JP2009084405A - Film forming composition, insulating film, and electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film forming composition with which a film having high heat resistance, high mechanical strength, low permittivity and excellent storage stability over time is formed, an insulating film obtained by using the film forming composition, and an electronic device having the insulating film. <P>SOLUTION: The insulating film forming composition includes a compound (A) having at least one substructure represented by general formula (1) in the molecule and a resin for the insulating film or its precursor (B), (in the formula, R<SP>1</SP>-R<SP>6</SP>respectively independently represent arbitral substituents, wherein arbitral substituents R<SP>1</SP>-R<SP>6</SP>may be connected to each other and form a ring structure, and two substituents on an identical carbon (R<SP>1</SP>and R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>, R<SP>5</SP>and R<SP>6</SP>) are united with each other so as to represent a double bond). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a composition for forming an insulating film, an insulating film obtained using the same, and an electronic device having the same.

In recent years, in the field of electronic materials, with the progress of higher integration, more functions, and higher performance, circuit resistance and capacitor capacity between wirings have increased, leading to an increase in power consumption and delay time. In particular, an increase in delay time is a major factor in reducing the signal speed of the device and the occurrence of crosstalk. Therefore, in order to reduce the delay time and speed up the device, it is necessary to reduce parasitic resistance and parasitic capacitance. It has been. As a specific measure for reducing the parasitic capacitance, an attempt has been made to cover the periphery of the wiring with a low dielectric interlayer insulating film. In addition, the interlayer insulating film is required to have excellent heat resistance that can withstand a subsequent process such as a thin film forming process, chip connection, and pinning during manufacturing of a mounting substrate, and chemical resistance that can withstand a wet process. Furthermore, in recent years, low resistance Cu wiring is being introduced from Al wiring, and along with this, planarization by CMP (Chemical Mechanical Polishing) has become common, and high mechanical strength that can withstand this process is high. It has been demanded.
As an organic polymer interlayer insulating film, polybenzoxazole, polyimide, polyarylene (ether), and the like have been disclosed for a long time (Patent Documents 1 and 2).

US Pat. No. 6,380,347 US Pat. No. 5,965,679

  However, the organic polymer-based interlayer insulating film as described above is not always satisfactory from the viewpoint of various performance requirements such as heat resistance, low dielectric property, and mechanical strength. In particular, these interlayer insulation films have the problem that the dielectric constant increases over time and the problem of heat resistance and mechanical strength reduction due to the introduction of vacancies in the film to reduce the dielectric constant. It was necessary.

  In view of the above problems, the present invention provides an insulating film forming composition capable of forming a film having high heat resistance, high mechanical strength, low dielectric constant, and good storage aging stability, It aims at providing the insulating film obtained using the composition for film formation.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by the following <1> to <8> configurations.

<1> A composition for forming an insulating film containing, in the molecule, a compound (A) having at least one partial structure represented by the general formula (1) and a resin for insulating film or a precursor thereof (B).

一般式（１）
（一般式（１）中、Ｒ^１〜Ｒ^６はそれぞれ独立に任意の置換基を表し、任意のＲ^１〜Ｒ^６がそれぞれ互いに連結していてもよく、同一炭素上の置換基（Ｒ^１とＲ^２、Ｒ^３とＲ^４、Ｒ^５とＲ^６）が２つ合わせて二重結合を表してもよい。）
＜２＞前記化合物（Ａ）が、一般式（３−１）で表される部分構造、一般式（３−２）で表される部分構造、一般式（３−３）で表される部分構造、一般式（３−４）で表される部分構造、または一般式（３−５）で表される部分構造を少なくとも一つ有する化合物である＜１＞に記載の絶縁膜形成用組成物。

General formula (1)
(In the general formula ^(1), R 1 ~R ⁶ each independently represent any substituent may be any of ^R 1 to R ⁶ are not connected to each other, a substituent on the same carbon ^{(R 1} And R ² , R ³ and R ⁴ , R ⁵ and R ⁶ ) may be combined to represent a double bond.)
<2> The compound (A) is a partial structure represented by the general formula (3-1), a partial structure represented by the general formula (3-2), and a part represented by the general formula (3-3). The composition for forming an insulating film according to <1>, which is a compound having at least one of a structure, a partial structure represented by the general formula (3-4), or a partial structure represented by the general formula (3-5) .

（一般式（３−１）中、Ｒ^７〜Ｒ^１０はそれぞれ独立に任意の置換基を表し、Ｌ^１はＣ^２とＣ^３を含む環状構造を表す。また、任意のＲ^７〜Ｒ^１０及びＬ^１がそれぞれ互いに連結して環を形成していてもよい。）

(In General Formula (3-1), R ^{7 to} R ¹⁰ each independently represents an arbitrary substituent, and L ¹ represents a cyclic structure containing C ² and C ^3. Also, arbitrary R ^{7 to} R ^10. And L ¹ may be connected to each other to form a ring.)

（一般式（３−２）中、Ｒ^１１〜Ｒ^１４はそれぞれ独立に任意の置換基を表し、Ｌ^２はＣ^１を含む環状構造を表す。また、任意のＲ^１１〜Ｒ^１４及びＬ^２がそれぞれ互いに連結して環を形成していてもよい。）

(In General Formula (3-2), R ^{11 to} R ¹⁴ each independently represents an arbitrary substituent, and L ² represents a cyclic structure containing C ^1. Also, any R ^{11 to} R ¹⁴ and L ² May be linked to each other to form a ring.)

（一般式（３−３）中、Ｒ^１５〜Ｒ^２０はそれぞれ独立に任意の置換基を表し、それぞれ互いに連結して環を形成していてもよい。）

(In the general formula (3-3), R ^{15 to} R ²⁰ each independently represents an arbitrary substituent, and may be connected to each other to form a ring.)

（一般式（３−４）中、Ｒ^２１〜Ｒ^２８はそれぞれ独立に任意の置換基を表し、それぞれ互いに連結して環を形成していてもよい。）

(In the general formula (3-4), R ^{21 to} R ²⁸ each independently represent an arbitrary substituent, and may be connected to each other to form a ring.)

（一般式（３−５）中、Ｒ^２９〜Ｒ^３４はそれぞれ独立に任意の置換基を表し、それぞれ互いに連結して環を形成していてもよい。）
＜３＞前記化合物（Ａ）が、一般式（２）で表される化合物である＜１＞また＜２＞に記載の絶縁膜形成用組成物。

(In General Formula (3-5), R ^{29 to} R ³⁴ each independently represents an arbitrary substituent, and may be connected to each other to form a ring.)
<3> The composition for forming an insulating film according to <1> or <2>, wherein the compound (A) is a compound represented by the general formula (2).

一般式（２）
（一般式（２）中、Ｘは一般式（３−１）で表される部分構造、一般式（３−２）で表される部分構造、一般式（３−３）で表される部分構造、一般式（３−４）で表される部分構造、または一般式（３−５）で表される部分構造のいずれか一つを有する基であり、Ｙは１〜１０価の脂肪族炭化水素基、１〜１０価の芳香族炭化水素基、または１〜１０価の複素環基を表す。ｎは１〜１０の整数を表す。ｎが２以上の場合、Ｘは同一であっても異なっていてもよい。）
＜４＞前記一般式（２）中のＸが、一般式（４）で表される基である＜３＞に記載の絶縁膜形成用組成物。

General formula (2)
(In the general formula (2), X is a partial structure represented by the general formula (3-1), a partial structure represented by the general formula (3-2), and a part represented by the general formula (3-3). A group having any one of a structure, a partial structure represented by the general formula (3-4), or a partial structure represented by the general formula (3-5), and Y is a 1 to 10-valent aliphatic group Represents a hydrocarbon group, a 1 to 10 valent aromatic hydrocarbon group, or a 1 to 10 valent heterocyclic group, n represents an integer of 1 to 10. When n is 2 or more, X is the same May be different.)
<4> The composition for forming an insulating film according to <3>, wherein X in the general formula (2) is a group represented by the general formula (4).

一般式（４）
（一般式（４）中、Ｚは一般式（５−１）で表される構造、一般式（５−２）で表される構造、一般式（５−３）で表される構造、一般式（５−４）で表される構造、一般式（５−５）で表される構造、一般式（５−６）で表される構造、または一般式（５−７）で表される構造のいずれか一つであり、Ｌは２〜７価の連結基、または単なる結合手を表す。ｍは１〜６の整数を表す。ｍが２以上の場合は、Ｚは同一であっても異なっていてもよい。Ｌが単なる結合手の場合、ｍと一般式（２）中のｎは同一となる。）

General formula (4)
(In general formula (4), Z is a structure represented by general formula (5-1), a structure represented by general formula (5-2), a structure represented by general formula (5-3), A structure represented by formula (5-4), a structure represented by general formula (5-5), a structure represented by general formula (5-6), or a general formula (5-7) Any one of the structures, L represents a divalent to 7-valent linking group, or a simple bond, m represents an integer of 1 to 6. When m is 2 or more, Z is the same (If L is a simple bond, m and n in the general formula (2) are the same.)

式中＊は一般式（４）のＬとの結合位置を示す。
＜５＞前記一般式（４）のＬが、アリーレン基、アルキレン基、アルケニレン基、エステル基、アミド基、およびエーテル基の群から選ばれる１つまたは２つ以上を組み合わせて構成された基である＜４＞に記載の絶縁膜形成用組成物。
＜６＞前記絶縁膜用樹脂またはその前駆体（Ｂ）が、カゴ型構造を有する化合物である＜１＞〜＜５＞のいずれかに記載の絶縁膜形成用組成物。
＜７＞＜１＞〜＜６＞のいずれかに記載の絶縁膜形成用組成物から得られる絶縁膜。
＜８＞＜７＞に記載の絶縁膜を有する電子デバイス。

In the formula, * represents a bonding position with L in the general formula (4).
<5> L in the general formula (4) is a group formed by combining one or two or more selected from the group of an arylene group, an alkylene group, an alkenylene group, an ester group, an amide group, and an ether group. The composition for forming an insulating film according to <4>.
<6> The composition for forming an insulating film according to any one of <1> to <5>, wherein the resin for an insulating film or a precursor thereof (B) is a compound having a cage structure.
<7> An insulating film obtained from the composition for forming an insulating film according to any one of <1> to <6>.
<8> An electronic device having the insulating film according to <7>.

  According to the present invention, an insulating film forming composition capable of forming a film having high heat resistance, high mechanical strength, low dielectric constant, and good storage aging stability, and the film forming composition are used. The obtained insulating film can be provided.

Next, the present invention will be described in more detail with reference to preferred embodiments.
The composition for forming an insulating film of the present invention contains a compound (A) that is a compound having a cyclopropane skeleton and a resin for insulating film or a precursor thereof (B).

<Compound (A)>
The composition for insulating film formation of this invention contains the compound (A) which has at least one partial structure represented by General formula (1) in a molecule | numerator. By adopting a compound containing a cyclopropane skeleton represented by the general formula (1) as the compound (A), among the heat resistance, mechanical strength, low dielectric constant, and dielectric constant stability of the dielectric film over time, etc. At least one performance improvement is possible. Although the detailed mechanism of the above effect is unknown, it is presumed that the reactive cyclopropane skeleton reacts with the film components in the insulating film to increase the crosslink density in the film and to increase the hydrophobicity of the film. The compound having a cyclopropane skeleton is highly reactive and can be reacted at a relatively low temperature of usually 200 ° C. or higher, preferably 250 ° C. or higher, and thus has excellent heat resistance and the like at a lower temperature and in a shorter time than before. An insulating film can be formed. That is, by using the compound (A), it is possible to provide an industrially very advantageous process. Furthermore, the compound (A) has a relatively high stability to air and is excellent in storage stability. Therefore, the compound (A) having a partial structure represented by the general formula (1) is considered to be a suitable crosslinkable compound for an insulating film resin or a precursor (B) described later. The present invention is not limited to this estimation.

一般式（１）
（一般式（１）中、Ｒ^１〜Ｒ^６はそれぞれ独立に任意の置換基を表し、任意のＲ^１〜Ｒ^６がそれぞれ互いに連結して環構造を形成していてもよい。同一炭素上の置換基（Ｒ^１とＲ^２、Ｒ^３とＲ^４、Ｒ^５とＲ^６）が２つ合わせて二重結合を表してもよい。）

General formula (1)
(In General Formula (1), R ^{1 to} R ⁶ each independently represent an arbitrary substituent, and arbitrary R ^{1 to} R ⁶ may be linked to each other to form a ring structure. ^Two substituents (R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ ) may represent a double bond.)

In general formula (1), R ^{1 to} R ⁶ each independently represents an arbitrary substituent. The optional substituent may be any substituent as long as the effects of the present invention are not impaired. Specifically, a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an alkyl group (a linear, branched or cyclic alkyl group, and a polycyclic alkyl group such as a bicycloalkyl group) The number of carbon atoms is preferably 1 to 20, and more preferably 1 to 15. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a 2-ethylhexyl group, A cyclohexyl group, a cyclopentyl group, and the like), an alkenyl group (which may be linear, branched, or cyclic. Preferably it has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms. Allyl group, prenyl group and the like), alkynyl group (which may be linear, branched or cyclic), preferably 2-20 carbon atoms, more preferably 2-15 carbon atoms. ), Aryl group, heterocyclic group (regarding the position of substitution), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group (the carbamoyl group having a substituent is, for example, N -Hydroxycarbamoyl group, N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N-carbamoylcarbamoyl group, thiocarbamoyl group, N-sulfamoylcarbamoyl group), carbazoyl group, carboxy group or a salt thereof, oxalyl group, oxamoyl group , A cyano group, a carbonimidoyl group (Carbonimidoyl group), a formyl group, a hydroxy group, an alkoxy group (including a group containing repeating ethyleneoxy group or propyleneoxy group units), an aryloxy group, a heterocyclic oxy group, an Ruoxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocyclic) amino group, acylamino group, sulfonamido group, ureido group, thioureido group, N -Hydroxyureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, N- (alkyl or aryl) sulfonyl Ureido group, N-acylureido group, N-acylsulfamoylamino group, hydroxyamino group, nitro group, heterocyclic group containing a quaternized nitrogen atom (eg, pyridinio group, imidazolio group, quinolinio group, isoquino group, Norinio group), isocyano group, imino group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, (alkyl, aryl, or heterocyclic) dithio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) A sulfinyl group, a sulfo group or a salt thereof, a sulfamoyl group (the sulfamoyl group having a substituent is, for example, an N-acylsulfamoyl group or an N-sulfonylsulfamoyl group) or a salt thereof, a phosphino group, a phosphinyl group, a phosphine group Examples thereof include a finyloxy group, a phosphinylamino group, and a silyl group. These groups may further have an arbitrary substituent.

In general formula (1), R ^{1 to} R ⁶ may be linked to each other to form a ring structure. ^Two substituents on the same carbon (R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ ) may be combined to represent a double bond.

  The compound (A) of the present invention has a partial structure represented by the general formula (3-1), a partial structure represented by the general formula (3-2), and a partial structure represented by the general formula (3-3). And a compound having at least one partial structure represented by the general formula (3-4) or a partial structure represented by the general formula (3-5).

（一般式（３−１）中、Ｒ^７〜Ｒ^１０はそれぞれ独立に任意の置換基を表し、Ｌ^１はＣ^２とＣ^３を含む環状構造を表す。また、任意のＲ^７〜Ｒ^１０及びＬ^１がそれぞれ互いに連結して環を形成していてもよい。）

(In General Formula (3-1), R ^{7 to} R ¹⁰ each independently represents an arbitrary substituent, and L ¹ represents a cyclic structure containing C ² and C ^3. Also, arbitrary R ^{7 to} R ^10. And L ¹ may be connected to each other to form a ring.)

（一般式（３−２）中、Ｒ^１１〜Ｒ^１４はそれぞれ独立に任意の置換基を表し、Ｌ^２はＣ^１を含む環状構造を表す。また、任意のＲ^１１〜Ｒ^１４及びＬ^２がそれぞれ互いに連結して環を形成していてもよい。）

(In General Formula (3-2), R ^{11 to} R ¹⁴ each independently represents an arbitrary substituent, and L ² represents a cyclic structure containing C ^1. Also, any R ^{11 to} R ¹⁴ and L ² May be linked to each other to form a ring.)

（一般式（３−３）中、Ｒ^１５〜Ｒ^２０はそれぞれ独立に任意の置換基を表し、それぞれ互いに連結して環を形成していてもよい。）

(In the general formula (3-3), R ^{15 to} R ²⁰ each independently represents an arbitrary substituent, and may be connected to each other to form a ring.)

（一般式（３−４）中、Ｒ^２１〜Ｒ^２８はそれぞれ独立に任意の置換基を表し、それぞれ互いに連結して環を形成していてもよい。）

(In the general formula (3-4), R ^{21 to} R ²⁸ each independently represent an arbitrary substituent, and may be connected to each other to form a ring.)

（一般式（３−５）中、Ｒ^２９〜Ｒ^３４はそれぞれ独立に任意の置換基を表し、それぞれ互いに連結して環を形成していてもよい。）

(In General Formula (3-5), R ^{29 to} R ³⁴ each independently represents an arbitrary substituent, and may be connected to each other to form a ring.)

R ^{7 to} R ¹⁰ in the general formula (3-1) each independently represent an arbitrary substituent. The definition of this arbitrary substituent is the same as the definition of the arbitrary substituent in the said General formula (1). L ¹ represents a cyclic structure containing C ² and C ³ . The cyclic structure may be any cyclic structure as long as the effects of the present invention are not impaired. Specifically, a saturated or unsaturated alicyclic hydrocarbon group (monocyclic or polycyclic may be used. The number of carbon atoms is preferably 3 to 10, and particularly preferably 5 to 6 carbon atoms. The alicyclic hydrocarbon group may have a substituent, specifically, a cyclohexyl group, a cyclopentyl group, a phenyl group, a naphthyl group, a bicyclo [1,2,2] heptan-2-yl group, A bicyclo [2,2,2] octan-2-yl group, etc.), a heterocyclic group (the heterocyclic group is a 3- to 10-membered saturated group containing at least one hetero atom of N, O or S; These are unsaturated heterocyclic groups, which may be monocyclic or may form condensed rings with other rings, specifically pyrrole, furan, thiophene, imidazole, oxazole, thiazole. , Pyrazole, pyridine, pyrida Emissions, pyrimidine, pyrazine, piperidine, piperazine, morpholine, tetrahydropyran.), And the like. Arbitrary R ^{7 to} R ¹⁰ and L ¹ may be connected to each other to form a ring.

R ^{11 to} R ¹⁴ in the general formula (3-2) each independently represent an arbitrary substituent. The definition of this arbitrary substituent is the same as the definition of the arbitrary substituent in the said General formula (1). L ² represents a cyclic structure containing C ¹ . The definition of the cyclic structure is the same as the definition of the cyclic structure of the general formula (3-1). Arbitrary R ^{11 to} R ¹⁴ and L ² may be connected to each other to form a ring.

In General Formula (3-3), R ^{15 to} R ²⁰ each independently represents an arbitrary substituent. The definition of this arbitrary substituent is the same as the definition of the arbitrary substituent in the said General formula (1). R ^{15 to} R ²⁰ may be connected to each other to form a ring.

In General Formula (3-4), R ^{21 to} R ²⁸ each independently represents an arbitrary substituent. The definition of this arbitrary substituent is the same as the definition of the arbitrary substituent in the said General formula (1). R ^{21 to} R ²⁸ may be connected to each other to form a ring.

In general formula (3-5), R < ²⁹ > -R < ³⁴ > represents an arbitrary substituent each independently. The definition of this arbitrary substituent is the same as the definition of the arbitrary substituent in the said General formula (1). R ^{29 to} R ³⁴ may be connected to each other to form a ring.

  The compound (A) of the present invention is preferably a compound represented by the general formula (2).

一般式（２）
（一般式（２）中、Ｘは一般式（３−１）で表される部分構造、一般式（３−２）で表される部分構造、一般式（３−３）で表される部分構造、一般式（３−４）で表される部分構造、または一般式（３−５）で表される部分構造のいずれか一つを有する基であり、Ｙは１〜１０価の脂肪族炭化水素基、１〜１０価の芳香族炭化水素基、または１〜１０価の複素環基を表す。ｎは１〜１０の整数を表す。ｎが２以上の場合、Ｘは同一であっても異なっていてもよい。）

General formula (2)
(In the general formula (2), X is a partial structure represented by the general formula (3-1), a partial structure represented by the general formula (3-2), and a part represented by the general formula (3-3). A group having any one of a structure, a partial structure represented by the general formula (3-4), or a partial structure represented by the general formula (3-5), and Y is a 1 to 10-valent aliphatic group Represents a hydrocarbon group, a 1 to 10 valent aromatic hydrocarbon group, or a 1 to 10 valent heterocyclic group, n represents an integer of 1 to 10. When n is 2 or more, X is the same May be different.)

  X in the general formula (2) is a partial structure represented by the general formula (3-1), a partial structure represented by the general formula (3-2), or a partial structure represented by the general formula (3-3). , A group having any one of a partial structure represented by the general formula (3-4) and a partial structure represented by the general formula (3-5).

  Y in the general formula (2) represents a 1 to 10 valent aliphatic hydrocarbon group, a 1 to 10 valent aromatic hydrocarbon group, or a 1 to 10 valent heterocyclic group. The bonding position between the group represented by Y and X may be anywhere in the Y group as long as the effects of the present invention are exhibited.

  The aliphatic hydrocarbon group is an alkyl group, an alkenyl group (in the present application, an unsaturated aliphatic group having a double bond including a cycloalkenyl group and a bicycloalkenyl group), and an alkynyl group.

The alkyl group is not particularly limited, and may be linear, branched or cyclic, and is preferably cyclic from the viewpoint of heat resistance. These may have a substituent. The linear or branched alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, and an n-octyl group.
Examples of the cyclic alkyl group include a cycloalkyl group, a bicycloalkyl group, and a group having a cage structure. The cycloalkyl group preferably has 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, and particularly preferably 5 to 6 carbon atoms. Specific examples include a cyclohexyl group and a cyclopentyl group. The bicycloalkyl group preferably has 4 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, and particularly preferably 6 to 8 carbon atoms. Specific examples include a bicyclo [1,2,2] heptan-2-yl group and a bicyclo [2,2,2] octan-2-yl group.

  A cage structure refers to a molecule whose volume is determined by a plurality of rings formed of covalently bonded atoms, and a point located within the volume cannot leave the volume without passing through the ring. For example, an adamantane structure is considered a cage structure. In contrast, a cyclic structure having a single bridge, such as norbornane (bicyclo [2.2.1] heptane), is not considered a cage structure because the ring of the single bridged cyclic compound does not define volume. .

  The group having a cage structure is, for example, an adamantane group, a biadamantane group, a diamantane group, a triamantane group, a tetramantane group, or a dodecahedrane group, more preferably an adamantane group, a biadamantane group, or a diamantane group, and a low dielectric constant. Particularly preferred is a biadamantane group or a diamantane group. 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 alkenyl group is not particularly limited, and may be linear, branched, or cyclic, and these may have a substituent. The linear or branched alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and particularly preferably 2 to 10 carbon atoms. Specific examples include a vinyl group and an allyl group. The cycloalkenyl group preferably has 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, and particularly preferably 5 to 6 carbon atoms. Specific examples include a cyclopentenyl group and a cyclohexenyl group.

  The alkynyl group is not particularly limited and may be linear, branched or cyclic, preferably has 2 to 20 carbon atoms, more preferably has 2 to 15 carbon atoms, and particularly preferably has 2 to 10 carbon atoms. Specific examples include an ethynyl group.

  The aromatic hydrocarbon group is not particularly limited as long as it is a ring having aromaticity, but preferably has 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 12 carbon atoms. . The aromatic hydrocarbon group may have a substituent. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, a trityl group, an anthracene group, a tetracene group, a pentacene group, a phenanthrene group, and a pyrene group, preferably a phenyl group, a naphthyl group, and a biphenyl group. It is.

  The heterocyclic group contains one or more hetero atoms such as a sulfur atom, an oxygen atom, and a nitrogen atom, and the number of ring members is not particularly limited, and may be a single ring or a polycyclic ring having a condensed ring. A monocyclic ring is preferable. The number of members in the case of a single ring is preferably 3 to 20, more preferably 4 to 15, and particularly preferably 5 to 10. Moreover, the number of members in the case of having a condensed ring is preferably 4-20, and more preferably 8-15. The heterocycle may be either aromatic or non-aromatic. Suitable examples include heterocyclic groups having 5 ring members and aromatic. Specific examples include a pyridine ring and a pyrazine ring.

  Y in the general formula (2) is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group from the viewpoint of low dielectric properties, mechanical strength, and compatibility with an insulating film resin, and includes a phenyl group, a biphenyl group, an adamantane group, More preferred are a diamantane group, a triamantane group, a tetraamantane group, and a biadamantane group.

  In the compound (A) of the present invention, X in the general formula (2) is preferably a group represented by the general formula (4) from the viewpoints of heat resistance and mechanical strength of the insulating film.

一般式（４）
（一般式（４）中、Ｚは一般式（５−１）で表される構造、一般式（５−２）で表される構造、一般式（５−３）で表される構造、一般式（５−４）で表される構造、一般式（５−５）で表される構造、一般式（５−６）で表される構造、または一般式（５−７）で表される構造のいずれか一つであり、Ｌは２〜７価の連結基、または単なる結合手を表す。ｍは１〜６の整数を表す。ｍが２以上の場合は、Ｚは同一であっても異なっていてもよい。Ｌが単なる結合手の場合、ｍと一般式（２）中のｎは同一となる。）

General formula (4)
(In general formula (4), Z is a structure represented by general formula (5-1), a structure represented by general formula (5-2), a structure represented by general formula (5-3), A structure represented by formula (5-4), a structure represented by general formula (5-5), a structure represented by general formula (5-6), or a general formula (5-7) Any one of the structures, L represents a divalent to 7-valent linking group, or a simple bond, m represents an integer of 1 to 6. When m is 2 or more, Z is the same (If L is a simple bond, m and n in the general formula (2) are the same.)

式中＊は一般式（４）のＬとの結合位置を示す。

In the formula, * represents a bonding position with L in the general formula (4).

  Z in the general formula (4) is a structure represented by the general formula (5-1), a structure represented by the general formula (5-2), a structure represented by the general formula (5-3), a general formula ( Of the structure represented by 5-4), the structure represented by the general formula (5-5), the structure represented by the general formula (5-6), or the structure represented by the general formula (5-7). One of them. Among them, the structure represented by the general formula (5-2), the structure represented by the general formula (5-3), the structure represented by the general formula (5-4), and the general formula (5-5) A structure represented by the general formula (5-6), a structure represented by the general formula (5-7), a structure represented by the general formula (5-6), or (5-7) The structure represented by is particularly preferable. In the case where Z is a structure represented by the general formula (5-3), the bonding position with L may be any position on the phenyl group. In the case where Z is a structure represented by the general formula (5-4), the bonding position with L may be any position on the cyclohexane group. In the case where Z is a structure represented by the general formula (5-5), the bonding position with L may be any position on the cyclopentane group. In the case where Z is a structure represented by the general formula (5-6), the bonding position with L may be any position on the cyclohexane group. In the case where Z is a structure represented by the general formula (5-7), the bonding position with L may be any position on the cyclopentane group.

  L in the general formula (4) represents a divalent to 7-valent linking group or a simple bond. The linking group is not particularly limited as long as Y and Z can be linked, and is a linking group consisting of an atomic group composed of at least one atom selected from a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. is there. Preferably, an alkylene group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, which may be bonded to Z and Y at any position, preferably cyclic), an alkenylene group. (Preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and Z and Y may be bonded at any position, preferably cyclic), an arylene group (preferably having a carbon number). 6 to 24, more preferably 6 to 18 carbon atoms, which may be bonded to Z and Y at any position), ester group, amide group, ether group, sulfoamide group, sulfonic acid ester group, ureido group, A sulfonyl group, a sulfinyl group, a thioether group, a carbonyl group, a —NR— group (where R represents a hydrogen atom, an alkyl group or an aryl group), an azo group, an azoxy group, and a heterocyclic group (monocyclic) 1 or 2 selected from the group consisting of 5 to 20 members, more preferably 5 to 10 members, and Z and Y may be bonded at any position. A group composed of two or more. Preferred are an alkylene group, an alkenylene group, an arylene group, an ester group, an amide group, and an ether group, and more preferred are an arylene group, an ester group, an amide group, and an ether group. The valence of the linking group is preferably 2 to 4, and more preferably 2 from the viewpoint of synthesis.

  The example of the coupling group comprised combining from the said group is shown below. The linking group of the present invention is not limited to these groups.

  When L is a simple bond, Z is directly bonded to Y. The bonding position of Y linked to Z may be anywhere as long as the effects of the present invention are exhibited.

  M in General formula (4) represents the integer of 1-10. Preferably it is 1-3, More preferably, it is 1. When m is 2 or more, Z may be the same or different. When L is a simple bond, m is the same integer as n in the general formula (2).

  In the composition for forming an insulating film of the present invention, the compound (A) may be used alone or in combination of two or more. Content of the compound (A) in the composition for insulating film formation of this invention is 0.1-60 mass% with respect to solid content of the film formation composition as a total amount, Preferably it is 1-50 mass%, Especially preferably, it is 5-45 mass%. Here, the solid content corresponds to all components constituting the film obtained using this composition. When the content of the compound (A) is within this range, it is preferable in terms of achieving both low dielectric constant and heat resistance.

  Compound (A) may be a commercially available product or may be synthesized by a known method.

  Preferred examples of the compound represented by the compound (A) include the following. The present invention is not limited to these.

<Insulating film resin or its precursor (B)>
The composition for insulating film formation of this invention contains resin for insulating films, or its precursor (B). The resin for insulating film or its precursor (B) is not particularly limited as long as it is a resin compound or its precursor compound that forms an insulating film, and the relative dielectric constant of the formed film is 4 or less, preferably 3 or less. Such a resin compound or a precursor thereof is preferable. Examples thereof include highly heat-resistant resins such as polyarylene resins, polyarylene ether resins, polybenzoxazole resins, polyquinoline resins, and polyquinoxaline resins, precursors of these resins, and compounds having a cage structure. Among these, a compound having a cage structure is preferable from the viewpoints of heat resistance and compatibility with the compound (A), and effects such as excellent dielectric constant stability with time can be seen. The definition of the cage structure is the same as that in the group having the cage structure. In addition, the compound (A) having a cyclopropane skeleton represented by the general formula (1) and including a group having a cage structure has a cage structure of the insulating film resin or its precursor (B). It is not included in the compound.

  Specific examples of the high heat-resistant resin that can be used for the insulating film resin or its precursor (B) include those described in JP-A-11-322929, JP-A-2003-12802, and JP-A-2004-18593. Benzoxazole, quinoline resin described in JP-A-2001-2899, JP-T 2003-530464, JP-T 2004-535497, JP-T 2004-504424, JP-T 2004-504455, JP-T No. 2005-501131, No. 2005-516382, No. 2005-514479, No. 2005-522528, JP-A 2000-100808, and US Pat. No. 6,509,415. JP, 2003-252992, A, JP, 2004-26, A Polyimide described in 50 JP thereof. Specific examples of the compound having a cage structure that can be used for the insulating film resin or its precursor (B) include JP-A Nos. 11-214382, 2001-332542, and 2003-252882. Examples thereof include polyadamantanes described in JP-A Nos. 2003-292878, 2004-2787, 2004-67877, and 2004-59444.

  The compound having a cage structure is a compound having a cage structure, and may be a low molecular compound or a high molecular compound (for example, a polymer (polymer)), but preferably has a cage structure. It is a polymer of the monomer (this monomer is synonymous with the precursor). 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 preferably adamantane, biadamantane, diamantane, triamantane, tetramantane or dodecahedrane, more preferably adamantane, biadamantane or diamantane, and a low dielectric constant. Particularly preferred is biadamantane or diamantane. 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 (fluorine atom, chloro atom, bromine atom or 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 Group (such as methoxycarbonyl), carbamoyl group having 1 to 10 carbon atoms (such as N, N-diethylcarbamoyl), aryl having 6 to 20 carbon atoms Alkoxy 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 catalyzed 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. Examples of organic peroxides include ketone peroxides such as Perhexa H, peroxyketals such as Perhexa TMH, hydroperoxides such as Perbutyl H-69, Parkmill D, and Perbutyl C, which are commercially available from Nippon Oil & Fat Co., Ltd. Dialkyl peroxides such as perbutyl D, diacyl peroxides such as Nyper BW, peroxyesters such as perbutyl Z and perbutyl L, and peroxydicarbonates such as peroyl TCP are preferably used. Examples of the organic azo compound include azonitrile compounds such as V-30, V-40, V-59, V-60, V-65, and V-70 that are commercially available from Wako Pure Chemical Industries, Ltd., VA-080. Azoamide compounds such as VA-085, VA-086, VF-096, VAm-110 and VAm-111, cyclic azoamidine compounds such as VA-044 and VA-061, and azoamidines such as V-50 and VA-057 Compounds and the like are 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. For example, a monomer having a polymerizable carbon-carbon double bond or carbon-carbon triple bond is a Pd-based catalyst such as tetrakistriphenylphosphine palladium (Pd (PPh ₃ ) ₄ ), palladium acetate (Pd (OAc) ₂ ), Ziegler-Natta catalysts, Ni-based catalyst such as nickel acetylacetonate, W-based catalyst such as WCl _6, Mo-based catalysts, such as MoCl _5, Ta catalysts such as TaCl _5, Nb based catalysts, such as NbCl _5, Rh-based catalyst Polymerization is preferably performed using a Pt-based catalyst or the like. Only one transition metal catalyst or a mixture of two or more transition metal catalysts may be used. The amount of the transition metal catalyst used is preferably 0.001 to 2 mol, more preferably 0.01 to 1 mol, and particularly preferably 0.05 to 0.5 mol, with respect to 1 mol of the monomer having a cage structure. It is.

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 compound 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. The definitions of the alkyl group, alkenyl group, alkynyl group and aromatic hydrocarbon group are the same as the definitions of the alkyl group, alkenyl group, alkynyl group and aromatic hydrocarbon group of Y in the general formula (2). . These linking groups may be substituted with a substituent, and for example, the above-described substituents are preferable examples. 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 are —C (R ³⁵ ) (R ³⁶ ) — and —CH═CH— from the viewpoint of low dielectric constant.

  The compound having a cage structure that can be used in the present invention is preferably a polymer of a monomer having a polymerizable carbon-carbon double bond or carbon-carbon triple bond. Furthermore, a polymer of a compound represented by the following formulas (6) to (11) is more preferable.

（式（６）〜（１１）中、Ｘ_１〜Ｘ_８はそれぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、シリル基、アシル基、アルコキシカルボニル基またはカルバモイル基などを表し、Ｙ_１〜Ｙ_８はそれぞれ独立に、ハロゲン原子、アルキル基、アリール基またはシリル基を表し、ｍ_１、ｍ_５は１〜１６の整数を表し、ｎ_１、ｎ_５は０〜１５の整数を表し、ｍ_２、ｍ_３、ｍ_６、ｍ_７はそれぞれ独立に１〜１５の整数を表し、ｎ_２、n_３、ｎ_６、ｎ_７は０〜１４の整数を表し、ｍ_４、ｍ_８は１〜２０の整数を表し、ｎ_４、ｎ_８は０〜１９の整数を表す。）

(In formulas (6) to (11), X _{1 to} X ₈ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a silyl group, an acyl group, an alkoxycarbonyl group or a carbamoyl group. Y _{1 to} Y ₈ each independently represents a halogen atom, an alkyl group, an aryl group or a silyl group, m ₁ and m ₅ represent an integer of ₁ to 16, and n ₁ and n ₅ represent 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 each} represents an integer of 0 to 14, m ₄ , m ₈ represents an integer of _{1~20, n 4,} n ₈ is an integer of 0 to 19.)

In formulas (6) to (11), X _{1 to} X ₈ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, An aryl group having 6 to 20 carbon atoms, a silyl group having 0 to 20 carbon atoms, an acyl group having 2 to 10 carbon atoms, an alkoxycarbonyl having 2 to 10 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms and the like are represented. Among these, Preferably a hydrogen atom, a C1-C10 alkyl group, a C6-C20 aryl group, a C0-C20 silyl group, a C2-C10 acyl group, C2-C10 An alkoxycarbonyl group and a carbamoyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom and an aryl group having 6 to 20 carbon atoms, and particularly preferably a hydrogen atom.
In formulas (6) to (11), Y _{1 to} Y ₈ are each independently a halogen atom (fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or carbon. Represents a silyl group having 0 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms which may have a substituent and an aryl group having 6 to 20 carbon atoms, particularly preferably an alkyl group (methyl group). Etc.).
X _{1 to} X ₈ and Y _{1 to} Y ₈ may be further substituted with another substituent.

In formula (6) or formula (9), 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. is there.
In formula (6) or formula (9), 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. is there.
In formula (7) or formula (10), m ₂ , m ₃ , m ₆ and m ₇ each independently represents an integer of 1 to 15, preferably 1 to 4, more preferably 1 to 3. Particularly preferably 2.
In formula (7) or formula (10), 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 formula (8) or formula (11), 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. is there.
In formula (8) or formula (11), n ₄ and n ₈ each independently represent an integer of 0 to 19, preferably 0 to 4, more preferably 0 or 1, particularly preferably 0. is there.

  The monomer having a cage structure that can be used in the present invention is preferably a compound represented by the above formula (6), formula (7), formula (9) or formula (10), more preferably the above formula. (6) or a compound represented by formula (7), particularly preferably a compound represented by formula (7).

  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.

  Specific examples of the monomer having a cage structure that can be used in the present invention are described below, but the present invention is not limited thereto.

  Further, examples of the monomer having a cage structure that can be used in the present invention include those in which —C≡C— in the above specific examples is changed to —CH═CH—.

  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. You may use things. For example, alcohol solvents such as water, methanol, ethanol, propanol, alcohol solvents such as alcohol acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, methyl benzoate Ester solvents such as dibutyl ether, anisole, etc., toluene, xylene, mesitylene, 1,2,4,5-tetramethylbenzene, pentamethylbenzene, isopropylbenzene, 1,4-diisopropylbenzene, t- Butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-triethylbenzene, 1,3,5-tri-t-butylbenzene, 4-t-butyl-orthoxylate , Aromatic hydrocarbon solvents such as 1-methylnaphthalene and 1,3,5-triisopropylbenzene, amide solvents such as N-methylpyrrolidinone and dimethylacetamide, carbon tetrachloride, dichloromethane, chloroform, 1,2-dichloroethane Halogen solvents such as chlorobenzene, 1,2-dichlorobenzene and 1,2,4-trichlorobenzene, and aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane can be used.
Among these, more preferred solvents are acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, ethyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, anisole, tetrahydrofuran, toluene, xylene, mesitylene, 1, 2, 4, 5-tetramethylbenzene, isopropylbenzene, t-butylbenzene, 1,4-di-t-butylbenzene, 1,3,5-tri-t-butylbenzene, 4-t-butyl-orthoxylene, 1-methyl Naphthalene, 1,3,5-triisopropylbenzene, 1,2-dichloroethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, more preferably tetrahydrofuran, γ-butyrolactone, Nisole, toluene, xylene, mesitylene, isopropylbenzene, t-butylbenzene, 1,3,5-tri-t-butylbenzene, 1-methylnaphthalene, 1,3,5-triisopropylbenzene, 1,2-dichloroethane, Chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, particularly preferably γ-butyrolactone, anisole, mesitylene, t-butylbenzene, 1,3,5-triisopropylbenzene, 1,2- Dichlorobenzene and 1,2,4-trichlorobenzene. These may be used alone or in admixture of two or more.
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 in the present invention 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, the temperature is 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.

For example, a compound having a cage structure is obtained by reacting with bromine in the presence or absence of an aluminum bromide catalyst using a commercially available diamantane as a raw material to introduce a bromine atom at a desired position, followed by aluminum bromide, aluminum chloride, chloride. It can be synthesized by conducting Friedel-Crafts reaction with vinyl bromide in the presence of a Lewis acid such as iron, introducing a 2,2-dibromoethyl group, followed by de-HBr conversion with a strong base and converting it to an ethynyl group. it can. 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.

  The content of the resin for an insulating film or the precursor (B) in the composition for forming an insulating film of the present invention is preferably 40 to 99.9% by mass with respect to the solid content of the film forming composition, Preferably it is 45-95 mass%, Most preferably, it is 50-90 mass%. Here, the solid content corresponds to all components constituting the film obtained using this composition. When the content of the compound (B) is within this range, it is preferable in terms of heat resistance and mechanical strength.

<Insulating film forming composition>
The composition for forming an insulating film of the present invention preferably has a sufficiently low metal content as an impurity. The metal concentration of the composition for forming an insulating film can be measured with high sensitivity by the ICP-MS method. In that case, the metal content other than the transition metal is preferably 30 ppm or less, more preferably 3 ppm or less, particularly preferably 300 ppb. It is as follows.
In addition, the transition metal has a high catalytic ability to promote oxidation, and from the viewpoint of increasing the dielectric constant of the film obtained in the present invention by an oxidation reaction in the prebaking and thermosetting processes, the content is preferably smaller. Preferably it is 10 ppm or less, More preferably, it is 1 ppm or less, Most preferably, it is 100 ppb or less.
The metal concentration of the composition for forming an insulating film can also be evaluated by performing total reflection X-ray fluorescence measurement on a film obtained using the composition for forming an insulating film of the present invention. When a W (tungsten) ray is used as an X-ray source, K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Pd can be observed as metal elements, each of which is 100 × 10 ¹⁰ atoms. · Cm ⁻² or less is preferable, 50 × 10 ¹⁰ atom · cm ⁻² or less is more preferable, and 10 × 10 ¹⁰ atom · cm ⁻² or less is particularly preferable. Moreover, Br which is halogen is also observable, and the residual amount is preferably 10,000 × 10 ¹⁰ atom · cm ⁻² or less, more preferably 1,000 × 10 ¹⁰ atom · cm ⁻² or less, and 400 × 10 ^10. Atom · cm ⁻² or less is particularly preferable. Further, although Cl can be observed as halogen, the remaining amount is preferably 100 × 10 ¹⁰ atom · cm ⁻² or less from the viewpoint of damaging a CVD apparatus, an etching apparatus, etc., and 50 × 10 ¹⁰ atom · cm ^−2. The following is more preferable, and 10 × 10 ¹⁰ atom · cm ⁻² or less is particularly preferable.

The composition for forming an insulating film of the present invention may contain an organic solvent. Although it does not specifically limit as an organic solvent, For example, alcohol solvents, such as methanol, ethanol, 2-propanol, 1-butanol, 2-ethoxymethanol, 3-methoxypropanol, 1-methoxy-2-propanol, acetone, acetylacetone, Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, cyclopentanone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, propionic acid Esters such as ethyl, propyl propionate, butyl propionate, isobutyl propionate, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, γ-butyrolactone, di Ether solvents such as sopropyl ether, dibutyl ether, ethyl propyl ether, anisole, phenetol, veratrol, aromatic hydrocarbon solvents such as mesitylene, ethylbenzene, diethylbenzene, propylbenzene, t-butylbenzene, N-methylpyrrolidinone, dimethyl Examples include amide solvents such as acetamide, and these may be used alone or in admixture of two or more.
More preferred organic solvents are 1-methoxy-2-propanol, propanol, acetylacetone, cyclohexanone, propylene glycol monomethyl ether acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, anisole, mesitylene, t-butylbenzene, Particularly preferred are 1-methoxy-2-propanol, cyclohexanone, 2-heptanone, propylene glycol monomethyl ether acetate, ethyl lactate, γ-butyrolactone, t-butylbenzene and anisole.

  The solid content concentration of the film-forming composition of the present invention is preferably 1 to 50% by mass, more preferably 2 to 15% by mass, and particularly preferably 3 to 10% by mass. Here, the solid content corresponds to all components constituting the film obtained using this composition.

<Additive to composition for insulating film formation>
Furthermore, the composition for forming an insulating film of the present invention includes a radical generator and colloidal silica as long as the properties of the obtained insulating film (heat resistance, dielectric constant, mechanical strength, coatability, adhesion, etc.) are not impaired. Further, additives such as a surfactant, a silane coupling agent, and an adhesive may be added.

  The insulating film forming composition of the present invention may contain colloidal silica. For example, a dispersion in which high-purity silicic acid is dispersed in a hydrophilic organic solvent or water, usually having an average particle size of 5 to 30 nm, preferably 10 to 20 nm, and a solid content concentration of 5 to 40% by mass. is there.

  The composition for forming an insulating film of the present invention may contain a surfactant. For example, nonionic surfactants, anionic surfactants, cationic surfactants, and the like, silicone surfactants, fluorine-containing surfactants, polyalkylene oxide surfactants, acrylic surfactants Agents. The surfactant that can be used in the present invention may be one type or two or more types. As the surfactant, silicone surfactants, nonionic surfactants, fluorine-containing surfactants, and acrylic surfactants are preferable, and silicone surfactants are particularly preferable. The content of the surfactant that can be used in the present invention is preferably 0.01% by mass or more and 1% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass with respect to the total amount of the film-forming coating solution. More preferably, it is at most mass%.

  In the present invention, the silicone-based surfactant is a surfactant containing at least one Si atom. The silicone surfactant used in the present invention may be any silicone surfactant and preferably has a structure containing alkylene oxide and dimethylsiloxane. A structure including the following chemical formula is more preferable.

上記式中、Ｒは水素原子または炭素数１〜５のアルキル基であり、ｘは１〜２０の整数であり、ａ、ｂはそれぞれ独立に２〜１００の整数である。また、Ｒが複数存在する場合、それぞれ同じであっても異なっていてもよい。

In said formula, R is a hydrogen atom or a C1-C5 alkyl group, x is an integer of 1-20, a and b are the integers of 2-100 each independently. Further, when there are a plurality of R, they may be the same or different.

  Examples of silicone surfactants that can be used in the present invention include BYK306, BYK307 (manufactured by BYK Chemie), SH7PA, SH21PA, SH28PA, SH30PA (manufactured by Toray Dow Corning Silicone), Troysol S366 (manufactured by Troy Chemical) And so on.

  The nonionic surfactant that can be used in the present invention may be any nonionic surfactant. 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 that can be used in the present invention may be any fluorine-containing surfactant. For example, perfluorooctyl polyethylene oxide, perfluorodecyl polyethylene oxide, perfluorodecyl polyethylene oxide and the like can be mentioned.

  The acrylic surfactant that can be used in the present invention may be any acrylic surfactant. For example, a (meth) acrylic acid type copolymer is mentioned.

  Any silane coupling agent may be used in the present invention. Examples of the silane coupling agent include 3-glycidyloxypropyltrimethoxysilane, 3-aminoglycidyloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 1 -Methacryloxypropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarboni -3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) 3-aminopropyl trimethoxysilane, etc. N- bis (oxyethylene) -3-aminopropyltriethoxysilane and the like. The silane coupling agent that can be used in the present invention may be used alone or in combination of two or more.

  Any adhesion promoter may be used in the present invention. Examples of the adhesion promoter include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane. , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, trimethoxyvinylsilane, γ-aminopropyltriethoxysilane, aluminum monoethylacetoacetate diisopropylate, vinyltris (2-methoxyethoxy) silane, N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylto Limethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane , Dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, benzotriazole, benzimidazole, Indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole , Mention may be made of 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, 1,1-dimethylurea, 1,3-dimethylurea, and thiourea compounds. Functional silane coupling agents are preferred as adhesion promoters. The amount of the adhesion promoter used is preferably 10 parts by mass or less, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total solid content.

In the present invention, within the range allowed by the mechanical strength of the film, the film can be made porous by using a pore forming factor to achieve a low dielectric constant. The pore-forming factor as an additive that becomes a pore-forming agent is not particularly limited, but a non-metallic compound is preferably used, and the solubility in a solvent used in the coating liquid for forming an insulating film, the insulating film It is necessary to satisfy the compatibility with the resin for resin or its precursor (B) at the same time.
A polymer can also be used as the pore-forming agent. Examples of the polymer that can be used as the pore-forming agent include polyvinyl aromatic compounds (polystyrene, polyvinyl pyridine, halogenated polyvinyl aromatic compounds, etc.), polyacrylonitrile, polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.), polyethylene, poly Lactic acid, polysiloxane, polycaprolactone, polycaprolactam, polyurethane, polymethacrylate (such as polymethyl methacrylate) or polymethacrylic acid, polyacrylate (such as polymethyl acrylate) and polyacrylic acid, polydiene (such as polybutadiene and polyisoprene), polyvinyl chloride , Polyacetal, and amine-capped alkylene oxide, other polyphenylene oxide, poly (dimethyl) Siloxane), polytetrahydrofuran, poly cyclohexyl ethylene, polyethyl oxazoline, polyvinyl pyridine, may be a polycaprolactone.
In particular, polystyrene can be suitably used as a pore forming agent. Examples of polystyrene include anionic polymerized polystyrene, syndiotactic polystyrene, unsubstituted and substituted polystyrene (for example, poly (α-methylstyrene)), and unsubstituted polystyrene is preferred.
Further, the boiling point or decomposition temperature of the pore-forming agent is preferably 100 to 500 ° C, more preferably 200 to 450 ° C, and particularly preferably 250 to 400 ° C. The molecular weight is preferably 200 to 50,000, more preferably 300 to 10,000, and particularly preferably 400 to 5,000. The addition amount is preferably 0.5 to 75% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 1 to 20% by mass with respect to the solid content of the composition for forming an insulating film.
Further, as a pore forming factor, a decomposable group may be contained in the insulating film resin or its precursor (B), and the decomposition temperature is preferably 100 to 500 ° C., more preferably 200 to 450. ° C, particularly preferably 250 to 400 ° C. The content of the decomposable group is preferably 0.5 to 75 mol%, more preferably 0.5 to 30 mol%, particularly preferably relative to the insulating film resin or precursor (B) forming the film. Is 1 to 20 mol%.

  Although the manufacturing method of the composition for forming an insulating film of the present invention described above is not particularly limited, for example, a compound (A) and a resin for insulating film or a precursor thereof (B) in a reaction vessel, and each of the above as necessary. It is possible to use a method in which optional ingredients are added and sufficiently stirred using a stirrer such as a mixing mixer.

  A film obtained using the composition for forming an insulating film of the present invention is obtained by applying the composition for forming an insulating film to a substrate by any method such as a spin coating method, a roller coating method, a dip coating method, or a scanning method. It can be formed by removing the solvent by heat treatment. 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, a clean truck series (manufactured by Tokyo Electron Co., Ltd.), D-spin series (manufactured by Dainippon Screen Mfg. Co., Ltd.), 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 from the viewpoint of in-plane uniformity of the film, a rotational speed of about 1,300 rpm is preferable for a 300 mm silicon substrate.

  In addition, the composition solution discharge method may be either dynamic discharge in which the composition solution is discharged onto a rotating substrate or static discharge in which the composition solution is discharged onto a stationary substrate. From the viewpoint of uniformity, 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 method of heat treatment is not particularly limited, however, 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. Commercially available equipment can be preferably used as the hot plate, and the clean track series (manufactured by Tokyo Electron Ltd.), D-Spin series (manufactured by Dainippon Screen Mfg. Co., Ltd.), SS series or CS series (Tokyo Ohka Kogyo Co., Ltd.) Etc.) can be preferably used. As the furnace, α series (manufactured by Tokyo Electron Ltd.) and the like can be preferably used.

The composition for forming an insulating film of the present invention is particularly preferably cured by heat treatment after coating on a substrate. For example, the polymerization reaction at the time of post-heating of the carbon triple bond remaining in the film formed from the insulating film forming composition can be used. The conditions for this post-heat treatment are preferably 100 to 450 ° C., more preferably 200 to 420 ° C., particularly preferably 350 to 400 ° C., preferably 1 minute to 2 hours, more preferably 10 minutes to 1.5 ° C. Time, particularly preferably in the range of 30 minutes to 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.
Moreover, in this invention, you may make it harden | cure by causing the polymerization reaction of the carbon triple bond which remain | survives in a film | membrane by irradiating a high energy ray instead of heat processing. 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 to 50 keV, more preferably 0 to 30 keV, and particularly preferably 0 to 20 keV. The total dose of the electron beam is preferably 0 to 5 μC / cm ² , more preferably 0 to ² μC / cm ² , and particularly preferably 0 to 1 μC / cm ² . 0-450 degreeC is preferable, as for the substrate temperature at the time of irradiating an electron beam, 0-400 degreeC is more preferable, and 0-350 degreeC is especially preferable. 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 film of the present invention, it is preferable to use an inert atmosphere such as Ar, He, or nitrogen as the atmosphere around the substrate. 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 in the present invention 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 using ultraviolet rays is preferably 190 to 400 nm, and the output is preferably 0.1 to 2,000 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 film 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.

A film obtained using the composition for forming an insulating film of the present invention can be suitably used as an insulating film, and can be more suitably used as an interlayer insulating film for a semiconductor. That is, the insulating film obtained using the composition for forming an insulating film of the present invention can be suitably used for an electronic device.
For example, when used as an interlayer insulating film for a semiconductor, in the wiring structure, there may be a barrier layer on the side surface of the wiring to prevent metal migration, and CMP (chemical In addition to the cap layer and interlayer adhesion layer that prevent peeling in mechanical and mechanical polishing, there may be an etching stopper layer, etc. Furthermore, the interlayer insulating film layer may be divided into multiple layers with other materials as required. Also good.

  A film obtained by using the composition for forming an insulating film of the present invention can be etched for copper wiring or other purposes. Etching may be either wet etching or dry etching, but dry etching is preferred. For dry etching, either ammonia-based plasma or fluorocarbon-based plasma can be used as appropriate. For these plasmas, not only Ar, but also oxygen, or a gas such as nitrogen, hydrogen, or helium can be used. In addition, after the etching process, ashing can be performed for the purpose of removing the photoresist used in the process, and further, cleaning can be performed to remove a residue at the time of ashing.

  The film obtained by using the composition for forming an insulating film of the present invention can be subjected to CMP to planarize the copper plating portion after the copper wiring processing. As the CMP slurry (chemical solution), commercially available slurries (for example, manufactured by Fujimi Incorporated, manufactured by Rodel Nitta, manufactured by JSR, manufactured by Hitachi Chemical Co., Ltd., etc.) can be used as appropriate. Moreover, as a CMP apparatus, a commercially available apparatus (Applied Materials Co., Ltd., Ebara Manufacturing Co., Ltd. etc.) can be used suitably. Further, cleaning can be performed to remove slurry residues after CMP.

The film obtained by using the composition for forming an insulating film of the present invention can be used for various purposes. For example, it is suitable as an insulating film for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, and electronic components such as multichip module multilayer wiring boards, semiconductor interlayer insulating film, etching stopper film, surface protection In addition to films, buffer coat films, 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. Can do.
Furthermore, as another application, the film of the present invention can be imparted with conductivity by doping with an electron donor or acceptor and used as a conductive film.

Although the relative dielectric constant of the insulating film of the present invention varies depending on the material used, it is usually preferably 4.0 or less, more preferably 1.5 to 3.5 at a measurement temperature of 25 ° C., More preferably, it is 1.8-3.0.
The dielectric constant of the insulating film of the present invention is calculated from the capacitance value at 1 MHz using a mercury probe manufactured by Four Dimensions and a HP4285ALCR meter manufactured by Yokogawa Hewlett Packard at a measurement temperature of 25 ° C. It is preferable.

The Young's modulus of the insulating film of the present invention varies depending on the material used, but is preferably 3.0 to 15.0 GPa, more preferably 5.0 to 15.0 GPa.
As a method for measuring the Young's modulus in the insulating film of the present invention, the measurement is performed using a nanoindenter SA2 manufactured by MTS.

  The mass reduction rate after heat treatment at 400 ° C. for 30 seconds in the air in the insulating film of the present invention varies depending on the material used, but is preferably 0.0 to 15.0%, and is preferably 0.0 to 5.0%. It is more preferable that

  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.

<Synthesis Example 1: Synthesis of tris (4-cyclopropylphenyl) trimesoyl ester (a)>
Compound (a) was synthesized according to the following scheme.

A) Synthesis of 4-cyclopropylacetophenone 4 g of 4-bromoacetophenone, 2.24 g of cyclopropylboronic acid, 0.226 g of palladium acetate, 0.564 g of tricyclopropylphosphine, phosphoric acid in a 200 ml three-necked flask under a nitrogen stream 14.9 g of tripotassium, 90 ml of toluene and 4.4 ml of water were added and stirred at 100 ° C. for 3 hours. After the reaction, the reaction solution was added to 220 ml of water and extracted with ethyl acetate. The extract was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily liquid. This was dissolved in a small amount of ethyl acetate and packed in silica gel chromatography, and column purification was performed using hexane / ethyl acetate as an eluent. The solvent of the obtained solution was distilled off under reduced pressure to obtain 3.14 g (yield: 97%) of 4-cyclopropylacetophenone as a colorless liquid.

B) Synthesis of 4-cyclopropylphenol Into a 100 ml eggplant flask was placed 3.14 g of 4-bromoacetophenone, 7.24 g of metachloroperbenzoic acid and 60 ml of methylene chloride, and the mixture was heated to reflux for 2 hours with a reflux tube attached. After the reaction, the reaction solution was added to 100 ml of ethyl acetate and washed with a saturated aqueous sodium thiosulfate solution and a saturated aqueous sodium bicarbonate solution. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain an oily liquid. To this, 20 ml of methanol, 2 ml of water and 2.76 g of potassium carbonate were added and stirred at room temperature for 1 hour. After the reaction, 1N HCl aqueous solution was added to the reaction solution until the pH reached 5-6, and the mixture was extracted with ethyl acetate. It dried with the anhydrous sodium sulfate and the solid product was obtained by depressurizingly distilling a solvent. This was dissolved in a small amount of ethyl acetate and packed in silica gel chromatography, and column purification was performed using hexane / ethyl acetate as an eluent. The solvent of the obtained solution was distilled off under reduced pressure to obtain 1.40 g (yield: 53%) of 4-cyclopropylphenol as a white solid.

C) Synthesis of Compound (a) Under a nitrogen stream, 1.40 g of 4-cyclopropylphenol, 10 ml of tetrahydrofuran and 1.84 ml of triethylamine were added to a 30 ml three-necked flask and stirred until uniform. While the vessel was cooled in an ice bath, 0.88 g of trimesoyl chloride was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 1 hour. After the reaction, ethyl acetate was added to the reaction solution, and the mixture was washed with a 1N HNO ₃ aqueous solution and a saturated sodium hydrogen carbonate aqueous solution. It dried with the anhydrous sodium sulfate and the solid product was obtained by depressurizingly distilling a solvent. This was dissolved in a small amount of ethyl acetate and packed in silica gel chromatography, and column purification was performed using hexane / ethyl acetate as an eluent. The solvent of the obtained solution was distilled off under reduced pressure to obtain 1.70 g (yield: 92%) of compound (a) as a white solid.
¹ H-NMR (DMSO) δ = 8.98 (s, 3H), 7.20 (m, 12H), 1.97 (m, 3H), 0.95 (m, 6H),
0.70 (m, 6H).

<Synthesis Example 2: Synthesis of tetrakis (4-cyclopropylphenyl) naphthalene-1,4,5,8-tetracarboxylic acid ester (b)>
According to the following scheme, it synthesize | combined using the method similar to the synthesis example 1.

<Synthesis Example 3: Synthesis of 4,9-dicyclopropyldiamantane (c)>
Compound (c) was synthesized according to the following scheme. However, 4,9-diethynyldiamantane was synthesized according to the synthesis method described in Macromolecules, page 5266 (1991).

A) Synthesis of 4,9-divinyldiamantane In a nitrogen stream, 16.5 g of 4,9-diethynyldiamantane and 30 ml of toluene were placed in a 200 ml three-necked flask, and the container was cooled in an ice bath. 150 ml of diisobutylaluminum hydride (1M, hexane solution) was slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 3 hours. After the reaction, the reaction solution was slowly added to 200 ml of a saturated aqueous ammonium chloride solution, and the precipitated solid was filtered. The filtrate was extracted with ethyl acetate and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a solid product. This 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 13.3 g (yield: 79%) of 4,9-divinyldiamantane as a white solid.

B) Synthesis of Compound (c) Under a nitrogen stream, 2.40 g of 4,9-divinyldiamantane and 60 ml of toluene were placed in a 200 ml three-necked flask, and 60 ml of diethylzinc (1M, hexane solution) was added dropwise with stirring. . 9.66 ml of diiodomethane was slowly added dropwise at room temperature, and stirred at 80 ° C. for 8 hours after the completion of the addition. After the reaction, ethyl acetate was added to the reaction solution and washed with 1N HCl and water. It dried with the anhydrous sodium sulfate and the solid product was obtained by depressurizingly distilling a solvent. This 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 2.20 g (yield: 82%) of compound (c) as a white solid.

<Example 1>
According to the synthesis method described in J. Polym. Sci. PART A Polym. Chem., Vol. 30, page 1747 (1992), 1,3,5-triethynyladamantane was synthesized.
Next, 10 g of 1,3,5-triethynyladamantane and 56 g of t-butylbenzene were placed in a reaction vessel and heated to an internal temperature of 120 ° C. with stirring under a nitrogen stream, and 1,3,5-triethynyl was obtained. The adamantane was completely dissolved. Next, a solution obtained by dissolving 2.2 g of dicumyl peroxide (Park Mill D, manufactured by NOF Corporation) in 1.9 g of diphenyl ether was added to the reaction solution over 1 hour while maintaining the internal temperature of the reaction solution at 120 to 130 ° C. It was dripped.
After the reaction, the reaction solution was cooled to 50 ° C., added to 0.4 L of 2-propanol, and the precipitated solid was filtered and washed with 2-propanol. The obtained polymer was dissolved in 40 ml of THF, added to 0.4 L of methanol, and purified by reprecipitation. After vacuum drying, 4.2 g of polymer (1) having a weight average molecular weight of about 60,000 was obtained.
With the compounding amounts shown in Table 1, the polymer (1) and the compounds (a) to (c) obtained in Synthesis Examples 1 to 3 were added to prepare 1.0 g, respectively. A coating solution was prepared by completely dissolving in 0 g. This solution was filtered through a tetrafluoroethylene filter having a pore size of 0.1 μm, spin-coated on a silicon wafer, this coating film was heated on a hot plate at 250 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen. As a result of baking in an oven at 400 ° C. for 60 minutes, a uniform film having no film thickness of 0.5 μm was obtained (Example 2-4).
When the relative dielectric constant (k value) (measurement temperature: 25 ° C.) of the film was calculated from the capacitance value at 1 MHz using a mercury probe manufactured by Four Dimensions and a HP4285ALCR meter manufactured by Yokogawa Hewlett Packard, They were 2.69, 2.72, and 2.65, respectively.
The appearance of the obtained insulating film was observed with a pocket micro loupe (50 times) manufactured by Peak Co., but no cracks were observed on the coating film surface.
The Young's modulus was measured using Nano Indenter SA2 manufactured by MTS.

<Example 2>
Next, 10 g of 1,3,5-trivinyladamantane and 56 g of t-butylbenzene were placed in a reaction vessel, and heated to an internal temperature of 120 ° C. with stirring under a nitrogen stream to obtain 1,3,5-trivinyl. The adamantane was completely dissolved. Next, a solution obtained by dissolving 2.2 g of dicumyl peroxide (Park Mill D, manufactured by NOF Corporation) in 1.9 g of diphenyl ether was added to the reaction solution over 1 hour while maintaining the internal temperature of the reaction solution at 120 ° C. to 130 ° C. It was dripped.
After the reaction, the reaction solution was cooled to 50 ° C., added to 0.4 L of 2-propanol, and the precipitated solid was filtered and washed with 2-propanol. The obtained polymer was dissolved in 40 ml of THF, added to 0.4 L of methanol, and purified by reprecipitation. After vacuum drying, 4.0 g of polymer (2) having a weight average molecular weight of about 60,000 was obtained.
With the compounding amounts shown in Table 1, the polymer (2) and the compounds (a) to (c) obtained in Synthesis Examples 1 to 3 were added to prepare 1.0 g, respectively. A coating solution was prepared by completely dissolving in 0 g. This solution was filtered through a tetrafluoroethylene filter having a pore size of 0.1 μm, spin-coated on a silicon wafer, this coating film was heated on a hot plate at 250 ° C. for 60 seconds under a nitrogen stream, and further purged with nitrogen. As a result of baking in an oven at 400 ° C. for 60 minutes, a uniform film having no film thickness of 0.5 μm was obtained (Example 6-8).
When the relative dielectric constant (k value) (measurement temperature: 25 ° C.) of the film was calculated from the capacitance value at 1 MHz using a mercury probe manufactured by Four Dimensions and a HP4285ALCR meter manufactured by Yokogawa Hewlett Packard, They were 2.67, 2.71, and 2.64, respectively.
The appearance of the obtained insulating film was observed with a pocket micro loupe (50 times) manufactured by Peak Co., but no cracks were observed on the coating film surface.
The Young's modulus was measured using Nano Indenter SA2 manufactured by MTS.

<Example 3>
A coating solution was prepared using 1.0 g of only the polymer (1) of Example 1. The obtained coating film was heated at 250 ° C. for 60 seconds on a hot plate under a nitrogen stream, and then baked in a 400 ° C. oven purged with nitrogen for 60 minutes. As a result, a uniform film having a film thickness of 0.5 μm was obtained. Was obtained (Example 1).
When the relative dielectric constant (k value) of the film (measurement temperature: 25 ° C., and so on) was calculated from the capacitance value at 1 MHz using a mercury probe manufactured by Four Dimensions and a HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard, 2.65.
The appearance of the obtained insulating film was observed with a pocket micro loupe (50 times) manufactured by Peak Co., but no cracks were observed on the coating film surface.
Moreover, it was 5.0 GPa when the Young's modulus was measured using Nano Indenter SA2 from MTS.

<Example 4>
A coating solution was prepared with 1.0 g of only the polymer (2) of Example 2. The obtained coating film was heated at 250 ° C. for 60 seconds on a hot plate under a nitrogen stream, and then baked in a 400 ° C. oven purged with nitrogen for 60 minutes. As a result, a uniform film having a film thickness of 0.5 μm was obtained. Was obtained (Example 5).
When the relative dielectric constant (k value) of the film (measurement temperature: 25 ° C., and so on) was calculated from the capacitance value at 1 MHz using a mercury probe manufactured by Four Dimensions and a HP4285ALCR meter manufactured by Yokogawa Hewlett-Packard, 2.63.
The appearance of the obtained insulating film was observed with a pocket micro loupe (50 times) manufactured by Peak Co., but no cracks were observed on the coating film surface.
Moreover, when the Young's modulus was measured using Nano Indenter SA2 manufactured by MTS, it was 3.5 GPa.

<Comparison of increase in dielectric constant with time, mechanical strength and heat resistance>
The increase in relative permittivity with time is represented by Δk.
The heat resistance was evaluated by measuring the change in mass after heating in air at 400 ° C. for 30 seconds.

表１中の化合物（Ａ）の含有量、及び、絶縁膜用樹脂（Ｂ）の含有量は、化合物（Ａ）と絶縁膜用樹脂（Ｂ）との合計量（固形分）に対する割合（質量％）として表した。

The content of the compound (A) in Table 1 and the content of the resin for insulating film (B) are the ratio (mass to the total amount (solid content) of the compound (A) and the resin for insulating film (B). %).

  It can be seen that the insulating film formed using the composition for forming an insulating film of the present invention is excellent in heat resistance and mechanical strength, and exhibits low dielectric constant and stability over time of dielectric constant. In particular, the stability over time is excellent.

Claims (8)

The composition for insulating film formation containing the compound (A) which has at least one partial structure represented by General formula (1) in the molecule | numerator, and resin for insulating films, or its precursor (B).

General formula (1)
(In General Formula (1), R ^{1 to} R ⁶ each independently represent an arbitrary substituent, and arbitrary R ^{1 to} R ⁶ may be linked to each other to form a ring structure. ^Two substituents (R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ ) may represent a double bond.) The compound (A) is a partial structure represented by the general formula (3-1), a partial structure represented by the general formula (3-2), a partial structure represented by the general formula (3-3), The composition for forming an insulating film according to claim 1, which is a compound having at least one partial structure represented by the formula (3-4) or a partial structure represented by the general formula (3-5).

(In the general formula (3-1), R ^{7 to} R ¹⁰ each independently represents an arbitrary substituent, and L ¹ represents a cyclic structure containing C ² and C ^3. Any R ^{7 to} R ¹⁰ and L ¹ may be connected to each other to form a ring.)

(In General Formula (3-2), R ^{11 to} R ¹⁴ each independently represents an arbitrary substituent, and L ² represents a cyclic structure containing C ^1. Each of R ^{11 to} R ¹⁴ and L ² represents They may be connected to each other to form a ring.)

(In the general formula (3-3), R ^{15 to} R ²⁰ each independently represents an arbitrary substituent, and may be connected to each other to form a ring.)

(In the general formula (3-4), R ^{21 to} R ²⁸ each independently represent an arbitrary substituent, and may be connected to each other to form a ring.)

(In General Formula (3-5), R ^{29 to} R ³⁴ each independently represents an arbitrary substituent, and may be connected to each other to form a ring.) The composition for forming an insulating film according to claim 1, wherein the compound (A) is a compound represented by the general formula (2).

General formula (2)
(In the general formula (2), X is a partial structure represented by the general formula (3-1), a partial structure represented by the general formula (3-2), and a part represented by the general formula (3-3). A group having any one of a structure, a partial structure represented by the general formula (3-4), or a partial structure represented by the general formula (3-5), and Y is a 1 to 10-valent aliphatic group Represents a hydrocarbon group, a 1 to 10 valent aromatic hydrocarbon group, or a 1 to 10 valent heterocyclic group, n represents an integer of 1 to 10. When n is 2 or more, X is the same May be different.) The composition for forming an insulating film according to claim 3, wherein X in the general formula (2) is a group represented by the general formula (4).

General formula (4)
(In general formula (4), Z is a structure represented by general formula (5-1), a structure represented by general formula (5-2), a structure represented by general formula (5-3), A structure represented by formula (5-4), a structure represented by general formula (5-5), a structure represented by general formula (5-6), or a general formula (5-7) Any one of the structures, L represents a divalent to 7-valent linking group, or a simple bond, m represents an integer of 1 to 6. When m is 2 or more, Z is the same (If L is a simple bond, m and n in the general formula (2) are the same.)

In the formula, * represents a bonding position with L in the general formula (4).   L in the general formula (4) is a group formed by combining one or two or more selected from the group of an arylene group, an alkylene group, an alkenylene group, an ester group, an amide group, and an ether group. 5. The composition for forming an insulating film according to 4.   The composition for forming an insulating film according to any one of claims 1 to 5, wherein the resin for an insulating film or a precursor thereof (B) is a compound having a cage structure.   The insulating film obtained from the composition for insulating film formation in any one of Claims 1-6.   An electronic device having the insulating film according to claim 7.