WO2012133040A1 - Dérivé de calixarène - Google Patents

Dérivé de calixarène Download PDF

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WO2012133040A1
WO2012133040A1 PCT/JP2012/057169 JP2012057169W WO2012133040A1 WO 2012133040 A1 WO2012133040 A1 WO 2012133040A1 JP 2012057169 W JP2012057169 W JP 2012057169W WO 2012133040 A1 WO2012133040 A1 WO 2012133040A1
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arene
group
resist
synthesis
calixarene derivative
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PCT/JP2012/057169
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English (en)
Japanese (ja)
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佐藤　誠
真由美 岸
誠司 東野
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株式会社トクヤマ
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

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  • the present invention relates to novel calixarene derivatives. More specifically, the present invention is a novel calix suitably used for a pattern for forming a fine structure represented by a semiconductor device, a semiconductor integrated circuit, an imprint mold, etc., or a photo mask, etc. It relates to an arene derivative. The present invention further relates to a resist material containing the calixarene derivative, and a pattern forming method using the resist material.
  • LSI semiconductor integrated circuits
  • photomasks in which patterns of electronic circuits are formed with a light shielding material on a transparent substrate
  • lithography processes using photoresists in manufacturing processes such as imprint molds It is microfabricated.
  • a thin film of photoresist is formed on a silicon substrate or a quartz substrate on which a light shielding thin film is laminated, and high energy radiation such as excimer laser, X-ray, electron beam or the like is selectively added to this. Only a portion is irradiated to form a latent image of a pattern, and thereafter, a resist pattern obtained by developing is used as a mask for etching.
  • a photosensitive material called a resist material dissolved in an organic solvent is coated on a substrate having a layer to be processed on the surface, and the organic solvent is evaporated by prebaking to form a resist. Form a film.
  • the resist film is partially irradiated with light, and an unnecessary portion of the resist film is dissolved and removed using a developing solution to form a resist pattern on the substrate.
  • the layer to be processed on the substrate having this resist pattern as a mask is dry etched or wet etched.
  • micropatterning is completed by removing the resist pattern.
  • a wide variety of organic resists sensitive to electron beams are known, and resist patterns are formed by various methods.
  • a polymer thin film of an ethylenically unsaturated monomer such as polymethyl methacrylate is provided on a substrate as a resist film, and then a predetermined image is formed by irradiating an electron beam, and a low molecular weight ketone such as acetone
  • Patent Document 1 A method of forming a fine pattern by developing using a kind is proposed (see Patent Document 1).
  • FIG. 2 of Patent Document 2 shows exposure characteristics (sensitivity curve) when exposed to an electron beam of 50 keV and developed with ethyl lactate or xylene. According to this exposure characteristic, the sensitivity of the resist used in this method is about 1 to 2 (mC / cm 2 ).
  • the resist sensitivity of the calix [4] arene derivative having high resolution is about 2 (mC / cm 2 ).
  • this sensitivity can be used, in order to improve the throughput and to improve the productivity, it is possible to use a resist material that can be further enhanced in sensitivity than the calix [4] arene derivative described in Patent Document 2.
  • Development was desired.
  • the resist sensitivity is obtained by setting the resist film thickness before development (the resist film thickness after applying a resist and performing prebaking as necessary) as a reference film thickness, and obtaining it after development minimum exposure the film thickness of the resist pattern that is comes to coincide with the reference thickness is the one represented by (mC / cm 2).
  • an object of the present invention is to provide a compound capable of forming a pattern having higher resolution and higher sensitivity and higher etching resistance than conventional calixarene derivatives, and to provide a resist material containing the compound. It is in.
  • Another object of the present invention is to provide an exposure method and a microfabrication method using the resist material.
  • X, Y and Z are each a hydrogen atom or a halogen atom
  • R 1 is an alkyl group or an acetyl group
  • R 2 and R 3 are each a hydrogen atom or a halogenated methyl group
  • n is an integer of 0 to 3
  • R 1, R 2, and where R 3 is present in plural the plurality of R 1, R 2, and R 3 are each be the same group or in different groups.
  • a resist material comprising the calixarene derivative.
  • a resist pattern forming method comprises the steps of forming a latent image and developing the latent image.
  • the calixarene derivative of the present invention is a compound into which a group having a specific double bond is introduced in the molecule. Therefore, a resist material containing the calixarene derivative can form a pattern with higher sensitivity than a resist material containing a conventional calixarene derivative, and the etching resistance can be enhanced by increasing the crosslink density. Industrial use value is high.
  • Example 7 is a sensitivity curve of Example 1.
  • the calixarene derivative of the present invention has the following formula (1)
  • R 1 is an alkyl group or an acetyl group.
  • R 1 may be the same or different groups.
  • the alkyl group includes an alkyl group having 1 to 10 carbon atoms, and may be linear or branched. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, isobutyl group, t-butyl group and hexyl group.
  • R 1 enhances the solubility of the calixarene derivative in various solvents, facilitates the formation of a resist film by the calixarene derivative, and makes the calixarene derivative with high sensitivity.
  • it is an alkyl group of 1 to 5 carbon atoms, and more preferably an alkyl group of 1 to 2 carbon atoms.
  • R 2 and R 3 are each a hydrogen atom or a halogenated methyl group.
  • R 2 there are a plurality, specifically, when n is 0, 1 or 2, R 2 may be be the same group or different groups.
  • R 3 may be the same or different groups.
  • halogenated methyl group what is a group which has one halogen atom is preferable.
  • the halogen atom include chlorine atom, bromine atom and iodine atom, among which chlorine atom is preferable. That is, the most preferred group is chloromethyl group.
  • This halogenated methyl group becomes a crosslinking point when exposed to high energy rays, and at least one of all R 2 and R 3 present in the molecule because it can sensitize the calixarene derivative. It is preferred that the group is a halogenated methyl group. More preferred is a case in which 2 to 4 of all R 2 and R 3 are halogenated methyl groups. It is more preferable that all R 2 and R 3 be groups of 3 or more and 4 or less be halogenated methyl groups, and particularly preferable that all R 2 and R 3 be halogenated methyl groups. Is the case.
  • the halogen atom includes a chlorine atom, a bromine atom and an iodine atom.
  • X and Y are hydrogen atoms
  • Z is a hydrogen atom, in order to make it easy to form a radical, and the resulting radical is stable and the resulting calixarene derivative exhibits higher sensitivity. It is preferably a hydrogen atom or a halogen atom, in particular a chlorine atom.
  • n is an integer of 0 to 3.
  • N is preferably from 0 to 2
  • particularly preferable compounds include compounds having the following groups.
  • R 1 is an alkyl group or an acetyl group
  • R 2 and R 3 are a hydrogen atom or a halogenated methyl group
  • at least three of R 2 and R 3 are a halogenated methyl group
  • X and Y are hydrogen atoms
  • Z is a hydrogen atom or a halogen atom
  • n is an integer of 0 to 2
  • the halogenated methyl group is preferably a chloromethyl group.
  • the compound include the following calixarene derivatives.
  • calixarene derivatives the following compounds are preferable as having particularly high sensitivity.
  • R 1 is an alkyl group having 1 to 2 carbon atoms
  • R 2 and R 3 are a hydrogen atom or a halogenated methyl group
  • at least three of R 2 and R 3 are a halogenated methyl group
  • X, Y and Z are hydrogen atoms
  • n is an integer of 0 to 2
  • the halogenated methyl group is preferably a chloromethyl group.
  • the compound include the following calixarene derivatives.
  • the method for producing the calixarene derivative of the present invention is not particularly limited, it can be produced by the following method.
  • the compound is de-t-butylated to produce 25, 26, 27, 28-tetrahydroxycalix [4] arene (hereinafter simply referred to as "calix [4] arene”).
  • a halogenated methyl group may be introduced as necessary.
  • a method generally known as Williamson's ether synthesis can be adopted.
  • non-patent literature GUITSCHE et al .: “Tetrahedron", 39, pp. 409-426, 1983
  • non-patent literature van LOON et al .: “Journal of Organic Chemistry", vol. 55, The method described in pp. 5639-5646 (1990) can be employed.
  • the number of n can be adjusted by adjusting the reaction conditions.
  • transduced this halogenated methyl group is also called “halogenated methyl aryloxy calix [4] arene” hereafter.
  • Patent Document 2 Non-patent Document (Nagasaki et al .: “Tetrahedron", Vol. 48, pp.
  • the calixarene derivative of the present invention can be produced by the method as described above.
  • the structure of the resulting calixarene derivative can be determined by IR, NMR, LC-MS and the like.
  • introduction of an allyl group can be confirmed from a characteristic signal of a proton attached to a double bond derived from an allyl group.
  • two types of double doublets are observed at ⁇ 5.0 to 6.0 ppm.
  • One is a proton located in cis with respect to the methylene group of the allyl group, and the coupling constants are 17.0 Hz and 2.0 Hz.
  • the other is a proton located in trans to the methylene group of the allyl group, and the coupling constants are 10.0 Hz and 2.0 Hz.
  • the present invention also provides a resist material comprising the above calixarene derivative. Next, this resist material will be described.
  • the resist material of the present invention contains the calixarene derivative represented by the above formula (1).
  • the calixarene derivative represented by the above formula (1) one type can be used alone, or a mixture of two or more types can be used. That is, it may be a mixture of ones having different numbers of n, or a mixture of ones in which a plurality of R 1 , R 2 and R 3 are different groups.
  • calixarene derivative even when a mixture of calixarene derivatives is used, it is simply described as a calixarene derivative.
  • the resist material of the present invention includes ethyl lactate (EL), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl propionate, n-butyl acetate, 2-heptanone and the like.
  • organic solvents such as In addition, if necessary, known additives such as surfactants can also be included.
  • the resist material of the present invention is prepared by dissolving all the components such as calixarene derivatives and additives added if necessary in the above organic solvent, and then filtering it using a membrane filter or the like as required. Be done.
  • the content of the calixarene derivative contained in the prepared resist material may be appropriately determined according to the desired film thickness of the resist film, the type of calixarene derivative, etc. It is up to 10% by mass.
  • Such resist materials can be used to form a pattern. Next, a method of forming this resist pattern will be described.
  • ⁇ Method of forming resist pattern> In order to form a resist pattern using the resist material, the following method may be employed. Specifically, after applying the resist material onto a substrate to be treated, a step of prebaking to form a resist film, and selectively exposing the resist film with high energy rays to form a latent image of a desired pattern. A resist pattern can be formed by performing the forming step and the developing step. Each step will be described in detail below.
  • the substrate to which the resist material is applied is not particularly limited, and a known substrate such as a silicon substrate, a photomask, and an oxide film, a nitride film, a metal thin film, etc. formed on the above substrate.
  • a filmed substrate is used.
  • the above resist material is coated on the substrate to be processed by a known method such as spin coating, and then baked (prebaked) to form a resist film containing the calixarene derivative.
  • pre-baking heat treatment is preferably performed at a temperature of 80 to 130 ° C. for about 10 seconds to 5 minutes using a hot plate or the like.
  • the film thickness of the formed resist film may be suitably determined in accordance with the application etc. to be used, but it is usually 5 to 300 nm.
  • a resist film containing the above calixarene derivative can be formed on a substrate to be treated.
  • the step of selectively exposing the resist film to high energy rays to form a latent image of a pattern will be described.
  • ⁇ Step of forming a latent image of a pattern> high energy rays are selectively exposed on the resist film on the substrate obtained in the resist film forming step to form a latent image of a pattern.
  • the high energy ray is not particularly limited as long as it is a radiation source capable of forming a latent image on the resist film by energy irradiation, and examples thereof include an electron beam, an X ray, and an ion beam.
  • the portion to which the high energy ray is exposed may be appropriately determined according to the pattern to be formed. Therefore, a known method can be adopted as a method of selectively exposing high energy rays, and for example, direct exposure or irradiation through a mask may be performed.
  • a latent image of a pattern can be formed on the resist film.
  • a substrate obtained by the above method that is, a resist film containing the above calixarene derivative is laminated, and the resist film is selectively exposed to high energy rays to form a latent image of a pattern.
  • the substrate thus obtained (hereinafter, also simply referred to as a substrate obtained in the latent image forming step) may be developed with a developer containing an organic solvent.
  • the latent image is developed by removing a portion of the resist film not exposed to the high energy beam with a developer containing an organic solvent.
  • the developing solution used in this development uses a solvent having different dissolution rates in the exposed area and the unexposed area.
  • the developer used in the present invention includes ethyl lactate (EL), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl propionate, n-butyl acetate, 2-butyl acetate used as a solvent for resist materials.
  • PGME propylene glycol monomethyl ether
  • PMEA propylene glycol monomethyl ether acetate
  • ethyl propionate ethyl propionate
  • n-butyl acetate ethyl propionate
  • 2-butyl acetate 2-butyl acetate
  • xylene xylene
  • alcohols ethanol, isopropyl alcohol and the like
  • glycol ethers hydrofluoroalkyl ether and the like
  • the method for developing the substrate obtained in the latent image forming step using the developer is not particularly limited, and a known method can be adopted. Specifically, a method of immersing the substrate in a bath filled with the developer (dip method), a method of placing the developer on the surface of the substrate (paddle method), and spraying the developer onto the substrate Method (spray method) is generally used. Among these methods, the paddle method or the spray method is preferred in order to reduce particles.
  • the substrate obtained in the latent image forming step is coated with the developer at a temperature of usually 10 ° C. or more and 35 ° C. or less, preferably 15 ° C. or more and 30 ° C. or less and allowed to stand. Or continue spraying the developer onto the substrate for a predetermined period of time.
  • the settling time or spraying time is not particularly limited, but is preferably 30 seconds or more and 5 minutes or less in consideration of throughput. If it is a combination of the calixarene derivative and the developer, a pattern can be sufficiently formed in the above temperature range and the above time.
  • the substrate on which the resist pattern has been formed by development according to the above method is, if necessary, removed of the remaining developer and the like by a rinse liquid.
  • the organic solvent used as the rinse solution may be the same as or different from the developer described above, but preferably has a boiling point of 150 ° C. or less at atmospheric pressure, and in view of drying easiness, the boiling point is 120 C. or less is more preferable.
  • the above-mentioned development step and this rinse step can be alternately repeated about 2 to 10 times.
  • the substrate is rotated at high speed or the like to shake off and remove the chemical solution to perform drying.
  • the calixarene derivative with the developer, a fine resist pattern is formed.
  • a calixarene derivative having a structure shown in Table 1 (Example) and Table 2 (Comparative Example) is synthesized according to the following synthesis example, and the calixarene derivative and propylene glycol monomethyl ether acetate (PGMEA) can be used as a calixarene derivative. It mixed and melt
  • HDPE high density polyethylene
  • an electron beam lithography system CAVL-9410NA manufactured by Crestec
  • CAVL-9410NA manufactured by Crestec
  • a beam current of 100 pA adjusting the exposure amount
  • a 200 ⁇ m wide line & space pattern was drawn for the sensitivity evaluation (latent image forming step).
  • IPA isopropyl alcohol
  • the sensitivity of the resist pattern thus obtained was evaluated by the following method.
  • ⁇ Sensitivity> The film thickness of the 200 ⁇ m wide line & space pattern was measured, the relationship between the exposure amount (irradiation amount) and the film thickness was plotted, and a sensitivity curve was created.
  • the electron beam exposure (exposure D) was determined from this sensitivity curve, and the exposure (D) was evaluated as an index of sensitivity.
  • ⁇ Etching resistance> A resist film formed on a silicon wafer was exposed at an electron beam irradiation dose of 2 mC / cm 2 at an acceleration voltage of 50 kV and a beam current of 100 pA using an electron beam lithography system CAVL-9410NA (made by Crestec), and a line of 200 ⁇ m width & Space pattern was drawn (latent image formation process). Subsequently, isopropyl alcohol (IPA) was applied at 23 ° C. on the substrate obtained in the latent image forming step, and development was performed for 60 seconds (developing step). After development, rinsing was performed by dropping a rinse solution (IPA) for 30 seconds while rotating the substrate at 300 rpm.
  • IPA isopropyl alcohol
  • the substrate was rotated at a speed of 2,000 revolutions per minute to shake off and remove the rinse solution, thereby forming a resist pattern.
  • the film thickness of this 200 ⁇ m wide line & space pattern was measured by a stylus type profilometer.
  • etching was performed under the following conditions, and the film thickness after the treatment was similarly measured. The etching rate was determined from the film thickness difference before and after the treatment and the treatment time. CHF 3 etching conditions; CHF 3 flow rate: 50 sccm, microwave power: 100 W, pressure: 2.0 Pa
  • the sensitivity curve about Example 1 was shown in FIG.
  • the sensitivity curve is obtained by measuring the film thickness of the exposed portion using a film thickness measuring instrument, the exposure amount on the horizontal axis, and the film thickness on the vertical axis.
  • the exposure amount (D) was determined.
  • the approximate straight line at the rising portion of the sensitivity curve (a straight line rising to the right shown by the dotted line in the figure) and the approximate straight line at the flat portion (the horizontal straight line shown by the dotted line in the figure).
  • the exposure amount at the intersection was determined as the exposure amount (D).
  • the above evaluations were performed using the exposure dose (D) for each example and comparative example, and the results are shown in Table 1 (example) and Table 2 (comparative example).
  • the solvent was distilled off with an evaporator to obtain a mixture of white crystals and a colorless transparent liquid.
  • To this mixture was slowly added 500 ml of methanol while stirring to reprecipitate.
  • the white crystals were filtered through a Kiriyama funnel and washed with 150 ml of methanol.
  • the obtained white crystals were dried under vacuum (for 12 hours or more at 50 ° C.) to obtain 66.4 g of the objective calix [4] arene.
  • the yield was 84.6%, and the HPLC purity was 97.3%.
  • the organic phase was then washed with 20% aqueous sodium chloride solution, predried over anhydrous magnesium sulfate and filtered.
  • the solvent was distilled off with an evaporator to obtain a yellow transparent liquid.
  • To this yellow liquid was slowly added 200 ml of methanol while stirring to reprecipitate.
  • the crystals were filtered through a Kiriyama funnel and washed with 100 ml of methanol.
  • the obtained white crystals were dried under vacuum (for 12 hours or more at 50 ° C.) to obtain 23.2 g of the target product, allyloxycalix [4] arene.
  • the yield was 70.4%, and the HPLC purity was 94.5%.
  • the structure was identified by 1 H-NMR and LC-MS.
  • the mixture was in the form of a white slurry, and the liquid temperature rose to about 40.degree.
  • the mixture was heated in an oil bath so that the liquid temperature would be 80 to 85.degree.
  • the mixture was uniformly dissolved when the liquid temperature exceeded 70 ° C., and became a colorless and transparent liquid.
  • the oil bath was removed and allowed to cool.
  • the reaction mixture was transferred to a separatory funnel, and 300 ml of chloroform was added to separate the organic phase.
  • the aqueous phase is extracted three times with 300 ml of chloroform and combined with the organic phase.
  • the organic phase was washed three times with 300 ml of water, and it was confirmed that the pH of the aqueous phase became neutral.
  • the organic phase was predried over anhydrous magnesium sulfate and filtered.
  • the solvent was distilled off with an evaporator to obtain an orange liquid.
  • the yield was 7.5%, and the HPLC purity was 99.6%.
  • the structure was identified by 1 H-NMR and LC-MS.
  • Synthesis Example 2 Synthesis of Calixarene Derivative of Example 2
  • the chloromethylation reaction was carried out using the allyloxycalix [4] arene synthesized in Synthesis Example 1.
  • the chloromethylation reaction was carried out in the same manner as in Synthesis Example 1 except that dioxane was changed to 1,2-dimethoxyethane.
  • the yield was 2.5%, and the HPLC purity was 99.2%.
  • the structure was identified by 1 H-NMR and LC-MS.
  • Synthesis Example 3 Synthesis of Calixarene Derivative of Example 3 First, using the calix [4] arene obtained in Synthesis Example 1, a dimethoxycalix [4] arene is synthesized, then, an allyl group is introduced, and finally, a halogenated methyl group is introduced to obtain calixarene. The derivative was synthesized. First, the synthesis of dimethoxycalixarene was performed by the following method.
  • a reactor was assembled by attaching a mechanical stirrer, a thermometer and a Dimroto to a 1 L glass four-necked flask. 50.0 g (0.12 mol) of calix [4] arene, 44.0 g (0.24 mol) of methyl p-toluenesulfonate, 18.0 g (0.13 mol) of anhydrous potassium carbonate, and 600 ml of dehydrated acetonitrile in a flask Charged and stirred at 300 rpm. The mixture was heated in an oil bath and reacted under reflux conditions for 5 hours.
  • the obtained white solid was dried under vacuum (50 ° C., 12 hours or more) to obtain 41.4 g of the target product dimethoxycalix [4] arene.
  • the yield was 77.4%, and the HPLC purity was 98.3%.
  • the synthesis of dimethoxydiaryroxycalix [4] arene was carried out by introducing an allyl group.
  • the white solid was dissolved in 300 ml chloroform and then 1000 ml methanol was slowly added with stirring to reprecipitate. The solid was filtered through a Kiriyama funnel and washed with 200 ml of methanol. The obtained white solid was dried under vacuum (for more than 12 hours at 50 ° C.) to obtain 36.4 g of the target product dimethoxydiaryloxycalix [4] arene. The yield was 72.7%, and the HPLC purity was 98.7%. Finally, introduction of a halogenated methyl group (chloromethyl group) was carried out by the following method.
  • Synthesis Example 4 Synthesis of Calixarene Derivative of Example 4 Using the calix [4] arene obtained by the method of Synthesis Example 1, synthesis of diacetoxycalix [4] arene was performed.
  • the aqueous phase is extracted three times with 200 ml of chloroform and combined with the organic phase.
  • the organic phase was washed 5 times with 300 ml of water, and it was confirmed that the pH of the aqueous phase became neutral.
  • the organic phase was predried over anhydrous magnesium sulfate and filtered.
  • the solvent was distilled off with an evaporator to obtain a pale yellow solid.
  • the solid was dissolved in 600 ml chloroform and then 1200 ml methanol was slowly added with stirring to reprecipitate. The solid was filtered through a Kiriyama funnel and washed with 200 ml of methanol.
  • the obtained white solid was dried under vacuum (for 12 hours or more at 50 ° C.) to obtain 41.4 g of the target product diacetoxycalix [4] arene.
  • the yield was 74.0%, and the HPLC purity was 99.1%.
  • synthesis of diacetoxydiaryloxycalix [4] arene by introducing an allyl group was performed.
  • Synthesis Example 5 Synthesis of Calixarene Derivative of Example 5 ⁇ Synthesis of Dipropoxycalix [4] arene> The synthesis was conducted in the same manner as in Synthesis Example 3 except that propyl iodide was used instead of methyl p-toluenesulfonate in the synthesis of dimethoxycalix [4] arene. The yield was 76.2%, and the HPLC purity was 99.3%. Subsequently, dipropoxydiaryloxycalix [4] arene was synthesized by introducing an allyl group.
  • Synthesis Example 6 Synthesis of Calixarene Derivative of Example 6 ⁇ Synthesis of trichloromethyldimethoxydiaryloxycalix [4] arene>
  • the chloromethylation reaction was carried out using the dimethoxydiaryroxycalix [4] arene synthesized in Synthesis Example 3 as a raw material.
  • the chloromethylation reaction was carried out in the same manner as in Synthesis Example 3 except that dioxane was changed to 1,2-dimethoxyethane.
  • the yield was 3.1%, and the HPLC purity was 97.6%.
  • the structure was identified by 1 H-NMR and LC-MS.
  • Synthesis Example 7 Synthesis of Calixarene Derivative of Example 7 ⁇ Synthesis of trichloromethyldiacetoxydiaryloxy [4] calixarene>
  • the chloromethylation reaction was carried out using diacetoxydiaryloxycalix [4] arene synthesized in Synthesis Example 4 as a raw material.
  • the chloromethylation reaction was carried out in the same manner as in Synthesis Example 4 except that dioxane was changed to 1,2-dimethoxyethane.
  • the yield was 2.8% and the HPLC purity was 98.9%.
  • the structure was identified by 1 H-NMR and LC-MS.
  • Synthesis Example 8 Synthesis of Calixarene Derivative of Example 8 ⁇ Synthesis of dichloroaryloxycalix [4] arene> The synthesis was conducted in the same manner as in Synthesis Example 1 except that 1,1-dichloroallyl bromide was used instead of allyl bromide in the synthesis of allyloxycalix [4] arene. The yield was 77.4%, and the HPLC purity was 98.6%. Then, the synthesis of chloromethyl dichloro aryloxy calix [4] arene by chloromethylation was performed by the following method.

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Abstract

L'invention concerne un dérivé de calixarène représenté par la formule (1). (Dans la formule, X, Y et Z représentent des atomes d'hydrogène ou des atomes d'halogène, R1 représente un groupe alkyle ou un groupe acétyle, R2 et R3 représentent des atomes d'hydrogène ou des groupes méthyle halogénés, n représente un entier de 0 à 3, et quand il existe une pluralité de R1, R2 et R3, alors la pluralité des R1, R2 et R3 peuvent représenter des groupes identiques ou des groupes différents.) Le dérivé de calixarène est utile en tant que matériau de résine photosensible à un faisceau électronique approprié à la microfabrication.
PCT/JP2012/057169 2011-03-28 2012-03-21 Dérivé de calixarène WO2012133040A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013073583A1 (fr) * 2011-11-18 2013-05-23 三菱瓦斯化学株式会社 Composé cyclique ainsi que son procédé de fabrication, composition sensible aux rayonnements, et procédé de formation de motif de réserve
US9182666B2 (en) 2011-11-18 2015-11-10 Mitsubishi Gas Chemical Co., Inc. Cyclic compound, method for producing the same, radiation-sensitive composition, and resist pattern formation method

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WO2013073583A1 (fr) * 2011-11-18 2013-05-23 三菱瓦斯化学株式会社 Composé cyclique ainsi que son procédé de fabrication, composition sensible aux rayonnements, et procédé de formation de motif de réserve
JPWO2013073583A1 (ja) * 2011-11-18 2015-04-02 三菱瓦斯化学株式会社 環状化合物、その製造方法、感放射線性組成物及びレジストパターン形成方法
US9182666B2 (en) 2011-11-18 2015-11-10 Mitsubishi Gas Chemical Co., Inc. Cyclic compound, method for producing the same, radiation-sensitive composition, and resist pattern formation method

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