JP2023001898A - Composition - Google Patents

Abstract

To provide a composition that can form a film having excellent moisture absorption resistance and the film.SOLUTION: A composition comprises a resin (A), a cycloolefinic polymer (B), and a phenolic antioxidant, where the HSP value distance between the phenolic antioxidant and the cycloolefinic polymer (B) is 2.1 or more and the HSP value distance between the resin (A) and the cycloolefinic polymer (B) is 6.0 or more.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a composition capable of forming a film that can be used as a substrate material for printed circuit boards and antenna substrates for high frequency bands, and to the film.

With the full-scale spread of the fifth-generation mobile communication system called 5G, there is a demand for printed circuits that can handle high-frequency bands and printed wiring boards that can be used as antennas. However, since the transmission loss derived from the substrate material has a significant effect in the high frequency band, it is important to select a substrate material that can suppress the transmission loss. For example, a copper-clad laminate called CCL has a structure in which copper foils are laminated on both surfaces of a resin layer via an adhesive. Since the transmission loss of the CCL can be suppressed by reducing the dielectric loss, particularly the dielectric loss tangent and the dielectric constant of the resin layer that serves as the transmission path, films with a low dielectric loss tangent are being studied. For example, Patent Document 1 discloses a low dielectric resin composition containing a resin (A) such as a polyimide resin and a cyclic olefin (co)polymer (B), and a film having a low dielectric loss tangent formed from the composition. is disclosed.

JP 2017-125176 A

It is known that the dielectric properties of the resin layer in the CCL, which is compatible with high-frequency bands, deteriorates when it absorbs moisture. .

Accordingly, an object of the present invention is to provide a composition capable of forming a film having excellent moisture absorption resistance, and the film.

The present inventors arrived at the present invention as a result of intensive studies in order to solve the above problems. That is, the present invention includes the following preferred embodiments.

［式（Ｐ）中、Ｒ^ｐ、Ｒ^ｑ、Ｒ^ｒ及びＲ^ｓは、互いに独立に、水素原子、炭素数１～１２のアルキル基又は炭素数５～１２のシクロアルキル基を表し、＊は結合手を表す］
で表される置換基Ｐを含み、フェノール系酸化防止剤中の置換基Ｐを水素原子に置換した構造Ｓとシクロオレフィン系ポリマー（Ｂ）とのＨＳＰ値間距離（１）は、フェノール系酸化防止剤とシクロオレフィン系ポリマー（Ｂ）とのＨＳＰ値間距離（２）より小さい、〔１〕に記載の組成物。
〔３〕 ＨＳＰ値間距離（１）とＨＳＰ値間距離（２）との差の絶対値は０．１以上である、〔２〕に記載の組成物。
〔４〕 フェノール系酸化防止剤とシクロオレフィン系ポリマー（Ｂ）とのＨＳＰ値間距離は１２．０以下である、〔１〕～〔３〕のいずれかに記載の組成物。
〔５〕 シクロオレフィン系ポリマー（Ｂ）は粒子状である、〔１〕～〔４〕のいずれかに記載の組成物。
〔６〕 シクロオレフィン系ポリマー（Ｂ）のガラス転移温度が１００℃以上である、〔１〕～〔５〕のいずれかに記載の組成物。
〔７〕 シクロオレフィン系ポリマー（Ｂ）は、式（Ｉ）：

［式（Ｉ）中、ｍは０以上の整数を表し、Ｒ^７～Ｒ^１８は、互いに独立に、水素原子、ハロゲン原子又は炭素原子数１～２０の炭化水素基を表し、Ｒ^１１～Ｒ^１４が複数存在する場合、それらは同一であってもよく、異なっていてもよく、Ｒ^１６とＲ^１７とは互いに結合し、それらが結合する炭素原子とともに環を形成してもよい］
で表されるシクロオレフィン由来の単量体単位（Ｉ）を含む、〔１〕～〔６〕のいずれかに記載の組成物。
〔８〕 シクロオレフィン系ポリマー（Ｂ）における前記単量体単位（Ｉ）の含有量は、シクロオレフィン系ポリマー（Ｂ）を構成する繰り返し単位の合計モル量に対して、６０モル％以上である、［７］に記載の組成物。
〔９〕 樹脂（Ａ）は、ポリイミド系樹脂、液晶ポリマー、フッ素系樹脂、芳香族ポリエーテル系樹脂及びマレイミド系樹脂からなる群から選択される少なくとも１つの樹脂である、〔１〕～〔８〕のいずれかに記載の組成物。
〔１０〕 樹脂（Ａ）のガラス転移温度は２００℃以上である、〔１〕～〔９〕のいずれかに記載の組成物。
〔１１〕 樹脂（Ａ）、シクロオレフィン系ポリマー（Ｂ）及びフェノール系酸化防止剤を含み、フェノール系酸化防止剤とシクロオレフィン系ポリマー（Ｂ）とのＨＳＰ値間距離は２．１以上であり、樹脂（Ａ）とシクロオレフィン系ポリマー（Ｂ）とのＨＳＰ値間距離は６以上であるフィルム。 [1] containing a resin (A), a cycloolefin polymer (B) and a phenolic antioxidant, wherein the distance between the HSP values of the phenolic antioxidant and the cycloolefinic polymer (B) is 2.1 or more; A composition in which the distance between the HSP values of the resin (A) and the cycloolefin polymer (B) is 6.0 or more.
[2] The phenolic antioxidant has the formula (P):

[In formula (P), R ^p , R ^q , R ^r and R ^s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
The distance (1) between the HSP values between the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom and the cycloolefin polymer (B) is phenolic oxidation The composition according to [1], which is smaller than the distance (2) between the HSP values between the inhibitor and the cycloolefin polymer (B).
[3] The composition according to [2], wherein the absolute value of the difference between the HSP value distance (1) and the HSP value distance (2) is 0.1 or more.
[4] The composition according to any one of [1] to [3], wherein the distance between the HSP values of the phenolic antioxidant and the cycloolefin polymer (B) is 12.0 or less.
[5] The composition according to any one of [1] to [4], wherein the cycloolefin polymer (B) is particulate.
[6] The composition according to any one of [1] to [5], wherein the cycloolefin polymer (B) has a glass transition temperature of 100°C or higher.
[7] The cycloolefin-based polymer (B) has the formula (I):

[In formula (I), m represents an integer of 0 or more, R ⁷ to R ¹⁸ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹ to R When there are a plurality of ¹⁴ , they may be the same or different, and R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring together with the carbon atom to which they are bonded.]
The composition according to any one of [1] to [6], comprising a cycloolefin-derived monomer unit (I) represented by:
[8] The content of the monomer unit (I) in the cycloolefin-based polymer (B) is 60 mol% or more with respect to the total molar amount of repeating units constituting the cycloolefin-based polymer (B). , the composition according to [7].
[9] The resin (A) is at least one resin selected from the group consisting of polyimide resins, liquid crystal polymers, fluorine resins, aromatic polyether resins and maleimide resins [1] to [8 ].
[10] The composition according to any one of [1] to [9], wherein the resin (A) has a glass transition temperature of 200° C. or higher.
[11] containing a resin (A), a cycloolefin polymer (B) and a phenolic antioxidant, wherein the distance between the HSP values of the phenolic antioxidant and the cycloolefinic polymer (B) is 2.1 or more; A film in which the distance between the HSP values of the resin (A) and the cycloolefin polymer (B) is 6 or more.

ADVANTAGE OF THE INVENTION According to this invention, the composition which can form the film excellent in moisture absorption resistance, and this film can be provided.

〔Composition〕
The composition of the present invention contains a resin (A), a cycloolefin polymer (B) and a phenolic antioxidant, and the HSP value distance between the phenolic antioxidant and the cycloolefinic polymer (B) is 2.0. It is 1 or more, and the distance between the HSP values of the resin (A) and the cycloolefin polymer (B) is 6.0 or more. In this specification, the "film formed from the composition" may be simply referred to as "film". In this specification, the dielectric property means a property related to dielectric including dielectric loss, relative permittivity and dielectric loss tangent. It shows that the dielectric loss tangent is reduced.

The present inventors have investigated the moisture absorption resistance of a film formed from a composition containing a resin (A) and a cycloolefin-based polymer (B), and found that during film formation of the composition, for example, at high temperature It has been found that the cycloolefin-based polymer (B) is oxidized during heat treatment, resulting in the generation of polar groups, which may reduce the hygroscopic resistance of the film formed from the composition. Therefore, the present inventors focused on the oxidation of the cycloolefin-based polymer (B) and further studied, and found that the distance between the HSP values with the cycloolefin-based polymer (B) is 2.1 or more. It has been found that the addition of an inhibitor can suppress the oxidation of the cycloolefin polymer (B) and improve the moisture absorption resistance of the formed film. Therefore, the composition of the present invention can form a film having excellent moisture absorption resistance.

<Phenolic antioxidant>
The composition of the present invention contains a phenolic antioxidant, and the distance between the HSP values between the phenolic antioxidant and the polymer (B) is 2.1 or more. Therefore, the cycloolefin polymer (B) (hereinafter sometimes simply referred to as "polymer (B)") contained in the composition of the present invention is resistant to oxidation even during film formation, and the composition of the present invention is resistant to moisture absorption. A film with excellent properties can be formed. This is because the phenolic antioxidant covers the periphery of the polymer (B), so that the antioxidant effect of the phenolic antioxidant on the polymer (B) can be obtained. ) is 2.1 or more, the affinity between the phenolic antioxidant and the polymer (B) is not excessively high, and the phenolic antioxidant uniformly disperses the polymer (B). This is believed to be because it becomes easier to cover and the antioxidation effect of the polymer (B) by the phenolic antioxidant increases. On the other hand, when the distance between the HSP values of the phenolic antioxidant and the solvent is less than 2.1, the affinity between the phenolic antioxidant and the polymer (B) is excessively increased, resulting in the phenolic antioxidant may be unevenly adsorbed on the polymer (B), resulting in a state in which the polymer (B) is not partially covered with the phenolic antioxidant. In such a case, the phenol-based antioxidant cannot provide a sufficient antioxidant effect, and the polymer (B) tends to be easily oxidized, which tends to lower the hygroscopic resistance of the resulting film.

In the composition of the present invention, the distance between the HSP values of the phenolic antioxidant and the polymer (B) is preferably 2.3 or more, more preferably 2.5 or more, still more preferably 3.0 or more, and particularly preferably is greater than or equal to 3.2. When the distance between the HSP values is at least the above lower limit, the phenolic antioxidant tends to uniformly cover the polymer (B), so it is easy to suppress oxidation of the polymer (B), and the phenolic antioxidant is a polymer Since it is easily formed into a film in the form of covering the periphery of (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film. The distance between the HSP values of the phenolic antioxidant and the polymer (B) is preferably 12.0 or less, more preferably 8.0 or less, even more preferably 6.0 or less, still more preferably 5.5 or less, especially It is preferably 5.0 or less, particularly more preferably 4.5 or less, and even more preferably 4.0 or less. When the distance between the HSP values is equal to or less than the above upper limit, the phenolic antioxidant tends to approach or adsorb to the polymer (B), and tends to cover the polymer (B), thereby suppressing oxidation of the polymer (B). and easily improve the moisture absorption resistance of the resulting film.

HSP is the Hansen Solubility Parameter (δ), defined by the three-dimensional parameters (δD, δP, δH) and represented by the formula (X):
δ ² = (δD) ² + (δP) ² + (δH) ² (X)
[In formula (X), δD represents a London dispersion force term, δP represents a molecular polarization term (dipole force term), and δH represents a hydrogen bond term]
is represented by Details of HSP are described in "PROPERTIES OF POLYMERS" (Author: D.W. VANKREVELEN, Publisher: ELSEVIER SCIENTFIC PUBLISHING COMPANY, 1989, 5th Edition). The Hansen Solubility Parameters δD, δP, and δH were obtained using HSPiP (Hansen Solubility Parameters in Practice), a program developed by Dr. Hansen's group who proposed the Hansen Solubility Sphere method, according to the Hansen Solubility Sphere method. For example, Ver. 4.1.07 and the like can be used. Details of the Hansen melting ball method are described below. A component of interest is dissolved in a solvent with a known HSP value, and the solubility of the component in a specific solvent is evaluated. Solubility evaluation is carried out by visually determining whether or not the target component is dissolved in the solvent. This is done for multiple solvents. As for the types of solvents, it is preferable to use solvents having a wide range of different δt. Next, the center coordinates (δd, δp, δh) of the Hansen sphere obtained by inputting the obtained solubility evaluation results into the HSPiP are used as the HSP with the target composition. In addition to the above method, the HSP may be obtained by using, for example, numerical values in the HSPiP database or literature values, or may be determined from the structural formula using HSPiP. In this specification, the value of the Hansen solubility parameter is referred to as the HSP value, and the HSP value represents the value at 25°C. The HSP value of the resin (A), the HSP value of the polymer (B), and the HSP value of the solvent may each be determined by any of the methods described above, for example, by the method described in Examples.

The distance between the Hansen solubility parameters (hereinafter sometimes abbreviated as HSP) of two substances is called the distance between HSP values. The inter-HSP distance (Ra) is an index representing the affinity between both substances, and the smaller the value, the higher the affinity between the two substances. Conversely, the larger the Ra value, the lower the affinity between the two substances, that is, the less compatible they are.
The distance between HSP values is the Hansen solubility parameters δA and δB of the two substances A and B, respectively,
δA = (δDA, δPA, δHA)
δB = (δDB, δPB, δHB)
Assuming that the distance between HSPs (Ra) is given by the formula (Y):
Ra=[4×(δDA−δDB) ² +(δPA−δPB) ² +(δHA−δHB) ² ] ^0.5 (Y)
can be calculated by
In this specification, the HSP value and the distance between HSP values are as defined above, and can be obtained according to the above method.

［式（Ｐ）中、Ｒ^ｐ、Ｒ^ｑ、Ｒ^ｒ及びＲ^ｓは、互いに独立に、水素原子、炭素数１～１２のアルキル基又は炭素数５～１２のシクロアルキル基を表し、＊は結合手を表す］
で表される置換基Ｐ（フェノール系活性部位ということがある）を含むことが好ましい。フェノール系酸化防止剤が置換基Ｐを含む場合、酸素の存在下でポリマー（Ｂ）に生じた不安定なラジカル、例えば炭素ラジカルやパーオキシラジカルと反応して不活化し、ラジカル連鎖反応を抑制することができるためポリマー（Ｂ）の酸化を抑制しやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。 The phenolic antioxidant in the present invention is not particularly limited as long as the distance between the HSP values with the polymer (B) is at least the above lower limit, but the following formula (P):

[In formula (P), R ^p , R ^q , R ^r and R ^s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
It is preferable to include a substituent P represented by (sometimes referred to as a phenolic active site). When the phenolic antioxidant contains a substituent P, it reacts with unstable radicals generated in the polymer (B) in the presence of oxygen, such as carbon radicals and peroxy radicals, and is inactivated to suppress the radical chain reaction. Since the polymer (B) can be easily oxidized, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.

In formula (P), R ^p , R ^q , R ^r and R ^s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms. Examples of alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Neopentyl group, n-hexyl group, n-octyl group, tert-amyl group and the like. Examples of the cycloalkyl group having 5 to 12 carbon atoms include cyclopentyl group, cyclohexyl group, cyclohexylmethyl group and the like.

In one embodiment of the present invention, R ^p , R ^q , R ^r and R ^s suppress the oxidation of the polymer (B) and easily improve the moisture ^absorption resistance and heat resistance of the resulting film. , R ^q , R ^r and R ^s is preferably not a hydrogen atom, more preferably any one of R ^p and R ^q is not a hydrogen atom, still more preferably R ^p , R ^q , R ^r and At least one of R ^s is a bulky substituent, more preferably at least one of R ^p and R ^q is a bulky substituent, and most preferably both R ^p and R ^q are bulky substituents. be. The bulky substituent may be a tert-butyl group, a neopentyl group, a tert-amyl group, etc., preferably a tert-butyl group. When the phenolic antioxidant has multiple substituents P, the structures of the substituents P may be the same or different. That is, when there are multiple substituents P, R ^p , R ^q , R ^r and R ^s in each substituent P may be the same or different. When at least one of R ^p and R ^q is not a hydrogen atom, preferably at least one of R ^p and R ^q is a bulky substituent, it reacts with unstable radicals such as carbon radicals and peroxy radicals, When converted to phenoxy radicals, the phenoxy radicals are further stabilized, so that the oxidation of the polymer (B) is easily suppressed, and the hygroscopic resistance of the obtained film is easily improved.

In one embodiment of the present invention, the phenolic antioxidant is a structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom (hereinafter also simply referred to as “structure S”) and a polymer (B). is preferably 1.5 or more, more preferably 2.0 or more, even more preferably 2.4 or more, and particularly preferably 2.6 or more. When the distance between the HSP values is at least the above lower limit, the affinity between the phenolic antioxidant and the polymer (B) is not too high, and the phenolic antioxidant tends to uniformly cover the polymer (B). It is easy to suppress the oxidation of (B), and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film. The distance between the HSP values of structure S and polymer (B) is preferably 7.5 or less, more preferably 6.5 or less, even more preferably 5.5 or less, even more preferably 5.0 or less, and particularly preferably It is 4.0 or less, particularly more preferably 3.5 or less, and even more preferably 3.0 or less. When the distance between the HSP values is equal to or less than the above upper limit, the phenolic antioxidant tends to approach or adsorb to the polymer (B), and tends to cover the polymer (B), thereby suppressing oxidation of the polymer (B). It is easy to improve the moisture absorption resistance and heat resistance of the resulting film.

In one embodiment of the present invention, the distance between the HSP values between the structure S and the polymer (B) (hereinafter also referred to as the distance between the HSP values (1)) is the HSP value between the phenolic antioxidant and the polymer (B) It is preferably smaller than the inter-HSP value distance (hereinafter also referred to as inter-HSP value distance (2)). When the distance between HSP values (1) is smaller than the distance between HSP values (2), the polymer (B) is less likely to be oxidized, and the resulting film tends to have improved moisture absorption resistance and heat resistance. It is believed that this is for the following reasons. The fact that the HSP value distance (1) is smaller than the HSP value distance (2) means that the portion of the structure S of the phenolic antioxidant has a particularly high affinity with the polymer (B), and oxidation Since the portion of the structure S of the inhibitor is easily adsorbed to the polymer (B) so that it is in contact with the polymer (B), the substituent P of the phenolic antioxidant tends to be uniformly present around the polymer (B), and as a result, the polymer ( The unstable radicals generated by the oxidation in B) are likely to be trapped by the substituent P. The radical of the substituent P generated by trapping the radical can further trap the radical of the polymer (B) and inactivate the polymer (B). For example, when both R ^p and R ^q are bulky substituents, after the substituent P is radicalized, the radical of the polymer (B) is trapped at the para position with respect to the hydroxyl group of the substituent P, It is easy to inactivate the polymer (B). Therefore, when the polymer (B) and the structure S are present close to each other, the para position of the hydroxyl group of the substituent P, which contributes to deactivation of the polymer (B), tends to be close to the polymer (B). , the substituent P radical tends to inactivate the polymer (B), so that the antioxidant function of the phenolic antioxidant tends to be exhibited. In addition, since the hydroxyl group of the substituent P of the phenolic antioxidant is moderately separated from the polymer (B), it is easy to prevent the trapped radicals from moving to the polymer (B).

In one embodiment of the present invention, when the HSP value distance (1) is smaller than the HSP value distance (2), the absolute value of the difference between the HSP value distance (1) and the HSP value distance (2) is , From the viewpoint of easily suppressing oxidation of the polymer (B) because the phenolic antioxidant easily covers the polymer (B) and easily improving the moisture absorption resistance and heat resistance of the film, it is preferably 0.1 or more, more preferably is 0.2 or more, more preferably 0.3 or more, even more preferably 0.4 or more, and particularly preferably 0.5 or more. Further, the difference between the distance between HSP values (1) and the distance between HSP values (2) makes it easier for the phenolic antioxidant to uniformly adsorb to the polymer (B), and the substitution of the phenolic antioxidant From the viewpoint of easily maintaining an appropriate space between the group P and the polymer (B), it is preferably 3.0 or less, more preferably 2.0 or less, further preferably 1.5 or less, and particularly preferably 1.0. It is below.

In one embodiment of the present invention, the distance between the HSP values of the phenolic antioxidant and the resin (A) is such that the phenolic antioxidant easily covers the polymer (B), so that the oxidation of the polymer (B) is easily suppressed. , From the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film, it is preferably 5.0 or more, more preferably 8.0 or more, still more preferably 8.5 or more, still more preferably 9.5 or more, and particularly preferably is 10.0 or more, and more preferably 11.0 or more. In addition, the distance between the HSP values of the phenolic antioxidant and the resin (A) is preferably 16.0 or less, more preferably 16.0 or less, more preferably from the viewpoint of easily preventing aggregation of the phenolic antioxidant in the composition or film. is 15.0 or less, more preferably 13.0 or less, still more preferably 12.5 or less.

In one embodiment of the present invention, the distance between the HSP values of structure S and resin (A) is preferably 5.0 or more, more preferably 7.0 or more, still more preferably 8.0 or more, still more preferably It is 9.0 or more, particularly preferably 10.0 or more, preferably 15.0 or less, more preferably 14.0 or less, still more preferably 13.0 or less, and even more preferably 12.0 or less. When the distance between HSP values is equal to or less than the upper limit or equal to or more than the lower limit, it is easy to suppress oxidation of the polymer (B), and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.

In one embodiment of the present invention, structure S preferably has an aromatic ring. When the phenol-based antioxidant has an aromatic ring as structure S, oxidation during film formation of the polymer (B) contained in the composition of the present invention and the formation of polar groups due to this can be effectively suppressed. A film with excellent hygroscopicity can be formed. The aromatic ring may have a substituent (sometimes referred to as a substituent Q) as long as it is different from the substituent P. Furthermore, even when the obtained film is exposed to a high-temperature environment, it is possible to effectively prevent deterioration due to oxidation of the polymer (B) and exhibit excellent heat resistance. Although the reason for this is not clear, if the structure S excluding the phenolic active site has an aromatic ring which may have a substituent, the heat resistance of the antioxidant itself is improved, and the heat resistance of the antioxidant with the polymer (B) is improved. It is presumed that this is because the affinity increases.

In one embodiment of the present invention, the aromatic ring of structure S is preferably an aromatic ring having 5 to 20 carbon atoms. Aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles.

Examples of aromatic hydrocarbon rings include monocyclic aromatic hydrocarbon rings, condensed polycyclic aromatic hydrocarbon rings, and ring-assembled aromatic hydrocarbon rings.

The monocyclic aromatic hydrocarbon ring is preferably a monocyclic aromatic hydrocarbon ring having 6 to 15 carbon atoms, such as a benzene ring. The condensed polycyclic aromatic hydrocarbon ring is preferably a condensed polycyclic aromatic hydrocarbon ring having 10 to 20 carbon atoms, examples of which include naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like. The ring-assembled aromatic hydrocarbon ring is two or more monocyclic aromatic hydrocarbon rings, two or more condensed polycyclic aromatic hydrocarbon rings, or one or more monocyclic aromatic hydrocarbon rings and one or more and the condensed polycyclic aromatic hydrocarbon rings of are bonded to each other through a single bond, and ring-assembled aromatic hydrocarbon rings having 10 to 40 carbon atoms are preferred. Examples thereof include biphenyl ring, phenylnaphthyl ring, terphenyl ring, perylene ring and the like. Among the aromatic hydrocarbon rings, a benzene ring, a naphthalene ring, a biphenyl ring and the like are preferable, and a benzene ring is more preferable, from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film.

Aromatic heterocycles include, for example, monocyclic aromatic heterocycles, condensed polycyclic aromatic heterocycles, and ring-assembled heteroaromatic rings. As used herein, the aromatic heterocycle also includes rings having tautomers, and even if the ring itself has no aromaticity, if the tautomers have aromaticity, the term " included in "aromatic heterocycle". For example, the isocyanuric ring (s-triazine-2,4,6-trione ring) is s-triazine-2,4,6-triol, which has an aromatic tautomer. , included in aromatic heterocycles. The monocyclic aromatic heterocycle contains at least one heteroatom selected from a sulfur atom, a nitrogen atom and an oxygen atom, and is preferably an aromatic heterocycle having 5 to 15 carbon atoms and heteroatoms, examples of which include: pyrrole ring, pyrazole ring, imidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, isocyanuric ring, diazabenzene ring, furan ring, thiophene ring, azole ring, diazole ring, triazole ring, oxazole ring, oxazi An azole ring, a thiadiazole ring, and the like can be mentioned. The condensed polycyclic aromatic heterocycle contains at least one heteroatom selected from a sulfur atom, a nitrogen atom and an oxygen atom, and is preferably a condensed polycyclic aromatic heterocycle having 8 to 20 carbon atoms and heteroatoms, Examples thereof include azanaphthalene (quinoline) ring, diazanaphthalene ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring, dibenzosilole ring, phenoxazine ring, phenothiazine ring, acridine ring, indole ring, pyrroloimidazole ring, pyrrolopyrazole ring. ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, thiazole ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanth Lysine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like. Ring-assembled aromatic heterocycles are two or more monocyclic aromatic heterocycles, two or more condensed polycyclic aromatic heterocycles, one or more monocyclic aromatic heterocycles and one or more condensed polycyclic aromatic rings. and one or more monocyclic aromatic hydrocarbon rings and one or more condensed polycyclic aromatic heterocycles, or one or more monocyclic rings It also includes those in which the formula aromatic heterocycle and one or more condensed polycyclic aromatic hydrocarbon rings are bonded to each other through a single bond. The ring-assembled aromatic heterocycle is preferably a ring-assembled aromatic heterocycle having 10 to 40 carbon atoms, and examples thereof include bipyridine ring, terpyridine ring and the like. Among the aromatic heterocycles, a triazine ring, an isocyanuric ring, and the like are preferable, and a triazine ring is more preferable, from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film.

Structure S in the phenolic antioxidant may have one or more aromatic rings which may have a substituent. When two or more optionally substituted aromatic rings are included, each aromatic ring is linked by a divalent or higher hydrocarbon group, more preferably a divalent or trivalent hydrocarbon group, more preferably an alkylene group. may have been Examples of the alkylene group include groups obtained by removing one hydrogen atom from the above-exemplified alkyl groups having 1 to 12 carbon atoms. A carbon atom in the alkylene may be replaced with at least one selected from a sulfur atom, a nitrogen atom and an oxygen atom.

Among the aromatic rings, aromatic hydrocarbon rings are preferable from the viewpoint of facilitating the enhancement of dielectric properties in addition to the hygroscopic resistance and heat resistance of the film. A cyclic aromatic hydrocarbon ring and/or a condensed polycyclic aromatic hydrocarbon ring is more preferable, a monocyclic aromatic hydrocarbon ring is more preferable, and a benzene ring is particularly preferable.

Examples of the substituent Q that the aromatic ring may have include a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an alkylthio group, a cycloalkylthio group, an alkylamino group, a cycloalkylamino group, an acyl group, and a mercapto group. , an amino group, a hydroxyl group, a group having an ester bond, and the like. These substituents Q can be used alone or in combination of two or more.

Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms. The alkyl group includes, for example, the above-exemplified alkyl groups having 1 to 12 carbon atoms. The cycloalkyl group includes, for example, the above-exemplified cycloalkyl groups having 5 to 12 carbon atoms. Examples of alkoxy groups include those having 1 to 12 carbon atoms such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, isobutoxy, tert-butoxy, pentyloxy and hexyloxy groups. An alkoxy group etc. are mentioned. Cycloalkoxy groups include, for example, cycloalkoxy groups having 5 to 12 carbon atoms such as cyclohexyloxy. Examples of alkylthio groups include alkylthio groups having 1 to 12 carbon atoms such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, pentylthio and hexylthio. etc. The cycloalkylthio group includes, for example, cycloalkylthio groups having 5 to 12 carbon atoms such as cyclohexylthio group. Examples of alkylamino groups include monoalkylamino groups and dialkylamino groups in which the alkyl moiety is the above-exemplified alkyl group having 1 to 12 carbon atoms. Examples of the cycloalkylamino group include monoalkylamino groups and dialkylamino groups in which the cycloalkyl moiety is the above-exemplified cycloalkyl group having 5 to 12 carbon atoms. Among these substituents, an alkyl group, an alkoxy group, or the like is preferable, an alkyl group is more preferable, and an alkyl group having 1 to 12 carbon atoms is even more preferable, from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film. 1 to 4 alkyl groups are even more preferred, with methyl and/or ethyl groups being particularly preferred.

The aromatic ring in structure S may or may not have a substituent, but from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film, it has a substituent. is preferred. The number of substituents on the aromatic ring in structure S is not particularly limited, but is preferably 0 or more, more preferably 1 or more, still more preferably 2 or more, still more preferably 3 or more, particularly preferably 4 or more, and particularly preferably 4 or more. Preferably 5 or more, preferably 12 or less, more preferably 11 or less, still more preferably 10 or less, still more preferably 9 or less, particularly preferably 8 or less, particularly more preferably 7 or less, and even more preferably is 6.

In the phenolic antioxidant, the number of substituents P is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 6 or less from the viewpoint of easily increasing the moisture absorption resistance and heat resistance of the film. , more preferably 5 or less, still more preferably 4 or less, and even more preferably 3.

The structure of the phenolic antioxidant is a structure in which the bond of the substituent P is bonded to the portion of the structure S from which the hydrogen atom has been removed. For example, when the structure S is an aromatic ring having a methyl group as the substituent Q, it may be a structure in which a bond of the substituent P is attached to a portion obtained by removing one hydrogen atom from the methyl group. A structure in which a bond of the substituent P is bonded to a portion from which one hydrogen atom has been removed may also be used. Thus, the substituent P may be bonded to the aromatic ring of the structure S, and bonded to a substituent obtained by removing one hydrogen atom from the substituent Q of the aromatic ring (also referred to as a substituent Q'). or if there are multiple substituents P, they may be bonded to both of them. From the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film, the substituent P is preferably bonded to at least the substituent Q' of the aromatic ring. In addition, the case where the substituent P is bonded to the aromatic ring is meant to include the case where it is bonded to a heteroatom (for example, a nitrogen atom).

The bonding position of the substituent P relative to the aromatic ring is not particularly limited. For example, when the aromatic ring is a benzene ring, the substituents P are attached to It is preferably bonded to non-adjacent carbon atoms directly or via a substituent Q', and more preferably bonded directly or via a substituent Q' to the 1,3-position or 1,3,5-position. Preferably, it is more preferably bonded to the 1, 3, and 5-positions via the substituent Q'. Further, for example, when the aromatic ring is a triazine ring, from the viewpoint of easily improving the hygroscopic resistance and heat resistance of the film, the substituent P is directly or via the substituent Q' at the 2,4-position or at the 2,4-position. It is more preferably bonded to the 6-position, and more preferably bonded to the 2-, 4-, and 6-positions via the substituent Q'. For example, when the aromatic ring is an isocyanuric ring, from the viewpoint of easily improving the hygroscopic resistance and heat resistance of the film, the substituent P is directly or via the substituent Q 'at the 1,3-position or at the 1,3,5-position. is preferably bonded to the nitrogen atoms of , more preferably directly bonded to the nitrogen atoms at the 1, 3, and 5 positions.

［各式中、Ｒ^ｐ、Ｒ^ｑ、Ｒ^ｒ及びＲ^ｓは、上記に示した定義と同じである］
なお、上記構造中、各フェノール系酸化防止剤において、置換基Ｐ中のＲ^ｐ、Ｒ^ｑ、Ｒ^ｒ及びＲ^ｓは、それぞれ同一であっても、異なっていてもよい。上記のような構造であると、フィルムの耐吸湿性及び耐熱性を向上しやすい。 In one embodiment of the present invention, phenolic antioxidants having an aromatic ring in which structure S may have a substituent include, for example, those having the following structures.

[In each formula, R ^p , R ^q , R ^r and R ^s are the same as defined above]
In the above structure, R ^p , R ^q , R ^r and R ^s in the substituent P may be the same or different in each phenolic antioxidant. With the above structure, it is easy to improve the moisture absorption resistance and heat resistance of the film.

In one embodiment of the present invention, specific examples of phenolic antioxidants include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6- trimethylbenzene, 4,4′,4″-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), pentaerythritol tetrakis(3-(3,5-di-tert- butyl-4-hydroxyphenyl)propionate)), 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz [d ,f][1.3.2]dioxaphosphepin, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 2,2′,6,6′ -tetra-tert-butyl-4,4'-dihydroxybiphenyl, 6,6'-di-tert-butyl-4,4'-butylidene-di-m-cresol, 2,5-di-tert-butylhydroquinone, Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid][oxalylbis(azanediyl)]bis(ethane-2,1-diyl), 2,5-di-tert-amyl Hydroquinone, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 4,4′-butylidenebis(6-tert-butyl-m-cresol), 3-(3,5-di- tert-butyl-4-hydroxyphenyl)-N'-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide, 2,4,6-tris(2,4-dihydroxy phenyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H ,3H,5H)-trione, tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 4-[[4,6-bis(n-octylthio)-1,3,5 -triazin-2-yl]amino]-2,6-di-tert-butylphenol, etc. Among these, 1,3,5-tris(3, 5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene is preferred.

In one embodiment of the present invention, the content of the phenolic antioxidant contained in the composition of the present invention is preferably 0.01 parts by mass or more, more preferably 0 parts by mass with respect to 100 parts by mass of the polymer (B). 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, particularly preferably 0.5 parts by mass or more, and even more preferably 2 parts by mass or more. When the content of the phenolic antioxidant is at least the above lower limit, the polymer (B) is easily covered with the phenolic antioxidant, and the oxidation of the polymer (B) is easily suppressed. Easy to improve heat resistance. The content of the phenolic antioxidant is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 7 parts by mass or less, and particularly preferably 5 parts by mass with respect to 100 parts by mass of the polymer (B). It is below. When the content of the phenolic antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.

<Cycloolefin polymer (B)>
The composition of the present invention contains a cycloolefin-based polymer (B), and in the composition of the present invention, the HSP value distance between the resin (A) and the polymer (B) is 6.0 or more. Therefore, since an interface is easily formed between the polymer (B) and the resin (A), the phenolic antioxidant is easily adsorbed so as to cover the polymer (B), preventing oxidation of the polymer (B). Cheap. On the other hand, if the distance between the HSP values of the resin (A) and the polymer (B) is less than 6.0, the resin (A) and the polymer (B) are likely to be compatible with each other, making it difficult to form an interface. It becomes difficult for the antioxidant to cover the polymer (B), the antioxidant effect of the phenolic antioxidant cannot be sufficiently obtained, and the polymer (B) tends to be easily oxidized.

In one embodiment of the present invention, the distance between the HSP values of resin (A) and polymer (B) is preferably 6.5 or more, more preferably 7.0 or more, and even more preferably 8.0 or more. If the distance between the HSP values of the resin (A) and the polymer (B) is at least the above lower limit, an interface is likely to form between the polymer (B) and the resin (A). It is easy to adsorb so as to cover the periphery of B), and it is easy to prevent oxidation of the polymer (B). Further, the distance between the HSP values of the resin (A) and the polymer (B) is preferably It is 30.0 or less, more preferably 25.0 or less, still more preferably 20.0 or less, still more preferably 15.0 or less.

In one embodiment of the present invention, polymer (B) may be particulate, acicular or fibrous, preferably particulate. When the polymer (B) is in the form of particles, the dispersibility of the polymer (B) in the composition and in the resulting film can be easily increased, and the hygroscopic resistance and heat resistance of the film can be easily improved. When the dispersibility of the polymer (B) in the composition increases, the dispersibility of the polymer (B) in the resulting film increases, so that the moisture absorption resistance, surface smoothness, dielectric properties, heat resistance and mechanical properties of the film are enhanced. It is easy to reduce physical properties of the film, such as variation in thermal conductivity of the film, coefficient of linear expansion (hereinafter referred to as CTE), and roughness of the surface of the film. As used herein, mechanical properties refer to mechanical properties including bending resistance and elastic modulus, and increasing or improving mechanical properties means, for example, increasing bending resistance and/or elastic modulus. show. A solvent can be used individually or in combination of 2 or more types. In this specification, the "particle size of the particulate polymer (B)" may be simply referred to as "particle size".

［式（Ｉ）中、ｍは０以上の整数を表し、
Ｒ^７～Ｒ^１８は、互いに独立に、水素原子、ハロゲン原子又は炭素数１～２０の炭化水素基を表し、Ｒ^１１～Ｒ^１４が複数存在する場合、それらは互いに独立に、同一であってもよく、異なっていてもよく、Ｒ^１６とＲ^１７とは互いに結合し、それらが結合する炭素原子とともに環を形成してもよい］
で表されるシクロオレフィン由来の単量体単位（Ｉ）を含むことが好ましい。 The monomer units constituting the cycloolefin-based polymer (B) are not particularly limited, but from the viewpoint of easily improving the dispersibility of the polymer (B) and from the viewpoint of easily improving the hygroscopic resistance and heat resistance of the resulting film. , formula (I)

[In the formula (I), m represents an integer of 0 or more,
R ⁷ to R ¹⁸ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ¹¹ to R ¹⁴ are present, they are each independently the same may be different, and R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring together with the carbon atom to which they are bonded]
It preferably contains a cycloolefin-derived monomer unit (I) represented by

In Formula (I), m is an integer of 0 or more. From the viewpoint of easily improving the dispersibility of the polymer (B), the moisture absorption resistance and heat resistance of the film, and being easily available, the upper limit of m is preferably an integer of 3 or less, more preferably an integer of 2 or less, More preferably, it is an integer of 1 or less.

Examples of hydrocarbon groups having 1 to 20 carbon atoms that are members of the substituents of R ⁷ to R ¹⁸ include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group and dodecyl group. Aryl groups such as phenyl group, tolyl group and naphthyl group; Aralkyl groups such as benzyl group and phenethyl group; mentioned. Among these, an alkyl group, an aryl group, or an aralkyl group is preferable from the viewpoint of easily improving the dispersibility of the polymer (B) and the hygroscopic resistance and heat resistance of the resulting film. That is, R ⁷ to R ¹⁸ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. More preferably, it is an alkyl group having 1 to 10 carbon atoms.

Examples of cycloolefins represented by formula (I) include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, and tricyclodecene. , tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene and the like. Among these, norbornene is preferable from the viewpoint of easy availability of raw material monomers, dispersibility of the polymer (B), and easiness in improving the hygroscopic resistance and heat resistance of the resulting film. The cycloolefins represented by formula (I) may be used alone or in combination of two or more.

In one embodiment of the present invention, the cycloolefin-based polymer preferably contains a double chain structure of monomer units (I). By containing the two-chain structure, the heat resistance is likely to be improved as compared with a polymer having a similar content of the monomer unit (I). The presence or absence of a double-chain structure can be determined by ¹³ C-NMR spectrum analysis. For example, in the case of tetracyclodecene-ethylene copolymer, signals derived from ethylene-tetracyclodecene-ethylene chains, which are isolated chains of tetracyclodecene, appear near 54.7 ppm and 51.1 ppm, and endo-exo bonds The signal derived from the ethylene-tetracyclodecene-tetracyclodecene-ethylene chain, which is the double chain of tetracyclodecene, is near 51.5 ppm and 50.8 ppm, and the exo-exo bond ethylene-tetracyclodecene-tetracyclo Since the signals derived from the decene-ethylene chain appear near 55.3 ppm and 54.3 ppm, the pattern of signals near 55 ppm and 50 ppm can be determined.

The two-chain structure of the monomer unit (I) includes a meso-type two-chain structure represented by the following structural formula (II-1) or the following structural formula (II-2), and/or the following structural formula (III- 1) or a racemo-type double linkage represented by the following structural formula (III-2).

The ratio of the meso-type double chain to the racemo-type double chain (hereinafter sometimes referred to as meso-type double chain/racemo-type double chain) is preferably 0.50 or less, more preferably 0.40 or less, and still more preferably It is 0.30 or less, particularly preferably 0.20 or less, preferably 0.01 or more, and more preferably 0.05 or more. When the ratio of the meso-type two-chain to the racemo-type two-chain is within the above range, the mechanical properties and heat resistance of the film are likely to be improved. The ratio of the meso-form bichain to the racemo-form bichain can be determined, for example, using ¹³ C-NMR, as described in RA Wendt, G. Fink, Macromol. JP-A-2008-285656", specifically, it can be calculated by the method described in Examples. As a method for adjusting the meso-type double chain and the racemo-type double chain within the above ranges, there is a method of selecting a catalyst having an appropriate ligand width with respect to the bulkiness of the monomer. As the catalyst, for example, the catalyst described in JP-A-9-183809 can be used.

The content of the monomer unit (I) in the cycloolefin-based polymer is preferably 60 mol% or more, more preferably 65 mol% or more, relative to the total molar amount of repeating units constituting the cycloolefin-based polymer, It is more preferably 70 mol % or more, particularly preferably 75 mol % or more, preferably 100 mol % or less, more preferably 99 mol % or less, still more preferably 98 mol % or less. When the content of the monomer unit (I) is at least the above lower limit, the glass transition temperature (hereinafter sometimes referred to as Tg) tends to increase, so the CTE of the film tends to decrease, and the resistance of the film increases. Easy to improve moisture absorption. Furthermore, it is easy to improve mechanical properties such as heat resistance and bending resistance of the film. When the content of the monomeric unit (I) is equal to or less than the above upper limit, mechanical properties such as bending resistance are likely to be enhanced. The content of the monomer unit (I) is determined using ¹³ C-NMR, based on the assignment described in "RA Wendt, G. Fink, Macromol. Chem. Phys., 2001, 202, 3490." For example, it can be calculated by the method described in Examples.

The cycloolefin-based polymer consists of ethylene, a linear α-olefin having 3 to 20 carbon atoms, and an aromatic vinyl compound having 8 to 20 carbon atoms, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film. It preferably contains a monomeric unit (II) derived from at least one selected from the group.

Linear α-olefins having 3 to 20 carbon atoms include, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. be done. Among these, propylene, 1-butene, 1-hexene, or 1-octene is preferable, and propylene is more preferable, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film. Linear α-olefins having 3 to 20 carbon atoms may be used singly or in combination of two or more. The term "straight-chain α-olefin" refers to a straight-chain olefin having a carbon-carbon unsaturated double bond at the α-position.

Examples of aromatic vinyl compounds having 8 to 20 carbon atoms include styrene, methylstyrene, dimethylstyrene, ethylstyrene, tert-butylstyrene, vinylnaphthalene, vinylanthracene, diphenylethylene, isopropenylbenzene, isopropenyltoluene, and isopropenyl. ethylbenzene, isopropenylpropylbenzene, isopropenylbutylbenzene, isopropenylpentylbenzene, isopropenylhexylbenzene, isopropenyloctylbenzene, isopropenylnaphthalene, isopropenylanthracene and the like. Among these, styrene, methylstyrene, or dimethylstyrene is preferable, and styrene is more preferable, from the viewpoints of easy availability of raw material monomers and easy improvement of moisture absorption resistance and heat resistance of the film. The aromatic vinyl compounds having 8 to 20 carbon atoms may be used singly or in combination of two or more.

In one embodiment of the present invention, the cycloolefin-based polymer is preferably selected from the group consisting of ethylene, propylene and styrene from the viewpoints of easy availability of raw material monomers and easy improvement of moisture absorption resistance and heat resistance of the film. It preferably contains monomer units (II) derived from at least one, more preferably monomer units (II) derived from at least one selected from the group consisting of ethylene and styrene.

The content of the monomer unit (II) in the cycloolefin-based polymer is preferably 0 mol% or more, more preferably 0.01 mol%, relative to the total molar amount of repeating units constituting the cycloolefin-based polymer. More preferably 1 mol% or more, still more preferably 2 mol% or more, preferably 40 mol% or less, more preferably 35 mol% or less, still more preferably 30 mol% or less, particularly preferably 25 mol% It is below. When the content of the monomeric unit (II) is at least the above lower limit, mechanical properties such as bending resistance, workability, and formability of the film are likely to be enhanced. When the content of the monomeric unit (II) is equal to or less than the above upper limit, it is easy to improve the hygroscopic resistance and heat resistance of the film.

In one embodiment of the present invention, the cycloolefin-based polymer is preferably a cycloolefin-based polymer from the viewpoint of easily improving mechanical properties such as heat resistance, workability, and bending resistance, and moisture absorption resistance, and has the formula ( I) is selected from the group consisting of the cycloolefin-derived monomer unit (I) represented by I) and ethylene, a linear α-olefin having 3 to 20 carbon atoms and an aromatic vinyl compound having 8 to 20 carbon atoms. It is more preferable that the cycloolefin-based polymer contains a monomer unit (II) derived from at least one of the monomer units (I) derived from norbornene and the monomer units (II) derived from ethylene. ), or a styrene-norbornene copolymer containing a monomer unit (I) derived from norbornene and a monomer unit (II) derived from styrene. .

The cycloolefin-based polymer may contain other monomer units (III). Other monomers constituting the monomer unit (III) include, for example, conjugated dienes such as butadiene or isoprene; non-conjugated dienes such as 1,4-pentadiene; acrylic acid; methyl acrylate or acrylic acid; acrylic acid esters such as ethyl; methacrylic acid; methacrylic acid esters such as methyl methacrylate or ethyl methacrylate; and vinyl acetate. Other monomer units (III) can be used singly or in combination of two or more.
Incidentally, the polymer (B) can be used alone or in combination of two or more.

In one embodiment of the present invention, at least one of the glass transition temperature and melting point of the polymer (B) is preferably 100° C. or higher. The Tg of the polymer (B) is preferably 100° C. or higher, more preferably 140° C. or higher, still more preferably 160° C. or higher, even more preferably 180° C. or higher, particularly preferably 200° C. or higher, and particularly preferably 220° C. or higher. , particularly preferably 240° C. or higher, particularly more preferably 260° C. or higher, preferably 500° C. or lower, more preferably 400° C. or lower, and still more preferably 320° C. or lower. Further, when the polymer (B) is a crystalline polymer having a melting point, the melting point of the polymer (B) is preferably 100° C. or higher, more preferably 140° C. or higher, still more preferably 160° C. or higher, still more preferably 180° C. ° C. or higher, particularly preferably 200 ° C. or higher, particularly more preferably 220 ° C. or higher, even more preferably 240 ° C. or higher, most preferably 260 ° C. or higher, preferably 500 ° C. or lower, more preferably 400 ° C. or lower, further preferably is below 350°C. When at least one of the Tg and melting point of the polymer (B) is at least the above lower limit, the CTE of the film is likely to be reduced, and mechanical properties such as wet water resistance, heat resistance and bending resistance are likely to be enhanced. When at least one of the Tg and melting point of the polymer (B) is equal to or less than the above upper limit, the mechanical properties of the film, particularly resistance to repeated bending, are likely to be enhanced. The Tg of the polymer (B) is a softening temperature measured by TMA based on JIS K 7196, and can be measured, for example, by the method described in Examples. The method of adjusting the Tg and melting point of the polymer (B) is not particularly limited, but for example, a method of appropriately adjusting the content of the monomer unit (I), the Mw of the polymer (B), the degree of crystallinity, etc. mentioned. The Tg and melting point of the polymer (B) tend to increase as at least one selected from the group consisting of the content of the monomer unit (I), the Mw of the polymer (B), and the degree of crystallinity increases. The melting point of the polymer (B) can be determined, for example, by using a differential scanning calorimeter (DSC) and measuring the melting peak temperature from the resulting melting curve. Although the DSC is not particularly limited, for example, a DSC manufactured by Hitachi High-Tech Science Co., Ltd. may be used.

In one embodiment of the present invention, the weight average molecular weight of the polymer (B) (hereinafter the weight average molecular weight may be abbreviated as Mw) is preferably 30,000 or more, more preferably 50,000 or more, and even more preferably It is 70,000 or more, particularly preferably 90,000 or more, preferably 2,000,000 or less, more preferably 1,000,000 or less, still more preferably 700,000 or less. When the Mw is at least the above lower limit, the hygroscopic resistance and heat resistance of the film are likely to be enhanced, and the strength is likely to be enhanced. When the Mw is equal to or less than the above upper limit, the hygroscopic resistance, mechanical properties and formability of the film are likely to be improved.

In one embodiment of the present invention, the ratio (Mw/Mn) between the Mw and the number average molecular weight (hereinafter the number average molecular weight may be abbreviated as Mn) of the polymer (B) is preferably 2.0 in terms of polystyrene. 5 or less, more preferably 2.2 or less, still more preferably 2.0 or less, even more preferably 1.95 or less, particularly preferably 1.90 or less, preferably 1.30 or more, more preferably 1.90 or less. It is 50 or more, more preferably 1.60 or more, and particularly preferably 1.65 or more. When the Mw/Mn ratio is at most the above upper limit, the hygroscopic resistance, heat resistance, and mechanical properties of the film are likely to be enhanced, and at the above lower limit or above, the formability is likely to be enhanced. In addition, Mw and Mn can be obtained by performing gel permeation chromatography (hereinafter sometimes abbreviated as GPC) measurement and converting to standard polystyrene, for example, by the method described in Examples.

In one embodiment of the present invention, the refractive index of the polymer (B) is preferably 1.600 or less, more preferably 1.570 or less, still more preferably 1.570 or less, from the viewpoint of easily obtaining a film with a reduced CTE. It is 550 or less, preferably 1.500 or more, more preferably 1.520 or more. The refractive index of the polymer (B) can be measured with a refractometer, for example, by the method described in Examples.

In one embodiment of the present invention, the CTE of polymer (B) is preferably 58 ppm/K or less, more preferably 55 ppm/K or less, even more preferably 50 ppm/K or less, preferably 0 ppm/K or more, more preferably is 0.01 ppm/K or more, more preferably 1 ppm/K or more, and even more preferably 5 ppm/K or more. When the CTE of the polymer (B) is equal to or less than the above upper limit, the CTE of the resulting film is likely to be reduced. In the case of producing a copper-clad laminate by laminating with a copper foil, it is preferable to adjust the CTE of the film to around 20 ppm/K from the viewpoint of preventing peeling of the laminate film. A polymer (B) having an optimum CTE can be selected depending on the CTE of the resin to be mixed. CTE can be measured, for example, by thermomechanical analysis (hereinafter sometimes referred to as TMA), and is determined by the method described in Examples.

In one embodiment of the present invention, when the polymer (B) is particulate, the median diameter of the particulate polymer (B) in the composition of the present invention is preferably 0.01 μm or more, more preferably 0.03 μm. More preferably 0.05 μm or more, preferably 15 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, even more preferably 3 μm or less, particularly preferably 1 μm or less, and particularly preferably 0.8 μm or less , and more preferably 0.5 μm or less. When the median diameter of the particulate polymer (B) in the composition is at least the above lower limit, the dielectric properties of the film formed from the composition are likely to be enhanced, and the film is easily produced. When the median diameter of the particulate polymer (B) in the composition is equal to or less than the above upper limit, the dispersibility of the polymer (B) in the composition and in the film is likely to be increased, and the resulting film has hygroscopic resistance and heat resistance. Easy to improve. Although the method for determining the median diameter of the particulate polymer (B) in the composition is not particularly limited, it can be determined, for example, using a centrifugal sedimentation particle size distribution analyzer or an ultrasonic attenuation particle size distribution analyzer. In the case of forming a composition by adding the resin (A) or the phenolic antioxidant to the particulate polymer (B) dispersion in an amount that does not affect the particle size of the particulate polymer (B). Alternatively, the median diameter of the particulate polymer (B) in the dispersion can be measured in advance and used as the median diameter of the particulate polymer (B) in the composition. In this specification, the median diameter is also referred to as D50, and indicates a value at which the number of particles of the particulate polymer (B) on the side smaller than that value is equal to the number of particles on the larger side. In the present specification, the term "particle size" means the median size and/or average primary particle size of the particulate polymer (B), unless otherwise specified.

In one embodiment of the present invention, the content of the polymer (B) contained in the composition of the present invention is usually 1% by mass or more, preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 10% by mass or more, particularly preferably 20% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass % by mass or less. When the content of the polymer (B) contained in the composition is at least the above lower limit, the formation of aggregates of the polymer (B) is likely to be suppressed, and thus the dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. Further, when the content of the polymer (B) contained in the composition is equal to or less than the above upper limit, film formation is facilitated, which is advantageous from the viewpoint of film production. If the dispersibility of the polymer (B) in the film is high, the uniformity of thermal conductivity and CTE will be high. easier to suppress.

<Method for producing cycloolefin polymer (B)>
The polymer (B) may be a commercially available product, and the production method is not particularly limited. In the presence, at least one selected from the group consisting of monomers forming a cycloolefin-based polymer, such as the cycloolefin represented by formula (I), the ethylene and linear α-olefins having 3 to 20 carbon atoms It is preferably prepared by polymerizing the monomers and optionally said other monomers. Since the transition metal complex (α) represented by the formula (IV) is used in the production of the cycloolefin-based polymer in the present invention, the content of the monomer unit (I) in the cycloolefin-based polymer is significantly increased. It is easy to adjust Tg within the above range.

［式（ＩＶ）中、Ｍは元素の周期律表の第４族の遷移金属元素を表し、
Ｃｐはシクロペンタジエニル骨格を有する基を表し、
Ａは元素の周期律表の第１６族の原子を表し、
Ｔは元素の周期律表の第１４族の原子を表し、
Ｄ^１及びＤ^２は、互いに独立に、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、炭素数１～２０のハロゲン化炭化水素基、炭素数１～２０のアルコキシ基、炭素数６～２０のアリールオキシ基又は炭素数２～２０の２置換アミノ基を表し、それらは同一であってもよく、異なってもよい。
Ｒ^１～Ｒ^６は、互いに独立に、水素原子、ハロゲン原子、炭素数１～２０の炭化水素基、炭素数１～２０のハロゲン化炭化水素基、炭素数１～２０のアルコキシ基、炭素数６～２０のアリールオキシ基、炭素数２～２０の２置換アミノ基又は炭素数１～２０のシリル基を表し、それらは同一であってもよく、異なってもよく、さらにそれらは任意に結合して環を形成してもよい。］

[In formula (IV), M represents a transition metal element in Group 4 of the periodic table of the elements,
Cp represents a group having a cyclopentadienyl skeleton,
A represents an atom of Group 16 of the Periodic Table of the Elements,
T represents an atom of Group 14 of the Periodic Table of the Elements;
D ¹ and D ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number It represents an aryloxy group having 6 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different.
R ¹ to R ⁶ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. represents an aryloxy group having 6 to 20 carbon atoms, a disubstituted amino group having 2 to 20 carbon atoms or a silyl group having 1 to 20 carbon atoms, which may be the same or different, and are optionally bonded may form a ring. ]

M is a transition metal element in Group 4 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989), examples of which include titanium atom, zirconium atom and hafnium atom.

Cp is a group having a cyclopentadienyl skeleton, such as cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl, substituted fluorenyl and the like. Specific examples include a cyclopentadienyl group, a methylcyclopentadienyl group, a tetramethylcyclopentadienyl group, an n-propylcyclopentadienyl group, an n-butylcyclopentadienyl group, and an isobutylcyclopentadienyl group. , phenylcyclopentadienyl group, indenyl group, methylindenyl group, n-propylindenyl group, n-butylindenyl group, isobutylindenyl group, phenylindenyl group, fluorenyl group, methylfluorenyl group, n -Propylfluorenyl group, phenylfluorenyl group, dimethylfluorenyl group and the like. Among these, cyclopentadienyl group, methylcyclopentadienyl group, tetramethylcyclopentadienyl group, n-butylcyclopentadienyl group, isobutylcyclopentadienyl group, indenyl group and methylindenyl group are preferred. or a fluorenyl group.

A is an atom of group 16 of the periodic table of elements, and examples thereof include an oxygen atom and a sulfur atom. Among these, an oxygen atom is preferred.

T is an atom of group 14 of the periodic table of elements, and examples thereof include carbon, silicon and germanium atoms. Among these, a carbon atom or a silicon atom is preferred.

D ¹ and D ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or It is an aryloxy group having 6 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different. Among these, a halogen atom is preferable.

Specific examples of D ¹ and D ² being halogen atoms include fluorine, chlorine, bromine and iodine atoms.

When D ¹ and D ² are hydrocarbon groups, the number of carbon atoms is preferably 1-10. Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group and n-hexyl. group, n-octyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, naphthyl group, benzyl group and the like.

Specific examples of D ¹ and D ² being halogenated hydrocarbon groups include fluoromethyl group, difluoromethyl group, 1-fluoroethyl group, 1,1-difluoroethyl group, 1,2-difluoroethyl group, 1,1,2-trifluoroethyl group, tetrafluoroethyl group, chloromethyl group, dichloromethyl group, 1-chloroethyl group, 1,1-dichloroethyl group, 1,2-dichloroethyl group, 1,1,2 -trichloroethyl group, 1,1,2,2-tetrachloroethyl group, bromomethyl group, dibromomethyl group, 1-bromoethyl group, 1,1-dibromoethyl group, 1,2-dibromoethyl group, 1,1,2 -tribromoethyl group, 1,1,2,2-tetrabromoethyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluoro phenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,3,4,5-tetrafluorophenyl group, 2,3,4,6-tetrafluorophenyl group, pentafluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2, 3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 2,3,4-trichlorophenyl group, 2,3,5-trichlorophenyl group, 2,3, 6-trichlorophenyl group, 2,3,4,5-tetrachlorophenyl group, 2,3,4,6-tetrachlorophenyl group, pentachlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,3-dibromophenyl group, 2,4-dibromophenyl group, 2,5-dibromophenyl group, 2,6-dibromophenyl group, 2,3,4-tribromophenyl group, 2,3,5 -tribromophenyl group, 2,3,6-tribromophenyl group, 2,3,4,5-tetrabromophenyl group, 2,3,4,6-tetrabromophenyl group, pentabromophenyl group and the like. be done.

Specific examples of D ¹ and D ² being alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n- pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group and the like.

Specific examples of D ¹ and D ² being aryloxy groups include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy and naphthyloxy groups.

When D ¹ and D ² are disubstituted amino groups, the disubstituted amino group is an amino group in which two substituents are bonded. Specific examples thereof include dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, diisobutylamino group, di-sec-butylamino group and di-tert-butyl. Amino group, di-n-hexylamino group, di-n-octylamino group, diphenylamino group and the like.

R ¹ to R ⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or represents an aryloxy group having 6 to 20 carbon atoms, a disubstituted amino group having 2 to 20 carbon atoms or a silyl group having 1 to 20 carbon atoms, which may be the same or different, and are optionally They may be combined to form a ring. Among these, hydrocarbon groups having 1 to 20 carbon atoms are preferred.

Specific examples of R ¹ to R ⁶ being halogen atoms include fluorine, chlorine, bromine and iodine atoms.

When R ¹ to R ⁶ are hydrocarbon groups, they preferably have 1 to 10 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group and n-hexyl group. , n-octyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group , 2,6-dimethylphenyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, pentamethylphenyl group and the like.

Specific examples where R ¹ to R ⁶ are a halogen atom, a halogenated hydrocarbon group, an alkoxy group, an aryloxy group, or a disubstituted amino group include D ¹ and D ² being a halogen atom or a halogenated hydrocarbon group. , an alkoxy group, an aryloxy group, and a disubstituted amino group include those exemplified above.

Specific examples when R ¹ to R ⁶ are silyl groups include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, triisobutylsilyl group, tri -sec-butylsilyl group, tri-tert-butylsilyl group, triphenylsilyl group and the like.

Specific examples of such compounds represented by formula (IV) include isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclo pentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(dimethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropyl Lidene (trimethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) ) titanium dichloride, isopropylidene (n-propylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (n-butylcyclopentadienyl) (3-tert-butyl -5-methyl-2-phenoxy) titanium dichloride, isopropylidene (isobutylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (phenylcyclopentadienyl) (3 -tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3- tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (dimethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylcyclopentadienyl) (3-tert-butyl- 2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (n-propylcyclopentadienyl) (3-tert-butyl-2 -phenoxy) titanium dichloride, isopropylidene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (isobutylcyclopentene) tadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(phenylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(cyclopentadienyl)(2- phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (dimethylcyclopentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (trimethylcyclopentadienyl) (2 -phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (n-propylcyclopentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (n-butylcyclo pentadienyl)(2-phenoxy)titanium dichloride, isopropylidene(isobutylcyclopentadienyl)(2-phenoxy)titanium dichloride, isopropylidene(phenylcyclopentadienyl)(2-phenoxy)titanium dichloride and the like.

Further, compounds in which titanium in the above specific examples is changed to zirconium or hafnium, and compounds in which isopropylidene is changed to dimethylsilylene, diphenylsilylene, and methylene can be exemplified in the same manner. Furthermore, compounds in which dichloride is changed to dibromide, diiodide, dimethyl, dibenzyl, dimethoxide and diethoxide can be similarly exemplified.

The transition metal complex (α) represented by formula (IV) above can be used as a catalyst for producing the polymer (B) according to one embodiment of the present invention in combination with various cocatalysts. A co-catalyst is a compound that interacts with the transition metal complex (α) to generate polymerization active species for cyclic olefins and alkenyl aromatic hydrocarbons. Examples thereof include organoaluminum compounds (β) and/or boron compounds (γ) represented by any of the following formulas (γ1) to (γ3). The structure of the polymerization active species generated by this is not clear.

Formula (γ1) BQ ¹ Q ² Q ³
Formula (γ2) J ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻
Formula (γ3) (L−H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻
[In the formulas (γ1) to (γ3), B represents a boron atom in a trivalent state,
Q ¹ to Q ⁴ each independently represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or a silyl group having 1 to 20 carbon atoms. represents a 20 alkoxy group or a disubstituted amino group having 2 to 20 carbon atoms,
J ⁺ represents an inorganic or organic cation,
L represents a neutral Lewis base and (LH) ⁺ represents a Bronsted acid. ]

A known organoaluminum compound can be used as the organoaluminum compound (β). Specific examples include an organoaluminum compound represented by formula (β1), a cyclic aluminoxane having a structure represented by formula (β2), and a linear aluminoxane having a structure represented by formula (β3). These may be used alone or in combination of two or more.

Formula (β1) E ¹ _a AlZ _3-a
Formula (β2) {-Al(E ² )-O-} _b
Formula (β3) E ³ {-Al(E ³ )-O-} _c AlE ³ ₂
[In formulas (β1) to (β3), E ¹ , E ² and E ³ each independently represent a hydrocarbon group having 1 to 8 carbon atoms, all E ¹ , all E ² and all E ³ may be the same or different, Z represents hydrogen or halogen, all Z may be the same or different, a represents an integer of 0 to 3 , b represents an integer of 2 or more, and c represents an integer of 1 or more. ]

Specific examples of formula (β1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride; Dialkylaluminum chlorides such as dihexylaluminum chloride; Alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride , and dialkylaluminum hydride such as dihexylaluminum hydride. Among these, trialkylaluminum is preferred, and triethylaluminum or triisobutylaluminum is more preferred.

Specific examples of E ² and E ³ in formula (β2) and formula (β3) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group and neopentyl. and alkyl groups such as Among these, a methyl group or an isobutyl group is preferred. b is an integer of 2 or more, preferably an integer of 2-40. c is an integer of 1 or more, preferably an integer of 1-40.

The aluminoxanes mentioned above are made in a variety of ways. The method is not particularly limited, and it may be produced according to a known method. For example, a method in which a solution of a trialkylaluminum such as trimethylaluminum dissolved in an appropriate organic solvent such as benzene or an aliphatic hydrocarbon is brought into contact with water; A method of contacting with a metal salt containing water of crystallization, such as copper sulfate hydrate, can be exemplified.

As the boron compound (γ), any one of the boron compounds represented by formula (γ1), formula (γ2), or formula (γ3) can be used.

In formula (γ1), B represents a boron atom in a trivalent state, and Q ¹ to Q ³ each independently represent a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms. represents a halogenated hydrocarbon group, a substituted silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different; good too. Q ¹ to Q ³ are each independently preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of the boron compound represented by formula (γ1) include tris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5- tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, phenylbis(pentafluorophenyl)borane and the like, preferably tris (Pentafluorophenyl)borane can be mentioned.

In formula (γ2), B represents a trivalent boron atom, and Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in formula (γ1) above. Also, J ⁺ represents an inorganic or organic cation.

Inorganic cations in J ⁺ include ferrocenium cations, alkyl-substituted ferrocenium cations, silver cations, and the like.
Examples of organic cations for J ⁺ include triphenylmethyl cations.
(BQ ¹ Q ² Q ³ Q ⁴ ) ^- includes tetrakis(pentafluorophenyl)borate anion, tetrakis(2,3,5,6-tetrafluorophenyl)borate anion, tetrakis(2,3,4,5- tetrafluorophenyl)borate anion, tetrakis(3,4,5-trifluorophenyl)borate anion, tetrakis(2,2,4-trifluorophenyl)borate anion, phenylbis(pentafluorophenyl)borate anion, tetrakis(3 ,5-bistrifluoromethylphenyl)borate anion and the like.

Specific combinations thereof include ferroceniumtetrakis(pentafluorophenyl)borate, 1,1'-dimethylferroceniumtetrakis(pentafluorophenyl)borate, silver tetrakis(pentafluorophenyl)borate, triphenylmethyltetrakis (Pentafluorophenyl)borate, triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)borate and the like, preferably triphenylmethyltetrakis(pentafluorophenyl)borate.

In formula (γ3), B represents trivalent boron, and Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in formula (γ1) above. Also, L represents a neutral Lewis base, and (LH) ⁺ represents a Bronsted acid.

In formula (γ3), Bronsted acid (LH) ⁺ includes trialkyl-substituted ammonium cations, N,N-dialkylanilinium cations, dialkylammonium cations, and triarylphosphonium cations.
(BQ ¹ Q ² Q ³ Q ⁴ ) ^- includes the same groups as those described above.

Specific combinations thereof include triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl) ) ammonium tetrakis(3,5-bistrifluoromethylphenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-2 , 4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bistrifluoromethylphenyl)borate, di-iso-propylammonium tetrakis(pentafluorophenyl)borate , dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, tri(dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, etc. are mentioned. Among these, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are preferred.

As the co-catalyst, it is preferable to use the organoaluminum compound (β) and the compound (γ) in combination.

The transition metal complex (α), organoaluminum compound (β) and/or compound (γ) represented by formula (IV) can be used in any order during polymerization, but any of these compounds You may use the reactant obtained by contacting previously the combination of.

The molar ratio of promoter/transition metal complex (α) is preferably 0.01 to 10,000, more preferably 0.5 to 2,000. When the catalyst component is used in solution, the concentration of the transition metal complex (α) is preferably 0.0001-5 mmol/L, more preferably 0.001-1 mmol/L. The amount of catalyst component used is preferably 0.00001 to 1 mol %, more preferably 0.0001 to 0.1 mol %, based on the total amount of all monomers used.

The polymerization method of the polymer (B) according to one embodiment of the present invention is not particularly limited. Any method such as a method or a slurry polymerization method can be adopted.

When using a solvent, various solvents can be used provided that they do not deactivate the catalyst. Examples of such solvents include hydrocarbon solvents such as benzene, toluene, pentane, hexane, heptane, and cyclohexane; Examples thereof include halogenated hydrocarbon solvents such as dichloromethane and ethylene dichloride.

When a solvent is used, the ethylene partial pressure in the system during polymerization is, for example, 50 to 400 kPa, preferably 50 to 300 kPa, and the hydrogen partial pressure is preferably 0 to 100 kPa. When ethylene and hydrogen are introduced into the system, it is preferable to pressurize with the partial pressure of hydrogen and then pressurize with the partial pressure of ethylene. Alternatively, toluene may be added after charging the solution of the cycloolefin represented by the formula (I) into the polymerization reactor.

The polymerization temperature is preferably 50°C or higher, more preferably 50 to 150°C, still more preferably 50 to 100°C. A chain transfer agent such as hydrogen may be added to adjust the molecular weight of the polymer.

<Resin (A)>
The resin (A) is a polymer different from the polymer (B) and has a distance between HSP values of 6.0 or more from the polymer (B). If the distance between the HSP values of the resin (A) and the polymer (B) is within the above range, the type of the resin (A) may differ from that of the polymer (B), such as the type and content of the monomer units constituting the resin. Different cycloolefin resins may be used.

Resin (A) is not particularly limited, and examples include diallyl phthalate resin, silicone resin, phenol resin, unsaturated polyester resin, polyurethane resin, melamine resin, urea resin, xylene resin, furan resin, aniline resin, and acetone-formaldehyde resin. , alkyd resins, maleimide resins, maleimide-cyanate ester resins, cyanate ester resins, benzoxazine resins, polybenzimidazole resins, and thermosetting resins selected from polycarbodiimide resins; olefin resins; acrylic resins; styrene-based resins; rubber-based resins; fluorine-based resins; vinyl-based resins; general-purpose engineering plastics; super engineering plastics; Among these, at least one selected from the group consisting of polyimide resins, liquid crystal polymers, fluorine resins, aromatic polyether resins, and maleimide resins, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the film. It is preferably a polyimide resin, more preferably a polyimide resin and/or a liquid crystal polymer, and even more preferably a polyimide resin. Resin (A) can be used alone or in combination of two or more.

The Tg of the resin (A) is preferably 100° C. or higher, more preferably 150° C. or higher, still more preferably 200° C. or higher, still more preferably 220° C. or higher, particularly preferably 300° C. or higher, and particularly preferably 350° C. or higher. Yes, preferably 550° C. or less. When the Tg of the resin (A) is at least the above lower limit, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film. When the Tg of the resin (A) is equal to or less than the above upper limit, it is easy to improve the mechanical properties. The Tg of the resin (A) can be obtained, for example, by dynamic viscoelasticity measurement (hereinafter sometimes abbreviated as DMA measurement), and can be measured by the method described in Examples.

Mw of the resin (A) is preferably 50,000 or more, more preferably 100,000 or more, more preferably 150,000 or more, still more preferably 200,000 or more, and still more preferably 250,000 in terms of polystyrene. or more, particularly preferably 300,000 or more, preferably 1,000,000 or less, more preferably 800,000 or less, still more preferably 700,000 or less, even more preferably 500,000 or less, particularly preferably 450 , 000 or less. When the Mw of the resin (A) is at least the above lower limit, the hygroscopic resistance, heat resistance and mechanical properties of the resulting film are likely to be improved. When the Mw of the resin (A) is equal to or less than the above upper limit, the moldability is likely to be improved. The Mw of the resin (A) can be determined by, for example, GPC measurement and standard polystyrene conversion, and can be determined, for example, by the method described in Examples.

A polyimide resin suitable as the resin (A) includes a resin containing a repeating structural unit containing an imide group (hereinafter sometimes referred to as a polyimide resin), and a repeating structural unit containing both an imide group and an amide group. It is meant to include resins (hereinafter sometimes referred to as polyamide-imide resins) and precursors prior to production of polyimide-based resins by imidization. The precursor prior to manufacturing the polyimide resin is polyamic acid. In addition, in this specification, a "repeating structural unit" may be called a "structural unit." In addition, a "constituent unit derived from" may be simply referred to as a "unit", and for example, a constituent unit derived from a compound may be referred to as a compound unit.

［式（１）中、Ｘは２価の有機基を表し、Ｙは４価の有機基を表し、＊は結合手を表す］
で表される構成単位を有するポリイミド系樹脂であることが好ましい。このようなポリイミド系樹脂であると、組成物及びフィルム中のポリマー（Ｂ）の分散性を高めやすく、得られるフィルムの耐吸湿性及び耐熱性を向上しやすい。 In a preferred embodiment of the invention, resin (A) has the formula (1):

[In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, and * represents a bond]
It is preferably a polyimide resin having a structural unit represented by. With such a polyimide resin, the dispersibility of the polymer (B) in the composition and film can be easily improved, and the hygroscopic resistance and heat resistance of the resulting film can be easily improved.

Each X in formula (1) independently represents a divalent organic group, preferably a divalent organic group having 2 to 100 carbon atoms. Examples of the divalent organic group include a divalent aromatic group and a divalent aliphatic group. Examples of the divalent aliphatic group include a divalent acyclic aliphatic group and a divalent Cycloaliphatic groups are included. Among these, from the viewpoint of easily suppressing the formation of aggregates of the polymer (B) and easily increasing the dispersibility of the polymer (B), and from the viewpoint of easily improving the hygroscopic resistance and heat resistance of the resulting film, 2 Preferred are divalent cycloaliphatic groups and divalent aromatic groups, more preferred are divalent aromatic groups. In the divalent organic group, hydrogen atoms in the organic group may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group or a halogenated hydrocarbon group, in which case the number of carbon atoms in these groups is preferably 1 ~8. In this specification, a divalent aromatic group is a divalent organic group having an aromatic group, and may contain an aliphatic group or other substituents in part of its structure. A divalent aliphatic group is a divalent organic group having an aliphatic group, and may contain other substituents in part of its structure, but does not contain an aromatic group.

In one embodiment of the present invention, the polyimide resin may contain multiple types of X, and the multiple types of X may be the same or different. X in formula (1) includes, for example, groups (structures) represented by formulas (2) to (8); hydrogen atoms in groups represented by formulas (5) to (8) are methyl groups. , ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, fluoro group, chloro group or trifluoromethyl group.

［式（２）及び式（３）中、Ｒ^ａ及びＲ^ｂは、互いに独立に、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、又は炭素数６～１２のアリール基を表し、Ｒ^ａ及びＲ^ｂに含まれる水素原子は、互いに独立に、ハロゲン原子で置換されていてもよく、Ｗは、互いに独立に、単結合、－Ｏ－、－ＣＨ_２－、－ＣＨ_２－ＣＨ_２－、－ＣＨ（ＣＨ_３）－、－Ｃ（ＣＨ_３）_２－、－Ｃ（ＣＦ_３）_２－、－ＣＯＯ－、－ＯＯＣ－、－ＳＯ_２－、－Ｓ－、－ＣＯ－又は－Ｎ（Ｒ^ｃ）－を表し、Ｒ^ｃは水素原子、ハロゲン原子で置換されていてもよい炭素数１～１２の一価の炭化水素基を表し、ｎは０～４の整数であり、ｔは０～４の整数であり、ｕは０～４の整数であり、＊は結合手を表す。
式（４）中、環Ａは炭素数３～８のシクロアルカンを表し、Ｒ^ｄは炭素数１～２０のアルキル基を表し、ｒは０以上であって（環Ａの炭素数－２）以下の整数を表し、Ｓ１及びＳ２は、互いに独立に、０～２０の整数を表し、＊は結合手を表す。］

[In the formulas (2) and (3), R ^a and R ^b are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a represents an aryl group, hydrogen atoms contained in R ^a and R ^b may be independently substituted with halogen atoms, W is independently a single bond, —O—, —CH ₂ — , -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -COO-, -OOC-, -SO ₂ -, -S -, -CO- or -N(R ^c )-, where R ^c represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom, n is 0 to is an integer of 4, t is an integer of 0 to 4, u is an integer of 0 to 4, and * represents a bond.
In formula (4), ring A represents a cycloalkane having 3 to 8 carbon atoms, R ^d represents an alkyl group having 1 to 20 carbon atoms, r is 0 or more (the number of carbon atoms in ring A is -2) The following integers are represented, S1 and S2 independently represent integers from 0 to 20, and * represents a bond. ]

Other examples of X in formula (1) include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, propylene group, 1,2-butanediyl group and 1,3-butanediyl group. , 1,12-dodecanediyl group, 2-methyl-1,2-propanediyl group, 2-methyl-1,3-propanediyl group and other linear or branched alkylene groups such as divalent acyclic Aliphatic groups are included. Hydrogen atoms in the divalent acyclic aliphatic group may be substituted with halogen atoms, and carbon atoms may be substituted with heteroatoms such as oxygen atoms, nitrogen atoms, and the like.

Among these, from the viewpoint of easily suppressing the formation of aggregates of the polymer (B) and easily increasing the dispersibility of the polymer (B), and from the viewpoint of easily achieving high moisture absorption resistance and heat resistance of the resulting film, The polyimide resin in the present invention preferably contains a structure represented by the formula (2) and / or a structure represented by the formula (3) as X in the formula (1), and represented by the formula (2) It is more preferred to include a structure that is

In formulas (2) and (3), the bonds of each benzene ring or cyclohexane ring are ortho-, meta- or para-positions, or α-, β- or γ-positions relative to -W-. It may be bonded to any position, and from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film, it is preferably at the meta-position or para-position, or at the β-position or at the γ-position, more preferably at the para-position or at the γ-position. can be bound to R ^a and R ^b each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2 -methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl group and the like. Examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy and cyclohexyloxy groups. mentioned. Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, tolyl group, xylyl group, naphthyl group and biphenyl group. Hydrogen atoms contained in R ^a and R ^b may be independently substituted with halogen atoms, and examples of the halogen atoms include fluorine, chlorine, bromine and iodine atoms. Among these, R ^a and R ^b are each independently an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group having 1 to 6 carbon atoms, from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film. group, more preferably an alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group having 1 to 3 carbon atoms, further preferably a methyl group or a trifluoromethyl group.

In formulas (2) and (3), t and u are independently integers of 0 to 4, and from the viewpoint of easily improving the moisture absorption resistance and heat resistance of the resulting film, preferably 0 to 2. , more preferably 0 or 1.

In formulas (2) and (3), W is independently a single bond, —O—, —CH ₂ —, —CH ₂ —CH ₂ —, —CH(CH ₃ )—, —C(CH ₃ ) represents ₂ -, -C(CF ₃ ) ₂ -, -COO-, -OOC-, -SO ₂ -, -S-, -CO- or -N(R ^c )-, and Single bonds, —O—, —CH ₂ —, —C(CH ₃ ) ₂ —, and —C(CF ₃ ) ₂ are preferred from the viewpoint of easily improving hygroscopicity, heat resistance and mechanical properties, especially bending resistance. -, -COO-, -OOC- or -CO-, more preferably a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ - . R ^c represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- pentyl group, 2-methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, n-nonyl group and n-decyl group etc., which may be substituted with a halogen atom. Halogen atoms include those mentioned above.

In formulas (2) and (3), n is an integer of 0 to 4, which facilitates increasing the dispersibility of the polymer (B) in the composition and film, and improves the moisture absorption resistance and heat resistance of the resulting film. It is preferably an integer of 0 to 3, more preferably 1 or 2, from the viewpoint of easy improvement. When n is 2 or more, a plurality of W, R ^a , and t may be the same or different, and the position of the bond of each benzene ring relative to -W- is also the same. may be different.

When the polyimide resin in the present invention contains both the structure represented by the formula (2) and the structure represented by the formula (3) as X in the formula (1), W in the formula (2), n , R ^a , R ^b , t and u may be independently the same as or different from W, n, R ^a , R ^b , t and u in formula (3).

In formula (4), ring A represents a cycloalkane having 3 to 8 carbon atoms. Cycloalkanes include, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane, preferably cycloalkanes having 4 to 6 carbon atoms. In ring A, each bond may or may not be adjacent to each other. For example, when ring A is cyclohexane, the two bonds may have a positional relationship of α-position, β-position or γ-position, preferably β-position or γ-position.

R ^d in formula (4) represents an alkyl group having 1 to 20 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include those exemplified above as the hydrocarbon group having 1 to 20 carbon atoms for R ⁷ to R ¹⁸ , preferably an alkyl group having 1 to 10 carbon atoms. r in formula (4) represents an integer of 0 or more and (the number of carbon atoms in ring A - 2) or less. r is 0 or more, preferably 4 or less. S1 and S2 in formula (4) each independently represent an integer of 0 to 20. S1 and S2 are each independently preferably 0 or more, more preferably 2 or more, and preferably 15 or less.

Specific examples of structures represented by formulas (2) to (4) include structures represented by formula (4') and formulas (9) to (30). In these formulas, * represents a bond.

In a preferred embodiment of the present invention, when X in formula (1) includes a structure represented by formula (2) and/or formula (3), X in formula (1) is represented by formula (2) and/or the proportion of the structural unit represented by formula (3) is preferably 30 mol% or more, more preferably 50 mol% or more, relative to the total molar amount of the structural units represented by formula (1), It is more preferably 70 mol % or more, particularly preferably 90 mol % or more, and preferably 100 mol % or less. When the proportion of structural units represented by formula (2) and/or formula (3) for X in formula (1) is within the above range, the formation of aggregates of the polymer (B) is easily suppressed, and the polymer It is easy to improve the dispersibility of (B). In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. The proportion of structural units in which Y in formula (1) is represented by formula (2) and/or formula (3) can be measured using, for example, ¹ H-NMR, or calculated from the feed ratio of raw materials. You can also

In formula (1), Y independently represents a tetravalent organic group, preferably a tetravalent organic group having 4 to 40 carbon atoms, more preferably a tetravalent organic group having 4 to 40 carbon atoms and having a cyclic structure. represents a valent organic group. Cyclic structures include alicyclic, aromatic and heterocyclic structures. A hydrogen atom in the organic group may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group, or a halogenated hydrocarbon group. In this case, the number of carbon atoms in these groups is preferably 1 to 8. is. The polyimide resin in the present invention may contain multiple types of Y, and the multiple types of Y may be the same or different. Y is a group (structure) represented by formulas (31) to (38); hydrogen atoms in the groups represented by formulas (34) to (38) are methyl group, ethyl group, n-propyl a group substituted with a group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, fluoro group, chloro group or trifluoromethyl group; tetravalent C1-8 chain formula A hydrocarbon group etc. are mentioned.

［式（３１）～式（３３）中、Ｒ^１９～Ｒ^２６は、互いに独立に、水素原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基又は炭素数６～１２のアリール基を表し、Ｒ^１９～Ｒ^２６に含まれる水素原子は、互いに独立に、ハロゲン原子で置換されていてもよく、
Ｖ^１及びＶ^２は、互いに独立に、単結合、－Ｏ－、－ＣＨ_２－、－ＣＨ_２－ＣＨ_２－、－ＣＨ（ＣＨ_３）－、－Ｃ（ＣＨ_３）_２－、－Ｃ（ＣＦ_３）_２－、－ＣＯＯ－、－ＯＯＣ－、－ＳＯ_２－、－Ｓ－、－ＣＯ－、－Ｎ（Ｒ^ｊ）－、式（ａ）又は式（ｂ）

（式（ａ）中、Ｒ^２７～Ｒ^３０は、互いに独立に、水素原子又は炭素数１～６のアルキル基を表し、Ｚは単結合、－Ｃ（ＣＨ_３）_２－又は－Ｃ（ＣＦ_３）_２－を表し、ｉは１～３の整数であり、＊は結合手を表す）を表し、Ｒ^ｊは、水素原子、又はハロゲン原子で置換されていてもよい炭素数１～１２の一価の炭化水素基を表し、ｅ及びｄは、互いに独立に、０～３の整数を表し（但し、ｅ＋ｄは０ではない）、ｆは１～３の整数を表し、ｇ及びｈは、互いに独立に、０～４の整数を表し、＊は結合手を表す］

[In the formulas (31) to (33), R ¹⁹ to R ²⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a representing an aryl group, hydrogen atoms contained in R ¹⁹ to R ²⁶ may be independently substituted with halogen atoms,
V ¹ and V ² are each independently a single bond, —O—, —CH ₂ —, —CH ₂ —CH ₂ —, —CH(CH ₃ )—, —C(CH ₃ ) ₂ —, —C (CF ₃ ) ₂ -, -COO-, -OOC-, -SO ₂ -, -S-, -CO-, -N(R ^j )-, formula (a) or formula (b)

(In formula (a), R ²⁷ to R ³⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z is a single bond, —C(CH ₃ ) ₂ — or —C(CF ₃ ) represents _2- , i is an integer of 1 to 3, * represents a bond), R ^j is a hydrogen atom, or a represents a monovalent hydrocarbon group, e and d independently represent an integer of 0 to 3 (provided that e + d is not 0), f represents an integer of 1 to 3, g and h are independently of each other, represents an integer of 0 to 4, * represents a bond]

Among these, from the viewpoint of easily improving the dispersibility of the polymer (B) in the composition and film and easily improving the hygroscopic resistance and heat resistance of the resulting film, the polyimide resin in the present invention has the formula (1) Y in the above preferably contains at least one structure selected from the group consisting of a structure represented by formula (31), a structure represented by formula (32), or a structure represented by formula (33) , more preferably a structure represented by formula (31).

In formulas (31) to (33), R ¹⁹ to R ²⁶ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. represents a group. The alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms are respectively the alkyl group having 1 to 6 carbon atoms and the carbon Examples of the alkoxy group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms are exemplified above. The hydrogen atoms contained in R ¹⁹ to R ²⁶ may be independently substituted with halogen atoms, and the halogen atoms include those exemplified above. Among these, from the viewpoint of easily increasing the dispersibility of the polymer (B) in the composition and film and easily improving the moisture absorption resistance and heat resistance of the resulting film, R ¹⁹ to R ²⁶ are each independently hydrogen. An atom or an alkyl group having 1 to 6 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom is even more preferred.

In formula (31), V ¹ and V ² are each independently a single bond, —O—, —CH ₂ —, —CH ₂ —CH ₂ —, —CH(CH ₃ )—, —C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -COO-, -OOC-, -SO ₂ -, -S-, -CO-, -N(R ^j )-, formula (a) or formula (b ), preferably a single bond, —O—, —CH ₂ from the viewpoint of easily increasing the dispersibility of the polymer (B) in the composition and film and easily improving the moisture absorption resistance and heat resistance of the resulting film. represents -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -COO-, -OOC- or -CO-, more preferably a single bond, -COO-, -O-, -C represents (CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -; R ^j represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include those exemplified above.

In formula (31), e and d independently represent an integer of 0 to 3, which facilitates increasing the dispersibility of the polymer (B) in the composition and film, and the resulting film's hygroscopic resistance and heat resistance is preferably 0 or 1, more preferably e+d=1, and e and d are preferably 3. Note that when e in formula (31) is 0, it indicates that formula (31) does not have -V ¹ - (two benzene rings are not bonded at -V ¹ -), and d is 0, it indicates that formula (31) does not have -V ² - (the two benzene rings are not linked at -V ² -).

In formula (32), f represents an integer of 1 to 3, and from the viewpoint of easily improving the dispersibility of the polymer (B) in the composition and film and improving the hygroscopic resistance and heat resistance of the resulting film, It is preferably 1 or 2, more preferably 1. When f is 2, a structure in which R ²³ and R ²⁴ are bonded to a naphthalene ring is shown, and when f is 3, a structure in which R ²³ and R ²⁴ are bonded to an anthracene ring is shown.

In formula (33), g and h independently represent an integer of 0 to 4, which facilitates increasing the dispersibility of the polymer (B) in the composition and film, and the resulting film hygroscopic resistance and heat resistance is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably g + h = an integer of 0 to 2.

In formula (a), R ²⁷ to R ³⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include those exemplified above as the alkyl group having 1 to 6 carbon atoms in the formulas (2) and (3). Among these, from the viewpoint of easily increasing the dispersibility of the polymer (B) in the composition and film and easily improving the moisture absorption resistance and heat resistance of the resulting film, R ²⁷ to R ³⁰ are each independently hydrogen. An atom or an alkyl group having 1 to 3 carbon atoms is more preferred, a hydrogen atom or a methyl group is even more preferred, and a hydrogen atom is even more preferred.

In formula (a), Z represents a single bond, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -. When Z has such a structure, the dispersibility of the polymer (B) in the composition and film can be easily improved, and the hygroscopic resistance and heat resistance of the obtained film can be easily improved. i represents an integer of 1 to 3, preferably 1 or 2 from the viewpoint of easily improving the dispersibility of the polymer (B) in the composition and the film and easily improving the moisture absorption resistance and heat resistance of the resulting film. be. When i is 2 or more, a plurality of Zs and R ²⁷ to R ³⁰ may be the same or different.

Specific examples of structures represented by formulas (31) to (33) include structures represented by formulas (39) to (51). In these formulas, * represents a bond.

In one embodiment of the present invention, when Y in formula (1) contains at least one selected from the group consisting of structures represented by formulas (31) to (33), in formula (1) Y is represented by at least one selected from the group consisting of structures represented by formulas (31) to (33). The amount is preferably 30 mol % or more, more preferably 50 mol % or more, still more preferably 70 mol % or more, particularly preferably 90 mol % or more, and preferably 100 mol % or less. Y in formula (1) is selected from the group consisting of structures represented by formulas (31) to (33). It is easy to improve the dispersibility of the polymer (B) inside and in the film, and it is easy to improve the moisture absorption resistance and heat resistance of the obtained film. Y in formula ( ¹ ) is represented by at least one selected from the group consisting of structures represented by formulas (31) to (33). It can be measured or calculated from the feed ratio of raw materials.

Polyimide resin in the present invention, in addition to the structural unit represented by the formula (1), the structural unit represented by the formula (52), the structural unit represented by the formula (53), and the formula (54) It may contain at least one selected from the group consisting of the structural units represented.

［式（５２）及び式（５３）中、Ｙ^１は４価の有機基を表し、
Ｙ^２は３価の有機基を表し、
Ｘ^１及びＸ^２は、互いに独立に、２価の有機基を表し、
＊は結合手を表す。
式（５４）中、Ｇ及びＸは、互いに独立に、２価の有機基を表し、
＊は結合手を表す。］

[In the formulas (52) and (53), Y ¹ represents a tetravalent organic group,
Y ² represents a trivalent organic group,
X ¹ and X ² independently represent a divalent organic group,
* represents a bond.
In formula (54), G and X independently represent a divalent organic group,
* represents a bond. ]

In a preferred embodiment of the present invention, in formulas (52) and (53), Y ¹ has the same meaning as Y in formula (1), and X ¹ and X ² have the same meaning as X in formula (1). be. Y ² in formula (53) is preferably a group in which one of the bonds of Y in formula (1) is replaced with a hydrogen atom. Y ² is a group in which any one of the bonds (structures) of the groups (structures) represented by formulas (31) to (38) is replaced with a hydrogen atom; a trivalent chain hydrocarbon having 1 to 8 carbon atoms and the like. In one embodiment of the present invention, the polyimide resin may contain multiple types of Y ¹ or Y ² , and the multiple types of Y ¹ or Y ² may be the same or different.

In formula (54), each G is independently a divalent organic group, preferably substituted with a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. may be substituted with a divalent organic group having 2 to 100 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms or a fluorine-substituted hydrocarbon group having 1 to 8 carbon atoms. It represents a divalent organic group having 2 to 100 carbon atoms and having a cyclic structure. Cyclic structures include alicyclic, aromatic and heterocyclic structures. Examples of the organic group for G include, for example, a group in which two non-adjacent bonds of the groups represented by formulas (31) to (38) are replaced with hydrogen atoms, and a divalent chain carbonization group having 6 or less carbon atoms. Examples thereof include hydrogen groups, and preferably groups in which two non-adjacent bonds of the groups represented by formulas (39) to (51) are replaced with hydrogen atoms.
X in formula (54) is synonymous with X in formula (1), and when the polyimide resin contains a structural unit represented by formula (1) and a structural unit represented by formula (54), each X in the structural units may be the same or different. In one embodiment of the present invention, the polyimide resin may contain multiple types of X or G, and the multiple types of X or G may be the same or different.

In one embodiment of the present invention, the polyimide resin is a structural unit represented by formula (1), and optionally a structural unit represented by formula (52), a structural unit represented by formula (53) and It consists of at least one structural unit selected from the structural units represented by formula (54). Further, from the viewpoint of easily improving the dispersibility of the polymer (B) in the composition and the film and easily improving the hygroscopic resistance and heat resistance of the resulting film, the polyimide resin is represented by the formula (1) The ratio of the structural units is the total structural units contained in the polyimide resin, for example, the structural units represented by the formula (1), and optionally the structural units represented by the formula (52), represented by the formula (53). is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more. In addition, in polyimide resin, the upper limit of the ratio of the structural unit represented by Formula (1) is 100 mol% or less. The above ratio can be measured, for example, using ¹ H-NMR, or can be calculated from the charging ratio of raw materials. Further, the polyimide resin in the present invention is preferably a polyimide resin from the viewpoint of easily increasing the dispersibility of the polymer (B) in the composition and the film and easily improving the hygroscopic resistance and heat resistance of the resulting film. .

In one embodiment of the present invention, the polyimide resin in the present invention may contain a halogen atom, preferably a fluorine atom, which can be introduced by, for example, the above halogen-containing atom substituent. When the polyimide resin contains a halogen atom, preferably a fluorine atom, it is easy to increase the dispersibility of the polymer (B) in the composition and the film, and the resulting film is easy to improve the hygroscopic resistance and heat resistance. , easy to improve the optical properties. Preferred fluorine-containing substituents for allowing the polyimide resin to contain fluorine atoms include, for example, a fluoro group and a trifluoromethyl group.

When the polyimide resin contains a halogen atom, the content of the halogen atom in the polyimide resin is preferably 0.1 to 40% by mass, more preferably 1 to 35% by mass, based on the mass of the polyimide resin. More preferably, it is 5 to 30% by mass. When the halogen atom content is at least the above lower limit, the dispersibility of the polymer (B) in the composition and the film is likely to be enhanced, and the hygroscopic resistance and heat resistance of the resulting film are likely to be enhanced. When the halogen atom content is equal to or less than the above upper limit, the CTE of the film can be reduced, and synthesis becomes easier.

The imidization rate of the polyimide resin is preferably 90% or more, more preferably 93% or more, still more preferably 95% or more, and usually 100% or less. From the viewpoint of easily improving the dielectric properties, optical properties, moisture absorption resistance, and heat resistance of the film, the imidization ratio is preferably at least the above lower limit. The imidization ratio indicates the ratio of the molar amount of imide bonds in the polyimide resin to twice the molar amount of the structural units derived from the tetracarboxylic acid compound in the polyimide resin. In the case where the polyimide resin contains a tricarboxylic acid compound, a value twice the molar amount of the structural units derived from the tetracarboxylic acid compound in the polyimide resin, and the molar amount of the structural units derived from the tricarboxylic acid compound It shows the ratio of the molar amount of imide bonds in the polyimide resin to the total of . Also, the imidization rate can be obtained by IR method, NMR method, or the like.

［式（１’）中、Ｙ及びＸはそれぞれ、式（１）におけるＹ及びＸを表す］
で表される構成単位を含む。 The polyimide resin in the present invention includes a precursor before imidization of the polyimide resin, as described above. When the polyimide resin is a polyamic acid, the polyamic acid has the formula (1′):

[In formula (1′), Y and X respectively represent Y and X in formula (1)]
Including the structural unit represented by.

In one embodiment of the present invention, the content of the resin (A) contained in the composition of the present invention is preferably 50% by mass or more, more than Preferably 60% by mass or more, more preferably 65% by mass or more, preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 93% by mass or less, still more preferably 90% by mass or less, especially Preferably, it is 80% by mass or less. When the content of the resin (A) is at least the above lower limit, film formation is facilitated, which is advantageous from the viewpoint of film production. When the content of the resin (A) is equal to or less than the above upper limit, the dispersibility of the polymer (B) in the composition is likely to be improved, and thus the hygroscopic resistance and heat resistance of the resulting film are likely to be improved.

In one embodiment of the present invention, the total mass of resin (A) and polymer (B) contained in the composition is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. It is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less. When the total mass of the resin (A) and the polymer (B) contained in the composition is within the above range, it is easy to suppress the formation of aggregates of the polymer (B), and the phenolic antioxidant is added to the polymer (B). Since it is easily adsorbed, it is easy to increase the dispersibility of the polymer (B). In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.

<Method for producing resin (A)>
Resin (A) may be a commercially available product or may be produced by a conventional method. In one embodiment of the present invention, the resin (A) is preferably a polyimide resin. The method for producing the polyimide resin is not particularly limited, but for example, the polyimide resin is produced by a method comprising a step of reacting a diamine compound and a tetracarboxylic acid compound to obtain a polyamic acid, and a step of imidizing the polyamic acid. can be manufactured. Moreover, when the resin (A) is a polyamic acid, a step of obtaining a polyamic acid may be carried out. In addition to the tetracarboxylic acid compound, a dicarboxylic acid compound and a tricarboxylic acid compound may be reacted.

The tetracarboxylic acid compounds used in the synthesis of the polyimide resin include aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic dianhydrides; and aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic dianhydrides. are mentioned. A tetracarboxylic acid compound may be used independently and may be used in combination of 2 or more type. The tetracarboxylic acid compound may be a dianhydride or a tetracarboxylic acid compound analog such as an acid chloride compound.

Specific examples of tetracarboxylic acid compounds include pyromellitic anhydride (hereinafter sometimes abbreviated as PMDA), 4,4'-(4,4'-isopropylidenediphenoxy) diphthalic anhydride (hereinafter abbreviated as BPADA). 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride (hereinafter sometimes abbreviated as BPDA), 4,4'-(Hexafluoroisopropylidene)diphthalic dianhydride (hereinafter sometimes abbreviated as 6FDA), 4,4'-oxydiphthalic anhydride (hereinafter sometimes abbreviated as ODPA), 2,2 ',3,3'-, 2,3,3',4'- or 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic acid acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-diphenylethertetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl ) ether dianhydride, 3,3″,4,4″-, 2,3,3″,4″- or 2,2″,3,3″-p-terphenyltetracarboxylic dianhydride, 2 , 2-bis (2,3- or 3,4-dicarboxyphenyl)-propane dianhydride, bis (2,3- or 3.4-dicarboxyphenyl) methane dianhydride, 1,1-bis ( 2,3- or 3,4-dicarboxyphenyl)ethane dianhydride, 1,2,7,8-, 1,2,6,7- or 1,2,9,10-phenanthrene-tetracarboxylic acid di anhydride, 2,2-bis(3,4-dicarboxyphenyl)tetrafluoropropane dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (hereinafter sometimes abbreviated as HPMDA), 2,3,5,6-cyclohexanetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, cyclopentane -1,2,3,4-tetracarboxylic dianhydride, 4,4′-bis(2,3-dicarboxyphenoxy)diphenylmethane dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter sometimes abbreviated as CBDA), norbornane-2-spiro-α'-spiro-2″-norbornane-5,5′,6,6′-tetracarboxylic anhydride, p-phenylene bis(trimellitate anhydride) (sometimes abbreviated as TAHQ), 3,3′,4, 4'-diphenylsulfonetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene- 1,2,5,6-tetracarboxylic dianhydride, 2,6- or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- (or 1,4,5,8-) tetrachloronaphthalene-1,4,5,8- (or 2,3,6,7-) tetracarboxylic dianhydride, 2,3,8,9-, 3,4,9,10-, 4,5,10,11- or 5,6,11,12-perylene-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, bis(2,3- or 3,4-dicarboxyphenyl ) sulfone dianhydride and the like. Among these, PMDA, BPDA, 6FDA, BPADA, ODPA, HPMDA, CBDA, and TAHQ are preferred from the viewpoint of easily improving the moisture absorption resistance, heat resistance, dielectric properties, and mechanical properties of the resulting film. These tetracarboxylic acid compounds can be used alone or in combination of two or more.

Diamine compounds used for synthesizing polyimide resins include, for example, aliphatic diamines, aromatic diamines, and mixtures thereof. In addition, in this embodiment, the “aromatic diamine” represents a diamine having an aromatic ring, and may contain an aliphatic group or other substituents in a part of its structure. This aromatic ring may be a single ring or a condensed ring, and examples include, but are not limited to, benzene ring, naphthalene ring, anthracene ring, and fluorene ring. Among these, a benzene ring is preferred. The term "aliphatic diamine" refers to a diamine having an aliphatic group, which may contain other substituents in part of its structure, but does not have an aromatic ring.

Specific examples of diamine compounds include 1,4-diaminocyclohexane, 4,4'-diamino-2,2'-dimethylbiphenyl (hereinafter sometimes referred to as m-TB), 4,4'-diamino- 3,3'-dimethylbiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl (hereinafter sometimes referred to as TFMB), 4,4'-diaminodiphenyl ether, 1,3 -bis(3-aminophenoxy)benzene (hereinafter sometimes abbreviated as 1,3-APB), 1,4-bis(4-aminophenoxy)benzene (hereinafter sometimes abbreviated as 1,4-APB) , 1,3-bis(4-aminophenoxy)benzene, 2,2′-bis[4-(4-aminophenoxy)phenyl]propane (hereinafter sometimes referred to as BAPP), 2,2′-dimethyl -4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,2-bis-[4-(3-aminophenoxy)phenyl]propane, bis[4-(4- aminophenoxy)]biphenyl, bis[4-(3-aminophenoxy)biphenyl, bis[1-(4-aminophenoxy)]biphenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[4-(4 -aminophenoxy)phenyl]methane, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)]benzophenone, bis[4-(3-aminophenoxy)]benzophenone, 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2 -bis-[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi-2,6-xylidine, 4,4'-methylene-2 ,6-diethylaniline, 4,4'-methylenedianiline, 3,3'-methylenedianiline, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane , 3,3′-diaminodiphenylethane, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,3-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, benzidine, 3,3′-di aminobiphenyl, 3,3′-dimethoxybenzidine, 4,4″-diamino-p-terphenyl, 3,3″-diamino-p-terphenyl, m-phenylenediamine, p-phenylenediamine (abbreviated as p-PDA ), resorcinol-bis(3-aminophenyl) ether, 4,4′-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 4,4′-[1,3-phenylenebis( 1-methylethylidene)]bisaniline, bis(p-aminocyclohexyl)methane, bis(p-β-amino-tert-butylphenyl)ether, bis(p-β-methyl-δ-aminopentyl)benzene, p-bis (2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis(β -amino-tert-butyl)toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, piperazine, 4,4′-diamino-2,2′-bis(trifluoromethyl)bicyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4″-diamino-p-terphenyl, bis(4-aminophenyl)terephthalate , 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene, 4,4′-(1,3-phenylenediisopropylidene)bisaniline, 1,4-bis[2-( 4-aminophenyl)-2-propyl]benzene, 2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene, 4,4'-bis(3-aminophenoxy) Biphenyl, 4,4'-(hexafluoropropylidene)dianiline, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane , 1,2-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 2-methyl-1,2-diaminopropane, 2-methyl-1,3-diaminopropane, 1,3-bis( aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, norbornanediamine, 2′-methoxy-4,4′-diaminobenzanilide, 4,4′-diaminobenzanilide, bis[4-( 4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene, 9,9-bis[4-( 3-aminophenoxy)phenyl]fluorene, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,5-diamino -1,3,4-oxadiazole, bis[4,4'-(4-aminophenoxy)]benzanilide, bis[4,4'-(3-aminophenoxy)]benzanilide, 2,6-diaminopyridine, 2,5-diaminopyridine and the like. Among these, 1,4-diaminocyclohexane, 4,4'-diaminodiphenyl ether, TFMB, and 4 are preferred from the viewpoint of easily increasing the dispersibility of the polymer (B) and easily improving the moisture absorption resistance and heat resistance of the resulting film. , 4′-methylenedianiline, 3,3′-methylenedianiline, p-PDA, BAPP, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-2,2′-bis(trifluoromethyl) Bicyclohexane, m-TB, 4,4″-diamino-p-terphenyl, bis(4-aminophenyl)terephthalate, 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene , 1,3-APB, 1,4-APB, resorcinol-bis(3-aminophenyl)ether, 4,4′-(1,3-phenylenediisopropylidene)bisaniline, 1,4-bis[2-( 4-aminophenyl)-2-propyl]benzene, 2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene, 4,4'-bis(3-aminophenoxy) Preferred are biphenyl, 4,4'-(hexafluoropropylidene)dianiline, etc. The diamine compounds can be used singly or in combination of two or more.

Incidentally, the polyimide resin, in addition to the tetracarboxylic acid compound used in the resin synthesis, other tetracarboxylic acids, dicarboxylic acids and tricarboxylic acids and their anhydrides and A derivative may be further reacted.

Other tetracarboxylic acids include water adducts of the above tetracarboxylic acid compound anhydrides.

Examples of dicarboxylic acid compounds include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, their analogous acid chloride compounds, acid anhydrides, and the like, which may be used alone or in combination of two or more. Specific examples include terephthalic acid; isophthalic acid; naphthalenedicarboxylic acid; 4,4′-biphenyldicarboxylic acid; 3,3′-biphenyldicarboxylic acid; compounds in which two benzoic acids are linked by a single bond, —O—, —CH ₂ —, —C(CH ₃ ) ₂ —, —C(CF ₃ ) ₂ —, —SO ₂ — or a phenylene group; acid chloride compounds.

Examples of tricarboxylic acid compounds include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, their analogous acid chloride compounds, acid anhydrides, and the like, which may be used alone or in combination of two or more. Specific examples include the anhydride of 1,2,4-benzenetricarboxylic acid; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; a single bond between phthalic anhydride and benzoic acid; , —CH ₂ —, —C(CH ₃ ) ₂ —, —C(CF ₃ ) ₂ —, —SO ₂ —, or compounds linked by a phenylene group.

In the production of the polyimide resin, the amount of the diamine compound, the tetracarboxylic acid compound, the dicarboxylic acid compound and the tricarboxylic acid compound to be used can be appropriately selected according to the desired ratio of each structural unit of the resin.
In a preferred embodiment of the present invention, the amount of the diamine compound used is preferably 0.94 mol or more, more preferably 0.96 mol or more, still more preferably 0.98 mol or more, and particularly It is preferably 0.99 mol or more, preferably 1.20 mol or less, more preferably 1.10 mol or less, still more preferably 1.05 mol or less, and particularly preferably 1.02 mol or less. When the amount of the diamine compound used relative to the tetracarboxylic acid compound is within the above range, the dispersibility of the polymer (B) in the composition and the film is easily improved, and the moisture absorption resistance and heat resistance of the resulting film are easily improved.

The reaction temperature of the diamine compound and the tetracarboxylic acid compound is not particularly limited, and may be, for example, 5 to 200° C., and the reaction time is also not particularly limited, and may be, for example, about 0.5 to 72 hours. . In a preferred embodiment of the present invention, the reaction temperature is preferably 5-50° C., more preferably 10-40° C., and the reaction time is preferably 3-24 hours. With such a reaction temperature and reaction time, it is easy to increase the dispersibility of the polymer (B) in the composition and the film, and it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.

The reaction between the diamine compound and the tetracarboxylic acid compound is preferably carried out in a solvent. The solvent is not particularly limited as long as it does not affect the reaction, but examples include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, Alcohol solvents such as 2-butoxyethanol and propylene glycol monomethyl ether; Phenolic solvents such as phenol and cresol; Ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone (hereinafter sometimes referred to as GBL) , γ-valerolactone, propylene glycol methyl ether acetate, ethyl lactate, and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone, and other ketone solvents; Aliphatic hydrocarbon solvents; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorine-containing solvent; amide solvents such as N,N-dimethylacetamide (hereinafter sometimes referred to as DMAc) and N,N-dimethylformamide (hereinafter sometimes referred to as DMF); dimethylsulfone, dimethylsulfoxide , sulfolane and the like; carbonate solvents such as ethylene carbonate and propylene carbonate; pyrrolidone solvents such as N-methylpyrrolidone; and combinations thereof. Among these, phenol-based solvents, amide-based solvents, and pyrrolidone-based solvents can be preferably used from the viewpoint of solubility.

The reaction between the diamine compound and the tetracarboxylic acid compound may be carried out under an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere or under reduced pressure conditions, for example, an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere. It is preferable to carry out with stirring in a strictly controlled dehydrated solvent.

In the imidization step, imidization may be performed using an imidization catalyst, imidization by heating, or a combination thereof. Examples of the imidization catalyst used in the imidization step include aliphatic amines such as tripropylamine, dibutylpropylamine and ethyldibutylamine; N-ethylpiperidine, N-propylpiperidine, N-butylpyrrolidine, N-butylpiperidine, and alicyclic amines (monocyclic) such as N-propylhexahydroazepine; azabicyclo[2.2.1]heptane, azabicyclo[3.2.1]octane, azabicyclo[2.2.2]octane, and Alicyclic amines (polycyclic) such as azabicyclo[3.2.2]nonane; and pyridine, 2-methylpyridine (2-picoline), 3-methylpyridine (3-picoline), 4-methylpyridine (4 -picoline), 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 3,4-cyclopentenopyridine, 5,6,7, Aromatic amines such as 8-tetrahydroisoquinoline and isoquinoline are included. Moreover, from the viewpoint of facilitating the imidization reaction, it is preferable to use an acid anhydride together with the imidization catalyst. Acid anhydrides include conventional acid anhydrides used in imidization reactions, and specific examples thereof include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, and aromatic acid anhydrides such as phthalic acid. and acid anhydrides. The imidization step by heating may be performed in a solvent in which the polyamic acid is dissolved, or may be performed in a film state as described later.

In one embodiment of the present invention, when imidating, the reaction temperature is usually 20 to 250° C., and the reaction time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours.

The polyimide resin may be separated and purified by a conventional method such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, or a combination thereof, and is preferably isolated. In an embodiment, a large amount of alcohol such as methanol is added to a reaction solution containing a resin to precipitate the resin, and the resin can be isolated by concentrating, filtering, drying, or the like.

Suitable liquid crystalline polymers for the resin (A) include liquid crystalline polyesters, preferably liquid crystalline polyesters containing structural units represented by the following formulas (a1), (a2) and (a3).
—O—Ar ¹ —CO— (a1)
—CO—Ar ² —CO— (a2)
-X-Ar ³ -Y- (a3)
[In the formulas (a1) to (a3), Ar ¹ represents a 1,4-phenylene group, a 2,6-naphthylene group or a 4,4′-biphenylene group,
Ar ² represents a 1,4-phenylene group, a 1,3-phenylene group or a 2,6-naphthylene group,
Ar ³ represents a 1,4-phenylene group or a 1,3-phenylene group,
X represents -NH-,
Y represents -O- or NH-. ]

The content of the structural unit represented by the formula (a1) is 30 to 80 mol%, and the content of the structural unit represented by the formula (a2) is 10 to 100 mol% of the total structural units of the liquid crystal polyester. A liquid crystalline polyester having a content of 35 mol % and a structural unit represented by formula (a3) of 10 to 35 mol % is preferred.

The structural unit represented by formula (a1) is a structural unit derived from an aromatic hydroxycarboxylic acid, the structural unit represented by formula (a2) is a structural unit derived from an aromatic dicarboxylic acid, and the structural unit represented by formula (a3) A structural unit derived from an aromatic diamine or an aromatic amine having a phenolic hydroxyl group.

In this embodiment, Ar ¹ is a 2,6-naphthylene group, Ar ² is a 1,3-phenylene group, Ar ³ is a 1,4-phenylene group, and Y is —O - is preferred.

Structural units represented by formula (a1) include structural units derived from p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, and 4-hydroxy-4'-biphenylcarboxylic acid. The liquid crystalline polyester may contain two or more of the structural units. Among these, structural units derived from 2-hydroxy-6-naphthoic acid are preferred.
The content of the structural unit represented by the formula (a1) is preferably 30 mol% or more and 80 mol% or less, more preferably 40 mol% or more and 70 mol%, based on 100 mol% of the total structural units of the liquid crystal polyester. mol % or less, more preferably 45 mol % or more and 65 mol % or less.

Examples of structural units represented by formula (a2) include structural units derived from terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid. The liquid crystalline polyester may contain two or more of the structural units. Among these, structural units derived from isophthalic acid are preferred.
The content of the structural unit represented by the formula (a2) is preferably 10 mol% or more and 35 mol% or less, more preferably 15 mol% or more and 30 mol%, relative to 100 mol% of the total structural units of the liquid crystal polyester. mol % or less, more preferably 17.5 mol % or more and 27.5 mol % or less.

Examples of structural units represented by formula (a3) include structural units derived from 3-aminophenol, 4-aminophenol, 1,4-phenylenediamine, 1,3-phenylenediamine, and 4-aminobenzoic acid. . The liquid crystalline polyester may contain two or more of the structural units. Among these, structural units derived from 4-aminophenol are preferred.
The content of the structural unit represented by the formula (a3) is preferably 10 mol% or more and 35 mol% or less, more preferably 15 mol% or more and 30 mol % or less, more preferably 17.5 mol % or more and 27.5 mol % or less.

The liquid crystalline polyester used in this embodiment can be produced, for example, by the method described in JP-A-2019-163431.

Further, the liquid crystalline polyester used in the present embodiment usually has a distance between HSP values of 6.0 or more to the polymer (B), as disclosed in JP-A-2022-041945. Therefore, an interface is easily formed between the polymer (B) and the liquid crystalline polyester, so that the phenolic antioxidant is easily adsorbed so as to cover the polymer (B), and the polymer (B) is easily prevented from being oxidized.

The aromatic polyether-based resin is not particularly limited, but examples thereof include aromatic polyetherimide, aromatic polyetherketone, and aromatic polyethersulfone.

Examples of maleimide resins include, but are not limited to, phenylmethane maleimide, metaphenylene bismaleimide, 4,4′-diphenylmethane bismaleimide, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 2, 2′-bis[4-(4-maleimidophenoxy)phenyl]propane, 4-methyl-1,3-phenylenebismaleimide, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 4,4 -diphenyl ether bismaleimide, 4,4-diphenylsulfone bismaleimide, polyphenylmethane maleimide, novolak type maleimide compounds, biphenyl aralkyl type maleimide compounds, prepolymers of these maleimide resins, and the like.

<Solvent>
In one embodiment of the present invention, the composition of the present invention preferably further contains a solvent from the viewpoint of easy preparation of the composition and easy film formation.

In one embodiment of the present invention, the solvent may contain a solvent having a distance between HSP values of 12.0 or more with respect to the phenolic antioxidant (hereinafter sometimes referred to as "first solvent"). preferable. When including such a first solvent, the polymer (B) contained in the composition of the present invention is less likely to be oxidized during film formation, and the composition of the present invention forms a film having excellent moisture absorption resistance and heat resistance. It's easy to do. This is because when the distance between the HSP values between the phenolic antioxidant and the solvent is 12.0 or more, the phenolic antioxidant is difficult to dissolve and disperse in the solvent, so the affinity with the polymer (B) is relatively high. The phenolic antioxidant becomes more likely to approach the polymer (B), and the phenolic antioxidant covers the polymer (B), so that the phenolic antioxidant can oxidize the polymer (B). It is considered that this is because the preventive effect increases. Furthermore, since the phenolic antioxidant is formed into a film in the form of covering the periphery of the polymer (B), it is easy to exhibit a heat resistance function, and even if the obtained film is exposed to a high temperature environment, the oxidation of the polymer (B) will occur. is easy to suppress.

In the composition of the present invention, the distance between the HSP values of the phenolic antioxidant and the first solvent is preferably 12.5 or more, more preferably 13.5 or more, still more preferably 15.4 or more, and even more preferably is 15.9 or more, particularly preferably 16.0 or more, particularly more preferably 16.5 or more, and even more preferably 17.0 or more. When the distance between the HSP values is at least the above lower limit, the phenolic antioxidant tends to surround the polymer (B), and the phenolic antioxidant surrounds the polymer (B) to form a film. Therefore, oxidation of the polymer (B) is easily suppressed, and the hygroscopic resistance and heat resistance of the obtained film are easily improved. Also, the upper limit of the distance between the HSP values of the phenolic antioxidant and the first solvent is preferably 30.0 or less, more preferably 25.0 or less, still more preferably 20.0 or less. When the distance between the HSP values is equal to or less than the above upper limit, the phenolic antioxidant tends to disperse in the solvent, so that oxidation of the polymer (B) can be easily suppressed.

In one embodiment of the present invention, the distance between the HSP values of the structure S of the phenolic antioxidant and the first solvent is preferably 10.0 or more, more preferably 12.3 or more, still more preferably 12.5 or more, Still more preferably 12.7 or more, particularly preferably 13.0 or more, particularly more preferably 13.5 or more, even more preferably 14.0 or more, even more preferably 15.0 or more, extremely preferably 16.0 or more. 0 or higher, and very more preferably 17.0 or higher. When the distance between the HSP values is at least the above lower limit, the phenolic antioxidant is difficult to dissolve and disperse in the solvent and easily covers the polymer (B). It is easy to improve the moisture absorption resistance and heat resistance of the resulting film. Also, the upper limit of the distance between the HSP values of Structure S and the solvent is preferably 30.0 or less, more preferably 25.0 or less, and even more preferably 20.0 or less. When the distance between the HSP values is equal to or less than the above upper limit, the phenolic antioxidant is prevented from aggregating in the composition, and the surroundings of the polymer (B) are easily covered, so oxidation of the polymer (B) is easily suppressed. .

The first solvent is not particularly limited. For example, N,N-dimethylacetamide (hereinafter sometimes referred to as DMAc), N—N-dimethylformamide (hereinafter sometimes referred to as DMF) and other amide-based Solvent; Lactone-based solvents such as γ-butyrolactone (hereinafter sometimes referred to as GBL) and γ-valerolactone; Sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide and sulfolane; Carbonate-based solvents such as ethylene carbonate and propylene carbonate solvents; pyrrolidone solvents such as N-methylpyrrolidone; and combinations thereof. Among these, amide solvents, lactone solvents and pyrrolidone solvents are preferred. With such a solvent, the affinity between the solvent and the polymer (B) is relatively increased, the aggregation of the polymer (B) is easily suppressed, and the dispersibility of the polymer (B) is easily improved. It is easy to improve the moisture absorption resistance and heat resistance of the film.

In one embodiment of the present invention, the distance between the HSP values of the first solvent and the polymer (B) is preferably 8.5 or more, more preferably 9.0 or more, still more preferably 10.0 or more, still more preferably is greater than or equal to 11.0. When the distance between the HSP values is at least the above lower limit, the affinity between the phenolic antioxidant and the polymer (B) is relatively increased, and the phenolic antioxidant is easily adsorbed to the polymer (B), and , it is easy to increase the dispersibility of the polymer (B). Also, the upper limit of the distance between the HSP values of the first solvent and the polymer (B) is preferably 30.0 or less, more preferably 25.0 or less, still more preferably 20.0 or less. When the distance between the HSP values of the first solvent and the polymer (B) is equal to or less than the above upper limit, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.

In one embodiment of the present invention, the first solvent is preferably a solvent in which the polymer (B) is insoluble. With such a solvent, an interface is easily formed, so the phenolic antioxidant is easily adsorbed to the polymer (B), and aggregation of the polymer (B) is easily suppressed, and the dispersibility of the polymer (B) is enhanced. Cheap. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. Here, in the present specification, the evaluation of whether "dissolves" or "does not dissolve" can be performed according to the method described in <Evaluation of Solubility> in Examples.

In one embodiment of the present invention, it is preferred that the distance between the HSP values of the first solvent and the polymer (B) is larger than the interaction radius of the polymer (B). With such a relationship, the polymer (B) is less likely to be dissolved in the first solvent, so aggregation of the polymer (B) is easily suppressed and the dispersibility of the polymer (B) is easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. In this specification, the interaction radius means a plurality of solvents capable of dissolving a specific polymer, that is, when the Hansen solubility parameters of good solvents are plotted in a three-dimensional HSP space, the plots of each good solvent are similar to each other. Where, in other words, they tend to cluster spherically at close positions, ie coordinates, and refer to the radius of that sphere, the Hansen melting sphere. A solute with a large interaction radius is soluble in many solvents, a solute with a small interaction radius is soluble in a small number of solvents, and is difficult to dissolve in a large number of solvents. For a specific unknown polymer, a solubility test is conducted to determine whether various solvents are good solvents or poor solvents. A radius is calculated. As used herein, the "interaction radius" is as defined above and can be determined according to the above method.

In one embodiment of the present invention, the distance between the HSP values of the first solvent and the resin (A) is preferably 11.0 or less, more preferably 10.0 or less, even more preferably 9.5 or less, and even more preferably is 9.0 or less, particularly preferably 8.5 or less, preferably 0.01 or more, more preferably 0.1 or more, still more preferably 1.0 or more, still more preferably 3.0 or more, particularly preferably is 5.0 or more. When the distance between the HSP values is the above upper limit or less, the affinity between the first solvent and the resin (A) can be improved, so that the dispersibility of the polymer (B) can be easily improved, and the durability of the resulting film can be improved. Easy to improve hygroscopicity and heat resistance.

In one embodiment of the present invention, the first solvent is preferably a solvent in which the resin (A) dissolves. Such a solvent facilitates dispersion of the polymer (B) in the resulting composition and film. In addition, the film tends to form a sea-island structure.

In one embodiment of the present invention, the distance between the HSP values of the first solvent and resin (A) is preferably smaller than the interaction radius of resin (A). With such a relationship, the resin (A) is easily dissolved in the first solvent, so aggregation of the polymer (B) is easily suppressed, and dispersibility of the polymer (B) is easily improved.

In one embodiment of the present invention, the content of the first solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, relative to the mass of the composition of the present invention. Even more preferably 80% by mass or more, particularly preferably 90% by mass or more, preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less. When the content of the first solvent is within the above range, an interface is easily formed, so the phenolic antioxidant is easily adsorbed to the polymer (B), and aggregation of the polymer (B) is easily suppressed.

In one embodiment of the present invention, the solvent may contain a second solvent in addition to the first solvent whose HSP value distance to the phenolic antioxidant is 12.0 or more. When the solvent contains the second solvent in addition to the first solvent, it is easy to prepare a composition containing the particulate polymer (B) with a reduced particle size.

Examples of the second solvent include hydrocarbon solvents such as benzene, toluene, pentane, hexane, heptane, cyclohexane, and xylene; halogenated hydrocarbon solvents such as dichloromethane and ethylene dichloride. Among these, hydrocarbon solvents are preferred. When the second solvent contains a hydrocarbon-based solvent, the solubility of the polymer (B) and the second solvent increases, so the formation of aggregates of the polymer (B) is easily suppressed, and the dispersibility of the polymer (B) is improved. Easy to raise. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. A 2nd solvent can be used individually or in combination of 2 or more types.

In one embodiment of the present invention, the distance between the HSP values of the second solvent and the phenolic antioxidant is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.0 or more, and even more preferably Preferably it is 1.5 or more. The upper limit of the distance between the HSP values of the second solvent and the phenolic antioxidant is usually 15 or less, preferably 10 or less, more preferably 8.0 or less, even more preferably 5.0 or less, and even more preferably It is 2.5 or less, particularly preferably 2.0 or less. When the distance between the HSP values is within the above range, the phenolic antioxidant is easily adsorbed to the polymer (B), and the resulting film is likely to have improved hygroscopic resistance and heat resistance.

In one embodiment of the present invention, the distance between the HSP values of the second solvent and the polymer (B) is preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less. When the distance between the HSP values is equal to or less than the above upper limit, the solubility of the polymer (B) in the second solvent is increased, so that the dispersibility of the polymer (B) is likely to be enhanced. Furthermore, since the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film. The lower limit of the distance between HSP values is usually greater than zero.

In one embodiment of the present invention, the second solvent is preferably a solvent in which polymer (B) dissolves. Such a solvent tends to enhance the dispersibility of the polymer (B). In addition, since the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.

In one embodiment of the present invention, it is preferred that the distance between the HSP values of the second solvent and the polymer (B) is smaller than the interaction radius of the polymer (B). With such a relationship, the polymer (B) is easily dissolved in the second solvent, so the formation of aggregates of the polymer (B) is easily suppressed, and the dispersibility of the polymer (B) is easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.

In one embodiment of the present invention, the distance between the HSP values of the second solvent and the resin (A) is preferably 4.0 or more, more preferably 5.0 or more, still more preferably 6.0 or more, still more preferably is 7.0 or more, particularly preferably 8.0 or more, and particularly more preferably 9.0 or more. When the distance between the HSP values is at least the above lower limit, the resin (A) is difficult to dissolve in the second solvent, so it is easy to suppress the formation of aggregates of the polymer (B), and the dispersibility of the polymer (B) is improved. Easy to raise. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. The upper limit of the distance between the HSP values of the second solvent and the resin (A) is preferably 30.0 or less, more preferably 27.0 or less, still more preferably 25.0 or less, still more preferably 23.0 or less, especially Preferably it is 21.0 or less. When the distance between the HSP values of the second solvent and the resin (A) is the above upper limit or less, aggregation of the polymer (B) is easily suppressed, so that the dispersibility of the polymer (B) is easily increased, and the resulting film It is easy to improve the moisture absorption resistance and heat resistance of

In one embodiment of the present invention, the second solvent is preferably a solvent in which the resin (A) does not dissolve. Such a solvent tends to improve the dispersibility of the polymer (B). Furthermore, since the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.

In one embodiment of the present invention, it is preferred that the distance between the HSP values of the second solvent and the resin (A) is larger than the interaction radius of the resin (A). With such a relationship, (A) is difficult to dissolve in the second solvent, so that the formation of aggregates of the polymer (B) is easily suppressed, and the dispersibility of the polymer (B) is easily improved. Furthermore, since the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.

In one embodiment of the present invention, the solubility of polymer (B) in the second solvent is preferably greater than the solubility of polymer (B) in the first solvent. Such a relationship tends to suppress the formation of aggregates of the polymer (B), and tends to increase the dispersibility of the polymer (B). Furthermore, since the phenolic antioxidant is easily adsorbed to the polymer (B), it is easy to improve the hygroscopic resistance and heat resistance of the resulting film. The solubility of the polymer (B) in solvents can be measured by the following method. 1000 mg of polymer (B) and 3 mL of solvent are added to a sample bottle and stirred at room temperature for 2 hours. Then, the solid phase and the liquid phase are separated by filtration, and the solid phase is dried under reduced pressure at 80° C. for 2 hours. Then, the mass: X (mg) is measured, and the solubility Y (mg/mL ) can be obtained.
Y=(1000−X)/3
In addition, for example, in the definition of this specification, when the polymer (B) corresponds to "dissolve" in the second solvent and corresponds to "does not dissolve" in the first solvent, the solubility in the second solvent is clearly is large, it is not necessary to measure the solubility.

In one embodiment of the present invention, the content of the second solvent that can be contained in the composition of the present invention is preferably 120 parts by mass or less, more preferably 100 parts by mass with respect to 100 parts by mass of the content of the first solvent. parts or less, more preferably 60 parts by mass or less, even more preferably 45 parts by mass or less, particularly preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably is less than 30 parts by mass, extremely preferably 25 parts by mass or less, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more. When the content of the second solvent is equal to or less than the above upper limit, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. It is easy to prepare a composition as content of a 2nd solvent is more than said minimum.

In one embodiment of the present invention, the solvent may contain a solvent other than the first solvent and the second solvent as long as the effects of the present invention are not impaired. Other solvents are not particularly limited, and commonly used solvents can be used.

In one embodiment of the present invention, the content of the solvent that can be contained in the composition of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less. When the content of the total solvent is within the above range, the formation of aggregates of the polymer (B) is easily suppressed, and the dispersibility of the polymer (B) is easily enhanced. Furthermore, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.

In one embodiment of the present invention, the total weight of the first solvent and the second solvent is preferably 50% by weight based on the total weight of the first solvent, the second solvent and other solvents that may be included in the composition. Above, more preferably 70% by mass or more, still more preferably 90% by mass or more, even more preferably 95% by mass or more, and preferably 100% by mass or less. When the total mass of the first solvent and the second solvent is within the above range, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. Furthermore, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film.

In one embodiment of the invention, the composition of the invention preferably further comprises a secondary antioxidant. By including the secondary antioxidant in addition to the phenolic antioxidant which is the primary antioxidant, it is easy to suppress oxidation of the polymer (B) and improve the hygroscopic resistance and heat resistance of the resulting film. Secondary antioxidants include phosphorus antioxidants, sulfur antioxidants, and the like, and these secondary antioxidants can be used alone or in combination of two or more.

In one embodiment of the present invention, phosphorus-based antioxidants include, for example, tris(2,4-di-tert-butylphenyl)phosphite, triphenylphosphite, tris(nonylphenyl)phosphite, trilaurylphosphite. , trioctadecyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert- Butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) ) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4′-diphenylenediphosphonite, 2,2′-methylenebis(4,6-di -tert-butylphenyl)2-ethylhexylphosphite, 2,2′-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, bis(2,4-di-tert-butyl-6-methyl phenyl)ethyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite, 2-(2,4,6-tri-tert-butylphenyl)-5-ethyl-5- Butyl-1,3,2-oxaphosphorinane, 2,2′,2″-nitrilo[triethyl-tris[3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2 ,2'-diyl]]phosphite, etc. These phosphorus-based antioxidants can be used alone or in combination of two or more.

In one embodiment of the present invention, sulfur-based antioxidants include, for example, dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, neopentanetetrayl tetrakis(3-laurylthiopropionate) and the like. These sulfur antioxidants can be used alone or in combination of two or more.

In one embodiment of the present invention, the content of the secondary antioxidant that can be contained in the composition of the present invention is preferably 0.002 parts by mass or more, more preferably 100 parts by mass of the polymer (B) 0.01 parts by mass or more, more preferably 0.04 parts by mass or more, still more preferably 0.1 parts by mass or more, and particularly preferably 1 part by mass or more. When the content of the secondary antioxidant is at least the above lower limit, the oxidation of the polymer (B) can be sufficiently suppressed, and the hygroscopic resistance and heat resistance of the film can be easily improved. The content of the secondary antioxidant is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 7 parts by mass with respect to 100 parts by mass of the polymer (B). parts or less, particularly preferably 5 parts by mass or less. When the content of the secondary antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.

In one embodiment of the present invention, the content of the secondary antioxidant that can be contained in the composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass with respect to 100 parts by mass of the phenolic antioxidant. It is at least 15 parts by mass, more preferably at least 20 parts by mass, particularly preferably at least 30 parts by mass. When the content of the secondary antioxidant is at least the above lower limit, the oxidation of the polymer (B) can be sufficiently suppressed, and the hygroscopic resistance and heat resistance of the film can be easily improved. The content of the secondary antioxidant is preferably 1000 parts by mass or less, more preferably 700 parts by mass or less, still more preferably 600 parts by mass or less, still more preferably 500 parts by mass or less, relative to 100 parts by mass of the phenolic antioxidant. Part by mass or less, particularly preferably 200 parts by mass or less, particularly more preferably 150 parts by mass or less, and even more preferably 100 parts by mass or less. When the content of the secondary antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.

In one embodiment of the present invention, the composition of the present invention may optionally contain additives within a range that does not impair the effects of the present invention. Examples of additives include flame retardants, cross-linking agents, surfactants, compatibilizers, imidization catalysts, weathering agents, lubricants, anti-blocking agents, antistatic agents, anti-fogging agents, anti-drip agents, pigments, fillers, etc. is mentioned. Additives can be used alone or in combination of two or more. In one embodiment of the present invention, the composition of the present invention effectively suppresses the formation of aggregates of the polymer (B) even without containing a compatibilizer, and the polymer (B) exhibits high dispersibility. Therefore, it is possible to form a film exhibiting high moisture absorption resistance and heat resistance. Therefore, in the composition of the present invention, the content of the compatibilizer is preferably 5 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0.1 parts by mass with respect to 100 parts by mass of the resin (A). parts or less, still more preferably less than 0.1 parts by mass, particularly preferably 0.05 parts by mass or less, particularly more preferably 0.01 parts by mass or less, even more preferably 0.001 parts by mass or less, and particularly further More preferably, it may be 0 parts by mass. Further, for example, when the resin (A) is a polyimide-based resin precursor such as polyamic acid and thermal imidization is required during film production, imidization may be inhibited by a compatibilizing agent or the compatibilizing agent may be removed by heating. From the viewpoint of preventing deterioration of the properties of the film due to deterioration, the content of the compatibilizer is preferably less than 0.1 part by mass within the above range. The above content of the compatibilizing agent may be based on 100 parts by mass of resin (A) and polymer (B) in total instead of 100 parts by mass of resin (A).

The composition of the present invention contains a resin (A), a polymer (B) and a phenolic antioxidant, the distance between the HSP values between the phenolic antioxidant and the polymer (B) is 2.1 or more, and the resin The distance between the HSP values of (A) and polymer (B) is 6 or more. Therefore, the oxidation of the polymer (B) can be suppressed, the moisture absorption resistance is excellent, and deterioration of the dielectric properties due to moisture absorption of the film can be effectively suppressed. Moreover, it is excellent in heat resistance, and even if the film is placed in a high-temperature environment, deterioration due to oxidation of the polymer (B) can be effectively suppressed. Therefore, the film of the present invention can achieve both excellent moisture absorption resistance and excellent heat resistance. This is presumably because, as described above, the specific phenolic antioxidant can effectively suppress the oxidation of the polymer (B) during film formation, which can reduce moisture resistance and the like. In addition, deterioration of moisture absorption resistance etc. may also occur due to deterioration of deposits adhering to the surface (for example, dispersants such as surfactants and protective materials). It is thought that the alteration of the

In a preferred embodiment of the present invention, the film formed from the composition of the present invention has the moisture absorption rate of the film of the present invention and the IR peak retention rate of the polymer (B) described in the section [Film] below. show similar values.

[Method for producing composition]
The method for producing the composition of the present invention is not particularly limited. It may be prepared or manufactured by mixing inhibitors, additives, etc., but in one preferred embodiment of the invention in which the polymer (B) is particulate, the following steps:
Step (I) of preparing a dispersion containing a particulate polymer (B) (hereinafter sometimes referred to as a particulate polymer (B) dispersion); and adding a resin (A) to the particulate polymer (B) dispersion Adding step (II)
and preferably produced by a method of adding a phenolic antioxidant in the step (I) and/or the step (II). When such a production method is used, aggregation of the particles of the polymer (B) can be suppressed, so that the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to obtain a film excellent in moisture absorption resistance and heat resistance.

<Step (I)>
Step (I) is a step of preparing a dispersion containing particulate polymer (B).

In one embodiment of the invention, step (I) comprises, for example, the following steps:
Step (1) of dissolving polymer (B) in a second solvent to obtain a polymer (B) solution; and after contacting the polymer (B) solution with the first solvent, distilling off the second solvent, Step (2) of obtaining a particulate polymer (B) dispersion
It is preferable that the step of preparing a particulate polymer (B) dispersion is performed by a method comprising: When such a step is included, aggregation of the particles of the polymer (B) can be suppressed, so that the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.

Step (1) is a step of dissolving polymer (B) in a second solvent to obtain a polymer (B) solution.

In step (1), the form of the polymer (B) to be dissolved in the second solvent is not particularly limited, and may be, for example, particulate, fibrous, sheet-like, or pellet-like.

The polymer (B) solution preferably contains 0.01 to 20% by weight of polymer (B) relative to the weight of the solution. The content of the polymer (B) in the polymer (B) solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass, relative to the mass of the solution. % or more, more preferably 0.5 mass % or more, preferably 20 mass % or less, more preferably 10 mass % or less, and even more preferably 5 mass % or less. When the content of the polymer (B) in the solution is at least the above lower limit, it is easy to prepare the composition. Moreover, when the content of the polymer (B) in the solution is equal to or less than the above upper limit, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.

The method of dissolving the polymer (B) in the second solvent is not particularly limited. For example, the second solvent may be added to the polymer (B), or the polymer (B) may be added to the second solvent. or both. Also, depending on the solubility of the second solvent in the polymer (B), it may be dissolved by heating or the like.

Step (2) is a step of bringing the polymer (B) solution into contact with the first solvent and then distilling off the second solvent to obtain a dispersion containing the particulate polymer (B).

In step (2), the method of bringing the polymer (B) solution into contact with the first solvent is not particularly limited, but examples include a method of mixing the polymer (B) solution and the first solvent. Specifically, a method of adding the polymer (B) solution to the first solvent and a method of adding the first solvent to the polymer (B) solution can be exemplified. By such contact, the particulate polymer (B) having a small particle size can be precipitated or dispersed in the mixture of the first solvent and the second solvent. A small amount of the resin (A) and other additives may be added at any timing during the step (2) as long as the particulate polymer (B) does not aggregate.

The amount of the polymer (B) solution to be brought into contact with the first solvent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 1 part by mass of the first solvent used. is 0.3 parts by mass or more, particularly preferably 0.7 parts by mass or more, preferably 100 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 3 parts by mass or less, particularly preferably 1.5 parts by mass It is below the department. When the amount of the polymer (B) solution to be brought into contact with the first solvent is within the above range, the formation of aggregates of the polymer (B) is likely to be suppressed, and the particle size is likely to be reduced, thus increasing the dispersibility. Cheap.

In step (2), after contacting the polymer (B) solution with the first solvent, the second solvent is distilled off. By distilling off the second solvent, the dispersion stability of the particulate polymer (B) can be enhanced. Further, the polymer (B) may be further precipitated by distilling off the second solvent. The second solvent may be at least partially distilled or removed, and the second solvent may remain in the particulate polymer (B) dispersion. From the standpoints of facilitating the suppression of aggregation of the polymer (B) and the facilitating preparation of the dispersion, it is preferred that the second solvent partially remain or partly be contained in the dispersion of the particulate polymer (B).

In the step (2), the method of distilling off the second solvent is not particularly limited, and a method of distilling off under reduced pressure using an evaporator or the like is exemplified. The pressure and temperature during distillation can be appropriately selected according to the characteristics such as the boiling points of the second solvent and the first solvent. In the preferred production method of the present invention, the second solvent is distilled off from the mixture of the second solvent and the first solvent, so the boiling point of the second solvent is usually lower than that of the first solvent. In this way, a particulate polymer (B) dispersion in which the polymer (B) is dispersed without containing aggregates of the polymer (B) can be obtained.

The content of the second solvent contained in the particulate polymer (B) dispersion obtained after distilling off the second solvent is preferably 120 parts by mass or less, more preferably 120 parts by mass or less with respect to 100 parts by mass of the first solvent. 100 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 45 parts by mass or less, particularly preferably 40 parts by mass or less, particularly preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, particularly It is more preferably less than 30 parts by mass, extremely preferably 25 parts by mass or less, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and still more preferably 0.1 parts by mass or more. When the content of the second solvent is equal to or less than the above upper limit, the formation of aggregates of the polymer (B) can be easily suppressed, and the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film. Moreover, when the content of the second solvent is at least the above lower limit, it is easy to prepare a dispersion.

In another embodiment of the invention, step (I) is, for example, the following steps:
Step (1′) of mixing particulate polymer (B) and solvent
It may be a step of preparing a particulate polymer (B) dispersion by a method comprising When such a step is included, aggregation of the particles of the polymer (B) can be suppressed, so that the dispersibility of the polymer (B) can be easily improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.

Step (1') is a step of mixing the particulate polymer (B) and a solvent to obtain a particulate polymer (B) dispersion.

The particulate polymer (B) used in step (1′) can be obtained, for example, by pulverizing the polymer (B) with a pulverizer, and if necessary, using a classifier, the particulate polymer (B ) may be adjusted within a desired range. Alternatively, the particulate polymer (B) taken out from the particulate polymer (B) dispersion obtained by the steps (1) and (2) may be used.

The median diameter of the particulate polymer (B) used in step (1′) is preferably 0.01 μm or more, more preferably 0.03 μm or more, still more preferably 0.05 μm or more, and preferably 15 μm or less. It is preferably 10 µm or less, more preferably 5 µm or less, and even more preferably 3 µm or less. When the median diameter of the particulate polymer (B) to be added is at least the above lower limit, the dielectric properties of the film formed from the composition are likely to be enhanced, and the film is easily produced. When the median diameter of the particulate polymer (B) is equal to or less than the above upper limit, the hygroscopic resistance and heat resistance of the film formed from the composition are likely to be improved.

In one embodiment of the present invention, the solvent to be mixed with the particulate polymer (B) is preferably a solvent containing the first solvent, from the viewpoint that the phenolic antioxidant easily adsorbs to the particulate polymer (B), More preferably, it is the first solvent.

In one embodiment of the present invention, the particulate polymer (B) dispersion obtained in step (I) contains a solvent other than the first solvent and the second solvent within a range that does not impair the effects of the present invention. You can Other solvents are not particularly limited, and commonly used solvents can be used.

In one embodiment of the present invention, the total content of the first solvent, the second solvent and other solvents that can be contained in the particulate polymer (B) dispersion obtained in step (I) is On the other hand, it is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, preferably 99.99% by mass or less, more preferably 99.9% by mass or more. It is 9% by mass or less, more preferably 99% by mass or less, and particularly preferably 95% by mass or less. When the content of the solvent is within the above range, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.

In one embodiment of the present invention, the total mass of the first solvent and the second solvent is the first solvent, the second solvent and other The total mass of the solvent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less. . When the total mass of the second solvent and the first solvent is within the above range, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be improved. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.

In one embodiment of the present invention, the content of the particulate polymer (B) contained in the particulate polymer (B) dispersion obtained in step (I) is, relative to the mass of the polymer (B) dispersion, Preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass Below, it is 5 mass % or less especially preferably. When the content of the particulate polymer (B) is within the above range, aggregation of the polymer (B) is likely to be suppressed, and dispersibility of the polymer (B) is likely to be enhanced. In addition, it is easy to improve the moisture absorption resistance and heat resistance of the resulting film.

In one embodiment of the present invention, when the resin (A) to be added is added in the form of varnish in step (II) described later, the particles contained in the particulate polymer (B) dispersion obtained in step (I) The content of the polymer (B) is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, relative to the mass of the polymer (B) dispersion, and preferably It is 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less.

The median diameter of the particulate polymer (B) contained in the particulate polymer (B) dispersion can be selected from the same range as the median diameter of the particulate polymer (B) in the composition of the present invention. When the median diameter of the particulate polymer (B) in the composition is at least the above lower limit, the dielectric properties of the film formed from the composition are likely to be enhanced, and the film is easily produced. When the median diameter of the particulate polymer (B) in the dispersion is equal to or less than the above upper limit, it is easy to improve the hygroscopic resistance and heat resistance of the resulting film. The median diameter of the particulate polymer (B) contained in the particulate polymer (B) dispersion can be determined by scattering particle size distribution measurement using laser diffraction, for example, by the method described in Examples. be able to.

<Step (II)>
Step (II) is a step of adding the resin (A) to the particulate polymer (B) dispersion.

In step (II), the resin (A) to be added may be in the form of a solid, preferably powder, or may be in the form of a varnish obtained by dissolving the resin (A) in a predetermined solvent, such as the first solvent. good. In one embodiment of the present invention, in step (II), when the resin (A) is a polyimide resin, the polyimide resin or polyamic acid can be added in solid, preferably powder form or varnish form. . When the resin (A) is added in the form of a varnish, the content of the resin (A) in the varnish is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the mass of the varnish. More preferably 5% by mass or more, still more preferably 10% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. When the content of the resin (A) in the varnish is within the above range, film formation is facilitated, which is advantageous from the viewpoint of film production.

Resin (A) added in step (II) is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 65% by mass with respect to the total mass of resin (A) and polymer (B). % or more, preferably 95% by mass or less, more preferably 93% by mass or less, and even more preferably 90% by mass or less. When the content of the resin (A) to be added is at least the above lower limit, film formation is facilitated, which is advantageous from the viewpoint of film production. Moreover, when the content of the resin (A) is equal to or less than the above upper limit, it is easy to improve the hygroscopic resistance and heat resistance of the obtained film, and it is easy to improve the dielectric properties of the film.

The method of adding the resin (A) to the particulate polymer (B) dispersion is not particularly limited, and the resin (A) may be added at once, or may be added in multiple portions. may

In the above method, the composition of the present invention can be produced by adding a phenolic antioxidant in the step (I) and/or the step (II). Addition of the phenolic antioxidant may be performed in either step (I) or step (II), or may be performed in both step (I) and step (II). The method of adding the phenolic antioxidant is not particularly limited, and the phenolic antioxidant may be added at once or may be added in multiple portions.

In one embodiment of the present invention, when the step (I) is a step including the step (1) and the step (2), the phenolic antioxidant is easily dispersed, and the polymer (B) is easily adsorbed uniformly. Therefore, it is preferable to add the phenolic antioxidant in step (I). Further, in one embodiment of the present invention, when the step (I) is a step including the step (1 '), the phenolic antioxidant is easily dispersed and uniformly adsorbed on the polymer (B). Addition of the phenolic antioxidant is preferably carried out in step (I).

When adding a phenolic antioxidant in step (I), it may be performed in any of steps (1), (2), and step (1′), but the phenolic antioxidant is dispersed. It is preferable to carry out in step (2) or step (1′), particularly step (1′), from the viewpoint of easy and uniform adsorption on the polymer (B).

When adding a phenolic antioxidant in step (II), the order of addition of the phenolic antioxidant and the resin (A) is not particularly limited, and the resin (A) is added after adding the phenolic antioxidant. Alternatively, the phenolic antioxidant may be added after adding the resin (A). In one embodiment of the present invention, from the viewpoint that the phenolic antioxidant is easily dispersed and uniformly adsorbed on the polymer (B), after adding the phenolic antioxidant to the particulate polymer (B) dispersion, It is preferred to add resin (A).

The phenolic antioxidant added in step (I) and/or step (II) is preferably 0.01 part per 100 parts by mass of the polymer (B) in the particulate polymer (B) dispersion or composition. Part by mass or more, more preferably 0.05 part by mass or more, still more preferably 0.1 part by mass or more, still more preferably 0.2 part by mass or more, particularly preferably 1 part by mass or more, particularly more preferably 2 parts by mass That's it. When the amount of the phenolic antioxidant added is at least the above lower limit, the polymer (B) is easily covered with the phenolic antioxidant, and the oxidation of the polymer (B) is easily suppressed. Easy to improve heat resistance. The content of the phenolic antioxidant is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 7 parts by mass with respect to 100 parts by mass of the polymer (B). parts or less, particularly preferably 5 parts by mass or less. When the content of the phenolic antioxidant is equal to or less than the above upper limit, the dielectric properties of the film are likely to be enhanced.

The above production method in the present invention may include steps other than steps (I) and (II) as long as the effects of the present invention are not impaired. Subantioxidants or additives may be added. Additives include those described above.
In a preferred embodiment of the present invention, the resin (A) is added to the polymer (B) dispersion, but the polymer (B) in powder form may be added to the resin (A) varnish. As shown in step (II) above, the varnish of resin (A) may be obtained by dissolving resin (A) in a predetermined solvent, for example, a first solvent, or may be a precursor of resin (A). may be a polyamic acid solution (a solution containing at least polyamic acid and a synthetic solvent) when the resin (A) is a polyimide resin.

〔the film〕
The present invention includes a resin (A), a polymer (B) and a phenolic antioxidant, the distance between the HSP values of the phenolic antioxidant and the polymer (B) is 2.1 or more, and the resin ( Films in which the distance between the HSP values of A) and polymer (B) is 6 or more are included. Since the film of the present invention is excellent in moisture absorption resistance and heat resistance, when the film of the present invention is used for the resin layer of CCL, it is easy to improve the dielectric properties and suppress dielectric loss and transmission loss.

In one embodiment of the invention, the polymer (B) contained in the film of the invention is preferably particulate. When the polymer (B) is in the form of particles, the dispersibility of the polymer (B) is likely to be enhanced, and the hygroscopic resistance and heat resistance of the film are likely to be improved.

In one embodiment of the present invention, when the polymer (B) is particulate, the average primary particle size of the particulate polymer (B) is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. , still more preferably 3 μm or less, particularly preferably 1 μm or less, particularly more preferably 0.8 μm or less, even more preferably 0.5 μm or less, preferably 0.01 μm or more, more preferably 0.03 μm or more, and further It is preferably 0.05 μm or more. When the average primary particle size of the particulate polymer (B) is at least the above lower limit, the mechanical properties of the film are likely to be enhanced. When the average primary particle size of the particulate polymer (B) is equal to or less than the above upper limit, the particle dispersibility of the particulate polymer (B) is likely to be enhanced, and the hygroscopic resistance and heat resistance of the film are likely to be enhanced. The average primary particle size of the particulate polymer (B) can be determined by image analysis of images taken with an electron microscope. For example, the cross section of the film is observed using a scanning transmission electron microscope (STEM), the particle diameters of 50 or more particles are measured from the observed image, and the average value thereof is the average primary particle diameter of the particulate cycloolefin copolymer. and can be measured, for example, by the method described in Examples.

In a preferred embodiment of the present invention, the film of the present invention is preferably a composite film in which the polymer (B) is dispersed, preferably uniformly dispersed, in the resin (A). For example, the composite film preferably has a sea-island structure, wherein the resin (A) is the sea and the polymer (B) is the islands. Such a composite film tends to improve moisture absorption resistance and heat resistance.

In a preferred embodiment of the present invention, the film of the present invention is preferably formed from the composition of the present invention. Since such a film is preferably formed by removing the solvent from the composition of the present invention, the components contained in the film of the present invention, such as resin (A), polymer (B), phenolic antioxidant and Descriptions regarding secondary antioxidants and the like are the same as those described in the section [Composition]. In a preferred embodiment of the present invention, when the film of the present invention contains a solvent, the type of the solvent and the distance between the HSP values between each component contained in the film of the present invention and the solvent are described in [Composition Item].

In one embodiment of the present invention, the total mass of the resin (A) and polymer (B) contained in the film is preferably 40% by mass or more, more preferably 60% by mass or more, based on the mass of the film. It is preferably 80% by mass or more, particularly preferably 90% by mass or more, and preferably 100% by mass or less. When the total mass of the resin (A) and the polymer (B) contained in the film is at least the above lower limit, the dispersibility of the polymer (B) is likely to be increased, and the hygroscopic resistance and heat resistance of the film are likely to be improved.

The thickness of the film of the present invention can be appropriately selected depending on the application, and is preferably 5 µm or more, more preferably 10 µm or more, still more preferably 20 µm or more, preferably 500 µm or less, more preferably 300 µm or less, and still more preferably. 100 μm or less, particularly preferably 80 μm or less. The thickness of the film can be measured using a film thickness meter or the like, for example, by the method described in Examples. When the film of the present invention is a multilayer film, the above thickness represents the average thickness of the single layer portion.

In one embodiment of the present invention, the moisture absorption rate of the film is preferably 0.64% by mass or less, more preferably 0.60% by mass or less, even more preferably 0.57% by mass or less, and even more preferably 0.54% by mass. % by mass or less, particularly preferably 0.52 mass % or less, particularly preferably 0.50 mass % or less. When the moisture absorption rate is equal to or less than the above upper limit, excellent moisture absorption resistance can be exhibited. Therefore, when the film of the present invention is used for the resin layer of CCL, it is easy to improve the dielectric properties and to suppress dielectric loss and transmission loss. Moreover, the moisture absorption rate of the film of the present invention may generally be 0.01% by mass or more. The moisture absorption rate of the film of the present invention can be determined by exposing the film to an environment with a temperature of 23° C. and a humidity of 50% for a certain period of time and measuring the moisture content of the film after the exposure with a moisture meter. It can be measured by the method described in .

In one embodiment of the present invention, the heat resistance of the film of the present invention may be evaluated by the IR peak retention rate of polymer (B) before and after the heat deterioration test. The retention rate of the IR peak of the polymer (B) is 2500 to 3500 cm ^-1 , preferably 2900 to 3500 cm -1 derived from the cycloolefin polymer when annealed at 360 ° C. for 5 minutes in the atmosphere (that is, before and after the heat deterioration test). It may be a peak retention rate in the range of 3000 cm ⁻¹ . In one embodiment of the present invention, the IR peak retention rate of polymer (B) is specifically expressed by the following formula:
IR peak maintenance rate = [(cycloolefin polymer peak intensity after deterioration test) / (peak intensity of resin (A) after deterioration test)] / [(cycloolefin polymer peak intensity before deterioration test) / (deterioration Peak intensity of resin (A) before test)]
[In the formula, the peak intensity of the cycloolefin polymer shows a peak top intensity of 2500 to 3500 cm ^-1 , preferably 2900 to 3000 cm ^-1 ]
It can be calculated by
In the cycloolefin-based polymer, the peak top intensity of 2500 to 3500 cm ⁻¹ indicates the C—H stretching vibration contained in the cycloolefin-based polymer.
Here, the peak intensity of the resin (A) indicates the peak intensity in the wavelength range with almost no change, preferably no change, in the heat deterioration test, and may be appropriately selected according to the type of the resin (A). Based on the peak intensity in the wavelength range where the resin (A) does not change (for example, in aromatic polyimides and aromatic polyesters, the peak indicating the C=C stretching vibration of the benzene ring can be mentioned), heat deterioration The rate of change in peak intensity of the cycloolefin polymer before and after the test can be determined.

In a preferred embodiment of the present invention, when the resin (A) is a polyimide resin (aromatic polyimide), the IR peak retention rate of the polymer (B) is specifically expressed by the following formula:
IR peak maintenance rate = [(cycloolefin polymer peak intensity after deterioration test) / (polyimide resin peak intensity after deterioration test)] / [(cycloolefin polymer peak intensity before deterioration test) / (deterioration test Peak intensity of the previous polyimide resin)]
[In the formula, the cycloolefin polymer peak intensity is 2500 to 3500 cm ^-1 , preferably 2900 to 3000 cm ^-1 peak top intensity, and the polyimide resin peak intensity is 1450 to 1550 cm ^-1 , preferably 1480 to 1520 cm shows a peak top intensity of ^-1 ]
It can be calculated by
In the cycloolefin-based polymer, the peak top intensity of 2500 to 3500 cm ^-1 indicates the stretching vibration of C-H contained in the cycloolefin-based polymer, and in the polyimide-based resin, the peak top intensity of 1480 to 1520 cm ^-1 is benzene. The C=C stretching vibration of the ring is shown. The IR peak retention rate of polymer (B) can be determined, for example, by the method described in Examples.

In one embodiment of the present invention, the IR peak retention rate of the polymer (B) is preferably 50% or higher, more preferably 60% or higher, even more preferably 70% or higher, still more preferably 80% or higher, particularly preferably 85% or more, particularly preferably 90% or more. When the IR peak retention rate of the polymer (B) is at least the above lower limit, excellent heat resistance tends to be exhibited. The upper limit of the IR peak retention rate is not particularly limited, and is usually 100% or less.

The moisture absorption rate and IR peak retention rate of the film are determined by the composition of the film, for example, the type of structural units constituting the resin (A) and / or polymer (B) contained in the film, their composition ratio, their molecular weight, can be adjusted by appropriately adjusting the content of the polymer (B) in, the particle size of the polymer (B) when it is particulate, the type and content of the phenolic antioxidant, the film production conditions, and the like. For example, the type of the polymer (B) described as a preferred embodiment, the type of structural units constituting the resin (A) and/or the polymer (B) and their composition ratio, the content of the polymer (B), the polymer (B ) is particulate, the particle size, the type of phenolic antioxidant, its content, the distance between the HSP values between the components contained in the film, and the film production method can be selected to determine the moisture absorption rate of the film. may be adjusted within the above range. In particular, when the composition of the present invention is used for film formation, it is easy to adjust the moisture absorption rate of the film within the above range.

The film of the present invention may be a single layer film or a multilayer film containing at least one layer comprising the composition of the present invention. The multilayer film can contain other layers (or other films). Even in such a case, the film including all layers is referred to as the film of the present invention. Other layers include, for example, functional layers. Examples of the functional layer include a primer layer, a gas barrier layer, an adhesive layer, and a protective layer. A functional layer can be used individually or in combination of 2 or more types.

The film of the present invention may be subjected to surface treatment such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc. by a method commonly employed industrially.

The composition and film of the present invention are not limited to the above embodiments, and various modifications are possible without departing from the gist of the present invention. In addition, the configurations, methods, etc. of the embodiments other than the above may be arbitrarily adopted and combined, and the configurations, methods, etc. according to the above one embodiment are applied to the configurations, methods, etc. according to the above other embodiments. You may

The film of the present invention is excellent in moisture absorption resistance, heat resistance and dielectric properties. Therefore, it can be suitably used as a substrate material compatible with printed circuit boards and antenna substrates for high frequency bands. For example, CCL has a structure in which copper foils are laminated on both surfaces of a resin layer via an adhesive. When the film of the present invention is used as the resin layer, transmission loss can be reduced because of its excellent moisture absorption resistance and low dielectric loss. When the film of the present invention is used as the resin layer, the surface smoothness is high, and the variation in physical properties and CTE are reduced. can be suppressed. In addition, since it is excellent in mechanical properties, particularly bending resistance, it is resistant to plastic deformation and does not tend to curl easily, and can be used as a material for flexible substrates.
The film of the present invention is also suitably used for industrial materials such as automobile parts and electric/electronic parts; optical materials such as lenses, prisms, optical fibers, and recording media.

[Film production method]
The method for producing the film of the present invention is not particularly limited, but for example the following steps:
(a) a composition preparation step of preparing a composition comprising a resin (A), a polymer (B), a phenolic antioxidant and optionally a solvent;
(b) a coating step of applying the composition to a substrate to form a coating film; and (c) a film forming step of drying the applied liquid (coating film) to form a film. be able to. When the resin (A) is a polyimide resin, the thermal imidization may include a step of completing the imidization reaction.

<Composition preparation step>
In the composition preparation step, for example, the composition may be adjusted by mixing the resin (A), the polymer (B), the phenolic antioxidant, and optionally the solvent and the additives. It is preferred to use the composition of the invention, in particular the composition obtained by using the above-described process for producing the composition of the invention. By using the composition of the present invention, a film excellent in dispersibility of the polymer (B) in the film, moisture absorption resistance and heat resistance can be formed.

<Coating step and film forming step>
The application step is a step of applying the composition obtained in the composition preparation step to a substrate to form a coating film.

In the coating step, a coating film is formed by coating the composition on the substrate by a known coating method. Known coating methods include, for example, wire bar coating, reverse coating, roll coating such as gravure coating, die coating, comma coating, lip coating, spin coating, screen coating, fountain coating, dipping, A spray method, a curtain coating method, a slot coating method, a casting method, and the like can be mentioned.

Examples of substrates include copper plates (including copper foil), SUS plates (including SUS foil and SUS belt), glass substrates, PET films, PEN films, other polyimide resin films, and polyamide resin films. Among them, SUS plate, glass substrate, PET film, PEN film, etc. are preferable from the viewpoint of excellent heat resistance, and SUS plate, glass substrate, PET film, etc. are more preferable from the viewpoint of adhesion to the film and cost. is mentioned.

In the film forming process, the film can be formed by drying the coating film and optionally peeling it off from the substrate. In one embodiment of the present invention, when the base material is a copper foil, a film is formed without peeling the coating film from the copper foil, and the obtained laminate is a copper-clad laminate in which the film is laminated on the copper foil. It can also be used for laminates. In the case of peeling, a drying process for further drying the film may be performed after peeling. Here, when the composition is applied to a substrate to form a film, the surface of the coating film on the substrate side is almost flat, but the surface opposite to the substrate side (hereinafter also referred to as the air surface). Due to the occurrence of surface roughness in the film, the thickness may vary and the surface smoothness of the film may be impaired. However, the use of the composition of the present invention effectively suppresses the formation of such surface roughness. Therefore, a film having excellent surface smoothness can be formed.
Drying of the coating film can be appropriately selected depending on the heat resistance of the resin (A), etc., and can be carried out at a temperature of usually 50 to 450°C, preferably 55 to 400°C, more preferably 70 to 380°C. , in another embodiment of the invention, at a temperature of 50-400°C, preferably 70-360°C. In a preferred embodiment of the invention, the drying is preferably done in stages. By performing stepwise drying, the composition can be dried uniformly, and the hygroscopic resistance of the resulting film can be easily improved. For example, after heating at a relatively low temperature of 50 to 150°C, it may be heated to 200 to 450°C, preferably 200 to 400°C, more preferably 200 to 350°C. The drying or heating time is preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours. Heating from a low temperature to a high temperature stepwise within such a range tends to improve the hygroscopic resistance, heat resistance, uniformity of thermal conductivity or thermal diffusivity, optical properties, and Tg of the resulting film. If necessary, the coating film may be dried under inert atmosphere conditions such as nitrogen or argon, under vacuum or reduced pressure conditions, and/or under ventilation.
When performing stepwise drying, after peeling the coating film from the substrate during stepwise drying, drying of the coating film may be continued, and after all drying is completed, the coating film ( film) may be peeled off. For example, after the first stage of drying, the coating film may be peeled off from the substrate and the second and subsequent drying stages may be performed, or after all the drying stages are completed, the coating film (film) may be peeled off from the substrate. good. Note that the drying in the first stage may be pre-drying.

When the substrate is a copper foil, for example, the film may be peeled off from the copper foil as the substrate by etching away the copper foil with a ferric chloride solution or the like.

In one embodiment of the present invention, when the resin (A) in the composition is a polyimide resin precursor, such as polyamic acid, and the polyimide resin is produced during film production, after applying the composition to the substrate, Thermal imidization by heating is preferred. By the heating, drying for removing the solvent and thermal imidization can be performed at the same time. The drying and imidization temperature is usually in the range of 50 to 450° C., and from the viewpoint of easily obtaining a smooth film having excellent moisture absorption resistance, it is preferable to carry out heating in stages. For example, after removing the solvent by heating at a relatively low temperature of 50 to 150°C, it may be heated stepwise to a temperature in the range of 300 to 450°C. The heating time can be selected, for example, from the same range as the above range.

When the film of the present invention is a multilayer film, it can be produced by a multilayer film forming method such as a coextrusion method, an extrusion lamination method, a heat lamination method, a dry lamination method, or the like.

EXAMPLES The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples. First, the measurement method will be explained.

<Hansen solubility parameter (HSP) and distance between HSP values>
The Hansen solubility parameters (HSP) of the phenolic antioxidant, the solvent, the cycloolefin copolymer and the polyimide resin, and the distance between the HSP values were obtained as follows.

(Hansen Solubility Parameter (HSP) of Phenolic Antioxidants and Solvents)
Various HSP values were determined using HSPiP (Ver.4.1.07), a program developed by Dr. Hansen's group who proposed the Hansen solubility parameters.
For the HSP value of the phenolic antioxidant, the values in the HSPiP database are used, and AO-330 has a δD of 17.9 MPa ^0.5 , a δP of 0.1 MPa ^0.5 and a δH of 0.9 MPa ^0.5 . , δD of Irganox 1010 is 18.7 MPa ^0.5 , δP is 0.8 MPa ^0.5 , δH is 7.4 MPa ^0.5 , Sumilizer GA80 has δD of 18.3 MPa ^0.5 , δP of 1.6 MPa ^0.5 and δH was 4.7 MPa ^0.5 .
The HSP value of structure S of the phenolic antioxidant was calculated from the structural ^formula using ^HSPiP . 1.4 MPa ^0.5 , δD of structure S of Irganox 1010 is 16.4 MPa ^0.5 , δP is 4.4 MPa ^0.5 , δH is 6.4 MPa ^0.5 , and structure S of Sumilizer GA80 is δD was 16.7 MPa ^0.5 , δP was 5.0 MPa ^0.5 and δH was 4.5 MPa ^0.5 .
The HSP value of the solvent is 18.0 MPa ^{0.5 for GBL, 16.6 MPa 0.5 for δP, 7.4 MPa 0.5 for δH} , and 16 for DMAc. 8 MPa ^0.5 , δP is 11.5 MPa ^0.5 , δH is 9.4 MPa ^0.5 and toluene has δD of 18.0 MPa ^0.5 , δP of 1.4 MPa ^0.5 , δH of 2.0 MPa 0.5 . It was 0 MPa ^0.5 .

(HSP of cycloolefin copolymer)
The solubility of cycloolefin copolymers in various solvents was evaluated. Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used: 2-(1-cyclohexenyl)cyclohexanone, 6-tert-butyl-2,4-xylenol, Methyl chloride, 1,4-dioxane, 1,4-dichlorobenzene, chloroform, toluene, 1-phenyloctane, p-xylene, styrene, ethanol, 1-butanol, N,N-dimethylformamide, dimethylsulfoxide, GBL, N -methylformamide, acetic acid) and 0.1 g of a cycloolefin copolymer were added to prepare a mixed solution. The resulting mixture was subjected to ultrasonic treatment for a total of 6 hours. The appearance of the mixed solution after ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria based on the obtained observation results.
(Evaluation criteria)
2: At room temperature, the appearance of the mixed solution is cloudy and precipitation occurs, but when heated to 50° C. and stirred with a stirrer for 30 minutes, the appearance of the mixed solution becomes transparent.
1: Appearance of mixture is transparent at room temperature.
0: At room temperature, the appearance of the mixture is cloudy and precipitation occurs, and even after heating to 50° C. and stirring with a stirrer for 30 minutes, the appearance of the mixture does not become clear.

From the results of evaluating the solubility of the obtained cycloolefin copolymer in a solvent, the HSP value was calculated by the Hansen dissolving sphere method described above using HSPiP.

(HSP of polyimide resin)
The solubility of the polyimide resin in various solvents was evaluated. Solubility evaluation was carried out using solvents with known solubility parameters in a transparent container (see HSPiP database, solvents used acetone, toluene, ethanol, tetrahydrofuran, N,N-dimethylformamide, dimethylsulfoxide, hexane, GBL, ethyl acetate , methyl ethyl ketone, propylene glycol monomethyl ether, 1-butanol, N-methylformamide, 1-methylnaphthalene, bromobenzene, 1-methylimidazole, pyrazole, acetic acid) and 0.1 g of polyimide resin were added to prepare a mixed solution. . The resulting mixture was subjected to ultrasonic treatment for a total of 6 hours. The appearance of the mixed solution after ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria based on the obtained observation results.
(Evaluation criteria)
1: The appearance of the mixed liquid is cloudy.
0: Appearance of mixed liquid is transparent.

From the evaluation result of the solubility of the obtained polyimide resin in a solvent, the HSP value was calculated by the Hansen dissolving sphere method described above using HSPiP.

(Distance between HSP values)
The distance (Ra) between the HSP values of the two substances was obtained according to formula (Y).

<Norbornene (NB) content>
The content of norbornene-derived monomer units (also referred to as “NB content”) in the cycloolefin copolymer was measured using ¹³ C-NMR. The ¹³ C-NMR measurement conditions are as follows.
Apparatus: Bruker AVANCE600, 10 mm cryoprobe Measurement temperature: 135°C
Measurement method: proton decoupling method Concentration: 100 mg/mL
Number of times of integration: 1024 times Pulse width: 45 degrees Pulse repetition time: 4 seconds Chemical shift value standard: Tetramethylsilane Solvent: 1,2-dichlorobenzene-d4 and 1,1,2,2 _- tetrachloroethane _- d2 The NB content in the cycloolefin copolymer is based on 1,2-dichlorobenzene (127.68 ppm) and is calculated according to RA Wendt, G. Fink, Macromol. , 2001, 202, 3490”. Specifically, signal integral values observed at chemical shift values of 44.0 to 52.0 ppm in a spectrum chart measured using ¹³ C-NMR: I _C2,C3 (carbons at positions 2 and 3 of the norbornene ring atom), signal integral value observed at a chemical shift value of 27.0-33.0 ppm: I _{C5, C6} + I _CE (derived from the carbon atoms at the 5 and 6 positions of the norbornene ring and the carbon atoms of the ethylene part ), it was obtained from the following formula.
NB content (mol%) = I _{C2, C3} / (I _{C5, C6} + I _CE ) x 100

<Meso type double chain/racemo type double chain>
The ratio of the meso-type double chain and the racemo-type double chain of the norbornene double-chain of the cycloolefin copolymer (meso-type double chain/racemo-type double chain) is measured using ¹³ C-NMR under the same conditions as the measurement of the NB content. Measured at
The meso-type double chain/racemo-type double chain of the norbornene double chain is based on 1,1,2,2-tetrachloroethane (74.24 ppm), and is described in RA Wendt, G. Fink, Macromol. Chem. Phys., 2001, 202, 3490” and “JP-A-2008-285656”. Specifically, the meso-type double chain/racemo-type double chain is observed at chemical shift values of 27.5 to 28.4 ppm in a spectrum chart measured using ¹³ C-NMR: signal integral value: IC5 _{, C6} -m (derived from carbon atoms at positions 5 and 6 of the norbornene ring of the meso-type double chain), signal integral values observed at chemical shift values 28.4-29.6 ppm: I _{C5, C6} -r (racemo type derived from carbon atoms at positions 5 and 6 of a double-chained norbornene ring), it was obtained from the following formula.
Meso-type bilinkage/racemo-type bilinkage=I _C5,C6 −m/I _C5,C6 −r

<Refractive index>
The refractive index of the cycloolefin copolymer was obtained by measuring under the following conditions using a sheet-like sample molded to a thickness of 100 μm with a vacuum press.
Equipment: Atago Co., Ltd. Abbe refractometer "TYPE-3"
Light source wavelength: 589.3 nm
Intermediate liquid: 1-bromonaphthalene Measurement temperature: 23 ± 1 ° C

<CTE>
The CTE of the cycloolefin copolymer was measured using TMA under the following conditions, and the CTE at 50°C to 100°C was calculated.
Apparatus: TMA/SS6200 manufactured by Hitachi High-Tech Science Co., Ltd.
Indenter (probe) diameter: 3.5 mm Load: 38.5 mN Temperature program: Temperature rise from 20°C to 130°C at a rate of 5°C/min Test piece: 10 mm x 10 mm x 1 mm rectangular parallelepiped

<Glass transition temperature>
(Tg of cycloolefin copolymer)
The Tg of the cycloolefin copolymer was obtained by measuring the softening temperature by TMA based on JIS K 7196. Specifically, a sample (thickness: 1.0 mm) obtained by molding a cycloolefin copolymer into a sheet with a vacuum press was measured under the following conditions, and the onset of the displacement when the indenter was sinking into the sample was taken as the softening temperature. bottom.
Apparatus: "TMA/SS6200" manufactured by Hitachi High-Tech Science Co., Ltd.
Indenter diameter: 1mm
Load: 780mN
Temperature program: Temperature rise from 20°C to 380°C at a rate of 5°C/min

(Tg of polyimide resin)
The Tg of the polyimide resin was determined by the following measurements. Using TA Instrument Co., Ltd., "DMA Q800", measured under the following samples and conditions to obtain a tan δ curve, which is the ratio of the values of loss modulus and storage modulus, and then the peak of the tan δ curve. Tg was calculated from the highest peak.
Sample: length 5-15 mm, width 5 mm
Experimental mode: DMA Multi-Frequency-Strain
Experiment mode detailed conditions:
(1) Clamp: Tension: Film
(2) Amplitude: 5 µm
(3) Frequency: 10 Hz (no change in all temperature intervals)
(4) Preload Force: 0.01N
(5) Force Track: 125N
Temperature conditions: (1) Range of temperature rise: Normal temperature to 400°C, (2) Rate of temperature rise: 5°C/min Main data collected: (1) Storage modulus (E'), (2) Loss modulus (Loss modulus, E″), (3) tan δ (E″/E′)

<Mw and Mn of cycloolefin copolymer>
The polystyrene equivalent Mw and Mn of the cycloolefin copolymer were measured using GPC. GPC measurement was performed under the following conditions, and peaks were designated by defining a baseline on the chromatogram based on the description of ISO16014-1.

(GPC device and software)
Apparatus: HLC-8121GPC/HT (manufactured by Tosoh Corporation)
Measurement software: GPC-8020 model II data collection Version 4.32 (manufactured by Tosoh Corporation)
Analysis software: GPC-8020 modelII data analysis Version 4.32 (manufactured by Tosoh Corporation)

(Measurement condition)
GPC column: TSKgel GMH6-HT inner diameter 7.8 mm × length 300 mm (manufactured by Tosoh Corporation) 3 columns connected Mobile phase: ortho-dichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) BHT [dibutylhydroxytoluene ] was added at a concentration of 0.1 g/100 mL.
Flow rate: 1 mL/min Column oven temperature: 140°C
Autosampler temperature: 140°C
System oven temperature: 40°C
Detection: Differential Refractive Index Detector (RID)
RID cell temperature: 140°C
Sample solution injection volume: 300 μL
Standard materials for GPC column calibration: Standard polystyrene manufactured by Tosoh Corp. was weighed out in combinations as shown in Table 1 below, and 5 mL of mobile phase was added to each combination and dissolved at room temperature for 2 hours to prepare.

(Sample solution preparation conditions)
Solvent: BHT was added to ortho-dichlorobenzene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., special grade) at a concentration of 0.1 g/100 mL.
Sample solution concentration: 1 mg/mL
Automatic shaker for dissolution: DF-8020 (manufactured by Tosoh Corporation)
Dissolution conditions: 5 mg of sample is enclosed in a 1,000 mesh SUS wire mesh bag, the wire mesh bag containing the sample is placed in a test tube, 5 mL of the mobile phase is added, the test tube is covered with aluminum foil, The test tube was set in the DF-8020 and stirred at 140° C. for 120 minutes at a stirring speed of 60 reciprocations/minute. GPC measurement was performed using the stirred solution as a sample.

<Mw of polyimide resin and polyamic acid>
The polystyrene equivalent Mw of the polyimide resin and polyamic acid was measured using GPC. GPC measurement was performed under the following conditions.
GPC measurement (1) Pretreatment method A DMF eluent (10 mmol/L lithium bromide-added DMF solution) was added to the sample to a concentration of 2 mg/mL, heated at 80°C for 30 minutes with stirring, and cooled. A measurement solution was obtained by filtration through a 0.45 μm membrane filter.
(2) Measurement conditions Column: TSKgel SuperAWM-H × 2 + SuperAW2500 × 1 (inner diameter 6.0 mm × length 150 mm, three connected)
Eluent: DMF (10 mmol/L lithium bromide added)
Flow rate: 1.0 mL/min Detector: RI detector Column temperature: 40°C
Injection volume: 100 μL
Molecular weight standard: standard polystyrene

<Evaluation of solubility>
Evaluation as to whether or not the cycloolefin copolymer, the polyimide resin and the polyamic acid are dissolved in the solvents used in the examples and comparative examples was performed as follows.
First, 9.9 g of the solvent is weighed into a 30-mL glass screw tube, and stirred with a magnetic stirrer. 0.1 g of polymer, resin or polyamic acid is added thereto and stirred at 24° C. for 24 hours. After stirring for 24 hours, when solids could not be visually confirmed and the solution was transparent, it was evaluated as "dissolved". On the other hand, when a solid was visually confirmed or the solution was opaque, it was evaluated as "not dissolved".

<Particle size of particulate cycloolefin copolymer in particulate cycloolefin copolymer dispersion and composition>
(Particle size of particulate cycloolefin copolymer in particulate cycloolefin copolymer dispersion obtained using cycloolefin copolymer solutions obtained in Production Examples 1 and 3)
The median diameter of the particulate cycloolefin copolymers in the particulate cycloolefin copolymer dispersions obtained in Examples 1 to 3, 5 to 7, 9, 11, 12, 14 and Comparative Examples 1 and 3 was measured by laser diffraction. It was determined by the scattering type particle size distribution measurement used.
Specifically, the particulate cycloolefin copolymer dispersions obtained in Examples 1 to 3, 5 to 7, 9, 11, 12, 14 and Comparative Examples 1 and 3 were placed in a glass cell having a capacity of 3.5 mL. Further, GBL was added to dilute 1000 times to obtain a dispersion liquid sample containing particulate cycloolefin copolymer. The resulting dispersion sample was measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by Malvern Panalytical, model: NanoZS, refractive index: 1.70-0.20i) to determine the particulate cycloolefin copolymer particles. The median diameter of
As described above, in Examples 1 to 3, 5 to 7, 9, 11, 12, and 14 and Comparative Examples 1 and 3, polyimide resin or polyamic acid was used in an amount within a range not affecting the particle size of the particulate cycloolefin copolymer. , and antioxidant were added to the dispersion to form the composition, the median size of the particulate cycloolefin copolymer in the dispersion was taken as the median size of the particulate cycloolefin copolymer in the composition.

(Particle size of particulate cycloolefin copolymer in particulate cycloolefin copolymer dispersion obtained using crushed cycloolefin copolymer powder obtained in Production Examples 2 and 4)
The median diameters of the particulate cycloolefin copolymers in the dispersions of the particulate cycloolefin copolymers obtained in Examples 4, 8, 10 and 13 and Comparative Examples 2 and 4 were measured by scattering particle size distribution using laser diffraction. obtained by
Specifically, the particulate cycloolefin copolymer obtained in Production Examples 2 and 4 was dispersed in isopropanol to obtain a dispersion sample containing the particulate cycloolefin copolymer. The resulting dispersion sample was measured using a laser diffraction/scattering particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., model: MT3300EX II) to determine the median diameter of the particulate cycloolefin copolymer.
As described above, in Examples 4, 8, 10, and 13 and Comparative Examples 2 and 4, polyamic acid was added to the dispersion in an amount within a range that did not affect the particle size of the particulate cycloolefin copolymer to form the composition. bottom. Also, particulate cycloolefin copolymers are not soluble in isopropanol, DMAc and GBL. Therefore, the median diameter of the particulate cycloolefin copolymer in the dispersion sample was taken as the median diameter of the particulate cycloolefin copolymer in the composition.

<Solvent Content in Particulate Cycloolefin Copolymer Dispersion>
The solvent content in the particulate cycloolefin copolymer dispersions obtained in Examples and Comparative Examples was measured by gas chromatography. Specifically, the measurement was performed under the following conditions, and the solvent content in the particulate cycloolefin copolymer dispersion was calculated by one-point calibration.
Apparatus: Agilent 7890B gas chromatograph (manufactured by Agilent Technologies Inc.)
Column: DB-5 (manufactured by Agilent Technologies Inc.)
Carrier gas: Helium Inlet temperature: 200°C
Detector temperature: 250°C
Internal standard solution: benzyl alcohol Solvent: chloroform

<Thickness of composite film>
The thickness of the composite films obtained in Examples and Comparative Examples was measured using a digimatic indicator (manufactured by Mitutoyo Co., Ltd., "ID-C112XBS"), and measuring the thickness at five or more arbitrary points of the film. Their average value was taken as the thickness of the composite film.

<Average primary particle size of particulate cycloolefin copolymer in film>
Cross-sectional observation of the composite films obtained in Examples and Comparative Examples was performed using a scanning transmission electron microscope (STEM). The particle diameters of 50 or more particles were measured from the observed image, and the average value thereof was taken as the average primary particle diameter of the particulate cycloolefin copolymer.
STEM observation and measurement conditions Apparatus name: HeLiоs G4UX manufactured by Japan FEI Co., Ltd. (flake preparation apparatus)
Hitachi High-Tech Co., Ltd. S-5500 (for STEM observation)
Accelerating voltage: 30kv
Magnification: 20000 times

<Moisture absorption rate of composite film>
The moisture absorption of the composite films obtained in Examples 1 to 4, 9 to 11 and Comparative Examples 1 and 2 was measured with a Karl Fischer moisture meter (evaporation type). Specifically, a film cut into a size of 20 mm × 20 mm is put in a vial bottle for a moisture vaporizer, and the temperature is 23 ° C. and the humidity is 50% (hereinafter also referred to as “23 ° C. 50%”) for 24 hours. more exposed. After that, the vial was sealed in the same environment, and the water content in the film was measured under the conditions shown below.
・ Karl Fischer device: 915 KF Ti-Touch manufactured by Metrohm
・ Titration reagent: Honeywell HYDRANAL (registered trademark)-Coulomat AG
・Conditioning before titration: stable at a drift value of 10 μg/min or less ・Titration conditions: generation current 400 mV, standby time 300 seconds, titration end point 50 mV
Moisture vaporizer: 860 KF thermoprep manufactured by Metrohm Film heating conditions: 150°C, conveyed at 50 mL/min of dry air.
-Blank measurement: An empty vial bottle was sealed in an environment of 23°C and 50%, and measured under the same conditions as above.
The moisture absorption rate of the composite films obtained in Examples and Comparative Examples was calculated from the following formula.
Moisture absorption rate = [(moisture content in film) - (moisture content in blank measurement)] ÷ (film mass after exposure for 24 hours or more at 23 ° C. 50% environment) × 100

<Heat resistance evaluation of composite film>
The heat resistance of the composite films obtained in Examples 5 to 8, 12 to 14 and Comparative Examples 3 and 4 was evaluated by the heat resistance test shown below and the single reflection "ATR FT-IR" of the cycloolefin copolymer before and after the heat resistance test. was evaluated from the rate of change in
・Heat test: Maintain the composite film at 360 ° C. for 5 minutes in the atmosphere ・Device: VARIAN 670-IR manufactured by VARIAN Co., Ltd.
・ATR unit: Specac silver gate ATR evolution (germanium flat plate)
・Measurement surface: The surface on the glass substrate side when the composite film was peeled from the glass substrate ・Measurement conditions: 32 integration times, wave number resolution 4 cm ⁻¹ , scan speed 5 kHz
• IR peak retention rate calculation: Calculated from the following formula.
IR peak retention rate = [(cycloolefin copolymer peak intensity after deterioration test) / (peak intensity of polyimide resin after deterioration test)] ÷ [(cycloolefin copolymer peak intensity before deterioration test) / (before deterioration test Peak intensity of polyimide resin)]
・ Cycloolefin copolymer peak intensity: 2900-3000 cm ^-1 peak top intensity (CH stretching vibration)
・ Polyimide resin peak intensity: 1480 to 1520 cm ^-1 peak top intensity (C = C stretching vibration of benzene ring)

<Details of reagents>
For the synthesis of the cycloolefin copolymer, toluene manufactured by Sumitomo Chemical Co., Ltd., styrene manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 2-norbornene manufactured by Arakawa Chemical Industries, Ltd. (hereinafter referred to as "NB"), Tosoh Co., Ltd. Triisobutylaluminum (hereinafter referred to as "TIBA") manufactured by Finechem Co., Ltd. and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (hereinafter referred to as "AB") manufactured by AGC Corporation were used.

Toluene is dehydrated using molecular sieves 13X (manufactured by Union Showa Co., Ltd.) and activated alumina ("NKHD-24" manufactured by Sumitomo Chemical Co., Ltd.), and then nitrogen gas is blown to remove dissolved oxygen. It was used.

NB is dissolved in toluene, dehydrated using molecular sieves 13X (manufactured by Union Showa Co., Ltd.) and activated alumina ("NKHD-24" manufactured by Sumitomo Chemical Co., Ltd.), and then nitrogen gas is blown. (hereinafter referred to as "NB solution"). The NB concentration in the NB solution was measured using gas chromatography.

Isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride (hereinafter referred to as "complex") was synthesized according to the method described in JP-A-9-183809. used.

[Production of cycloolefin copolymer]
<Synthesis Example 1>
1,500 mL of NB solution (NB concentration: 3.00 mol/L) was added to the autoclave whose inside was dried under reduced pressure, and the temperature was raised to 60°C. While stirring the inside of the system, hydrogen partial pressure: 5 kPa, ethylene partial pressure: 100 kPa. 7.0 mL of a toluene solution (concentration: 10 mmol/L) was added to initiate polymerization of ethylene and NB. During the polymerization, the temperature in the system was kept at 60° C., and ethylene was continuously supplied to keep the pressure in the system at the initial value. After 3 hours from the initiation of polymerization, 5.0 mL of water was added to terminate the polymerization, and the solution in the autoclave was extracted. To the extracted solution, 1,500 g of toluene and 100 g of magnesium sulfate were added and stirred, then 100 mL of water was added and stirred, and solids were removed by filtration. The resulting liquid was added dropwise to acetone, and the precipitated powder was isolated by filtration. The isolated powder was further washed with acetone and dried under reduced pressure at 120° C. for 2 hours to obtain 216 g of cycloolefin copolymer. In the resulting cycloolefin copolymer, the NB content is 82.5 mol%, the Tg is 297°C, the Mw is 343,000, the Mw/Mn is 1.79 and the CTE is 47.0 ppm/ was K. The cycloolefin copolymer had a δD of 17.4 MPa ^0.5 , a δP of 1.6 MPa ^0.5 , a δH of 3.8 MPa 0.5 and a meso/racemo bilink of ^0.5 . 11 and the refractive index was 1.54. Table 2 shows the synthesis conditions of Synthesis Example 1.

<Synthesis Example 2>
1,427 mL of NB solution (NB concentration: 3.00 mol/L) and 55.2 mL of styrene were added to an autoclave whose inside was dried under reduced pressure, and the temperature was raised to 80°C. While stirring the system, 3.0 mL of hexane solution of TIBA (concentration: 1.0 mol / L), 0.32 g of AB, and 15.0 mL of toluene solution of complex (concentration: 10 mmol / L) were added, and NB and styrene were added. started to polymerize. The temperature in the system was kept at 80°C during the polymerization. Two hours after the initiation of polymerization, 3.0 mL of water was added to terminate the polymerization, and the solution in the autoclave was extracted. The resulting liquid was added dropwise to a large excess amount of acetone to the extracted solution, and the precipitated powder was isolated by filtration. The isolated powder was further washed with acetone and dried under vacuum at 150° C. for 2 hours to yield 198.3 g of cycloolefin copolymer. In the resulting cycloolefin copolymer, the NB content was 96.3 mol%, Mw was 79,000, Mw/Mn was 1.83 and Tg was greater than 300°C. The cycloolefin copolymer had a δD of 17.4 MPa ^{0.5, a δP of 1.6 MPa 0.5 and} a δH of 3.8 MPa ^0.5 . Table 3 shows the synthesis conditions of Synthesis Example 2.

<Production Example 1: Production of cycloolefin copolymer solution 1>
A cycloolefin copolymer solution 1 was obtained by dissolving the cycloolefin copolymer obtained in Synthesis Example 1 in toluene at a concentration of 2% by mass.

<Production Example 2: Production of crushed cycloolefin copolymer powder 1>
The cycloolefin copolymer obtained in Synthesis Example 1 was pulverized with a counter jet mill manufactured by Kitamura Co., Ltd. and classified by a filter to obtain crushed cycloolefin copolymer powder 1 having a median diameter of 2.6 μm. .

<Production Example 3: Production of cycloolefin copolymer solution 2>
A cycloolefin copolymer solution 2 was obtained by dissolving the cycloolefin copolymer obtained in Synthesis Example 2 in toluene at a concentration of 2% by mass.

<Production Example 4: Production of crushed cycloolefin copolymer powder 2>
The cycloolefin copolymer obtained in Synthesis Example 2 was pulverized with a counter jet mill manufactured by Kitamura Co., Ltd. and classified by a filter to obtain crushed cycloolefin copolymer powder 2 having a median diameter of 2.7 μm. rice field.

[Synthesis of polyimide resin]
A reactor comprising a separable flask equipped with a silica gel tube, a stirrer and a thermometer, and an oil bath were prepared. After the flask was filled with dry nitrogen to create a nitrogen atmosphere, 75.52 g of 6FDA and 54.44 g of TFMB were added. While this was stirred at 400 rpm, 519.84 g of DMAc was added and stirring was continued until the contents of the flask became a homogeneous solution. Subsequently, stirring was continued for an additional 20 hours while adjusting the temperature in the container to be in the range of 20 to 30° C. using an oil bath, and the mixture was reacted to produce polyamic acid. After 30 minutes, the stirring speed was changed to 100 rpm. After stirring for 20 hours, the temperature of the reaction system was returned to room temperature, and 649.8 g of DMAc was added to adjust the polymer concentration to 10% by mass. Further, 32.27 g of pyridine and 41.65 g of acetic anhydride were added, and imidization was carried out by stirring at room temperature for 10 hours. The polyimide varnish was removed from the reaction vessel. The resulting polyimide varnish was dropped into methanol for reprecipitation, and the resulting powder was dried by heating to remove the solvent to obtain a polyimide resin as a solid content. The resulting polyimide resin had a δD of 18.1 MPa ^{0.5, a δP of 8.3 MPa 0.5 ,} and a δH of 9.3 MPa ^0.5 . The polyimide resin had an Mw of 334,300 and a Tg of 361°C. The distance between the HSP values of the polyimide resin and the cycloolefin copolymer obtained in Production Example 1 was 8.3.

[Synthesis of polyamic acid]
A reactor was prepared by attaching a silica gel tube, a stirrer and a thermometer to a separable flask. After creating a nitrogen atmosphere in the flask using dry nitrogen, 399.20 g of DMAc and 16.00 g (0.148 mol) of p-PDA were added, followed by stirring at room temperature to dissolve p-PDA in DMAc. rice field. To this was added 21.2869 g (0.0724 mol) of BPDA and 33.1603 g (0.0724 mol) of TAHQ while stirring at 400 rpm. After that, the mixture was stirred at room temperature for 3 hours to obtain a polyamic acid solution.

[Example 1]
100.0 g of the cycloolefin copolymer solution obtained in Production Example 1 and 98.0 g of GBL were mixed and distilled off under reduced pressure at 50 hPa and 80° C. so that the toluene content was 7 parts by mass with respect to 100 parts by mass of GBL. Then toluene was distilled off to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.14 µm.
To 51.3 g of the resulting dispersion (1.9% by mass of the cycloolefin copolymer), Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4 -Hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.0487 g was added and stirred, and then 2.0 g of the polyimide resin obtained above was added to obtain a polyimide-cycloolefin copolymer mixture, A composition was obtained. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. No cycloolefin copolymer aggregates larger than 1 mm were observed in the resulting composition.
The resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes and peeling the film from the glass substrate, the film was fixed with a metal frame and further heated at 360 ° C. for 15 minutes in the atmosphere to obtain a polyimide-cycloolefin having a thickness of 50 μm. A copolymer composite film was obtained. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 µm.
The distance between the HSP values between the cycloolefin copolymer and the polyimide resin used in Example 1 is 8.8, the distance between the HSP values between the cycloolefin copolymer and toluene is 2.2, and the distance between the polyimide resin and toluene is 8.8. The distance between HSP values is 10.0, the distance between HSP values between the cycloolefin copolymer and GBL is 15.5, the distance between HSP values between polyimide resin and GBL is 8.5, and AO-330 The distance between HSP values between and GBL is 17.7, the distance between HSP values between structure S of AO-330 and GBL is 17.6, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4, and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values between AO-330 and the polyimide resin is 11.7, the distance between the HSP values between the structure S of AO-330 and the polyimide resin is 11.5, and the distance between AO-330 and toluene The distance between HSP values was 1.7.
According to the above solubility evaluation method, the cycloolefin copolymer used in Example 1 dissolved in toluene but did not dissolve in GBL. Also, the polyimide resin dissolved in GBL but did not dissolve in toluene.

[Example 2]
Instead of AO-330, BASF Japan Co., Ltd. Irganox 1010; In the same manner as in Example 1, a composition as a polyimide-cycloolefin copolymer mixed liquid and a polyimide-cycloolefin copolymer composite film having a thickness of 50 μm were obtained. The content of Irganox 1010 is 5.0 parts by weight per 100 parts by weight of the cycloolefin copolymer. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 µm.
The distance between the HSP values between the cycloolefin copolymer and the polyimide resin used in Example 2 is 8.8, the distance between the HSP values between the cycloolefin copolymer and toluene is 2.2, and the cycloolefin copolymer and GBL The distance between HSP values between polyimide resin and toluene is 15.5, the distance between HSP values between polyimide resin and toluene is 10.0, the distance between HSP values between polyimide resin and GBL is 8.5, and Irganox 1010 and The distance between HSP values with GBL is 15.9, the distance between HSP values between Structure S of Irganox 1010 and GBL is 12.7, and the distance between HSP values between Irganox 1010 and cycloolefin copolymer is 4.5. and the distance between the HSP values of structure S of Irganox 1010 and the cycloolefin copolymer was 4.3. Further, the distance between the HSP values between Irganox 1010 and the polyimide resin is 7.8, the distance between the HSP values between the structure S of Irganox 1010 and the polyimide resin is 5.9, and the distance between the HSP values between Irganox 1010 and toluene. was 5.6.

[Example 3]
Instead of AO-330, BASF Japan Co., Ltd. Irganox 1010 0.0487 g, BASF Japan Co., Ltd. Irgafos 168; (tris (2,4-di-tert-butylphenyl) phosphite) 0.0292 g was added. Except for this, in the same manner as in Example 1, a composition as a polyimide-cycloolefin copolymer mixed solution and a polyimide-cycloolefin copolymer composite film having a thickness of 50 μm were obtained. The respective contents of Irganox 1010 and Irgafos 168 are 5.0 parts by mass and 3.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 µm.
The distance between the HSP values between the cycloolefin copolymer and the polyimide resin used in Example 3 is 8.8, the distance between the HSP values between the cycloolefin copolymer and toluene is 2.2, and the cycloolefin copolymer and GBL The distance between HSP values between polyimide resin and toluene is 15.5, the distance between HSP values between polyimide resin and toluene is 10.0, the distance between HSP values between polyimide resin and GBL is 8.5, and Irganox 1010 and The distance between HSP values with GBL is 15.9, the distance between HSP values between Structure S of Irganox 1010 and GBL is 12.7, and the distance between HSP values between Irganox 1010 and cycloolefin copolymer is 4.5. and the distance between the HSP values of structure S of Irganox 1010 and the cycloolefin copolymer was 4.3. In addition, the distance between the HSP values between Irganox 1010 and the polyimide resin is 7.8, the distance between the HSP values between the structure S of Irganox 1010 and the polyimide resin is 5.9, and the distance between the HSP values between Irganox 1010 and toluene The distance was 5.6.

[Comparative Example 1]
Sumilizer GA80 manufactured by Sumitomo Chemical Co., Ltd. instead of AO-330; Polyimide-cycloolefin copolymer was prepared in the same manner as in Example 1, except that 0.0487 g of tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl) was added. A composition as a mixed liquid and a polyimide-cycloolefin copolymer composite film having a thickness of 50 μm were obtained, and the content of Sumilizer GA80 was 5.0 parts by weight per 100 parts by weight of the cycloolefin copolymer. In the film, the content of the particulate cycloolefin copolymer was 32.8% by weight based on the total weight of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size was 0.16 μm.
The distance between the HSP values between the cycloolefin copolymer and the polyimide resin used in Comparative Example 1 was 8.8, the distance between the HSP values between the cycloolefin copolymer and toluene was 2.2, and the cycloolefin copolymer and GBL The distance between HSP values is 15.5, the distance between HSP values between polyimide resin and toluene is 10.0, the distance between HSP values between polyimide resin and GBL is 8.5, and Sumilizer GA80 and The distance between HSP values with GBL is 15.3, the distance between HSP values between Structure S of Sumilizer GA80 and GBL is 12.2, and the distance between HSP values between Sumilizer GA80 and cycloolefin copolymer is 2.0. and the distance between the HSP values of Structure S of Sumilizer GA80 and the cycloolefin copolymer was 3.7. Further, the distance between the HSP values between Sumilizer GA80 and the polyimide resin is 8.1, the distance between the HSP values between the structure S of Sumilizer GA80 and the polyimide resin is 6.5, and the distance between the HSP values between Sumilizer GA80 and toluene The distance was 2.8.

[Example 4]
7.31 g of the crushed cycloolefin copolymer powder 1 obtained in Production Example 2, 52.03 g of DMAc and 0.365 g of AO-330 were mixed and stirred to obtain a dispersion liquid. 100 g of polyamic acid solution (15% by mass of polyamic acid) was added to the resulting dispersion to obtain a composition as a polyamic acid-cycloolefin copolymer mixed solution. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer.
The resulting composition was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 50° C. for 80 minutes and peeling the polyamic acid-cycloolefin copolymer composite film from the glass substrate, the film was fixed with a metal frame and further heated at 360° C. for 15 minutes in the atmosphere to obtain a polyamic film. The acid was imidized to obtain a 50 μm thick polyimide-cycloolefin copolymer composite film. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 μm.
The distance between the HSP values between the cycloolefin copolymer and the polyamic acid used in Example 4 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and DMAc is 11.4, and AO-330 and DMAc The distance between HSP values of AO-330 is 14.4, the distance between HSP values between Structure S of AO-330 and DMAc is 14.0, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4. and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values of the cycloolefin copolymer used in Example 4 and the polyimide resin obtained by imidating the polyamic acid was 6.0 or more.
According to the above solubility evaluation method, the polyamic acid used in Example 4 dissolved in DMAc but did not dissolve in toluene.

[Comparative Example 2]
A composition as a polyamic acid-cycloolefin copolymer mixture and a thickness of 50 μm were prepared in the same manner as in Example 4 except that 0.365 g of Sumilizer GA80 manufactured by Sumitomo Chemical Co., Ltd. was added instead of AO-330. A polyimide-cycloolefin copolymer composite film was obtained. The content of Sumilizer GA80 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 μm.
The distance between the HSP values between the cycloolefin copolymer used in Comparative Example 2 and DMAc was 11.4, the distance between the HSP values between Sumilizer GA80 and DMAc was 11.4, and the distance between Structure S of Sumilizer GA80 and DMAc was 11.4. The HSP value distance is 8.1, the HSP value distance between Sumilizer GA80 and the cycloolefin copolymer is 2.0, and the HSP value distance between Structure S of Sumilizer GA80 and the cycloolefin copolymer is 3.7. there were.

[Example 5]
A composition prepared in the same manner as in Example 1 was cast on a glass substrate to form a coating film at a line speed of 0.4 m/min. After heating the coating film at 70 ° C. for 60 minutes, peeling the film from the glass substrate, fixing the film with a metal frame, and further heating at 200 ° C. for 60 minutes in a nitrogen atmosphere, a 50 μm thick polyimide- A cycloolefin copolymer composite film was obtained. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 µm.

[Example 6]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 5 except that a composition prepared in the same manner as in Example 2 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 µm.

[Example 7]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 5 except that a composition prepared in the same manner as in Example 3 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 μm.

[Example 8]
A coating film was prepared from the composition prepared in the same manner as in Example 4 by casting on a glass substrate at a line speed of 0.4 m/min. The coating film was heated at 50°C for 80 minutes, the polyamic acid-cycloolefin copolymer composite film was peeled off from the glass substrate, the film was fixed with a metal frame, and the temperature was increased stepwise to 360°C in a nitrogen atmosphere. The polyamic acid was imidized by heating at 360° C. for 5 minutes to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 50 μm. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 µm.

[Comparative Example 3]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 5 except that the composition prepared in the same manner as in Comparative Example 1 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.16 µm.

[Comparative Example 4]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 8, except that the composition prepared in the same manner as in Comparative Example 2 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 µm.

[Example 9]
100.0 g of the cycloolefin copolymer solution 2 obtained in Production Example 3 and 98.0 g of DMAc were mixed, and the pressure was reduced at 50 hPa and 80° C. so that the toluene content of DMAc was 0.6 parts by mass with respect to 100 parts by mass of DMAc. Toluene was removed by distillation to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.13 µm.
To 30.0 g of the obtained dispersion (2.0% by mass of the cycloolefin copolymer), Adekastab AO-330 manufactured by ADEKA Corporation; (1,3,5-tris(3,5-di-tert-butyl-4 -Hydroxyphenylmethyl)-2,4,6-trimethylbenzene) 0.03 g was added and stirred, and then 8.0 g of the polyamic acid solution obtained above was added to obtain a polyamic acid-cycloolefin copolymer mixed solution. As, the composition was obtained. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. No cycloolefin copolymer aggregates larger than 1 mm were observed in the resulting composition.
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 4, except that the composition obtained above was used. In the obtained film, the content of the particulate cycloolefin copolymer was 33.3% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 µm.
The distance between the HSP values between the cycloolefin copolymer and the polyamic acid used in Example 9 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and toluene is 2.2, and the cycloolefin copolymer and DMAc The distance between HSP values is 11.4, the distance between HSP values between AO-330 and DMAc is 14.4, and the distance between HSP values between structure S of AO-330 and DMAc is 14.0. , the distance between the HSP values of AO-330 and the cycloolefin copolymer was 3.4, and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values of the cycloolefin copolymer used in Example 9 and the polyimide resin obtained by imidizing the polyamic acid was 6.0 or more.
According to the solubility evaluation method described above, the cycloolefin copolymer used in Example 9 dissolved in toluene but did not dissolve in DMAc. Polyamic acid dissolved in DMAc but did not dissolve in toluene.

[Example 10]
A composition as a polyamic acid-cycloolefin copolymer mixed solution was prepared in the same manner as in Example 4, except that the cycloolefin copolymer crushed powder 2 obtained in Production Example 4 was added instead of the cycloolefin copolymer crushed powder 1. and a polyimide-cycloolefin copolymer composite film with a thickness of 50 μm. The content of AO-330 is 5.0 parts by mass with respect to 100 parts by mass of the cycloolefin copolymer. In the obtained film, the content of the particulate cycloolefin copolymer was 32.8% by mass based on the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 μm.
The distance between the HSP values between the cycloolefin copolymer and the polyamic acid used in Example 10 is 6.0 or more, the distance between the HSP values between the cycloolefin copolymer and DMAc is 11.4, and AO-330 and DMAc The distance between HSP values of AO-330 is 14.4, the distance between HSP values between Structure S of AO-330 and DMAc is 14.0, and the distance between HSP values between AO-330 and cycloolefin copolymer is 3.4. and the distance between the HSP values of structure S of AO-330 and the cycloolefin copolymer was 2.8. Further, the distance between the HSP values of the cycloolefin copolymer used in Example 10 and the polyimide resin obtained by imidizing the polyamic acid was 6.0 or more.
According to the solubility evaluation method described above, the cycloolefin copolymer used in Example 10 dissolved in toluene but did not dissolve in DMAc. Polyamic acid dissolved in DMAc but did not dissolve in toluene.

[Example 11]
100.0 g of the cycloolefin copolymer solution 1 obtained in Production Example 1 and 98.0 g of DMAc were mixed and distilled under reduced pressure at 50 hPa and 80° C. so that the toluene content was 7 parts by mass with respect to 100 parts by mass of DMAc. toluene was distilled off to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion and composition measured by the above method was 0.13 µm.
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 1, except that the particulate cycloolefin copolymer dispersion prepared above was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the obtained composite film was 0.14 µm.
The distance between the HSP values between the cycloolefin copolymer used in Example 11 and toluene was 2.2, the distance between the HSP values between the cycloolefin copolymer and DMAc was 11.4, and the distance between AO-330 and DMAc was The inter-HSP value distance was 14.4, and the inter-HSP value distance between structure S of AO-330 and DMAc was 14.0.
According to the above solubility evaluation method, the cycloolefin copolymer used in Example 11 dissolved in toluene but did not dissolve in DMAc. Also, the polyimide resin dissolved in DMAc but did not dissolve in toluene.

[Example 12]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 8 except that a composition prepared in the same manner as in Example 9 was used. The content of the particulate cycloolefin copolymer in the resulting composite film was 33.3% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 µm.

[Example 13]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 8 except that a composition prepared in the same manner as in Example 10 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 2.7 μm.

[Example 14]
A polyimide-cycloolefin copolymer composite film having a thickness of 50 μm was obtained in the same manner as in Example 5 except that a composition prepared in the same manner as in Example 11 was used. The content of the particulate cycloolefin copolymer in the obtained composite film was 32.8% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer. The average primary particle size of the particulate cycloolefin copolymer in the resulting composite film was 0.15 µm.

The moisture absorption of the polyimide-cycloolefin copolymer composite films obtained in Examples 1-4, 9-11 and Comparative Examples 1 and 2 was measured according to the above method. Table 4 shows the results obtained.
The IR peak retention rate of the polyimide-cycloolefin copolymer composite films obtained in Examples 5-8, 12-14 and Comparative Examples 3 and 4 was measured according to the above method. Table 5 shows the results obtained.

As shown in Table 4, the films obtained in Examples 1 to 4 and 9 to 11 had low hygroscopicity, and were superior to Comparative Examples 1 and 2 in hygroscopic resistance. In addition, as shown in Table 5, the films obtained in Examples 5 to 8 and 12 to 14 had higher COC IR peak retention rates and superior heat resistance than Comparative Examples 3 and 4.

Claims (11)

The resin (A), the cycloolefin-based polymer (B), and a phenolic antioxidant are contained, and the distance between the HSP values between the phenolic antioxidant and the cycloolefin-based polymer (B) is 2.1 or more, and the resin ( A composition in which the distance between the HSP values of A) and the cycloolefin polymer (B) is 6.0 or more. The phenolic antioxidant has the formula (P):

[In formula (P), R ^p , R ^q , R ^r and R ^s each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms, and * represents a bond]
The distance (1) between the HSP values between the structure S in which the substituent P in the phenolic antioxidant is substituted with a hydrogen atom and the cycloolefin polymer (B) is phenolic oxidation 2. The composition according to claim 1, wherein the distance (2) between the HSP values between the inhibitor and the cycloolefinic polymer (B) is smaller. 3. The composition according to claim 2, wherein the absolute value of the difference between the HSP value distance (1) and the HSP value distance (2) is 0.1 or more. The composition according to claim 1 or 2, wherein the distance between the HSP values of the phenolic antioxidant and the cycloolefinic polymer (B) is 12.0 or less. The composition according to claim 1 or 2, wherein the cycloolefin polymer (B) is particulate. The composition according to claim 1 or 2, wherein the cycloolefin polymer (B) has a glass transition temperature of 100°C or higher. The cycloolefin polymer (B) has the formula (I):

[In formula (I), m represents an integer of 0 or more, R ⁷ to R ¹⁸ each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹ to R When there are a plurality of ¹⁴ , they may be the same or different, and R ¹⁶ and R ¹⁷ may be bonded to each other to form a ring together with the carbon atom to which they are bonded.]
3. The composition according to claim 1 or 2, comprising a cycloolefin-derived monomer unit (I) represented by: The content of the monomer unit (I) in the cycloolefin-based polymer (B) is 60 mol% or more with respect to the total molar amount of repeating units constituting the cycloolefin-based polymer (B). 8. The composition according to 7. The composition according to claim 1 or 2, wherein the resin (A) is at least one resin selected from the group consisting of polyimide resins, liquid crystal polymers, fluorine resins, aromatic polyether resins and maleimide resins. thing. The composition according to claim 1 or 2, wherein the resin (A) has a glass transition temperature of 200°C or higher. The resin (A), the cycloolefin-based polymer (B), and a phenolic antioxidant are contained, and the distance between the HSP values between the phenolic antioxidant and the cycloolefin-based polymer (B) is 2.1 or more, and the resin ( A film in which the distance between the HSP values of A) and the cycloolefin polymer (B) is 6 or more.