JP2007211138A - Alicyclic polyether, its production method, and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alicyclic polyether having low dielectric constant, high strength, high heat resistance, and high transparency and its production method. <P>SOLUTION: The alicyclic polyether is represented by formula (1), and its production method comprises a process for dimerizing at least one kind of adamantanone derivative by the condensation reaction with hydrazine, a process for polyetherifying by a triazine addition transition reaction, a process for azotizing by hydrolysis reaction in the coexistence of chlorine, and a process for nitrogen gas removal by thermal decomposition reaction in the coexistence of a base. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel alicyclic polyether that is useful as a low dielectric material, a high strength material, and a heat-resistant material used as a semiconductor interlayer insulating film material in the electric / electronic field.

  A low dielectric material is widely used as a material in electric and electronic parts in order to solve problems such as charging and an increase in resistance value. Low dielectric materials are required to improve economy and lower dielectric constant, but besides this, they are often used in parts that generate heat or are used as thin films, so heat resistance and strength are improved at the same time. It has been demanded. In particular, a material that is useful as a semiconductor interlayer insulating film and has a low dielectric constant, high heat resistance, high strength, and economy has been actively developed.

  Currently, siloxane compounds are mainly used as semiconductor interlayer insulating film materials, which are the main applications of low dielectric materials. Siloxane compounds are mainly composed of silicon and oxygen. Since the dielectric constant increases as the dipole moment of the molecule increases, a siloxane compound having many unshared electron pairs is disadvantageous. However, until now, the required value of the dielectric constant has been about k = 4 to 3, so that a siloxane compound has been used from the balance of strength and adhesion to a silicon wafer.

  Due to the demand for higher performance of semiconductors, miniaturization of the width of the semiconductor circuit is required, and it has become necessary to further lower the dielectric constant. At that time, since the problem of dielectric breakdown due to the strength of the entire semiconductor chip and physical stress becomes serious, it is necessary to maintain the strength as a thin film. From the viewpoint of lowering the dielectric constant, siloxane compounds have been introduced from the inorganic siloxane compounds to the organic siloxane compounds, and the introduction of controlled nanometer-level vacancies and technology have progressed. However, in order to cope with the further lowering of the dielectric constant, if the amount of introduced holes is increased, the strength is lowered.

  Therefore, new materials such as organic polymers have been proposed. However, in addition to insulation, low dielectric constant and high strength, there is no material having high heat resistance that can withstand the heat load applied during semiconductor manufacturing. An organic / inorganic polymer such as borazine-silicon polymer exemplified in Patent Document 1 has also been proposed, but has a low dielectric constant, high strength, and high heat resistance, but is a platinum catalyst necessary for polymerization. Since there is no process for removing, there remains a problem in terms of dielectric breakdown caused by residual platinum atoms and low stability.

  Furthermore, there is a proposal of a naphthyl ether polymer exemplified in Patent Document 2 or Patent Document 3 similarly having low dielectric constant, high strength, and high heat resistance, but it is applied to future image display devices and semiconductor devices. Therefore, further high transparency and low dielectric constant are required.

The current nanometer level vacancy introduction method has a limit in reducing the dielectric constant without reducing the strength, so it is necessary to introduce angstrom level vacancies. That is, it is nothing but increasing the intermolecular free volume. In order to further reduce the dielectric constant, it is necessary to reduce the polarizability of the molecule by reducing π electrons and hydrogen atoms, so a polymer compound constructed only from an alicyclic structure typified by an adamantane structure is suitable. . However, a polymer compound constructed only from an alicyclic structure typified by an adamantane structure is generally insoluble and insoluble, and cannot be used as a thin film structure.
JP 2002-359240 A WO2004 / 083278 pamphlet WO2005 / 092946 pamphlet

The present invention has been made in view of the above-described problems, and eliminates various problems caused by an increase in the amount of holes introduced into an interlayer insulating film material using a conventionally known low dielectric material and requires introduction of holes. An object of the present invention is to provide an alicyclic polyether having a low dielectric constant, high strength, high heat resistance and high transparency.
Another object of the present invention is to provide an electronic material, a low dielectric material, a semiconductor interlayer insulating film material, a transparent material, an optical material, a high strength material, a heat resistant material, and a thin film comprising the alicyclic polyether. .
Another object of the present invention is to provide a semiconductor device, an image display device, an electronic circuit device, and a surface protective film including the thin film.
Another object of the present invention is to provide a paint in which the alicyclic polyether is dissolved in an organic solvent.

The present inventors have found that a thin film can be easily obtained by introducing an ether bond into the alicyclic structure, and that the dielectric constant can be reduced, the heat resistance can be improved, and the strength can be improved. I let you.
According to the present invention, the following alicyclic polyethers and the like are provided.
1. An alicyclic polyether represented by the following formula (1).
(In formula (1), each R ₁ is independently hydrogen, a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, or a substituted or unsubstituted branched aliphatic group having 1 to 20 carbon atoms. Group, substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms, substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, substituted or unsubstituted alicyclic ether group having 4 to 50 carbon atoms , A nitro group, a hydroxyl group, a carboxyl group, a silyl group, a siloxy group, a fluorine-containing aliphatic group or a fluorine-containing aromatic group.
R ₂ independently represents hydrogen or a substituent represented by R ₁ or an alicyclic substituent represented by the following formula (2).
R ₃ represents a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon group having 5 to 50 carbon atoms. It represents an alicyclic substituent, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, a silyl group, a fluorine-containing aliphatic group, or a fluorine-containing aromatic group.
n is an integer of 0 or more and 10,000 or less.
(In the formula _(2), R 1, but _{R 3} is the same as _R 1, _{R 3} in the formula (1), _R 1, _{R 3} and _R 1 of formula (1) in equation (2), R ₃ is independent from each other. —X— is an ether bond or a single bond. M is an integer of 0 or more and 10,000 or less.))
2. A step of dimerizing one or more adamantanone derivatives selected from the compounds represented by the following formulas (3a) and (3b) with hydrazine, and dimerizing the obtained dimer by a triazone addition rearrangement reaction. 1 comprising a step of polyetherification, a step of hydrolyzing the obtained polyether in the presence of a base to azotize, and a step of thermally decomposing the obtained azoated polyether in the presence of a base to denitrogenate 1 The manufacturing method of alicyclic polyether of description.
(In formulas (3a) and (3b), R ₁ and R ₂ are the same as R ₁ and R _{2 in} formula (1)).
An electronic material comprising the alicyclic polyether according to 3.1.
A low dielectric material comprising the alicyclic polyether according to 4.1.
An interlayer insulating film material for a semiconductor comprising the alicyclic polyether according to 5.1.
A transparent material comprising the alicyclic polyether according to 6.1.
An optical material comprising the alicyclic polyether according to 7.1.
A high-strength material comprising the alicyclic polyether according to 8.1.
A heat-resistant material comprising the alicyclic polyether according to 9.1.
A thin film comprising the alicyclic polyether according to 10.1.
A semiconductor device including the thin film according to 11.10.
12. An image display device comprising the thin film according to 10.10.
An electronic circuit device including the thin film according to 13.10.
14. A surface protective film comprising the thin film according to 10.10.
15. A paint in which the alicyclic polyether according to 15.1 is dissolved in an organic solvent.
16. A polytriazone adamantyl ether derivative represented by the following formula.
(In the formula, each R is independently hydrogen, a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 1 to 20 carbon atoms, substituted or unsubstituted, It represents an unsubstituted alicyclic substituent having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms.
_{R 1, R 2, R 3} , n are the same as _{R 1, R 2, R 3} , n in the above formula (1). )
17. A polydiazoadamantyl ether derivative represented by the following formula.
_{(Wherein, R 1, R 2, R 3} , n are the same as _{R 1, R 2, R 3} , n in the above formula (1).)

According to the present invention, an alicyclic polyether having a low dielectric constant, high strength, high heat resistance and high transparency can be provided.
According to the present invention, it is possible to provide an electronic material, a low dielectric material, a semiconductor interlayer insulating film material, a transparent material, an optical material, a high strength material, a heat resistant material, and a thin film made of the alicyclic polyether.
According to the present invention, a semiconductor device, an image display device, an electronic circuit device, and a surface protective film including the thin film can be provided.
According to this invention, the coating material which dissolved the said alicyclic polyether in the organic solvent can be provided.

(1) Structure and properties of alicyclic polyether The alicyclic polyether of the present invention is represented by the following formula (1).

In formula (1), each R ₁ is independently hydrogen, a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 1 to 20 carbon atoms, Substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms, substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, substituted or unsubstituted alicyclic ether group having 4 to 50 carbon atoms, nitro Represents a group, a hydroxyl group, a carboxyl group, a silyl group, a siloxy group, a fluorine-containing aliphatic group or a fluorine-containing aromatic group.

In the formula (1), R ₂ each independently represents hydrogen or a substituent represented by the above R ₁ , or an alicyclic substituent represented by the following formula (2).

_R 1, _{R 3} of formula (2) is the same as above _R 1, _{R 3.}
-X- in the formula (2) is an ether bond or a single bond.

In Formula (1), R ₃ represents a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted group. An alicyclic substituent having 5 to 50 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, a silyl group, a fluorine-containing aliphatic group, or a fluorine-containing aromatic group.

  In the formulas (1) and (2), n and m are each independently an integer of 0 or more and 10,000 or less, preferably 3 or more and 1000 or less, more preferably 3 or more and 50 or less. If it is less than 3, the heat resistance and stability will be low, and if it exceeds 1000, the solubility in an organic solvent will decrease, and it may be difficult to form a desired shape such as a thin film.

R ₁ is specifically hydrogen; methyl group, ethyl group, n-propyl group, iso-propyl group, cyclopropyl group, n-butyl group, iso-butyl group, tert-butyl group, 2-ethylhexyl. (Cyclo) alkyl groups having 1 to 20 carbon atoms such as a group, n-decyl group, n-dodecyl group, cyclohexyl group, norbornyl group, adamantyl group and biadamantyl group; carbon such as vinyl group, isopropenyl group and allyl group An alkynyl group having 1 to 20 carbon atoms; an alkynyl group having 1 to 20 carbon atoms such as an ethynyl group; an aromatic group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthrenyl group; a tolyl group and a cumyl group An aromatic group having 6 to 20 carbon atoms substituted with an alkyl group having 1 to 20 carbon atoms; a methoxy group, an ethoxy group, an adamantyloxy group, and biadamanche C1-C20 alkoxy group such as ruoxy group; C1-C20 alkenyloxy group such as vinyloxy group and allyloxy group; Phenoxy group; C1-C20 (cyclo) such as methylthio group and adamantylthio group Alkylthio group; alkenylthio group having 1 to 20 carbon atoms such as vinylthio group; phenylthio group; ester group such as acetoxy group, acryloxy group and methacryloxy group; epoxy group; alkyl epoxy group having 1 to 20 carbon atoms such as epoxymethyl group Silyl group; trialkylsilyl group such as trimethylsilyl group and tert-butyldimethylsilyl group; triphenylsilyl group; siloxy group; trialkylsiloxy group such as trimethylsiloxy group and tert-butyldimethylsiloxy group; triphenylsiloxy group; Fluorine; charcoal such as trifluoromethyl group A fluorinated alkyl group having 1 to 20 carbon atoms; a fluorinated alkenyl group having 1 to 20 carbon atoms such as a hexafluoroisopropenyl group; a fluorinated alkoxy group having 1 to 20 carbon atoms such as a pentafluorophenyl group and a trifluoromethoxy group; A fluorinated alkenyloxy group having 1 to 20 carbon atoms such as a hexafluoroisopropenoxy group; a pentafluorophenoxy group; a p-trifluoromethylphenyl group, a p-trifluoromethylphenoxy group, a vinyladamantyl group, a vinyladamantyloxy group, Examples thereof include a substituent formed by combining two or more of the above-described substituents such as a vinylviadamantyloxy group, a dimethylbiadamantyl group, a dibutylbiadamantyl group, a dicyclohexylbiadamantyl group, and a didecylbiadamantyl group.

Preferably, R ₁ is hydrogen, butyl group, decyl group, cyclohexyl group, norbornyl group, adamantyl group, biadamantyl group, dimethylbiadamantyl group, dibutylbiadamantyl group, dicyclohexylbiadamantyl group, didecylbiadamantyl group, pentafluoro A phenyl group and a trifluoromethyl group;
By using these, the dielectric constant is lowered and the transparency can be improved.

The dielectric constant (k) of the alicyclic polyether of the present invention varies depending on the types of the substituents R ₁ and R ₂ , the substitution position, and the number of substitutions, but is preferably 2.8 or less, more preferably 2. 5 or less, more preferably 2.3 or less. In the alicyclic polyether of the present invention, the dielectric constant can be adjusted within the above range by appropriately selecting the main chain structure, molecular weight, type of substituent, substitution position, and number of substitutions.

  The heat resistance of the alicyclic polyether of the present invention is brought about by an adamantane skeleton and an ether bond, and the adamantane skeleton is added to the diamond crystal lattice as described in the literature (Chemical Review, 277, 64, 1964). It has a corresponding three-dimensional structure, has very little strain, and is thermally and chemically stable. Since the ether bond is also thermally and chemically stable as is generally known, the alicyclic polyether of the present invention has high heat resistance.

  The evaluation method of heat resistance can be performed by general thermophysical property evaluation such as a differential scanning calorimeter (DSC) and a simultaneous differential thermothermal weight measuring device (TG / DTA). The shape of the evaluation sample can be selected as appropriate within the limits of the apparatus used for the evaluation method, whether it is in the form of a thin film or a powder or block as its precursor.

  The heat resistant temperature is defined by two kinds of temperatures, the glass transition temperature obtained by the above method, and the lower one of the melting temperature and the thermal decomposition starting temperature. The heat-resistant temperature varies depending on the main chain structure, molecular weight, type of substituent, substitution position, and number of substitution, but is preferably in the range of 300 ° C to 700 ° C, more preferably in the range of 350 ° C to 700 ° C.

  The strength, substrate adhesion and stability of the alicyclic polyether of the present invention cannot be defined unequivocally because the evaluation results differ depending on the structure of the alicyclic polyether, each evaluation method, etc. It has a sufficient value as an interlayer insulating film material of a wiring structure.

  As described above, the alicyclic polyether of the present invention has a three-dimensional structure corresponding to the crystal lattice of diamond with an adamantane skeleton, has extremely low strain, is thermally and chemically stable, and has a rigid structure. The strength is high because of the small displacement between molecules when stress is applied, the breakage of chemical bonds, and the three-dimensional structural change of each molecule. In addition, since it has an ether bond, interaction between oxygen atoms and polar groups such as hydroxyl groups on the substrate surface occurs, and therefore, adhesion at the interface with the substrate is high. Furthermore, due to its thermal and chemical stability, the alicyclic polyether of the present invention hardly changes over time under specific conditions.

(2) Production method of alicyclic polyether The alicyclic polyether of the present invention is a) one or more kinds selected from adamantane derivatives represented by the following formulas (3a) and (3b) that are generally available: Dimerization reaction by condensation reaction with hydrazine using raw materials, a) polytellation reaction by triazone addition, c) azolation reaction by base treatment, and d) denitrogenation reaction by heating in the presence of base Can be appropriately synthesized.

Wherein (3a) and _(3b), R 1, _{R 2} is the same as _R 1, _{R 2} described above Formula (1). The substitution positions of R ₁ , R ₂ , hydroxyl group, and carbonyl group are arbitrary.

When R ₁ and R ₂ are hydrogen, the compounds represented by formulas (3a) and (3b) are specifically 1-hydroxy-2-adamantanone, 3-hydroxy-2-adamantanone, 4- Hydroxy-2-adamantanone, 5-hydroxy-2-adamantanone, 6-hydroxy-2-adamantanone, 7-hydroxy-2-adamantanone, 8-hydroxy-2-adamantanone, 9-hydroxy-2-adaman It is tanone or 10-hydroxy-2-adamantanone.

The above process will be specifically described below by using, as an example, a compound represented by the formula (3a) in which a hydroxyl group is bonded to the 5-position and an oxo group is bonded to the 2-position as an adamantane derivative. The following description is the same for other adamantane derivatives.
A) Dimerization reaction by condensation reaction with hydrazine Adiamantane derivative can be condensed with hydrazine to obtain a diazabiadamantanol derivative. The reaction temperature is usually in the range of −78 ° C. to 100 ° C. The solvent, the ratio of the respective compound charges, and the reaction time cannot be defined unconditionally because they vary depending on the compounds used, but the general conditions used for similar reactions It is the same.

A) Polyetherization reaction by addition of triazone A polytriazone adamantyl ether derivative is obtained by adding the diazabiadamantanol derivative obtained in the previous step using a triazone represented by the following reaction formula. The reaction temperature is usually in the range of 0 ° C to 100 ° C. Although the solvent cannot be defined unconditionally because the ratio of each compound charge and the reaction time differ depending on the compound to be used, it is the same as the general conditions used for similar reactions.
In addition, -OR _{3 at} the right end of the compound represented by the formula (5), when water is added as a polymerization terminator, R ₃ becomes hydrogen and becomes -OH, and is stopped with any alcohol R ₃ OH. In this case, it becomes -OR ₃ .

  R of triazone is hydrogen, a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number of 5 Represents a -50 alicyclic substituent or a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms.

  R is specifically hydrogen; methyl group, ethyl group, n-propyl group, iso-propyl group, cyclopropyl group, n-butyl group, iso-butyl group, tert-butyl group, 2-ethylhexyl group , N-decyl group, n-dodecyl group, cyclohexyl group, norbornyl group, adamantyl group, biadamantyl group and the like (Cyclo) alkyl group such as vinyl group, isopropenyl group and allyl group An alkynyl group having 1 to 20 carbon atoms; an alkynyl group having 1 to 20 carbon atoms such as an ethynyl group; an aromatic group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthracenyl group and a phenanthrenyl group; C6-C20 aromatic group substituted by C1-C20 alkyl group; methoxy group, ethoxy group, adamantyloxy group, biadamantyl An alkoxy group having 1 to 20 carbon atoms such as a xy group; an alkenyloxy group having 1 to 20 carbon atoms such as a vinyloxy group and an allyloxy group; a phenoxy group; a (cyclo) having 1 to 20 carbon atoms such as a methylthio group and an adamantylthio group Alkylthio group; alkenylthio group having 1 to 20 carbon atoms such as vinylthio group; phenylthio group; ester group such as acetoxy group, acryloxy group and methacryloxy group; epoxy group; alkyl epoxy group having 1 to 20 carbon atoms such as epoxymethyl group Silyl group; trialkylsilyl group such as trimethylsilyl group and tert-butyldimethylsilyl group; triphenylsilyl group; siloxy group; trialkylsiloxy group such as trimethylsiloxy group and tert-butyldimethylsiloxy group; triphenylsiloxy group; Fluorine; carbon such as trifluoromethyl group A fluorinated alkyl group having 1 to 20 carbon atoms; a fluorinated alkenyl group having 1 to 20 carbon atoms such as a hexafluoroisopropenyl group; a fluorinated alkoxy group having 1 to 20 carbon atoms such as a pentafluorophenyl group and a trifluoromethoxy group; C1-C20 fluorinated alkenyloxy group such as fluoroisopropenoxy group; pentafluorophenoxy group; p-trifluoromethylphenyl group, p-trifluoromethylphenoxy group, vinyladamantyl group, vinyladamantyloxy group, vinyl Examples thereof include a substituent formed by combining two or more of the above substituents such as a biadamantyloxy group, a pentamethylphenyl group, a pentafluorophenyl group, and a trifluoromethyl group.

Preferably, R is a phenyl group, a tolyl group, a cumyl group, a pentamethylphenyl group, a pentafluorophenyl group, a trifluoromethyl group, a naphthyl group, or an anthracenyl group.
By using these, heat resistance and stability can be improved.

C) Azolation reaction by base treatment A polydiazoadamantyl ether derivative is obtained by subjecting the polytriazone adamantyl ether derivative obtained in the previous step to a hydrolysis reaction in the presence of a base. The reaction temperature is usually in the range of 0 ° C to 200 ° C. Although the ratio of each compound charge and the reaction time differ depending on the compound used, they cannot be defined unconditionally, but are the same as the general conditions used for similar reactions. Any solvent may be used as long as it does not adversely affect the reaction even if a commonly known organic solvent, water or the like is used. As the base, inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as pyridine and triethylamine can be preferably used.

D) Denitrogenation reaction by heating in the presence of a base An alicyclic polyether is obtained by subjecting the polydiazoadamantyl ether derivative obtained in the previous step to a thermal decomposition reaction in the presence of a base and denitrogenating gas. The reaction temperature is usually in the range of 0 ° C to 200 ° C. Although the ratio of each compound charge and the reaction time differ depending on the compound used, they cannot be defined unconditionally, but are the same as the general conditions used for similar reactions. Any solvent may be used as long as it does not adversely affect the reaction even if a commonly known organic solvent, water or the like is used. As the base, inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as pyridine and triethylamine can be preferably used. This reaction may be carried out continuously with the preceding stage azotization reaction or after post-treatment such as removal of the solvent.

The alicyclic polyether of the present invention can be purified by purification such as washing, ion exchange resin treatment, reprecipitation, recrystallization, microfiltration, and drying, for example, ionic impurities such as Fe ³⁺ , Cl ⁻ , Na ⁺ , and Ca ^2+. By removing the reaction solvent, the post-treatment solvent, moisture, etc., the dielectric constant is lowered and the heat resistance or strength is improved.

  The intermediates (formulas (4) to (6)) obtained in the reaction steps (a) to (e) above can be combined with other reactions to synthesize various compounds. Not only are they used for the production of cyclic polyethers, they are also industrially useful per se.

(3) Use of alicyclic polyether Properties such as dielectric constant, heat resistance, strength, substrate adhesion, and stability, which are listed as characteristics required when used as an interlayer insulating film material of ULSI multilayer wiring structure in semiconductor manufacturing Since the required value of the site | part which uses this material changes, it cannot unambiguously define those specific values.

  In general, it is desirable that the dielectric constant and the like are low and the heat resistance, strength, substrate adhesion, stability and the like are high, and the alicyclic polyether of the present invention has these properties. In addition, high-temperature polymerization (thermal curing) after thinning is not required, and the chemical structure can be manufactured from simple and inexpensive raw materials. Therefore, conventionally used and proposed thermosetting organic layers In addition to being economical with respect to the insulating film material, it does not require a catalyst or a cross-linking agent that is necessary for thermosetting, and therefore can be suitably used as an interlayer insulating film material because there is no residual of these.

  Since the alicyclic polyether of the present invention can be dissolved in a generally known organic solvent, it is generally known such as a coating method using an organic solvent solution such as a spin coating method or a spray coating method, a CVD method or the like. By this method, it is possible to form a thin film having a thickness of 10 nm to 10 μm, so that it can be suitably used as an interlayer insulating film for a semiconductor circuit.

  Specific examples of common organic solvents used in the coating method include dichloromethane, 1,1,2,2-tetrachloroethane, ethyl lactate, propylene glycol methyl ether acetate, cyclohexanone, methoxyethanol, dimethylformamide, toluene and the like. The

  The present invention is not limited by the following examples. In addition, 5-hydroxy-2-adamantanone used in the examples was manufactured by Sigma-Aldrich, and other catalysts and reagents were prepared according to commercially available products or methods described in known literature.

Production Example 1
[Synthesis of Intermediate Diazabia Damantanol (Process A)]
Under a nitrogen atmosphere, 5-hydroxy-2-adamantanone (5.3 g, 35 mmol) tert-butyl alcohol in a 200-ml flask equipped with a dropping funnel and Jim Roth condenser while heating to reflux To the (60 ml) solution, hydrazine monohydrate (1.3 g, 26 mmol) was added dropwise over 45 minutes. After completion of the dropping, the mixture was heated to reflux for 12 hours, and then the heating was stopped and stirring was continued at room temperature for 24 hours. The reaction solution was collected, concentrated using a rotary evaporator, and dissolved in n-hexane to obtain diazabia damantanol (4.3 g, yield 75%). The structure was confirmed by ¹ H-NMR (FIG. 1).

Production Example 2
[Synthesis of Intermediate Polytriazone Adamantyl Ether (Process A)]
Stainless steel having a capacity of 50 ml of 4-phenyl-1,2,4-triazoline-3,5-dione (1.8 g, 10 mmol) and diazabiadamantanol (1.6 g, 5 mmol) synthesized in Preparation Example 1 The glove box was placed in a sealed container and filled with circulating nitrogen. In the glove box, chloroform (20 ml) was placed in a stainless steel sealed container, sealed, and stirred at 100 ° C. for 3 hours. After stirring, reprecipitation was performed by adding n-hexane, and the obtained solid was filtered by suction filtration to obtain polytriazone adamantyl ether (1.6 g, yield 95%, n: 14). . The structure was confirmed by ¹ H-NMR (FIG. 2).

Production Example 3
[Synthesis of Intermediate Polytriazone Adamantyl Ether (Process A)]
In the same manner as in Production Example 2, except that dimethyl sulfoxide was used instead of chloroform used for the reaction in Production Example 2 and n-hexane containing 5% ethanol was used instead of n-hexane used for reprecipitation. Polytriazone adamantyl ether was obtained (1.5, yield 90%, n: 14). The structure was ¹ H-NMR (identified by FIG. 3 and the same structure as the polytriazone adamantyl ether obtained in Production Example 2).

Production Example 4
[Synthesis of Intermediate Polydiazoadamantyl Ether (Process C)]
Mr. Jim Roth in a nitrogen atmosphere was charged with polytriazone adamantyl ether (1.5 g, 4.5 mmol per monomer unit), triethylamine (5 ml) and chloroform (20 ml) synthesized in Production Example 2 and Production Example 3. The mixture was stirred at 0 ° C. for 3 hours in a 50-ml flask equipped with a condenser. After stirring, reprecipitation was performed by adding n-hexane, and the resulting solid was filtered by suction filtration to obtain polydiazoadamantyl ether (0.7 g, yield 85%, n: 14). The structure was confirmed by ¹ H-NMR (FIG. 4).

Example 1
[Synthesis of alicyclic polyether (process d)]
Polydiazoadamantyl ether synthesized in Production Example 4 (0.7 g, 3.9 mmol per monomer unit), triethylamine (5 ml), chloroform (20 ml) in a nitrogen atmosphere and a capacity equipped with a Jim Roth condenser Stir at 50 ° C. for 3 hours in a 50 ml flask. After stirring, reprecipitation was performed by adding n-hexane, and the obtained solid was filtered by suction filtration to obtain an alicyclic polyether having an adamantyl structure in the alicyclic portion (0.6 g, yield). Rate 98%, n: 14). The structure was confirmed by ¹ H-NMR (FIG. 5).

Evaluation Example 1
[Performance evaluation of alicyclic polyether]
Using the alicyclic polyether having an adamantyl structure in the alicyclic part obtained in Example 1, the thermal decomposition starting temperature was 410 ° C. measured by TG / DTA under a nitrogen stream, and extremely high heat resistance was obtained. It turned out to have. In addition, when a 1,1,2,2-tetrachloroethane solution (concentration: 10 weight percent) was formed on a silicon substrate by spin coating, a thin film having a uniform thickness was obtained. It was found that the film forming property was extremely high. The elastic modulus was 6 GPa by the nanoindentation method using the thin film, and it was found to have high thin film strength. Moreover, when the total light transmittance was measured using this thin film, it turned out that it has very high transparency as 88%. Further, when the dielectric constant was measured by the mercury probe method using the thin film, it was found to have a dielectric constant as low as 2.5.

  From the above results, the obtained alicyclic polyether can be suitably used as an electronic material, a low dielectric material, an interlayer insulating film material for a semiconductor, a transparent material, an optical material, a high strength material, or a heat resistant material, and Proved to show extremely high performance.

  The alicyclic polyether of the present invention can be used as an electronic material, a low dielectric material, a semiconductor interlayer insulating film material, a transparent material, an optical material, a high strength material, and a heat resistant material. Moreover, the thin film which consists of an alicyclic polyether of this invention can be used for a semiconductor device, an image display apparatus, an electronic circuit device, a surface protective film, etc. In particular, the low dielectric material comprising the alicyclic polyether of the present invention can be used as an interlayer insulating film material, and can improve the performance of a semiconductor such as ULSI.

2 is a ¹ H-NMR chart of diazabiadamantanol obtained in Production Example 1. FIG. 2 is a ¹ H-NMR chart of polytriazone adamantyl ether obtained in Production Example 2. FIG. 2 is a ¹ H-NMR chart of polytriazone adamantyl ether obtained in Production Example 3. FIG. 6 is a ¹ H-NMR chart of polydiazoadamantyl ether obtained in Production Example 4. FIG. 2 is a ¹ H-NMR chart of an alicyclic polyether obtained in Example 1. FIG.

Claims (17)

An alicyclic polyether represented by the following formula (1).
(In formula (1), each R ₁ is independently hydrogen, a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, or a substituted or unsubstituted branched aliphatic group having 1 to 20 carbon atoms. Group, substituted or unsubstituted alicyclic substituent having 5 to 50 carbon atoms, substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, substituted or unsubstituted alicyclic ether group having 4 to 50 carbon atoms , A nitro group, a hydroxyl group, a carboxyl group, a silyl group, a siloxy group, a fluorine-containing aliphatic group or a fluorine-containing aromatic group.
R ₂ independently represents hydrogen or a substituent represented by R ₁ or an alicyclic substituent represented by the following formula (2).
R ₃ represents a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon group having 5 to 50 carbon atoms. It represents an alicyclic substituent, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, a silyl group, a fluorine-containing aliphatic group, or a fluorine-containing aromatic group.
n is an integer of 0 or more and 10,000 or less.
(In the formula _(2), R 1, but _{R 3} is the same as _R 1, _{R 3} in the formula (1), _R 1, _{R 3} and _R 1 of formula (1) in equation (2), R ₃ is independent from each other. —X— is an ether bond or a single bond. M is an integer of 0 or more and 10,000 or less.)) A step of dimerizing one or more adamantanone derivatives selected from the compounds represented by the following formulas (3a) and (3b) by a condensation reaction with hydrazine;
A step of converting the obtained dimer into a polyether by a triazone addition rearrangement reaction,
The alicyclic ring according to claim 1, comprising a step of hydrolyzing the obtained polyether in the presence of a base to azotize, and a step of thermally decomposing the obtained azotized polyether in the presence of a base to denitrogenate. A method for producing a formula polyether.
(In formulas (3a) and (3b), R ₁ and R ₂ are the same as R ₁ and R _{2 in} formula (1)).   An electronic material comprising the alicyclic polyether according to claim 1.   A low dielectric material comprising the alicyclic polyether according to claim 1.   An interlayer insulating film material for a semiconductor comprising the alicyclic polyether according to claim 1.   A transparent material comprising the alicyclic polyether according to claim 1.   An optical material comprising the alicyclic polyether according to claim 1.   A high-strength material comprising the alicyclic polyether according to claim 1.   A heat-resistant material comprising the alicyclic polyether according to claim 1.   A thin film comprising the alicyclic polyether according to claim 1.   A semiconductor device comprising the thin film according to claim 10.   An image display device comprising the thin film according to claim 10.   An electronic circuit device comprising the thin film according to claim 10.   A surface protective film comprising the thin film according to claim 10.   A paint in which the alicyclic polyether according to claim 1 is dissolved in an organic solvent. A polytriazone adamantyl ether derivative represented by the following formula.
(In the formula, each R is independently hydrogen, a substituted or unsubstituted linear aliphatic group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic group having 1 to 20 carbon atoms, substituted or unsubstituted, It represents an unsubstituted alicyclic substituent having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms.
_{R 1, R 2, R 3} , n are the same as _{R 1, R 2, R 3} , n in the above formula (1). ) A polydiazoadamantyl ether derivative represented by the following formula.
_{(Wherein, R 1, R 2, R 3} , n are the same as _{R 1, R 2, R 3} , n in the above formula (1).)