JP5153680B2 - Compound with Diels-Alder reaction addition part - Google Patents

Description

  The present invention relates to a compound, and more particularly, an insulating film that is useful as an interlayer insulating film material in a semiconductor element and the like, can form a coating film having an appropriate uniform thickness, and has excellent dielectric constant characteristics. The present invention relates to a compound that can be produced, and a composition containing the compound.

Conventionally, a silica (SiO ₂ ) film formed by a vacuum process such as a vapor deposition (CVD) method is frequently used as an interlayer insulating film in a semiconductor element or the like. In recent years, for the purpose of forming a more uniform interlayer insulating film, a coating type insulating film called a SOG (Spin on Glass) film containing a hydrolysis product of tetraalkoxylane as a main component has been used. It has become. In addition, with high integration of semiconductor elements and the like, an interlayer insulating film having a low dielectric constant, which is mainly composed of polyorganosiloxane called organic SOG, has been developed.

However, even the CVD-SiO ₂ film showing the lowest dielectric constant among the inorganic material films has a relative dielectric constant of about 4. The relative dielectric constant of the SiOF film, which has been recently studied as a low dielectric constant CVD film, is about 3.3 to 3.5. This film has high hygroscopicity, and the dielectric constant increases while being used. There is a problem of doing.

  Under such circumstances, a method of obtaining a film having a low refractive index and a low density by applying a solution obtained by adding a low molecular weight cage compound to an organic polymer has been proposed (see Patent Document 1). However, in this method, the dielectric constant and mechanical strength of the obtained film are not always satisfactory from a practical viewpoint. Furthermore, since the film loss during firing is large when the film is hardened, there is a problem that cracks and the like are likely to occur in the obtained film, and application to devices and the like is limited.

JP 2000-334881 A

  In order to solve the above-described problems, the present invention is suitable for use as a material for an interlayer insulating film in a semiconductor element device or the like, has a small film loss during hardening, and has an excellent dielectric constant and mechanical strength. It is an object of the present invention to provide a compound capable of producing a compound, a composition containing the compound, and a film obtained from the composition.

As a result of intensive studies, the present inventors use a compound having a Diels-Alder reaction addition part obtained from a compound having a conjugated diene structure having a substituent having a predetermined number of carbon atoms and a compound having a dienophile structure. It has been found that the above problem can be solved.
That is, it has been found that the above object of the present invention can be achieved by the following means.
<1> Diels-Alder of a compound (A) having a dienophile structure and a compound (B) having a conjugated diene structure represented by any one of the following general formulas (B-1) to (B-3) A compound which is formed by a reaction and releases the compound (B) having the conjugated diene structure through a reverse Diels-Alder reaction by heating, light irradiation, radiation irradiation or a combination thereof.

(In the general formula (B-1), W represents —O—, —S—, —C (O) —, —C (O) O—, —S (O) —, —S (O) ₂ —, —C (X ¹⁷ ) (X ¹⁸ ) — or —N (X ¹⁹ ) —, where X ^{1 to} X ⁶ and X ^{17 to} X ¹⁹ each independently represent a hydrogen atom or a substituent. Is —O—, —S—, —C (O) —, —C (O) O—, —S (O) — or —S (O) ₂ —, at least one of X ^{1 to} X ⁶ Represents a substituent having 5 or more carbon atoms, and when W is —C (X ¹⁷ ) (X ¹⁸ ) —, at least one of X ^{1 to} X ⁶ , X ¹⁷ and X ¹⁸ is a substituent having 5 or more carbon atoms. When W is —N (X ¹⁹ ) —, at least one of X ^{1 to} X ⁶ and X ¹⁹ represents a substituent having 5 or more carbon atoms.
In general formula (B-2), W represents —O—, —S—, —C (O) —, —C (O) O—, —S (O) —, —S (O) ₂ —, —. C (X ¹⁷ ) (X ¹⁸ ) — or —N (X ¹⁹ ) — is represented. X ^{7 to} X ¹⁰ and X ^{17 to} X ¹⁹ each independently represent a hydrogen atom or a substituent. When W is —O—, —S—, —C (O) —, —C (O) O—, —S (O) — or —S (O) ₂ —, X ^{7 to} X ¹⁰ At least one of them represents a substituent having 5 or more carbon atoms. When W is —C (X ¹⁷ ) (X ¹⁸ ) —, at least one of X ^{7 to} X ¹⁰ , X ¹⁷ and X ¹⁸ represents a substituent having 5 or more carbon atoms. When W is —N (X ¹⁹ ) —, at least one of X ^{7 to} X ¹⁰ and X ¹⁹ represents a substituent having 5 or more carbon atoms.
In General Formula (B-3), X ^{11 to} X ¹⁶ each independently represent a hydrogen atom or a substituent, and at least one represents a substituent having 5 or more carbon atoms. )
<2> The compound according to <1>, wherein the compound (B) having a conjugated diene structure has a molecular weight in the range of 150 to 600.
<3> The compound according to <1> or <2>, wherein the compound (A) having a dienophile structure is a compound having a siloxane structure.
<4> The compound (A) having the dienophile structure has m RSi (O _0.5 ) ₃ units (m represents an integer of 8 to 16, and R represents a hydrogen atom or a substituent). The compound according to <3>, wherein each unit is the compound (I) or a polymer thereof in which each unit shares an oxygen atom in each unit and is linked to another unit to form a cage structure.
<5> The compound according to <4>, wherein the compound (I) is a compound represented by any one of the following general formulas (Q-1) to (Q-7).

(In General Formulas (Q-1) to (Q-7), each R independently represents a hydrogen atom or a substituent. In each of General Formulas (Q-1) to (Q-7), And at least one of R represents an alkenyl group or an alkynyl group.)
<6> A composition comprising the compound according to any one of <1> to <5>.
<7> The composition according to <6>, further comprising a solvent.
<8> The composition according to <6> or <7>, which is used for insulating film formation.
<9> A method for producing an insulating film, wherein the composition according to any one of <6> to <8> is applied onto a substrate and then hardened.
<10> An insulating film manufactured using the manufacturing method according to <9>.
<11> An electronic device having the insulating film according to <10>.

  The present invention is suitable for use as a material for an interlayer insulating film in a semiconductor element device or the like, a compound capable of producing a film having a small film loss at the time of hardening and excellent in dielectric constant and mechanical strength, And a composition containing the compound, and a film obtained from the composition.

Hereinafter, the compound of the present invention, a composition containing the compound, and a film obtained from the composition will be described in detail.
The compound of the present invention (hereinafter also referred to as compound (X)) comprises a compound (A) having a dienophile structure and a conjugated diene represented by any one of the general formulas (B-1) to (B-3). It is formed by Diels-Alder reaction with at least one compound (B) having a structure. Furthermore, it is a compound in which the reverse Diels-Alder reaction proceeds by heating, light irradiation, radiation irradiation or a combination thereof, and the compound (B) having a conjugated diene structure is eliminated.
In the coating film containing this compound (X), reverse Diels-Alder reaction can be promoted by performing a hardening treatment using heating, light irradiation, radiation irradiation, or a combination thereof. As a result, the compound (B) having a conjugated diene structure is volatilized from the compound (X) and the film voids are increased. Further, a curing reaction occurs between the residues, so that low dielectric constant, high mechanical strength, and high heat resistance are exhibited. A film with a small film loss can be formed. In particular, in the present invention, by using the compound (B) having a bulky substituent, the occupied volume of the compound (B) in the film increases, and the film gap after the compound (B) volatilizes increases. Thus, a film having a lower dielectric constant can be formed. Further, by using the compound (B) having a bulky substituent (5 or more carbon atoms), the reverse Diels-Alder reaction temperature of the compound (B) is increased, so that the dura is partially formed before the film void formation. It progresses and the film loss at the time of film | membrane void | space formation can be suppressed.
First, the compound (A) having a dienophile structure and the compound (B) having a conjugated diene structure as raw materials for the compound (X) will be described.

<Compound (A) having a dienophile structure>
One of the raw materials of the compound of the present invention is a compound (A) having a dienophile structure.
The dienophile structure is not particularly limited as long as it is an unsaturated structure that additionally reacts with a conjugated diene structure described later (Diels-Alder reaction) to give a cyclic structure, an alkenyl group having a carbon-carbon double bond, And an alkynyl group having a carbon-carbon triple bond. Preferable examples of the dienophile structure include the following structures. Of these, (E-1) skeleton, (E-2) skeleton, (E-3) skeleton and the like are preferable.

In the skeletons (E-1) to (E-16), Y _{1 to} Y ₇ each independently represents a hydrogen atom or a substituent. The definition of a substituent is synonymous with the substituent demonstrated by R in general formula (I) mentioned later.

The compound (A) is not particularly limited as long as it has a dienophile structure as described above, and may be a low molecular compound or a high molecular compound (for example, a resin compound). Examples thereof include highly heat-resistant resins such as polyarylene resins, polyarylene ether resins, polybenzoxazole resins, polyquinoline resins, and polyquinoxaline resins, or precursors of these resins. In addition, a compound having a cage structure selected from the group consisting of adamantane, biadamantane, diamantane, triamantane, tetramantane, and dodecahedrane (hereinafter also simply referred to as a compound having a cage structure), a siloxane structure (Si— Preferred examples include compounds having an O bond.
Among these, from the viewpoint of heat resistance and low dielectric properties, a compound having a cage structure or a compound having a siloxane structure is preferable, and a compound having a siloxane structure is particularly preferable.

  Specific examples of the high heat resistant resin include polybenzoxazoles described in JP-A-11-322929, JP-A-2003-12802, JP-A-2004-18593, and JP-A-2001-2899. Quinoline resin, Japanese translations of PCT publication No. 2003-530464, Japanese translations of PCT publication No. 2004-535497, Japanese translations of PCT publication No. 2004-504424, Japanese translations of PCT publication No. 2004-504455 JP-A-2005-514479, JP-A-2005-522528, JP-A No. 2000-100808, US Pat. No. 6,509,415, JP-A No. 2003-252992, and JP-A No. 2004-2004 And the polyimide described in Japanese Patent No. 26850. . Specific examples of the compound having a cage structure include JP-A-11-214382, JP-A-2001-332542, JP-A-2003-252882, JP-A-2003-292878, and JP-A-2004-2787. Examples thereof include polyadamantanes described in JP-A No. 2004-67877 and JP-A No. 2004-59444.

<Compound having siloxane structure>
When the compound (A) is a compound having a siloxane structure (Si—O bond), any compound having a siloxane structure may be used as long as the effects of the present invention are not impaired. The compound having a siloxane structure includes a low molecular compound and a high molecular compound. A compound having a siloxane structure composed of silicon atoms and oxygen atoms exhibits excellent heat resistance. As content of the siloxane structure in the compound which has a siloxane structure, 30-100 mass% is preferable with respect to the compound whole quantity which has a siloxane structure, and 60-100 mass% is more preferable.

  The compound having a siloxane structure is preferably a silsesquioxane compound from the viewpoint of excellent low dielectric properties and mechanical properties. The silsesquioxane compound is a compound having at least a silsesquioxane structure. The silsesquioxane structure is a structure in which each silicon atom is bonded to three oxygen atoms and each oxygen atom is bonded to two silicon atoms (the number of oxygen atoms is 1.5 with respect to the number of silicon atoms). is there. Examples of the silsesquioxane compound include a ladder type, a cage type, an incomplete cage type lacking a part of the cage type, and a mixture thereof. From the viewpoint of heat resistance, stability over time, etc. A mold is preferred. The cage structure is a structure in which the volume is determined by a plurality of rings formed by covalently bonded atoms, and a point located in the volume cannot be separated from the volume without passing through the ring. A silsesquioxane compound having a cage structure is also referred to as a cage silsesquioxane compound.

The cage-type silsesquioxane compound is formed by connecting m RSi (O _0.5 ) ₃ units to other RSi (O _0.5 ) ₃ units while sharing the oxygen atom. And a compound having a cage structure (hereinafter also referred to as compound (I)), a polymer having the same as a repeating unit, and the like.
R represents a hydrogen atom or a substituent.

  Preferred examples of the substituent for R include, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a silicon atom-containing group, or a group obtained by combining them.

  The alkyl group represented by R may have a substituent, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. You may do it. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group And a branched alkyl group such as a linear alkyl group such as isopropyl group, isobutyl group, t-butyl group, neopentyl group, and 2-ethylhexyl group.

  The cycloalkyl group represented by R may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, may be polycyclic, or may have an oxygen atom in the ring. Good. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.

  The aryl group represented by R may have a substituent and is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

  The aralkyl group represented by R may have a substituent, preferably an aralkyl group having 7 to 20 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, or a naphthylethyl group. It is done.

  The alkoxy group represented by R may have a substituent, preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy group, ethoxy group, propoxy group, n-butoxy group, pentyl. An oxy group, a hexyloxy group, a heptyloxy group, etc. are mentioned.

The silicon atom-containing group represented by R is not particularly limited as long as silicon is contained, but a group represented by the following formula is preferred.
* -L ¹ -Si- (R ²⁰ ) ₃

In the above formula, * represents a bonding position with a silicon atom. L ¹ represents an alkylene group, —O—, —S—, —Si (R ²¹ ) (R ²² ) —, —N (R ²³ ) —, or a divalent linking group obtained by combining these. L ¹ is preferably an alkylene group, —O—, or a divalent linking group obtained by combining these.
As an alkylene group, C1-C12 is preferable and C1-C6 is more preferable. R ²¹ , R ²² , R ²³ and R ²⁰ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group or an alkoxy group. Preferred examples of the group represented by R ²¹ , R ²² , R ²³ and R ²⁰ include a methyl group, an ethyl group, a butyl group, a cyclohexyl group, a vinyl group, and an ethynyl group.
As the silicon atom-containing group, a silyloxy group (trimethylsilyloxy, triethylsilyloxy, t-butyldimethylsilyloxy) is most preferable.

  Examples of the alkenyl group represented by R include a group having a double bond at any position of the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, and silicon atom-containing group. C1-C12 is preferable and C1-C6 is more preferable. For example, a vinyl group, an allyl group, etc. are mentioned, and a vinyl group is preferable from the viewpoint of ease of polymerization control and mechanical strength.

  Examples of the alkynyl group represented by R include a group having a triple bond at any position of the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, and silicon atom-containing group. C1-C12 is preferable and C1-C6 is more preferable. From the viewpoints of ease of polymerization control and mechanical strength, an ethynyl group is preferred.

  M in compound (I) represents an integer of 8 to 16. From the viewpoint of the effect of lowering the dielectric constant, m is preferably 8, 10, 12, 14, or 16, more preferably 8, 10, 12 from the viewpoint of availability, and most preferably 8, 12 from the viewpoint of polymerization controllability.

  Preferable examples of compound (I) include compounds represented by general formula (Q-1) to general formula (Q-7) below. Among these, from the viewpoints of availability, polymerization controllability, and solubility, the compound represented by General Formula (Q-6) is most preferable.

  R in the compounds represented by the general formula (Q-1) to the general formula (Q-7) independently represents a hydrogen atom or a substituent. Several R may be same or different and at least 1 shows an alkenyl group and an alkynyl group.

  The substituent represented by R has the same definition as the substituent described in detail above, preferably 1 to 20 carbon atoms, specifically, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, Examples thereof include an alkenyl group, an alkynyl group, an alkoxy group, a silicon atom-containing group, or a group obtained by combining them.

  At least one of R represents an alkenyl group or an alkynyl group. Preferably, two or more of R are preferably an alkenyl group or an alkynyl group, more preferably three or more, and particularly preferably all. When there are multiple alkenyl groups and alkynyl groups in this way, a large number of dienophile alkenyl and alkynyl groups are generated in the film by reverse Diels-Alder reaction at the time of hardening, and the cross-linking reaction (curing reaction) by these is better Proceed to. As a result, the mechanical strength of the resulting film is improved, and the film loss during dura is further improved.

  Specific examples of the cage silsesquioxane compound represented by compound (I) include the following, but the present invention is not limited thereto.

  Compound (I) may be one that can be purchased from Aldrich, Hybrid Plastics, Polymers, 20, 67-85, 2008, Journal of Inorganic and Organometallic Polymers, 11 (3), 123-154, 2001. , Journal of Organometallic Chemistry, 542, 141-183, 1997, Journal of Macromolecular Science. A. Chemistry, 44 (7), 659-664, 2007, Chem. Rev., 95, 1409-1430, 1995, Journal of Inorganic and Organometallic Polymers, 11 (3), 155-164, 2001, Dalton Transactions, 36-39, 2008, Macromolecules, 37 (23), 8517-8522, 2004, Chem. Mater., 8, 1250-1259, 1996, etc. It may be synthesized by a known method described in 1.

It is also preferred that R in the compound (I) of the present invention is a group represented by the following general formula (II). In this case, the group represented by the general formula (II) can be synthesized by reacting a compound represented by the following general formula (III) with a compound represented by the following general formula (IV).
(R ¹ ) ₃ —Si—O— (II)
[MO-Si (O _0.5 ) ₃ ] _m (III)
(R ¹ ) ₃ —Si—Cl (IV)

  The compound represented by the general formula (II) can be synthesized according to the method described in, for example, Angew. Chem. Int. Ed. Engl., 1997, 36, No. 7, 743-745.

In these formulas, R ¹ independently represents a substituent, and specific examples of the substituent represented by R ¹ include an alkyl group, an aryl group, a vinyl group, and an ethynyl group. m and R ¹ are respectively synonymous with m and R in the compound (I). M represents a metal atom (for example, Na, K, Cu, Ni, Mn) or an onium cation (for example, tetramethylammonium). When M is a polyvalent metal atom, it means a form in which a plurality of —O—Si (O _0.5 ) ₃ is bonded to the polyvalent metal atom M.

The reaction between the compound represented by the general formula (III) and the compound represented by the general formula (IV) is carried out, for example, in a solvent by combining the compound represented by the general formula (III) and the general formula (III) 1 to 100 times moles of the compound represented by the general formula (IV) of the number of Si-OM groups contained in the compound represented by the formula: .
As the solvent, organic solvents such as toluene, hexane, and tetrahydrofuran (THF) are preferable. When the compound represented by the general formula (III) and the compound represented by the general formula (IV) are reacted, a base such as triethylamine or pyridine may be added.

<Polymer>
One preferred embodiment of the compound (A) is a polymer having the compound (I) as a repeating unit (preferably represented by any one of the above general formulas (Q-1) to (Q-7)). And a polymer of a plurality of different compounds (I) may be contained. In that case, the copolymer which consists of several different compound (I) may be sufficient, and the mixture of a homopolymer may be sufficient. When the composition of the present invention includes a copolymer composed of a plurality of different compounds (I), it is a copolymer of a mixture of two or more compounds (I) selected from m = 8, 10, and 12. Preferably there is.

The polymer may be a copolymer with a compound other than the compound (I). The compound used in that case is preferably a compound having a plurality of polymerizable carbon-carbon unsaturated bonds or SiH groups. Examples of preferable compounds include vinyl silanes, vinyl siloxanes, phenylacetylenes, vinyl adamantanes, [(HSiO _0.5 ) ₃ ] _{8 and the} like.
In this case, the component derived from the compound (I) is preferably 50% by mass or more, and most preferably 70% by mass or more in the copolymer.
The content of the unreacted compound (I) contained in the production of the polymer having the compound (I) as a repeating unit is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total solid content. And most preferably 7% by mass or less. Thereby, the coated surface state can be improved. In addition, total solid means the total component of the polymer of compound (I) and an unreacted substance.

The weight average molecular weight (M _w ) of the polymer is preferably 2.0 × 10 ⁴ to 70 × 10 ⁴ except for the compound (I) monomer, and 3.0 × 10 ⁴ to 30 × 10. ⁴ is more preferable, and 4.0 × 10 ^{4 to} 20 × 10 ⁴ is most preferable.
The number average molecular weight of the polymer _{(M n),} except for Compound (I) monomers is preferably from ^{1.0 × 10 4 ~30 × 10 4} , 1.0 × 10 4 ~15 × 10 ⁴ is more preferable, and 2.0 × 10 ⁴ to 10 × 10 ⁴ is most preferable.
The Z + 1 average molecular weight (M _{Z + 1} ) of the polymer is preferably 1.0 × 10 ^{4 to} 60 × 10 ⁴ except for the compound (I) monomer, and is 2.0 × 10 ^{4 to} 45 × 10. ⁴ is more preferable, and 3.0 × 10 ⁴ to 30 × 10 ⁴ is most preferable.
By setting the weight average molecular weight and number average molecular weight within the above ranges, solubility in organic solvents and filter filterability can be improved, and a film having a low dielectric constant can be formed with improved surface condition of the coating film. it can.

  From the viewpoints of solubility in organic solvents and filter filterability, the polymer preferably does not substantially contain a component having a molecular weight of 3 million or more, more preferably does not substantially contain a component having a molecular weight of 2 million or more. Most preferably, it contains no more than 10,000 components.

It is preferable that unreacted alkenyl group and alkynyl group derived from compound (I) remain in the polymer of compound (I). Among alkenyl groups and alkynyl groups derived from compound (I), 10 to 90 It is preferable that the mol% remains unreacted, preferably 20 to 80 mol% remains unreacted, and most preferably 30 to 70 mol% remains unreacted. If it is in the said range, the sclerosis | hardenability and mechanical strength of the film | membrane obtained will improve more.
In the polymer of compound (I), a polymerization initiator, an additive, or a polymerization solvent may be bound by 0.1 to 40% by mass with respect to the total amount of the polymer. Their content is preferably from 0.1 to 20% by mass, more preferably from 0.1 to 10% by mass, most preferably from 0.1 to 5% by mass, based on the total amount of the polymer.
About these, it can quantify from the NMR spectrum etc. of a composition.

As a method for producing a polymer of compound (I), a polymerization reaction of a carbon-carbon unsaturated bond of compound (I), a hydrosilylation reaction (see paragraph No. [0037] of JP-A-2007-092019) ), Production method using sol-gel reaction using acid or base catalyst (see Application of sol-gel method to nanotechnology (CMC, 2005), development of sol-gel method application (CMC, 2008)) .
The polymerization reaction of the carbon-carbon unsaturated bond of compound (I) may be any polymerization reaction. For example, radical polymerization, cationic polymerization, anionic polymerization, ring-opening polymerization, polycondensation, polyaddition, addition condensation, transition Examples include metal catalyst polymerization.

  As a method for producing the polymer, a polymerization reaction of a carbon-carbon unsaturated bond of compound (I) is preferable, and radical polymerization is most preferable. As the synthesis method, the compound (I) and the initiator are dissolved in a solvent and the polymerization is performed by heating, and the compound (I) is dissolved in the solvent and heated, and the initiator solution is heated for 1 to 10 hours. Examples thereof include a dropping polymerization method (continuous addition) that is added dropwise over a period of time, a split addition polymerization method (split addition) in which an initiator is divided into a plurality of times and added. Split addition and continuous addition are preferred because the film strength and molecular weight reproducibility are further improved.

The reaction temperature of the polymerization reaction is usually 0 ° C to 200 ° C, preferably 40 ° C to 170 ° C, more preferably 80 ° C to 160 ° C.
Moreover, in order to suppress the inactivation of the polymerization initiator by oxygen, it is preferable to make it react under inert gas atmosphere (for example, nitrogen, argon, etc.). The oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.

  The concentration of compound (I) in the reaction solution during polymerization is preferably 30% by mass or less, more preferably 20% by mass or less, and more preferably 15% by mass or less with respect to the total mass of the reaction solution. More preferred is 10% by mass or less. By setting the concentration range, the generation of impurities such as gelling components can be suppressed.

The solvent used in the polymerization reaction is not particularly limited as long as the compound (I) can be dissolved at a necessary concentration and does not adversely affect the characteristics of the film formed from the obtained polymer.
Examples of the solvent include the solvents described in paragraph No. [0038] of JP-A-2008-218639. More preferable solvents are ester solvents, ether solvents and aromatic hydrocarbon solvents, and specifically, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, pentyl acetate, hexyl acetate, methyl propionate, propylene. Glycol monomethyl ether acetate, tetrahydrofuran, diphenyl ether, anisole, toluene, xylene, mesitylene and t-butylbenzene are preferred, and ethyl acetate, butyl acetate, diphenyl ether, anisole, mesitylene and t-butylbenzene are particularly preferred. These may be used alone or in admixture of two or more.
The boiling point of the solvent is preferably 65 ° C. or higher so that the reaction solution can be heated to a temperature necessary for decomposing the polymerization initiator during the reaction.

The polymerization reaction of compound (I) is preferably performed in the presence of a nonmetallic polymerization initiator. For example, the polymerization can be performed in the presence of a polymerization initiator that exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by heating.
As the polymerization initiator, an organic peroxide or an organic azo compound is particularly preferably used. As the organic peroxide and the organic azo compound, compounds described in Paragraph Nos. [0033] to [0035] of Japanese Patent Publication No. 2008-239585 can be used.

The polymerization initiator is preferably an organic azo compound in view of the safety of the reagent itself and the molecular weight reproducibility of the polymerization reaction, and particularly an azo ester compound such as V-601 in which harmful cyano is not taken into the polymer.
The 10-hour half-life temperature of the polymerization initiator is preferably 100 ° C. or lower. If the 10-hour half-life temperature is 100 ° C. or lower, it is easy to prevent the polymerization initiator from remaining at the end of the reaction.
Only one polymerization initiator or a mixture of two or more polymerization initiators may be used.
The amount of the polymerization initiator used is preferably 0.0001 to 2 mol, more preferably 0.003 to 1 mol, and particularly preferably 0.001 to 0.5 mol with respect to 1 mol of the monomer.

The weight average molecular weight (M _w ) of the polymer at the end of the polymerization reaction is preferably 2 × 10 ⁴ to 50 × 10 ⁴ , more preferably 3 × 10 ⁴ to 40 × 10 ⁴ , and 4 ×. Most preferably, it is 10 ⁴ to 40 × 10 ⁴ .
The Z + 1 average molecular weight (M _{Z + 1} ) of the polymer at the end of the polymerization reaction is preferably 10 × 10 ^{4 to} 60 × 10 ⁴ , more preferably 9 × 10 ^{4 to} 55 × 10 ⁴ , and 8 × 10 ^4. Most preferred is ˜40 × 10 ⁴ .
The polymer at the end of the polymerization reaction is preferably substantially free of components having a molecular weight of 300 × 10 ⁴ or more, more preferably substantially free of components of 200 × 10 ⁴ or more, and 100 × 10 ⁴ or more. It is most preferable not to contain these components.
When these molecular weight conditions are satisfied at the time of polymerization, a film-forming composition having a good coating surface shape and a small film loss at the time of firing can be produced with high yield.

  When producing the compound (X) of the present invention, the reaction solution obtained by subjecting the compound (I) to the polymerization reaction may be used as it is, but it is preferable to carry out a purification treatment after the completion of the reaction. Purification methods include washing with water and a liquid-liquid extraction method that removes residual monomers and oligomer components by combining with an appropriate solvent, ultrafiltration, centrifugal separation, and column that extract and remove only those with a specific molecular weight or less. A purification method in a solution state such as chromatography, a reprecipitation method in which the polymer is coagulated in the poor solvent by dropping the polymer solution into the poor solvent, and the residual monomer is removed. A usual method such as a purification method in a solid state such as washing the combined slurry with a poor solvent can be applied.

<Compound having a cage structure>
When the compound (A) is a compound having a cage structure, the compound (A) is a compound having a cage structure selected from the group consisting of adamantane, biadamantane, diamantane, triamantane, tetramantane, and dodecahedrane, "Is the same as defined above. The compound having a cage structure may be a low molecular compound or a high molecular compound (for example, a polymer (polymer)), but preferably a monomer having a cage structure (the monomer is synonymous with the precursor). It is a polymer of Here, the monomer having a cage structure refers to a monomer that is polymerized to be a dimer or higher polymer. The polymer may be a homopolymer or a copolymer.
When the compound having a cage structure is a polymer, the weight average molecular weight is preferably 1,000 to 500,000, more preferably 5,000 to 200,000, and particularly preferably 10,000 to 100,000. It is. When the compound having a cage structure is a low molecular compound, the molecular weight is preferably 150 to 3,000, more preferably 200 to 2,000, and particularly preferably 220 to 1,000.

  The cage structure of the compound having a cage structure is more preferably adamantane, biadamantane or diamantane, and particularly preferably biadamantane or diamantane from the viewpoint of a low dielectric constant. The cage structure may contain either a saturated or unsaturated bond and may contain a heteroatom such as oxygen, nitrogen or sulfur, but a saturated hydrocarbon is preferred from the viewpoint of a low dielectric constant.

  The cage structure of the compound having a cage structure is preferably a divalent to tetravalent group. At this time, the group bonded to the cage structure may be a monovalent or higher valent substituent or a divalent or higher linking group. The cage structure is more preferably a divalent or trivalent group, and particularly preferably a divalent group.

  The cage structure of the compound having a cage structure may have one or more substituents. Examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom or an iodine atom), carbon A linear, branched or cyclic alkyl group having 1 to 10 carbon atoms (methyl, t-butyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group having 2 to 10 carbon atoms (vinyl, propenyl, etc.), and an alkynyl group having 2 to 10 carbon atoms. (Ethynyl, phenylethynyl, etc.), C6-C20 aryl groups (phenyl, 1-naphthyl, 2-naphthyl, etc.), C2-C10 acyl groups (benzoyl, etc.), C2-C10 alkoxycarbonyl A group (such as methoxycarbonyl), a carbamoyl group having 1 to 10 carbon atoms (such as N, N-diethylcarbamoyl), an aryl group having 6 to 20 carbon atoms Shi group (such as phenoxy), (such as phenylsulfonyl) arylsulfonyl group having 6 to 20 carbon atoms, a nitro group, a cyano group, a silyl group (triethoxysilyl, methyldiethoxysilyl, trivinylsilyl or the like) and the like.

  The polymerization reaction of the monomer having a cage structure is caused by the polymerizable group substituted for the monomer. Here, the polymerizable group refers to a reactive substituent that polymerizes the monomer. The polymerization reaction may be any polymerization reaction, and examples thereof include radical polymerization, cationic polymerization, anionic polymerization, ring-opening polymerization, polycondensation, polyaddition, addition condensation, or transition metal catalyst polymerization.

  The polymerization reaction of the monomer having a cage structure is preferably performed in the presence of a nonmetallic polymerization initiator. For example, a monomer having a polymerizable carbon-carbon double bond or carbon-carbon triple bond may be polymerized in the presence of a polymerization initiator that exhibits activity by generating free radicals such as carbon radicals and oxygen radicals by heating. it can. As the polymerization initiator, an organic peroxide or an organic azo compound is preferably used, and an organic peroxide is particularly preferable. As the organic peroxide, the above organic peroxide is preferably used. As the organic azo compound, the above organic azo compound is preferably used.

Only one polymerization initiator or a mixture of two or more polymerization initiators may be used. The amount of the polymerization initiator used is preferably 0.001 to 2 mol, more preferably 0.01 to 1 mol, particularly preferably 0.05 to 0.5 mol, per 1 mol of the monomer having a cage structure. It is.
The polymerization reaction of the monomer having a cage structure is also preferably performed in the presence of a transition metal catalyst described in paragraphs [0030] to [0031] of JP-A-2008-239585.

The cage structure may be substituted as a pendant group in the polymer and may be a part of the polymer main chain, but a form that is a part of the polymer main chain is more preferable. Here, the form which is a part of the polymer main chain means that the polymer chain is cleaved when the cage structure is removed from the polymer. In this form, the cage structure is directly single-bonded or connected by an appropriate divalent linking group. Examples of the linking group include, for example, —C (R ³⁵ ) (R ³⁶ ) —, —C (R ³⁷ ) ═C (R ³⁸ ) —, —C≡C—, arylene group, —CO—, —O—. , —SO ₂ —, —N (R ³⁹ ) —, —Si (R ⁴⁰ ) (R ⁴¹ ) — or a combination thereof. Here, each represent R ³⁵ to R ⁴¹ independently represent a hydrogen atom, an alkyl group, alkenyl group, alkynyl group or aromatic hydrocarbon group. Among these, more preferred linking groups are —C (R ³⁵ ) (R ³⁶ ) —, —CH═CH—, —C≡C—, arylene group, —O—, —Si (R ⁴⁰ ) (R ⁴¹ ). -Or a combination thereof, and particularly preferred is -C ( ^R35 ) ( ^R36 )-, -CH = CH- from the viewpoint of low dielectric constant.

  The compound having a cage structure used in the present invention is preferably a monomer having a polymerizable carbon-carbon double bond or carbon-carbon triple bond or a polymer thereof. Furthermore, a compound represented by any one of the following general formulas (G-1) to (G-6) or a polymer thereof is more preferable.

(In General Formulas (G-1) to (G-6), V _{1 to} V ₈ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a silyl group, an acyl group, or an alkoxycarbonyl group. or an such carbamoyl _groups, in Z 1 to Z ₈ each independently represents a halogen atom, an alkyl group, an aryl group or a silyl _group, m 1, _{m 5} represents an integer of 1 to _16, n 1, _{n 5} Represents an integer of 0 to 15, m ₂ , m ₃ , m ₆ and m ₇ each independently represents an integer of 1 to 15; n ₂ , n ₃ , n ₆ and n ₇ represent an integer of 0 to 14; M ₄ and m ₈ represent an integer of 1 to 20, and n ₄ and n ₈ represent an integer of 0 to 19).

In general formulas (G-1) to (G-6), V _{1 to} V ₈ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), or an alkenyl group (preferably having 2 carbon atoms). -10), an alkynyl group (preferably 2 to 10 carbon atoms), an aryl group (preferably 6 to 20 carbon atoms), a silyl group (preferably 0 to 20 carbon atoms), an acyl group (preferably carbon Represents 2 to 10), alkoxycarbonyl (preferably 2 to 10 carbon atoms), carbamoyl group (preferably 1 to 20 carbon atoms), and the like. Among these, a hydrogen atom, an alkyl group, an aryl group, a silyl group, an acyl group, an alkoxycarbonyl group, and a carbamoyl group are preferable, a hydrogen atom and an aryl group having 6 to 20 carbon atoms are more preferable, and hydrogen is particularly preferable. Is an atom.
In general formulas (G-1) to (G-6), Z _{1 to} Z ₈ are each independently a halogen atom (fluorine, chlorine, bromine, etc.), an alkyl group (preferably having 1 to 10 carbon atoms), aryl A group (preferably having 6 to 20 carbon atoms) or a silyl group (preferably having 0 to 20 carbon atoms) is represented. More preferred are an optionally substituted alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, and particularly preferred is an alkyl group (such as a methyl group).
V _{1 to} V ₈ and Z _{1 to} Z ₈ may be further substituted with another substituent.

In General Formula (G-1) or General Formula (G-4), m ₁ and m ₅ each independently represents an integer of 1 to 16, preferably 1 to 4, more preferably 1 to 3, particularly preferably. 2.
In General Formula (G-1) or General Formula (G-4), n ₁ and n ₅ each independently represents an integer of 0 to 15, preferably 0 to 4, more preferably 0 or 1, particularly preferably. 0.
In General Formula (G-2) or General Formula (G-5), m ₂ , m ₃ , m ₆ and m ₇ each independently represent an integer of 1 to 15, preferably 1 to 4, more preferably 1 to 3, particularly preferably 2.
In General Formula (G-2) or General Formula (G-5), n ₂ , n ₃ , n ₆ and n ₇ each independently represent an integer of 0 to 14, preferably 0 to 4, more preferably 0. Or 1, particularly preferably 0.
In general formula (G-3) or general formula (G-6), m ₄ and m ₈ each independently represents an integer of 1 to 20, preferably 1 to 4, more preferably 1 to 3, particularly preferably. 2.
In General Formula (G-3) or General Formula (G-6), n ₄ and n ₈ each independently represents an integer of 0 to 19, preferably 0 to 4, more preferably 0 or 1, particularly preferably. 0.

  The monomer having a cage structure is preferably a compound represented by General Formula (G-1), General Formula (G-2), General Formula (G-4), or General Formula (G-5), More preferred are compounds represented by general formula (G-1) or general formula (G-2), and particularly preferred are compounds represented by general formula (G-2).

Two or more compounds having a cage structure may be used in combination. Two or more monomers having a cage structure that can be used in the present invention may be copolymerized.
As the compound having a cage structure, for example, compounds described in paragraph numbers [0041] to [0044] of JP-A-2008-166384 can be used.

  The compound having a cage structure preferably has sufficient solubility in an organic solvent. The solubility of the compound having a cage structure is preferably 3% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more with respect to cyclohexanone or anisole at 25 ° C.

Any solvent can be used in the polymerization reaction as long as the monomer having a cage structure as a raw material can be dissolved at a necessary concentration and does not adversely affect the characteristics of the film formed from the obtained polymer. Things may be used. Examples thereof include the solvents described in paragraph No. [0038] of JP2008-21839A.
The concentration of the monomer having a cage structure in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass.

The optimum conditions for the polymerization reaction vary depending on the polymerization initiator, the monomer having a cage structure, the type of solvent, the concentration, etc., but preferably the internal temperature is 0 ° C. to 200 ° C., more preferably 50 ° C. to 170 ° C., particularly preferably. Is in the range of 100 ° C. to 150 ° C., preferably 1 to 50 hours, more preferably 2 to 20 hours, and particularly preferably 3 to 10 hours.
Moreover, in order to suppress inactivation of the polymerization initiator by oxygen, it is preferable to make it react in inert gas atmosphere (for example, nitrogen, argon, etc.). The oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.
The preferred range of the weight average molecular weight of the polymer obtained by polymerization is 1,000 to 500,000, more preferably 5,000 to 300,000, and particularly preferably 10,000 to 200,000.

As a method for synthesizing a compound having a cage structure, first, for example, a commercially available diamantane is used as a raw material and reacted with bromine in the presence or absence of an aluminum bromide catalyst to introduce a bromine atom at a desired position. Subsequently, a Friedel-Crafts reaction is performed with vinyl bromide in the presence of a Lewis acid such as aluminum bromide, aluminum chloride, or iron chloride to introduce a 2,2-dibromoethyl group. Furthermore, it can be synthesized by de-HBration with a strong base and converting it to an ethynyl group. Specifically, it is synthesized according to the method described in Macromolecules, 1991, 24, 5266-5268, 1995, 28, 5554-5560, Journal of Organic Chemistry, 39, 2995-3003 (1974), etc. I can do it.
Moreover, an alkyl group or a silyl group can be introduced by anionizing a hydrogen atom of a terminal acetylene group with butyllithium or the like and reacting this with an alkyl halide or a silyl halide.

<Compound (B) having conjugated diene structure>
The compound (B) having a conjugated diene structure is a compound having a conjugated diene structure capable of Diels-Alder reaction with the compound (A) described above, and any one of the following general formulas (B-1) to (B-3) It is represented by In addition, the compound (B) which has a conjugated diene structure may be used individually by 1 type, and may use 2 or more types together.

In general formula (B-1), W represents —O—, —S—, —C (O) —, —C (O) O—, —S (O) —, —S (O) ₂ —, —. C (X ¹⁷ ) (X ¹⁸ ) — or —N (X ¹⁹ ) — is represented. X ^{1 to} X ⁶ and X ^{17 to} X ¹⁹ each independently represent a hydrogen atom or a substituent. In the case where W is —O—, —S—, —C (O) —, —C (O) —, —S (O) — or —S (O) ₂ —, among X ^{1 to} X ⁶ At least one represents a substituent having 5 or more carbon atoms. When W is —C (X ¹⁷ ) (X ¹⁸ ) —, at least one of X ^{1 to} X ⁶ , X ¹⁷ and X ¹⁸ represents a substituent having 5 or more carbon atoms. When W is —N (X ¹⁹ ) —, at least one of X ^{1 to} X ⁶ and X ¹⁹ represents a substituent having 5 or more carbon atoms.
In general formula (B-2), W represents —O—, —S—, —C (O) —, —C (O) O—, —S (O) —, —S (O) ₂ —, —. C (X ¹⁷ ) (X ¹⁸ ) — or —N (X ¹⁹ ) — is represented. X ^{7 to} X ¹⁰ and X ^{17 to} X ¹⁹ each independently represent a hydrogen atom or a substituent. When W is —O—, —S—, —C (O) —, —C (O) O—, —S (O) — or —S (O) ₂ —, X ^{7 to} X ¹⁰ At least one of them represents a substituent having 5 or more carbon atoms. When W is —C (X ¹⁷ ) (X ¹⁸ ) —, at least one of X ^{7 to} X ¹⁰ , X ¹⁷ and X ¹⁸ represents a substituent having 5 or more carbon atoms. When W is —N (X ¹⁹ ) —, at least one of X ^{7 to} X ¹⁰ and X ¹⁹ represents a substituent having 5 or more carbon atoms.
In General Formula (B-3), X ^{11 to} X ¹⁶ each independently represent a hydrogen atom or a substituent, and at least one represents a substituent having 5 or more carbon atoms.

The substituents represented by X ^{1 to} X ¹⁹ in the general formulas (B-1) to (B-3) are not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, Preferable examples include alkynyl groups, alkoxy groups, silicon atom-containing groups, substituents having a cage structure, or a combination thereof. Of these, an alkyl group, a cycloalkyl group, an aryl group, a silicon atom-containing group, a substituent having a cage structure, and the like are preferable.

  An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, and a silicon atom-containing group have the same meanings as the groups described for R in the general formula (I).

  Specific examples of the substituent having a cage structure include an adamantyl group, a diamantyl group, a triamantyl group, and a tetramantyl group.

The substituent having 5 or more carbon atoms is not particularly limited as long as it is a substituent containing 5 or more carbon atoms. Especially, C5-C18 is preferable and 5-12 are more preferable. If it is in the said range, the improvement of the dielectric constant of the film | membrane obtained and the reduction | decrease of film reduction will be achieved with sufficient balance. If the number of carbon atoms is smaller than 5, the temperature at which the compound (B) is desorbed by the reverse Diels-Alder reaction is low, which is not preferable because the film loss during hardening is large. If the number of carbon atoms exceeds 18, it will be difficult to volatilize, so that it will remain in the film and a sufficient film gap will not be formed, and the effect of lowering the dielectric constant may be small.
Specific examples of the substituent include an aromatic hydrocarbon group having 5 or more carbon atoms (for example, a phenyl group, a biphenyl group, and a naphthyl group), a chain or cyclic aliphatic hydrocarbon group having 5 or more carbon atoms (for example, , Alkyl groups, alkenyl groups, cycloalkyl groups) and substituents having an cage structure with 5 or more carbon atoms (adamantyl group, diamantyl group, triamantyl group) and the like. These substituents having 5 or more carbon atoms may further have a substituent such as a halogen atom (for example, a fluorine atom) or an alkyl group.
The substituent having 5 or more carbon atoms preferably has a cyclic structure (aromatic hydrocarbon group, cyclic aliphatic hydrocarbon group, substituent having a cage structure).
More specifically, a substituent represented by the following general formula (K) is preferable.
* -LU General Formula (K)
(In General Formula (K), U represents any functional group selected from the group consisting of a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a diamantyl group. Represents a single bond or a divalent linking group.)

  The functional group represented by U may further have a substituent. For example, a halogen atom (a fluorine atom, a chlorine atom, etc.), an alkyl group, an alkyleneoxy group, an aryl group and the like can be mentioned.

The divalent linking group represented by L is not particularly limited, but is an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, isopropylene group, etc.), alkenylene group (for example, vinylene group, Butene group), alkyleneoxy group, arylene group (for example, o-phenylene group, m-phenylene group, p-phenylene group, 1,4-naphthylene group, etc.), aryleneoxy group, -Si (X ²⁰ ) (X ²¹ )-, -O-, -COO- and the like are preferable. Of these, an alkylene group and an alkyleneoxy group are preferable. X ²⁰ and X ²¹ each independently represents an alkyl group (preferably a methyl group) or an aryl group (preferably a phenyl group). In addition, the total carbon number of the group represented by L and U should just be in the said range (5 or more carbon atoms).
In the case of a single bond, U in the general formula (K) is directly bonded to the carbon atom in the general formulas (B-1) to (B-3).

In general formulas (B-1) and (B-2), W represents —O—, —S—, —C (O) —, —C (O) O—, —S (O) —, — S (O) ₂ —, —C (X ¹⁷ ) (X ¹⁸ ) — or —N (X ¹⁹ ) — is represented. Among these, —C (X ¹⁷ ) (X ¹⁸ ) — is preferable from the viewpoint that the obtained film exhibits lower dielectric properties.

  The molecular weight of the compound (B) having a conjugated diene structure is not particularly limited, but is preferably 100 to 1000, more preferably 120 to 800, and particularly preferably 150 to 600. When the molecular weight is 600 or less, the compound (B) released by the reverse Diels-Alder reaction during the hardening process is sufficiently volatilized, and a sufficient film gap for lowering the dielectric constant can be formed. Moreover, if the molecular weight is 150 or more, the film shrinkage rate at the time of hardening becomes smaller. Therefore, when the molecular weight of the compound (B) is in the range of 150 to 600, a film excellent in terms of low dielectric constant and process suitability can be formed.

  The compound (B) having a conjugated diene structure has a 5% weight loss temperature of 100 in thermogravimetric analysis (nitrogen flow rate 100 ml / min, heating rate 20 ° C./min) because the resulting film exhibits low dielectric properties. It is preferable that it is C-450 degreeC, It is more preferable that it is 150-400 degreeC, It is especially preferable that it is 200-350 degreeC. In particular, when the 5% weight loss temperature is in the range of 200 ° C. to 350 ° C., a film excellent in terms of low dielectric constant and process suitability can be formed.

  Specific examples of the compound (B) having a conjugated diene structure are described below, but the present invention is not limited thereto.

  The addition amount (content) of the compound having a conjugated diene structure in the compound (X) is preferably from 5 to 80 mass%, more preferably from 5 to 60 mass%, more preferably from 10 to 50, based on the total amount of the compound (X). More preferred is mass%. If it is the said range, the production | generation of a connection hole will be suppressed and it is preferable at the point of film | membrane flatness. Addition amount of compound having conjugated diene structure is NMR spectrum, thermogravimetric analysis (TGA) measuring mass change while heating or cooling, differential thermal analysis (DTA) measuring differential heat or reaction heat and differential scanning calorie It can be quantified by measurement (DSC).

<Reaction conditions>
The conditions under which the Diels-Alder reaction is performed between the compound (A) and the compound (B) are appropriately selected depending on the type of compound used.
The reaction solvent for performing the Diels-Alder reaction is not particularly limited as long as the compound to be used dissolves and does not affect the reaction. For example, the solvent etc. which are used for polymerization reaction of said compound (I) are mentioned.
The reaction temperature is not particularly limited, but is usually 25 ° C to 250 ° C, preferably 50 ° C to 200 ° C, more preferably 80 ° C to 200 ° C.

The concentration of the compound (A) in the reaction solution is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less with respect to the total amount of the reaction solution. By setting the concentration range, the generation of impurities such as gelling components can be suppressed.
Moreover, in order to suppress inactivation of the polymerization initiator by oxygen, it is preferable to make it react under inert gas atmosphere (for example, nitrogen, argon, etc.). The oxygen concentration during the reaction is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 20 ppm or less.
It is preferable to carry out a purification treatment after completion of the reaction.
In the production process of compound (X), it is preferable to add a polymerization inhibitor in order to suppress the polymerization reaction. Examples of the polymerization inhibitor include 4-methoxyphenol, 2,6-bis (1,1-dimethylethyl) -4-methylphenol, catechol and the like. Of these, 4-methoxyphenol and 2,6-bis (1,1-dimethylethyl) -4-methylphenol are particularly preferable. The addition amount of the polymerization inhibitor is preferably 5% by mass or more based on the total amount of the compound (A).

<Compound (X)>
A compound (X) having a functional group formed from a conjugated diene structure and a dienophile structure (hereinafter also referred to as a Diels-Alder reaction addition part) by a Diels-Alder reaction between the compound (A) and the compound (B). can get.
As described above, the compound (X) may be a low molecular compound or a high molecular compound (for example, a resin), and the structure thereof is not particularly limited. For example, in the case of a polymer compound, the weight average molecular weight (M _w ) is preferably 2.0 × 10 ⁴ to 50 × 10 ⁴ , and preferably 3.0 × 10 ⁴ to 30 × 10 ^4. More preferred. The number average molecular weight (M _n ) is preferably 1.0 × 10 ^{4 to} 25 × 10 ⁴ , and more preferably 1.5 × 10 ⁴ to 15 × 10 ⁴ .

<Diels Alder reaction addition part>
As described above, the Diels-Alder reaction addition part is a functional group obtained by the addition reaction between the conjugated diene structure and the dienophile structure, and the reverse Diels-Alder reaction proceeds by heating, light irradiation, radiation irradiation, or a combination thereof. Thus, a conjugated diene structure and a dienophile structure are generated.
The optimum conditions for heating conditions, light irradiation conditions, etc. vary depending on the compounds used. In general, the reverse Diels-Alder reaction proceeds under the conditions of heat treatment during film formation described later or irradiation with high energy rays.

  The number of Diels-Alder reaction addition parts in compound (X) is not particularly limited, and an optimal number is appropriately selected depending on the application.

  Preferable examples of the Diels-Alder reaction addition part include functional groups represented by the following general formula (F-1) to general formula (F-4). If these functional groups are used, the progress of the reverse Diels-Alder reaction can be more easily controlled, and can be suitably used for applications such as an insulating film described later.

(In general formula (F-2) to general formula (F-4), W represents -O-, -S-, -C (O)-, -C (O) O-, -S (O)- _{, -S (O) 2 -,} - C (Y 12) (Y 13) - or ^{-N (Y 14) - .Y 1} ~Y 14 representing a each independently represent a hydrogen atom or a substituent, At least one represents a substituent having 5 or more carbon atoms.
In general formula (F-1) to general formula (F-4), * represents a bonding position with compound (X). )

The substituent represented by Y < ¹ > -Y < ¹⁴ > is synonymous with the substituent represented by X < ¹ > -X < ¹⁹ > in the said general formula (B-1)-(B-3). Among these, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a silicon atom-containing group, and a substituent having a cage structure are preferable.

In general formula (F-2) to general formula (F-4), W represents —O—, —S—, —C (O) —, —C (O) O—, —S (O) —, _{-S (O) 2 -, -} C (Y 12) (Y 13) - or -N (Y ¹⁴⁾ - represents a. Of these, —O—, —C (O) —, and —C (Y ¹² ) (Y ¹³ ) — are preferable.
Y ^{12 to} Y ¹⁴ each independently represents a hydrogen atom or a substituent, and among them, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a silicon atom-containing group, and a substituent having a cage structure are preferable. .

  Compound (X) can be used for various applications, for producing a film (for example, an insulating film) (film forming composition), a low refractive index film, a low refractive index material, a gas adsorbing material, a resist. Materials and the like.

<Composition>
The composition of the present invention contains the above compound (X). In addition, the solution which compound (X) melt | dissolved in the organic solvent may be sufficient as the composition of this invention, and the solid substance containing the reaction material of compound (X) may be sufficient as it.
The composition of the present invention can be used for various applications, and the type of the content of the compound (X) and the additive to be added is determined according to the purpose.

  Although content of compound (X) is not specifically limited among solid content contained in a composition, When using for the film formation mentioned later, it is 70 mass% or more with respect to the total solid content. More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more. As these contents in the solid content increase, the coating property is improved and a film having a lower dielectric constant can be formed. In addition, solid content means the solid component which comprises the film | membrane mentioned later, and a solvent etc. are not contained.

  The total content of the unreacted compound (A) and the compound (B) having an unreacted conjugated diene structure in the solid content contained in the composition of the present invention is 15% by mass or less based on the total solid content. More preferably, it is 10 mass% or less, Most preferably, it is 7 mass% or less. If it is the said range, a film | membrane with a better coating surface shape and a film | membrane with a low dielectric constant can be formed.

The composition of the present invention may contain a solvent. That is, it is preferable to use the compound (X) by dissolving it in an appropriate solvent and coating it on a support.
As the solvent, a solvent capable of dissolving 5% by mass or more (preferably 10% by mass or more) of the compound (X) at 25 ° C. is preferable. Specifically, the solvent described in paragraph [0044] of JP-A-2008-214454 can be mentioned.
Among these, preferable solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclohexanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl. Ether, propylene glycol monoethyl ether, ethylene carbonate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, tetrahydrofuran, methyl isobutyl ketone, xylene, Mention may be made of mesitylene and diisopropylbenzene.

  A solution obtained by dissolving the composition of the present invention in a suitable solvent is also included in the scope of the composition of the present invention. When the composition contains a solvent, the total solid content concentration in the composition is preferably 1 to 30% by mass with respect to the total amount of the composition, and is appropriately adjusted according to the purpose of use. When it is within the above range, the film thickness of the coating film is in an appropriate range, and the storage stability of the coating solution is further improved.

  The composition of the present invention may contain a polymerization initiator. In particular, when it is necessary to harden the composition of the present invention at a low temperature, the polymerization initiator is preferably included. In this case, the type of the polymerization initiator is not particularly limited, and examples thereof include a polymerization initiator used in the polymerization of the compound (I) described above. For this purpose, it is also possible to use initiators that cause polymerization by radiation.

<Additives>
Furthermore, the composition of the present invention includes a radical generator and colloidal silica as long as the characteristics (heat resistance, dielectric constant, mechanical strength, coatability, adhesion, etc.) of the film obtained using the composition are not impaired. Additives such as surfactants and adhesives may be added.

  Any surfactant may be used in the composition of the present invention as long as the object of the present invention is not impaired. For example, nonionic surfactants, anionic surfactants, cationic surfactants, and the like, silicone surfactants, fluorine-containing surfactants, polyalkylene oxide surfactants, acrylic surfactants Agents. Only one type of surfactant may be used, or two or more types may be used in combination. As the surfactant, silicone surfactants, nonionic surfactants, fluorine-containing surfactants, and acrylic surfactants are preferable, and silicone surfactants are particularly preferable.

  The addition amount of the surfactant used in the present invention is preferably 0.01% by mass or more and 1% by mass or less, and 0.01% by mass or more and 0.5% by mass or less with respect to the total amount of the composition. More preferably.

  Examples of the silicone-based surfactant used in the present invention include BYK306, BYK307 (manufactured by Big Chemie), SH7PA, SH21PA, SH28PA, SH30PA (manufactured by Toray Dow Corning Silicone), Troysol S366 (manufactured by Troy Chemical). Can be mentioned.

  The nonionic surfactant used in the present invention may be any nonionic surfactant as long as the object of the present invention is not impaired. For example, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene dialkyl esters, sorbitan fatty acid esters, fatty acid-modified polyoxyethylenes, polyoxyethylene-polyoxypropylene block copolymers, etc. Can do.

  The fluorine-containing surfactant used in the present invention may be any fluorine-containing surfactant as long as the object of the present invention is not impaired. For example, perfluorooctyl polyethylene oxide, perfluorodecyl polyethylene oxide, perfluorodecyl polyethylene oxide and the like can be mentioned.

  The acrylic surfactant used in the present invention may be any acrylic surfactant as long as the object of the present invention is not impaired. For example, a (meth) acrylic acid type copolymer etc. are mentioned.

Any adhesion promoter may be used in the composition of the present invention as long as the object of the present invention is not impaired. Examples of the adhesion promoter include 3-glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-aminopropyltrimethoxysilane. . In addition, the compounds described in paragraph No. [0048] of JP-A-2008-243945 are used. Only one type of adhesion promoter used in the present invention may be used, or two or more types may be used in combination.
Although the preferable usage-amount of an adhesion promoter is not restrict | limited in particular, Usually, it is preferable that it is 10 mass% or less with respect to the total solid in a composition, especially 0.05-5 mass%.

  The composition of the present invention is preferably used for film formation after removing insolubles, gelled components and the like by filter filtration. The pore size of the filter used at that time is preferably 0.005 to 0.5 μm, more preferably 0.005 to 0.2 μm, and most preferably 0.005 to 0.1 μm. The material of the filter is more preferably polytetrafluoroethylene, polyethylene, polypropylene, or nylon.

<Membrane manufacturing method>
The composition of the present invention can be used for various applications as described above. For example, as its use, it can be used for producing a film (preferably an insulating film) (hereinafter also referred to as a film-forming composition as appropriate).
The film (coating film) obtained by using the film forming composition of the present invention can be prepared by spin coating, roller coating, dip coating, scanning, spraying, bar coating, etc. After applying to a substrate such as a silicon wafer, a SiO ₂ wafer, a SiN wafer, glass, or a plastic film by any method, the solvent can be removed by heat treatment as necessary.
As a method of applying to the substrate, a spin coating method or a scanning method is preferable. Particularly preferred is the spin coating method. For spin coating, commercially available equipment can be used. For example, the clean track series (manufactured by Tokyo Electron), D-spin series (manufactured by Dainippon Screen), SS series or CS series (manufactured by Tokyo Ohka Kogyo Co., Ltd.) can be preferably used.
The spin coating conditions may be any rotational speed, but a rotational speed of about 1300 rpm is preferable for a 300 mm silicon substrate from the viewpoint of in-plane uniformity of the film. In addition, the method for discharging the composition solution may be either dynamic discharge for discharging the composition solution onto a rotating substrate or static discharge for discharging the composition solution onto a stationary substrate. From the viewpoint of performance, dynamic ejection is preferable. In addition, from the viewpoint of suppressing the consumption of the composition, it is also possible to use a method in which only the main solvent of the composition is preliminarily discharged onto the substrate to form a liquid film, and then the composition is discharged from there. it can. The spin coating time is not particularly limited, but is preferably within 180 seconds from the viewpoint of throughput. Further, from the viewpoint of transporting the substrate, it is also preferable to perform processing (edge rinse, back rinse) so as not to leave the film at the edge portion of the substrate.
The heat treatment method is not particularly limited, but generally used hot plate heating, heating method using a furnace, light irradiation heating using a xenon lamp by RTP (Rapid Thermal Processor), etc. are applied. Can do. A heating method using hot plate heating or furnace is preferable. As the hot plate, a commercially available device can be preferably used, and the clean track series (manufactured by Tokyo Electron), D-Spin series (manufactured by Dainippon Screen), SS series or CS series (manufactured by Tokyo Ohka Kogyo) and the like can be preferably used. As the furnace, α series (manufactured by Tokyo Electron) and the like can be preferably used.

  The composition of the present invention is preferably hardened after it is applied on a substrate to form a coating film. Hardened means that the composition on the substrate is cured and the film is given solvent resistance. As a method of hardening, it is particularly preferable to perform heat treatment (firing). For example, a polymerization reaction during post-heating of vinyl groups remaining in the polymer can be used. The conditions for the post-heat treatment are preferably 100 to 600 ° C., more preferably 200 to 500 ° C., particularly preferably 200 ° C. to 450 ° C., preferably 1 minute to 3 hours, more preferably 1 minute to 2 hours, Especially preferably, it is the range of 1 minute-1 hour. The post-heating treatment may be performed in several times. Further, this post-heating is particularly preferably performed in a nitrogen atmosphere in order to prevent thermal oxidation by oxygen.

Further, in the present invention, not by heat treatment but by irradiating with high energy rays such as light irradiation and radiation irradiation, for example, a vinyl group or ethynyl group remaining in the polymer may be polymerized to cause hardening. Good. Examples of high energy rays include electron beams, ultraviolet rays, and X-rays, but are not particularly limited to these methods.
The energy when an electron beam is used as the high energy beam is preferably 0.1 to 50 keV, more preferably 0.2 to 30 keV, and particularly preferably 0.5 to 20 keV. The total dose of the electron beam is preferably 0.01 to 5 μC / cm ² , more preferably 0.01 to ² μC / cm ² , and particularly preferably 0.01 to 1 μC / cm ² . The substrate temperature at the time of irradiation with an electron beam is preferably 0 to 500 ° C, more preferably 20 to 450 ° C, and particularly preferably 20 to 400 ° C. The pressure is preferably 0 to 133 kPa, more preferably 0 to 60 kPa, and particularly preferably 0 to 20 kPa.
From the viewpoint of preventing oxidation of the polymer of the present invention, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, a gas such as oxygen, hydrocarbon, or ammonia may be added for the purpose of reaction with plasma, electromagnetic waves, or chemical species generated by interaction with an electron beam. The electron beam irradiation may be performed a plurality of times. In this case, the electron beam irradiation conditions need not be the same each time, and may be performed under different conditions each time.

Ultraviolet rays may be used as the high energy rays. The irradiation wavelength region when ultraviolet rays are used is preferably 160 to 400 nm, and the output is preferably 0.1 to 2000 mWcm ⁻² immediately above the substrate. The substrate temperature at the time of ultraviolet irradiation is preferably 250 to 450 ° C., more preferably 250 to 400 ° C., and particularly preferably 250 to 350 ° C. From the viewpoint of preventing oxidation of the polymer of the present invention, the atmosphere around the substrate is preferably an inert atmosphere such as Ar, He, or nitrogen. Further, the pressure at that time is preferably 0 to 133 kPa.

  The film may be hardened by performing heat treatment and high energy ray treatment irradiation such as light irradiation and radiation irradiation simultaneously or sequentially.

The film thickness when forming the film may be a dry film thickness of about 0.05 to 1.5 μm by one coating, and a coating film of about 0.1 to 3 μm by two coatings. it can.
Since the cage structure does not decompose during firing, it is preferred that groups (hydroxyl groups, silanol groups, etc.) that nucleophilically attack Si atoms during the production of the composition and film are substantially absent.

  More specifically, the film-forming composition of the present invention is applied onto a substrate (usually a substrate having metal wiring) by, for example, spin coating, preliminarily heat-treated to dry the solvent, and then 300 An insulating film having a low dielectric constant can be formed by performing a final heat treatment (annealing) at a temperature of 430 ° C. to 430 ° C.

<Membrane>
The thickness of the film (porous film) obtained from the film-forming composition described above is not particularly limited, but is preferably 0.005 to 10 μm, preferably 0.01 to 5 μm from the viewpoint of application to an insulating film or the like. 0 μm is more preferable, and 0.01 to 1.0 μm is more preferable.
Here, the thickness of the film of the present invention means a simple average value when three or more arbitrary positions are measured with an optical interference type film thickness measuring instrument.

  The relative dielectric constant of the film obtained by the above-described method of the present invention varies depending on the material used. From a practical viewpoint, the relative dielectric constant is 2.5 or less, preferably 2.4 or less at a measurement temperature of 25 ° C. That is, it is preferably 1.8 to 2.4.

  The film of the present invention has a small film thickness reduction (hereinafter also referred to as film reduction) at the time of the above hardening, and is preferably 0 to 15%, and preferably 0 to 10% from a practical viewpoint. More preferred. Note that 0% means that the film thickness does not decrease.

<Application>
The film of the present invention can be used for various purposes, and can be suitably used for an electronic device, particularly as an insulating film. An electronic device means a wide range of electronic equipment including a semiconductor device and a magnetic recording head. For example, it is suitable as an insulating film in semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, and electronic parts such as multichip module multilayer wiring boards, semiconductor interlayer insulating film, etching stopper film, surface In addition to protective films and buffer coat films, it is used as LSI passivation films, alpha ray blocking films, flexographic printing plate cover lay films, overcoat films, flexible copper-clad cover coats, solder resist films, liquid crystal alignment films, etc. be able to. It can also be used as a surface protective film, an antireflection film, or a retardation film for optical devices.

  EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited by these examples.

In the following GPC measurement, Waters 2695 and Shodex GPC column KF-805L (3 columns directly connected) were used. As shown below, tetrahydrofuran was flowed at a flow rate of 1 ml per minute, and the sample peak was detected by an RI detector (Waters 2414) and a UV detector (Waters 2996). M _w , M _n and M _{z + 1} were calculated using a calibration curve prepared using standard polystyrene.

  Compounds having a conjugated diene structure (dienes C-1 to C-11) were synthesized according to the method described in the following synthesis examples. Diene C-7 (1,2,3,4,5-pentaphenyl-1,3-cyclopentadiene) and diene C-9 (tetraphenylcyclopentadienone) were made by using a reagent made by Tokyo Chemical Industry.

<Synthesis of Diene C-1>
A three-necked flask equipped with a condenser tube was purged with nitrogen, 43.4 mL of phenylmagnesium bromide (1M, THF solution) was added, and 5 g of 2,3,4,5-tetramethyl-2-cyclopentenone was added to room temperature. For 3 minutes. Thereafter, the mixture was heated to reflux for 2 hours and cooled to room temperature. Ice was added thereto, 15 mL of concentrated hydrochloric acid was added with stirring, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was extracted with cyclopentyl methyl ether, the organic layer was washed twice with water and once with brine, dried over sodium sulfate, and the solution was concentrated under reduced pressure. The obtained crude product was dissolved in a small amount of hexane and packed in silica gel chromatography, and column purification was performed using hexane as an eluent. The solvent of the obtained solution was distilled off under reduced pressure to obtain 6.6 g of a liquid target product (diene C-1) (yield: 92%). As a result of thermogravimetric analysis (nitrogen flow rate 100 ml / min, heating rate 20 ° C./min), the 5% weight loss temperature was 234 ° C. The results of ¹ H-NMR measurement were as follows.
¹ H-NMR (300 MHz, CDCl ₃ ): 0.95 (d, 3H), 1.87 (s, 3H), 1.93 (s, 3H), 2.03 (s, 3H), 3.19 (m, 1H), 7.16-7.37 (m, 5H)

<Synthesis of Diene C-2>
Pentafluorophenyl magnesium bromide was synthesized according to the method described in the literature (Tetrahedron Lett., Vol. 40, 7449-7454 (1999)). Diene C-2 was obtained in the same manner as diene C-1, except that pentafluorophenyl magnesium bromide was used instead of phenyl magnesium bromide in the synthesis of diene C-1.

<Synthesis of Diene C-5>
To a 500 mL three-necked flask equipped with a condenser, 5 g of 1-adamantane ethanol, 18.4 g of carbon tetrabromide, and 220 mL of acetonitrile were added and heated to reflux. To this, 21.8 g of triphenylphosphine dissolved in 200 mL of acetonitrile was added dropwise over 10 minutes. Thereafter, the mixture was heated to reflux for 3 hours and cooled to room temperature. The reaction solution was concentrated under reduced pressure, and the resulting crude product was dissolved in a small amount of ethyl acetate and packed in silica gel chromatography, and column purification was performed using hexane as an eluent. The solvent of the obtained solution was distilled off under reduced pressure to obtain 7.4 g of 1- (2-bromoethyl) adamantane as a white solid (yield: 97%).
After putting 0.81 g of magnesium pieces into a three-necked flask equipped with a condenser and replacing with nitrogen, 7.4 g of 1- (2-bromoethyl) adamantane dissolved in 30 mL of tetrahydrofuran was added dropwise over 15 minutes. Thereafter, the mixture was heated to reflux for 30 minutes to obtain a THF solution of 2- (1-adamantyl) ethylmagnesium bromide.
A three-necked flask equipped with a condenser tube was purged with nitrogen, and the whole amount of 2- (1-adamantyl) ethylmagnesium bromide in THF obtained above was added, and 2,3,4,5-tetramethyl-2 was added thereto. -3.83 g of cyclopentenone was added dropwise at room temperature over 3 minutes. Thereafter, the mixture was heated to reflux for 2 hours and cooled to room temperature. Ice was added thereto, 15 mL of concentrated hydrochloric acid was added with stirring, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was extracted with cyclopentyl methyl ether, the organic layer was washed twice with water and once with brine, dried over sodium sulfate, and the solution was concentrated under reduced pressure. The obtained crude product was dissolved in a small amount of hexane and packed in silica gel chromatography, and column purification was performed using hexane as an eluent. The solvent of the obtained solution was distilled off under reduced pressure to obtain 5.8 g of the target product (diene C-5) as a white solid (yield: 74%). As a result of thermogravimetric analysis (nitrogen flow rate 100 ml / min, heating rate 20 ° C./min), the 5% weight loss temperature was 264 ° C. The results of ¹ H-NMR measurement were as follows.
¹ H-NMR (300 MHz, CDCl ₃ ): 1.41-1.81 (m, 28H), 1.93 (br s, 3H), 2.61 (m, 1H)

<Synthesis of Diene C-4>
1-adamantane methylmagnesium bromide was synthesized according to the method described in the literature (J. Chem. Soc. Dalton Trans., 1879-1887 (1980)). Diene C-5 was synthesized in the same manner as diene C-5 except that 1-adamantanemethyl magnesium bromide was used instead of 2- (1-adamantyl) ethyl magnesium bromide in the synthesis of diene C-5. Got.

<Synthesis of Diene C-6>
After adding 20.3 g of zirconocene dichloride to the three-necked flask and replacing with nitrogen, 700 mL of toluene was added and cooled to -78 ° C. To this, 87 mL of n-butyllithium (1.6 M, hexane solution) was added dropwise over 1 hour. During the addition, the reaction solution gradually became yellow. After stirring at −78 ° C. for 10 minutes, 27.1 g of 7-tetradecine was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at room temperature for 2 hours. The reaction solution gradually changed from yellow to reddish brown. 1-Heptanal (15.9 g) and aluminum (III) chloride (18.6 g) were added at room temperature, and the mixture was further stirred at room temperature for 1 hour. After cooling the reaction solution to 0 ° C., 100 mL of 3N hydrochloric acid was added to stop the reaction. The resulting reaction solution was extracted with ethyl acetate, the organic layer was washed twice with water and once with brine, dried over sodium sulfate, and the solution was concentrated under reduced pressure. The obtained crude product was dissolved in a small amount of hexane and packed in silica gel chromatography, and column purification was performed using hexane as an eluent. The solvent of the obtained solution was distilled off under reduced pressure to obtain 20.3 g of the target product (diene C-6) as a white solid (yield: 60%). The results of ¹ H-NMR measurement were as follows. ¹ H-NMR (300 MHz, CDCl ₃ ): 0.68-1.01 (m, 15H), 1.13-1.65 (m, 40H), 1.92-2.57 (m, 11H)

<Synthesis of Diene C-3>
1-adamantanecarbaldehyde was synthesized according to the method described in the literature (J. Med. Chem., Vol. 48, 5025-5037 (2005)). In the synthesis of diene C-6, the reaction was carried out in the same manner as the synthesis of diene C-6, except that 2-butyne was used instead of 7-tetradecine and 1-adamantanecarbaldehyde was used instead of 1-heptanal. C-3 was obtained.

<Synthesis of Diene C-8>
After adding 328 g of benzyl alcohol to a 1 L three-necked flask equipped with a condenser and a Dean Stark and purging with nitrogen, 25 g of a sodium piece was added over 1 hour while taking care to keep the internal temperature at 120 ° C. or lower. To this, 200 mL of tetralin was added, and 7 g of dicyclopentadiene dissolved in 50 mL of tetralin was further added. The mixture was heated to reflux for 24 hours and then cooled to room temperature. Dean Stark traps water (about 8 mL) generated in the reaction system. The reaction solution was washed with 600 mL of water, extracted three times with toluene, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained crude product was dissolved in 2 L of heated methanol and left overnight at room temperature. Furthermore, it left still at -30 degreeC for 6 hours, and 17.3g of target objects (diene C-8) of white solid was obtained by filtering the precipitated crystal | crystallization (yield: 36%). The results of ¹ H-NMR measurement were as follows.
¹ H-NMR (300 MHz, CDCl ₃ ): 3.07 (s, 2H), 3.19-3.22 (m, 1H), 3.43 (d, 2H), 3.48 (d, 2H), 3.56 (d, 2H), 3.84 (d, 2H), 6.70-6.73 (m, 4H), 7.02-7.28 (m, 21H)

<Synthesis of Diene C-10>
Diene C-10 was synthesized according to the method described in the literature (Org. Lett., Vol. 8, 2945-2947 (2006)).

<Synthesis of Diene C-11>
Diene C-11 was synthesized according to the method described in the literature (J. Mater. Chem., Vol. 11, 2974-2978 (2001)).

Hereinafter, a method for synthesizing a compound (compound (I)) having a cage structure composed of ₃ units of m RSi (O _0.5 ) will be described in detail.

<Synthesis of Compound Im>
A mixed solution of 67 g of electronic grade concentrated hydrochloric acid, 305 g of n-butanol and 133 g of ion-exchanged water was cooled to 10 ° C., and 59 g of vinyltriethoxysilane was added dropwise thereto over 15 minutes. Thereafter, the mixture was further stirred at 25 ° C for 18 hours. The precipitated crystals were collected by filtration and washed with 50 g of electronic grade methanol. This was dissolved in 42 g of tetrahydrofuran, and 42 g of electronic grade methanol and then 127 g of ion-exchanged water were added dropwise with stirring. The precipitated crystals were collected by filtration and dried to obtain 4.2 g of the desired product (Compound Im) as a white solid. The results of ¹ H-NMR measurement were as follows. ¹ H-NMR (300 MHz, CDCl3): 6.13-5.88 (m, 24H)

<Synthesis of Compound I-k>
A mixed solution of 136 g of electronic grade concentrated hydrochloric acid, 1 L of n-butanol and 395 g of ion-exchanged water was cooled to 10 ° C., and a mixed solution of 78.3 g of vinyltriethoxysilane and 73.3 g of methyltriethoxysilane was added to this over 15 minutes. It was dripped. Thereafter, the mixture was further stirred at 25 ° C for 18 hours. The precipitated crystals were collected by filtration and washed with 100 mL of electronic grade methanol. This was dissolved in 500 mL of tetrahydrofuran, and 200 mL of electronic grade methanol and then 200 mL of ion-exchanged water were added dropwise with stirring. The precipitated crystals were collected by filtration and dried to obtain 7.8 g of the desired product (Compound Ik) as a white solid. The results of ¹ H-NMR measurement were as follows. ¹ H-NMR (300 MHz, CDCl3): 0.28-0.18 (m, 12H), 6.08-5.88 (m, 12H)

  With reference to the said manufacture example, the compound Ia, the compound Ij, and the compound Ir were synthesize | combined. In addition, each compound corresponds to the compound described as an exemplary compound of said compound (I).

<Synthesis of Resin A-1>
50 g of compound (Im) was added to 1320 g of electronic grade butyl acetate. The obtained solution was heated to 120 ° C. in a nitrogen stream, and 0.47 g of V-601 (10-hour half-temperature 66 ° C.) manufactured by Wako Pure Chemical Industries, Ltd. and 2,6-bis (1,1-dimethyl) as a polymerization initiator. 50.4 ml of a solution prepared by dissolving 113 mg of ethyl) -4-methylphenol in 235 ml of electronic grade butyl acetate was added dropwise over 80 minutes. After completion of dropping, the mixture was further stirred at 120 ° C. for 1 hour. After the completion of stirring, 3 L of electronic grade methanol and 3 L of ion exchange water were added to the reaction solution, and the precipitated solid was collected by filtration and washed with 100 mL of electronic grade methanol. This was dissolved in 724 g of tetrahydrofuran, and 50 g of electronic grade methanol and then 150 g of water were added dropwise with stirring. After stirring for 1 hour, the supernatant was discarded by decantation, and 200 g of electronic grade methanol was added. The precipitated solid was collected by filtration and dried to obtain 17.7 g of the desired product (resin A-1) as a white solid.
When the obtained resin was analyzed by GPC, it was _Mw = 8.7 * 10 < ⁴ _> , _Mn = 5.4 * 10 < ⁴ _> . In the solid, the unreacted compound (Im) was 2% by mass or less, and no component having a molecular weight of 3 million or more was observed. When ¹ H-NMR spectrum was measured using deuterated chloroform as a measurement solvent, an alkyl group-derived proton peak (0.2 to 3.0 ppm) generated by polymerization of the vinyl group and a residual vinyl group proton peak ( 4.9-6.8 ppm) was observed at an integration ratio of 2.6 / 5.4.

<Synthesis of Resin A-2>
109 g of compound (Im) was added to 2878 g of diphenyl ether. The obtained solution was heated to 120 ° C. in a nitrogen stream, and 15.0 ml of a solution obtained by dissolving 168 mg of V-601 (10 hours half-temperature 66 ° C.) manufactured by Wako Pure Chemical Industries, Ltd. in 74 g of diphenyl ether as a polymerization initiator for 30 minutes. It was dripped over. After completion of dropping, the mixture was further stirred at 120 ° C. for 1 hour. After completion of the stirring, 5.4 L of electronic grade methanol and 200 mL of water were added to the reaction solution, and the precipitated solid was collected by filtration and washed with 200 mL of electronic grade methanol. This was dissolved in 1 L of tetrahydrofuran, 2 L of electronic grade methanol and then 125 g of ion-exchanged water were added with stirring, and the precipitated solid was collected by filtration and washed with 200 mL of electronic grade methanol. This operation was repeated twice in total and dried to obtain 7.26 g of a white solid target product (Resin A-2).
When the obtained resin was analyzed by GPC, it was _Mw = 8.1 * 10 < ⁴ _> , _Mn = 4.98 * 10 < ⁴ _> . In the solid, the unreacted compound (Im) was 0.2% by mass or less, and no component having a molecular weight of 3 million or more was observed. When ¹ H-NMR spectrum was measured using deuterated chloroform as a measurement solvent, an alkyl group-derived proton peak (0.2 to 3.0 ppm) generated by polymerization of the vinyl group and a residual vinyl group proton peak ( 4.9-6.8 ppm) was observed at an integration ratio of 2.2 / 5.8.

<Synthesis of Resin A-3>
30 g of compound (Im) was added to 792 g of diphenyl ether. The resulting solution was heated to 150 ° C. in a nitrogen stream, and 112 mg of VR-110 (Azodi-tert-octane, 10 hour half-temperature 110 ° C.) manufactured by Wako Pure Chemical Industries, Ltd. as a polymerization initiator and 2,6-bis (1 , 1-dimethylethyl) -4-methylphenol 22 ml of a solution obtained by dissolving 22 mg of diphenyl ether in 49.8 g was added dropwise over 30 minutes. After completion of dropping, the mixture was further stirred at 150 ° C. for 1 hour. After completion of the stirring, 3.5 L of electronic grade methanol and 150 mL of ion exchange water were added to the reaction solution, and the precipitated solid was collected by filtration and washed with 200 mL of electronic grade methanol. This was dissolved in 300 mL of tetrahydrofuran, 30 mL of electronic grade methanol and then 60 mL of ion-exchanged water were added with stirring, and the precipitated solid was collected by filtration and washed with 100 mL of electronic grade methanol. This operation was repeated twice in total and dried to obtain 12.5 g of a white solid target product (Resin A-3).
When the obtained resin was analyzed by GPC, it was _Mw = 18.3 * 10 < ⁴ _{> and Mn} = 5.58 * 10 < ⁴ _> . In the solid, the unreacted compound (Im) was 2% by mass or less, and no component having a molecular weight of 3 million or more was observed. When ¹ H-NMR spectrum was measured using deuterated chloroform as a measurement solvent, an alkyl group-derived proton peak (0.2 to 3.0 ppm) generated by polymerization of the vinyl group and a residual vinyl group proton peak ( 4.9-6.8 ppm) was observed with an integral ratio of 1.3 / 6.7.

<Synthesis of Resin A-4>
1 g of compound (Im) was added to 26.4 g of electronic grade butyl acetate. While heating and refluxing the resulting solution at an internal temperature of 127 ° C. in a nitrogen stream, 1.8 mg of V-601 (10-hour half-temperature 66 ° C.) as a polymerization initiator was dissolved in 2 ml of electronic grade butyl acetate. The solution was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further heated to reflux for 1 hour. After adding 20 mg of 4-methoxyphenol as a polymerization inhibitor, the mixture was cooled to room temperature. Thereafter, the solution was concentrated under reduced pressure to 2 g, 20 ml of electronic grade methanol was added and stirred for 1 hour, and then the solid was collected by filtration and dried. This was dissolved in 15 ml of tetrahydrofuran, and 5 ml of ion-exchanged water was added dropwise with stirring. After stirring for 1 hour, the supernatant was discarded by decantation and 10 ml of electronic grade methanol was added. The solid content was collected by filtration and dried to obtain 0.60 g of the desired product (resin A-4) as a white solid.
When the resulting resin is analyzed by _{GPC, and} was _{^{M w = 11.8 × 10 4,}} M n = 3.1 × 10 4, M z + 1 = 27 × 10 4. In the solid, the unreacted compound (Im) was 3% by mass or less, and no component having a molecular weight of 3 million or more was observed. When ¹ H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, the proton peak (0.2 to 3.0 ppm) derived from the alkyl group produced by polymerization of the vinyl group and the remaining vinyl group A proton peak (4.9-6.8 ppm) was observed with an integral ratio of 42/58.

<Synthesis of Resin A-5>
1 g of compound (Im) was added to 13.2 g of electronic grade butyl acetate. While heating and refluxing the obtained solution at an internal temperature of 127 ° C. in a nitrogen stream, 1 mg of W-40 (manufactured by Wako Pure Chemical Industries, Ltd.) V-40 (10 hours half temperature 88 ° C.) was dissolved in 1 ml of electronic grade butyl acetate. The solution was added dropwise over 4 hours. After completion of dropping, the mixture was heated to reflux for 1 hour. After adding 20 mg of 4-methoxyphenol as a polymerization inhibitor, the mixture was cooled to room temperature. Thereafter, the solution was concentrated under reduced pressure to 2 g of the liquid, 20 ml of electronic grade methanol was added and stirred for 1 hour, and then the solid was collected by filtration and dried. This was dissolved in 10 ml of tetrahydrofuran, and 1.8 ml of ion-exchanged water was added dropwise with stirring. After stirring for 1 hour, the supernatant was discarded by decantation and 10 ml of electronic grade methanol was added. The solid content was collected by filtration and dried to obtain 0.41 g of the desired product (resin A-5) as a white solid.
When the resulting resin is analyzed by _{GPC, and} was _{^{M w = 12.8 × 10 4,}} M n = 3.3 × 10 4, M z + 1 = 38 × 10 4. In the solid, the unreacted exemplary compound (Im) was 3% by mass or less, and no component having a molecular weight of 3 million or more was observed. When ¹ H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, the proton peak (0.2 to 3.0 ppm) derived from the alkyl group produced by polymerization of the vinyl group and the remaining vinyl group A proton peak (4.9-6.8 ppm) was observed at an integration ratio of 53:47.

  With reference to said manufacture example, resin A-6-resin A-11 were synthesize | combined. Table 1 shows the type and composition of the compound (I) used in the synthesis of each resin, and the weight average molecular weight and number average molecular weight.

<Synthesis of Resin H-1>
According to the method described in JP-A No. 2007-161788, a 1,3-diethynyladamantane polymer (G-1) was synthesized. When the obtained polymer was analyzed by GPC, it was _Mw = 1.37 * 10 < ⁴ _> , _Mn = 0.39 * 10 < ⁴ _> .
12.9 g of the polymer (G-1) was dissolved in 30 mL of toluene, and 175 mL of DIBAL-H (1M, hexane solution) was added while the toluene solution was cooled to 0 ° C. Thereafter, the mixture was stirred at room temperature for 3 hours. Next, 230 mL of a saturated aqueous solution of ammonium chloride was cooled, the reaction solution was added thereto and filtered, and then the filtrate was extracted with ethyl acetate. After drying the organic layer with sodium sulfate, the solution was concentrated under reduced pressure. The obtained crude product was dissolved in a small amount of tetrahydrofuran, the solution was added to 300 mL of methanol, and the precipitated solid was collected by filtration and dried to obtain 10.3 g of the desired product (resin H-1) as a white solid. When the obtained resin was analyzed by GPC, it was _Mw = 1.35 * 10 < ⁴ _> , _Mn = 0.39 * 10 < ⁴ _> .

<Synthesis of Resin H-2>
According to the method described in JP-A-2007-161786, a polymer (G-2) of 4,9-diethynyldiamantane was synthesized. When the obtained polymer was analyzed by GPC, it was _Mw = 1.66 * 10 < ⁴ _> , _Mn = 0.54 * 10 < ⁴ _> .
Resin (H-1) was synthesized in the same manner as the synthesis of resin (H-1) except that polymer (G-2) was used instead of polymer (G-1). H-2) was obtained. When the obtained resin was analyzed by GPC, it was _Mw = 1.65 * 10 < ⁴ _> , _Mn = 0.51 * 10 < ⁴ _> .

<Synthesis of Resin H-3>
A polyarylene ether having a vinyl group (resin H-3) was synthesized according to the method described in JP-T-2003-520864.

<Synthesis of Compound H-4>
In the method for synthesizing tetrakis (tranyl) adamantane described in JP-T-2004-504455, compound (G-4) is synthesized using a mixture (equimolar amount) of phenylacetylene and (trimethylsilyl) acetylene instead of phenylacetylene. did. Next, according to the method described in JP-A-2007-314778, the (trimethylsilyl) ethynyl group was converted to a vinyl group to obtain a compound (H-4).

(R ¹ is a mixture of a phenyl group and a trimethylsilyl group, and R ² is a mixture of a phenylethynyl group and a vinyl group.)

<Synthesis of Resin H-5>
Polybenzoxazole (resin H-5) having a vinyl group was synthesized according to the method described in International Publication No. 2005-019305 pamphlet.

<Synthesis of Resin X-1>
Resin (A-1) 800 mg, 2,6-bis (1,1-dimethylethyl) -4-methylphenol 278 mg, and diene (C-1) 1.16 g were added to diphenyl ether 5 g. The resulting solution was heated to 180 ° C. in a nitrogen stream and stirred for 3 hours. After completion of the stirring, the reaction solution was added to 200 ml of electronic grade methanol, and the precipitated solid was collected by filtration and dried, and the target product (resin X-) having a Diels-Alder reaction addition portion represented by the general formula (F-2) 1) 1.10 g was obtained.
When the obtained resin was analyzed by GPC, it was _Mw = 9.29 * 10 < ⁴ _> , _Mn = 5.70 * 10 < ⁴ _> . In the solid material, unreacted diene (C-1) and components having a molecular weight of 3 million or more were not observed. When a ¹ H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, an alkyl group formed by polymerization of a vinyl group and a proton peak derived from an alkyl group formed by Diels-Alder reaction (0.2 to 3.0 ppm), a proton peak derived from the remaining vinyl group (4.9 to 6.5 ppm), and a proton peak derived from the phenyl group (6.5 to 7.8 ppm) at an integration ratio of 62:18:20. Observed. As a result of thermogravimetric analysis (using TA Instruments SDT Q600, increasing the nitrogen flow rate at 100 ml / min, 20 ° C / min), a weight loss of 33% was observed at 350 ° C. The added amount (mass%) of C-1) was confirmed.

<Synthesis of Resin X-3>
Resin (A-1) 800 mg, 4-methoxyphenol 157 mg, and diene (C-8) 3.03 g were added to diphenyl ether 5 g. The resulting solution was heated to 180 ° C. in a nitrogen stream and stirred for 3 hours. After completion of the stirring, the reaction solution was added to 200 ml of electronic grade methanol, and the precipitated solid was collected by filtration and dried, and the target product (resin X-) having a Diels-Alder reaction addition portion represented by the general formula (F-2) 3) 0.91 g was obtained.
When the obtained resin was analyzed by GPC, M _w = 10.1 × 10 ⁴ and M _n = 5.96 × 10 ⁴ . Unreacted diene (C-8) and components having a molecular weight of 3 million or more were not observed in the solid. When a ¹ H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, an alkyl group formed by polymerization of a vinyl group and a proton peak derived from an alkyl group formed by Diels-Alder reaction (0.2 to 3.0 ppm), a proton peak derived from the remaining vinyl group (4.9 to 6.5 ppm), and a proton peak derived from the phenyl group (6.5 to 7.8 ppm) at an integration ratio of 30:26:44. Observed. As a result of thermogravimetric analysis (TA Instruments SDT Q600, nitrogen flow rate 100 ml / min, temperature rise at 20 ° C / min), a 16% weight loss was observed at 320 ° C. The added amount (mass%) of C-8) was confirmed.

<Synthesis of Resin X-5>
Resin (A-2) 800 mg, 2,5-di-t-butylhydroquinone 281 mg, and diene (C-5) 1.67 g were added to diphenyl ether 5 g. The resulting solution was heated to 180 ° C. in a nitrogen stream and stirred for 3 hours. After completion of the stirring, the reaction solution was added to 200 ml of electronic grade methanol, and the precipitated solid was collected by filtration and dried, and the target product (resin X-) having a Diels-Alder reaction addition portion represented by the general formula (F-2) 5) 1.24 g was obtained.
When the obtained resin was analyzed by GPC, it was _Mw = 8.74 * 10 < ⁴ _> , _Mn = 5.21 * 10 < ⁴ _> . Unreacted diene (C-5) and components having a molecular weight of 3 million or more were not observed in the solid. When a ¹ H-NMR spectrum of solid content was measured using deuterated chloroform as a measurement solvent, an alkyl group formed by polymerization of a vinyl group and a proton peak derived from an alkyl group formed by Diels-Alder reaction (0.2 to 3.0 ppm) and a proton peak derived from the remaining vinyl group (4.9 to 6.8 ppm) were observed at an integration ratio of 83:17. As a result of thermogravimetric analysis (using TA Instruments SDT Q600, increasing the nitrogen flow rate at 100 ml / min, 20 ° C / min), a 39% weight loss was observed at 345 ° C, and diene in resin X-5 ( The added amount (mass%) of C-5) was confirmed.

With reference to said manufacture example, resin X-2, resin X-4, resin X-6-resin X-29 were synthesize | combined. Tables 1 and 2 show the types of resin A, resin H, and diene compound used for the synthesis of each resin, and the weight average molecular weight and number average molecular weight.
In addition, the addition amount of diene B in Table 1 and Table 2 is the mass% (wt%) of diene B in resin X.

<Preparation of composition>
The resin obtained above was dissolved in a solvent as shown in Table 3 below, and a solution having a solid content of 10% by mass was prepared for each. The obtained solution was filtered through a 0.1 μm tetrafluoroethylene filter, and then applied onto a 4 inch silicon wafer by spin coating, and then on a hot plate at 110 ° C. for 1 minute, then at 200 ° C. for 1 minute. The substrate was preliminarily dried to form a coating film having a thickness of 600 nm.

The obtained coating film was cured by any of the following methods.
(1) Heating It was heated at 400 ° C. for 60 minutes in a clean oven under a nitrogen atmosphere by a clean oven CLH-21CD (III) manufactured by Koyo Thermo.
(2) EB irradiation An electron acceleration voltage of 20 keV and an electron beam dose of 1 μCcm ⁻² were irradiated for 5 minutes under the conditions of Ar atmosphere, pressure of 100 kPa, and substrate temperature of 350 ° C. using Mini-EB manufactured by USHIO.
(3) UV irradiation Using a dielectric barrier discharge excimer lamp UER20-172 manufactured by Ushio Electric Co., Ltd., a 172 nm wavelength light of 100 mJ / cm ² was irradiated for 5 minutes on a 350 ° C. hot plate under a nitrogen stream.

The obtained cured film was evaluated by the following method. The results are shown in Table 3.
In Table 3, the content of the surfactant represents mass% with respect to the total amount of the composition (coating liquid). On the other hand, the content of the adhesion promoter is represented by mass% with respect to the total solids in the composition (coating liquid).

<Relative permittivity>
Using a mercury probe manufactured by Four Dimensions and an HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard, the capacity value at 1 MHz (measurement temperature: 25 ° C.) was used for calculation.
<Film reduction rate during dura>
It calculated from the film thickness after preliminary drying and the film thickness after hardening by heating, EB irradiation, or UV irradiation.

From the results shown in Table 3, when the film-forming composition of the present invention is used, the relative dielectric constant is low and the film shrinkage rate at the time of hardening is small by various curing methods such as heating, EB irradiation, and UV irradiation. It was confirmed that a film was obtained.
On the other hand, the film obtained in Comparative Examples 1 and 2 that does not release the diene compound during the curing treatment has a high relative dielectric constant, and the film obtained in Comparative Example 3 that releases cyclopentadiene during the hardening treatment is The film contraction rate of was large. Moreover, also in Comparative Example 4 using t-butylcyclopentanediene having a substituent having 4 carbon atoms, the film shrinkage rate during hardening was large.

<Young's modulus>
The Young's modulus of Examples 1-2 and Comparative Examples 1-2 was measured using MTS nanoindenter SA2. Example 1 was 5.6 GPa, Example 2 was 5.3 GPa, Comparative Example 1 was 3.1 GPa, and Comparative Example 2 was 2.9 GPa. It has been found that films obtained using the compounds of the present invention exhibit better mechanical strength.

Claims (8)

Formed by Diels-Alder reaction between a compound (A) having a dienophile structure and a compound (B) having a conjugated diene structure represented by any one of the following general formulas (B-1) to (B-3) A compound that releases the compound (B) having the conjugated diene structure through reverse Diels-Alder reaction by heating, light irradiation, radiation irradiation, or a combination thereof , wherein the compound (A) having the dienophile structure is The compound which is a polymer of the compound represented by either of the following general formula (Q-1)-(Q-7) .

(In the general formula (B-1), W represents —O—, —S—, —C (O) —, —C (O) O—, —S (O) —, —S (O) ₂ —, ^{-C (X 17) (X 18} ) - or ^{-N (X 19) - .X 1} ~X 6 and X ¹⁷ to X ¹⁹ represents a each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl A group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a silicon atom-containing group, an adamantyl group, a diamantyl group, a triamantyl group, or a combination thereof , where W represents —O—, —S—, —. In the case of C (O) —, —C (O) O—, —S (O) — or —S (O) ₂ —, at least one of X ^{1 to} X ⁶ is an aromatic hydrocarbon having 6 or more carbon atoms. Group, a chain or cyclic aliphatic hydrocarbon group having 5 or more carbon atoms, an adamantyl group, a diamantyl group, or a triamantyl group , wherein W represents —C (X ¹⁷ ) (X ¹⁸ ) —, at least one of X ^{1 to} X ⁶ , X ¹⁷ and X ¹⁸ is an aromatic hydrocarbon group having 6 or more carbon atoms, a chain or cyclic aliphatic hydrocarbon having 5 or more carbon atoms Represents a group, an adamantyl group, a diamantyl group, or a triamantyl group, and when W is —N (X ¹⁹ ) —, at least one of X ^{1 to} X ⁶ and X ¹⁹ is an aromatic hydrocarbon having 6 or more carbon atoms. Group, a chain or cyclic aliphatic hydrocarbon group having 5 or more carbon atoms, an adamantyl group, a diamantyl group, or a triamantyl group .
In general formula (B-2), W represents —O—, —S—, —C (O) —, —C (O) O—, —S (O) —, —S (O) ₂ —, —. C (X ¹⁷ ) (X ¹⁸ ) — or —N (X ¹⁹ ) — is represented. X ^{7 to} X ¹⁰ and X ^{17 to} X ¹⁹ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, silicon atom-containing group, adamantyl group, It represents a diamantyl group, a triamantyl group, or a group obtained by combining them . When W is —O—, —S—, —C (O) —, —C (O) O—, —S (O) — or —S (O) ₂ —, X ^{7 to} X ¹⁰ Among them, at least one represents an aromatic hydrocarbon group having 6 or more carbon atoms, a chain or cyclic aliphatic hydrocarbon group having 5 or more carbon atoms, an adamantyl group, a diamantyl group, or a triamantyl group . When W is —C (X ¹⁷ ) (X ¹⁸ ) —, at least one of X ^{7 to} X ¹⁰ , X ¹⁷ and X ¹⁸ is an aromatic hydrocarbon group having 6 or more carbon atoms or a chain having 5 or more carbon atoms Represents a cyclic or cyclic aliphatic hydrocarbon group, an adamantyl group, a diamantyl group, or a triamantyl group . When W is —N (X ¹⁹ ) —, at least one of X ^{7 to} X ¹⁰ and X ¹⁹ is an aromatic hydrocarbon group having 6 or more carbon atoms, a chain or cyclic aliphatic hydrocarbon having 5 or more carbon atoms Represents a group, an adamantyl group, a diamantyl group, or a triamantyl group .
In the general formula ^{(B-3), X 11} ~X 16 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a silicon atom-containing group, Represents an adamantyl group, a diamantyl group, a triamantyl group, or a combination thereof , at least one of which is an aromatic hydrocarbon group having 6 or more carbon atoms, a chain or cyclic aliphatic hydrocarbon group having 5 or more carbon atoms, an adamantyl group, It represents a diamantyl group or a triamantyl group .
In general formulas (Q-1) to (Q-7), each R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or a silicon atom. It represents a containing group or a combination thereof. In each of General Formula (Q-1) to General Formula (Q-7), at least one of R represents an alkenyl group or an alkynyl group. )   The compound of Claim 1 whose molecular weight of the compound (B) which has the said conjugated diene structure is the range of 150-600. A composition comprising the compound according to claim 1 or 2 . Furthermore, the composition of Claim 3 containing a solvent. The composition according to claim 3 or 4 , which is used for insulating film formation. A method for producing an insulating film, wherein the composition according to claim 3 is applied onto a substrate and then hardened. An insulating film manufactured using the manufacturing method according to claim 6 . An electronic device having the insulating film according to claim 7 .