WO2012133040A1

WO2012133040A1 - Calixarene derivative

Info

Publication number: WO2012133040A1
Application number: PCT/JP2012/057169
Authority: WO
Inventors: 佐藤　誠; 真由美岸; 誠司東野
Original assignee: 株式会社トクヤマ
Priority date: 2011-03-28
Filing date: 2012-03-21
Publication date: 2012-10-04
Also published as: TW201247616A; JPWO2012133040A1

Abstract

Provided is a calixarene derivative represented by formula (1). (In the formula, X, Y, and Z are hydrogen atoms or halogen atoms, R¹ is an alykl group or an acetyl group, R² and R³ are hydrogen atoms or halogenated methyl groups, n is an integer from 0 to 3, and when there is a plurality of R¹, R², and R³then the plurality of R¹, R² and R³ may be the same groups or different groups.) The calixarene derivative is useful as an electron-beam resist material suitable for microfabrication.

Description

Calixarene derivatives

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.

Semiconductor devices such as semiconductor integrated circuits (LSI), etc., photomasks in which patterns of electronic circuits are formed with a light shielding material on a transparent substrate, and lithography processes using photoresists in manufacturing processes such as imprint molds It is microfabricated. In this method, 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.

More specifically, in the photolithography technology, first, 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. Next, 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. Thereafter, the layer to be processed on the substrate having this resist pattern as a mask is dry etched or wet etched. Finally, micropatterning is completed by removing the resist pattern.

In the manufacturing process of a photomask and a mold for imprint, in many cases, a pattern is already formed using an electron beam drawing apparatus or a laser drawing apparatus. Also, with regard to semiconductor elements such as LSIs formed on a silicon substrate, examination of pattern formation using an electron beam drawing apparatus and the like has been started for further miniaturization. Therefore, in recent years, development of processes using resists for electron beams has been actively promoted. Such electron beam resists are desired to have high etching resistance, high resolution, and high sensitivity.

A wide variety of organic resists sensitive to electron beams are known, and resist patterns are formed by various methods. For example, 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 A method of forming a fine pattern by developing using a kind is proposed (see Patent Document 1). Similarly, after a thin film of a resist material containing a calixarene derivative is provided as a resist film, a predetermined image is formed by irradiating an electron beam, and ethyl lactate, propylene glycol monomethyl ether, or 2-heptanone or the like is used. A method of forming a fine pattern by development is proposed (see Patent Document 2).

According to the method of Patent Document 1, a fine pattern can be produced. However, since polymers of ethylenically unsaturated monomers such as polymethyl methacrylate have low etching resistance, when etching a layer to be processed deeply using this resist as a mask, the aspect ratio of the resist pattern is increased to make the pattern It was necessary to raise the height. In addition, since the developer is a low molecular weight ketone having a low flash point, it has been necessary to provide an explosion-proof device and the like.

On the other hand, according to the method of Patent Document 2, since a resist material containing a calixarene derivative is used, the etching resistance is high, and a pattern having a pattern width of 10 nm or less can be formed. However, the resist material containing the calixarene derivative used in this method has low sensitivity as compared with other resist materials, and there is room for improvement in that the amount of exposure has to be increased. For example, 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 ). In particular, the resist sensitivity of the calix [4] arene derivative having high resolution is about 2 (mC / cm ² ). Although 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. According to Patent Document 2, 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).

JP-A-8-262738 WO 2004/022513 pamphlet

Therefore, 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.

The present inventors diligently studied to achieve the above object. As a result, it has been found that a compound in which a specific substituent (specific allyl group) is introduced into a calix [4] arene derivative can solve the above problems, and the present invention has been completed.

That is, according to the present invention,
Following formula (1)

(In the formula,
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,
When 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. )
There is provided a calixarene derivative shown by

According to the present invention, there is also provided a resist material comprising the calixarene derivative.

Further, according to the present invention, after applying the resist material onto a substrate to be treated, prebaking to form a resist film, and selectively exposing the resist film with high energy rays to form a desired pattern A resist pattern forming method is provided, which 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.

7 is a sensitivity curve of Example 1;

Hereinafter, the present invention will be described in detail. First, calixarene derivatives are described.

The calixarene derivative of the present invention has the following formula (1)

It is a compound shown by these.

In the calixarene derivative represented by the above formula (1), R ¹ is an alkyl group or an acetyl group. When a plurality of R ¹ are present, specifically, when n is 2 or 3, 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. Among the above groups, 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. Preferably, it is an alkyl group of 1 to 5 carbon atoms, and more preferably an alkyl group of 1 to 2 carbon atoms.

In Formula (1), R ² and R ³ are each a hydrogen atom or a halogenated methyl group. In the case where 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. When a plurality of R ³ are present, specifically, when n is 2 or 3, R ³ may be the same or different groups.

As a halogenated methyl group, what is a group which has one halogen atom is preferable. Specific examples of 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 greatest feature of the calixarene derivative of the present invention is that it has a group having a specific double bond in the molecule, ie, -CHXCY = CZ ₂ group. By having this specific group, it is considered that a pattern can be formed with high sensitivity. In this -CHXCY = CZ ₂ group, X, Y and Z are each a hydrogen atom or a halogen atom. The halogen atom includes a chlorine atom, a bromine atom and an iodine atom. Among them, X and Y are hydrogen atoms, and 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. Among these, X, Y and Z are preferably hydrogen atoms, in particular, in that the above-mentioned effects are most exhibited. That is, the —CHXCY = CZ ₂ group is most preferably an allyl group.

In the calixarene derivative represented by the formula (1), n is an integer of 0 to 3. N is preferably from 0 to 2, and n is from 0 to 1 in terms of increasing the ratio of -CHXCY = CZ ₂ groups contributing to high sensitivity to increase the sensitivity. More preferable.

Among the above-mentioned calixarene derivatives, particularly preferable compounds include compounds having the following groups.

That is, in the formula (1),
R ¹ is an alkyl group or an acetyl group,
R ² and R ³ are a hydrogen atom or a halogenated methyl group, and 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,
Are calixarene derivatives such as Among them, the halogenated methyl group is preferably a chloromethyl group.

Specific examples of the compound include the following calixarene derivatives.

Among these calixarene derivatives, the following compounds are preferable as having particularly high sensitivity.

That is, in the formula (1),
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, and 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,
Are calixarene derivatives such as Among them, the halogenated methyl group is preferably a chloromethyl group.

Specific examples of the compound include the following calixarene derivatives.

Next, a method for producing the above calixarene derivative and a method for identifying the derivative thereof will be described.

<Production Method and Identification Method of Calixarene Derivative>
Although the method for producing the calixarene derivative of the present invention is not particularly limited, it can be produced by the following method. First, for example, commercially available 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix [4] arene (hereinafter simply referred to as "t-butylcalix [4] arene") The compound is de-t-butylated to produce 25, 26, 27, 28-tetrahydroxycalix [4] arene (hereinafter simply referred to as "calix [4] arene"). Then, a -CHXCY = CZ ₂ group (hereinafter, also simply referred to as an allyl group) may be introduced to this, and then a halogenated methyl group may be introduced as necessary.

As a method for introducing a —CHXCY = CZ ₂ group into the hydroxyl group of calix [4] arene as a raw material, a method generally known as Williamson's ether synthesis can be adopted. For example, non-patent literature (GUTSCHE et al .: "Tetrahedron", 39, pp. 409-426, 1983), or non-patent literature (van LOON et al .: "Journal of Organic Chemistry", vol. 55, The method described in pp. 5639-5646 (1990) can be employed. At this time, the number of n can be adjusted by adjusting the reaction conditions.

Next, if necessary, a halogenated methyl group is introduced into the compound having a —CHXCY = CZ ₂ group introduced (hereinafter also referred to as “allyloxycalix [4] arene”) by the above method. That is, hydrogen of the benzene ring is converted to a halogenated methyl group. The compound which introduce | transduced this halogenated methyl group is also called "halogenated methyl aryloxy calix [4] arene" hereafter. As a method for introducing a halogenated methyl group, for example, Patent Document 2, Non-patent Document (Nagasaki et al .: "Tetrahedron", Vol. 48, pp. 797-804, 1992), or JP-A-2004-123586 The method described in the publication can be adopted. At this time, by adjusting the reaction conditions, it is possible to adjust the number of n, R ² and the introduction ratio of the halogenated methyl group to R ³ .

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. In particular, in ¹ H-NMR, for example, 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. Specifically, two types of double doublets are observed at δ 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.

<Resist material>
The resist material of the present invention contains the calixarene derivative represented by the above formula (1). As 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.

In the following description, even when a mixture of calixarene derivatives is used, it is simply described as a calixarene derivative.

In addition to the calixarene derivatives, 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. And 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.

<Step of Forming a Resist Film>
In the present invention, 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. At this time, as 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.

By the above method, a resist film containing the above calixarene derivative can be formed on a substrate to be treated. Next, 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>
In the present invention, 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.

Further, 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.

By the above method, a latent image of a pattern can be formed on the resist film.

<Development process>
Next, in the present invention, 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.

In the present invention, in the substrate obtained in the latent image forming step, 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. Besides heptanone and the like, xylene, alcohols (ethanol, isopropyl alcohol and the like), glycol ethers, hydrofluoroalkyl ether and the like are used. These developers can be used alone or in combination.

Next, a method of developing the substrate obtained in the latent image forming step using the developer will be described.

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.

A more specific developing method will be described. 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.

By performing the above steps, a resist pattern can be formed. Next, post-processing of these steps will be described.

<Post-processing>
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. In addition, the above-mentioned development step and this rinse step can be alternately repeated about 2 to 10 times.

After that, the substrate is rotated at high speed or the like to shake off and remove the chemical solution to perform drying. As described above, by combining the calixarene derivative with the developer, a fine resist pattern is formed.

EXAMPLES The present invention will be more specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[Examples 1 to 8 and Comparative Examples 1 to 4]
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 | dissolved so that a density | concentration might be 2 mass%. Then, the obtained solution was filtered with a membrane filter made of high density polyethylene (HDPE) with a pore size of 0.05 μm to prepare a resist material. The resist material was spin-coated on a 4-inch silicon wafer and baked on a hot plate at 110 ° C. for 60 seconds to form a resist film having a thickness of about 35 nm (as a solid) (resist film forming step).

Then, using a resist film formed on a silicon wafer, an electron beam lithography system CAVL-9410NA (manufactured by Crestec) is used to adjust the electron beam irradiation amount at an acceleration voltage of 50 kV and a beam current of 100 pA (adjusting the exposure amount ) And a 200 μm wide line & space pattern was drawn for the sensitivity evaluation (latent image forming step).

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. Finally, 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 sensitivity of the resist pattern thus obtained was evaluated by the following method.

<Sensitivity>
The film thickness of the 200 μm 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 μm 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. Finally, 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 μm wide line & space pattern was measured by a stylus type profilometer. Next, 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

In addition, 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. In the same manner as in each of the examples and the comparative examples, such a sensitivity curve was created, and the exposure amount (D) was determined. Specifically, as shown in FIG. 1, 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). And the exposure amount at the intersection (about 0.5 mC / cm ^{2 in} FIG. 1) 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).

<Composition example>
Examples of synthesis of calixarene derivatives of Examples 1 to 8 are shown below.

Synthesis Example 1 Synthesis of Calixarene Derivative of Example 1
Using t-butylcalix [4] arene as a raw material, the reaction is carried out in the order of de-t-butylation reaction first, then introduction reaction of allyl group, and finally halogenated methylation reaction, Roxicalix [4] arene was synthesized. First, the synthesis of calix [4] arene by the de-t-butylation reaction was carried out by the following method.

<Synthesis of Calix [4] arene>
The reactor was assembled by attaching a mechanical stirrer, a thermometer and a gas introduction pipe to a 2 L glass four-necked flask. Quickly charge 120.0 g (0.19 mol) of t-butylcalix [4] arene (made by Sugai Chemical Co., Ltd.), 83.5 g (0.89 mol) of phenol and 1360 ml of dehydrated toluene in a flask, under a nitrogen flow, 300 rpm Stir. At this time, t-butylcalix [4] arene, which is a raw material, was suspended without being dissolved. Next, 125.8 g (0.94 mol) of anhydrous aluminum chloride (III) weighed in a glove bag was charged at once to the flask. After the addition, the solution temperature rose to about 30 ° C. It dissolved uniformly in about 5 minutes, becoming a pale yellow clear solution. After reacting for 5 hours at room temperature, 400 ml of 1 N hydrochloric acid was slowly added to quench the reaction. The reaction mixture was transferred to a separatory funnel and the organic phase was separated. The aqueous phase is then extracted three times with 300 ml of chloroform and combined with the organic phase. The organic phase was predried over anhydrous magnesium sulfate and filtered. 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%.

Subsequently, synthesis of aryloxycalix [4] arene by introduction of an allyl group was performed by the following method.

<Synthesis of aryloxycalix [4] arene>
A mechanical stirrer, a thermometer, a dropping funnel and a gas inlet tube were attached to a 1 L glass four-necked flask to assemble a reactor. The flask was charged with 24.0 g (0.057 mol) of calix [4] arene as a raw material, 40 ml of dehydrated N, N-dimethylformamide and 400 ml of dehydrated tetrahydrofuran and stirred at 300 rpm under a nitrogen flow. The raw material calix [4] arene dissolved immediately and became a colorless and transparent solution. Next, 38.1 g (0.339 mol) of potassium t-butoxide was quickly charged into the flask. The mixture exothermed to about 30 ° C. and turned into an orange slurry from a colorless and transparent solution. After the liquid temperature reached about room temperature, 82.1 g (0.678 mol) of allyl bromide was added dropwise over 30 minutes. The liquid temperature became about 40 ° C. After reaction for 2 hours after completion of dropwise addition, 400 ml of 1 N hydrochloric acid was slowly added to quench the reaction. The reaction mixture was transferred to a separatory funnel, and 700 ml of chloroform was added to separate the organic phase. 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 results are as follows: ¹ H-NMR (500 MHz, CDCl ₃ ): δ 3.0 to 4.5 ppm (m, 16 H), δ 4.8 to 5.4 ppm (m, 8 H), δ 5.8 to 6.2 ppm (m, 4H), δ 6.3 to 7.3 ppm (m, 12H), LC-MS: M = 584, M + 1 = 585. Finally, introduction of a halogenated methyl group (chloromethyl group) was carried out by the following method.

<Synthesis of Halogenated Methyl (Chloromethyl) Allyloxycalix [4] arene: Synthesis of Calixarene Derivative>
A reactor was assembled by attaching a mechanical stirrer, a thermometer and a Dimroto to a 1 L glass four-necked flask. A flask is charged with 10.0 g (0.017 mol) of allyloxycalix [4] arene, 10.5 g (0.350 mol) of paraformaldehyde, 500 ml of dioxane, 100 ml of concentrated hydrochloric acid, 50 ml of acetic acid, and 75 ml of 85% phosphoric acid. Stir at 350 rpm. 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. After reacting at 80 to 85 ° C. for 4 hours, 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 crude product was purified by column chromatography (filler: Wakogel C-200, developing solvent: tetrahydrofuran / hexane = 1/4) to obtain 1.0 g of a white solid. The yield was 7.5%, and the HPLC purity was 99.6%. The structure was identified by ¹ H-NMR and LC-MS. The results are as follows: ¹ H-NMR (500 MHz, CDCl ₃ ): δ 3.56 ppm (s, 8 H), δ 4.18 ppm (m, 8 H), δ 4.38 ppm (s, 8 H), δ 5.08 ppm (dd, J = 17) .0, 2.0 Hz, 4 H), .delta. 5.22 ppm (dd, J = 10.0, 2.0 Hz, 4 H), .delta. 5.94 ppm (m, 4 H), .delta. 6.99 ppm (s, 8 H), LC-MS M = 776, M + 2 = 778, M + 4 = 780, and M + 6 = 782. From the above results, it was found that this was a calixarene derivative having the structure shown in Table 1.

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. The results are as follows: ¹ H-NMR (500 MHz, CDCl ₃ ): δ 3.5 to 4.5 ppm (m, 22 H), δ 5.0 to 6.0 ppm (m, 12 H), δ 6.3 to 7.3 ppm (m, 9H), LC-MS: M = 728, M + 2 = 730, M + 4 = 732, M + 6 = 734. From the above results, it was found that this was a calixarene derivative having the structure shown in Table 1.

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.

<Synthesis of Dimethoxycalix [4] arene>
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. Thereafter, 200 ml of 1 N hydrochloric acid was slowly added to quench the reaction. The reaction mixture was transferred to a separatory funnel, and 600 ml of chloroform was added to separate the organic phase. 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 white solid. The white solid was dissolved in 500 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 (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%. Then, the synthesis of dimethoxydiaryroxycalix [4] arene was carried out by introducing an allyl group.

<Synthesis of Dimethoxydiaryloxycalix [4] arene>
A mechanical stirrer, a thermometer, a dropping funnel and a gas inlet tube were attached to a 1 L glass four-necked flask to assemble a reactor. The flask was charged with 40.0 g (0.094 mol) of the starting material dimethoxycalix [4] arene, 50 ml of dehydrated N, N-dimethylformamide and 500 ml of dehydrated tetrahydrofuran and stirred at 300 rpm under a nitrogen flow. Next, 31.5 g (0.281 mol) of potassium t-butoxide was quickly charged into the flask. The mixture exothermed to about 30 ° C. to give a pale yellow slurry. After the liquid temperature reached about room temperature, 68.0 g (0.562 mol) of allyl bromide was added dropwise over 10 minutes. The liquid temperature became about 40 ° C. After reacting for 5 hours after completion of the dropwise addition, 200 ml of 1 N hydrochloric acid was slowly added to quench the reaction. The reaction mixture was transferred to a separatory funnel, 800 ml of chloroform was added, and the organic phase was separated. 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 white solid. 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 of Halogenated Methyl (Chloromethyl) Dimethoxydiaryloxycalix [4] arene: Synthesis of Calixarene Derivative>
A reactor was assembled by attaching a mechanical stirrer, a thermometer and a Dimroto to a 1 L glass four-necked flask. 32.0 g (0.060 mol) of dimethoxydiaryroxycalix [4] arene, 36.0 g (1.20 mol) of paraformaldehyde, 500 ml of dioxane, 100 ml of concentrated hydrochloric acid, 50 ml of acetic acid and 50 ml of 85% phosphoric acid in a flask Charge and stir at 350 rpm. The mixture became a white slurry and all did not dissolve. The mixture was heated in an oil bath so that the liquid temperature would be 80 to 85.degree. As the solution temperature exceeded 70 ° C., the mixture turned from a white slurry to an almost colorless and clear solution. After reacting at 80 to 85 ° C. for 7 hours, the oil bath was removed and allowed to cool. The reaction mixture was transferred to a separatory funnel, and 200 ml of chloroform was added to separate the organic phase. 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 an orange solid. The crude product was purified by column chromatography (filler: Wakogel C-200, developing solvent: tetrahydrofuran / hexane = 1/4) to obtain 4.5 g of a white solid. The yield was 10.3%, and the HPLC purity was 97.4%. The structure was identified by ¹ H-NMR and LC-MS. The results are as follows: ¹ H-NMR (500 MHz, CDCl ₃ ): δ 3.0 to 4.6 ppm (m, 26 H), δ 5.3 to 6.1 ppm (m, 6 H), δ 7.0 to 7.3 ppm (m, 8H), LC-MS: M = 724, M + 2 = 726, M + 4 = 728, M + 6 = 730. From the above results, it was found that this was a calixarene derivative having the structure shown in Table 1.

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.

<Synthesis of Diacetoxycalix [4] arene>
A mechanical stirrer, a thermometer and a dropping funnel were attached to a 2 L glass four-necked flask to assemble a reactor. The flask was charged with 45.0 g (0.11 mol) of calix [4] arene as a raw material, 22.4 g (0.22 mol) of acetic anhydride and 680 ml of trifluoroacetic acid, and the mixture was stirred at 300 rpm. After reacting for 3 hours at room temperature, 600 ml of water was slowly added to quench the reaction. The reaction mixture was transferred to a separatory funnel, and 800 ml of chloroform was added to separate the organic phase. 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%. Next, synthesis of diacetoxydiaryloxycalix [4] arene by introducing an allyl group was performed.

<Synthesis of Diacetoxydiaryroxycalix [4] arene>
The same procedure as in Synthesis Example 3 was repeated except that diacetoxycalix [4] arene was used instead of dimethoxycalix [4] arene. The yield was 70.2%, and the HPLC purity was 98.9%. Finally, introduction of a halogenated methyl group (chloromethyl group) was carried out by the following method.

<Synthesis of Halogenated Methyl (Chloromethyl) Diacetoxydiaryloxycalix [4] arene: Synthesis of Calixarene Derivative>
In the synthesis of chloromethyldimethoxydiaryloxycalix [4] arene of Synthesis Example 3, except that diacetoxydiaryloxycalix [4] arene was used instead of dimethoxydiaryloxycalix [4] arene as a raw material I did the same. The yield was 12.6% and the HPLC purity was 98.8%. The structure was identified by ¹ H-NMR and LC-MS. The results are as follows: ¹ H-NMR (500 MHz, CDCl ₃ ): δ 1.53 ppm (s, 6 H), δ 3.5 to 4.6 ppm (m, 20 H), δ 5.0 to 6.0 ppm (m, 6 H), δ 7 .0 to 7.3 ppm (m, 8H), LC-MS: M = 780, M + 2 = 782, M + 4 = 784, M + 6 = 786. From the above results, it was found that this was a calixarene derivative having the structure shown in Table 1.

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 of Dipropoxydiaryroxycalix [4] arene>
The same procedure as in Synthesis Example 3 was repeated except that dipropoxy calix [4] arene was used in place of dimethoxycalix [4] arene in the synthesis of dimethoxydiaryloxy calix [4] arene. The yield was 73.5%, and the HPLC purity was 97.8%. Finally, introduction of a halogenated methyl group (chloromethyl group) was carried out by the following method.

<Synthesis of Halogenated Methyl (Chloromethyl) dipropoxydiaryloxycalix [4] arene: Synthesis of Calixarene Derivative>
In the synthesis of chloromethyldimethoxydiaryloxycalix [4] arene of Synthesis Example 3, except that dipropoxydiaryloxycalix [4] arene was used instead of dimethoxydiaryloxycalix [4] arene as the raw material. I did the same. The yield was 12.8% and the HPLC purity was 98.1%. The structure was identified by ¹ H-NMR and LC-MS. The results are as follows: ¹ H-NMR (500 MHz, CDCl ₃ ): δ 1.05 ppm (t, J = 7.0 Hz, 6 H), δ 1.91 ppm (m, 4 H), δ 3.5 to 4.5 ppm (m, 24 H) 5.0-6.0 ppm (m, 6H), δ 7.0-7.3 ppm (m, 8H), LC-MS: M = 780, M + 2 = 782, M + 4 = 784, M + 6 = 786. From the above results, it was found that this was a calixarene derivative having the structure shown in Table 1.

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. The results are as follows: ¹ H-NMR (500 MHz, CDCl ₃ ): δ 3.0 to 4.6 ppm (m, 24 H), δ 5.3 to 6.1 ppm (m, 6 H), δ 7.0 to 7.3 ppm (m, 9H), LC-MS: M = 676, M + 2 = 678, M + 4 = 680, M + 6 = 682. From the above results, it was found that this was a calixarene derivative having the structure shown in Table 1.

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. The results are as follows: ¹ H-NMR (500 MHz, CDCl ₃ ): δ 1.53 ppm (s, 6 H), δ 3.5 to 4.6 ppm (m, 18 H), δ 5.0 to 6.0 ppm (m, 6 H), δ 7 .0 to 7.3 ppm (m, 9H), LC-MS: M = 732, M + 2 = 734, M + 4 = 736, M + 6 = 738. From the above results, it was found that this was a calixarene derivative having the structure shown in Table 1.

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.

<Synthesis of Chloromethyldichloroalyloxycalix [4] arene>
The same procedure as in Synthesis Example 1 was repeated except that dichloroallyloxycalix [4] arene was used instead of allyloxycalix [4] arene as a raw material. The yield was 8.3%, and the HPLC purity was 98.1%. The structure was identified by ¹ H-NMR and LC-MS. The results are as follows: ¹ H-NMR (500 MHz, CDCl ₃ ): δ 3.5 to 4.6 ppm (m, 24 H), δ 5.4 to 6.0 ppm (m, 4 H), δ 7.0 to 7.3 ppm (m, 8H), LC-MS: M = 1048, M + 2 = 1050, M + 4 = 1052, M + 6 = 1054, M + 8 = 1056, M + 10 = 1058, M + 12 = 1060. From the above results, it was found that this was a calixarene derivative having the structure shown in Table 1.

Claims

Following formula (1)

(In the formula,
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,
When 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. )
Calixarene derivative shown in the.
A resist material comprising the calixarene derivative according to claim 1.
A resist material according to claim 2 is coated on a substrate to be treated, and then prebaked to form a resist film, and the resist film is selectively exposed to high energy rays to form a latent image of a desired pattern. A resist pattern forming method comprising: forming; and developing the latent image.