WO2022045358A1 - Composition - Google Patents

Abstract

Provided is a composition not containing aggregates of particles. The composition contains a resin (A), a particulate cycloolefin-based polymer (B), and a solvent. The solvent contains a first solvent and a second solvent. The HSP value distance between the second solvent and the cycloolefin-based polymer (B) is 8.5 or more.

Description

Composition

The present invention relates to a composition capable of forming a film that can be used as a substrate material compatible with a printed circuit board for a high frequency band and an antenna substrate, and the film.

With the full-scale spread of the 5th 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 for antennas. However, in the high frequency band, the transmission loss derived from the substrate material has a significant effect, so 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. The transmission loss of the CCL can be suppressed by reducing the dielectric loss of the resin layer serving as the transmission line, particularly the dielectric loss tangent and the relative permittivity.
A cycloolefin-based polymer is known as a substrate material having a dielectric loss tangent or a low relative permittivity, and a film in which this cycloolefin-based polymer is composited with another resin has been studied. For example, Patent Document 1 describes a composition containing a specific resin (A), a cycloolefin polymer (B), a compatibilizer (C), and a solvent, and a composite film formed from the composition. There is.

Japanese Unexamined Patent Publication No. 2017-125176

The resin layer in the CCL, which can handle the high frequency band, has a film surface to reduce dielectric loss, increase the density of wiring, improve processing accuracy during miniaturization, and prevent peeling from copper foil. Smoothness is required. However, according to the study of the present inventor, in a composition containing a cycloolefin polymer in the form of particles in addition to a resin and a solvent, the particles may form aggregates in the manufacturing process or the like, and it is difficult to form a film. It turned out that there is. Further, even if it is possible to form a film, the surface smoothness of the film is not sufficient, and when it is used as a resin layer in CCL, for example, the thickness of the wiring becomes non-uniform, or when it is used with a copper foil. It was found that peeling may occur.

Therefore, an object of the present invention is to provide a composition free of agglomerates of particles.
Another object of the present invention is to provide a film having excellent surface smoothness.

As a result of diligent studies to solve the above problems, the present inventor has determined that the solvent is the first solvent and the second solvent in the composition containing the resin (A), the particulate cycloolefin polymer (B) and the solvent. The present invention has been completed by finding that the above problems can be solved when the distance between the HSP values of the second solvent and the cycloolefin polymer (B) is 8.5 or more. That is, the present invention includes the following suitable forms.

[1] A composition containing a resin (A), a particulate cycloolefin polymer (B), and a solvent.
A composition comprising the first solvent and the second solvent, and the distance between the HSP values of the second solvent and the cycloolefin polymer (B) is 8.5 or more.
[2] The composition according to [1], wherein the first solvent is a solvent in which the cycloolefin polymer (B) is dissolved.
[3] The composition according to [1] or [2], wherein the second solvent is a solvent in which the cycloolefin polymer (B) is insoluble.
[4] The composition according to any one of [1] to [3], wherein the distance between the HSP values of the first solvent and the cycloolefin polymer (B) is 4.0 or less.
[5] The composition according to any one of [1] to [4], wherein the second solvent is a solvent in which the resin (A) is dissolved.
[6] The composition according to any one of [1] to [5], wherein the distance between the HSP values of the second solvent and the resin (A) is 10.0 or less.
[7] The composition according to any one of [1] to [6], wherein the distance between the HSP values of the resin (A) and the cycloolefin polymer (B) is 6 or more.
[8] The composition according to any one of [1] to [7], wherein the content of the first solvent is 120 parts by mass or less with respect to 100 parts by mass of the second solvent.
[9] The content of the particulate cycloolefin polymer (B) is 5 to 50% by mass with respect to the total mass of the resin (A) and the particulate cycloolefin polymer (B), [1] to The composition according to any one of [8].
[10] The cycloolefin polymer (B) has the formula (I) :.

[In the formula (I), m represents an integer of 0 or more, R ⁷ to R ¹⁸ represent hydrogen atoms, halogen atoms or hydrocarbon groups having 1 to 20 carbon atoms independently of each other, and R ¹¹ to R. When a plurality of ¹⁴ are present, they may be independently the same or different from each other, and R ¹⁶ and R ¹⁷ may be bonded to each other and form a ring with the carbon atom to which they are bonded. ]
The composition according to any one of [1] to [9], which comprises a monomer unit (1) derived from cycloolefin represented by.
[11] The resin (A) is at least one resin selected from the group consisting of a polyimide resin, a liquid crystal polymer, a fluororesin, an aromatic polyether resin and a maleimide resin, [1] to [10]. ] The composition according to any one of.
[12] The composition according to any one of [1] to [11], wherein the resin (A) has a glass transition temperature of 180 ° C. or higher.
[13] A film containing the resin (A) and the particulate cycloolefin polymer (B).
A film in which the standard deviation of the average thickness obtained in each of the 10 measurement regions obtained by dividing a region of a straight line of 1 mm on the surface of the film into 10 equal parts is 2.5 or less.
[14] The film according to [13], wherein the distance between the HSP values of the resin (A) and the cycloolefin polymer (B) is 6 or more.
[15] The film according to [13] or [14], wherein the particulate cycloolefin polymer (B) has an average primary particle diameter of 15 μm or less.

The composition of the present invention does not contain agglomerates of particles. Further, the film of the present invention has excellent surface smoothness. Therefore, the film of the present invention can be suitably used as a material for a printed wiring board or the like that can be used for a printed circuit board or an antenna board.

[Composition]
The composition of the present invention contains a resin (A), a particulate cycloolefin polymer (B) and a solvent, the solvent containing a first solvent and a second solvent, and a second solvent and a cycloolefin polymer (B). ) And the distance between the HSP values is 8.5 or more. In the present specification, the "cycloolefin polymer (B)" is simply "polymer (B)", and the "particulate cycloolefin polymer (B)" is simply "particulate polymer (B)", "particle polymer (B)". The "particle size of B)" may be simply referred to as "particle size", and the "film formed from the composition" may be simply referred to as "film". Further, in the present specification, the dielectric property means a property related to dielectric including dielectric loss, relative permittivity and dielectric loss tangent, and that the dielectric property is enhanced or improved is, for example, dielectric loss, relative permittivity and / or. It shows that the dielectric loss tangent is reduced. Further, in the present specification, the mechanical property means the mechanical property including the bending resistance and the elastic modulus, and when the mechanical property is enhanced or improved, for example, the bending resistance and / or the elastic modulus is increased. Show that.

The present inventors have focused on the relationship between the aggregation of the particulate polymer (B) and the distance between the HSP values of the polymer and the solvent. As a result, two kinds of solvents were used, and among these, two kinds of solvents were used. When a solvent having an HSP value distance of 8.5 or more from the cycloolefin polymer (B) is used as the second solvent, the aggregation of the particulate polymer (B) can be suppressed and the aggregate of the particulate polymer (B) can be suppressed. It has been found that a composition containing no solvent can be formed. Therefore, the composition of the present invention does not contain an aggregate of the particulate polymer (B) (hereinafter, also simply referred to as an aggregate). Further, since the composition of the present invention does not contain aggregates, a film having excellent surface smoothness can be formed.

<Second solvent>
The composition of the present invention contains a second solvent. The distance between the HSP values of the second solvent and the polymer (B) is 8.5 or more. Therefore, it is possible to form a film having excellent surface smoothness without containing aggregates of the particulate polymer (B). If the distance between the HSP values of the second solvent and the polymer (B) is less than 8.5, aggregates are formed in the manufacturing process, and the obtained composition may contain the aggregates, which makes film formation difficult. Tend to be.

In the composition of the present invention, the distance between the HSP values of the second solvent and the polymer (B) is preferably 9.0 or more, more preferably 10.0 or more, still more preferably 11.0 or more. When the distance between the HSP values is at least the above lower limit, it is easy to suppress the aggregation of the particulate polymer (B), so that it is easy to form a composition containing no aggregates, and it is easy to improve the surface smoothness of the obtained film. .. Further, since the particle size of the particulate polymer (B) can be easily reduced, the dispersibility of the particles can be easily improved. Further, it is easy to improve mechanical properties such as particle dispersibility, heat resistance and bending resistance of the obtained film. The upper limit of the distance between the HSP values of the second solvent and the polymer (B) is preferably 30.0 or less, more preferably 25.0 or less, still more preferably 20.0. When the distance between the HSP values of the second solvent and the polymer (B) is not more than the above upper limit, it is easy to suppress the aggregation of the particulate polymer (B), so that the dispersibility of the particles can be easily improved and obtained. It is easy to improve the particle dispersibility of the film.

HSP is a Hansen solubility parameter (δ), defined by a three-dimensional parameter of (δD, δP, δH), and the formula (X) :.
δ ² = (δD) ² + (δP) ² + (δH) ² ... (X)
[In equation (X), δD represents the Lоndоn dispersion force term, δP represents the molecular polarization term (dipole interpole force term), and δH represents the hydrogen bond term].
Represented by. Details of HSP are described in "PROPERTIES OF POLYMERS" (Author: WDVANKREVEREN, Publisher: ELSEVIER SCIENTFIC PUBLISHING COMPANY, 1989, 5th edition). The Hansen solubility parameters δD, δP, and δH can be calculated using HSPiP (Hansen Sоlubility Parameters in Practice), a program developed by Dr. Hansen's group who proposed the Hansen solubility parameter, for example, in Examples. The described Ver. 4.1.07 and the like can be used. The details of the Hansen-dissolved sphere method will be described below. The component of interest is dissolved in a solvent having a known HSP value, and the solubility of the component in a specific solvent is evaluated. The solubility is evaluated by visually determining whether or not the target component is dissolved in the solvent. This is done for multiple solvents. As the type of the solvent, it is preferable to use a solvent having a wide range of δt, more specifically, 10 kinds or more, more preferably 15 kinds or more, still more preferably 18 kinds or more. Next, the HSP having a composition targeting the center coordinates (δd, δp, δh) of the Hansen sphere obtained by inputting the obtained solubility evaluation result into HSPiP is used. In addition to the above methods, HSP may be obtained from a structural formula using, for example, numerical values or literature values in a database of HSPiP, or HSPiP may be used. In the present specification, the value of the Hansen solubility parameter is referred to as an HSP value, and the HSP value represents a 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 be obtained by any of the above methods, for example, by the method described in Examples. ..

The distance between the Hansen solubility parameters (hereinafter, may be abbreviated as HSP) of two substances is called the distance between HSP values. The distance between HSPs (Ra) is an index showing the affinity between the two substances, and the smaller the value, the higher the affinity between the two substances. On the contrary, the larger the Ra value, the lower the affinity between the two substances, that is, the more difficult it is to be compatible.
The distance between the HSP values determines 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 the equation (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 the HSP values are as defined above, and can be obtained according to the above method.

The second solvent is not particularly limited, and is an amide-based solvent such as N, N-dimethylacetamide (hereinafter, may be referred to as DMAc), N-N-dimethylformamide (hereinafter, may be referred to as DMF) and the like. Solvent; lactone-based solvent such as γ-butyrolactone (hereinafter, may be referred to as GBL), γ-valerolactone, etc .; sulfur-containing solvent such as dimethylsulfone, dimethylsulfoxide, sulfolane; carbonate-based solvent such as ethylene carbonate, propylene carbonate, etc. Solvents; pyrrolidone-based solvents such as N-methylpyrrolidone (hereinafter, may be abbreviated as NMP); and combinations thereof may be mentioned. Among these, from the viewpoint that it is easy to suppress the formation of aggregates of the particulate polymer (B) and it is easy to improve the dispersibility because the particle size is easily reduced, and the surface smoothness and particle dispersibility of the obtained film. At least one selected from the group consisting of an amide-based solvent, a lactone-based solvent, and a pyrrolidone-based solvent from the viewpoint of easily increasing heat resistance and mechanical properties and easily reducing the linear expansion coefficient (hereinafter, may be referred to as CTE). It is preferable that the number is one. Further, the polymer (B) dispersion liquid may contain water, an alcohol solvent, a ketone solvent, an acyclic ester solvent, an ether solvent and the like. The second solvent can be used alone or in combination of two or more. When the composition is produced by the preferred method described later, the second solvent is preferably a solvent capable of producing the particulate polymer (B) by contact with the polymer (B) solution.

In one embodiment of the present invention, the second solvent is preferably a solvent in which the polymer (B) does not dissolve. With such a solvent, the formation of aggregates of the particulate polymer (B) is likely to be suppressed, and the particle size is likely to be reduced, so that the dispersibility is likely to be improved. Further, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and flexibility of the obtained film, and it is easy to reduce CTE. Here, in the present specification, the evaluation of "dissolving" or "not dissolving" can be performed according to the method described in <Evaluation of solubility> in Examples.

In one embodiment of the present invention, it is preferable that the distance between the HSP values of the second solvent and the polymer (B) is larger than the interaction radius of the polymer (B). With such a relationship, the polymer (B) is difficult to dissolve in the second solvent, so that it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle size is easily reduced, so that the dispersion is dispersible. Easy to increase. Further, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and flexibility of the obtained film, and it is easy to reduce CTE. In addition, in this specification, the interaction radius is a plurality of solvents capable of dissolving a specific polymer, that is, when the Hansen solubility parameter of a good solvent is plotted in a three-dimensional HSP space, the plots of the good solvents are similar to each other. In other words, it tends to gather in a spherical shape at a close position, that is, at the coordinates, and refers to the radius of the sphere, that is, the Hansen solubility sphere. It can be said that a solute having a large interaction radius is easily soluble in many solvents, and a solute having a small interaction radius is easily soluble in a small number of solvents and difficult to be soluble in many solvents. For a specific unknown polymer, it is investigated whether various solvents are good solvents or poor solvents by conducting a solubility test, and the results are input to HSPiP to interact with the polymers. The radius is calculated. In the present specification, the "radius of interaction" is as defined above and can be determined according to the above method.

In one embodiment of the present invention, the second solvent is preferably a solvent in which the resin (A) is dissolved. With such a solvent, the formation of aggregates of the particulate polymer (B) is likely to be suppressed, and the particle size is likely to be reduced, so that the dispersibility is likely to be improved. Further, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and flexibility of the obtained film, and it is easy to reduce CTE. In addition, the film formed from the composition tends to form the sea-island structure described later.

In one embodiment of the present invention, the HSP value distance between the second solvent and the resin (A) is preferably 10.0 or less, more preferably 9.5 or less, still more preferably 9.0 or less, and particularly preferably 8. It is 5.5 or less, preferably 0.01 or more, and more preferably 0.1 or more. When the distance between the HSP values is not more than the above upper limit, the affinity between the second solvent and the resin (A) can be improved, so that the formation of aggregates of the particulate polymer (B) can be easily suppressed, and the formation of aggregates can be easily suppressed. Since the particle size is easily reduced, it is easy to improve the dispersibility. Further, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and bending resistance of the obtained film, and it is easy to reduce CTE.

In one embodiment of the present invention, the distance between the HSP values of the second solvent and the resin (A) is preferably smaller than the interaction radius of the resin (A). With such a relationship, the resin (A) is easily dissolved in the second solvent, so that it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle size is easily reduced, so that the dispersibility is good. Easy to increase. Further, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and flexibility of the obtained film, and it is easy to reduce CTE.

<First solvent>
The composition of the present invention contains a first solvent. Examples of the first solvent include hydrocarbon solvents such as benzene, toluene, pentane, hexane, heptane, cyclohexane and xylene; and halogenated hydrocarbon solvents such as dichloromethane and ethylene dichloride. Of these, hydrocarbon solvents are preferred. When the first solvent contains a hydrocarbon solvent, the solubility of the polymer (B) and the first solvent is increased, so that it is easy to suppress the formation of aggregates of the particulate polymer (B) and the particle size is reduced. It is easy to improve the dispersibility because it is easy to do. Further, it is easy to improve the surface smoothness, particle dispersibility, heat resistance and mechanical properties of the obtained film, and it is easy to reduce CTE. The first solvent can be used alone or in combination of two or more.

In one embodiment of the present invention, the first solvent is preferably a solvent in which the polymer (B) is dissolved. With such a solvent, the formation of aggregates of the particulate polymer (B) is likely to be suppressed, and the particle size is likely to be reduced, so that the dispersibility is likely to be improved. Further, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and flexibility of the obtained film, and it is easy to reduce CTE.

In one embodiment of the present invention, the distance between the HSP values of the first 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 not more than the above upper limit, the solubility of the first solvent and the polymer (B) is enhanced, so that it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle diameter is also increased. Is easy to reduce, so it is easy to improve the dispersibility. Further, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and flexibility of the obtained film, and it is easy to reduce CTE. The lower limit of the distance between HSP values usually exceeds 0.

In one embodiment of the present invention, it is preferable that the distance between the HSP values of the first 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 first solvent, so that it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle size is easily reduced, so that the dispersibility is good. Easy to increase. Further, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and flexibility of the obtained film, and it is easy to reduce CTE.

In one embodiment of the present invention, the first solvent is preferably a solvent in which the resin (A) does not dissolve. With such a solvent, the formation of aggregates of the particulate polymer (B) is likely to be suppressed, and the particle size is likely to be reduced, so that the dispersibility is likely to be improved. Further, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and flexibility of the obtained film, and it is easy to reduce CTE.

In one embodiment of the present invention, the distance between the HSP values of the first solvent and the resin (A) is preferably 5.0 or more, more preferably 6.0 or more, still more preferably 7.0 or more, still more preferably. Is 8.0 or more, particularly preferably 9.0 or more. When the distance between the HSP values is not less than the above lower limit, the resin (A) is difficult to dissolve in the first solvent, so that it is easy to suppress the formation of aggregates of the particulate polymer (B) and the particle size is reduced. It is easy to improve the dispersibility because it is easy to do. Further, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and flexibility of the obtained film, and it is easy to reduce CTE. The upper limit of the distance between the HSP values of the first 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, and particularly. It is preferably 21.0 or less. When the distance between the HSP values of the first solvent and the resin (A) is not more than the above upper limit, it is easy to suppress the aggregation of the particulate polymer (B), so that the dispersibility of the particles can be easily improved and obtained. It is easy to improve the particle dispersibility of the film.

In one embodiment of the present invention, it is preferable that the distance between the HSP values of the first solvent and the resin (A) is larger than the interaction radius of the resin (A). With such a relationship, the resin (A) is difficult to dissolve in the first solvent, so that it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle size is easily reduced, so that the dispersion is dispersible. Easy to increase. Further, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and flexibility of the obtained film, and it is easy to reduce CTE.

In one embodiment of the present invention, the solubility of the polymer (B) in the first solvent is preferably greater than the solubility of the polymer (B) in the second solvent. With such a relationship, it is easy to suppress the formation of aggregates of the particulate polymer (B), and it is easy to reduce the particle size, so that it is easy to improve the dispersibility. Further, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and flexibility of the obtained film, and it is easy to reduce CTE. The solubility of the polymer (B) in the solvent can be measured by the following method. Add 1,000 mg of polymer (B) and 3 mL of solvent to the sample bottle, and stir at room temperature for 2 hours. Next, the solid phase and the liquid phase were separated by filtration, and the solid phase was dried at 80 ° C. for 2 hours under reduced pressure, and then the mass: X (mg) was measured, and the solubility Y (mg / mL) was measured by the following formula. ) Can be obtained.
Y = (1,000-X) / 3
In addition, for example, in the definition of the present specification, when the polymer (B) corresponds to "soluble" in the first solvent and "insoluble" in the second solvent, the solubility in the first solvent is clearly higher. Therefore, it is not necessary to measure the solubility.

In one embodiment of the present invention, the content of the first solvent contained in the composition of the present invention is preferably 120 parts by mass or less, more preferably 100 parts by mass, based on 100 parts by mass of the content of the second solvent. Below, 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 more preferably 35 parts by mass or less, particularly still more preferably 30 parts by mass or less, and particularly even more preferably. It is less than 30 parts by mass, most preferably 25 parts by mass or less, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more. When the content of the first solvent is not more than the above upper limit, it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle size is easily reduced, so that the dispersibility is easily improved. Further, it is easy to improve the surface smoothness, particle dispersibility, heat resistance and mechanical properties of the obtained film, and it is easy to reduce CTE. When the content of the first solvent is at least the above lower limit, it is easy to prepare the composition.

In one embodiment of the present invention, the content of the solvent contained in the composition of the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70 with respect to the mass of the composition. It is 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, still more preferably 95% by mass or less. When the content of the solvent is in the above range, the formation of aggregates of the particulate polymer (B) is likely to be suppressed, and the particle size is likely to be reduced, so that the dispersibility is likely to be improved. Further, it is easy to improve the surface smoothness, particle dispersibility, heat resistance and mechanical properties of the obtained film, and it is easy to reduce CTE.

The solvent contained in the composition of the present invention may contain a solvent other than the first solvent and the second solvent as long as the effect of the present invention is not impaired. The other solvent is not particularly limited, and a conventional solvent can be used. In one embodiment of the present invention, the total mass of the first solvent and the second solvent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably, with respect to the mass of the solvent contained in the composition. Is 90% by mass or more, 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 in the above range, it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle size is easily reduced, so that the dispersibility is easily improved. .. Further, it is easy to improve the surface smoothness, particle dispersibility, heat resistance and mechanical properties of the obtained film, and it is easy to reduce CTE.

<Particulate cycloolefin polymer (B)>
The monomer unit constituting the cycloolefin polymer (B) is not particularly limited, but it is easy to suppress the formation of aggregates of the particulate polymer (B) and the particle size is easily reduced, so that the dispersibility is improved. The polymer (B) is a polymer (B) from the viewpoint of easy improvement, surface smoothness, particle dispersibility, heat resistance, water absorption resistance, dielectric property and mechanical property of the obtained film, and easy reduction of CTE. Equation (I)

[In equation (I), m represents an integer of 0 or more,
R ⁷ to R ¹⁸ represent hydrogen atoms, halogen atoms or hydrocarbon groups having 1 to 20 carbon atoms independently of each other, and when a plurality of R ¹¹ to R ¹⁴ are present, they are independently and identical to each other. Well, they may be different, and R ¹⁶ and R ¹⁷ may bond to each other and form a ring with the carbon atoms they bond to.]
It is preferable to contain the monomer unit (I) derived from cycloolefin represented by.

In equation (I), m is an integer of 0 or more. From the viewpoint that it is easy to suppress the formation of aggregates of the particulate polymer (B) and it is easy to improve the dispersibility because the particle size is easily reduced, the surface smoothness, particle dispersibility, heat resistance and bending resistance of the obtained film are easy. The upper limit of m is preferably an integer of 3 or less, more preferably an integer of 2 or less, and further preferably 1 from the viewpoint of easily enhancing mechanical properties such as, and easily reducing CTE, and also being easily available. It is the following integer.

Examples of the hydrocarbon group having 1 to 20 carbon atoms, which is a member of the substituents of R ⁷ to R ¹⁸ , include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group and a dodecyl group. An aryl group such as a phenyl group, a trill group, or a naphthyl group; an aralkyl group such as a benzyl group or a phenethyl group; a group in which a part of the hydrogen atom of the alkyl group, the aryl group or the aralkyl group is substituted with a halogen atom and the like can be mentioned. Be done. Among these, from the viewpoint that it is easy to suppress the formation of aggregates of the particulate polymer (B) and it is easy to improve the dispersibility because the particle size is easily reduced, and the surface smoothness and particle dispersibility of the obtained film. Alkyl groups, aryl groups or aralkyl groups are preferable from the viewpoints that heat resistance, water absorption resistance, dielectric properties and mechanical properties can be easily enhanced and CTE can be easily reduced. 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, and are preferably a hydrogen atom or an aralkyl group having 1 to 20 carbon atoms. More preferably, it is an alkyl group of ~ 10.

Examples of the cycloolefin represented by the 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, from the viewpoint that it is easy to suppress the formation of aggregates of the particulate polymer (B) and it is easy to improve the dispersibility because the particle size is easily reduced, the surface smoothness, the particle dispersibility, and the heat resistance of the obtained film are easy. Norbornene is preferable from the viewpoint of easily enhancing mechanical properties such as properties and bending resistance, easily reducing CTE, and easily obtaining a raw material monomer. The cycloolefin represented by the formula (I) may be used alone or in combination of two or more.

In one embodiment of the invention, the polymer (B) preferably comprises a two-chain structure of monomeric units (I). By including the two-chain structure, the heat resistance is likely to be improved as compared with a polymer having the same content of the monomer unit (I). The presence or absence of the two-chain structure can be determined by ¹³ C-NMR spectrum analysis. For example, in the case of a tetracyclodecene-ethylene copolymer, signals derived from the ethylene-tetracyclodecene-ethylene chain, which is an isolated chain of tetracyclodecene, appear at around 54.7 ppm and around 51.1 ppm, and endo-exo bond. Ethylene-tetracyclodecene-tetracyclodecene-ethylene chain-derived signals, which are two chains of tetracyclodecene, are located near 51.5 ppm and around 50.8 ppm, and are exo-exo-bonded ethylene-tetracyclodecene-tetracyclo. Since the signal derived from the decene-ethylene chain appears at around 55.3 ppm and around 54.3 ppm, it can be determined by the signal pattern around 55 ppm and around 50 ppm.

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 two chain represented by the following structural formula (III-2) is included.

The ratio of the meso-type two-chain to the racemo-type two-chain (hereinafter, may be referred to as meso-type two-chain / racemo-type two-chain) is preferably 0.50 or less, more preferably 0.40 or less, 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 racemic-type two-chain is within the above range, the mechanical properties and heat resistance of the obtained film can be easily improved. The ratio of the meso-type two-chain to the racemic-type two-chain is, for example, using ¹³ C-NMR in "RA Wendt, G. Fink, Macromol. Chem. Phys., 2001, 202, 3490" and "Special. It can be calculated based on the attribution described in "Kai 2008-285656", and specifically, it can be calculated by the method described in Examples. As a method for adjusting the meso-type two-chain and the racemo-type two-chain within the above range, 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 polymer (B) is preferably 60 mol% or more, more preferably 65 mol% or more, still more preferably 65 mol% or more, based on the total molar amount of the repeating units constituting the polymer (B). Is 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, it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle size is easily reduced, so that the dispersibility is easily improved. Therefore, it is easy to improve the surface smoothness of the obtained film. Further, since it is easy to raise the glass transition temperature (hereinafter, may be referred to as Tg), it is easy to reduce the CTE of the obtained film, and it is easy to improve the mechanical properties such as heat resistance and bending resistance. When the content of the monomer unit (I) is not more than the above upper limit, it is easy to enhance mechanical properties such as bending resistance. The content of the monomeric unit (I) is based on the attribution described in "RA Wendt, G. Fink, Macromol. Chem. Phys., 2001, 202, 3490" using ¹³ C-NMR. It can be calculated, for example, by the method described in Examples.

The polymer (B) can easily suppress the formation of aggregates of the particulate polymer (B), and can easily improve the dispersibility because the particle size is easily reduced, as well as the surface smoothness of the obtained film and the particles. From ethylene, linear α-olefins having 3 to 20 carbon atoms, and aromatic vinyl compounds having 8 to 20 carbon atoms, from the viewpoint of easily enhancing mechanical properties such as dispersibility and bending resistance and easily reducing CTE. It is preferable to contain a monomer unit (II) derived from at least one selected from the group, and more preferably to contain a monomer unit (II) derived from ethylene.

Examples of the linear α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like. .. Among these, from the viewpoint that it is easy to suppress the formation of aggregates of the particulate polymer (B) and it is easy to improve the dispersibility because the particle size is easily reduced, and the surface smoothness and particle dispersibility of the obtained film. And, from the viewpoint of easily enhancing mechanical properties such as bending resistance and easily reducing CTE, propylene, 1-butene, 1-hexene or 1-octene is preferable, and propylene is more preferable. As the linear α-olefin having 3 to 20 carbon atoms, one type may be used alone, or two or more types may be used in combination. The "linear α-olefin" refers to a linear olefin having a carbon-carbon unsaturated double bond at the α-position.

Examples of the aromatic vinyl compound having 8 to 20 carbon atoms include styrene, methylstyrene, dimethylstyrene, ethylstyrene, tert-butylstyrene, vinylnaphthalene, vinylanthracene, diphenylethylene, isopropenylbenzene, isopropenyltoluene and isopropenyl. Examples thereof include 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 the raw material monomer, easy reduction of CTE of the film, and easy improvement of mechanical properties such as bending resistance. .. As the aromatic vinyl compound having 8 to 20 carbon atoms, one kind may be used alone, or two or more kinds may be used in combination.

In one embodiment of the present invention, the polymer (B) is made from ethylene, propylene and styrene from the viewpoints of easy availability of a raw material monomer, easy reduction of CTE of a film, and easy improvement of mechanical properties such as bending resistance. It may contain a monomer unit (II) derived from at least one selected from the group consisting of ethylene and styrene, more preferably a monomer unit (II) derived from at least one selected from the group consisting of ethylene and styrene. preferable.

The content of the monomer unit (II) in the polymer (B) is preferably 0 mol% or more, more preferably 0.01 mol% or more, based on the total molar amount of the repeating units constituting the polymer (B). It is 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, and particularly preferably 25 mol% or less. When the content of the monomer unit (II) is at least the above lower limit, it is easy to improve the mechanical properties such as processability, moldability and bending resistance of the obtained film. When the content of the monomer unit (II) is not more than the above upper limit, it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle size is easily reduced, so that the dispersibility is easily improved. .. Further, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and bending resistance of the obtained film, and it is easy to reduce CTE.

In one embodiment of the present invention, the formation of aggregates of the particulate polymer (B) is easily suppressed, the particle size is easily reduced, so that the dispersibility is easily improved, and the surface smoothness of the obtained film is smooth. The polymer (B) is preferably a cycloolefin-based copolymer from the viewpoint of easily enhancing mechanical properties such as particle dispersibility, processability, heat resistance and bending resistance, and easily reducing CTE, and formula (I). ), At least selected from the group consisting of the monomer unit (I) derived from the cycloolefin represented by), ethylene, a linear α-olefin having 3 to 20 carbon atoms, and an aromatic vinyl compound having 8 to 20 carbon atoms. A cycloolefin-based polymer containing a monomer unit (II) derived from one is more preferable, and a monomer unit (I) derived from norbornen and a monomer unit (II) derived from ethylene are used. It is more preferable to use an ethylene-norbornene copolymer containing the above, or a styrene-norbornene copolymer containing a monomer unit (I) derived from norbornen and a monomer unit (II) derived from styrene.

The polymer (B) may contain other monomeric units (III). Other monomeric units (III) include, for example, conjugated diene such as butadiene or isoprene; non-conjugated diene such as 1,4-pentadien; acrylic acid; acrylic acid ester such as methyl acrylate or ethyl acrylate; methacrylic. Acids; methacrylic acid esters such as methyl methacrylate or ethyl methacrylate; vinyl acetate and the like. The other monomer unit (III) can be used alone or in combination of two or more.
The polymer (B) can be used alone or in combination of two or more.

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, still 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 Mw is at least the above lower limit, the heat resistance of the film is likely to be increased and the strength is likely to be improved. When Mw is not more than the above upper limit, the formation of aggregates of the particulate polymer (B) is likely to be suppressed, and the particle size is likely to be reduced, so that the dispersibility is likely to be improved. Further, it is easy to improve the mechanical properties and moldability of the film.

In one embodiment of the present invention, the ratio (Mw / Mn) of Mw of the polymer (B) to the number average molecular weight (hereinafter, the number average molecular weight may be abbreviated as Mn) is preferably 2. 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, still more preferably 1. It is 50 or more, more preferably 1.60 or more, and particularly preferably 1.65 or more. When the Mw / Mn ratio is not more than the above upper limit, it is easy to improve the mechanical properties of the film. Further, when the Mw / Mn ratio is at least the above lower limit, the moldability is likely to be improved. In addition, Mw and Mn can be determined by gel permeation chromatography (hereinafter, may be abbreviated as GPC) measurement and converted to standard polystyrene, and can be determined, 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. It is 550 or less, preferably 1.500 or more, and more preferably 1.520 or more. The refractive index of the polymer (B) can be measured by a refractometer, for example, by the method described in Examples.

In one embodiment of the present invention, the CTE of the polymer (B) is preferably 58 ppm / K or less, more preferably 55 ppm / K or less, still 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, still more preferably 5 ppm / K or more. When the CTE of the polymer (B) is not more than the above upper limit, it is easy to reduce the CTE of the obtained film. Further, when a copper-clad laminate is produced by laminating with a copper film, it is preferable to adjust the CTE of the film to around 20 ppm / K from the viewpoint of preventing the laminated film from peeling off. The polymer (B) having the optimum CTE can be selected according to the CTE of the resin to be mixed. The CTE can be measured by, for example, thermomechanical analysis (hereinafter, may be referred to as TMA), and can be obtained by the method described in Examples.

In one embodiment of the present invention, at least one of the Tg and the 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, still more preferably 180 ° C. or higher, particularly preferably 200 ° C. or higher, and particularly more preferably 220 ° C. or higher. In particular, it is more preferably 240 ° C. or higher, most preferably 260 ° C. or higher, preferably 500 ° C. or lower, more preferably 400 ° C. or lower, still more preferably 320 ° C. or lower. 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. or higher. ° C. or higher, particularly preferably 200 ° C. or higher, particularly more preferably 220 ° C. or higher, particularly still more preferably 240 ° C. or higher, most preferably 260 ° C. or higher, preferably 500 ° C. or lower, still more preferably 400 ° C. or lower, still more preferable. Is 350 ° C. or lower. When at least one of the Tg and the melting point of the polymer (B) is at least one of the above lower limit, it is easy to prevent the coalescence of the particulate polymer (B) and to improve the dispersibility of the particulate polymer (B). It is easy to reduce the CTE of the film and to improve the mechanical properties such as heat resistance and bending resistance. When at least one of the Tg and the melting point of the polymer (B) is not more than the above upper limit, the particulate polymer (B) is uniformly dissolved in the solvent, and it is easy to prevent aggregation and undissolved residue, and the particulate polymer (B) ) It is easy to improve the dispersibility, and it is easy to improve the mechanical properties, especially the resistance to repeated bending. The Tg of the polymer (B) is the softening temperature measured by TMA based on JIS K7196, and can be measured by, for example, the method described in Examples. The method for adjusting the Tg and melting point of the polymer (B) is not particularly limited, but for example, a method for appropriately adjusting the content of the monomer unit (I), the Mw of the polymer (B), the degree of crystallinity, and the like can be used. Can be mentioned. The larger the content of the monomer unit (I), the Mw of the polymer (B), and at least one selected from the group consisting of the degree of crystallinity, the higher the Tg and melting point of the polymer (B) tend to be. The melting point of the polymer (B) can be determined by measuring the melting peak temperature from the melting curve obtained by using, for example, a differential scanning calorimeter (DSC, manufactured by Hitachi High-Tech Science Corporation).

The median diameter of the particulate polymer (B) in the composition in the present invention is preferably 0.01 μm or more, more preferably 0.03 μm or more, still more preferably 0.05 μm or more, preferably 15 μm or less, more preferably. Is 10 μm or less, 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, and particularly still 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, it is easy to improve the dielectric properties of the film formed from the composition, and it is easy to manufacture the film. When the median diameter of the particulate polymer (B) in the composition is not more than the above upper limit, mechanical properties such as particle dispersibility, surface smoothness, water absorption resistance and bending resistance of the film formed from the composition are deteriorated. Easy to raise. The method for determining the median diameter of the particulate polymer (B) in the composition is not particularly limited, but can be determined by, for example, a centrifugal sedimentation type particle size distribution measuring device or an ultrasonic attenuation type particle size distribution measuring device. Further, when the resin (A) is added to the particulate polymer (B) dispersion in an amount within a range that does not affect the particle size of the particulate polymer (B) to form a composition, the dispersion is prepared in advance. The median diameter of the particulate polymer (B) in the composition can be measured and used as the median diameter of the particulate polymer (B) in the composition. In the present specification, the median diameter is also referred to as D50, and indicates a value in which the number of particles of the particulate polymer (B) on the side smaller than the value is equal to the number of particles on the side larger than the value. Further, in the present specification, "particle diameter" means to include the median diameter and / or the average primary particle diameter of the particulate polymer (B) unless otherwise specified.

<Manufacturing method of cycloolefin polymer (B)>
As the polymer (B), a commercially available product may be used, and the production method is not particularly limited, but the polymer is a polymer in the presence of a catalyst using the transition metal complex (α) represented by the formula (IV) as one component. From the monomer forming (B), for example, the cycloolefin represented by the formula (I), the ethylene, the linear α-olefin having 3 to 20 carbon atoms, and the aromatic vinyl compound having 8 to 20 carbon atoms. It is preferably produced by polymerizing at least one monomer selected from the group, and optionally the other monomer. In the production of the polymer (B) in the present invention, since the transition metal complex (α) represented by the formula (IV) is used, the content of the monomer unit (I) in the polymer (B) is significantly increased. It is easy to adjust Tg within the above range.

[In equation (IV), M represents a Group 4 transition metal element in the Periodic Table of the Elements.
Cp represents a group having a cyclopentadienyl skeleton and represents
A represents a group 16 atom in the periodic table of elements,
T represents an atom of Group 14 in the periodic table of elements.
D ¹ and D ² are 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 6 to 20 carbon atoms. It represents an aryloxy group or a disubstituted amino group having 2 to 20 carbon atoms, which may be the same or different.
R ¹ to R ⁶ are 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 an aryl having 6 to 20 carbon atoms. Represents an oxy group, 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 they may be arbitrarily bonded to form a ring. You may. ]

M is a transition metal element of Group 4 of the Periodic Table of Elements (IUPAC Inorganic Chemistry Naming Method Revised Edition 1989), and examples thereof include a titanium atom, a zirconium atom, and a hafnium atom.

Cp is a group having a cyclopentadienyl skeleton, and examples thereof include 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 -A propylfluorenyl group, a phenylfluorenyl group, a dimethylfluorenyl group and the like can be mentioned. Among these, preferably a cyclopentadienyl group, a methylcyclopentadienyl group, a tetramethylcyclopentadienyl group, an n-butylcyclopentadienyl group, an isobutylcyclopentadienyl group, an indenyl group, a methylindenyl group. Alternatively, a fluorenyl group may be mentioned.

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

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

D ¹ and D ² are independent of each other, 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 of carbon atoms. It is an aryloxy group of 6 to 20 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 cases where D ¹ and D ² are halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When D ¹ and D ² are hydrocarbon groups, the number of carbon atoms thereof is preferably 1 to 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. Examples thereof include a group, an n-octyl group, a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a naphthyl group, a benzyl group and the like.

Specific examples of cases where D ¹ and D ² are halogenated hydrocarbon groups include a fluoromethyl group, a difluoromethyl group, a 1-fluoroethyl group, a 1,1-difluoroethyl group, and a 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 the cases where D ¹ and D ² are alkoxy groups include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group and n-. Examples thereof include a pentoxy group, a neopentoxy group, an n-hexoxy group, an n-octoxy group and the like.

Specific examples of the cases where D ¹ and D ² are aryloxy groups include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a naphthyloxy group and the like.

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. Examples thereof include an amino group, a di-n-hexylamino group, a di-n-octylamino group, and a diphenylamino group.

R ¹ to R ⁶ are independent of each other, 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 of carbon atoms. It represents an aryloxy group of 6 to 20, a disubstituted amino group of 2 to 20 carbon atoms or a silyl group of 1 to 20 carbon atoms, which may be the same or different, and they may be optionally bonded. May form a ring. Among these, a hydrocarbon group having 1 to 20 carbon atoms is preferable.

When R ¹ to R ⁶ are hydrocarbon groups, the number of carbon atoms is preferably 1 to 10. Specific 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 and neopentyl group. 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 can be mentioned.

Specific examples of cases where R ¹ to R ⁶ are a halogen atom, a halogenated hydrocarbon group, an alkoxy group, an aryloxy group, and a disubstituted amino group include D ¹ and D ² as a halogen atom and a halogenated hydrocarbon group. As specific examples in the case of an alkoxy group, an aryloxy group, and a disubstituted amino group, those exemplified above can be mentioned.

Specific examples of cases where R ¹ to R ⁶ are silyl groups include a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a tri-n-butylsilyl group, a triisobutylsilyl group, and a tri. Examples thereof include -sec-butylsilyl group, tri-tert-butylsilyl group and triphenylsilyl group.

Specific examples of such a compound represented by the formula (IV) include isopropanol (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride and isopropyridene (methylcyclo). Pentazienyl) (3-tert-butyl-5-methyl-2-phenoxy) Titanium dichloride, isopropylidene (dimethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) Titanium dichloride, isopropi Reden (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, isopropyridene (trimethylcyclopentadienyl) (3-tert-butyl- 2-Phenoxy) Titanium dichloride, isopropanol (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) Titanium dichloride, isopropyridene (n-propylcyclopentadienyl) (3-tert-butyl-2) -Phenoxy) Titanium dichloride, isopropylidene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) Titanium dichloride, isopropyridene (isobutylcyclope) Ntadienyl) (3-tert-butyl-2-phenoxy) Titanium dichloride, isopropylidene (phenylcyclopentadienyl) (3-tert-butyl-2-phenoxy) Titanium dichloride, isopropylidene (cyclopentadienyl) (2- Phenoxy) Titanium Dichloride, Isopropyridene (Methylcyclopentadienyl) (2-Phenoxy) Titanium Dichloride, Isopropylidene (dimethylcyclopentadienyl) (2-Phenoxy) Titanium Dichloride, Isopropyridene (trimethylcyclopentadienyl) (2) -Phenoxy) Titanium Dichloride, Isopropyridene (Tetramethylcyclopentadienyl) (2-Phenoxy) Titanium Dichloride, Isopropyridene (n-propylcyclopentadienyl) (2-Phenoxy) Titanium Dichloride, Isopropyridene (n-Butylcyclo) Examples thereof include pentadienyl) (2-phenoxy) titanium dichloride, isopropylidene (isobutylcyclopentadienyl) (2-phenoxy) titanium dichloride, isopropyridene (phenylcyclopentadienyl) (2-phenoxy) titanium dichloride and the like.

Further, the compound in which titanium is changed to zirconium or hafnium in the above specific example, and the compound in which isopropridene is changed to dimethylsilylene, diphenylcilylene, and methylene including them can be similarly exemplified. Further, a compound in which dichloride is changed to dibromide, diiodide, dimethyl, dibenzyl, dimethoxydo, or diethoxyde can be similarly exemplified.

The transition metal complex (α) represented by the above formula (IV) can be used as a catalyst for producing the polymer (B) according to the embodiment of the present invention in combination with various co-catalysts. The cocatalyst is a compound that interacts with the transition metal complex (α) to produce a 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), and these co-catalysts are used. The structure of the polymerization active species produced by this is not clear.

Equation (γ1) BQ ¹ Q ² Q ³
Equation (γ2) J ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^－
Equation (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 valence state.
^Q1 to ^Q4 are independent of each other, 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, and 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 (L—H) ⁺ represents a Bronsted acid. ]

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

Equation (β1) E ¹ _a AlZ _3-a
Equation (β2) {-Al (E ² ) -O-} _b
Equation (β3) E ³ {-Al (E ³ ) -O-} _c AlE ³ ₂
[In formulas (β1) to (β3), E1 ^, E2 and E3 represent hydrocarbon groups having ¹ to ⁸ carbon atoms independently of ^{each other} , and all E1, all E2 and all. E ³ may be the same or different, Z may represent hydrogen or halogen, all Z may be the same or different, and a represents an integer of 0-3. , B represent an integer of 2 or more, and c represents an integer of 1 or more. ]

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

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

The above aluminoxane is made by various methods. The method is not particularly limited, and it may be produced according to a known method. For example, a method for making a solution of trialkylaluminum, for example, trimethylaluminum, etc. in a suitable organic solvent, for example, benzene, an aliphatic hydrocarbon, etc., in contact with water, trialkylaluminum, for example, trimethylaluminum, etc. An example is a method of making the solution by contacting it with a metal salt containing water of crystallization, for example, copper sulfate hydrate.

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

In the formula (γ1), B represents a boron atom in a trivalent valence state, and ^Q1 to ^Q3 are independent of each other, a halogen atom, a hydrocarbon group containing a carbon atom, and a halogenation having 1 to 20 carbon atoms. It represents a 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. .. ^Q1 to ^Q3 are independent of each other, 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 the formula (γ1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4,5-). Examples thereof include tetrafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, and the like, and tris is preferable. (Pentafluorophenyl) Borane can be mentioned.

In the formula (γ2), B represents a boron atom in a trivalent valence state, and ^Q1 to ^Q4 are the same as ^Q1 to ^Q3 in the above formula (γ1). Further, J ⁺ represents an inorganic or organic cation.

Examples of the inorganic cation in J ⁺ include a ferrosenium cation, an alkyl-substituted ferrosenium cation, and a silver cation.
Examples of the organic cation in J ⁺ include triphenylmethyl cation and the like.
(BQ ¹ Q ² Q ³ Q ⁴ ) ^-As 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 ferrosenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrosenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, and triphenylmethyl tetrakis. Examples thereof include (pentafluorophenyl) borate, triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, and preferably triphenylmethyltetrakis (pentafluorophenyl) borate.

In the formula (γ3), B represents boron in a trivalent valence state, and ^Q1 to ^Q4 are the same as ^Q1 to ^Q3 in the above formula (γ1). Further, L represents a neutral Lewis base, and (L—H) ⁺ represents a Bronsted acid.

In the formula (γ3), examples of the Bronsted acid (L—H) ⁺ include trialkyl-substituted ammonium cations, N, N-dialkylanilinium cations, dialkylammonium cations, and triallylphosphonium cations.
As (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , the same as described above can be mentioned.

Specific combinations thereof include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, and tri (n-butyl). ) Ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (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) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, etc. Can be mentioned. Among these, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate is preferable.

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

The transition metal complex (α) represented by the formula (IV), the organoaluminum compound (β) and / or the compound (γ) can be charged and used in any order at the time of polymerization, but any of them can be used. You may use the reaction product obtained by contacting the combination of the above in advance.

The molar ratio of the co-catalyst / 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 to 5 mmol / L, more preferably 0.001 to 1 mmol / L. The amount of the 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 the monomers used.

The polymerization method of the polymer (B) according to the embodiment of the present invention is not particularly limited, and for example, a batch type or continuous type gas phase polymerization method, a bulk polymerization method, or a solution weight using an appropriate solvent is used. Any method such as a legal method or a slurry polymerization method can be adopted.

When a solvent is used, various solvents can be used under the condition that the catalyst is not inactivated, and examples of such a solvent 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. Further, after the solution of the cycloolefin represented by the formula (I) is charged into the polymerization reaction tank, toluene may be further charged.

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

<Resin (A)>
The resin (A) is a polymer different from the polymer (B). When the resin (A) is a cycloolefin-based resin, it may be a cycloolefin-based resin having a different type from the polymer (B), for example, a different type of monomer unit constituting the resin, its content, and the like.

The resin (A) is not particularly limited, and for example, diallyl phthalate resin, silicone resin, phenol resin, unsaturated polyester resin, polyurethane resin, melamine resin, urea resin, xylene resin, furan resin, aniline resin, acetone-formaldehyde resin. Thermocurable resin selected from alkyd resin, maleimide resin, maleimide-cyanic acid ester resin, cyanate ester resin, benzoxazine resin, polybenzimidazole resin, and polycarbodiimide resin; olefin resin; acrylic resin; Styrene-based resin; Rubber-based resin; Fluorine-based resin; Vinyl-based resin; General-purpose engineering plastic; Super-engineering plastic such as liquid crystal polymer and aromatic polyether resin; Polyamide resin; Polygonide resin, Polyethyleneimide resin and other polyimide-based resin; In addition, biodegradable plastics and the like can be mentioned. Among these, from the viewpoint that it is easy to suppress the formation of aggregates of the particulate polymer (B) and it is easy to improve the dispersibility because the particle size is easily reduced, and the surface smoothness and particle dispersibility of the obtained film. From the viewpoint of easily enhancing the dielectric property and heat resistance, it is preferable that the resin is at least one selected from the group consisting of a polyimide resin, a liquid crystal polymer, a fluororesin, an aromatic polyether resin, and a maleimide resin. , Polyimide-based resin and / or liquid crystal polymer is more preferable. The 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 180 ° C. or higher, still more preferably 200 ° C. or higher, particularly preferably 300 ° C. or higher, and particularly more preferably 350 ° C. or higher. It is preferably 550 ° C. or lower. When the Tg of the resin (A) is at least the above lower limit, the surface smoothness, particle dispersibility and heat resistance of the obtained film can be easily improved, and the CTE can be easily reduced. When the Tg of the resin (A) is not more than the above upper limit, the mechanical properties are likely to be enhanced. The Tg of the resin (A) can be obtained, for example, by performing dynamic viscoelasticity measurement (hereinafter, may be abbreviated as DMA measurement), and can be measured by the method described in Examples.

The Mw of the resin (A) is preferably 30,000 or more, more preferably 100,000 or more, more preferably 150,000 or more, still more preferably 200,000 or more, still more preferably 250,000 in terms of polystyrene. The above is 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, still more preferably 500,000 or less, and particularly preferably 450. It is less than 000. When the Mw of the resin (A) is equal to or higher than the above lower limit, it is easy to suppress the formation of aggregates of the particulate polymer (B) and the particle size is easily reduced, so that the dispersibility can be easily improved. It is easy to improve the surface smoothness, mechanical properties, particle dispersibility and heat resistance of the film, and it is easy to reduce CTE. When the Mw of the resin (A) is not more than the above upper limit, the moldability is likely to be improved. The Mw of the resin (A) can be obtained by, for example, GPC measurement and converted to standard polystyrene, and can be obtained by, for example, the method described in Examples.

The polyimide-based resin suitable as the resin (A) includes a resin containing a repeating structural unit containing an imide group (hereinafter, may be 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 a resin (hereinafter, may be referred to as a polyamide-imide resin) and a precursor before producing a polyimide-based resin by imidization. The precursor before producing the polyimide resin is a polyamic acid. In addition, in this specification, a "repeating structural unit" may be referred to as a "constituent unit". Further, the "constituent unit derived from" may be simply referred to as "unit", and for example, the constituent unit derived from a compound may be referred to as a compound unit.

In a preferred embodiment of the present invention, the resin (A) is represented by the formula (1) :.

[In formula (1), X represents a divalent organic group, Y represents a tetravalent organic group, and * represents a bond].
It is preferable that the polyimide resin has a structural unit represented by. With such a polyimide resin, it is easy to improve mechanical properties such as surface smoothness, particle dispersibility, heat resistance and bending resistance of the obtained film, and it is easy to reduce CTE.

X in the formula (1) represents a divalent organic group independently of each other, and preferably represents 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, and examples of the divalent aliphatic group include a divalent acyclic aliphatic group or a divalent aliphatic group. Cyclic aliphatic groups can be mentioned. Among these, from the viewpoint that it is easy to suppress the formation of aggregates of the particulate polymer (B) and it is easy to improve the dispersibility because the particle size is easily reduced, and the surface smoothness and particle dispersibility of the obtained film. A divalent cyclic aliphatic group and a divalent aromatic group are preferable, and a divalent aromatic group is more preferable, from the viewpoint of easily enhancing heat resistance, dielectric properties and mechanical properties, and easily reducing CTE. .. In the divalent organic group, the 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 which case the carbon number of these groups is preferably 1. ~ 8. In the present specification, the divalent aromatic group is a divalent organic group having an aromatic group, and an aliphatic group or another substituent may be contained in a part of the structure thereof. Further, the divalent aliphatic group is a divalent organic group having an aliphatic group, and a part of the structure thereof may contain other substituents, but does not contain an aromatic group.

In one embodiment of the present invention, the polyimide-based resin may contain a plurality of types of X, and the plurality of types of X may be the same as or different from each other. As X in the formula (1), for example, the group (structure) represented by the formulas (2) to (8); the hydrogen atom in the group represented by the formulas (5) to (8) is a methyl group. , 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 substituted group and the like.

[In the formulas (2) and (3 ^{), Ra and R b are} independent of each other, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 6 to 12 carbon atoms. The hydrogen atoms contained in Ra and R ^b may be substituted with halogen atoms independently of each other, and W is independent of each other, single _{-bonded, -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 )-, R ^c represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a halogen atom, and n represents 0 to 0 to. 4 is an integer, 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 ring having 3 to 8 carbon atoms.
R ^d represents an alkyl group having 1 to 20 carbon atoms.
r represents an integer greater than or equal to 0 and less than or equal to (the number of carbon atoms in ring A-2).
S1 and S2 represent integers from 0 to 20 independently of each other.
* Represents a bond. ]

Other examples of X in the formula (1) include, for example, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a propylene group, a 1,2-butanediyl group, and a 1,3-butanediyl group. , 1,12-Dodecandyl group, 2-methyl-1,2-propanediyl group, 2-methyl-1,3-propanediyl group and other linear or branched alkylene groups with divalent acyclic Examples include aliphatic groups. The hydrogen atom in the divalent acyclic aliphatic group may be substituted with a halogen atom, and the carbon atom may be substituted with a hetero atom, for example, an oxygen atom, a nitrogen atom or the like.

Among these, from the viewpoint that it is easy to suppress the formation of aggregates of the particulate polymer (B) and it is easy to improve the dispersibility because the particle size is easily reduced, and the high surface smoothness and high particles of the obtained film. The polyimide resin in the present invention is represented by the formula (2) as X in the formula (1) from the viewpoint of easily achieving dispersibility, high dielectric properties, low CTE, high heat resistance and high mechanical properties. It is preferable to include a structure and / or a structure represented by the formula (3), and more preferably to include a structure represented by the formula (2).

In formulas (2) and (3), the bond of each benzene ring or each cyclohexane ring is at the ortho-position, meta-position or para-position, or α-position, β-position or γ-position, respectively, based on −W—. It may be bonded to any of the above, preferably at the meta-position or the para-position, and more preferably at the para-position from the viewpoint of easily reducing the CTE of the film and easily increasing the heat resistance and mechanical properties. .. R ^a and R ^b 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 the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group, and 2 -Methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl group and the like can be mentioned. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group and a hexyloxy group. Examples include a group and a cyclohexyloxy group. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and a biphenyl group. The hydrogen atom contained in Ra and R ^b may be substituted with ^a halogen atom independently of each other, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, from the viewpoint of easily improving the surface smoothness, dielectric properties and heat resistance of the obtained film and easily reducing CTE, ^{Ra and R b are} independent of each other and have an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms. It is preferably an alkyl fluoride group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms or an alkyl fluoride group having 1 to 3 carbon atoms, and a methyl group or a trifluoromethyl group. It is more preferable to have.

In the formulas (2) and (3), t and u are independently integers of 0 to 4, and it is easy to improve the particle dispersibility, heat resistance and mechanical properties of the obtained film, and reduce CTE. From the viewpoint of easy operation, it is preferably an integer of 0 to 2, and more preferably 0 or 1.

In equations (2) and (3), W is single-bonded independently of each other, -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 )-represented, and the particles of the obtained film. From the viewpoint of dispersibility, heat resistance and mechanical properties, particularly easy to increase bending resistance and easy to reduce CTE, single bond, -O-, -CH _2- , -C (CH ₃ ) ₂ -,-is preferable. Represents C (CF ₃ ) _2- , -COO-, -OOC- or -CO-, more preferably single bond, -O-, -CH _2- , -C (CH ₃ ) _2- or -C (CF). ₃ ) Represents _2- . R ^c represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a halogen atom. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-. Pentyl group, 2-methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl, 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. Examples of the halogen atom include the same as above.

In the formulas (2) and (3), n is an integer of 0 to 4, and is preferably an integer of 0 to 3 from the viewpoint of easily improving the particle dispersibility, heat resistance and mechanical properties of the obtained film. More preferably, it is 1 or 2. When n is 2 or more, the plurality of Ws, Ras, and ts may be the same or different from each other, and the positions of the bonds of each benzene ring with respect to ^−W— are also the same. It may or may not be different.

When the polyimide-based 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 and n in the formula (2). , R ^a , R ^b , t and u may be the same as or different from W, n, R ^a , R ^b , t and u in the formula (3) independently of each other.

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

R ^d in the 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 in ^R7 to R18, and preferably represent an alkyl group having 1 to 10 carbon atoms. In equation (4), r represents an integer of 0 or more and (number of carbon atoms of ring A-2) or less. r is preferably 0 or more, and preferably 4 or less. S1 and S2 in the formula (4) represent integers of 0 to 20 independently of each other. S1 and S2 are independent of each other, preferably 0 or more, more preferably 2 or more, and preferably 15 or less.

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

In a preferred embodiment of the present invention, when X in the formula (1) includes a structure represented by the formula (2) and / or the formula (3), the X in the formula (1) is the formula (2). And / or the ratio of the structural unit represented by the formula (3) is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably, with respect to the total molar amount of the structural unit represented by the formula (1). Is 70 mol% or more, particularly preferably 90 mol% or more, and preferably 100 mol% or less. When the ratio of the structural unit represented by the formula (2) and / or the formula (3) is in the above range, X in the formula (1) is likely to suppress the formation of aggregates of the particulate polymer (B). In addition, since the particle size is easily reduced, it is easy to improve the dispersibility. Further, it is easy to improve the surface smoothness, particle dispersibility, heat resistance, dielectric property and mechanical property of the obtained film, and it is easy to reduce CTE. The ratio of the structural unit in which Y in the formula (1) is represented by the formula (2) and / or the formula (3) can be measured using, for example, ¹ H-NMR, or calculated from the charging ratio of the raw materials. You can also do it.

In the formula (1), Y represents a tetravalent organic group independently of each other, preferably a tetravalent organic group having 4 to 40 carbon atoms, and more preferably 4 having a cyclic structure and 4 to 40 carbon atoms. Represents a valence organic group. Examples of the cyclic structure include an alicyclic ring, an aromatic ring, and a heterocyclic structure. In the organic group, the 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 which case the carbon number of these groups is preferably 1 to 8. Is. The polyimide-based resin in the present invention may contain a plurality of types of Y, and the plurality of types of Y may be the same as or different from each other. As Y, the group (structure) represented by the formulas (31) to (38); the hydrogen atom in the group represented by the formulas (34) to (38) is a methyl group, an ethyl group, or n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, fluoro group, chloro group or trifluoromethyl group substituted group; tetravalent chain type with 1 to 8 carbon atoms. Examples include a hydrocarbon group.

[In formulas (31) to (33), R ¹⁹ to R ²⁶ have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 6 to 12 carbon atoms independently of each other. Hydrogen atoms representing an aryl group and contained in R ¹⁹ to R ²⁶ may be substituted with halogen atoms independently of each other.
V ¹ and V ² are independent of each other, 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 the formula (a), R ²⁷ to R ³⁰ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms independently of each other.
Z represents -C (CH ₃ ) ₂ -or-C (CF ₃ ) _2-
i is an integer from 1 to 3, and * represents a bond).
^Rj represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a halogen atom.
e and d represent integers from 0 to 2 independently of each other.
f represents an integer of 1 to 3 and represents
g and h represent integers from 0 to 4 independently of each other.
* Represents a bond]

Among these, from the viewpoint of easily improving the particle dispersibility, heat resistance and mechanical properties of the obtained film and easily reducing CTE, the polyimide-based resin in the present invention is represented by the formula (Y) in the formula (1). It preferably contains at least one structure selected from the group consisting of the structure represented by 31), the structure represented by the formula (32), or the structure represented by the formula (33), and is represented by the formula (31). It is more preferable to include the structure to be used.

In formulas (31) to (33), R ¹⁹ to R ²⁶ are independent of each other, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl 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 include the alkyl group having 1 to 6 carbon atoms in the formulas (2) and (3), respectively. Examples of the alkoxy group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms are mentioned above. The hydrogen atoms contained in R ¹⁹ to R ²⁶ may be substituted with halogen atoms independently of each other, and examples of the halogen atoms include those mentioned above. Among these, from the viewpoint of easily improving the heat resistance and dielectric properties of the film, R ¹⁹ to R ²⁶ are preferably hydrogen atoms or alkyl groups having 1 to 6 carbon atoms independently of each other, and hydrogen atoms or 1 to 3 carbon atoms are preferable. Alkyl groups are more preferred, and hydrogen atoms are even more preferred.

In formula (31), V ¹ and V ² are single-bonded independently of each other, -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 )-, equation (a) or equation (b) ), Which is preferable from the viewpoint of easily improving the particle dispersibility, heat resistance and mechanical properties of the obtained film and easily reducing the CTE, preferably single bond, —O—, _−CH2- , −C (CH ₃ ). ) _2- , -C (CF ₃ ) _2- , -COO-, -OOC- or -CO-, more preferably single bond, -O-, -C (CH ₃ ) _2- or -C (CF) ₃ ) Represents _2- . R ^j represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a halogen atom. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include those exemplified above.

In the formula (31), e and d represent integers of 0 to 2 independently of each other, and from the viewpoint of easily improving the particle dispersibility, heat resistance and mechanical properties of the obtained film and reducing CTE. It is preferably 0 or 1, and more preferably e + d = 1.

In the formula (32), f represents an integer of 1 to 3, and is preferably 1 or 2 from the viewpoint of easily improving the particle dispersibility, heat resistance and mechanical properties of the obtained film and easily reducing CTE. It is preferably 1.

In the formula (33), g and h represent integers of 0 to 4 independently of each other, and from the viewpoint of easily improving the particle dispersibility, heat resistance and mechanical properties of the obtained film and reducing CTE. It is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably an integer of g + h = 0 to 2.

In the formula (a), R ²⁷ to R ³⁰ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms independently of each other. 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 improving the particle dispersibility, heat resistance and mechanical properties of the obtained film and easily reducing CTE, R ²⁷ to R ³⁰ are independent of each other and have hydrogen atoms or 1 to 3 carbon atoms. Alkyl groups are more preferred, and hydrogen atoms are even more preferred.

In formula (a), Z represents -C (CH ₃ ) _2- or -C (CF ₃ ) _2- . When Z has such a structure, it is easy to improve the particle dispersibility, heat resistance, dielectric property and mechanical property of the obtained film. i represents an integer of 1 to 3, and is preferably 1 or 2 from the viewpoint of easily enhancing particle dispersibility, heat resistance, and mechanical properties, and easily reducing CTE. When i is 2 or more, the plurality of Z and R ²⁷ to R ³⁰ may be the same as each other or may be different from each other.

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

In one embodiment of the present invention, when Y in the formula (1) includes at least one selected from the group consisting of the structures represented by the formulas (31) to (33), the formula (1) is used. Y is selected from the group consisting of the structures represented by the formulas (31) to (33), and the ratio of the constituent units represented by at least one is the total mole of the constituent units represented by the formula (1). With respect to the amount, it 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. It is obtained when the ratio of the structural unit represented by at least one of Y in the formula (1) selected from the group consisting of the structures represented by the formulas (31) to (33) is in the above range. It is easy to improve the particle dispersibility, water absorption resistance, dielectric property and mechanical property of the film, and it is easy to reduce CTE. The ratio of the structural unit represented by at least one selected from the group consisting of the structures represented by the formulas (31) to (33) in the formula (1) is determined by using, for example, ¹ H-NMR. It can be measured or calculated from the raw material charge ratio.

The polyimide-based resin in the present invention has a structural unit represented by the formula (52), a structural unit represented by the formula (53), and a structural unit represented by the formula (54), in addition to the structural unit represented by the formula (1). It may contain at least one selected from the group consisting of the represented building blocks.

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

In a preferred embodiment of the invention, in formulas (52) and (53), Y ¹ is synonymous with Y in formula (1), and X ¹ and X ² are synonymous with X in formula (1). be. It is preferable that Y ² in the formula (53) is a group in which any one of the bonds of Y in the formula (1) is replaced with a hydrogen atom. As Y ² , a group in which any one of the bonds of the groups (structures) represented by the formulas (31) to (38) is replaced with a hydrogen atom; a chain hydrocarbon having a trivalent carbon number of 1 to 8 is used. The group etc. can be mentioned. In one embodiment of the present invention, the polyimide-based resin may contain a plurality of types of Y ¹ or Y ² , and the plurality of types of Y ¹ or Y ² may be the same as or different from each other.

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

In one embodiment of the present invention, the polyimide resin is a structural unit represented by the formula (1), and in some cases, a structural unit represented by the formula (52), a structural unit represented by the formula (53), and a structural unit represented by the formula (53). It consists of at least one structural unit selected from the structural units represented by the formula (54). Further, from the viewpoint that the particle dispersibility, heat resistance, dielectric property and water absorption resistance of the obtained film can be easily improved and the CTE can be easily reduced, the ratio of the structural units represented by the formula (1) in the polyimide resin is described. Is all the structural units contained in the polyimide resin, for example, the structural unit represented by the formula (1), and in some cases, the structural unit represented by the formula (52), the structural unit represented by the formula (53), and Based on the total molar amount of at least one structural unit selected from the structural units represented by the formula (54), it is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more. In the polyimide resin, the upper limit of the ratio of the structural unit represented by the formula (1) is 100 mol% or less. The above ratio can be measured using, for example, 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 particle dispersibility, heat resistance, dielectric properties and water absorption resistance of the obtained film and easily reducing CTE.

In one embodiment of the present invention, the polyimide-based resin may contain a halogen atom, preferably a fluorine atom, which can be introduced by, for example, the above-mentioned halogen-containing atom substituent or the like. When the polyimide resin contains a halogen atom, preferably a fluorine atom, it is easy to improve the heat resistance, the dielectric property and the optical property of the film. Preferred fluorine-containing substituents for containing a fluorine atom in the polyimide-based resin include, for example, a fluoro group and a trifluoromethyl group.

When the polyimide-based resin contains a halogen atom, the content of the halogen atom in the polyimide-based resin is preferably 0.1 to 40% by mass, more preferably 1 to 35% by mass, based on the mass of the polyimide-based resin. More preferably, it is 5 to 30% by mass. When the content of halogen atoms is at least the above lower limit, the heat resistance and dielectric properties of the film are likely to be improved. When the content of the halogen atom is not more than the above upper limit, the CTE can be reduced and the synthesis becomes easy.

The imidization ratio of the polyimide resin is preferably 90% or more, more preferably 93% or more, further preferably 95% or more, and usually 100% or less. From the viewpoint of easily improving the optical properties, dielectric properties and water absorption resistance of the film, the imidization rate is preferably at least the above lower limit. The imidization ratio indicates the ratio of the molar amount of the imide bond in the polyimide-based resin to the value of twice the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyimide-based resin. When the polyimide resin contains a tricarboxylic acid compound, the value is twice the molar amount of the structural unit derived from the tetracarboxylic acid compound in the polyimide resin, and the molar amount of the structural unit derived from the tricarboxylic acid compound. The ratio of the molar amount of the imide bond in the polyimide resin to the total of the above is shown. The imidization rate can be determined by an IR method, an NMR method, or the like.

As described above, the polyimide-based resin in the present invention includes a precursor before imidization of the polyimide-based resin. When the polyimide resin is a polyamic acid, the polyamic acid is the formula (1'):

[In equation (1'), Y and X represent Y and X in equation (1), respectively]
Includes building blocks represented by.

<Manufacturing method of resin (A)>
The 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, and the polyimide resin is, for example, by a method including a step of reacting a diamine compound with a tetracarboxylic acid compound to obtain a polyamic acid and a step of imidizing the polyamic acid. Can be manufactured. When the resin (A) is a polyamic acid, the step of obtaining the polyamic acid may be carried out. In addition to the tetracarboxylic acid compound, a dicarboxylic acid compound or a tricarboxylic acid compound may be reacted.

Examples of the tetracarboxylic acid compound used for synthesizing the polyimide resin include aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic acid dianhydride; and aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic acid dianhydride. Can be mentioned. The tetracarboxylic acid compound may be used alone or in combination of two or more. The tetracarboxylic acid compound may be a tetracarboxylic acid compound analog such as an acid chloride compound in addition to the dianhydride.

Specific examples of the tetracarboxylic acid compound include pyromellitic anhydride (hereinafter, may be abbreviated as PMDA), 4,4'-(4,4'-isopropylidene diphenoxy), and diphthalic anhydride (hereinafter, BPADA). (May be abbreviated), 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (hereinafter, may be abbreviated as BPDA), 4,4'-(Hexafluoroisopropylidene) diphthalic acid dianhydride (hereinafter, may be abbreviated as 6FDA), 4,4'-oxydiphthalic acid anhydride (hereinafter, may be abbreviated as ODPA), 2,2 ', 3,3'-, 2,3,3', 4'-or 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,3', 3,4'-biphenyltetracarboxylic Acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride, 2,3', 3,4'-diphenyl ether tetracarboxylic acid dianhydride, bis (2,3-dicarboxyphenyl) ) Ether dianhydride, 3,3 ", 4,4"-, 2,3,3 ", 4"-or 2,2 ", 3,3" -p-terphenyltetracarboxylic acid 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) 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 acid dianhydride (hereinafter, may be abbreviated as HPMDA), 2,3,5,6-Cyclohexanetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, cyclopentane -1,2,3,4-tetracarboxylic acid dianhydride, 4,4'-bis (2,3-dicarboxyphenoxy) diphenylmethane dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (Hereinafter, sometimes abbreviated as CBDA), norbornan-2-spiro-α'-spiro-2 "-norbornan-5,5', 6,6'-tetracarboxylic acid anhydride, p-phenylenebis (trimeritate) Anhydride), 3,3', 4,4'-diphenylsulfonate Tracarboxylic acid dianhydride, 2,3,6,7-anthracentetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5 , 6-Tetracarboxylic acid dianhydride, 2,6- or 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-(or 1,4) , 5,8-) Tetrachloronaphthalene-1,4,5,8- (or 2,3,6,7-) Tetracarboxylic acid dianhydride, 2,3,8,9-,3,4,9 , 10-, 4,5,10,11-or 5,6,11,12-perylene-tetracarboxylic acid dianhydride, pyrazine-2,3,5,6-tetracarboxylic acid dianhydride, pyrrolidine-2 , 3,4,5-Tetracarboxylic acid dianhydride, thiophene-2,3,4,5-tetracarboxylic acid dianhydride, bis (2,3- or 3,4-dicarboxyphenyl) sulfonate dianhydride And so on. Among these, PMDA, BPDA, 6FDA, BPADA, ODPA, HPMDA, from the viewpoint of easily improving the particle dispersibility, heat resistance, water absorption resistance, dielectric property and mechanical property of the obtained film and reducing CTE. CBDA and p-phenylene bis (trimeritate anhydride) are preferable. These tetracarboxylic acid compounds can be used alone or in combination of two or more.

Examples of the diamine compound used for synthesizing the polyimide resin include aliphatic diamines, aromatic diamines and mixtures thereof. In addition, in this embodiment, "aromatic diamine" represents a diamine having an aromatic ring, and an aliphatic group or another substituent may be contained in a part of the structure thereof. The aromatic ring may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring, but the aromatic ring is not limited thereto. Among these, a benzene ring is preferable. Further, the "aliphatic diamine" represents a diamine having an aliphatic group, and may contain other substituents as a part of its structure, but does not have an aromatic ring.

Specific examples of the diamine compound include 1,4-diaminocyclohexane, 4,4'-diamino-2,2'-dimethylbiphenyl (hereinafter, may be abbreviated as m-TB), and 4,4'-diamino-3. , 3'-dimethylbiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl (hereinafter abbreviated as TFMB), 4,4'-diaminodiphenyl ether, 1,3-bis (3-Aminophenoxy) benzene (hereinafter, may be abbreviated as 1,3-APB), 1,4-bis (4-aminophenoxy) benzene (hereinafter, may be abbreviated as 1,4-APB), 1 , 3-Bis (4-aminophenoxy) benzene, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 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- (3-aminophenoxy)] Aminophenoxy) Biphenyl, bis [1- (4-aminophenoxy)] biphenyl, bis [1- (3-aminophenoxy)] biphenyl, bis [4- (4-aminophenoxy) phenyl] methane, bis [4- (4- (4-aminophenoxy)] 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'-methylenedi. Aniline, 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'-diaminobiphenyl, 3,3'-dimethoxybenze Gin, 4,4 "-diamino-p-terphenyl, 3,3" -diamino-p-terphenyl, m-phenylenediamine, p-phenylenediamine (sometimes abbreviated as p-PDA), 2,2- Bis [4- (4-aminophenoxy) phenyl] Propane (sometimes abbreviated as BAPP), 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 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-xylylene diamine, p-xylylene diamine, 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-phenylenediisopropyridene) 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'- (Hexafluoropropyridene) dianiline, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexinsan, 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 (Aminomethi) Le) Cyclohexane, norbornandiamine, 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'-diamino Diphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,5-diamino-1,3,4-oxadiazole, bis [4, Examples thereof include 4'-(4-aminophenoxy)] benzanilide, bis [4,4'-(3-aminophenoxy)] benzanilide, 2,6-diaminopyridine, and 2,5-diaminopyridine. Among these, from the viewpoint that it is easy to suppress the formation of aggregates of the particulate polymer (B) and it is easy to improve the dispersibility because the particle size is easily reduced, and the surface smoothness and particle dispersibility of the obtained film. 1,4-Diaminocyclohexane, 4,4'-diaminodiphenyl ether, TFMB, 4,4'-methylene from the viewpoint of easily increasing heat resistance, water absorption resistance, dielectric property and mechanical property, and easily reducing CTE. Dianiline, 3,3'-methylenedianiline, p-PDA, benzene, 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-phenylenediisopropyridene) 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 '-(Hexafluoropropyridene) dianiline and the like are preferable. The diamine compound can be used alone or in combination of two or more.

In addition to the tetracarboxylic acid compounds used in the resin synthesis, the polyimide-based resin contains other tetracarboxylic acids, dicarboxylic acids, tricarboxylic acids, and anhydrides thereof, as long as the various physical properties of the film are not impaired. The derivative may be further reacted.

Examples of other tetracarboxylic acids include water adducts of the anhydrides of the above tetracarboxylic acid compounds.

Examples of the dicarboxylic acid compound include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, acid chloride compounds related thereto, acid anhydrides, and the like, and they may be used alone or in combination of two or more. Specific examples include a dicarboxylic acid compound of terephthalic acid; isophthalic acid; naphthalenedicarboxylic acid; 4,4'-biphenyldicarboxylic acid; 3,3'-biphenyldicarboxylic acid; a chain hydrocarbon having 8 or less carbon atoms, and 2 Compounds in which one benzoic acid is linked by a single bond, -O-, -CH _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -SO _2- or a phenylene group, and their compounds. Examples include acid chloride compounds.

Examples of the tricarboxylic acid compound include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, acid chloride compounds related thereto, acid anhydrides, and the like, and they may be used alone or in combination of two or more. Specific examples include anhydrate of 1,2,4-benzenetricarboxylic acid; 2,3,6-naphthalentricarboxylic acid-2,3-anhydride; a single bond of phthalic anhydride and benzoic acid, -O-. , -CH _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -SO _2- or compounds linked with a phenylene group.

In the production of the polyimide-based 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 ratio of each structural unit of the desired 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, particularly preferably 0.98 mol or more, relative to 1 mol of the tetracarboxylic acid compound. 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 with respect to the tetracarboxylic acid compound is within the above range, it is easy to improve the particle dispersibility, heat resistance, water absorption resistance, mechanical properties, dielectric properties and optical properties of the obtained film, and reduce CTE. It's easy to do.

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 30 minutes to 72 hours. In a preferred embodiment of the 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 improve the particle dispersibility, heat resistance, water absorption resistance, mechanical properties, dielectric properties and optical properties of the obtained film, and it is easy to reduce CTE.

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, and is, for example, water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, and the like. Alcohol-based 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, GBL, γ-valerolactone, propylene glycol methyl ether acetate, lactic acid. Ester solvent such as ethyl; Ketone solvent such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone; aliphatic hydrocarbon solvent such as pentane, hexane, heptane; alicyclic type such as ethyl cyclohexane Hydrobromide solvent; Aromatic hydrocarbon solvent such as toluene and xylene; nitrile solvent such as acetonitrile; ether solvent such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvent such as chloroform and chlorobenzene; amide solvent such as DMAc and DMF; Sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide and sulfolane; carbonate solvents such as ethylene carbonate and propylene carbonate; pyrrolidone solvents such as N-methylpyrrolidone; and combinations thereof can be mentioned. Among these, a phenol-based solvent, an amide-based solvent, and a pyrrolidone-based solvent 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 conditions of an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere or a reduced pressure, if necessary, and is strictly controlled under a nitrogen atmosphere or an argon atmosphere or the like. It is preferable to carry out the process with stirring in the dehydrated solvent.

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

In one embodiment of the present invention, when imidized, the reaction temperature is usually 20 to 250 ° C., and the reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours.

The polyimide-based resin may be separated and purified by a conventional method, for example, a separation means such as filtration, concentration, extraction, crystallization, recrystallization, or column chromatography, or a separation means combining these, which is preferable. In the embodiment, it can be isolated by adding a large amount of alcohol such as methanol to the reaction solution containing the resin, precipitating the resin, and performing concentration, filtration, drying and the like.

Suitable liquid crystal polymers of the resin (A) include liquid crystal polyesters, and preferably liquid crystal 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 10 to 100 mol% of the total structural unit of the liquid crystal polyester. Liquid crystal polyester having a content of 35 mol% and a structural unit represented by the formula (a3) of 10 to 35 mol% is preferable.

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

In the present 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. The liquid crystal polyester which is − is preferable.

Examples of the structural unit represented by the formula (a1) include p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, and structural units derived from 4-hydroxy-4'-biphenylcarboxylic acid. The liquid crystal polyester may contain two or more kinds of the structural units. Of 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, with respect to 100 mol% of the total structural unit of the liquid crystal polyester. It is mol% or less, more preferably 45 mol% or more and 65 mol% or less.

Examples of the structural unit represented by the formula (a2) include terephthalic acid, isophthalic acid, and structural units derived from 2,6-naphthalenedicarboxylic acid. The liquid crystal polyester may contain two or more kinds of the structural units. Of 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, and more preferably 15 mol% or more and 30% with respect to 100 mol% of the total structural unit of the liquid crystal polyester. It is 17.5 mol% or more, more preferably 27.5 mol% or less, and more preferably 17.5 mol% or more.

Examples of the structural unit represented by the formula (a3) include 3-aminophenol, 4-aminophenol, 1,4-phenylenediamine, 1,3-phenylenediamine, and structural units derived from 4-aminobenzoic acid. .. The liquid crystal polyester may contain two or more kinds of the structural units. Of these, structural units derived from 4-aminophenol are preferable.
The content of the structural unit represented by the formula (a3) is preferably 10 mol% or more and 35 mol% or less, and more preferably 15 mol% or more and 30% with respect to 100 mol% of the total structural unit of the liquid crystal polyester. It is 17.5 mol% or more, more preferably 27.5 mol% or less, and more preferably 17.5 mol% or more.

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

<Composition>
The composition of the present invention contains a resin (A), a particulate cycloolefin polymer (B) and a solvent, the solvent containing a first solvent and a second solvent, and a second solvent and a cycloolefin polymer (B). ), Since the distance between the HSP values is 8.5 or more, the aggregation of the particulate polymer (B) can be suppressed, and the aggregate of the particulate polymer (B) is not contained. Further, since the composition of the present invention does not contain aggregates, a film having excellent surface smoothness can be formed.

In one embodiment of the present invention, in the present invention, even if the distance between the HSP values of the resin (A) and the polymer (B) is relatively large, the aggregation of the particulate polymer (B) is effectively suppressed and the particulate polymer (B) is in the form of particles. A composition containing no aggregate of the polymer (B) can be obtained, and a film having excellent surface smoothness and particle dispersibility can be formed. Therefore, in the composition and film of the present invention, the distance between the HSP values of the resin (A) and the polymer (B) is preferably 6.0 or more, more preferably 7.0 or more, still more preferably 8.0 or more. Is. The distance between the HSP values of the resin (A) and the polymer (B) is preferably 30 or less, more preferably 25 or less, still more preferably 20 or less, still more preferably 20 or less, from the viewpoint of the affinity between the resin and the polymer. It is 15 or less.

The content of the particulate polymer (B) contained in the composition of the present invention is usually 1% by mass or more, preferably 5 with respect to the total mass of the resin (A) and the particulate cycloolefin polymer (B). It is 7% by mass or more, more preferably 7% by mass or more, further preferably 10% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less. When the content of the particulate polymer (B) contained in the composition is at least the above lower limit, the formation of aggregates of the particulate polymer (B) is likely to be suppressed, and the particle size is likely to be reduced. It is easy to increase the dispersibility. Further, it is easy to improve the surface smoothness, particle dispersibility, heat resistance and mechanical properties of the obtained film, and it is easy to reduce CTE. Further, when the content of the particulate polymer (B) contained in the composition is not more than the above upper limit, film formation becomes easy, which is advantageous from the viewpoint of film production. If the dispersibility of the particles in the film is high, the thermal conductivity and the uniformity of CTE are high. Therefore, for example, when the film is used as the resin layer of CCL, it is easy to suppress the peeling of the film and the copper foil. Become.

In one embodiment of the present invention, the total mass of the resin (A) and the particulate polymer (B) contained in the composition is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass. The above is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less. When the total mass of the resin (A) and the particulate polymer (B) contained in the composition is in the above range, it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle size is reduced. Since it is easy, it is easy to improve the dispersibility. Further, it is easy to improve the surface smoothness, particle dispersibility, heat resistance and mechanical properties of the obtained film, and it is easy to reduce CTE.

The composition of the present invention may contain additives, if necessary, as long as the effects of the present invention are not impaired. Additives include, for example, antioxidants, flame retardants, cross-linking agents, surfactants, compatibilizers, imidization catalysts, weathering agents, lubricants, antiblocking agents, antistatic agents, antifogging agents, drip-free agents, pigments. , Fillers and the like. 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 does not contain aggregates because it can effectively suppress the formation of aggregates of the particulate polymer (B) even if it does not contain a compatibilizer. , The particle size of the polymer (B) is small and the dispersibility is excellent. 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 further preferably 0.1 part by mass with respect to 100 parts by mass of the resin (A). More than parts, 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, and even more preferably 0.001 parts by mass or less, most preferably. May be 0 parts by mass. Further, for example, when the resin (A) is a polyimide resin precursor such as polyamic acid and thermal imidization is required at the time of film production, inhibition of imidization by a compatibilizer or a compatibilizer by heating may be used. From the viewpoint of preventing deterioration of the characteristics 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 content of the compatibilizer may be based on 100 parts by mass of the total of the resin (A) and the polymer (B) instead of 100 parts by mass of the resin (A).

[Method for producing composition]
The method for producing the composition of the present invention is not particularly limited, but for example, the following steps:
Step (1) of dissolving the cycloolefin polymer (B) in the first solvent to obtain a cycloolefin polymer (B) solution; after contacting the cycloolefin polymer (B) solution with the second solvent, the first step. Step (2) to obtain a dispersion solution containing the particulate cycloolefin polymer (B) (hereinafter, may be referred to as a particulate polymer (B) dispersion solution) by distilling off one solvent; and a resin in the dispersion solution. A method including the step (3) of adding (A) is preferable. By using such a method, the composition can be easily and efficiently formed. In the present invention, even if such a production method is used, the distance between the HSP values of the second solvent and the cycloolefin polymer (B) is 8.5 or more, so that the aggregate of the particulate polymer (B) is agglomerated. The formation can be suppressed, and an aggregate-free composition can be formed. Further, the composition can form a film having excellent surface smoothness.

<Process (1)>
The step (1) is a step of dissolving the cycloolefin polymer (B) in the first solvent to obtain a cycloolefin polymer (B) solution (hereinafter, may be referred to as a polymer (B) solution).

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

The polymer (B) solution contains preferably 0.01 to 20% by mass of the polymer (B) with respect to the mass 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, still more preferably 0.1% by mass, based on the mass of the solution. % Or more, more preferably 0.5% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less. When the content of the polymer (B) in the solution is at least the above lower limit, the composition can be easily adjusted. Further, when the content of the polymer (B) in the solution is not more than the above upper limit, it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle size is easily reduced, so that the dispersibility is improved. Easy to raise. Further, it is easy to improve the surface smoothness, particle dispersibility, heat resistance and mechanical properties of the obtained film, and it is easy to reduce CTE.

The method for dissolving the polymer (B) in the first solvent is not particularly limited, but for example, the first solvent may be added to the polymer (B), or the polymer (B) may be added to the first solvent. It may be either or both. Further, it may be dissolved by heating or the like depending on the solubility of the first solvent in the polymer (B).

<Process (2)>
The step (2) is a step of contacting the polymer (B) solution with the second solvent and then distilling off the first solvent to obtain a dispersion liquid containing the particulate polymer (B).

In the step (2), the method of contacting the polymer (B) solution with the second solvent is not particularly limited, and examples thereof include a method of mixing the polymer (B) solution and the second solvent. Specifically, a method of adding the polymer (B) solution to the second solvent and a method of adding the second solvent to the polymer (B) solution can be exemplified. By contacting in this way, the particulate polymer (B) having a small particle size can be precipitated or dispersed in the mixed solution of the second solvent and the first solvent. A small amount of the resin (A) may be added at any time 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 second solvent is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, still more preferably, with respect to 1 part by mass of the amount of the second 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, still more preferably 3 parts by mass or less, and particularly preferably 1.5 parts by mass. It is less than a part. When the amount of the polymer (B) solution to be brought into contact with the second solvent is within the above range, it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle size is easily reduced, so that the dispersion is dispersible. Easy to increase.

In step (2), the polymer (B) solution is brought into contact with the second solvent, and then the first solvent is distilled off. Distillation of the first solvent can enhance the dispersion stability of the particulate polymer (B). Further, the polymer (B) may be further precipitated by distilling off the first solvent. The first solvent may be distilled off or removed at least partially, and the first solvent may remain in the particulate polymer (B) dispersion. From the viewpoint that the aggregation of the particulate polymer (B) can be easily suppressed and the dispersion liquid can be easily prepared, the first solvent may be partially left or partially contained in the particulate polymer (B) dispersion liquid. preferable.

In the step (2), the method for distilling off the first solvent is not particularly limited, and a method for distilling off under reduced pressure using an evaporator or the like is exemplified. The pressure and temperature at the time of distillation can be appropriately selected according to the characteristics such as the boiling points of the first solvent and the second solvent. In the preferred production method of the present invention, since the first solvent is distilled off from the mixed solution of the first solvent and the second solvent, the boiling point of the first solvent is usually lower than the boiling point of the second solvent. In this way, it is possible to obtain a particulate polymer (B) dispersion liquid in which the particulate polymer (B) having a small particle size is dispersed without containing the aggregate of the particulate polymer (B).

The content of the first solvent contained in the particulate polymer (B) dispersion obtained after distilling off the first solvent is preferably 120 parts by mass or less, more preferably 120 parts by mass with respect to 100 parts by mass of the content of the second solvent. 100 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 45 parts by mass or less, particularly preferably 40 parts by mass or less, particularly more preferably 35 parts by mass or less, particularly still more preferably 30 parts by mass or less, particularly further. It is more preferably less than 30 parts by mass, most preferably 25 parts by mass or less, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more. When the content of the first solvent is not more than the above upper limit, it is easy to suppress the formation of aggregates of the particulate polymer (B), and the particle size is easily reduced, so that the dispersibility is easily improved. Further, it is easy to improve the surface smoothness, particle dispersibility, heat resistance and mechanical properties of the obtained film, and it is easy to reduce CTE. Further, when the content of the first solvent is at least the above lower limit, it is easy to prepare the dispersion liquid.

In one embodiment of the present invention, the content of the solvent contained in the particulate polymer (B) dispersion is preferably 50% by mass or more, more preferably 70% by mass or more, and further, with respect to the mass of the dispersion. It is 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 less, still more preferably 99% by mass or less, and particularly preferably 95% by mass. It is as follows. When the content of the solvent is in the above range, the aggregation of the particulate polymer (B) is easily suppressed, and the particle size is easily reduced, so that the dispersibility is easily improved. Further, it is easy to improve the surface smoothness, particle dispersibility, heat resistance and mechanical properties of the obtained film, and it is easy to reduce CTE.

In one embodiment of the present invention, the solvent contained in the particulate polymer (B) dispersion may contain other solvents other than the first solvent and the second solvent as long as the effects of the present invention are not impaired. .. The other solvent is not particularly limited, and a conventional solvent can be used. In one embodiment of the present invention, the total mass of the first solvent and the second solvent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably, with respect to the mass of the solvent contained in the dispersion liquid. Is 90% by mass or more, 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 in the above range, it is easy to suppress the aggregation of the particulate polymer (B), so that it is easy to reduce the particle size and improve the dispersibility of the particles. As a result, it is easy to improve the particle dispersibility, surface smoothness, mechanical properties, etc. of the obtained film.

The content of the particulate polymer (B) contained in the particulate polymer (B) dispersion obtained after distilling off the first solvent is preferably 0.01% by mass with respect to the mass of the polymer (B) dispersion. The above is more preferably 0.1% by mass or more, further 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 or less, and particularly preferably 5% by mass. % Or less. When the content of the particulate polymer (B) is in the above range, it is easy to suppress the aggregation of the particulate polymer (B) and to improve the particle dispersibility, so that the particle dispersibility and surface smoothness of the obtained film are easy to be improved. , And it is easy to improve the mechanical properties.

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 above composition of the present invention. When the median diameter of the particulate polymer (B) in the composition is at least the above lower limit, it is easy to improve the dielectric properties of the film formed from the composition, and it is easy to manufacture the film. When the median diameter of the particulate polymer (B) in the dispersion is not more than the above upper limit, it is easy to improve the particle dispersibility, surface smoothness, water absorption resistance and mechanical properties of the film formed from the composition. The median diameter of the particulate polymer (B) contained in the particulate polymer (B) dispersion can be determined by a scattering type particle size distribution measurement using laser diffraction, for example, by the method described in Examples. be able to.

<Process (3)>
The step (3) is a step of adding the resin (A) to the particulate cycloolefin polymer (B) dispersion liquid.

In the step (3), 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 in which the resin (A) is dissolved in a predetermined solvent, for example, a second solvent. good. In one embodiment of the invention, in step (3), the polyimide resin or polyamic acid can be added in the form of a solid, preferably powder or varnish. 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. It is 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, still more preferably 20% by mass or less. When the content of the resin (A) in the varnish is in the above range, film formation is facilitated, which is advantageous from the viewpoint of film production.

The resin (A) added in the step (3) is preferably 50% by mass or more, more preferably 50% by mass or more, based on the total mass of the resin (A) and the polymer (B) in the particulate polymer (B) dispersion. It is 60% by mass or more, more preferably 65% by mass or more, preferably 95% by mass or less, more preferably 93% by mass or less, still more preferably 90% by mass or less. When the content of the resin (A) added in the step (3) is at least the above lower limit, film formation becomes easy, which is advantageous from the viewpoint of film production. Further, when the content of the particulate polymer (B) contained in the composition is not more than the above upper limit, the aggregation of the particulate polymer (B) can be suppressed and the particulate polymer (B) in the composition can be suppressed. Since the dispersibility is easily improved, the particle dispersibility, surface smoothness, heat resistance and mechanical properties of the obtained film are easily improved, and the CTE is easily reduced.

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 the resin (A) may be added in a plurality of times. You may.

The above-mentioned production method in the present invention may include steps other than the steps (1) to (3) as long as the effects of the present invention are not impaired, and the polymer or addition other than the resin (A) and the polymer (B) may be included. Agents may be added. Examples of the additive include the additives described above.
In a preferred embodiment of the present invention, the resin (A) is added to the granular polymer (B) dispersion, but if the resulting composition can be adjusted to contain the first solvent and the second solvent. , The polymer (B) in powder form may be added to the varnish of the resin (A).

[the film]
The present invention includes a resin (A) and a particulate cycloolefin polymer (B).
It includes a film in which the standard deviation of the average thickness obtained in each of the 10 measurement regions obtained by dividing a region of a straight line of 1 mm on the surface of the film into 10 equal parts is 2.5 or less. Since such a film has excellent surface smoothness, for example, when the film is used as a resin layer of CCL, high processing accuracy at the time of high density and miniaturization of wiring can be achieved, and the film and copper foil can be achieved. It is possible to effectively suppress the peeling of the film.
On the other hand, if the standard deviation of the thickness exceeds 2.5, the surface smoothness of the film tends to decrease. Therefore, for example, when the film is used as the resin layer of CCL, the density of wiring is lowered, the processing accuracy at the time of miniaturization is lowered, and the film and the copper foil are likely to be peeled off.

In the film of the present invention, the standard deviation of the thickness is preferably 2.0 or less, more preferably 1.70 or less, still more preferably 1.50 or less, still more preferably 1.00 or less, and particularly preferably 0.80 or less. Below, it is particularly more preferably 0.60 or less. When the standard deviation of the thickness is not more than the above upper limit, the surface smoothness of the film can be further improved. It is easy to achieve high processing accuracy, and it is easy to suppress peeling between the film and the copper foil. The lower limit of the standard deviation of the thickness is usually 0.01 or more, preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.2 or more. When the standard deviation of the thickness is not more than the above lower limit, for example, when the film is attached to the copper foil by using an adhesive or the like, the adhesion is easily improved by the anchor effect.

For the standard deviation of the film thickness, a continuous straight 1 mm region of the film surface is arbitrarily selected, the region is divided into 10 equal parts to set 10 measurement regions, and then a contact type or non-contact type film is used. Obtained by measuring the average thickness in each of the 10 measurement areas using a thickness gauge, step meter, surface shape measuring instrument, etc., and calculating the standard deviation of the average thickness in each obtained measurement area. Can be done. For example, it can be obtained by the method described in Examples. The average thickness in each measurement area may be an average value calculated from a plurality of thicknesses measured at arbitrary points in the measurement area.

The standard deviation of the film thickness is the composition of the film, for example, the type and / or composition ratio of the constituent units constituting the resin (A) and / or the particulate polymer (B) contained in the optical film, and / or its molecular weight. Can be adjusted within the above range by appropriately adjusting the above; by using a suitable method for producing a film, which will be described later. For example, in the resin (A) and / or the particulate polymer (B), the standard deviation of the film thickness is described above as likely to enhance the surface smoothness of the film. , The content of the resin (A) and the particulate polymer (B) and the like may be appropriately selected; the composition of the present invention may be used for film formation and the like may be adjusted to the above range, and in particular, film formation. When the composition of the present invention is used and the ratio of the first solvent to the second solvent in the composition is adjusted to the above range, the standard deviation of the thickness can be easily adjusted to the above range.

In the film of the present invention, the average primary particle size of the particulate polymer (B) is 15 μm or less, preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, still more preferably 1 μm or less, and particularly preferably. It is 0.8 μm or less, more preferably 0.5 μm or less, preferably 0.01 μm or more, more preferably 0.03 μm or more, still more preferably 0.05 μm or more. When the average primary particle diameter of the particulate polymer (B) is at least the above lower limit, it is easy to prevent aggregation of the particulate polymer (B) and improve dispersibility, and it is easy to improve the mechanical properties of the film. When the average primary particles of the particulate polymer (B) are not more than the above upper limit, it is easy to prevent the precipitation of the particulate polymer (B) and improve the particle dispersibility in the film, and the surface smoothness, water absorption resistance and bending resistance are easily improved. It is easy to improve mechanical properties such as. The average primary particle diameter of the particulate polymer (B) can be determined by image analysis observed with an electron microscope, and can be determined, 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 particulate cycloolefin polymer (B) is dispersed, preferably uniformly dispersed, with respect to the resin (A). For example, it is preferable that the composite film has a sea-island structure, the resin (A) is the sea, and the particulate polymer (B) is the island. Such a composite film tends to improve heat resistance, dielectric properties and mechanical properties, and tends to reduce CTE.

In one embodiment of the present invention, the film of the present invention has particle dispersibility, surface smoothness, heat resistance, dielectric properties, and even if the distance between the HSP values of the resin (A) and the polymer (B) is relatively large. It has excellent mechanical properties and can reduce CTE. The distance between the HSP values of the resin (A) and the polymer (B) is preferably 6 or more, and the distance between the HSP values can be selected from the range described in the above [Composition] section. By setting the distance between the HSP values of the resin (A) and the polymer (B) to be equal to or higher than the above lower limit, the formation of aggregates of the particulate polymer (B) is effectively suppressed, and the particulate polymer (B) is contained in the film. ) Can be easily dispersed evenly.

In one embodiment of the invention, the film of the invention can have a low CTE. The CTE of the film can be appropriately designed according to the application. When CCL is produced by laminating with a copper film, it is preferable to adjust the CTE of the film to around 20 ppm / K from the viewpoint of preventing peeling of the laminated film. The CTE of the film can be adjusted by the CTE of the resin (A) and the particulate polymer (B) to be mixed, the mixing amount, and the like. From the viewpoint of reducing CTE, it is preferable to mix the particulate polymer (B) having a high Tg. The CTE can be measured by TMA, for example, by the method described in Examples.

The average thickness of the film in the present invention can be appropriately selected depending on the intended use, and is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 20 μm or more, still more preferably 30 μm or more, and particularly preferably 40 μm or more. It is preferably 500 μm or less, more preferably 300 μm or less, still more preferably 100 μm or less, and particularly preferably 80 μm or less. The average thickness of the film can be measured using a film thickness meter or the like, and can be calculated, for example, by the method described in Examples. When the film of the present invention is a multilayer film, the average thickness represents the average thickness of the single layer portion.

In a preferred embodiment of the present invention, the film of the present invention is preferably formed from the above 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 composition of the present invention, such as the resin (A), the particulate polymer (B) and the additive, etc. The types and proportions of are the same.
For example, the content of the particulate polymer (B) is usually 1% by mass or more, preferably 5% by mass or more, more preferably, with respect to the total mass of the particulate polymer (B) and the resin (A) contained in the film. Is 10% by mass or more, more preferably 15% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less. When the content of the particulate polymer (B) is in the above range, it is easy to improve the particle dispersibility, surface smoothness, dielectric property and mechanical property of the film. Further, in the film in which the particulate polymer (B) is dispersed, the dispersibility of the particulate polymer (B) is high, and as a result, it is easy to reduce the physical characteristics of the film, for example, variations in the surface roughness and thermal conductivity of the film. ..

In one embodiment of the present invention, the total mass of the resin (A) and the particulate 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 more 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 particulate polymer (B) contained in the film is at least the above lower limit, it is easy to improve the particle dispersibility, surface smoothness, dielectric properties and mechanical properties of the film. Further, in the film in which the particulate polymer (B) is dispersed, the dispersibility of the particulate polymer (B) is high, and as a result, it is easy to reduce the physical characteristics of the film, for example, variations in the surface roughness and thermal conductivity of the film. ..

The film of the present invention may be a single-layer film or a multilayer film containing at least one layer made of the film of the present invention. The multilayer film can include other layers (or other films). Even in such a case, the film of the present invention includes all the layers. Examples of the other layer include a functional layer and the like. Examples of the functional layer include a primer layer, a gas barrier layer, an adhesive layer, and a protective layer. The functional layer can be used alone or in combination of two or more.

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 usually industrially adopted.

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

In addition to the low dielectric loss, the film according to the embodiment of the present invention has excellent surface smoothness and can reduce CTE as compared with the conventional composite film containing a cycloolefin polymer. It also has excellent heat resistance and mechanical properties. Therefore, it can be suitably used as a substrate material compatible with a printed circuit board for a high frequency band and an antenna substrate. 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, the surface smoothness is high and the CTE is reduced, so that peeling between the copper foil and the resin layer can be effectively suppressed as compared with the conventional film. Further, since it has excellent mechanical properties, particularly bending resistance, it is resistant to plastic deformation, does not easily have curl, and can be used as a flexible substrate material.
The film of the present invention is also suitably used for other industrial materials such as automobile parts and electric / electronic parts; optical materials such as lenses, prisms, optical fibers, and recording media.

[Film manufacturing method]
The method for producing the film of the present invention is not particularly limited, but for example, the following steps:
(A) Composition preparation step for preparing a composition containing the resin (A), the particulate cycloolefin polymer (B) and the solvent.
It is produced by a method including (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, a step of completing the imidization reaction may be included in the thermal imidization.

<Composition preparation process>
In the composition adjusting step, the composition may be adjusted by, for example, mixing the resin (A), the particulate polymer (B) and the solvent, and optionally the additive. It is preferable to use the composition of the present invention, particularly the composition obtained by using the above-mentioned production method of the composition of the present invention. By using the composition of the present invention, a film having excellent surface smoothness, particle dispersibility, heat resistance and mechanical properties and a low CTE can be formed.

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

In the coating process, the composition is applied onto the substrate by a known coating method to form a coating film. Known coating methods include, for example, wire bar coating method, reverse coating, roll coating method such as gravure coating, die coating method, comma coating method, lip coating method, spin coating method, screen printing coating method, fountain coating method, and dipping method. , Spray method, curtain coating method, slot coating method, hypersalivation forming method and the like.

Examples of the base material include a copper plate (including copper foil), a SUS plate (including SUS foil and SUS belt), a glass substrate, a PET film, a PEN film, another polyimide resin film, a polyamide resin film and the like. Among them, copper plate, SUS plate, glass substrate, PET film, PEN film and the like are preferable from the viewpoint of excellent heat resistance, and copper plate, SUS plate, glass substrate and the like are more preferable from the viewpoint of adhesion to the film and cost. Alternatively, a PET film or the like can be mentioned.

In the film forming step, the film can be formed by drying the coating film and peeling it 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 a laminate in which the film is laminated on the obtained copper foil is copper-clad. It can also be used for laminated boards. In the case of peeling, a drying step of further drying the film may be performed after the 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 an air surface). When the surface roughness occurs, the thickness may vary and the surface smoothness of the film may be impaired. However, when the composition of the present invention is used, the formation of such surface roughness is effectively suppressed. Therefore, a film having excellent surface smoothness can be formed.
The drying of the coating film can be appropriately selected depending on the heat resistance of the resin (A) and the like, but in one embodiment of the present invention, it is 50 to 450 ° C., preferably 55 to 400 ° C., more preferably 70 ° C. to 380 ° C. In another embodiment of the present invention, it can be carried out at a temperature of 50 to 350 ° C., preferably 70 to 300 ° C. In a preferred embodiment of the present invention, it is preferable to carry out drying step by step. By performing the drying step by step, the composition can be uniformly dried and the surface smoothness of the obtained film can be improved. Therefore, when the film is used as the resin layer of CCL, the copper foil and the resin layer are used. Peeling with and can be effectively suppressed. For example, after heating at a relatively low temperature of 50 to 150 ° C., heating may be performed at 200 to 450 ° C., preferably 200 to 350 ° C. The drying or heating time is preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours. By gradually heating from a low temperature to a high temperature in such a range, the surface smoothness of the obtained film can be easily improved. If necessary, the coating film may be dried under inert atmosphere conditions such as nitrogen and argon, under vacuum or reduced pressure conditions, and / or under ventilation.
In the case of stepwise drying, the coating film may be continuously dried after the coating film is peeled off from the base material during the stepwise drying, and after all the drying is completed, the coating film is applied from the base material ( The film) may be peeled off. For example, the coating film may be peeled off from the substrate after the first step of drying to perform the second and subsequent drying steps, or the coating film (film) may be peeled off from the substrate after all the drying steps are completed. good. The first step of drying may be pre-drying.

When the base material is a copper foil, for example, the film may be peeled off from the copper foil as the base material by etching and removing 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 (for example, polyamic acid) and a polyimide resin is produced during film production, after the composition is applied to a substrate. , It is preferable to heat imidize by heating. 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, it is preferable to perform heating step by step. For example, the solvent may be removed by heating at a relatively low temperature of 50 to 150 ° C., and then gradually heated to a temperature in the range of 300 to 450 ° C. The heating time can be selected from the same range as the above range, for example.

When the film of the present invention is a multilayer film, it can be produced by, for example, a multilayer film forming method such as a coextrusion processing method, an extrusion laminating method, a thermal laminating method, or a dry laminating method.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. First, the measurement method will be described.

<Norbornene (NB) content>
The content of the monomer unit derived from norbornene (also referred to as “NB content”) in the cycloolefin copolymer obtained in the production example was measured using ¹³ C-NMR. ¹³ C-NMR measurement conditions are as follows.
Equipment: Bruker AVANCE600, 10mm cryoprobe Measurement temperature: 135 ° C
Measurement method: Proton decoupling method Concentration: 100 mg / mL
Number of integrations: 1024 Pulse width: 45 degrees Pulse repetition time: 4 seconds Chemical shift value Criteria: Tetramethylsilane Solvent: 1,2-dichlorobenzene-d ₄ and 1,1,2,2-tetrachloroethane-d ₂ The NB content in the mixed solvent cycloolefin copolymer having a volume ratio of 85:15 is based on 1,2-dichlorobenzene (127.68 ppm) as "RA Wendt, G. Fink, Macromol. Chem. Phys. It was calculated based on the attribution described in ", 2001, 202, 3490". Specifically, the signal integral value observed at the chemical shift value of 44.0-52.0 ppm in the spectrum chart measured using ¹³ C-NMR: _{IC2, C3} (carbon at the 2nd and 3rd positions of the norbornene ring). (Derived from the atom), signal integrated value observed at a chemical shift value of _27.0-33.0 ppm: IC5 _{, C6} + ICE (derived from the carbon atom at the 5th and 6th positions of the norbornene ring and the carbon atom of the ethylene part ) From the following formula.
NB content (mol%) = _{IC2, C3} / ( _{IC5, C6} + _ICE ) x 100

<Distance between Hansen solubility parameter (HSP) and HSP value>
The Hansen solubility parameter (HSP) of the cycloolefin copolymer, polyimide resin, liquid polyester and solvent obtained in the production example, and the distance between HSP values were determined as follows.

(Hansen solubility parameter (HSP) of solvent)
For the HSP value of the solvent, the values in the database of HSPiP (Ver. 4.1.07) were used, and δD of GBL was 18.0 MPa ^0.5 , δP was 16.6 MPa ^0.5 , and δH was 7.4 MPa ^0. The DMAc δD is 16.8 MPa ^0.5 , the δP is 11.5 MPa ^0.5 , the δH is 9.4 MPa ^0.5 , the NMP δD is 18.0 MPa ^0.5 , and the ^δP is 12.3 MPa ⁰ . 5.5, ^δH is 7.2 MPa ^0.5 , δD of amyl acetate is 15.3 MPa ^0.5 , δP is 3.1 MPa ^0.5 , δH is 7.0 MPa ^0.5 , and δD of xylene is 17. 6MPa ^0.5 , δP is 1.0MPa ^0.5 , δH is 3.1MPa ^0.5 , toluene δD is 18.0MPa ^0.5 , δP is 1.4MPa ^0.5 , and δH is 2.0MPa ⁰ . It was set to ^5.5 .

(HSP of cycloolefin copolymer)
The solubility of the cycloolefin copolymer in various solvents was evaluated. For the evaluation of solubility, use a solvent with a known solubility parameter in a transparent container (refer to the HSPiP database, solvent used: methyl chloride, 1,4-dichlorobenzene, chloroform, toluene, p-xylene, GBL, DMAc, NMP. , Water, acetone, diiodomethane, butyl benzoate) 10 mL and 0.1 g of cycloolefin copolymer were added to prepare a mixed solution. The obtained mixed solution was subjected to ultrasonic treatment for a total of 6 hours. The appearance of the mixed solution after the ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria from the obtained observation results.
(Evaluation criteria)
2: The appearance of the mixed solution is cloudy and precipitates at room temperature, but the appearance of the mixed solution becomes transparent by heating to 50 ° C. and stirring with a stirrer for 30 minutes.
1: The appearance of the mixture is transparent at room temperature.
0: The appearance of the mixed solution is cloudy and precipitates at room temperature, and the appearance of the mixed solution does not become transparent even when heated to 50 ° C. and stirred with a stirrer for 30 minutes.

From the evaluation results of the solubility of the obtained cycloolefin copolymer in a solvent, the HSP value was calculated by the above-mentioned Hansen-dissolved sphere method using HSPiP.

(HSP of polyimide resin)
The solubility of the polyimide resin in various solvents was evaluated. For evaluation of solubility, use a solvent with known solubility parameters in a transparent container (see HSPiP database, solvents used: acetone, toluene, ethanol, tetrahydrofuran, N, N-dimethylformamide, dimethyl sulfoxide, hexane, GBP, ethyl. Acetate, methyl ethyl ketone, propylene glycol monomethyl ether, 1-butanol, N-methylformamide, 1-methylnaphthalene, bromobenzene, 1-methylimidazole, pyrazole, acetic acid) 10 mL and 0.1 g of polyimide resin are added to make a mixed solution. Prepared. The resulting mixture was sonicated for a cumulative total of 6 hours. The appearance of the mixed solution after the ultrasonic treatment was visually observed, and the solubility of each resin in the solvent was evaluated based on the following evaluation criteria from the obtained observation results.
(Evaluation criteria)
1: The appearance of the mixed solution is cloudy.
0: The appearance of the mixed solution is transparent.

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

(Liquid crystal polyester HSP)
Using HSPiP (Ver. 4.1.07), HSP was obtained from the structural formula.

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

<Meso-type two-chain / Racemo-type two-chain>
The ratio of the meso-type two-chain of the norbornene two-chain to the racemo-type two-chain (meso-type two-chain / racemo-type two-chain) of the cycloolefin copolymer obtained in the production example is the above-mentioned NB content using ¹³ C-NMR. It was measured under the same conditions as the measurement of.
The meso-type / racemo-type two-chain of the norbornene two-chain is based on 1,1,2,2-tetrachloroethane (74.24 ppm), and is described in “RAWendt, G.Fink, Macromol.Chem. It was calculated based on the attribution described in "Phys., 2001, 202, 3490" and "Japanese Patent Laid-Open No. 2008-285656". Specifically, the meso-type two-chain / racemo-type two-chain has a signal integral value observed at a chemical shift value of 27.5-28.4 ppm in the spectrum chart measured using ¹³ C-NMR: IC5 _{. C6} -m (derived from carbon atoms at positions 5 and 6 of the meso-type two-chain norbornene ring), signal integrated values observed at a chemical shift value of 28.4-29.6 ppm: IC5 _{, C6} -r (racemo type) It was obtained from the following formula from the carbon atom at the 5th and 6th positions of the two-chain norbornene ring).
Meso-type two-chain / Racemo-type two-chain = IC5 _{, C6} -m / _{IC5, C6} -r

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

<Glass transition temperature>
(Cycloolefin copolymer)
The Tg of the cycloolefin copolymer obtained in the production example was determined 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 is measured under the following conditions, and the onset of displacement when the indenter sinks into the sample is defined as the softening temperature. did.
Equipment: "TMA / SS6200" manufactured by Hitachi High-Tech Science Corporation
Indenter diameter: 1 mm
Load: 780mN
Temperature program: Temperature rise from 20 ° C to 380 ° C at a rate of 5 ° C / min

(Polyimide resin and liquid crystal polyester)
The Tg of the polyimide resin and the liquid crystal polyester obtained in the production example was determined by the following measurements. Using "DMA Q800" manufactured by TA Instrument, measurement was performed under the following samples and conditions to obtain a tan δ curve, which is the ratio of the loss modulus to the storage modulus, and then the peak of the tan δ curve. Tg was calculated from the highest point.
Sample: length 5-15 mm, width 5 mm
Experimental mode: DMA Multi-Freequency-Strine
Detailed experimental mode conditions:
(1) Clamp: Tension: Film
(2) Implement: 5 μm
(3) Frequency: 10Hz (no fluctuation in all temperature sections)
(4) Preload Force: 0.01N
(5) Force Track: 125N
Temperature conditions: (1) Temperature rise range: Room temperature to 400 ° C., (2) Temperature rise rate: 5 ° C./min Main collected data: (1) Storage modulus (E'), (2) Loss elastic modulus (Loss modulus, E "), (3) tanδ (E" / E')

<Mw and Mn of cycloolefin copolymer>
The polystyrene-equivalent Mw and Mn of the cycloolefin copolymer obtained in the production example were measured using GPC. The GPC measurement was performed under the following conditions, and the peak was specified by defining the baseline on the chromatogram based on the description of ISO16014-1.

(GPC device and software)
Equipment: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Measurement software: GPC-8020 modelII 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 connected mobile phase: Orthodichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) 2,6-di -Tert-Butyl-4-methylphenol (hereinafter, may be referred to as BHT) was added and used at a concentration of 0.1 w / V, that is, 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 Refractometer Detector (RID)
RID cell temperature: 140 ° C
Sample solution injection amount: 300 μL
Standard material for GPC column calibration: Standard polystyrene manufactured by Tosoh Corporation is weighed in the combinations shown in Table 1 below, 5 mL of orthodichlorobenzene (same composition as the mobile phase) is added to each combination, and the mixture is dissolved at room temperature for 2 hours. Prepared. The column was calibrated using the obtained GPC column calibration standard material, and then the sample was measured as shown below.

(Sample solution preparation conditions)
Solvent: BHT was added to orthodichlorobenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) at a concentration of 0.1 w / V, that is, 0.1 g / 100 mL.
Sample solution concentration: 1 mg / mL
Automatic shaker for melting: DF-8020 (manufactured by Tosoh Corporation)
Dissolution conditions: A 5 mg 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, and 5 mL of orthodichlorobenzene having the same composition as the mobile phase is added to the test tube. The lid was covered with aluminum foil, the test tube was set in DF-8020, and the mixture was stirred at 140 ° C. for 120 minutes at a stirring rate of 60 reciprocating / min. GPC measurement was performed using the stirred solution as a sample.

<Mw of polyimide resin>
The polystyrene-equivalent Mw of the polyimide resin obtained in the production example was measured using GPC. GPC measurement was performed under the following conditions.
GPC measurement (1) Pretreatment method Add DMF eluent (10 mmol / L lithium bromide-added DMF solution) to the sample to a concentration of 2 mg / mL, heat with stirring at 80 ° C. for 30 minutes, cool, and then cool. The solution filtered by a 0.45 μm membrane filter was used as a measurement solution.
(2) Measurement condition column: TSKgel SuperAWM-H x 2 + SuperAW2500 x 1 (6.0 mm ID x 150 mm x 3)
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

<Liquid crystal polyester Mw>
The Mw of the liquid crystal polyester was measured by GPC under the following conditions.
(1) Pretreatment method About 2 mL of pentafluorophenol was added to about 4.86 mg of the sample, and the mixture was heated and stirred for 2 hours, and then cooled to 40 to 50 ° C. while stirring as it was. Approximately 4.24 mL of chloroform was added with stirring, and the solution was filtered through a 0.45 μm membrane filter as the measurement solution.
(2) GPC equipment HLC8220GPC manufactured by Tosoh Corporation
(3) Measurement conditions Column: TSKgel SuperHM-H × 2
(Two pieces with an inner diameter of 6.0 mm and a length of 150 mm are connected)
Eluent: Pentafluorophenol (PFP) / chloroform (mass ratio 35/65)
Flow rate: 0.4 mL / min Detector: Differential refractometer (RI) detector Column temperature: 40 ° C
Injection volume: 20 μL
Molecular weight standard: Standard polystyrene

<Evaluation of solubility>
The evaluation of whether or not the cycloolefin copolymer, the polyimide resin and the liquid crystal polyester were dissolved in the solvents used in Examples and Comparative Examples was performed as follows.
First, 9.9 g of the solvent is weighed in a 30 mL glass screw tube, and a magnetic stirrer is further added and stirred. 0.1 g of the polymer or resin is added thereto, and the mixture is stirred at 24 ° C. for 24 hours. After stirring for 24 hours, if the solid could not be visually confirmed and the solution was transparent, it was evaluated as "dissolved". On the other hand, if the solid can be visually confirmed or the solution is opaque, it is evaluated as "not soluble".

<Thickness of composite film>
For the thickness of the composite film obtained in Examples and Comparative Examples, a Digimatic Indicator (ID-C112XBS, manufactured by Mitutoyo Co., Ltd.) was used to measure the thickness of any 5 or more points of the film, and the thickness thereof was measured. The average value was taken as the thickness of the composite film.

<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 carried out under the following conditions, and the solvent content in the particulate cycloolefin copolymer dispersion was calculated from one inspection amount.
Equipment: Agilent 7890B gas chromatograph (manufactured by Agilent Technologies)
Column: DB-5 (manufactured by Agilent Technologies, Inc.)
Carrier gas: Helium inlet temperature: 200 ° C
Detector temperature: 250 ° C
Internal standard: Benzyl alcohol Solvent: Chloroform

<Standard deviation of average thickness of composite film>
The standard deviation of the average thickness of the composite films obtained in Examples and Comparative Examples was calculated as follows.
On the surface of the film fixed so as to be in close contact with the glass substrate, a palpation type surface shape measuring instrument (Dektak XTE Co., Ltd.) is used, and the glass substrate is used as a reference surface in an arbitrary continuous straight line 1 mm region. A thickness profile (height profile) was obtained. The region was divided into 10 equal parts to set 10 measurement regions, and then the average thickness (average height) of each of the 10 measurement regions was determined. Then, the standard deviation was calculated from the average thickness data of 10 points in each of the obtained measurement regions.

<Evaluation of aggregates>
In Examples and Comparative Examples, the polyimide resin was added to the dispersion in an amount not affecting the particle size of the particulate cycloolefin copolymer to form a composition, so that aggregates of the particulate cycloolefin copolymer were contained in the dispersion. If it is not present, the aggregate will not be present in the composition either. Therefore, in the evaluation of whether or not the compositions obtained in Examples and Comparative Examples contain aggregates, it is confirmed whether or not the particulate cycloolefin copolymer dispersion liquid contains aggregates as follows. I went by doing.
When the dispersion of the particulate cycloolefin copolymer is observed with an optical microscope (VHX-7000 manufactured by KEYENCE CORPORATION) and the agglomerates of the cycloolefin copolymer exceeding 1 mm are contained, the agglomerates are evaluated as "presence". When no aggregate of cycloolefin copolymer larger than 1 mm was contained, the aggregate was evaluated as "none".

<CTE>
(Film CTE)
The CTEs of the composite films obtained in Examples and Comparative Examples were measured by TMA. Specifically, the measurement was performed under the following conditions, and the CTE at 50 ° C to 100 ° C was calculated.
Equipment: TMA / SS7100 manufactured by Hitachi High-Tech Science Corporation
Indenter (probe) diameter: 3.5 mm
Load: 50.0mN
Temperature program: Temperature rise from 20 ° C to 130 ° C at a rate of 5 ° C / min Specimen: 40 mm × 10 mm × 50 μm rectangular parallelepiped

(CTE of cycloolefin copolymer)
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.
Equipment: TMA / SS6200 manufactured by Hitachi High-Tech Science Corporation
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 Specimen: 10 mm x 10 mm x 1 mm rectangular parallelepiped

<Median diameter in particulate cycloolefin copolymer dispersion and composition>
The median diameter of the particulate cycloolefin copolymer in the particulate cycloolefin copolymer dispersion obtained in the examples was determined by the scattering type particle size distribution measurement using laser diffraction.
Specifically, in a glass cell having a capacity of 3.5 mL, the particulate cycloolefin copolymer dispersion obtained in the example was further added 1000 times by GBL, NMP or DMAc (using the same solvent as the dispersion). Diluted to obtain a dispersion sample containing the particulate cycloolefin copolymer. The obtained dispersion sample was measured using a laser diffraction / scattering type particle size distribution measuring device (manufactured by Malvern Panasonic, model: NanоZS, refractive index: 1.70-0.20i), and the particulate cycloolefin copolymer was measured. The median diameter was quantified.
As described above, in the examples, since the polyimide resin or the liquid crystal polyester was added to the dispersion liquid in an amount within a range not affecting the particle size of the particulate cycloolefin copolymer to form the composition, the particulate cycloolefin in the dispersion liquid was formed. The median diameter of the copolymer was defined as the median diameter of the particulate cycloolefin copolymer in the composition.

<Average primary particle size of particulate cycloolefin copolymer in film>
For the composite film obtained in the examples, a cross-sectional observation of each composite film was performed using a scanning transmission electron microscope (STEM), and the particle size of 50 or more particles was measured from the image of the observed cross-section. The average value thereof was taken as the average primary particle size.
(STEM observation measurement conditions)
Device name: HeLiоsG4UX (flake making device) manufactured by Japan FEI Co., Ltd.
Hitachi High-Tech Co., Ltd. S-5500 (for STEM observation)
Acceleration voltage: 30kv
Magnification: 20,000 times (SEM observation measurement conditions)
Device name: VE9800 manufactured by KEYENCE CORPORATION
Acceleration voltage: 2.0kv
Magnification: 500 times

<Details of reagents>
Toluene manufactured by Sumitomo Chemical Co., Ltd., styrene manufactured by Wako Pure Chemical Industries, Ltd., 2-norbornene manufactured by Arakawa Chemical Industry Co., Ltd. (hereinafter referred to as NB), and Toso Finechem Co., Ltd. are used for the synthesis of cycloolefin copolymers. ) Triisobutylaluminum (hereinafter referred to as TIBA) and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (hereinafter referred to as AB) manufactured by AGC Inc. were used.

Toluene was 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 was blown into it to remove dissolved oxygen. It was used.

After dissolving NB in toluene, it is dehydrated using Molecular Sieves 13X (manufactured by Union Showa Co., Ltd.) and activated alumina (manufactured by Sumitomo Chemical Co., Ltd., NKHD-24), and then nitrogen gas is blown into the NB. A solution from which dissolved oxygen was removed was used (hereinafter referred to as NB solution). The NB concentration in the NB solution was measured by using gas chromatography.

Isopropyridene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) Titanium dichloride (hereinafter referred to as a complex) is synthesized according to the method described in JP-A-9-183809. did.

[Manufacturing of cycloolefin copolymer]
<Manufacturing example 1>
To the autoclave whose inside was dried under reduced pressure, 1,501 mL (NB concentration: 3.00 mol / L) of the NB solution was added, and the temperature was raised to 60 ° C. After pressurizing with ethylene partial pressure: 100 kPa while stirring the inside of the system, 4.0 mL (concentration: 1.0 mol / L) of hexane solution of TIBA, 0.16 g of AB, and 10.0 mL of toluene solution of the complex ( 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 starting value. After 3 hours had passed from the start of the polymerization, 5.0 mL of water was added to stop the polymerization, and the solution in the autoclave was withdrawn. To the extracted solution, 1,500 g of toluene and 100 g of magnesium sulfate were added and stirred, and then 100 mL of water was added and stirred, and the solid was removed by filtration. The obtained 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 210.0 g of a cycloolefin copolymer having a median diameter of 335 μm. In the obtained cycloolefin copolymer, the NB content is 84.1 mol%, Tg is 293 ° C., Mw is 521,000, Mw / Mn is 1.87, and CTE is 49.4 ppm /. K, δD is 17.7 MPa ^0.5 , δP is 2.1 MPa ^0.5 , δH is 3.9 MPa ^0.5 , and meso-type two-chain / racemo-type two-chain is 0.19. The refractive index was 1.538. Table 2 shows the synthesis conditions of Production Example 1.

<Manufacturing example 2>
To the autoclave whose inside was dried under reduced pressure, 1,427 mL of NB solution (NB concentration: 3.00 mol / L) and 55.2 mL of styrene were added, and the temperature was raised to 80 ° C. While stirring the inside of the system, add 3.0 mL (concentration: 1.0 mol / L) of a hexane solution of TIBA, 0.32 g of AB, and 15.0 mL (concentration: 10 mmol / L) of a toluene solution of the complex. Polymerization of NB and styrene was started. The temperature in the system was kept at 80 ° C. during the polymerization. After 2 hours from the start of the polymerization, 3.0 mL of water was added to stop the polymerization, and the solution in the autoclave was withdrawn. The obtained liquid was added dropwise to acetone in the extracted solution, and the precipitated powder was isolated by filtration. The isolated powder was further washed with acetone and dried under reduced pressure at 150 ° C. for 2 hours to give 198.3 g of a cycloolefin copolymer. In the obtained cycloolefin copolymer, the NB content was 96.3 mol%, Mw was 79,000, Mw / Mn was 1.83, and Tg was more than 300 ° C. The δD of the cycloolefin copolymer was 17.7 MPa ^0.5 , the δP was 2.1 MPa ^0.5 , and the δH was 3.9 MPa ^0.5 . Table 3 shows the synthesis conditions of Production Example 2.

[Synthesis of polyimide resin]
<Manufacturing example 3>
A reactor equipped with a silica gel tube, a stirrer and a thermometer in a separable flask, and an oil bath were prepared. After making the inside of the flask a nitrogen atmosphere using dry nitrogen, 75.52 g of 6FDA and 54.44 g of TFMB were added. While stirring this at 400 rpm, 519.84 g of DMAc was added, and stirring was continued until the contents of the flask became a uniform solution. Subsequently, stirring was continued for another 20 hours while adjusting the temperature inside the container to be in the range of 20 to 30 ° C. using an oil bath, and the reaction was carried out to generate a polyamic acid. After 30 minutes, the stirring speed was changed to 100 rpm. After stirring for 20 hours, the reaction system temperature 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 the mixture was stirred at room temperature for 10 hours for imidization. The polyimide varnish was taken out from the reaction vessel. The obtained polyimide varnish was dropped into methanol for reprecipitation, and the obtained powder was heated and dried to remove the solvent to obtain a polyimide resin as a solid content. The δD of the obtained polyimide resin was 18.1 MPa ^{0.5, the δP was 8.3 MPa 0.5 ,} and the δH was 9.3 MPa ^0.5 . The Mw of the polyimide resin was 334,300, and the Tg was 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]
<Manufacturing example 4>
A reactor equipped with a silica gel tube, a stirrer and a thermometer in a separable flask, and an oil bath were prepared. 27.83 g of BPDA, 13.76 g of PMDA, and 34.00 g of m-TB were placed in this flask. While stirring this at 400 rpm, 428.35 g of DMAc was added, and stirring was continued until the contents of the flask became a uniform solution. Subsequently, stirring was continued for another 3 hours while adjusting the temperature inside the container to be in the range of 20 to 30 ° C. using an oil bath, and the reaction was carried out to obtain a polyamic acid solution dispersed in a solvent.

[Preparation of liquid crystal polyester solution]
<Manufacturing example 5>
Reactor equipped with stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 6-hydroxy-2-naphthoic acid 940.9 g, N-acetyl-4-aminophenol 377.9 g, isophthalic acid After adding 415.3 g and 867.8 g of anhydrous acetic acid and replacing the gas in the reactor with nitrogen gas, the temperature was raised from room temperature to 140 ° C. over 60 minutes with stirring under a nitrogen gas stream at 140 ° C. It was refluxed for 3 hours. Then, while distilling off by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 150 ° C. to 300 ° C. over 5 hours, held at 300 ° C. for 30 minutes, and then the contents were taken out from the reactor and brought to room temperature. Cooled. The obtained solid matter was pulverized with a pulverizer to obtain a powdery liquid crystal polyester (L1).
The liquid crystal polyester (L1) is heated from room temperature to 160 ° C. over 2 hours and 20 minutes under a nitrogen atmosphere, then heated from 160 ° C. to 180 ° C. over 3 hours and 20 minutes, and held at 180 ° C. for 5 hours. As a result, solid-phase polymerization was carried out, the mixture was cooled, and then the mixture was pulverized with a pulverizer to obtain a powdery liquid crystal polyester (L2).
The temperature of the liquid crystal polyester (L2) is raised from room temperature to 180 ° C. for 1 hour and 25 minutes under a nitrogen atmosphere, then the temperature is raised from 180 ° C. to 255 ° C. for 6 hours and 40 minutes, and the temperature is maintained at 255 ° C. for 5 hours. After solid-phase polymerization, the mixture was cooled to obtain a powdery liquid crystal polyester (L). The δD of the obtained liquid crystal polyester (L) was 20.9 MPa ^{0.5, the δP was 8.3 MPa 0.5 ,} and the δH was 4.7 MPa ^0.5 . The Mw of the liquid crystal polyester was 180,000, and the Tg was 190 ° C.
8 parts by mass of liquid crystal polyester (L) was added to 92 parts by mass of NMP, and the mixture was stirred at 140 ° C. for 4 hours under a nitrogen atmosphere to prepare a liquid crystal polyester solution.

[Example 1]
The cycloolefin copolymer obtained in Production Example 1 was dissolved in a toluene solution at a concentration of 2% by mass to obtain a cycloolefin copolymer solution.
The obtained cycloolefin copolymer solution is mixed with the same amount of DMAc as the amount of toluene in the solution, and the amount of toluene is 0.6 parts by mass with respect to 100 parts by mass of DMAc at 50 hPa at 80 ° C. Toluene was distilled off under reduced pressure for a period of time to obtain a particulate cycloolefin copolymer dispersion.
A composition was obtained as a polyimide-cycloolefin copolymer mixed solution by adding 1.9 g of the polyimide resin obtained above to 30.0 g (cycloolefin copolymer 2.0% by mass) of the obtained dispersion. .. In the composition, the content of the particulate cycloolefin copolymer was 24% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
The obtained composition was salivated on a glass substrate, and a coating film was formed at a linear velocity of 0.4 m / min. The coating film is heated at 70 ° C. for 60 minutes, the film is peeled off from the glass substrate, the film is fixed with a metal frame, and the film is further heated at 200 ° C. for 1 hour to obtain a 70 μm-thick polyimide-cycloolefin copolymer composite film. Got The CTE of the obtained composite film was 45 ppm / K.

[Example 2]
The cycloolefin copolymer obtained in Production Example 1 was dissolved in toluene at a concentration of 2% by mass to obtain a cycloolefin copolymer solution.
The obtained cycloolefin copolymer solution is mixed with GBL having the same amount of toluene as the amount of toluene in the solution, and 2 at 50 hPa and 80 ° C. until the amount of toluene becomes 0.6 parts by mass with respect to 100 parts by mass of GBL. Toluene was distilled off under reduced pressure for a period of time to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion and the composition measured by the above method was 0.14 μm.
A composition was obtained as a polyimide-cycloolefin copolymer mixed solution by adding 1.9 g of the polyimide resin obtained above to 30.0 g (cycloolefin copolymer 2.0% by mass) of the obtained dispersion. .. In the composition, the content of the particulate cycloolefin copolymer was 24% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
The obtained composition was salivated on a glass substrate, and a coating film was formed at a linear velocity of 0.4 m / min. The coating film is heated at 70 ° C. for 60 minutes, the film is peeled off from the glass substrate, the film is fixed with a metal frame, and the film is further heated at 200 ° C. for 1 hour to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 50 μm. Got The average primary particle size of the particulate cycloolefin copolymer in the obtained composite film was 0.16 μm. The CTE of the composite film was 44 ppm / K.

[Example 3]
The cycloolefin copolymer obtained in Production Example 1 was dissolved in xylene at a concentration of 2% by mass to obtain a cycloolefin copolymer solution.
The obtained cycloolefin copolymer solution is mixed with the same amount of DMAc as the amount of xylene in the solution, and toluene is used at 50 hPa and 85 ° C. until the amount of xylene becomes 0.6 parts by mass with respect to 100 parts by mass of DMAc. Was distilled off to obtain a particulate cycloolefin copolymer dispersion.
A composition was obtained as a polyimide-cycloolefin copolymer mixed solution by adding 1.9 g of the polyimide resin obtained above to 30.0 g (cycloolefin copolymer 2.0% by mass) of the obtained dispersion. .. In the composition, the content of the particulate cycloolefin copolymer was 24% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
The obtained composition was salivated on a glass substrate, and a coating film was formed at a linear velocity of 0.4 m / min. The coating film is heated at 70 ° C. for 60 minutes, the film is peeled off from the glass substrate, the film is fixed with a metal frame, and the film is further heated at 200 ° C. for 1 hour to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 60 μm. Got The CTE of the obtained composite film was 45 ppm / K.

[Example 4]
The cycloolefin copolymer obtained in Production Example 1 was dissolved in xylene at a concentration of 2% by mass to obtain a cycloolefin copolymer solution.
The obtained cycloolefin copolymer solution is mixed with GBL having the same amount of xylene as the amount of xylene in the solution, and xylene at 50 hPa and 85 ° C. until the amount of xylene becomes 0.6 parts by mass with respect to 100 parts by mass of GBL. Was distilled off to obtain a particulate cycloolefin copolymer dispersion.
A composition was obtained as a polyimide-cycloolefin copolymer mixed solution by adding 1.9 g of the polyimide resin obtained above to 30.0 g (cycloolefin copolymer 2.0% by mass) of the obtained dispersion. .. In the composition, the content of the particulate cycloolefin copolymer was 24% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
The obtained composition was salivated on a glass substrate, and a coating film was formed at a linear velocity of 0.4 m / min. The coating film is heated at 70 ° C. for 60 minutes, the film is peeled off from the glass substrate, the film is fixed with a metal frame, and the film is further heated at 200 ° C. for 1 hour to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 60 μm. Got The CTE of the obtained composite film was 45 ppm / K.

[Example 5]
The cycloolefin copolymer obtained in Production Example 1 was dissolved in toluene at a concentration of 2% by mass to obtain a cycloolefin copolymer solution.
The obtained cycloolefin copolymer solution is mixed with the same amount of GBL as the amount of toluene in the solution, and toluene is retained at 50 hPa and 85 ° C. until the amount of toluene becomes 7 parts by mass with respect to 100 parts by mass of GBL. The mixture was removed to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion measured by the above method was 0.15 μm.
By adding 1.9 g of the polyimide resin obtained above to 32.1 g (cycloolefin copolymer 1.9% by mass) of the obtained dispersion, a composition was obtained as a polyimide-cycloolefin copolymer mixed solution. In the composition, the content of the particulate cycloolefin copolymer was 24% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
The obtained composition was subjected to salivation molding on a glass substrate to form a coating film at a linear speed of 0.4 m / min. The coating film is heated at 70 ° C. for 60 minutes, the film is peeled off from the glass substrate, the film is fixed with a metal frame, and the film is further heated at 200 ° C. for 1 hour to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 60 μm. Got The CTE of the obtained composite film was 44 ppm / K.

[Example 6]
The cycloolefin copolymer obtained in Production Example 1 was dissolved in toluene at a concentration of 2% by mass to obtain a cycloolefin copolymer solution.
The obtained cycloolefin copolymer solution is mixed with the same amount of GBL as the amount of toluene in the solution, and toluene is retained at 50 hPa and 85 ° C. until the amount of toluene reaches 20 parts by mass with respect to 100 parts by mass of GBL. The mixture was removed to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion measured by the above method was 0.14 μm.
By adding 1.9 g of the polyimide resin obtained above to 35.9 g (1.7% by mass of cycloolefin copolymer) of the obtained dispersion, a composition was obtained as a polyimide-cycloolefin copolymer mixed solution. In the composition, the content of the particulate cycloolefin copolymer was 24% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
The obtained composition was subjected to salivation molding on a glass substrate to form a coating film at a linear speed of 0.4 m / min. The coating film is heated at 70 ° C. for 60 minutes, the film is peeled off from the glass substrate, the film is fixed with a metal frame, and the film is further heated at 200 ° C. for 1 hour to obtain a 60 μm-thick polyimide-cycloolefin copolymer composite film. Got The CTE of the obtained composite film was 44 ppm / K.

[Example 7]
The cycloolefin copolymer obtained in Production Example 1 was dissolved in toluene at a concentration of 2% by mass to obtain a cycloolefin copolymer solution.
The obtained cycloolefin copolymer solution is mixed with the same amount of GBL as the amount of toluene in the solution, and toluene is retained at 50 hPa and 85 ° C. until the amount of toluene becomes 40 parts by mass with respect to 100 parts by mass of GBL. The mixture was removed to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion measured by the above method was 0.13 μm.
By adding 1.9 g of the polyimide resin obtained above to 41.8 g (1.4% by mass of cycloolefin copolymer) of the obtained dispersion, a composition was obtained as a polyimide-cycloolefin copolymer mixed solution. In the composition, the content of the particulate cycloolefin copolymer was 24% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
The obtained mixed solution was subjected to salivation molding on glass to form a coating film at a linear speed of 0.4 m / min. The coating film is heated at 70 ° C. for 60 minutes, the film is peeled off from the glass substrate, the film is fixed with a metal frame, and the film is further heated at 200 ° C. for 1 hour to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 60 μm. Got The CTE of the obtained composite film was 44 ppm / K.

[Example 8]
The cycloolefin copolymer obtained in Production Example 1 was dissolved in toluene at a concentration of 2% by mass to obtain a cycloolefin copolymer solution.
The obtained cycloolefin copolymer solution is mixed with the same amount of NMP as the amount of toluene in the solution, and toluene is added at 50 hPa and 85 ° C. until the amount of toluene becomes 0.6 parts by mass with respect to 100 parts by mass of NMP. Was distilled off to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the particulate cycloolefin copolymer dispersion measured by the above method was 0.14 μm.
17.5 g of a liquid crystal polyester solution was added to 30.0 g (2.0% by mass of the particulate cycloolefin copolymer) of the obtained particulate cycloolefin copolymer dispersion liquid to prepare a composition as a liquid crystal polyester-cycloolefin copolymer mixed solution. Obtained. In the composition, the content of the particulate cycloolefin copolymer was 30.0% by mass with respect to the total mass of the liquid crystal polyester and the particulate cycloolefin copolymer.
The obtained composition was subjected to salivation molding on a copper foil to prepare a coating film at a linear speed of 0.4 m / min. The coating film was heated at 60 ° C. for 4 hours to obtain a laminate having a copper foil and a liquid crystal polyester precursor-cycloolefin copolymer composite film, and then the laminate was fixed with a metal frame and further under a nitrogen atmosphere, 310. By heating the laminate at ° C. for 4 hours, a laminate having a copper foil and a liquid crystal polyester-cycloolefin copolymer composite film was obtained. The obtained laminate was immersed in a ferric chloride solution for 10 minutes to remove the copper foil by etching to obtain a liquid crystal polyester-cycloolefin copolymer composite film having a thickness of 30 μm. The CTE of the obtained composite film was 47 ppm / K. The distance between the HSP values of the liquid crystal polyester obtained in Production Example 5 and the cycloolefin copolymer obtained in Production Example 1 was 8.9.

[Example 9]
The cycloolefin copolymer obtained in Production Example 1 was dissolved in toluene at a concentration of 2% by mass to obtain a cycloolefin copolymer solution.
The obtained cycloolefin copolymer solution is mixed with the same amount of NMP as the amount of toluene in the solution, and toluene is retained at 50 hPa and 85 ° C. until the amount of toluene becomes 40 parts by mass with respect to 100 parts by mass of NMP. The mixture was removed to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the particulate cycloolefin copolymer dispersion measured by the above method was 0.14 μm.
17.1 g of a liquid crystal polyester solution was added to 41.8 g (1.4% by mass of the cycloolefin copolymer) of the obtained particulate cycloolefin copolymer dispersion liquid to obtain a composition as a liquid crystal polyester-cycloolefin copolymer mixed solution. .. In the composition, the content of the particulate cycloolefin copolymer was 30.0% by mass with respect to the total mass of the liquid crystal polyester and the particulate cycloolefin copolymer.
The obtained composition was subjected to salivation molding on a copper foil to prepare a coating film at a linear speed of 0.4 m / min. The coating film was heated at 60 ° C. for 4 hours to obtain a laminate having a copper foil and a liquid crystal polyester precursor-cycloolefin copolymer composite film, and then the laminate was fixed with a metal frame and further under a nitrogen atmosphere, 310. By heating the laminate at ° C. for 4 hours, a laminate having a copper foil and a liquid crystal polyester-cycloolefin copolymer composite film was obtained. The obtained laminate was immersed in a ferric chloride solution for 10 minutes to remove the copper foil by etching to obtain a liquid crystal polyester-cycloolefin copolymer composite film having a thickness of 30 μm. The CTE of the obtained composite film was 48 ppm / K.

[Example 10]
The cycloolefin copolymer obtained in Production Example 2 was dissolved in toluene at a concentration of 2% by mass to obtain a cycloolefin copolymer solution.
The obtained cycloolefin copolymer solution is mixed with GBL having the same amount of toluene as the amount of toluene in the solution, and the amount of toluene is 0.6 parts by mass with respect to 100 parts by mass of GBL at 50 hPa at 80 ° C. Toluene was distilled off under reduced pressure for a period of time to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the dispersion and the composition measured by the above method was 0.13 μm.
By adding 1.9 g of the polyimide resin obtained above to 30.0 g of the obtained particulate cycloolefin copolymer dispersion (2.0% by mass of the cycloolefin copolymer), a polyimide-cycloolefin copolymer mixed solution can be obtained. The composition was obtained. In the composition, the content of the particulate cycloolefin copolymer was 24% by mass with respect to the total mass of the polyimide resin and the particulate cycloolefin copolymer.
The obtained composition was salivated on a glass substrate, and a coating film was formed at a linear velocity of 0.4 m / min. The coating film is heated at 70 ° C. for 60 minutes, the film is peeled off from the glass substrate, the film is fixed with a metal frame, and the film is further heated at 200 ° C. for 1 hour to obtain a 60 μm-thick polyimide-cycloolefin copolymer composite film. Got The CTE of the obtained composite film was 45 ppm / K. The distance between the HSP values of the polyimide resin obtained in Production Example 3 and the cycloolefin copolymer obtained in Production Example 2 was 8.3.

[Example 11]
The cycloolefin copolymer obtained in Production Example 2 was dissolved in toluene at a concentration of 2% by mass to obtain a cycloolefin copolymer solution.
The obtained cycloolefin copolymer solution is mixed with the same amount of DMAc as the amount of toluene in the solution, and the amount of toluene is 0.6 parts by mass with respect to 100 parts by mass of DMAc at 50 hPa at 80 ° C. Toluene was distilled off under reduced pressure for a period of time to obtain a particulate cycloolefin copolymer dispersion. The median diameter of the particulate cycloolefin copolymer in the particulate cycloolefin copolymer dispersion measured by the above method was 0.13 μm.
8.0 g of a polyamic acid solution was added to 30.0 g of the obtained particulate cycloolefin copolymer dispersion (2.0% by mass of the particulate cycloolefin copolymer) to prepare a composition as a polyamic acid-cycloolefin copolymer mixed solution. Obtained. In the composition, the content of the particulate cycloolefin copolymer was 33.3% by mass with respect to the total mass of the polyamic acid and the particulate cycloolefin copolymer.
The obtained composition was subjected to salivation molding on a glass substrate to prepare a coating film at a linear speed of 0.4 m / min. The coating film is heated at 70 ° C. for 60 minutes, the polyamic acid-cycloolefin copolymer composite film is peeled off from the glass substrate, the film is fixed with a metal frame, and the polyamic acid is gradually increased to 360 ° C. in 30 minutes under a nitrogen atmosphere. By heating the acid-cycloolefin copolymer composite film, the polyamic acid was imidized to obtain a polyimide-cycloolefin copolymer composite film having a thickness of 30 μm. The CTE of the obtained composite film was 21 ppm / K. The distance between the HSP values of the polyamic acid obtained in Production Example 4 and the cycloolefin copolymer obtained in Production Example 2 was 6.0 or more. Further, in the film, the distance between the HSP values of the polyimide resin formed by imidizing the polyamic acid and the cycloolefin copolymer obtained in Production Example 2 was 6.0 or more.

[Comparative Example 1]
The cycloolefin copolymer obtained in Production Example 1 was dissolved in toluene at a concentration of 2% by mass to obtain a cycloolefin copolymer solution.
The obtained cycloolefin copolymer solution is mixed with amyl acetate in the same amount as the amount of toluene in the solution, and the amount of toluene is 50 hPa at 85 ° C. until the amount of toluene becomes 0.6 parts by mass with respect to 100 parts by mass of amyl acetate. Toluene was distilled off to obtain a particulate cycloolefin copolymer dispersion. At this time, aggregates of the cycloolefin copolymer exceeding 1 mm were confirmed, and it was difficult to form a film.

According to the above measurement method, the results of evaluating the presence or absence of aggregates in the compositions obtained in Examples and Comparative Examples, and the average value of the average thickness in each of the 10 measurement regions of the composite film and the average thickness thereof. The results of measuring the standard deviation are shown in Table 4. Further, the content ratio of the first solvent to 100 parts by mass of the second solvent in the dispersion liquid and the composition, the distance between the HSP values of each solvent and the polyimide resin, the polyamic acid, the liquid crystal polyester, or the cycloolefin copolymer, and each solvent. Table 4 also shows the evaluation results of the solubility of the polyimide resin, polyamic acid, liquid crystal polyester or cycloolefin copolymer in the solvent. Regarding the distance between HSP values, for example, in the case of the distance between the HSP values of the first solvent and the resin (A), it is expressed as "HSP distance (first solvent pair (A))", and the first solvent and the cycloolefin copolymer. In the case of the distance between HSP values, it is expressed as "HSP distance (first solvent vs. COC)". The same applies to the case of the second solvent. In the evaluation of solubility according to the above, "dissolved" is indicated as "dissolved", and "insoluble" is indicated as "insoluble". In Table 4, the first solvent indicates toluene or xylene, and the second solvent indicates GBL, DMAc, NMP or amyl acetate.

As shown in Table 4, the compositions obtained in Examples 1 to 11 did not contain aggregates. Further, the films obtained in Examples 1 to 11 had a low standard deviation in thickness and were excellent in surface smoothness. On the other hand, the composition obtained in Comparative Example 1 contained aggregates, and it was difficult to form a film.

Claims (15)

1. A composition comprising a resin (A), a particulate cycloolefin polymer (B), and a solvent.
   The composition comprises a first solvent and a second solvent, and the distance between the HSP values of the second solvent and the cycloolefin polymer (B) is 8.5 or more.
2. The composition according to claim 1, wherein the first solvent is a solvent in which the cycloolefin polymer (B) is dissolved.
3. The composition according to claim 1 or 2, wherein the second solvent is a solvent in which the cycloolefin polymer (B) is insoluble.
4. The composition according to any one of claims 1 to 3, wherein the distance between the HSP values of the first solvent and the cycloolefin polymer (B) is 4.0 or less.
5. The composition according to any one of claims 1 to 4, wherein the second solvent is a solvent in which the resin (A) is dissolved.
6. The composition according to any one of claims 1 to 5, wherein the distance between the HSP values of the second solvent and the resin (A) is 10.0 or less.
7. The composition according to any one of claims 1 to 6, wherein the distance between the HSP values of the resin (A) and the cycloolefin polymer (B) is 6 or more.
8. The composition according to any one of claims 1 to 7, wherein the content of the first solvent is 120 parts by mass or less with respect to 100 parts by mass of the second solvent.
9. Any of claims 1 to 8, wherein the content of the particulate cycloolefin polymer (B) is 5 to 50% by mass with respect to the total mass of the resin (A) and the particulate cycloolefin polymer (B). The composition described in Crab.
10. The cycloolefin polymer (B) has the formula (I) :.
    

    

    [In the formula (I), m represents an integer of 0 or more, R ⁷ to R ¹⁸ represent hydrogen atoms, halogen atoms or hydrocarbon groups having 1 to 20 carbon atoms independently of each other, and R ¹¹ to R When a plurality of ¹⁴ are present, they may be independently the same or different from each other, and R ¹⁶ and R ¹⁷ may be bonded to each other and form a ring with the carbon atom to which they are bonded. ]
    The composition according to any one of claims 1 to 9, which comprises a monomer unit (1) derived from cycloolefin represented by.
11. The resin (A) is any one of claims 1 to 10, wherein the resin (A) is at least one resin selected from the group consisting of a polyimide resin, a liquid crystal polymer, a fluororesin, an aromatic polyether resin, and a maleimide resin. The composition described.
12. The composition according to any one of claims 1 to 11, wherein the resin (A) has a glass transition temperature of 180 ° C. or higher.
13. A film containing the resin (A) and the particulate cycloolefin polymer (B).
    A film in which the standard deviation of the average thickness obtained in each of the 10 measurement regions obtained by dividing a region of a straight line of 1 mm on the surface of the film into 10 equal parts is 2.5 or less.
14. The film according to claim 13, wherein the distance between the HSP values of the resin (A) and the cycloolefin polymer (B) is 6 or more.
15. The film according to claim 13 or 14, wherein the particulate cycloolefin polymer (B) has an average primary particle diameter of 15 μm or less.