JP5540784B2 - Container with film forming composition - Google Patents

Description

  The present invention relates to a container containing a film-forming composition.

  In the field of electronic materials, as semiconductor devices become more highly integrated, faster and have higher performance, delay time due to increased resistance between wires and increased capacitance of semiconductor integrated circuits has become a major problem. In order to reduce the delay time and increase the speed of the semiconductor device, it is necessary to use an insulating film having a low dielectric constant for the circuit.

  For the formation of the insulating film, a liquid composition containing an organic material is widely used. When such a composition is used, the characteristics and reliability of the formed insulating film may be deteriorated due to generation of irregularities in the formed insulating film. In order to solve such problems, various film-forming compositions have been proposed (for example, see Patent Document 1).

  However, even when the above composition is used, conventionally, particles are generated in the composition at the time of transportation, storage, and the like, and therefore, the composition is formed using the composition. It has been difficult to make the characteristics and reliability of the insulating film sufficiently excellent.

JP 2007-161786 A

  An object of the present invention is to provide a container containing a film-forming composition that hardly generates particles.

Such an object is achieved by the present invention described in the following (1) to (11) .
(1) A polymerizable compound having a partial structure containing an adamantane cage structure in the molecule and a polymerizable reactive group contributing to the polymerization reaction, and / or a polymer obtained by partially polymerizing the polymerizable compound. A container containing a film-forming composition comprising a liquid film-forming composition containing the container,
When the storage amount of the storage portion for storing the film forming composition in the container is V [cm ³ ] and the internal surface area of the storage portion is S [cm ² ], the relationship of S / V ≦ 0.85 is established. Satisfied ,
The polymerizable reactive group of the polymerizable compound contained in the film-forming composition housed in the container has an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring, In the polymerizable compound, the number of carbons derived from the aromatic ring is 15% or more and 38% or less with respect to the number of carbons in the entire polymerizable compound.

(2) The film-forming composition-containing container according to (1) , wherein the aromatic ring is directly bonded to the cage structure.

(3) The polymerizable reactive group has two ethynyl groups or vinyl groups, and the one ethynyl group or the vinyl group is present at the meta position of the other ethynyl group or the vinyl group. A container containing the film-forming composition as described in (1) or (2) above.

(4) Two of the ethynyl group or the vinyl group are all the aromatic ring composition for film formation according to the above (3) being present in the meta position of the site for binding to said cage structure Monoiri container.

(5) The container containing a film-forming composition according to any one of (1) to (4) , wherein the partial structure has an adamantane structure.

(6) The film-containing composition-containing container according to (5) , wherein the adamantane structure has a methyl group as a substituent.

［式中、ｎは１〜５の整数を表す。］

［式中、ｎは１〜５の整数を表す。］ (7) The container containing the composition for film formation according to (6) , wherein the polymerizable compound has a structure represented by the following formula (1) or the following formula (5).

[Wherein n represents an integer of 1 to 5. ]

[Wherein n represents an integer of 1 to 5. ]

(8) The film-containing composition-containing container according to any one of (1) to (7) , wherein the partial structure has a diamantane structure.

(9) The polymerizable compound has two polymerizable reactive groups, and has a structure in which the polymerizable reactive groups are symmetrically bonded around the partial structure. Thru | or the container containing the composition for film formation in any one of (8) .

(10) The film-forming composition-containing container according to any one of (1) to (9) , wherein the film-forming composition contains a silane coupling agent.

(11) The film forming composition as described in any one of (1) to (10) above, wherein the inner surface of the storage portion is made of a material having a contact angle with water at 20 ° C. of 65 ° or more. Container with goods.

  ADVANTAGE OF THE INVENTION According to this invention, the container containing the composition for film formation which cannot produce a particle easily can be provided.

It is a longitudinal cross-sectional view which shows an example of the method of forming the interlayer insulation film patterned by the predetermined shape. It is a longitudinal section showing an example of a semiconductor device typically.

Hereinafter, the present invention will be described in detail.
<Container for film forming composition>
The container with a film-forming composition of the present invention is obtained by storing a liquid film-forming composition in a container.
First, the film forming composition stored in the container will be described in detail.

(Film forming composition)
The container containing the film-forming composition of the present invention comprises a polymerizable compound having a partial structure containing an adamantane cage structure and a polymerizable reactive group contributing to the polymerization reaction in the molecule and / or the polymerizable compound. A liquid film-forming composition containing a partially polymerized polymer is stored in a container, and the storage amount of the storage part for storing the film-forming composition in the container is V [cm ³ ], When the inner surface area of the storage portion (the area where the film-forming composition can be contacted) is S [cm ² ], the relationship of S / V ≦ 0.85 is satisfied. Thereby, generation | occurrence | production of the particle | grains at the time of transportation, a preservation | save, etc. can be prevented effectively, and the container containing the composition for film formation which can be used for formation of the film | membrane of the stable quality can be provided. As described above, the film-forming composition-containing container of the present invention is obtained by storing a predetermined liquid film-forming composition in a container. Hereinafter, the film forming composition will be described in detail.

(Film forming composition)
As described above, the composition (film forming composition) constituting the film forming composition-containing container includes a partial structure A containing an adamantane cage structure in the molecule and a polymerizable reaction that contributes to the polymerization reaction. As long as it contains a polymerizable compound having a group B and / or a polymer obtained by partially polymerizing the polymerizable compound, the polymerizable compound X and / or the polymerizable compound X as described below may be used. It is preferable to include a partially polymerized polymer.

[1] Polymerizable compound X
The polymerizable reactive group B of the polymerizable compound X has an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring. In the polymerizable compound X, the number of carbons derived from the aromatic ring is The total number of carbon atoms in the polymerizable compound X is preferably 15% or more and 38% or less, more preferably 18% or more and 27% or less. Accordingly, it is possible to provide an insulating film that has a low dielectric constant, exhibits stable insulating properties, is excellent in strength, and suppresses unintentional variations in film thickness and characteristics.

  In addition, since the ethynyl group or vinyl group which the polymerizable reactive group B has is a polymerizable group when the polymerizable compounds are polymerized and exhibits the same function, the polymerizable reactive group will be described below. The case where B has an ethynyl group will be described representatively.

Hereinafter, the partial structure A and the polymerizable reactive group B will be described.
[1.1] Partial structure A
The partial structure A possessed by the polymerizable compound X includes an adamantane cage structure. Thereby, the film (insulating film) formed using the film-forming composition can have a low density, and the dielectric constant of the formed film can be reduced. In addition, since the reactivity of the polymerizable compound X having the polymerizable reactive group B as described later in detail can be made appropriate, film formation on a member (for example, a semiconductor substrate) on which a film is to be formed When applying the composition for the film, the viscosity of the film-forming composition is surely suitable, and unintentional variations in thickness and characteristics at each part of the formed film can be suppressed, The strength of the finally formed film can be made excellent. Furthermore, the etching rate in the etching process for patterning the film (insulating film) formed using the film forming composition into a predetermined shape can be made relatively low.

Examples of the partial structure A of the polymerizable compound X include adamantane, polyadamantane (eg, biadamantane, triadamantane, tetraadamantane, pentaadamantane, hexaadamantane, heptaadamantane, etc.), polyamantane (eg, diamantane, triamantane, Tetramantane, pentamantane, hexamantane, heptamantane, etc.), divalent groups such as compounds in which at least a part of hydrogen atoms constituting these compounds are substituted with alkyl groups or halogen atoms (two hydrogen atoms constituting the above compounds) A structure having two or more of these divalent groups (for example, a bi (diamantane) skeleton, a tri (diamantane) skeleton, a tetra (diamantane) skeleton, etc.) Things (Poly (Gia (Having a poly (triamantane) skeleton), such as a bi (triamantane) skeleton, a tri (triamantane) skeleton, and a tetra (triamantane) skeleton. An adamantane skeleton (or a polyadamantane skeleton) and a polyamantane skeleton, etc.) and the like. Hereinafter, a part of the example of the partial structure A is shown by a chemical structural formula, but the partial structure A is not limited to these. However, in the following formulas (A-1) to (A-7), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or a halogen group, and l, m, and n are each independently 1 represents an integer of 1 or more.

  The partial structure A preferably has an adamantane structure. Thereby, the dielectric constant of the film (insulating film) formed using the film-forming composition can be made particularly low, and the reactivity of the polymerizable compound X can be made more suitable. When applying a film-forming composition onto a member (for example, a semiconductor substrate) on which a film is to be formed, the viscosity of the film-forming composition is more surely suitable, and the film to be formed Unintentional variations in thickness and characteristics at each part can be more effectively suppressed, and the strength of the finally formed film can be made particularly excellent.

  The adamantane structure preferably has a methyl group as a substituent. Thereby, the dielectric constant of the film | membrane formed using the composition for film | membrane formation can be made especially low. In addition, the generation of particles during transportation and storage can be more effectively prevented, and the stability of the quality of the film (insulating film) formed using the film-forming composition is particularly excellent. can do. Further, the reactivity of the polymerizable compound X can be made more suitable, and when the composition for film formation on a member (for example, a semiconductor substrate) on which a film is to be formed is applied, The viscosity of the composition is more surely suitable, and it is possible to more effectively suppress unintentional variations in thickness and characteristics at each part of the formed film, and the film formed finally The strength can be made particularly excellent.

  From the above, as the partial structure A, one having a structure represented by the following formula (2) is particularly suitable. In the following formula (2), n represents an integer of 1 or more.

  By selecting the structure having such a structure as the partial structure A, the film (insulating film) formed using the film forming composition exhibits the above-described effects more remarkably.

  In addition, it is preferable that the partial structure A having such a structure is a structure having symmetry itself. That is, in the above formula (2), n is preferably an even number. Thereby, the reactivity of the polymerizable compound X can be made more appropriate, and when the composition for forming a film on a member (for example, a semiconductor substrate) on which a film is to be formed is applied, the film formation is performed. The viscosity of the composition for use is more surely suitable, and it is possible to more effectively suppress unintentional variations in thickness and characteristics at each part of the formed film, and the film finally formed Can be made particularly excellent in strength.

  The partial structure A may have a diamantane structure. Thereby, the dielectric constant of the film | membrane formed using the composition for film formation can be made low. In addition, the generation of particles during transportation and storage can be more effectively prevented, and the stability of the quality of the film (insulating film) formed using the film-forming composition is particularly excellent. can do. Further, the reactivity of the polymerizable compound X can be made more suitable, and when the composition for film formation on a member (for example, a semiconductor substrate) on which a film is to be formed is applied, The viscosity of the composition is more surely suitable, and it is possible to more effectively suppress unintentional variations in thickness and characteristics at each part of the formed film, and the film formed finally The strength can be made particularly excellent.

[1.2] Polymerizable reactive group B
In addition to the partial structure A as described above, the polymerizable compound X has a polymerizable reactive group B that contributes to the polymerization reaction.

  The polymerizable compound X may have one polymerizable reactive group B, but has two, and these have a structure in which they are symmetrically bonded around the partial structure A. preferable. Thereby, the reactivity of the polymerizable compound X can be made appropriate, and when the film-forming composition is applied onto a member (for example, a semiconductor substrate) on which a film is to be formed, The viscosity of the composition is surely suitable, and it is possible to suppress unintentional variations in the thickness and characteristics of each part of the film to be formed, and the strength of the film finally formed is excellent. It can be.

  As described above, the polymerizable compound X has two polymerizable reactive groups B together with the partial structure A, and furthermore, these have a specific arrangement, so that particularly excellent effects are exhibited.

  The aromatic ring constituting the polymerizable reactive group B is not particularly limited, and for example, a benzene ring, naphthalene ring, anthracene ring, naphthacene ring, phenanthrene ring, chrysene ring, pyrene ring, perylene ring, coronene ring, biphenyl ring, Hydrocarbon aromatic rings such as terphenyl ring and azulene ring, pyridine ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, indole ring, purine ring, benzofuran ring, benzothiophene ring, carbazole ring, imidazole ring, Examples thereof include heterocyclic aromatic rings such as thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, quinoline ring, and terthienyl ring. Of these, a benzene ring is preferred as the aromatic ring. Thereby, application | coating of the composition for film formation on the member (for example, semiconductor substrate) which should form a film | membrane can be performed more easily. In addition, the generation of particles during transportation and storage can be more effectively prevented, and the stability of the quality of the film (insulating film) formed using the film-forming composition is particularly excellent. can do. Moreover, the elasticity modulus of the film | membrane formed using the film forming composition can be made suitable, and the intensity | strength and heat resistance of the film | membrane formed, adhesiveness to the said member (semiconductor substrate etc.), etc. It can be made particularly excellent.

  The aromatic ring constituting the polymerizable reactive group B may be bonded to the cage structure constituting the partial structure A via at least one other atom, but the cage structure constituting the partial structure A It is preferable that it is directly bonded to. As a result, the reactivity of the polymerizable compound X can be made more suitable, and the film formation can be performed when a film forming composition is applied onto a member (for example, a semiconductor substrate) on which a film is to be formed. The viscosity of the composition for use is more surely suitable, and it is possible to more effectively suppress unintentional variations in thickness and characteristics at each part of the formed film, and the film finally formed Can be made particularly excellent in strength.

  The polymerizable reactive group B may have one ethynyl group, but has two ethynyl groups, and two ethynyl groups are directly bonded to the aromatic ring as described above. Is preferred. Further, since the polymerizable reactive group B has two ethynyl groups as reaction sites, an initial reaction with respect to the polymerizable compound X easily occurs. On the other hand, when one of the two ethynyl groups of the polymerizable reactive group B reacts (polymerization reaction), the electronic state of the aromatic ring changes, and the reactivity of the other ethynyl group rapidly increases. descend. For this reason, only one ethynyl group of the two ethynyl groups of the polymerizable reactive group B can be selectively reacted under relatively mild conditions. And since the polymerizable compound X preferably has two polymerizable reactive groups B in the molecule, one of the two polymerizable reactive groups B present in the molecule of the polymerizable compound X is Only the ethynyl group can be reacted selectively. In this case, for example, a polymer (chain-like prepolymer) in which a plurality of polymerizable compounds X are polymerized one-dimensionally by a reaction shown in the following formula (3). Polymer).

（式（３）中、Ａは部分構造Ａを示し、Ａｒは重合性反応基Ｂを構成する芳香環を示す。また、ｎは、２以上の整数を表す。）

(In formula (3), A represents the partial structure A, Ar represents an aromatic ring constituting the polymerizable reactive group B, and n represents an integer of 2 or more.)

  In the case where the polymerizable reactive group B has a vinyl group instead of an ethynyl group, a polymer in which a plurality of polymerizable compounds X are polymerized one-dimensionally by a reaction shown in the following formula (3 ′) ( A chain prepolymer) is obtained.

（（３’）中、Ａは部分構造Ａを示し、Ａｒは重合性反応基Ｂを構成する芳香環を示す。また、ｎは、２以上の整数を表す。）

(In (3 ′), A represents the partial structure A, Ar represents an aromatic ring constituting the polymerizable reactive group B, and n represents an integer of 2 or more.)

  When the reaction as described above occurs, the polymerizable compound X reacts excessively during storage of the film-forming composition, and the film-forming composition becomes extremely viscous (for example, gelation). Can be reliably prevented, and the viscosity of the film-forming composition is surely suitable for applying the film-forming composition onto a member (for example, a semiconductor substrate) on which a film is to be formed. Can be. As a result, it is possible to reliably suppress the occurrence of unintentional variations in thickness and characteristics at each site of the formed film.

  On the other hand, since the polymer obtained by the reaction as described above (prepolymer obtained by partial polymerization reaction) has an unreacted ethynyl group, the firing conditions described in detail later ( Under the heating conditions on the semiconductor substrate, the remaining ethynyl groups can be reacted with certainty, and the film finally formed has a three-dimensionally cross-linked structure. As a result, the formed film is particularly excellent in heat resistance and the like.

  As described above, when each polymerizable reactive group B constituting the polymerizable compound X has two ethynyl groups, in the polymerizable reactive group B, one ethynyl group is a meta of the other ethynyl group. It is preferable that it exists in a position. Thereby, in the state in which one ethynyl group of the two ethynyl groups of the polymerizable reactive group B has reacted (polymerization reaction), the electronic effect of the aromatic ring or the like is more significantly exhibited, and the other ethynyl group The reactivity can be reduced more effectively, the reacted site becomes an appropriate steric hindrance, and the reactivity of the other ethynyl group (unreacted ethynyl group) can be more suitably controlled. . As a result, the reactivity of the two ethynyl groups of the polymerizable reactive group B (reactivity for the first stage reaction and reactivity for the second stage reaction) is made higher. In addition, it is possible to perform a baking step as will be described in detail later under more suitable conditions (conditions capable of forming a film with excellent productivity while preventing damage to the semiconductor substrate).

  In addition, when the polymerizable reactive group B has two ethynyl groups, it is preferable that both of the two ethynyl groups are present at the meta position where the aromatic ring is bonded to the cage structure. Thereby, in the state in which one ethynyl group of the two ethynyl groups of the polymerizable reactive group B has reacted (polymerization reaction), the electronic effect of the aromatic ring or the like is more significantly exhibited, and the other ethynyl group The reactivity can be reduced more effectively, and the reacted site and the partial structure A described above become an appropriate steric hindrance, and the reactivity of the other ethynyl group (unreacted ethynyl group) can be reduced. It can control more suitably. As a result, the reactivity of the two ethynyl groups of the polymerizable reactive group B (reactivity for the first stage reaction and reactivity for the second stage reaction) is made higher. In addition, it is possible to perform a baking step as will be described in detail later under more suitable conditions (conditions capable of forming a film with excellent productivity while preventing damage to the semiconductor substrate).

  A polymerizable compound X that satisfies the above conditions, that is, a preferable one as the partial structure A and the polymerizable reactive group B is selected, and an aromatic ring-derived carbon in the polymerizable compound X is set to an appropriate number. Examples of the polymerizable compound X include those having a structure represented by the following formula (1). In the following formula (1), n represents an integer of 1 to 5.

［式中、ｎは１〜５の整数を表す。］

[Wherein n represents an integer of 1 to 5. ]

  In the case where the polymerizable reactive group B has a vinyl group, the polymerizable compound X that satisfies the above-described conditions is an ethynyl group in the structure represented by the above formula (1). In other words, a structure having a structure represented by the following formula (5) is used.

［式中、ｎは１〜５の整数を表す。］

[Wherein n represents an integer of 1 to 5. ]

  By selecting a compound having such a structure as the polymerizable compound X, a film (insulating film) formed using the film-forming composition exhibits the above-described effects more remarkably.

  In addition, in the polymerizable compound X having the structure represented by the above formula (1), those having two polymerizable reactive groups B are exemplified, but other polymerizable compounds having one polymerizable reactive group B are exemplified. Examples of X include those having a structure represented by the following formula (1 ′). In the following formula (1 ′), n represents an integer of 1 or 2.

  When a compound in which the polymerizable reactive group B is a vinyl group is used as the polymerizable compound X, a compound having a structure in which the ethynyl group in the above formula (1 ′) is replaced with a vinyl group can also be used.

  The polymerizable compound X may have a partial structure other than the partial structure A and the polymerizable reactive group B.

  The polymerizable compound X as described above has two polymerizable reactive groups B, and when the polymerizable reactive group B has two ethynyl groups, for example, it can be synthesized as follows. it can.

  That is, a compound A ′ corresponding to partial structure A (a compound in which two hydrogen atoms are bonded to A as a divalent group) is reacted with bromine, and a dibromo form of A ′ (two bromo groups are bonded to partial structure A) A compound obtained by reacting a dibromo form of A ′ with dibromobenzene to obtain a bis (dibromophenyl) form of A ′ (a compound in which two dibromophenyl groups are bonded to partial structure A), and A Reacting a dibromophenyl form of 'with trimethylsilylacetylene to obtain a bis (di (trimethylsilylethynyl) phenyl) form of A' (a compound in which two di (trimethylsilylethynyl) phenyl groups are bonded to partial structure A); And a step of hydrolyzing (detrimethylsilylating) the bis (di (trimethylsilylethynyl) phenyl) form of It can be obtained that the polymerizable compound X.

  In the case where the polymerizable reactive group B has two vinyl groups instead of two ethynyl groups, the polymerizable compound X can be synthesized, for example, as follows.

  That is, after synthesizing the polymerizable compound X having the two ethynyl groups described above, although not particularly limited, Lindlar reduction using hydrogen gas, Brich reduction using sodium and liquid ammonia, diimide reduction using diimide, etc. By carrying out, the target polymeric compound X can be obtained.

  The film-forming composition may contain the polymerizable compound X alone as described above. For example, the polymerizable compound X has two polymerizable reactive groups B and / or polymerizes. When the polymerizable reactive group B has two ethynyl groups, a polymer in which the polymerizable compound X is partially polymerized (a prepolymer in which only one polymerizable reactive group B of the two polymerizable reactive groups B is polymerized or reacted) And a prepolymer obtained by polymerization reaction of only one ethynyl group of the two ethynyl groups of the polymerizable reactive group B. When the film-forming composition contains a polymer (prepolymer) in which the polymerizable compound X is partially polymerized, the viscosity of the film-forming composition is more surely suitable, and each part of the film to be formed In addition, it is possible to more effectively suppress unintentional variations in thickness and characteristics of the film, and it is possible to make the strength of the finally formed film particularly excellent. Moreover, even if the film | membrane which should be formed is a comparatively thick thing, it can form suitably. In addition, when the film-forming composition contains a prepolymer of the polymerizable compound X, when a film is formed on a member (for example, a semiconductor substrate), the amount of heat applied on the member can be reduced. Damage to the member due to heating can be prevented more reliably. Such a film-forming composition containing a prepolymer of the polymerizable compound X can be suitably used as an insulating film varnish.

  The step of partially polymerizing the polymerizable compound X to form a prepolymer includes, for example, a method by thermal polymerization in which a reaction is performed without using a catalyst, benzoyl peroxide, t-butyl peroxide, azobisisobutyronitrile. A method by radical polymerization using a radical initiator such as, a method by photo radical polymerization using light irradiation or the like, dichlorobis (triphenylphosphine) palladium (II), bis (benzonitrile) palladium (II) dichloride and tetrakis (tri A method using polymerization using a palladium catalyst such as phenylphosphine) palladium (0), a method using polymerization using a transition metal catalyst such as copper (II) acetate, molybdenum chloride (V), tungsten chloride (VI) and tantalum chloride ( V) and other methods using polymerization with transition metal chlorides Can. Among these, since a desired polymer can be easily obtained by controlling the reaction, and impurities need not be removed by remaining a metal catalyst or the like, a method by thermal polymerization or radical polymerization using a radical initiator is desirable.

  When preparing by the thermal polymerization method, the heat treatment conditions are preferably heating temperature: 120 to 190 ° C., heating time: 3 to 11 hours, heating temperature: 140 to 180 ° C., heating time: 3 to 3 hours. More preferably, it is 9 hours. When a radical initiator is used, the heat treatment conditions are preferably heating temperature: 40 to 190 ° C., heating time: 0.5 to 11 hours, heating temperature: 60 to 180 ° C., heating time: 0. More preferably, 5 to 9 hours. Moreover, you may perform the heat processing with respect to the composition (composition containing a polymeric compound) obtained at the said process combining different conditions. For example, in the thermal polymerization, for the composition (composition containing a polymerizable compound) obtained in the above step, the first is performed under the conditions of heating temperature: 150 to 190 ° C. and heating time: 1 to 6 hours. It is also possible to appropriately select the heat treatment and the second heat treatment performed under the conditions of heating temperature: 120 to 160 ° C. and heating time: 2 to 9 hours, or further multi-stage heat treatment. Even in the case of using a radical initiator, for example, a first heat treatment performed under the conditions of heating temperature: 60 to 190 ° C., heating time: 0.5 to 6 hours, heating temperature: 40 to 160 ° C., heating time: A second heat treatment performed under a condition of 0.5 to 9 hours or a multistage heat treatment can be appropriately selected. In addition, it is preferable to perform the above heat processing in the state which melt | dissolved the composition (composition containing a polymeric compound) obtained at the said process in the solvent. In addition, the synthesis of the prepolymer by the heat treatment as described above may be performed in a solvent as a component of the film-forming composition to be prepared, and what is a component of the film-forming composition? You may perform in the solvent of a different composition. That is, after a polymerizable compound is polymerized using a predetermined solvent to obtain a prepolymer, the solvent may be replaced with a solvent as a component of the target film-forming composition. Examples of the solvent (reaction solvent) that can be used for the synthesis of a polymer (prepolymer) in which a polymerizable compound is partially polymerized include alcohol solvents such as methanol, ethanol, isopropanol, 1-butanol, and 2-butanol. ; Ketone solvents such as acetone, acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pentanone, 2-heptanone; esters such as ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate Solvents such as diisopropyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran, anisole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,4-dimethoxybenzene, etc. Solvents; aromatic and aliphatic hydrocarbon solvents such as benzene, toluene, mesitylene, ethylbenzene, diethylbenzene, propylbenzene, heptane, hexane, n-octane; chloromethane, dichloroethane, chloroform, dichloroethane, carbon tetrachloride, etc. Halide-based solvents; amide-based solvents such as N-methylpyrrolidone and the like can be mentioned, and one or more selected from these can be used in combination.

  In addition, when the film-forming composition contains a prepolymer of the polymerizable compound X, the unreacted polymerizable compound X is removed by purification (the unreacted polymerizable compound X is not included as much as possible). Is preferred. Thereby, various characteristics, such as the intensity | strength of the film | membrane formed using the film forming composition, can be made more reliably excellent.

  The content of the polymerizable compound X in the film-forming composition and a polymer in which the polymerizable compound X is partially polymerized (for example, only one polymerizable reactive group B out of two polymerizable reactive groups B undergoes a polymerization reaction). The sum of the prepolymer and the content of the prepolymer obtained by polymerization reaction of only one ethynyl group of the two ethynyl groups of the polymerizable reactive group B is preferably 1.0 to 30 wt%.

  In the above description, a case where a polymerizable compound having a polymerizable reactive group having an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring (polymerizable compound X) is representatively described. However, in the present invention, the polymerizable compound only needs to have a partial structure including an adamantane cage structure and a polymerizable reactive group that contributes to the polymerization reaction. Other than the polymerizable compound X as described above It may be. For example, in the present invention, the polymerizable compound may not have an aromatic ring. Further, in the present invention, the polymerizable compound has a polymerizable reactive group as a functional group other than an ethynyl group and a vinyl group (for example, a group in which a hydrogen atom of an ethynyl group is substituted with another atom or an atomic group, a vinyl group, In which at least one of the hydrogen atoms constituting is substituted with another atom or atomic group).

  In addition, when the ethynyl group has a substituent, the trimethylsilylacetylene is substituted with an alkyl group-substituted acetylene such as propyne, butyne, pentine, or the like, or an aryl group such as phenylacetylene acetylene, naphthylacetylene, fluorenylacetylene, or the like. A polymerizable compound having a corresponding substituted ethynyl group can be obtained by performing the above steps other than detrimethylsilylation by replacing with substituted acetylene, and further with a cycloalkyl group-substituted acetylene such as cyclohexylacetylene, adamantylacetylene and the like.

  Further, when the polymerizable compound has a substituted vinyl group, the corresponding substituted vinyl group can be synthesized by performing the same reduction reaction on the substituted ethynyl group.

[2] Solvent The film-forming composition is in the form of a liquid and may contain any polymerizable compound and / or a polymer obtained by partially polymerizing the polymerizable compound, but usually dissolves them. It contains a solvent.

  Specific examples of the solvent include cyclohexanone, tetrahydrofuran, anisole and the like, and one or more selected from these can be used in combination. Of these, cyclopentanone and cyclohexanone are preferable as the solvent. Examples of the solvent constituting the film forming composition include a solvent (reaction solvent) used for the synthesis of a polymerizable compound and the above-described polymer (a prepolymer obtained by partially polymerizing a polymerizable compound). It may be a thing.

  Although the content rate of the solvent in the composition for film formation is not specifically limited, It is preferable that it is 70 to 99 wt%.

[3] Other components The film-forming composition may contain components other than those described above. Examples of such components include surfactants; coupling agents such as silane coupling agents; catalysts such as radical initiators and disulfides.

  In particular, the film-forming composition preferably contains a silane coupling agent. Thereby, the adhesiveness with respect to the member (member which should form a film | membrane) of the film | membrane formed using the film forming composition can be improved, and the reliability of the semiconductor device can be further improved. Productivity can also be particularly excellent. Further, conventionally, when the film-forming composition contains a silane coupling agent, particles are particularly easily generated during transportation or storage, and the film formed using the film-forming composition Although the problem that reliability is particularly low was likely to occur, in the present invention, even when the film-forming composition contains a silane coupling agent, the occurrence of the above-mentioned problem is surely prevented. can do. That is, the effect of the present invention is more remarkably exhibited when the film-forming composition contains a silane coupling agent.

  The film-forming composition may contain a naphthoquinone diazide compound as a photosensitizer. Thereby, the composition for film formation can be used suitably for formation of the surface protection film which has photosensitivity.

  In the present invention, it is preferable that the film-forming composition does not contain a pore-forming material that foams due to thermal decomposability and forms pores in the formed film. Conventionally, a pore forming material has been used for the purpose of reducing the dielectric constant of the film. However, when such a pore forming material is used, the strength of the formed film is reduced, There have been problems such as undesired thickness variations at the sites and variations in properties. However, the polymerizable compound as described above further has two polymerizable reactive groups B, and / or Alternatively, when the polymerizable reactive group B has two ethynyl groups, a polymer in which the polymerizable compound is partially polymerized (a prepolymer in which only one polymerizable reactive group B out of the two polymerizable reactive groups B undergoes a polymerization reaction). The dielectric constant of the film formed without using a pore-forming material because it contains a polymer and a prepolymer in which only one ethynyl group of the two reactive ethynyl groups of the polymerizable reactive group B undergoes a polymerization reaction) Can be low enoughAnd generation | occurrence | production of the above problems can be prevented reliably by not containing a void | hole formation material.

(container)
Next, the container which comprises the container containing the composition for film formation of this invention is demonstrated.

  The container constituting the film-forming composition-containing container of the present invention contains the film-forming composition as described above.

As described above, in the present invention, the storage amount of the storage portion that stores the film-forming composition in the container, that is, the volume of the film-forming composition amount stored in the container is V [cm ³ ], and the inner surface area of the storage portion. When S (cm ² ) is defined as (area that can be contacted by the film-forming composition), the relationship of S / V ≦ 0.85 may be satisfied. It is preferable to satisfy the relationship, and it is more preferable to satisfy the relationship of 0.30 ≦ S / V ≦ 0.75. As a result, the above-described effects can be exhibited more remarkably, and the occurrence of problems such as an increase in the size of the container and difficulty in transportation can be effectively prevented, and transportation and storage are suitably performed. Can do.

Storage amount V of the receiving portion of the container is not particularly limited, but is preferably 80～200000Cm ^3, more preferably from 400～18000Cm ^3, even more preferably 800~18000cm ^3. Thereby, the effects as described above are more remarkably exhibited.

The inner surface area S of the housing portion of the container is not particularly limited, but is preferably 120～20000Cm ^2, more preferably from 300～4500Cm ^2, even more preferably 500~4500cm ^2. Thereby, the effects as described above are more remarkably exhibited.

  The inner surface of the storage part preferably exhibits liquid repellency with respect to the liquid film-forming composition. As a result, the generation of particles during transportation or storage can be more effectively prevented, and the quality of the film (insulating film) formed using the film-forming composition is particularly excellent. It can be.

  The inner surface of the storage portion is preferably made of a material having a contact angle with water at 20 ° C. of 65 ° or more, and more preferably made of a material of 70 ° or more. Thereby, the above effects are more remarkably exhibited. In the above, water is used for the measurement of the contact angle. The solvent constituting the film-forming composition is preferably the one described in the section of [2] Solvent. This is because the film-forming composition according to the present invention containing a solvent, a polymerizable compound and the like shows a high correlation with water in the measurement of the contact angle.

  Examples of the constituent material of the inner surface of the storage unit include fluororesin, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, and the like, among which fluororesin and polyethylene are more preferable. As a result, the generation of particles during transportation or storage can be more effectively prevented, and the quality of the film (insulating film) formed using the film-forming composition is particularly excellent. It can be.

  The film-forming composition in the container containing the film-forming composition may be used as it is for film formation, but prior to being applied on a member (for example, a semiconductor substrate) on which a film is to be formed, It may be subjected to a heat treatment. Thereby, the film-forming composition can include a polymer (prepolymer) in which the polymerizable compound is partially polymerized, and the viscosity of the film-forming composition is more surely suitable and formed. In addition, it is possible to more effectively suppress unintentional variations in the thickness and characteristics of each part of the film to be formed, and to make the finally formed film particularly excellent in strength. In addition, the film forming composition is subjected to heat treatment prior to applying the film forming composition onto the member (for example, a semiconductor substrate) on which the film is to be formed, so that the film to be formed is relatively thick. Even if it is a thing, it can form suitably. In addition, by applying a heat treatment to the film-forming composition prior to applying the film-forming composition onto a member (for example, a semiconductor substrate) on which a film is to be formed, the amount of heat applied on the member is reduced. Therefore, damage to the member due to heating can be prevented more reliably. When such heat treatment is performed, the heat treatment conditions are preferably heating temperature: 40 to 190 ° C., heating time: 0.5 to 11 hours, heating temperature: 60 to 180 ° C., heating time: 0. More preferably, it is 5 to 9 hours. Moreover, you may perform the above heat processing combining a different condition. For example, the first heat treatment performed under the conditions of heating temperature: 80 to 190 ° C., heating time: 0.5 to 6 hours, and heating temperature: 60 to 160 ° C., heating time: 0.5 to 9 hours A second heat treatment may be performed.

<Insulating film>
By applying the film-forming composition in the film-forming composition-containing container onto a member such as a semiconductor substrate, and applying a treatment (firing treatment) such as heating or irradiation with active energy rays to the film ( Insulating film) is formed.

  By performing the baking treatment as described above, the polymerizable compound or the unreacted polymerizable reactive group of the prepolymer in which the polymerizable compound is partially polymerized undergoes a polymerization reaction, and is composed of a polymer (cured product). An insulating film is obtained. As described above, in the container containing the film-forming composition of the present invention, since the generation of particles in the container is effectively prevented, the formed insulating film is highly reliable. Moreover, the insulating film comprised with the polymer (hardened | cured material) which has the above chemical structures is excellent in intensity | strength, heat resistance, etc. Further, the insulating film obtained as described above has a low dielectric constant. Further, the insulating film obtained as described above is one in which unintentional variations in film thickness and characteristics at each part are suppressed. For this reason, the insulating film as described above can be suitably used as an insulating film constituting a semiconductor device.

  Examples of the method for applying the film-forming composition onto the member include a spin coating method using a spinner, a spray coating method using a spray coater, dipping, printing, and roll coating.

  Prior to the firing treatment, for example, a treatment (desolvation treatment) for removing the solvent from the film-forming composition applied on the member may be performed. Such solvent removal treatment can be performed, for example, by heat treatment, reduced pressure treatment, or the like.

  The baking treatment is preferably performed under conditions of, for example, a processing temperature: 200 to 450 ° C. and a processing time of 1 to 60 minutes, and a processing temperature of 250 to 400 ° C. and a processing time of 1 to 30 minutes. More preferred. In the baking step, heat treatments with different conditions may be combined.

  Further, when such an insulating film is applied to, for example, an interlayer insulating film that insulates wiring layers formed on a semiconductor substrate, vias (conductor posts) that electrically connect the wiring layers included in the semiconductor substrate are provided between the layers. It is formed so as to penetrate in the thickness direction of the insulating film. Therefore, the interlayer insulating film needs to have a predetermined shape patterned corresponding to the shape of the via (conductor post).

  The interlayer insulating film having a predetermined shape as described above can be formed as follows, for example.

  FIG. 1 is a longitudinal sectional view showing an example of a method for forming an interlayer insulating film patterned in a predetermined shape. In the following description, the upper side in FIG. 1 is referred to as “upper” and the lower side is referred to as “lower”.

  First, a semiconductor substrate 1 on which a general SiCN film 2 is formed as a barrier film or an etch stop film is prepared, and an interlayer insulating film 3, a hard mask layer 4 and a photoresist layer 8 are arranged on the SiCN film 2 in this order. (See FIG. 1A).

  In addition, the interlayer insulation film 3 is formed by the method mentioned above using the film forming composition in the container containing the film forming composition of the present invention.

  Next, by exposing and developing the photoresist layer 8 using a photomask, a photoresist layer 8 patterned into a shape having an opening at a position where a via (conductor post) or a wiring groove is formed is obtained (FIG. 1 (b).)

Next, the hard mask layer 4 is formed using the photoresist layer 8 as a mask by a reactive ion etching method using a gas generally used for patterning a hard mask material such as a fluorine-based gas such as CF ₄ as a processing gas. By etching, a hard mask layer 4 having a predetermined shape is formed (see FIG. 1C).

  Next, an interlayer insulating film using the hard mask layer 4 as a mask by a reactive ion etching method using a mixed gas of nitrogen and hydrogen generally used for etching of an organic film or the like as a processing gas, or ammonia gas, etc. 3 is etched to form an interlayer insulating film 3 having a predetermined shape (see FIG. 1D).

  As described above, the interlayer insulating film 3 having a predetermined shape is obtained. In the present invention, the interlayer insulating film 3 is formed using the film forming composition in the container containing the film forming composition as described above. Occurrence of a problem of deterioration in reliability due to existence is reliably prevented. Further, in the present embodiment, since the interlayer insulating film 3 is formed using the film forming composition as described above, the interlayer insulating film 3 is more appropriately suppressed or prevented from increasing in dielectric constant. And the properties of the membrane can be reliably maintained.

  Furthermore, the insulating film is preferably in contact with a member (for example, a semiconductor substrate, an intermediate film, etc.) made of SiOC, SiCN, or SiO. Thereby, the adhesiveness etc. of the insulating film with respect to the member can be made particularly excellent.

  The thickness of the insulating film is not particularly limited, but when the insulating film is used as an interlayer insulating film for a semiconductor, it is preferably 0.01 to 20 μm, more preferably 0.02 to 10 μm, More preferably, it is 0.03-0.7 micrometer.

  In the case where the insulating film is used as a protective film for a semiconductor, the thickness of the insulating film is preferably 0.01 to 70 μm, and more preferably 0.05 to 50 μm.

<Semiconductor device>
Next, a semiconductor device will be described based on a preferred embodiment.
FIG. 2 is a longitudinal sectional view schematically showing an example of the semiconductor device.

  As shown in FIG. 2, a semiconductor device 100 includes a semiconductor substrate 1 on which elements are formed, a SiCN film 2 that is a general barrier film or etch stop film provided on the upper side (upper side in FIG. 2) of the semiconductor substrate 1, and And a copper wiring layer 7 covered with an interlayer insulating film 3 and a barrier metal 6 provided on the SiCN film 2. The semiconductor device 100 according to the present embodiment includes an interlayer insulating film 3 as a film (insulating film) formed using the film forming composition in the above-described container for forming a film forming composition.

A recess corresponding to the pattern to be wired is formed in the interlayer insulating film 3, and a copper wiring layer 7 is provided in the recess.
In addition, a modified treatment layer 5 is provided between the interlayer insulating film 3 and the copper wiring layer 7.

  A hard mask layer 4 is formed on the upper side of the interlayer insulating film 3 (on the side surface opposite to the SiCN film 2).

The semiconductor device 100 as described above can be manufactured, for example, as follows.
First, by using the method described in the above insulating film, insulation having a predetermined shape in which a penetrating via or wiring groove is formed at a predetermined position of the insulating film constituted by the interlayer insulating film 3 and the hard mask layer 4. A film is formed.

  Next, a modified treatment layer 5 is formed on the inner surface of the wiring groove by plasma treatment or the like, and further a barrier composed of Ta, Ti, TaN, TiN, WN or the like by a method such as PVD method or CVD method. Metal 6 is formed.

  Further, a copper wiring layer 7 to be a wiring layer is formed by electrolytic plating or the like, and then the copper wiring layer and the barrier metal other than the wiring portion are polished and removed and planarized by CMP to obtain the semiconductor device 100. be able to.

  The interlayer insulating film 3 can be formed by the method described in the above description of the insulating film, but a resin film dry film is prepared in advance, and this is formed on the SiCN film 2 of the semiconductor substrate 1. It can also be formed so as to be laminated on top. More specifically, a resin film is formed on a member in advance using a film-forming composition and dried to obtain a dry film. The dry film is peeled off from the member, and the semiconductor substrate is separated from the semiconductor substrate. The interlayer insulating film 3 may be formed by stacking on the SiCN film 2 and irradiating with heat and / or radiation.

  Since the semiconductor device as described above includes the interlayer insulating film as described above (the insulating film formed by using the film forming composition in the container for forming a film of the present invention), adverse effects due to particles Is reliably prevented and the reliability is high. Moreover, in this embodiment, since the film forming composition as described above is used, the dimensional accuracy is excellent and the insulation can be sufficiently exerted, so that the connection reliability is particularly excellent.

  In addition, since the interlayer insulating film as described above has excellent adhesion to the wiring layer, the connection reliability of the semiconductor device can be further improved.

  In addition, since the interlayer insulating film as described above has an excellent elastic modulus, it can be suitably adapted to a process (for example, a baking process) for forming a wiring of a semiconductor device.

  In addition, as described above, the interlayer insulating film can suppress or prevent etching damage during wiring processing, and thus can suppress or prevent changes in the characteristics of the insulating film during semiconductor device fabrication.

  In addition, since the interlayer insulating film as described above has excellent dielectric characteristics, signal loss of the semiconductor device can be reduced.

  In addition, since the interlayer insulating film as described above has excellent dielectric characteristics, wiring delay can be reduced.

  As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to the above.

  For example, in the above description, an example in which the interlayer insulating film 3 as an insulating film formed using the film forming composition in the container for forming a film of the present invention is formed on the SiCN film 2 is representative. However, the position where the insulating film is formed is not limited to this.

  In the above-described embodiments, the insulating film formed using the film-forming composition in the film-forming composition-containing container of the present invention is representatively described as having an interlayer insulating film. This container for forming a film may be used in addition to the formation of an interlayer insulating film.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.
[1] Synthesis of polymerizable compound

(Synthesis Example 1)
First, 1,3-dimethyladamantane was prepared, and carbon tetrachloride: 700 mL and bromine: 35 g (0.22 mol) were placed in a 4-neck 2000 mL flask equipped with a thermometer, a stirrer, and a reflux tube, and stirred. However, the prepared 1,3-dimethyladamantane: 32.9 g (0.2 mol) was added little by little. During the addition, the internal temperature was kept at 20-30 ° C.

After the addition was completed, the reaction was continued for another hour after the temperature did not rise.
Then, it poured into about 2000 mL of cold water, and the crude product was separated by filtration, washed with pure water, and dried.

The crude product was recrystallized from hot ethanol. The obtained recrystallized product was dried under reduced pressure to obtain 37.4 g of a product. IR analysis shows bromo group absorption at 690-515 cm ⁻¹ , and mass analysis molecular weight of 322 indicates that the product is 3,5-dimethyl-1,7-dibromoadamantane. It was.

  Next, 3,5-dimethyl-1,7-dibromoadamantane: 33.2 g (103.2 mmol) and 1,3-dibromobenzene: 1217 g (5161.6 mmol) obtained above were stirred in the flask, At 25 ° C. under dry nitrogen, 24.8 g (93.0 mmol) of aluminum (III) bromide was added in small portions. This was heated to 60 ° C. and stirred for 8 hours, and then returned to room temperature to obtain a reaction solution. The reaction solution was added to 700 ml of 5% aqueous hydrochloric acid solution and stirred. The aqueous layer was removed, and the organic layer was put into 2000 ml of acetone. The precipitate was filtered and washed with acetone: 1000 ml three times to obtain 57 g of 3,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane. From the result of the molecular weight by mass spectrometry being 632, it was shown that the product was 3,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane.

  Next, 3,5,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane obtained above: 39.8 g (62.9 mmol), dichlorobistriphenylphosphine palladium: 3.53 g (5 0.0 mmol), triphenylphosphine: 6.60 g (25.2 mmol), copper (II) iodide: 4.79 g (25.2 mmol), and triethylamine: 750 ml were added to the flask and stirred. After raising the temperature to 75 ° C., 37.1 g (377.7 mmol) of trimethylsilylacetylene was slowly added. This was stirred at 75 ° C. for 7 hours and then heated to 120 ° C. to distill off triethylamine. Then, it returned to room temperature and added dichloromethane: 1000ml to the reaction liquid, and stirred for 20 minutes. The precipitate was removed by filtration, and 5% aqueous hydrochloric acid solution (1000 ml) was added to the filtrate for liquid separation. The organic layer was washed three times with 1000 ml of water, and then the solvent of the organic layer was removed under reduced pressure. The obtained compound was dissolved in 1500 ml of hexane. Insoluble matter was removed by filtration, and hexane in the filtrate was removed under reduced pressure. Acetone: 1000 ml was added thereto, and the precipitate was washed with acetone three times to obtain 3,5-dimethyl-1,7-bis (3,5-ditrimethylsilylethynylphenyl) adamantane: 36.1 g. . From the result of the molecular weight of 701 by mass spectrometry, it was shown that the product was 3,5-dimethyl-1,7-bis (3,5-ditrimethylsilylethynylphenyl) adamantane.

  Furthermore, 3,5-dimethyl-1,7-bis (3,5-ditrimethylsilylethynylphenyl) adamantane obtained above: 32.3 g (46.1 mmol) and potassium carbonate: 1.46 g (10.6 mmol) Were stirred in a mixed solvent of tetrahydrofuran: 600 ml and methanol: 300 ml under a nitrogen atmosphere at room temperature for 4 hours. This was poured into 10% aqueous hydrochloric acid solution: 1000 ml, the precipitate was filtered, and the resulting precipitate was washed with water: 1000 ml, further washed with acetone: 1000 ml, and then dried to obtain polymerizable compound X. 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane: 15.0 g was obtained.

  The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane.

Appearance: White solid MS (FD) (m / z): 413 (M +)
Elemental analysis: Theoretical value (/%) C; 93.16, H; 6.84, Measured value (/%) C; 93.11, H; 6.82

  By repeating the above reaction, 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane as the polymerizable compound X was obtained in a necessary amount in the examples.

(Synthesis Examples 2 to 5)
A polymerizable compound X was obtained in the same manner as in Synthesis Example 1 except that tetramethylbiadamantane, hexamethyltriadamantane, octamethyltetraadamantane, and decamethylpentaadamantane were prepared instead of dimethyladamantane.

  The structural formula of the polymerizable compound X obtained in Synthesis Examples 1 to 5 is shown in the following formula (1). In the following formula (1), n represents an integer of 1 to 5, and the number of n corresponds to the number of each synthesis example.

  In addition, the external appearance of n = 2 polymerizable compound X (Synthesis example 2) in the said Formula (1), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 574 (M +)
Elemental analysis: Theoretical value (/%) C; 91.93, H; 8.07, Actual value (/%) C; 91.87, H; 8.00

  Moreover, the external appearance of the said compound (1) n = 3 polymeric compound X (synthesis example 3), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 737 (M +)
Elemental analysis: Theoretical value (/%) C; 91.25, H; 8.75, Actual value (/%) C; 91.21, H; 8.77

  The external appearance of the said compound (1) n = 4 polymeric compound X (synthesis example 4), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 899 (M +)
Elemental analysis: Theoretical value (/%) C; 90.81, H; 9.19, Measured value (/%) C; 90.75, H; 9.16

  The external appearance of the said compound (1) n = 5 polymeric compound X (Synthesis example 5), the result of mass spectrometry, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 1062 (M +)
Elemental analysis: theoretical value (/%) C; 90.51, H; 9.49, actual measurement value (/%) C; 90.49, H; 9.47

(Synthesis Example 6)
First, 4,9-dibromodiamantane was synthesized according to the synthesis method described in Journal of Organic Chemistry., 39, 2987-3003 (1974). Absorption of bromo group was observed at 690 to 515 cm ⁻¹ by IR analysis, and the result of molecular weight 346 by mass spectrometry indicated that the product was 4,9-dibromodiamantane.

  Next, in the synthesis of 3,5-dimethyl-1,7-bis (3,5-dibromophenyl) adamantane as a synthesis intermediate in Synthesis Example 1, in the synthesis of 3,5-dimethyl-1,7-dibromoadamantane, Instead, 4,9-bis (3,5-dibromophenyl) was reacted in the same manner as in Synthesis Example 1 except that 3,5.7 g (103.1 mmol) of 4,9-dibromodiamantane was used. ) Diamantane: 56 g was obtained. From the result of the molecular weight of 656 by mass spectrometry, it was shown that the product was 4,9-bis (3,5-dibromophenyl) diamantane.

  Next, in the synthesis of 3,5-dimethyl-1,7-bis (3,5-ditrimethylsilylethynylphenyl) adamantane as a synthesis intermediate in Synthesis Example 1, 3,5, -dimethyl-1,7- Synthesis Example 1 except that 41.2 g (62.8 mmol) of 4,9-bis (3,5-dibromophenyl) diamantane obtained above was used instead of bis (3,5-dibromophenyl) adamantane By reacting in the same manner as above, 3,5.5 g of 4,9-bis (3,5-ditrimethylsilylethynylphenyl) diamantane was obtained. From the result of the molecular weight measured by mass spectrometry of 725, it was shown that the product was 4,9-bis (3,5-ditrimethylsilylethynylphenyl) diamantane.

  Further, in the synthesis of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane as the final product in Synthesis Example 1, 3,5-dimethyl-1,7-bis (3, Synthetic Example 1 except that instead of 5-ditrimethylsilylethynylphenyl) adamantane, 38.8 g (53.5 mmol) of 4,9-bis (3,5-ditrimethylsilylethynylphenyl) diamantane obtained above was used. By reacting in the same manner, 14.3 g of 4,9-bis (3,5-diethynylphenyl) diamantane as the polymerizable compound X was obtained.

  The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 4,9-bis (3,5-diethynylphenyl) diamantane.

Appearance: White solid MS (FD) (m / z): 436 (M +)
Elemental analysis: Theoretical value (/%) C; 93.54, H; 6.46, Actual value (/%) C; 93.46, H; 6.38

  By repeating the above reaction, 4,9-bis (3,5-diethynylphenyl) diamantane as the polymerizable compound X was obtained in a necessary amount in the examples.

(Synthesis Examples 7-9)
A polymerizable compound X was obtained in the same manner as in Synthesis Example 6 except that dibromodi (diamantane), dibromotri (diamantane), and dibromotetra (diamantane) were prepared instead of dibromodiamantane.

  The structural formula of the polymerizable compound X obtained in Synthesis Examples 6 to 9 is shown in the following formula (4). In following formula (4), n represents the integer of 1-4 and the number of n respond | corresponds to (number-5 of each synthesis example).

  In addition, the external appearance of the said Formula (4) n = 2 polymerizable compound X (Synthesis example 7), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 622 (M +)
Elemental analysis: Theoretical value (/%) C; 92.56, H; 7.44, Measured value (/%) C; 92.53, H; 7.41

  Moreover, the external appearance of the said compound (4) n = 3 polymeric compound X (synthesis example 8), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 809 (M +)
Elemental analysis: Theoretical value (/%) C; 92.03, H; 7.97, Actual value (/%) C; 92.01, H; 7.94

  The external appearance of the said compound (4) n = 4 polymeric compound X (Synthesis example 9), the result of mass spectrometry, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 995 (M +)
Elemental analysis: theoretical value (/%) C; 91.70, H; 8.30, actual value (/%) C; 91.67, H; 8.28

(Synthesis Example 10)
First, in a 4-neck 2000 mL flask equipped with a thermometer, a stirrer and a reflux tube, 3,5-dimethyl-1-bromoadamantane: 45.5 g (187.1 mmol) and 1,3-dibromobenzene: 1217 g ( 5161.6 mmol) and stirred, and at 25 ° C. under dry nitrogen, aluminum bromide (III): 24.8 g (93.0 mmol) was added in small portions. This was heated to 60 ° C. and stirred for 8 hours, and then returned to room temperature to obtain a reaction solution.

  Next, the reaction solution was added to 700 mL of 5% hydrochloric acid aqueous solution and stirred. The aqueous layer was removed, and the organic layer was poured into 2000 mL of acetone. The precipitate was filtered and washed 3 times with acetone: 1000 mL to obtain 3,5,5-dimethyl-1- (3,5-dibromophenyl) adamantane: 51.4 g. From the result of the molecular weight of 398 by mass spectrometry, it was shown that the product was 3,5, -dimethyl-1- (3,5-dibromophenyl) adamantane.

  Next, 3,5, -dimethyl-1- (3,5-dibromophenyl) adamantane obtained above: 47.1 g (118.4 mmol), dichlorobistriphenylphosphine palladium: 6.66 g (9.5 mmol) , Triphenylphosphine: 179.5 g (47.3 mmol), copper (II) iodide: 248.7 g (47.3 mmol), and triethylamine: 750 mL were added to the flask and stirred. After raising the temperature to 75 ° C., 34.9 g (355.2 mmol) of trimethylsilylacetylene was slowly added. This was stirred at 75 ° C. for 7 hours and then heated to 120 ° C. to distill off triethylamine. Then, it returned to room temperature and added dichloromethane: 1000mL to the reaction liquid, and stirred for 20 minutes. The precipitate was removed by filtration, and 5% hydrochloric acid aqueous solution: 1000 mL was added to the filtrate for liquid separation. The organic layer was washed 3 times with 1000 mL of water, and then the solvent of the organic layer was removed under reduced pressure. The obtained compound was dissolved in hexane: 1500 mL. Impurities were removed by filtration, and hexane in the filtrate was removed under reduced pressure. Acetone: 1000 mL was added thereto, and the precipitate was washed with acetone three times to obtain 37 g of 3,5-dimethyl-1- (3,5-ditrimethylsilylethynylphenyl) adamantane. The result of the molecular weight measured by mass spectrometry was 432, indicating that the product was 3,5-dimethyl-1- (3,5-ditrimethylsilylethynylphenyl) adamantane.

  Further, the 3,5-dimethyl-1- (3,5-ditrimethylsilylethynylphenyl) adamantane obtained above (36 g, 83.1 mmol) and potassium carbonate: 2.7 g (19.3 mmol) were mixed with tetrahydrofuran: 600 mL. In a mixed solvent of methanol: 300 mL, the mixture was stirred at room temperature for 4 hours under a nitrogen atmosphere. This was poured into 10% aqueous hydrochloric acid solution: 1000 mL, the precipitate was filtered, and the resulting precipitate was washed with water: 1000 mL, further washed with acetone: 1000 mL, and then dried to obtain 3 as a polymerizable compound. , 5-Dimethyl-1- (3,5-diethynylphenyl) adamantane: 19 g was obtained.

  The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 3,5-dimethyl-1- (3,5-diethynylphenyl) adamantane.

Appearance: White solid MS (FD) (m / z): 288 (M +)
Elemental analysis: Theoretical value (/%) C; 91.61, H; 8.39, Actual value (/%) C; 91.59, H; 8.37

  By repeating the above reaction, 3,5-dimethyl-1- (3,5-diethynylphenyl) adamantane as the polymerizable compound X was obtained in a necessary amount in the examples.

(Synthesis Example 11)
A polymerizable compound X was obtained in the same manner as in Synthesis Example 10 except that tetramethylbromobiadamantane was prepared instead of dimethylbromoadamantane.

  The structural formula of the polymerizable compound X obtained in Synthesis Examples 10 and 11 is shown in the following formula (1 ′). In the following formula (1 '), n represents an integer of 1 to 2, and the number of n corresponds to (Number-9 in each synthesis example).

  The appearance, mass analysis, and elemental analysis results of the polymerizable compound X (Synthesis Example 11) having the formula (1 ′) n = 2 are shown.

Appearance: White solid MS (FD) (m / z): 450 (M +)
Elemental analysis: theoretical value (/%) C; 90.61, H; 9.39, actual value (/%) C; 90.59, H; 9.36

(Synthesis Example 12)
First, 4-bromodiamantane: 50 g (187.1 mmol) and 1,3-dibromobenzene: 1217 g (5161.6 mmol) were placed in a 4-neck 2000 mL flask equipped with a thermometer, a stirrer and a reflux tube. Then, 24.8 g (93.0 mmol) of aluminum bromide (III) was added little by little at 25 ° C. under dry nitrogen. This was heated to 60 ° C. and stirred for 8 hours, and then returned to room temperature to obtain a reaction solution.

  Next, the reaction solution was added to 700 mL of 5% hydrochloric acid aqueous solution and stirred. The aqueous layer was removed, and the organic layer was poured into 2000 mL of acetone. The precipitate was filtered and washed 3 times with acetone: 1000 mL to obtain 56 g of 4- (3,5-dibromophenyl) diamantane. The result of the molecular weight of 422 by mass spectrometry showed that the product was 4- (3,5-dibromophenyl) diamantane.

  Next, 4- (3,5-dibromophenyl) diamantane obtained above: 50 g (118.4 mmol), dichlorobistriphenylphosphine palladium: 6.66 g (9.5 mmol), triphenylphosphine: 179.5 g ( 47.3 mmol), copper (II) iodide: 248.7 g (47.3 mmol), and triethylamine: 750 mL were added to the flask and stirred. After raising the temperature to 75 ° C., 34.9 g (355.2 mmol) of trimethylsilylacetylene was slowly added. This was stirred at 75 ° C. for 7 hours and then heated to 120 ° C. to distill off triethylamine. Then, it returned to room temperature and added dichloromethane: 1000mL to the reaction liquid, and stirred for 20 minutes. The precipitate was removed by filtration, and 5% hydrochloric acid aqueous solution: 1000 mL was added to the filtrate for liquid separation. The organic layer was washed 3 times with 1000 mL of water, and then the solvent of the organic layer was removed under reduced pressure. The obtained compound was dissolved in hexane: 1500 mL. Impurities were removed by filtration, and hexane in the filtrate was removed under reduced pressure. Acetone: 1000 mL was added thereto, and the precipitate was washed with acetone three times to obtain 41 g of 4- (3,5-ditrimethylsilylethynylphenyl) diamantane. From the result of the molecular weight measured by mass spectrometry being 456, it was shown that the product was 4- (3,5-ditrimethylsilylethynylphenyl) diamantane.

  Furthermore, 4- (3,5-ditrimethylsilylethynylphenyl) diamantane obtained above (40 g, 87.6 mmol) and potassium carbonate: 2.7 g (19.3 mmol) were mixed with tetrahydrofuran: 600 mL and methanol: 300 mL. The mixture was stirred for 4 hours at room temperature in a nitrogen atmosphere. This was poured into 10% aqueous hydrochloric acid solution: 1000 mL, the precipitate was filtered, and the resulting precipitate was washed with water: 1000 mL, further washed with acetone: 1000 mL, and then dried to obtain 4 as a polymerizable compound. -(3,5-diethynylphenyl) diamantane: 23 g was obtained.

  The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 4- (3,5-diethynylphenyl) diamantane.

Appearance: White solid MS (FD) (m / z): 312 (M +)
Elemental analysis: Theoretical value (/%) C; 92.26, H; 7.74, Actual value (/%) C; 92.12, H; 7.70

  By repeating the above reaction, 4- (3,5-diethynylphenyl) diamantane as the polymerizable compound X was obtained in a necessary amount in the examples.

(Synthesis Example 13)
A polymerizable compound X was obtained in the same manner as in Synthesis Example 12 except that bromobi (diamantane) was prepared instead of bromodiamantane.

  The structural formula of the polymerizable compound X obtained in Synthesis Examples 12 and 13 is represented by the following formula (4 ′). In the following formula (4 '), n represents an integer of 1 to 2, and the number of n corresponds to (No. 11 of each synthesis example).

  The appearance, mass analysis, and elemental analysis results of the polymerizable compound X (Synthesis Example 13) having the formula (4 ′) n = 2 are shown.

Appearance: White solid MS (FD) (m / z): 498 (M +)
Elemental analysis: Theoretical value (/%) C; 91.51, H; 8.94, Actual value (/%) C; 91.49, H; 8.46

(Synthesis Example 14)
In a 5-L eggplant flask, 14.4 g (34.9 mmol) of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane obtained in Synthesis Example 1 and 67.4 g (522 mmol) of quinoline were obtained. 5% palladium-calcium carbonate 0.37 g (0.174 mmol), tetrahydrofuran (1000 mL) and a stirrer were added, and stirring was started at room temperature under a hydrogen stream. When 3.35 L (139 mmol) of hydrogen was consumed, nitrogen was introduced to stop the reaction. After filtering the reaction solution, the filtrate was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography to obtain 3,5-dimethyl-1,7-bis (3,5- Divinylphenyl) adamantane 18.1 g was obtained.

  The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data indicate that the compound obtained above is 3,5-dimethyl-1,7-bis (3,5-divinylphenyl) adamantane.

Appearance: White solid MS (FD) (m / z): 420 (M +)
Elemental analysis: Theoretical value (/%) C; 91.37, H; 8.63, Actual value (/%) C; 91.35, H; 8.60

  By repeating the above reaction, 3,5-dimethyl-1,7-bis (3,5-divinylphenyl) adamantane as the polymerizable compound X was obtained in a necessary amount in the examples.

(Synthesis Examples 15-22)
The same as Synthesis Example 14 except that the polymerizable compound obtained in Synthesis Examples 2 to 9 was prepared instead of 3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane. Thus, a polymerizable compound X was obtained.

  The structural formula of the polymerizable compound X obtained in Synthesis Examples 14 to 18 is shown in the following formula (5), and the structural formula of the polymerizable compound X obtained in Synthesis Examples 19 to 22 is shown in the following formula (6). . Moreover, in Formula (5), n represents the integer of 1-5, the number of n respond | corresponds to (number-13 of each synthesis example), and in Formula (6), n represents the integer of 1-4. , N corresponds to (number -18 in each synthesis example).

  In addition, the external appearance of the said Formula (5) n = 2 polymerizable compound X (Synthesis example 15), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 582 (M +)
Elemental analysis: theoretical value (/%) C; 90.66, H; 9.34, actual measurement value (/%) C; 90.63, H; 9.31

  Moreover, the external appearance of the said compound (5) n = 3 polymeric compound X (synthesis example 16), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 745 (M +)
Elemental analysis: theoretical value (/%) C; 90.26, H; 9.74, actual measurement value (/%) C; 90.24, H; 9.70

  The external appearance of the said compound (5) n = 4 polymeric compound X (Synthesis example 17), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 907 (M +)
Elemental analysis: Theoretical value (/%) C; 90.00, H; 10.00, Actual value (/%) C; 89.96, H; 9.97

  The external appearance of the said compound (5) n = 5 polymeric compound X (Synthesis example 18), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 1069 (M +)
Elemental analysis: Theoretical value (/%) C; 89.82, H; 10.18, Actual value (/%) C; 89.80, H; 10.14

  The external appearance of the said compound (6) n = 1 polymeric compound X (Synthesis example 19), the result of mass spectrometry, and an elemental analysis are shown.

Appearance: White solid
MS (FD) (m / z): 444 (M +)
Elemental analysis: Theoretical value (/%) C; 91.84, H; 8.16, measured value (/%) C; 91.81, H; 8.13

  The external appearance of the said compound (6) n = 2 polymerizable compound X (synthesis example 20), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid
MS (FD) (m / z): 630 (M +)
Elemental analysis: Theoretical value (/%) C; 91.37, H; 8.63, Actual value (/%) C; 91.32, H; 8.61

  The external appearance of the said Formula (6) n = 3 polymeric compound X (Synthesis example 21), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid
MS (FD) (m / z): 817 (M +)
Elemental analysis: Theoretical value (/%) C; 91.12, H; 8.88, measured value (/%) C; 91.10, H; 8.84

  The external appearance of the said Formula (6) n = 4 polymeric compound X (Synthesis example 22), the result of a mass analysis, and an elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 1003 (M +)
Elemental analysis: Theoretical value (/%) C; 90.96, H; 9.04, measured value (/%) C; 90.93, H; 9.01

(Synthesis Example 23)
A reaction was carried out in the same manner as in Synthesis Example 1 except that dodecamethyl hexaadamantane was prepared instead of dimethyladamantane to obtain a product.
The appearance of the obtained product, the results of mass spectrometry and elemental analysis are shown.

Appearance: White solid MS (FD) (m / z): 1223 (M +)
Elemental analysis: Theoretical value (/%) C; 90.28, H; 9.72, Actual value (/%) C; 90.26, H; 9.70

  These data indicate that the obtained product is a compound represented by n = 6 in the formula (1).

Next, polymerizable compound X was obtained in the same manner as in Synthesis Example 14 using the ethynyl compound.
The appearance of the product, the results of mass spectrometry and elemental analysis are shown below. These data show that the compound (polymerizable compound X) obtained above is a compound represented by n = 6 in the formula (5).

Appearance: White solid MS (FD) (m / z): 1231 (M +)
Elemental analysis: theoretical value (/%) C; 89.69, H; 10.31, actual value (/%) C; 89.66, H; 10.29

  By repeating the above reaction, a necessary amount of the compound represented by n = 6 in the formula (5) as a polymerizable compound was obtained in the examples.

(Synthesis Example 24)
According to the synthesis method described in Macromolecules, 5266 (1991), 4,9-diethynyldiamantane was synthesized.
The appearance of the obtained product, the results of mass spectrometry and elemental analysis are shown. These data indicate that the product obtained is 4,9-diethynyldiamantane.

Appearance: White solid MS (FD) (m / z): 236 (M +)
Elemental analysis: Theoretical value (/%) C; 91.47, H; 8.53, measured value (/%) C; 91.45, H; 8.57

  By repeating the above reaction, a necessary amount of 4,9-diethynyldiamantane as a polymerizable compound was obtained in the examples.

[2] Preparation of film-forming composition and storage in container (Example 1)
3,5-dimethyl-1,7-bis (3,5-diethynylphenyl) adamantane: 5 g as a polymerizable compound synthesized in Synthesis Example 1 was dissolved in 45 g of 1,3-dimethoxybenzene and dried. The reaction was carried out at 170 ° C. for 3 hours under nitrogen, and the reaction solution was once cooled to room temperature. When the molecular weight was measured by GPC, the number average molecular weight was 46,000. The reaction solution was heated again and reacted at 150 ° C. for 6 hours. The reaction solution was added dropwise to a 10-fold volume of a mixed solvent of methanol / tetrahydrofuran = 3/1, and the precipitate was collected and dried. A prepolymer was obtained (yield: 56%).

  By repeating the above reaction, the required amount of the prepolymer was obtained in the examples.

  Thereafter, the obtained prepolymer: 750 g and 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine: 22.5 g as a silane coupling agent were dissolved in cyclopentanone: 15 liters, By filtering with a filter, it was set as the film forming composition as a varnish for organic insulating films.

  The film-forming composition obtained as described above was stored in a container having an internal surface area as shown in Table 1 in the storage amount shown in Table 1 to obtain a container containing the film-forming composition.

(Examples 2 to 23)
As the polymerizable compound, except that the compounds synthesized in Synthesis Examples 2 to 23 were used, a polymerization reaction was performed in the same manner as in Example 1 to obtain a prepolymer. Further, using the prepolymer, cyclopentanone was used. A film-forming composition as a varnish for an organic insulating film was obtained by performing the same treatment as described in Example 1 except that the solvent types shown in Table 1 were used. Then, the container containing the composition for film formation was obtained by accommodating the storage amount shown in Table 1 in the container which has an internal surface area as shown in Table 1.

(Example 24)
4,9-diethynyldiamantane as a polymerizable compound synthesized in Synthesis Example 24: 5 g was dissolved in 45 g of 1,3-dimethoxybenzene, and 0.1 g of bis (benzonitrile) palladium (II) dichloride was added. The reaction solution was reacted at 190 ° C. for 6 hours under dry nitrogen, and the reaction solution was dropped into 10 times the volume of methanol to form a precipitate, which was collected and dried to obtain 3.0 g of a prepolymer. (Yield: 60%).

  By repeating the above reaction, the required amount of the prepolymer was obtained in the examples.

  Then, the obtained prepolymer: 750 g and 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine: 22.5 g as a silane coupling agent were dissolved in cyclohexanone: 15 liters, and filtered. By filtering, it was set as the film forming composition as a varnish for organic insulating films.

  The film-forming composition obtained as described above was stored in a container having an internal surface area as shown in Table 1 in the storage amount shown in Table 1 to obtain a container containing the film-forming composition.

(Comparative Example 1)
Using the same film forming composition as the organic insulating film varnish as in Reference Example 23, the container for storing the film forming composition, and the amount of the film forming composition stored under the conditions shown in Table 1 A container with a film-forming composition was obtained in the same manner as in Reference Example 23, except for changing to.

(Comparative Example 2)
Using the same film forming composition as the organic insulating film varnish as in Reference Example 24, the container for storing the film forming composition and the storage amount of the film forming composition have the conditions shown in Table 1. A container with a film-forming composition was obtained in the same manner as in Reference Example 24, except for changing to.

In Table 1, for each example , each reference example and each comparative example, the conditions of the container (housing part), and the number of carbons derived from the aromatic ring of the polymerizable compound used for the preparation of the film-forming composition, Table 1 shows the number of carbons derived from the polymerizable reactive group, the number of carbons derived from the partial structure, and the ratio of carbon derived from the aromatic ring. In Table 1, polytetrafluoroethylene is "PTFE", low density polyethylene is "LDPE", high density polyethylene is "HDPE", polypropylene is "PP", polyethylene terephthalate is "PET", stainless steel is "SUS"". Moreover, (theta) in a table | surface shows the contact angle with the water in 20 degreeC of the inner surface of a storage part.

[3] Evaluation of generation state of particles The containers containing the film-forming compositions of the above Examples and Comparative Examples were shaken for 6 hours under the conditions of shaking number: 200 times / min and amplitude: 45 mm. Then, the mixture was allowed to stand for 18 hours. This was defined as one cycle (24 hours), and this cycle was repeated 10 times.

For each sample at the end of the 10th cycle treatment (10th continuous standing for 18 hours), particle measurement in the varnish was performed using a light scattering type in-liquid particle detector KS-41 manufactured by Rion Co., Ltd. And evaluated. A count value of 0.2 μm or more was measured at a flow rate of 10 cm ³ / min and a measurement sample amount of 10 cm ³ . The above measurement was repeated three times with the same varnish, and the value obtained by dividing the average value by 10 was defined as the amount of particles per cm ³ .

[4] Formation of insulating film (production of substrate with film)
An insulating film was formed as follows using the film-forming composition in each container for film-forming composition subjected to the treatment [3].

  First, a film forming composition as a varnish for an organic insulating film was applied on a silicon wafer by a spin coater. At this time, the rotation speed and time of the spin coater were set so that the thickness of the insulating film after the heat treatment was 100 nm.

  Next, the silicon wafer provided with the coating film as described above was placed on a hot plate at 200 ° C. for 1 minute to remove the solvent (cyclopentanone) contained in the coating film.

  Thereafter, the silicon wafer provided with the dried coating film is subjected to a heat treatment (baking treatment) for 30 minutes in a nitrogen atmosphere in an oven at 400 ° C., thereby curing the prepolymer constituting the coating film, Thus, a substrate with a film (substrate with an insulating film) was obtained.

[5] Evaluation of Insulating Film (Substrate with Film) [5.1] Appearance Evaluation Regarding the insulating film (substrate with film) according to each of the examples and comparative examples, the surface state was observed, and the following 5 Evaluation was made according to the criteria of the stage.

A: No generation of bumps is observed.
B: Almost no occurrence of bumps is observed.
C: Slight generation is observed.
D: Generation of irregularities is clearly recognized.
E: Remarkable generation of bumps.
[5.2] Dielectric constant The dielectric constant was evaluated using an automatic mercury probe CV measuring device SSM495 manufactured by Nippon SSM Co., Ltd.
[5.3] Breakdown voltage The breakdown voltage was evaluated using an automatic mercury probe CV measuring device SSM495 manufactured by Nippon SSM Co., Ltd., as with the dielectric constant.

The breakdown voltage is a voltage applied when a current of 1 × 10 ⁻² A flows, and a breakdown voltage, and the electric field strength (voltage (MV) applied when a current of 1 × 10 ⁻² A flows) is expressed as a film thickness (cm The value divided by), expressed in units of MV / cm).

  Each sample forming film was formed using each film forming composition, and the above evaluation was performed. These results are shown in Table 2. Regarding the dielectric constant and breakdown voltage, the variation amount between 10 samples (difference between the maximum value and the minimum value) is also shown.

  As is apparent from Table 2, excellent results were obtained with the present invention, whereas satisfactory results were not obtained with the comparative example.

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 SiCN film 3 Interlayer insulating film 4 Hard mask layer 5 Modification processing layer 6 Barrier metal 7 Copper wiring layer 8 Photoresist layer 100 Semiconductor device

Claims (11)

A liquid containing a polymerizable compound having a partial structure including an adamantane-type cage structure and a polymerizable reactive group contributing to the polymerization reaction in the molecule and / or a polymer obtained by partially polymerizing the polymerizable compound. A film-containing composition-containing container obtained by storing a film-forming composition in a container,
When the storage amount of the storage portion for storing the film forming composition in the container is V [cm ³ ] and the internal surface area of the storage portion is S [cm ² ], the relationship of S / V ≦ 0.85 is established. Satisfied ,
The polymerizable reactive group of the polymerizable compound contained in the film-forming composition housed in the container has an aromatic ring and an ethynyl group or a vinyl group directly bonded to the aromatic ring, In the polymerizable compound, the number of carbons derived from the aromatic ring is 15% or more and 38% or less with respect to the number of carbons in the entire polymerizable compound . The container with a film forming composition according to claim 1 , wherein the aromatic ring is directly bonded to the cage structure. The polymerizable reactive group has two ethynyl groups or vinyl groups, one of the ethynyl group or the vinyl group, according to claim 1 in which in the meta-position of the other of the ethynyl group or the vinyl group Or a container containing the film-forming composition according to 2 . 4. The film-forming composition-containing container according to claim 3 , wherein each of the two ethynyl groups or the vinyl group is present at a meta position of a site where the aromatic ring is bonded to the cage structure. The partial structure, according to claim 1 to the film forming composition containing container according to any one of 4 those having an adamantane structure. The container containing a film-forming composition according to claim 5 , wherein the adamantane structure has a methyl group as a substituent. The container for film-forming composition according to claim 6 , wherein the polymerizable compound has a structure represented by the following formula (1) or the following formula (5).

[Wherein n represents an integer of 1 to 5. ]

[Wherein n represents an integer of 1 to 5. ] The partial structure, according to claim 1 to the film forming composition containing container according to any one of 7 and has a diamantane structure. The polymerizable compound, the polymerizable reactive group has two, around the partial structure, one of the claims 1 to 8 The polymerizable reactive group is one that forms a symmetrically bonded structure A container containing the film forming composition according to claim 1. The container for film-forming composition according to any one of claims 1 to 9 , wherein the film-forming composition contains a silane coupling agent. The container with a film-forming composition according to any one of claims 1 to 10 , wherein an inner surface of the storage portion is made of a material having a contact angle with water at 20 ° C of 65 ° or more.

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