JP4730724B2 - Method for producing borazine resin - Google Patents

Description

  The present invention relates to a method for producing a borazine resin, a borazine resin composition, an insulating coating, a method for forming the same, and an electronic component.

  With recent miniaturization, higher output, and higher signal speed of communication equipment, along with the realization of film flattening by CMP, insulating coatings for electronic components (IMD: metal interlayer insulating film, ILD: metal lower layer) In addition to heat resistance, mechanical properties, hygroscopicity, adhesiveness, moldability, high etch selectivity, etc., a low dielectric constant is particularly required for the inter-layer insulating film, PMD (premetal insulating film, etc.).

  In general, the signal propagation speed (v) of the wiring and the relative dielectric constant (ε) of the insulating material in contact with the wiring material have a relationship represented by v = k / √ε (k is a constant). In order to increase the signal propagation speed and reduce the wiring delay, it is necessary to increase the frequency region to be used or to reduce the relative dielectric constant of the insulating material as much as possible.

  As such an insulating coating material, a low dielectric constant material which is currently put into practical use on a mass production basis includes a SiOF film (CVD method) having a relative dielectric constant of about 3.5, and in addition, a relative dielectric constant of 2 Studies of organic SOG (Spin On Glass), organic polymers, etc. of 5 to 3.0 are in progress.

As another organic low dielectric constant material, borazine having a molecular structure in which carbon atoms of benzene are substituted with nitrogen atoms and boron atoms is known to have a lower calculated dielectric constant than benzene. (For example, refer to Patent Document 1). Further, a heat-resistant borazine obtained by mixing a B, B ′, B ″ -trialkynylborazine compound and a silicon compound having at least two hydrosilyl groups in the presence of a platinum catalyst and coating the solution. Containing silicon polymer thin films are also known (see, for example, Patent Document 2).
JP 2000-340689 A JP 2002-155143 A

  By the way, although the organic SOG described above is promising as a low dielectric constant material, in order to cope with further miniaturization and multilayering of electronic components composed of semiconductor devices such as memory elements and logic elements, further reduction of the dielectric constant is required. It is eager. On the other hand, the borazine-containing silicon polymer thin film disclosed in Japanese Patent Application Laid-Open No. 2002-155143 is expected as a next-generation insulating film because of its high heat resistance and low dielectric constant.

  However, such a borazine-containing silicon polymer thin film is obtained by directly applying a solution obtained by mixing a B, B ′, B ″ -trialkynylborazine compound and a silicon compound having a hydrosilyl group in the presence of a platinum catalyst as described above. As a result, the platinum catalyst inevitably remains as an impurity in the thin film, for example, if a metallic impurity is present in the interlayer insulating film, a leakage current is generated and the performance as the insulating film is reduced or deteriorated. Therefore, when the thin film disclosed in Japanese Patent Laid-Open No. 2002-155143 is used for the interlayer insulating film, it is easily imagined that the platinum catalyst becomes a metallic impurity and a leakage current is generated.

  Therefore, the present invention has been made in view of such circumstances, an insulating coating that can reduce the occurrence of leakage current with little metallic impurities, a manufacturing method thereof, and a borazine-based resin composition that can effectively form the insulating coating. An object of the present invention is to provide a method for producing a borazine resin that is a main component of the borazine resin composition. Another object of the present invention is to provide an electronic component that can sufficiently suppress the occurrence of leakage current and sufficiently prevent deterioration and deterioration of characteristics.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research, and as a result, after polymerizing a predetermined borazine compound and a predetermined silicon compound in the presence of the solid catalyst, the solid catalyst is removed, It has been found that metallic impurities derived from the catalyst can be significantly reduced, and the present invention has been completed.

  That is, the present invention is a method for producing a borazine-based resin that is a polymer having a borazine skeleton in the main chain or side chain, wherein B, B ′, B ″ -trialkynylborazines and hydrosilanes are solidified. A borazine-based resin production method comprising: a first step of polymerizing in the presence of a catalyst; and a second step of removing the solid catalyst after performing the first step. To do.

  In the method for producing a borazine resin having such a structure, in the first step, B, B ′, B ″ -trialkynylborazines and hydrosilanes are polymerized, and an organosilicon borazine polymer as a borazine resin is obtained. However, since the solid catalyst is used as the catalyst, the catalyst is removed very easily and with a low residual rate in the second step, and as a result, the organosilicon in which the metal component is sufficiently removed. A borazine-based polymer is obtained.

  Here, the solid catalyst is preferably a supported catalyst in which a catalyst is supported on a compound carrier. By using such a catalyst, it is possible to filter the catalyst from the reaction system as compared with the case where a supported catalyst (for example, a platinum carbon catalyst) in which the catalyst is supported on a non-compound carrier, where it is difficult to increase the catalyst particle size. Since it becomes easy to separate, metallic impurities can be significantly reduced. Further, there is no fear of generation of a leakage current based on the conductivity of the carrier, which is a concern with a catalyst (for example, platinum carbon catalyst) in which a catalyst is supported on a carbon-based carrier.

で表されるものであると好ましい。ここで、式中、Ｒ¹はアルキル基、アリール基、アラルキル基又は水素原子を示し、Ｒ²はアルキル基、アリール基、アラルキル基又は水素原子を示す。 As B, B ′, B ″ -trialkynylborazines, the following formula (1);

It is preferable that it is represented by. Here, in the formula, R ¹ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R ² represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom.

又は下記式（３）；

で表されるものであると有用である。ここで、式中、Ｒ³及びＲ⁴はアルキル基、アリール基、アラルキル基及び水素原子の中から選ばれる同一又は異なる１価の基を示し、Ｒ⁵は置換若しくは未置換の芳香族の２価の基、オキシポリ（ジメチルシロキシ）基、又は酸素原子を示し、Ｒ⁶はアルキル基、アリール基、アラルキル基又は水素原子を示し、ｎは２以上の整数を示す。 More specifically, hydrosilanes are represented by the following formula (2);

Or the following formula (3);

It is useful to be represented by Here, in the formula, R ³ and R ⁴ represent the same or different monovalent groups selected from an alkyl group, an aryl group, an aralkyl group and a hydrogen atom, and R ⁵ represents a substituted or unsubstituted aromatic group 2. A valent group, an oxypoly (dimethylsiloxy) group or an oxygen atom, R ⁶ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and n represents an integer of 2 or more.

  The borazine-based resin composition according to the present invention includes a polymer having a borazine skeleton in the main chain or side chain, and a solvent capable of dissolving the polymer, and has a solid content concentration of 0.5% by mass or more. (The upper limit is preferably 80% by mass), and the metal impurity content is 30 ppm or less. The polymer is a borazine resin produced by the method of producing a borazine resin according to the present invention and exhibits a low relative dielectric constant, and is dissolved in a solvent such as a semiconductor substrate. It can be easily applied on a substrate.

  When the solid content concentration in the borazine-based resin composition is less than 0.5% by mass, the thickness of the coating film obtained by one application is reduced when applied on the substrate, the strength of the film and There are disadvantages in that the heat resistance and the reliability of the insulating properties when dried to form an insulating coating are reduced. Further, if the metal impurity content exceeds 30 ppm, the low relative dielectric constant required when this borazine-based resin composition is used, for example, as an interlayer insulating film of a multilayer wiring having an ultrafine structure may not be achieved. Or generation | occurrence | production of leak current will become remarkable and there exists a possibility of producing the deterioration of device characteristics, such as an element. The “solid content concentration” represents the amount of a component remaining when a volatile component such as a solvent is dried in the resin composition.

で表される繰り返し単位を有するものであると、成膜性、化学的安定性の観点から好ましい。 Furthermore, the polymer is represented by the following formula (4);

It is preferable from a viewpoint of film forming property and chemical stability to have a repeating unit represented by

Here, in the formula, R ¹ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, R ² represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, R ³ and R ⁴ represent an alkyl group, an aryl group R ⁵ represents a substituted or unsubstituted aromatic divalent group, an oxypoly (dimethylsiloxy) group, or an oxygen atom, and represents the same or different monovalent group selected from a group, an aralkyl group and a hydrogen atom. , R ⁶ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, a represents a positive integer, b represents 0 or a positive integer, p represents 0 or a positive integer, and q represents 0 or Indicates a positive integer.

  The method for forming an insulating coating according to the present invention is a method for forming an insulating coating on a substrate. The borazine-based resin composition according to the present invention is coated on a substrate to form a coating film, and the coating film is formed. It is characterized by drying.

  In addition, the insulating coating according to the present invention is provided on the substrate and is formed by the method for forming an insulating coating according to the present invention, and in particular, adjacent to each other among the plurality of conductive layers provided on the substrate. It is useful as an interlayer insulating film that is formed between the conductive layers, that is, it is necessary to sufficiently reduce the leakage current.

  And the electronic component by this invention comprises electronic devices, such as an electronic component by which the insulating film by this invention is formed, a semiconductor device, and a liquid crystal device.

  According to the borazine-based resin, the production method thereof, and the borazine-based resin composition of the present invention, it is possible to form an insulating film that has few metallic impurities and can sufficiently suppress the occurrence of leakage current. Further, according to the insulating coating and the manufacturing method thereof of the present invention, it is possible to sufficiently suppress the occurrence of leakage current and improve various characteristics such as heat resistance. Furthermore, according to the electronic component of the present invention, it is possible to sufficiently suppress the occurrence of leakage current and sufficiently prevent deterioration and deterioration of characteristics.

  Hereinafter, preferred embodiments of a method for producing a borazine-based resin, a borazine-based resin composition, a method for forming an insulating film, an insulating film, and an electronic component according to the present invention will be described with reference to chemical formulas and drawings.

(Method for producing borazine resin)
First, the borazine resin produced by this production method will be described. In this production method, the borazine resin produced by polymerizing B, B ′, B ″ -trialkynylborazines and hydrosilanes as monomer components has a borazine skeleton in the main chain or side chain. A polymer (hereinafter, a polymer having such a structure is simply referred to as “borazine resin”).

The borazine-based resin may be a polymer having a substituted or unsubstituted borazine skeleton in the main chain or the side chain. For example, see Chemical Review, vol 90, pp. 73-91 (1990). And CHEMTECH, July 1994, pp. 29-37. The polymers described can be mentioned. Specifically, a polymer having at least one repeating unit shown below is suitable.

  The molecular weight of borazine resin (Mn; number average molecular weight measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve) is preferably 500 to 5000000, more preferably 1000 to 1 million. When this molecular weight (Mn) is excessively low, for example less than 500, the heat resistance and the mechanical properties of the insulating coating described later tend to be inferior. For example, pre-baking is difficult when using such an insulating coating as an interlayer insulating film. There is a risk that peeling or the like is likely to occur when planarization after film formation is performed by CMP. On the other hand, if the molecular weight (Mn) is excessively high, for example, exceeds 5000000, the workability of the insulating coating deteriorates. For example, a via hole for forming a metal plug such as W is formed in the insulating coating in a desired shape. May be difficult to control.

As the borazine-based resin, an organosilicon borazine-based polymer having a repeating unit represented by the following formula (4) or formula (5) is excellent in film formability and chemical stability. A more preferable example can be given.

は、以下のいずれかを示し、

これと同様に、

は、以下のいずれかを示す。

In equations (4) and (5),

Indicates one of the following:

Like this,

Indicates one of the following:

は、以下のいずれかを示す。

And

Indicates one of the following:

  Moreover, the broken line in Formula (4) means that the bond has arisen in the carbon derived from the alkynyl group in a borazine residue, and the broken line in Formula (5) has a bond in the carbon derived from the alkenyl group in the borazine residue. It means that it has occurred.

In the formulas (4) and (5), R ¹ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom. In this case, the carbon number of the alkyl group is preferably 1 to 24, more preferably 1 to 12. Moreover, carbon number of an aryl group becomes like this. Preferably it is 6-20, More preferably, it is 6-10. Furthermore, the carbon number of the aralkyl group is preferably 7 to 24, more preferably 7 to 12. More specifically, as the group R ¹ , an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and an octyl group, an aryl group such as a phenyl group, a naphthyl group, and a biphenyl group, a benzyl group, and a phenethyl group And an aralkyl group such as a hydrogen atom, and the like. Among these, a methyl group, an ethyl group, a phenyl group, or a hydrogen atom is more preferable.

And in Formula (4) and (5), R < ² > shows an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom, Preferably carbon number of an alkyl group is 1-24, More preferably, it is 1-12. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Moreover, carbon number of an aralkyl group becomes like this. Preferably it is 7-24, More preferably, it is 7-12. More specifically, the group R ² includes an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and an octyl group, an aryl group such as a phenyl group, a naphthyl group, a biphenyl group, and an anthracenyl group, and a benzyl group. , An aralkyl group such as a phenethyl group and a fluorenyl group, a hydrogen atom, and the like. Among these, a methyl group, a phenyl group, or a hydrogen atom is more preferable.

Further, in the formulas (4) and (5), R ³ and R ⁴ represent the same or different monovalent groups selected from an alkyl group, an aryl group, an aralkyl group or a hydrogen atom. A group, an aryl group or a hydrogen atom is more preferable. In this case, the carbon number of the alkyl group is preferably 1 to 24, more preferably 1 to 12. Moreover, carbon number of an aryl group becomes like this. Preferably it is 6-20, More preferably, it is 6-10. Furthermore, the carbon number of the aralkyl group is preferably 7 to 24, more preferably 7 to 12. More specifically, as the groups R ³ and R ⁴ , alkyl groups such as methyl group, ethyl group, isopropyl group, t-butyl group and octyl group, aryl groups such as phenyl group, naphthyl group and biphenyl group, benzyl group , An aralkyl group such as a phenethyl group, a hydrogen atom, and the like. Among these, a methyl group, a phenyl group, or a hydrogen atom is more preferable.

Furthermore, in the formulas (4) and (5), R ⁵ represents a substituted or unsubstituted aromatic divalent group, an oxypoly (dimethylsiloxy) group, or an oxygen atom. In this case, the carbon number of the aromatic divalent group is preferably 6 to 24, more preferably 6 to 12. This aromatic divalent group includes an arylene group containing a heteroatom such as oxygen as a linking group in addition to a divalent aromatic hydrocarbon group (arylene group or the like). In addition, examples of the substituent that may be bonded to the aromatic divalent group include an alkyl group, an aryl group, and an aralkyl group. More specifically, examples of the group R5 include arylene groups such as a phenylene group, naphthylene group, and biphenylene group, substituted arylene groups such as a diphenyl ether group, oxygen atoms, and the like. Among these, a phenylene group, a diphenyl ether group, or an oxygen atom Is more preferable.

Furthermore, in the formulas (4) and (5), R ⁶ represents an alkyl group, an aryl group or an aralkyl group. In this case, the carbon number of the alkyl group is preferably 1 to 24, more preferably 1 to 12. Moreover, carbon number of an aryl group becomes like this. Preferably it is 6-20, More preferably, it is 6-10. Furthermore, the carbon number of the aralkyl group is preferably 7 to 24, more preferably 7 to 12. More specifically, the group R ⁶ includes an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and an octyl group, an aryl group such as a phenyl group, a naphthyl group, and a biphenyl group, a benzyl group, and a phenethyl group. And aralkyl groups such as

  Moreover, in Formula (4) and (5), a and b represent the number of repeating units, respectively, a is a positive integer, Preferably it is 1-20000, More preferably, it is 3-10000, Especially preferably Is 5 to 10,000. B is 0 or a positive integer, preferably 0 to 1000, more preferably 0 to 100. However, a and b show those constituent ratios, and are not limited to any form of bonding state (block copolymerization, random copolymerization, etc.).

  In such a copolymer, the ratio (a: b) of the number of each of a and b is not particularly limited, and the a / b ratio is larger, that is, the ratio of the chain structure in the polymer main chain is larger. When the amount is relatively large, it is expected that the processability of the copolymer is improved by increasing the solubility of the copolymer in the solvent and decreasing the melting point. On the other hand, when the a / b ratio is small, that is, when the ratio of the crosslinked structure in the polymer main chain is relatively large, the heat resistance and combustion resistance of the copolymer are expected to be improved. Therefore, the optimum a / b ratio of the copolymer that gives good processability, heat resistance, and combustion resistance depending on the use etc., or on the structure of each monomer unit of the copolymer and the combination thereof. The range can be set as appropriate.

  Further, in the formulas (4) and (5), p represents 0 or a positive integer, q represents 0 or a positive integer, and n described later has a relationship of p + q + 2 = n. The preferable range of p is 0 to 10, more preferably 1 to 8. Moreover, the preferable range of q is 0-10, More preferably, it is 1-8.

又は下記式（７）；

で表される２価の基であり、同一分子鎖において、Ｚ¹が式（６）又は（７）のいずれか一方の構造で構成されていても、或いは、両方の構造が同一分子鎖内に含まれていても構わない。なお、式（６）及び（７）におけるＲ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、ｐ及びｐは前述したものと同様である。 Furthermore, in the formulas (4) and (5), Z ¹ represents the following formula (6);

Or the following formula (7);

In the same molecular chain, Z ¹ is composed of either one of the structures of formula (6) or (7), or both structures are within the same molecular chain. May be included. In the formulas (6) and (7), R ³ , R ⁴ , R ⁵ , R ⁶ , p and p are the same as those described above.

  Next, a preferred embodiment of each step in the method for producing a borazine resin according to the present invention will be described.

The B, B ′, B ″ -trialkynylborazines (x) used in the first step are preferably compounds represented by the following formula (1).

In the above formula (1), R ¹ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom. In this case, the alkyl group has 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. Moreover, carbon number of an aryl group is 6-20, Preferably it is 6-10. Furthermore, the carbon number of the aralkyl group is 7 to 24, preferably 7 to 12. More specifically, as the group R ¹ , an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and an octyl group, an aryl group such as a phenyl group, a naphthyl group, and a biphenyl group, a benzyl group, and a phenethyl group An aralkyl group such as a hydrogen atom and the like, and among them, a methyl group, an ethyl group, a phenyl group or a hydrogen atom is more preferable.

In the formula (1), R ² represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom. In this case, the alkyl group has 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. Moreover, carbon number of an aryl group is 6-20, Preferably it is 6-10. Furthermore, the carbon number of the aralkyl group is 7 to 24, preferably 7 to 12. More specifically, the group R ² includes an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and an octyl group, an aryl group such as a phenyl group, a naphthyl group, a biphenyl group, and an anthracenyl group, and a benzyl group. , An aralkyl group such as a phenethyl group and a fluorenyl group, a hydrogen atom, and the like. Among these, a methyl group, a phenyl group, or a hydrogen atom is more preferable.

  More specifically, the B, B ′, B ″ -trialkynylborazines (x) represented by the formula (1) are specifically exemplified as B, B ′, B ″ -triethynylborazine, B, B ′, B ″. -Triethynyl-N, N ', N "-trimethylborazine, B, B', B" -tri (1-propynyl) borazine, B, B ', B "-triphenylethynylborazine, B, B', B" -Triphenylethynyl-N, N ', N "-trimethylborazine, B, B', B" -triethynyl-N, N ', N "-triphenylborazine, B, B', B" -triphenylethynyl- N, N ', N "-triphenylborazine, B, B', B" -ethynyl-N, N ', N "-tribenzylborazine, B, B', B" -tris (1-propynyl) -N , N ′, N ″ -trimethylborazine and the like. However, it is not limited to these. Further, one kind of B, B ′, B ″ -trialkynylborazines can be used alone, but two or more kinds of B, B ′, B ″ -trialkynylborazines may be used in combination.

The hydrosilanes (y) used in the first step are preferably those represented by the following formula (2) or the following formula (3).

In the formula (2), R ³ and R ⁴ represent the same or different monovalent group selected from an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and among these, an alkyl group, an aryl group or a hydrogen atom Atoms are more preferred. In this case, the alkyl group has 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. Moreover, carbon number of an aryl group is 6-20, Preferably it is 6-10. Furthermore, the carbon number of the aralkyl group is 7 to 24, preferably 7 to 12. More specifically, as the groups R ³ and R ⁴ , alkyl groups such as methyl group, ethyl group, isopropyl group, t-butyl group and octyl group, aryl groups such as phenyl group, naphthyl group and biphenyl group, benzyl group , An aralkyl group such as a phenethyl group, a hydrogen atom, and the like. Among these, a methyl group, a phenyl group, or a hydrogen atom is more preferable.

In the formula (2), R ⁵ represents a substituted or unsubstituted aromatic divalent group, an oxypoly (dimethylsiloxy) group, or an oxygen atom. In this case, the aromatic divalent group has 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms. This aromatic divalent group includes an arylene group containing a heteroatom such as oxygen as a linking group in addition to a divalent aromatic hydrocarbon group (arylene group or the like). In addition, examples of the substituent that may be bonded to the aromatic divalent group include an alkyl group, an aryl group, and an aralkyl group. More specifically, examples of the group R ⁵ include arylene groups such as a phenylene group, naphthylene group, and biphenylene group, substituted arylene groups such as a diphenyl ether group, oxygen atoms, and the like. Among these, a phenylene group, a diphenyl ether group, or an oxygen atom Atoms are more preferred.

Further, in the formula (3), R ⁶ represents an alkyl group, an aryl group or an aralkyl group. In this case, the alkyl group has 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. Moreover, carbon number of an aryl group is 6-20, Preferably it is 6-10. Furthermore, the carbon number of the aralkyl group is 7 to 24, preferably 7 to 12. More specifically, the group R ⁶ includes an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and an octyl group, an aryl group such as a phenyl group, a naphthyl group, and a biphenyl group, a benzyl group, and a phenethyl group. And aralkyl groups such as

  Furthermore, in the formula (3), n represents a positive integer of 2 or more. P and q in the above formula (4) have a relationship of p + q + 2 = n. The preferable range of n is 2 to 10, more preferably 3 to 8. When n is excessively large (in other words, the ring is large) and exceeds 10, for example, the heat resistance and the mechanical properties of the insulating film described later tend to be disadvantageously lowered.

  Hydrosilanes (y) represented by formula (2) or (3) include bis (monohydrosilane) s, bis (dihydrosilanes), bis (trihydrosilanes), and poly (hydrosilanes). Specific examples include m-bis (dimethylsilyl) benzene, p-bis (dimethylsilyl) benzene, 1,4-bis (dimethylsilyl) naphthalene, 1,5-bis (dimethylsilyl) naphthalene, m-bis (methyl Ethylsilyl) benzene, m-bis (methylphenylsilyl) benzene, p-bis (methyloctylsilyl) benzene, 4,4′-bis (methylbenzylsilyl) biphenyl, 4,4′-bis (methylphenethylsilyl) diphenyl ether M-bis (methylsilyl) benzene, m-disilylbenzene, 1,1,3,3-tetramethyl-1,3-disiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3 , 5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7-tetraethylcyclotetrasiloxane Emissions, 1,3,5 triphenyl cyclotrisiloxane, 1,3,5,7-tetraphenyl cyclotetrasiloxane, 1,3,5,7-tetra benzyl cyclotetrasiloxane and the like. However, it is not limited to these.

  Among these, m-bis (dimethylsilyl) benzene, p-bis (dimethylsilyl) benzene or 1,1,3,3-tetramethyl-1,3-disiloxane, 1,3,5,7-tetra More preferred is methylcyclotetrasiloxane. One hydrosilane (y) can be used alone, but two or more hydrosilanes (y) may be used in combination.

  The solid catalyst (z) used in the first step promotes the polymerization reaction (hydrosilylation polymerization) of B, B ′, B ″ -trialkynylborazines (x) and hydrosilanes (y) described above, A metal-containing catalyst that does not elute into the reaction substrate (x and y) or a polymerization solvent that can be optionally added, which will be described later, and can be removed by filtration after the completion of polymerization is preferred.

Specific examples of the solid catalyst (z) include simple metal powders such as platinum powder, palladium powder and nickel powder; a catalyst in which a catalyst is supported on a carbon-based support such as platinum carbon, palladium carbon and rhodium carbon; a compound-based support ( Examples thereof include a supported catalyst in which a catalyst is supported on a non-carbon carrier. Examples of supported catalysts in which a catalyst is supported on a compound carrier include platinum oxide, platinum silica, palladium alumina, palladium silica, rhodium alumina, rhodium silica and other metal oxide carrier supported catalysts; Raney nickel and other alloy catalysts; Marciniec ed, Comprehensive Handbook on Hydrosilylation, Pergamon Press (1992) and Polymer Journal, 34,97-102 polymer-supported rhodium catalyst according to _{(2002) (polym-PPh 2} · RhCl (PPh 3) 3, polym-PPh 2 · RhCl ₃ , polym-CH ₂ Cl ₂ .RhCl (CO) (PPh ₃ ) ₂ ); polymer-supported platinum catalyst (Polym-CH ₂ SH / H ₂ PtCl ₆ ) (where poly is poly (styrene-co- A main chain skeleton such as divinylbenzene)); surface functionalized silica gel supported platinum catalyst (Silica- (CH ₂ ) ₃ —SH / H ₂ PtCl ₆ ). These catalysts may be used alone or in combination of two or more.

  The solid catalyst (z) is preferably a supported catalyst in which a catalyst is supported on a single metal powder or a compound carrier, and a supported catalyst in which a catalyst is supported on a compound carrier is particularly preferable. Since the catalyst particle size can be easily controlled, those having a large particle size can be produced relatively easily. By using a catalyst of such a size, it is easy to filter the catalyst from the reaction system. become. Moreover, generation | occurrence | production of the leakage current at the time of using the obtained borazine type resin as an insulating film can be suppressed especially effectively. On the other hand, since a catalyst in which a catalyst is supported on a carbon-based carrier exists as a fine powder, the sedimentation rate in the reaction system is slow, and it is not always easy to remove the catalyst to a sufficient level. In addition, since the support is made of conductive carbon, there is a possibility that a leakage current is generated in the insulating film when the catalyst is present in a very small amount.

  In the first step, when the polymerization reaction of B, B ′, B ″ -trialkynylborazines (x) and hydrosilanes (y) is caused, the fluidity of the system during the polymerization is maintained, In order to facilitate the removal of the solid catalyst (z) later, a polymerization solvent (s) may be added to the system, and the polymerization solvent (s) may be one that reacts with the raw materials (x, y) or a solid. Various solvents other than those in which the catalyst (z) is decomposed or the metal component elutes can be used, such as aromatic hydrocarbons, saturated hydrocarbons, aliphatic ethers, aromatics. Examples include ether-based solvents, and more specifically, toluene, benzene, xylene, ethylbenzene, propylbenzene, hexylbenzene, hexane, tetrahydrofuran, ethylene glycol dimethyl ether, diphenyl Ether and the like. These polymerization solvents may be used alone or may be used in combination.

  In the first step, the charged molar ratio of B, B ′, B ″ -trialkynylborazines (x) and hydrosilanes (y) is 1 mol of B, B ′, B ″ -trialkynylborazines. The bis (hydrosilane) is preferably in the range of 0.1 to 10 mol, and more preferably, the bis (hydrosilane) is in the range of 0.1 to 1 mol of B, B ′, B ″ -trialkynylborazines. The range is 2 to 5 mol.

  In the first step, the amount of the solid catalyst (z) used is such that the molar ratio of the metal atom to the raw material compound having a smaller molar amount of B, B ′, B ″ -trialkynylborazines or hydrosilanes. It is suitable in the range of 0.000001-5.

  In the first step, when the polymerization solvent (s) is used, 50 to 100,000 parts by weight of the polymerization solvent (s) with respect to 100 parts by weight of the total amount of B, B ′, B ″ -trialkynylborazines and hydrosilanes. It is desirable to use it.

  The reaction temperature and reaction time in the first step are not particularly limited as long as B, B ′, B ″ -trialkynylborazines and hydrosilanes are polymerized to obtain an organosilicon borazine polymer having a desired molecular weight. Specifically, although it depends on the reactivity of the raw materials and the activity of the catalyst, the reaction temperature can be cooled or heated in the range of −20 ° C. to 200 ° C. The more preferable reaction temperature is 0 ° C. to 150 ° C. The reaction time is preferably 1 minute to 10 days, more preferably 1 hour to 10 days, and particularly preferably 2 hours to 7 days.

  The first step is desirably performed in an inert atmosphere such as dry nitrogen or argon, and can be performed in the air from the viewpoint of simplifying the apparatus configuration.

  After the first step, the solid catalyst (z) is removed in the second step. The removal is preferably carried out by filtering off the reaction solution obtained in the first step. As a filtering method, commonly used filtration methods such as natural filtration, suction filtration, and pressure filtration can be used. In addition, filter paper, filter cloth, resin film, and the like can be used as the filter medium, and further, removal of the catalyst by natural sedimentation, centrifugation, or the like is also included in another aspect of filtration. Thus, by removing the solid catalyst (z), a filtrate containing a borazine resin (organosilicon borazine polymer) having a reduced metal impurity content can be obtained.

After the second step, a borazine-based resin may be obtained as a solid polymer by removing the polymerization solvent (z) by concentrating the obtained filtrate under reduced pressure or heating. Further, borazine-based resin may be obtained by fractionation by reprecipitation, gel filtration column, GPC (gel permeation chromatogram) column or the like. In addition, the filtrate obtained in the second step can be used as it is as a borazine-based resin composition (C) described later.
(Borazine resin composition (C))

  Next, a preferred embodiment of the borazine-based resin composition (C) according to the present invention will be described.

  The borazine-based resin composition (C) can be produced by uniformly mixing a borazine-based resin obtained by the above-described borazine-based resin production method and a solvent described later. Specifically, the filtrate obtained in the second step may be used as it is as the borazine-based resin composition (C), and a solvent having a boiling point higher than that of the polymerization solvent is added to the filtrate obtained in the second step. Alternatively, it may be produced by distilling off the low boiling polymerization solvent. In the latter case, the borazine resin composition (C) is a mixture of a high boiling point solvent and a borazine resin. The borazine-based resin composition (C) may be produced by dissolving the solid borazine polymer produced as described above in a solvent described later after the second step.

  The solvent capable of dissolving the borazine resin is preferably a solvent capable of dissolving the borazine resin without reacting with it. Such solvents include hydrocarbon solvents such as toluene, benzene, xylene, mesitylene, ethylbenzene, propylbenzene, hexylbenzene, tetralin, pentane, hexane, heptane, cyclohexane, dimethylcyclohexane, ethylene glycol dimethyl ether, tetrahydrofuran, 1,4- Ether solvents such as dioxane and diphenyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, pentyl acetate and γ-butyrolactone, N , N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, quinoline, etc. Nitrogen-containing solvents, halogenated solvents such as chloroform, and dimethyl sulfoxide.

  These solvents may be used alone or in combination. The amount of the solvent used is preferably such that the solid content concentration of the borazine-based resin is preferably 0.5 to 80% by mass, more preferably 1 to 70% by mass, and further preferably 2 to 60% by mass. When this solid content concentration is less than 0.5% by mass, the thickness of the coating film obtained by a single application is reduced when applied on the substrate, and the strength and heat resistance of the film are reduced. As a result, the reliability of the insulation characteristics when an insulating film is formed tends to be lowered. On the other hand, when the solid content concentration exceeds 80% by mass, the viscosity of the borazine-based resin composition (C) is excessively increased, and it tends to be difficult to form a uniform thin film.

  The thus-configured borazine-based resin composition (C) has a sufficiently reduced content of impurities such as metal components derived from the solid catalyst (z) and further halogen. The metal impurity content in the borazine-based resin composition (C) does not adversely affect the insulating coating production apparatus, and when such an insulating coating is used as an interlayer insulating film, a leak current is generated, the dielectric constant, etc. From the standpoint that the characteristics of the insulating film are not deteriorated, it is preferably 30 ppm or less, more preferably 10 ppm or less, still more preferably 5 ppm or less in the borazine-based resin composition (C).

By the way, as another method for reducing the impurity concentration, a method of diluting the borazine-based resin composition (C) with a solvent having a very low impurity concentration is also assumed. However, this method can reduce the damage to the insulating film production apparatus, but has the disadvantage that the solid concentration in the borazine-based resin composition (C) is also lowered at the same time. In addition, the ratio of the impurity concentration to the solid concentration is not reduced.
(Insulation film formation method, insulation film and electronic parts)

  Next, preferred embodiments of the insulating film forming method, the insulating film, and the electronic component according to the present invention will be described.

  Using the borazine-based resin composition (C) described above, an insulating film according to the present invention can be formed by, for example, the method described below. That is, a borazine resin composition (C) is applied on a substrate such as a silicon wafer, a metal substrate, or a ceramic substrate by a dipping method, a spray method, a screen printing method, a spin coating method, or the like, and a coating film is first formed. . Subsequently, the coating film is heated and dried in air or an inert gas such as nitrogen at 60 to 500 ° C. for 10 seconds to 2 hours to remove the solvent. Thereby, an insulating coating composed of a thin film without stickiness can be obtained. Although the thickness of the insulating coating is not particularly limited, it is preferably 0.05 to 50 μm, more preferably 0.1 to 10 μm, and particularly preferably 0.2 to 5 μm from the viewpoint of heat resistance and the like.

  Further, examples of the electronic component according to the present invention using the insulating coating formed in this way include those having an insulating coating such as a semiconductor element, a liquid crystal element, and a multilayer wiring board. The insulating coating of the present invention is used as an insulating film such as a surface protective film, a buffer coat film and an interlayer insulating film in a semiconductor element, as a surface protective film and an insulating film in a liquid crystal element, and as an interlayer insulating film in a multilayer wiring board. It can be preferably used as a film.

  Specifically, as semiconductor elements, individual semiconductor elements such as diodes, transistors, capacitors, compound semiconductor elements, thermistors, varistors, thyristors, DRAMs (dynamic random access memories), SRAMs (static random access memories). Memory (memory), EPROM (erasable programmable read only memory), mask ROM (mask read only memory), EEPROM (electrically erasable programmable read only memory), flash memory, etc. (memory) ) Theory (circuit) elements such as elements, microprocessors, DSPs, ASICs, etc., integrated circuit elements such as compound semiconductors represented by MMIC (monolithic microwave integrated circuits), hybrid integrated circuits Hybrid IC), light emitting diode, a photoelectric conversion element such as a charge coupled device, the light emitting element, such as a semiconductor laser element and the like. Examples of the multilayer wiring board include a high-density wiring board such as MCM.

  Here, FIG. 4 is a schematic cross-sectional view showing a preferred embodiment of the electronic component according to the present invention. The memory capacitor cell 8 (electronic component) functions as a gate electrode 3 (word line) provided via a gate insulating film 2B made of an oxide film on the silicon wafer 1 (base) on which the diffusion regions 1A and 1B are formed. )) And a counter electrode 8C provided thereabove, interlayer insulating films 5 and 7 (insulating films) having a two-layer structure are formed. Side wall oxide films 4A and 4B are formed on the side wall of the gate electrode 3, and a field oxide film 2A is formed in the diffusion region 1B on the side of the gate electrode to separate elements.

  The interlayer insulating film 5 is deposited on the gate electrode 3 and the field oxide film 2A, and is formed by spin coating the borazine resin composition (C) of the present invention. Near the gate electrode 3 in the interlayer insulating film 5, a contact hole 5A in which an electrode 6 functioning as a bit line is embedded is formed. Further, a planarized interlayer insulating film 7 is deposited on the planarized interlayer insulating film 5, and a storage electrode 8A is embedded in a contact hole 7A formed so as to penetrate both. . The interlayer insulating film 7 is formed by spin-coating the borazine-based resin composition (C) of the present invention in the same manner as the interlayer insulating film 5. A counter electrode 8C is provided on the storage electrode 8A via a capacitor insulating film 8B made of a high dielectric material. The interlayer insulating films 5 and 7 may have the same composition or different compositions.

  According to the electronic component such as the memory capacitor cell 8 formed with the insulating film of the present invention configured as described above, the relative dielectric constant of the insulating film is sufficiently reduced as compared with the conventional one. The delay time can be sufficiently shortened and the occurrence of leakage current can be effectively prevented. As a result, high performance of the element can be achieved and at the same time high reliability can be realized.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

<Example 1>
(Production of borazine-based resin composition 1)
B, B ′, B ″ -triethynyl-N, N ′, N ″ -trimethylborazine 0.1 g (0.50 mmol) and p-bis (dimethylsilyl) benzene 0.1 g (0.50 mmol) were dissolved in 4 ml of ethylbenzene. Then, 0.4 g (0.1 mmol in terms of platinum) of 5% platinum / alumina, which is a supported catalyst having a catalyst supported on a compound carrier, was added and stirred at 50 ° C. for 7 days. A part of the reaction solution was taken out and subjected to gas chromatography (GC) analysis. As a result, B, B ′, B ″ -triethynyl-N, N ′, N ″ -trimethylborazine and p-bis (dimethylsilyl) as monomers were used. ) It was confirmed that the benzene peak almost disappeared.

  FIG. 1 is a graph showing a gas chromatogram of the reaction liquid immediately after the start of polymerization, and FIG. 2 is a graph showing a gas chromatogram of the reaction liquid after stirring for 3 days from the start of polymerization. “A” in FIG. 1 is a peak corresponding to p-bis (dimethylsilyl) benzene, and “b” in FIGS. 1 and 2 is B, B ′, B ″ -triethynyl-N, N ′, N ″. -A peak corresponding to trimethylborazine.

  Moreover, the molecular weight (standard polystyrene standard) of the product was Mn = 2500 (Mw / Mn = 2.0) from GPC analysis. FIG. 3 is a graph showing a GPC chart of the obtained polymer. The reaction liquid containing the platinum / alumina catalyst was filtered through a disposable membrane filter unit (average pore diameter of the filter: 0.5 μm) manufactured by ADVANTEC to obtain a borazine-based resin composition 1.

<Example 2>
(Production of borazine-based resin composition 2)
B, B ′, B ″ -triethynyl-N, N ′, N ″ -trimethylborazine 0.1 g (0.50 mmol), 1,3,5,7-tetramethylcyclotetrasiloxane 0.12 g (0.50 mmol) Was dissolved in 4 ml of ethylbenzene, 0.4 g (0.1 mmol in terms of platinum) of 5% platinum / alumina, which was a supported catalyst in which the catalyst was supported on a compound carrier, was added and stirred at 50 ° C. for 7 days. A part of the reaction solution was taken out and subjected to gas chromatography (GC) analysis. As a result, the peak of the monomer B, B ′, B ″ -triethynyl-N, N ′, N ″ -trimethylborazine almost disappeared. I confirmed. Moreover, the molecular weight (standard polystyrene standard) of the product from GPC analysis was Mn = 3000 (Mw / Mn = 2.2). The reaction solution containing the platinum / alumina catalyst was filtered with a disposable membrane filter unit (average pore size of the filter: 0.5 μm) manufactured by ADVANTEC to obtain a borazine-based resin composition 2.

<Example 3>
(Production of borazine-based resin composition 3)
A polymer-supported platinum catalyst (Polym-CH ₂ SH / H ₂ PtCl ₆ ) described in Polymer Journal, 34, 97-102 (2002) (0.01 mmol in terms of platinum) as a supported catalyst in which a catalyst is supported on a compound carrier. A borazine-based resin composition 3 was obtained in the same manner as in Example 1, except that

<Example 4>
A borazine-based resin composition was obtained in the same manner as in Example 1 except that a platinum carbon catalyst, which was a catalyst in which a catalyst was supported on a carbon-based carrier, was used as the solid catalyst, but a disposable membrane filter unit manufactured by ADVANTEC ( In the filtration with the average pore diameter of the filter: 0.5 μm, the platinum carbon catalyst remained in the filtrate. Therefore, the filter was refiltered with the above unit with the average pore diameter of the filter being 0.2 μm, and the borazine resin composition 4 was obtained. Obtained.

<Comparative example 1>
(Production of borazine-based resin composition 5)
B, B ′, B ″ -triethynyl-N, N ′, N ″ -trimethylborazine (0.50 mmol) and p-bis (dimethylsilyl) benzene (0.50 mmol) are dissolved in ethylbenzene (8 ml), and the homogeneous metal catalyst platinum divinyltetra 10 μl of a methyldisiloxane xylene solution (containing 2% platinum) was added and stirred at room temperature under nitrogen for 3 days. A part of the reaction solution was taken out and subjected to gas chromatography (GC) analysis. As a result, B, B ′, B ″ -triethynyl-N, N ′, N ″ -trimethylborazine and p-bis (dimethylsilyl) as monomers were used. ) The benzene peak was confirmed to have disappeared. Moreover, the molecular weight (standard polystyrene standard) of the product was Mn = 4300 (Mw / Mn = 2.5) from GPC analysis. This reaction solution was designated as a borazine-based resin composition 5.

<Example 5>
(Manufacture of insulating coating 1)
The borazine-based resin composition 1 obtained in Example 1 was filtered and the filtrate was dropped on a low resistivity silicon wafer (substrate; resistivity <10 Ωcm) and spin coated. The silicon wafer was then heated on a hot plate in a nitrogen atmosphere at 200 ° C. for 1 hour, and then baked at 300 ° C. for 30 minutes and at 400 ° C. for 30 minutes to obtain the insulating coating 1 of the present invention.

<Example 6>
(Manufacture of insulating coating 2)
An insulating coating 2 of the present invention was obtained in the same manner as in Example 5 except that the borazine-based resin composition 2 obtained in Example 2 was used instead of the borazine-based resin composition 1.

<Example 7>
(Manufacture of insulating coating 3)
An insulating coating 3 of the present invention was obtained in the same manner as in Example 5 except that the borazine-based resin composition 3 obtained in Example 3 was used instead of the borazine-based resin composition 1.

<Example 8>
(Manufacture of insulating coating 4)

  An insulating coating 4 of the present invention was obtained in the same manner as in Example 5 except that the borazine-based resin composition 4 obtained in Example 4 was used instead of the borazine-based resin composition 1.

<Comparative example 2>
(Manufacture of insulating coating 5)
An insulating coating 5 was obtained in the same manner as in Example 5 except that the borazine-based resin composition 5 obtained in Comparative Example 1 was used instead of the borazine-based resin composition 1.

<Example 9>
(Production of borazine-based resin composition 6)
B, B ′, B ″ -tris (1′-propynyl) -N, N ′, N ″ -trimethylborazine 0.1 g (0.50 mmol), 1,3,5,7-tetramethylcyclotetrasiloxane 12 g (0.50 mmol) was dissolved in 4 ml of ethylbenzene, and 0.4 g (0.1 mmol in terms of platinum) of 5% platinum / alumina, which is a supported catalyst obtained by supporting the catalyst on a compound carrier, was added at 50 ° C. under nitrogen. Stir for 7 days. A part of the reaction solution was taken out and subjected to gas chromatography (GC) analysis. As a result, B, B ′, B ″ -tris (1′-propynyl) -N, N ′, N ″ -trimethylborazine as a monomer and It was confirmed that the peak of 1,3,5,7-tetramethylcyclotetrasiloxane almost disappeared. Moreover, the molecular weight (standard polystyrene standard) of the product from GPC analysis was Mn = 7000 (Mw / Mn = 5.0). The reaction solution containing the platinum / alumina catalyst was filtered with a disposable membrane filter unit (average pore diameter of the filter: 0.5 μm) manufactured by ADVANTEC to obtain a borazine-based resin composition 6.

<Example 10>
(Manufacture of insulating coating 6)
An insulating coating 6 of the present invention was obtained in the same manner as in Example 5 except that the borazine-based resin composition 6 obtained in Example 9 was used instead of the borazine-based resin composition 1.

<Relative permittivity measurement>
The relative dielectric constant of each insulating coating obtained in each example and each comparative example was measured. Here, the “relative permittivity” of the insulating coating in the present invention means a value measured in an atmosphere of 23 ° C. ± 2 ° C. and humidity of 40 ± 10%. Al metal and an N-type low resistivity substrate (Si It is obtained from the measurement of the charge capacity between the wafers.

  Specifically, after forming an insulating film in each of the examples and comparative examples, an Al metal is vacuum-deposited on the insulating film by a vacuum vapor deposition device so as to have a thickness of about 0.1 μm in a circle with a diameter of 2 mm. To do. As a result, a structure in which the insulating coating is disposed between the Al metal and the low resistivity substrate is formed. Next, the charge capacity of this structure is measured using a device in which a dielectric test fixture (Yokogawa Electric: HP16451B) is connected to an LF impedance analyzer (Yokogawa Electric: HP4192A) at a use frequency of 1 MHz. It was measured.

And the measured value of the charge capacity is given by the following formula:
Insulating film relative dielectric constant = 3.597 × 10 ⁻² × charge capacity (pF) × insulating film thickness (μm),
And the relative dielectric constant of the insulating coating was calculated. In addition, as the film thickness of the insulating coating, a value measured with an ellipsometer L116B manufactured by Gartner was used.

Table 1 shows the platinum contents of borazine-based resin compositions 1 to 3, 5, and 6. The platinum content was measured by SPQ9000 type ICP-MS manufactured by Seiko Instruments after acid decomposition of a certain amount of sample. Table 2 shows the measurement results of the relative dielectric constants and leakage current values of the insulating coatings 1 to 3 and 5 and 6.

  From Table 1, the metal impurity (platinum) content of borazine resin compositions 1 to 3 and 6 using a supported catalyst as a polymerization catalyst is untreated (borazine resin composition 5 obtained in Comparative Example). It was confirmed that it was significantly reduced. Further, from Table 2, relative dielectric constants and leakage currents of the insulating coatings 1 to 3 and 6 formed with the borazine resin compositions 1 to 3 and 6 having a low metallic impurity content are shown in FIG. It was found that the amount was sufficiently reduced as compared with the insulating film 5 formed in (1).

2 is a graph showing a gas chromatogram of a reaction solution immediately after the start of polymerization in Example 1. FIG. 2 is a graph showing a gas chromatogram of a reaction solution after stirring for 3 days from the start of polymerization in Example 1. FIG. 2 is a graph showing a GPC chart of the polymer obtained in Example 1. FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of an electronic component according to the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Silicon wafer (base | substrate), 1A, 1B ... Diffusion region, 2A ... Field oxide film, 2B ... Gate insulating film, 3 ... Gate electrode, 4A, 4B ... Side wall oxidation Film, 5, 7 ... Interlayer insulating film (insulating film), 5A, 7A ... Contact hole, 6 ... Bit line, 8 ... Memory cell capacitor (electronic component), 8A ... Storage electrode 8B ... capacitor insulating film, 8C ... counter electrode, peak corresponding to a ... p-bis (dimethylsilyl) benzene, b ... B, B ', B "-triethynyl-N, N Peak corresponding to ', N "-trimethylborazine.

Claims (2)

A method for producing a borazine-based resin, which is a polymer having a borazine skeleton in the main chain or side chain,
A first step of polymerizing B, B ′, B ″ -trialkynylborazines and hydrosilanes in the presence of a solid catalyst;
A second step of removing the solid catalyst after performing the first step;
With
The solid catalyst is a metal oxide supported catalyst selected from platinum alumina, platinum silica, palladium alumina, palladium silica, rhodium alumina and rhodium silica, a polymer supported rhodium catalyst, a polymer supported platinum catalyst, a surface functionalized silica gel supported platinum catalyst, or Ri these Kumiawasedea,
The hydrosilane is represented by the following formula (2):

(Wherein R ³ and R ⁴ represent the same or different monovalent groups selected from an alkyl group, an aryl group, an aralkyl group and a hydrogen atom, and R ⁵ represents a substituted or unsubstituted aromatic divalent group. Group, oxypoly (dimethylsiloxy) group, or oxygen atom), or the following formula (3);

(Wherein R ⁶ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and n represents an integer of 2 or more),
A method for producing a borazine-based resin, represented by : The B, B ′, B ″ -trialkynylborazines are represented by the following formula (1):

(Wherein R ¹ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R ² represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom),
The manufacturing method of the borazine-type resin of Claim 1 represented by these.

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