min.
The top of the endothermic peak during re-heating was taken as the melting point, and the amount of heat at the endothermic peak was taken as the enthalpy of crystal fusion. Crystal melting enthalpy is determined from the peak area in the temperature range from the start to the end of melting. For the enthalpy of crystal fusion, the average value of the values obtained by measurements performed at ten arbitrary locations was used.

Melting point was evaluated according to the following criteria.
◎: 300℃ or higher (excellent);
○: 270°C or more and less than 300°C (good);
△: 240°C or more and less than 270°C (no practical problem);
×: Less than 240°C (practical problem).

Crystal fusion enthalpy was evaluated according to the following criteria.
◎: 25 J/g or more (excellent);
△: 15 J/g or more and less than 25 J/g (no practical problem);
×: Less than 15 J/g (practical problem).

(3) Film elongation recovery rate (flexibility), hysteresis loss rate (rubber elastic modulus)
A test piece having the shape of JIS K6251 No. 3 was prepared from the obtained film, and the elongation recovery rate and hysteresis loss rate were measured using a 2020 type testing machine manufactured by INTESCO. In a 23°C environment, under conditions of a chuck distance of 70 mm and a tensile test speed of 5 mm/min, it was pulled 14 mm and immediately returned to its original state at the same speed, and the residual strain A (mm) when the stress became zero was determined. For the elongation recovery rate and hysteresis loss rate, the average value of the values measured using 10 test pieces obtained at 10 arbitrary locations on the film was used.
The elongation recovery rate was calculated using the residual strain A using the following formula.
Elongation recovery rate (%) = (14-A)/14×100

Furthermore, it was calculated using the following formula from the obtained hysteresis curve.
Hysteresis loss rate (%) = Area (Oabcd) / Area (OabeO) x 100
For example, in FIG. 1, the area (Oabcd) is the area of the region indicated by the broken line (vertical broken line), and 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.

(4) Tensile strength at break, tensile elongation at break, tensile modulus (flexibility), and 10% elongation strength of film Measured in accordance with JIS K 7127 at a temperature of 20° C. and a humidity of 65%. The size of the sample was 10 mm x 150 mm, the initial distance between the chucks was 100 mm, and the pulling speed was 500 mm/min.
The tensile strength at break, tensile elongation at break, tensile modulus, and 10% elongation strength of the film were determined by measuring physical properties at least in the MD direction.
Note that the tensile strength at break, tensile elongation at break, tensile modulus, and 10% elongation strength of the film were the average values of the values measured using 10 samples obtained at 10 arbitrary locations on the film. .
10% elongation strength (MD) was evaluated according to the following criteria.
◎◎: 25 MPa or less (best);
◎: More than 25 MPa and less than 35 MPa (excellent);
○: More than 35 MPa and less than 50 MPa (good);
△: More than 50 MPa and less than 70 MPa (no practical problem);
×: Over 70 MPa (practical problem).

(5) Heat shrinkage rate of film According to JIS K 7133, the shrinkage rate of the film was measured when heat treated at 200°C for 15 minutes.

(6) Uniform expandability of film 1
A 10×10 grid with a spacing of 10 mm was stamped on the film before expansion, and the grid spacing after the film was expanded was measured. ◎◎ if the magnification difference between the center and edge is less than 2.5%, ◎ if it is 2.5% or more and less than 5%, ○ if it is 5% or more and less than 7.5% % or more and less than 10% was judged as Δ, and when it was 10% or more, it was judged as ×.

(7) Uniform expandability of film 2
From the single-sided laminate of the polyamide film obtained in Examples and Comparative Examples, 5 x 5 squares of 10 mm x 10 mm were prepared at 0.5 mm intervals by etching, and the spacing between the squares was measured after the film was expanded by pushing up the cylinder. . If there is no distortion in the squares and the difference between the square spacing in the center and the square spacing at the edges is less than 25%, ◎◎, if it is 25% or more and less than 50%, ◎, and if it is 50% or more, ○. I judged it. On the other hand, a case where distortion occurred in the orientation or shape of the square was judged as △, and a case where a crack occurred in the square was judged as ×.

(8) Uniform expandability of film 3
Concentric circles with radii of 10 mm, 20 mm, 30 mm, 40 mm, and 50 mm with a line width of 0.5 mm were produced by etching from the single-sided polyamide film laminates obtained in Examples and Comparative Examples, and the concentric circles after thermal deformation into spherical shapes were The diameter was measured. If the diameter difference between the MD direction and the TD direction is less than 2%, ◎◎, if it is 2% or more and less than 4%, ◎, if it is 4% or more and less than 6%, ○, if it is 6% or more (concentric circle cutting) (No) was judged as △, and when the concentric circles were cut, it was judged as ×. The cutting of concentric circles means that the concentric circles created by etching are disconnected.

(9) Uniformity after heat treatment 1
The film, which was stamped with 10×10 grids with 10 mm spacing and expanded evenly, was heat-treated and conditioned at 23° C. and 50% relative humidity for 24 hours, and then the grid spacing was measured again. ◎◎ if the magnification difference between the center and edge is less than 2.5%, ◎ if it is 2.5% or more and less than 5%, ○ if it is 5% or more and less than 7.5% % or more and less than 10% was judged as Δ, and when it was 10% or more, it was judged as ×.

(10) Uniformity after heat treatment 2
5 x 5 squares of 10 mm x 10 mm were prepared at 0.5 mm intervals from a single-sided copper foil laminate by etching, the uniformly expanded film was heat treated, and the square spacing was measured again. If there is no distortion in the squares and the difference between the square spacing in the center and the square spacing at the edges is less than 25%, ◎◎, if it is 25% or more and less than 50%, ◎, and if it is 50% or more, ○. did. On the other hand, a case where distortion occurred in the orientation or shape of the square was judged as △, and a case where a crack occurred in the square was judged as ×.

(11) Uniformity after heat treatment 3 (molding)
Concentric circles were created by etching from a single-sided copper foil laminate, and the film expanded into a spherical shape and the melted film were laminated and molded, and then the diameter of the concentric circles was measured again. ◎◎ when the diameter difference between MD direction and TD direction is less than 2%, ◎ when it is 2% or more and less than 4%, ○ when it is 4% or more and less than 6%, ○ when it is 7.5% or more and less than 10%. The case (no cutting of concentric circles) was judged as Δ, and the case of cutting of concentric circles was judged as ×.

(12) Restorability after re-deformation 1
The evenly expanded and heat-treated film was expanded again by stamping a 10×10 grid with 1 cm spacing and held for 60 seconds. The grid size (total length) was measured 60 seconds after the tension was released. The restoration rate was calculated using the following formula from the dimensions and deformation before and after re-expansion. ◎◎ if the recovery rate is 60% or more, ◎ if it is 50% or more and less than 60%, ○ if it is 40% or more and less than 50%, △ if it is 30% or more and 40% or more. was judged as ×.
Restoration rate = (dimension before re-expansion + amount of deformation - dimension after re-expansion) / amount of deformation x 100

(13) Restorability after re-deformation 2
5 x 5 10 mm x 10 mm squares were etched at 0.5 mm intervals from a single-sided copper foil laminate, uniformly expanded and heat treated, and the square portion of the film was pushed up with a rod and held in that state for 60 seconds. 60 seconds after the rod was released, the depth and height of the deformation mark were measured. ◎◎ if the height of the deformation mark is less than 0.5 mm, ◎ if the height is 0.5 mm or more and less than 1 mm, ○ if the height is 1 mm or more and less than 2 mm, △ if the height is 2 mm or more and less than 4 mm, and △ if the height is 4 mm or more. It was set as ×.

(14) Restorability after re-deformation 3
Concentric circles were created by etching from a single-sided copper foil laminate, and a cylinder was pressed against the molded product of the spherically expanded film and the molten film to deform it, and this state was held for 60 seconds. Sixty seconds after the cylinder was released, the depth of the deformation mark was measured. ◎◎ if the deformation mark depth is less than 0.5mm, ◎ if it is 0.5mm or more and less than 1mm, ○ if it is 1mm or more and less than 2mm, △ if it is 2mm or more and less than 4mm, and △ if it is 4mm or more. It was set as ×.

(15) Heat resistance The evaluation results of the melting point of the film in "(2) Melting point of the film, enthalpy of crystal fusion" above were used as the evaluation results of the heat resistance.

(16) Flexibility of film The elongation recovery rate and tensile modulus of the film described above were evaluated according to the following criteria. Among these evaluation results, the lower evaluation result was used as the evaluation result of flexibility.

・Elongation recovery rate ◎: 50% or more (excellent);
○: 40% or more and less than 50% (good);
△: 30% or more and less than 40% (no practical problem);
×: Less than 30% (practical problem).

・Tensile modulus (MD)
◎: 600MPa or less (excellent)
○: More than 600 MPa and less than 1300 MPa (good);
△: More than 1300 MPa and less than 1500 MPa (no practical problem);
×: Over 1500 MPa (no practical problem).

(17) Comprehensive evaluation In Tables 2 and 4, the evaluation results of the above-mentioned items (6), (9), (12), (15) and (16) were comprehensively evaluated. Specifically, among these evaluation results, the lowest evaluation result was used as the result of the comprehensive evaluation.
In Table 5, the evaluation results of the above-mentioned items (7), (10), (13), (15), and (16) were comprehensively evaluated. Specifically, among these evaluation results, the lowest evaluation result was used as the result of the comprehensive evaluation.
In Table 6, the evaluation results of the above-mentioned items (8), (11), (14), (15), and (16) were comprehensively evaluated. Specifically, among these evaluation results, the lowest evaluation result was used as the result of the comprehensive evaluation.

B. Raw materials The following raw materials were used.
・Dimer acid: Pripol 1009 manufactured by Croda
·Terephthalic acid:
・Dimer diamine: Priamine 1075 manufactured by Croda
・Decanediamine:
・Sodium hypophosphite:
・Heat stabilizer: Sumilizer GA-80 manufactured by Sumitomo Chemical Co., Ltd.

Example 1
・Polyamide P1
23.5 parts by mass of terephthalic acid and 0.1 parts by mass of sodium hypophosphite monohydrate were charged into a ribbon blender type reactor, and the mixture was heated to 170° C. with stirring at a rotational speed of 30 rpm under nitrogen sealing. Then, while maintaining the temperature at 170°C and the rotation speed at 30 rpm, 24.4 parts by mass of 1,10-decanediamine heated to 100°C was added over 2.5 hours using a liquid injection device. was added continuously (continuous injection method) to obtain a reaction product. The molar ratio of the raw material monomers was terephthalic acid:1,10-decanediamine=50.0:50.0.
26.7 parts by mass of dimer acid and 25.3 parts by mass of dimer diamine were charged into a reaction vessel equipped with a heating mechanism and a stirring mechanism. After stirring at 100° C. for 1 hour, 47.9 parts by mass of the above reaction product was added while stirring.
Thereafter, the mixture was heated to 260° C. with stirring, and polymerization was carried out at 260° C. under a nitrogen stream at normal pressure for 5 hours while removing condensed water from the system. During the polymerization, the system was in a suspended solution state.
After the polymerization was completed, it was discharged, cut, and dried to obtain polyamide P1 in the form of pellets.

・Production of polyamide film 100 parts by mass of the obtained pellets and 0.4 parts by mass of Sumilizer GA-80 were dry-blended and put into a twin-screw extruder with a screw diameter of 26 mm heated to a cylinder temperature of 330°C. The mixture was melt-kneaded and extruded into a strand. Thereafter, it was cooled and cut to obtain pellets.
The obtained pellets were put into a single screw extruder (screw diameter 50 mm) heated to a cylinder temperature of 330° C. and melted to obtain a molten polymer. The molten polymer was filtered using a metal fiber sintered filter (manufactured by Nippon Seisen Co., Ltd., "NF-13", nominal filtration diameter: 60 μm). Thereafter, the molten polymer was extruded into a film through a T-die heated to 330°C to obtain a film-like melt Y1. 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 found to be the same as the resin composition of the polyamide used.
The obtained substantially non-oriented unstretched polyamide film M1 was heat-treated at 250° C. to obtain a crystallized unstretched polyamide film AM1.

- Uniform expansion of polyamide film The obtained crystallized unstretched film AM1 was cut out to 150 mm x 150 mm, and after stamping a 10 x 10 grid with 1 cm intervals, simultaneous biaxial stretching was carried out in a batch type while holding the four sides with clips. Biaxial stretching was performed using a machine. The expansion conditions were 23°C, MD expansion strain rate of 40%/sec, TD expansion strain rate of 40%/sec, MD expansion rate of 1.5 times, and TD expansion rate of 1.5 times. .

- Heat treatment of polyamide film The film after uniform expansion was heat-set at 250° C. while holding the clip.

- Re-expansion of polyamide film The four sides of the film after the above heat treatment were again expanded using a batch-type simultaneous biaxial stretching machine while holding the film again with clips. Expansion conditions were 23°C, MD expansion rate 1 mm/sec, and TD expansion rate 1 mm/sec.

Examples 2 to 9
Polyamides P2 to P9 were obtained by carrying out the same operation as in Example 1, except that the amount of monomer charged into the reaction vessel was 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 heat treatment to obtain crystallized unstretched polyamide films AM2 to AM9. .
When the resin composition of the polyamide component of the obtained crystallized unstretched polyamide film was determined, it was found to be the same as the resin composition of the polyamide used.
Using the obtained crystallized unstretched films AM2 to AM9, uniform expansion, heat treatment, and re-expansion were performed in the same manner as in Example 1.

Example 10
In a reaction vessel equipped with a heating mechanism and a stirring mechanism, 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 hypochlorite were added. 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 a nitrogen stream at normal pressure for 5 hours while removing condensed water from the system. During the polymerization, the system was in suspension.
After the polymerization was completed, it was discharged, cut, and dried to obtain polyamide P10 in the form of pellets.
Further, using the obtained pellets, the same operations as in Example 1 were performed to perform melt-kneading, preparation of an unstretched film M10, and heat treatment to obtain a crystallized unstretched polyamide film AM10.
When the resin composition of the polyamide component of the obtained unstretched film was determined, it was found to be the same as the resin composition of the polyamide used.
Using the obtained crystallized unstretched film AM10, uniform expansion, heat treatment, and re-expansion were performed in the same manner as in Example 1.

Examples 11 and 12
Polyamides P11 and 12 were obtained by carrying out the same operation as in Example 10, except that the amounts of dimer acid, dimer diamine, terephthalic acid, and 1,10-decanediamine 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 heat treatment to obtain crystallized unstretched polyamide films AM11 and 12. .
When the resin composition of the polyamide component of the obtained unstretched film was determined, it was found to be the same as the resin composition of the polyamide used.
Using the obtained crystallized unstretched films AM11 and AM12, uniform expansion, heat treatment, and re-expansion were performed in the same manner as in Example 1.

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, and hypochlorite were added. 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 a nitrogen stream at normal pressure for 5 hours while removing condensed water from the system. During the polymerization, the system was in suspension.
After the polymerization was completed, it was discharged, cut, and dried to obtain polyamide P13 in the form of pellets.
Further, using the obtained pellets, the same operations as in Example 1 were performed to perform melt-kneading, preparation of an unstretched film M13, and heat treatment to obtain a crystallized unstretched polyamide film AM13.
When the resin composition of the polyamide component of the obtained unstretched film was determined, it was found to be the same as the resin composition of the polyamide used.
Using the obtained crystallized unstretched film AM13, uniform expansion, heat treatment, and re-expansion were performed in the same manner as in Example 1.

Comparative example 2
Polyamide P14 was obtained by carrying out the same operation as in Example 10, except that the amounts of dimer acid, dimer diamine, terephthalic acid, and 1,10-decanediamine 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 an unstretched film M14, and heat treatment to obtain a crystallized unstretched polyamide film AM14.
When the resin composition of the polyamide component of the obtained unstretched film was determined, it was found to be the same as the resin composition of the polyamide used.
Using the obtained crystallized unstretched film AM14, uniform expansion, heat treatment, and re-expansion were performed in the same manner as in Example 1.

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. Thereafter, the reaction product was heated to 250° C. with stirring, and polymerization was carried out at 250° C. under a nitrogen stream at normal pressure for 7 hours while removing condensed water from the system. During the polymerization, the system was in a powder state.
After the polymerization was completed, it was discharged to obtain polyamide P15 in powder form. Further, using the obtained powder, the same operations as in Example 1 were carried out to perform melt kneading, production of an unstretched film M15 from the film-like melt Y15, heat treatment, and crystallization of an unstretched polyamide film AM15. I got it.
Using the obtained crystallized unstretched film AM15, uniform expansion, heat treatment, and re-expansion were performed in the same manner as in Example 1.

Comparative example 4
A reaction vessel 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 a nitrogen stream at normal pressure for 5 hours while removing condensed water from the system. During the polymerization, the system was in a homogeneous molten state.
After the polymerization was completed, it was discharged, cut, and dried to obtain polyamide P16 in the form of pellets.
In addition, using the obtained pellets, the same operations as in Example 1 were performed to melt-knead, produce an unstretched film M16 from the film-like melt Y16, and heat treat it, but the pellets could not withstand the heat treatment and crystallized. It was not possible to obtain an unstretched film that was oriented.

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 an amino group in place of the hydroxyl group at both ends, 28.3 parts by mass of terephthalic acid, 20.6 parts by mass of 1,10-decanediamine and 0.1 parts 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 a nitrogen stream at normal pressure for 5 hours while removing condensed water from the system. During the polymerization, the system was in a suspended solution state.
After the polymerization was completed, it was discharged, cut, and dried to obtain polyamide P17 in the form of pellets, but it was brittle and unsuitable for practical use.

Example 13
・Polyamide P18
55 parts by mass of polyamide P8 pellets obtained in Example 8, 45 parts by mass of polyamide P9 pellets obtained in Example 9, and 0.4 parts by mass of Sumilizer GA-80 were dry blended, and the cylinder temperature was set at 330°C. The mixture was put into a twin-screw extruder with a screw diameter of 26 mm and heated to 26 mm, melt-kneaded, and extruded into a strand. Thereafter, it was cooled and cut to obtain polyamide P18 in the form of pellets.

・Production of polyamide film 100 parts by mass of the obtained pellets and 0.4 parts by mass of Sumilizer GA-80 were dry-blended and put into a twin-screw extruder with a screw diameter of 26 mm heated to a cylinder temperature of 330°C. The mixture was melt-kneaded and extruded into a strand. Thereafter, it was cooled and cut to obtain pellets.
The obtained pellets were put into a single screw extruder (screw diameter 50 mm) heated to a cylinder temperature of 330° C. and melted to obtain a molten polymer. The molten polymer was filtered using a metal fiber sintered filter (manufactured by Nippon Seisen Co., Ltd., "NF-13", nominal filtration diameter: 60 μm). Thereafter, the molten polymer was extruded into a film from a T-die heated to 330°C to obtain a film-like melt Y18. 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 M18.
When the resin composition of the polyamide component of the obtained unstretched polyamide film M18 was determined, it was found to be the same as the resin composition of the polyamide used.
The obtained substantially non-oriented unstretched polyamide film M18 was heat-treated at 250°C to obtain a crystallized unstretched polyamide film AM18.

- Uniform expansion of polyamide film The obtained crystallized unstretched film AM18 was cut out to 150 mm x 150 mm, and after stamping a 10 x 10 grid with 1 cm spacing, batch-type simultaneous biaxial stretching was carried out while holding the four sides with clips. Biaxial stretching was performed using a machine. The expansion conditions were 23°C, MD expansion strain rate of 40%/sec, TD expansion strain rate of 40%/sec, MD expansion rate of 1.5 times, and TD expansion rate of 1.5 times. .

- Re-expansion of polyamide film The four sides of the film after the above heat treatment were again expanded using a batch-type simultaneous biaxial stretching machine while holding the film again with clips. The expansion conditions were 23° C., the MD expansion rate was 1 mm/sec, and the TD expansion rate was 1 mm/sec.

Examples 14-22
Polyamides P19 to P27 were obtained by carrying out the same operation as in Example 13, except that the type of polyamide used and the amount of dry blending were changed as shown in Table 3. Further, using the obtained pellets, the same operations as in Example 13 were performed to perform melt-kneading, production of unstretched films M19 to M27, and heat treatment to obtain crystallized unstretched polyamide films AM19 to AM27. .
When the resin composition of the polyamide component of the obtained crystallized unstretched polyamide film was determined, it was found to be the same as the resin composition of the polyamide used.
Using the obtained crystallized unstretched films AM19 to AM27, uniform expansion, heat treatment, and re-expansion were performed in the same manner as in Example 13.

Example 23
・Production of simultaneous biaxially stretched polyamide film While gripping both ends of the substantially non-oriented unstretched polyamide film M1 obtained in Example 1 with clips, biaxially stretching was carried out using a flat type simultaneous biaxially stretching machine. was carried out. The stretching conditions are: the temperature of the preheating section is 80°C, the temperature of the stretching section is 80°C, the MD stretching strain rate is 2400%/min, the TD stretching strain rate is 2400%/min, and the MD stretching ratio is 1.5. The TD stretching ratio was 1.5 times. After stretching, the film was continuously heat-set at 270° C. in the same tenter of a biaxial stretching machine, and the film was subjected to a 6% relaxation treatment in the width direction to obtain a simultaneously biaxially stretched polyamide film.

・Preparation of polyamide film laminate Both sides of the obtained simultaneously biaxially stretched polyamide film were stacked so that they were in contact with 18 μm thick electrolytic copper foil (surface roughness Rz = 1.2 μm), and set in a vacuum press machine. Then, heat and pressure treatment was performed at 230° C. and 1 MPa for 5 minutes to obtain a polyamide film laminate having copper foil layers on both sides.
A piece of 200 mm x 200 mm was cut out from the obtained polyamide film laminate, a protective layer was provided on one side, etching treatment was performed, and the metal layer on the side on which no protective layer was provided was removed, resulting in a single-sided polyamide film having a metal layer on only one side. A laminate was obtained.

- Uniform expansion of polyamide film laminate From the obtained stretched polyamide film single-sided laminate, a total of 25 squares of 10 mm x 10 mm were made at 0.5 mm intervals, 5 rows in the MD direction and 5 rows in the TD direction, with a diameter of 150 mm. The film was sandwiched between two metal disks with a hole in it, and the film was fixed so that the center of the square was in the center of the hole. A cylinder with an inner diameter of 140 mm and an outer diameter of 145 mm was pushed up from below the film. The deformation temperature was 23°C, the deformation speed was 10 mm/sec, and the deformation amount was 10 mm.

- Heat treatment of polyamide film laminate Hot air at 250° C. was applied to an area of 10 mm from the outer periphery toward the center of the uniformly expanded film to remove slack in the film.

・Deformation of polyamide film laminate With the film after the above heat treatment fixed on a metal disk, a square rod with an area of 10 mm x 10 mm is pushed up 10 mm from the bottom of the square at a speed of 1 mm/sec. It was held for 60 seconds.

Examples 24, 26-33
A stretched polyamide film was obtained by carrying out the same operation as in Example 23, except that the unstretched polyamide film and the stretching conditions were changed as shown in Table 5.
Using the obtained stretched polyamide film, a single-sided laminate was prepared, uniformly expanded, heat treated, and deformed in the same manner as in Example 23.

Example 25
- Production of sequentially biaxially stretched polyamide film The substantially non-oriented unstretched polyamide film M1 obtained in Example 1 was biaxially stretched using a flat type sequentially oriented stretching machine. First, an unstretched polyamide film M3 was heated to 80° C. by roll heating, infrared heating, etc., and stretched 3.0 times in the MD at a stretching strain rate of 2400%/min to obtain a longitudinally stretched film. Subsequently, both ends of the film in the width direction were gripped by clips of a transverse stretching machine, and transverse stretching was performed continuously. The temperature of the preheating part for TD stretching was 85°C, the temperature of the stretching part was 85°C, the stretching strain rate was 2400%/min, and the TD stretching ratio was 3.0 times. Then, heat setting was performed at 270° C. in the same tenter of a transverse stretching machine, and a 6% relaxation treatment was performed in the width direction of the film to obtain a sequentially biaxially stretched polyamide film.
Using the obtained polyamide film, a single-sided laminate was prepared, uniformly expanded, heat treated, and deformed in the same manner as in Example 23.

Comparative example 6
A stretched polyamide film was obtained by carrying out the same operation as in Example 23, except that the unstretched polyamide film and the stretching conditions were changed as shown in Table 5.
Using the obtained stretched polyamide film, a single-sided laminate was prepared, uniformly expanded, heat treated, and deformed in the same manner as in Example 23.

Example 34
・Production of simultaneous biaxially stretched polyamide film While gripping both ends of the substantially non-oriented unstretched polyamide film M1 obtained in Example 1 with clips, biaxially stretching was carried out using a flat type simultaneous biaxially stretching machine. was carried out. The stretching conditions are: the temperature of the preheating part is 80°C, the temperature of the stretching part is 80°C, the MD stretching strain rate is 2400%/min, the TD stretching strain rate is 2400%/min, and the MD stretching ratio is 2.3. The TD stretching ratio was 2.3 times. After stretching, the film was continuously heat-set at 270° C. in the same tenter of a biaxial stretching machine, and the film was subjected to a 6% relaxation treatment in the width direction to obtain a simultaneously biaxially stretched polyamide film.

- Production of polyamide film laminate A polyamide film laminate was produced in the same manner as in Example 23 using the above stretched polyamide film to obtain a single-sided polyamide film laminate.

・Equal expansion of polyamide film From the obtained stretched polyamide film single-sided laminate, concentric circles with a radius of 10 mm to 50 mm with a line width of 0.5 mm were created at 10 mm intervals, and placed in a mold having a spherical surface with a diameter of 150 mm and a depth of 5 mm. The film was fixed with the surface on which the concentric circles were made facing up so that the center of the concentric circles was located at the center of the spherical part, and the temperature of the mold was set at 50°C. A mold having a spherical surface with a diameter of 150 mm and a height of 5 mm, set at 50° C., was pressed from the opposite side at a speed of 10 mm/sec.

- Molding with molten sheet Only the uniformly expanded portion was cut out from the obtained uniformly expanded film, and set along the above mold heated to 50°C with the concentric circle production side facing up. The obtained film-like melt Y1 was sandwiched between the other mold heated to 50° C. to obtain a spherical molded product.

- Re-deformation of polyamide film A cylinder with a diameter of 2.5 mm was pressed 5 mm into the spherical molded article at a speed of 1 mm/sec, and this state was held for 60 seconds.

Examples 35-43
The same operations as in Example 34 were performed except that the type of unstretched film, the depth of the mold, the temperature of the mold, and the material to be laminated were changed as shown in Table 6 to produce a single-sided laminate and uniform expansion. , sheet molding, and deformation of the molded product.

Comparative examples 7 to 9
A single-sided laminate was prepared by performing the same operations as in Example 34, except that the type of unstretched film, the depth of the mold, the temperature of the mold, and the mating material of the laminate were changed as shown in Table 6. We performed uniform expansion, sheet molding, and deformation of the molded product.

Table 1 shows the manufacturing conditions and evaluation of the polyamides obtained in Examples 1 to 12 and Comparative Examples 1 to 5.

The abbreviations in Table 1 are as follows.
A = fatty acid dicarboxylic acid (A) having 18 or more carbon atoms (dimer acid)
C = aromatic dicarboxylic acid (C) having 12 or less carbon atoms (terephthalic acid)
B = Aliphatic diamine (B) having 18 or more carbon atoms (dimer 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

Table 2 shows the polyamides used in the polyamide films obtained in Examples 1 to 12 and Comparative Examples 1 to 5, the stretching conditions and their evaluation, and the expansion conditions and evaluation.

Table 3 shows the manufacturing conditions and evaluation of the polyamides obtained in Examples 13 to 22.

The abbreviations in Table 3 are as follows.
A = fatty acid dicarboxylic acid (A) having 18 or more carbon atoms (dimer acid)
C = aromatic dicarboxylic acid (C) having 12 or less carbon atoms (terephthalic acid)
B = Aliphatic diamine (B) having 18 or more carbon atoms (dimer diamine)
D = aliphatic diamine (D) having 12 or less carbon atoms (decanediamine)

In Examples 13 to 22, the melting point is usually 240°C or higher, preferably 270°C or higher, and more preferably 300°C or higher.

Table 4 shows the polyamides used in the polyamide films obtained in Examples 13 to 22, stretching conditions, and evaluation thereof, as well as expansion conditions and evaluation.

Table 5 shows the unstretched films used for the polyamide films obtained in Examples 23 to 33 and Comparative Example 6, stretching conditions, thickness, heating and pressing conditions of the obtained polyamide film laminate, expansion conditions, and evaluation. show.

The abbreviations in Table 5 are as follows.
Cu foil: Electrolytic copper foil

The unstretched films used for the polyamide films obtained in Examples 34 to 43 and Comparative Examples 7 to 9, stretching conditions, thickness, heating and pressing conditions of the obtained polyamide film laminate, molding conditions, and evaluation are shown. 6.

The abbreviations in Table 6 are as follows.
Cu foil: Electrolytic copper foil

The polyamide films of Examples 1 to 22 all have a melting point of 240°C or higher, which is an index of heat resistance, an elongation recovery rate of 30% or higher in a hysteresis test, which is an index of flexibility, and a tensile strength. The elastic modulus was 1,500 MPa or less, and it had excellent heat resistance and flexibility. Further, the films of Examples 1 to 22 had excellent rubber elasticity because the polyamide films used had a crystal fusion enthalpy, which is an index of crystallinity, of 15 J/g or more. As a result, the films of Examples 1 to 22 all had good uniform expandability, maintained uniformity after heat treatment (especially heat resistance uniformity), and had good recovery properties after re-deformation.

For the polyamide films of Examples 1 to 9, polyamide films containing only block-type polyamide as the polyamide were used. The polyamide films of Examples 10 to 12 were polyamide films containing only random polyamide as the polyamide. The former polyamide film had a higher elongation recovery rate and crystal fusion enthalpy, and higher flexibility and rubber elasticity than the latter polyamide film. As a result, the polyamide films of Examples 1 to 9 had better uniform expandability than the polyamide films of Examples 10 to 12, and had better uniformity after heat treatment and better recovery after re-deformation.

The polyamide films of Examples 13 to 15 were polyamide films containing only two types of block polyamides as polyamides.
For the polyamide films of Examples 16 to 18, polyamide films containing block type polyamide and random type polyamide were used as the polyamide.
The polyamide films of Examples 19 to 21 were polyamide films containing only two types of random polyamides as polyamides.
Compare Examples 13, 16 and 19 with the same monomer composition to each other; Compare Examples 14, 18 and 20 with the same monomer composition to each other; and Examples 15, 17 and 21 with the same monomer composition to each other. The following points were clarified by comparing:
・Polyamide films containing more block-type polyamides have higher elongation recovery and crystal fusion enthalpy, lower tensile modulus, and higher flexibility and rubber elasticity than polyamide films containing less block-type polyamides. Ta.
- As a result, the polyamide films of Examples 13 to 15 had better uniform expansibility than the polyamide films of Examples 16 to 21, and had better uniformity after heat treatment and better restorability after re-deformation. The polyamide films of Examples 16 to 18 had better uniform expandability than the polyamide films of Examples 19 to 21, and had better uniformity after heat treatment and better recovery after re-deformation.

The polyamide films of Examples 23 to 33 all have a melting point of 240°C or higher, which is an index of heat resistance, an elongation recovery rate of 30% or higher in a hysteresis test, which is an index of flexibility, and a tensile strength. The elastic modulus was 1,500 MPa or less, and it had excellent heat resistance and flexibility.
The films of Examples 1 to 12 had excellent rubber elasticity because the polyamide films used had a crystal fusion enthalpy, which is an index of crystallinity, of 15 J/g or more.
As a result, even if the expansion method was changed, the films of Examples 23 to 33 had good uniform expandability, good splitting properties of the laminate, maintained uniformity after heat treatment, and maintained uniformity after deformation treatment. The recovery was also good.

For the polyamide films of Examples 23 to 27, polyamide films containing only block-type polyamide as the polyamide were used. The polyamide films of Examples 28 and 29 were polyamide films containing only random polyamide as the polyamide. The former polyamide film had a higher elongation recovery rate and crystal fusion enthalpy, and had higher flexibility and rubber elasticity than the latter polyamide film. As a result, the polyamide films of Examples 23 to 27 had better uniform expansibility than the polyamide films of Examples 28 and 29, and had better divisibility of the laminate, uniformity after heat treatment, and recovery after deformation treatment. there were.

For the polyamide films of Examples 30 and 31, polyamide films containing two types of block polyamides were used as polyamides.
The polyamide films of Examples 32 and 33 contained one type of block type polyamide and one type of random type polyamide as polyamides.
By comparing Examples 30 and 32 with the same monomer composition and comparing Examples 31 and 33 with the same monomer composition, the following was clarified:
・Polyamide films containing more block-type polyamides have higher elongation recovery and crystal fusion enthalpy, lower tensile modulus, and higher flexibility and rubber elasticity than polyamide films containing less block-type polyamides. Ta.
・As a result, the polyamide films of Examples 30 and 31 were superior to the polyamide films of Examples 32 and 33 in terms of uniform expansibility, as well as in the splitting property of the laminate, the uniformity after heat treatment, and the recovery property after deformation treatment. It was good.

By comparing Examples 34 to 36, it was found that by adjusting the mold temperature, uniform expandability could be improved even when the molding depth was increased, and uniformity could be maintained even after sheet molding. Recognize.

For the polyamide films of Examples 34 and 37, polyamide films containing only block-type polyamide as the polyamide were used. The polyamide films of Examples 38 and 39 were polyamide films containing only random polyamide as the polyamide. The former polyamide film had a higher elongation recovery rate and crystal fusion enthalpy, and had higher flexibility and rubber elasticity than the latter polyamide film. The results show that the polyamide films of Examples 34 and 37 have better uniform expandability than the polyamide films of Examples 38 and 39, and can maintain uniformity even after sheet forming.

The polyamide films of Examples 40 and 41 were polyamide films containing only two types of block polyamides as polyamides.
For the polyamide films of Examples 42 and 43, polyamide films containing one type of block type polyamide and one type of block type polyamide were used as polyamides.
By comparing Examples 40 and 42 with the same monomer composition and comparing Examples 41 and 43 with the same monomer composition, the following was clarified:
・Polyamide films containing more block-type polyamides have higher elongation recovery and crystal fusion enthalpy, lower tensile modulus, and higher flexibility and rubber elasticity than polyamide films containing less block-type polyamides. Ta.
- The results show that the polyamide films of Examples 40 and 41 have better uniform expandability than the polyamide films of Examples 42 and 43, and can maintain uniformity even after sheet forming.

The polyamide films of Comparative Examples 3 and 6 were made of polyamides that did not contain the soft segment forming components (A) and (B), and had a low elongation recovery rate. Uniformity and recovery after re-deformation were also not good.

The polyamide films of Comparative Examples 7 to 9 were made of polyamides that did not contain the soft segment forming components (A) and (B), and had a low elongation recovery rate, so they had low uniform extensibility and the mold temperature Adjustment did not improve uniform expandability or uniformity after molding. In addition, recovery after deformation treatment was also low.

The polyamide film of the present invention can be suitably used as a material for molding and decoration, a film for substrates, a film for semiconductor processing (particularly dicing tape), a shock absorbing material, and the like.

Claims

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 a unit consisting of an aromatic dicarboxylic acid (C) having 12 or less carbon atoms, Contains a polyamide (E) containing a unit consisting of an aliphatic diamine (D) having 12 or less carbon atoms, a melting point of 240°C or higher, an elongation recovery rate of 30% or higher in a hysteresis test, a tensile modulus of 1500 MPa or lower, 10 A polyamide film having a % elongation strength of 70 MPa or less and a crystal melting enthalpy of 15 J/g or more.
The aliphatic dicarboxylic acid having 18 or more carbon atoms (A) is a dimer acid, the aliphatic diamine having 18 or more carbon atoms (B) is a dimer diamine, the aromatic dicarboxylic acid having 12 or less carbon atoms (C) is terephthalic acid, The polyamide film according to claim 1, wherein the aliphatic diamine (D) having 12 or less carbon atoms is 1,10-decanediamine.
The total content of the units consisting of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and the unit consisting of the aliphatic diamine having 18 or more carbon atoms (B) is the total monomer component constituting the polyamide (E). The polyamide film according to claim 1 or 2, wherein the amount is 10 to 90% by mass.
The content of the unit consisting of the aliphatic dicarboxylic acid (A) having 18 or more carbon atoms is 3 to 45% by mass based on the total monomer components constituting the polyamide (E),
The content of the unit consisting of the aliphatic diamine (B) having 18 or more carbon atoms is 3 to 45% by mass based on the total monomer components constituting the polyamide (E),
The content of the unit consisting of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms is 3 to 45% by mass based on the total monomer components constituting the polyamide (E),
Any one of claims 1 to 3, wherein the content of the unit consisting of the aliphatic diamine (D) having 12 or less carbon atoms is 3 to 52% by mass based on the total monomer components constituting the polyamide (E). The polyamide film described in Crab.
The polyamide film according to any one of claims 1 to 4, wherein the crystal melting enthalpy is 25 J/g or more.
According to claim 5, the content of the unit consisting of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms is 8 to 35% by mass based on the total monomer components constituting the polyamide (E). Polyamide film.
The polyamide (E) comprises a unit consisting of the aromatic dicarboxylic acid (C) having 12 or less carbon atoms, a hard segment consisting of the unit consisting of the aliphatic diamine (D) having 12 or less carbon atoms, and the above 18 carbon atoms. Any one of claims 1 to 6, comprising a block polyamide containing a soft segment consisting of a unit consisting of the above aliphatic dicarboxylic acid (A) and a unit consisting of an aliphatic diamine (B) having 18 or more carbon atoms. polyamide film.
The polyamide film according to claim 7, wherein the content of the block type polyamide is 10% by mass or more based on the total amount of the polyamide (E).
The polyamide film according to claim 7, wherein the content of the block polyamide is 40% by mass or more based on the total amount of the polyamide (E).
A method for producing a polyamide film according to any one of claims 1 to 9, comprising:
An aromatic dicarboxylic acid (C) having 12 or more carbon atoms and an aliphatic diamine (D) having 12 or less carbon atoms are combined with an aliphatic dicarboxylic acid (A) having 18 or more carbon atoms and an aliphatic diamine having 18 or more carbon atoms (B). ) A method for producing a polyamide film, which comprises reacting separately with polyamide (E) to obtain polyamide (E).
A polyamide film laminate comprising the polyamide film according to any one of claims 1 to 9 and at least one layer selected from the group consisting of a resin layer, a metal layer, and an inorganic material layer provided on the polyamide film. .
A decorative molding film comprising the polyamide film according to any one of claims 1 to 9 or the polyamide film laminate according to claim 11.
A dicing film comprising the polyamide film according to any one of claims 1 to 9 or the polyamide film laminate according to claim 11.
A flat or curved printed circuit board comprising the polyamide film according to any one of claims 1 to 9 or the polyamide film laminate according to claim 11.
A planar or curved antenna substrate comprising the polyamide film according to any one of claims 1 to 9 or the polyamide film laminate according to claim 11.