JP2002006481A - Very strong organic acid generator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a very strong organic acid generator, a composition containing the generator and having reactivity to active energy beams and a polymer pattern forming method using the composition. SOLUTION: The organic very strong acid generator comprises a cyclohexane derivative of formula (1) (where X is H or F; R1 is a substituent having an aromatic substituent constant σ1 of +0.00 to +0.70 and is situated in the 3- and/or 4-position relative to the substituent -OSO2[CX2]tCF3; R2 is a substituent having an aromatic substituent constant σ1 of -0.03 to +0.70; (t) is an integer of 0 or 1; (n) is an integer of 1 or 2; (m) is an integer of 0-4; and n+m=1-5).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic superacid generator, a composition containing the organic superacid generator and having reactivity to active energy rays, and a method for forming a polymer pattern using the composition.

[0002]

2. Description of the Related Art As in a photoengraving technique, a photosensitive resin mainly composed of a polymer material is widely used as a photosensitive material having a large amount and high resolution (Ao Yamaoka, (See "Photopolymer Technology," edited by Mototaro Nagamatsu, Nikkan Kogyo Shimbun (1988)). The polymer-based photosensitive material has many advantages such as excellent resolution, a wide range of photosensitive wavelengths can be set by selecting a photochemical reaction, and it can be manufactured at relatively low cost. However, the photosensitive speed is extremely low compared to silver halide photosensitive materials, and even though it is the most sensitive polymer-based photosensitive material, it does not reach one-thousandth of the photosensitive speed exhibited by silver halide materials. There is a strong demand for higher sensitivity. On the other hand, ultraviolet or electron beam curing technology for rapidly curing a liquid coating film by cationic polymerization has attracted attention. Unlike radical polymerization, cationic polymerization has an advantage in that it has no oxygen inhibition effect, and
In the case of a ring-opening polymerization reaction such as an epoxy group, since the degree of volume shrinkage is very small, stress distortion is reduced.
Further, the adhesive layer has good adhesiveness and adhesion to the substrate surface due to the polarity of the oxygen atom derived from the epoxy group, and also has a feature of providing a cured film having excellent flexibility. Furthermore, the properties of the cured film can be further improved by heat treatment during or after irradiation with energy rays. However, from the viewpoint of energy saving, a more efficient curing material is required.

Hitherto, various attempts have been made to improve the photospeed of high-molecular photosensitive materials. Among them, chemically amplified photoresist materials are based on the principle of converting acid-reactive molecules chemically or physically bonded to or mixed with a polymer using an acid generated by a photochemical reaction as a catalyst. Is achieved. However, in practice, there is a limit to the improvement in sensitivity. An acid propagation reaction has been proposed as a principle for realizing a drastic increase in sensitivity of the chemically amplified photoresist material (Japanese Patent Application Laid-Open No. 8-248561). That is, a thermochemical reaction is caused by the catalytic action of the acid generated by the photochemical reaction, whereby the acid is newly generated and the acid is multiplied autocatalytically. A thermal acid generator having such a function is called an acid proliferating agent. That is, if one acid molecule can decompose one acid proliferating agent molecule to generate one acid, one acid molecule multiplies by one reaction to produce a total of two acid molecules. If this reaction occurs in a chain, the generation of acid will increase in mice. If a thermal acid generator having such properties is added to a chemically amplified photoresist, the acid rapidly increases, so that the stop of the acid-catalyzed reaction by a basic substance can be suppressed, and the disappearance of the acid due to a side reaction is also prevented. In addition, the acid-catalyzed reaction can be greatly accelerated, and the sensitivity can be improved.
In addition, since the cationic polymerization rate is also improved, curing by ultraviolet rays or electron beams can be performed efficiently.

[0004] A proliferative thermal acid generator is a compound which is easily decomposed by an acid itself. In order to put a photosensitive material containing the same into practical use, it is essential that the material is thermally stable and does not deteriorate even during long-term storage. It is. Since this reaction occurs explosively due to autocatalytic decomposition, it is essential to ensure the storage stability of the acid multiplying agent itself and the storage stability of the photosensitive material. Further, in order to improve the speed of the acid catalyzed reaction or the cationic polymerization reaction, it is desired that the strength of the acid generated from the acid multiplying agent is high. As a growth agent,
Acetoacetate derivatives (K. Arimitsu et al., J. A.
Chem. Soc., 120, 37 (1998)), ketal sulfonate derivatives (K. Kudo et al., Mol. Cryst. Liq. Cryst.,
280, 307 (1996)), 1,2-diol monosulfonate derivative (S. Noguchi et al., J. Photopolym. Sci. Tech)
nol., 10, 315 (1997)). However, these all generate alkane sulfonic acid or allene sulfonic acid, and in order to further improve the performance of the active energy ray resin composition, a super strong acid which is an acid having a larger acid strength is used. There is a need for a proliferating agent to be generated. That is, in cationic polymerization of epoxy, sulfonic acid reacts with an epoxy group, so that polymerization does not occur efficiently.On the other hand, if the acid is a super strong acid, the nucleophilicity of the corresponding sulfonate group is reduced. The cationic polymerization initiation ability will be improved. In order to improve resist characteristics such as sensitivity and resolution of a chemically amplified resist, a super strong acid multiplying agent has been required.

As a stronger acid than alkanesulfonic acid or arenesulfonic acid, fluorine-substituted alkanesulfonic acid represented by trifluoromethanesulfonic acid is well known, and is regarded as an organic superacid.
Therefore, by replacing the sulfonic acid ester site of the above-mentioned acid multiplying agent with a fluorinated alkanesulfonic acid ester, an acid multiplying agent capable of generating a super strong acid can be produced in principle. However, organic chemistry shows that the greater the acid strength, the greater the ability as a leaving group. Actually, cycloalkane-1,2-diol monoalkane or arenesulfonic acid ester has a good thermal stability among the acid proliferating agents reported so far, but its fluorine-containing alkanesulfonic acid ester is very poor. Thermally unstable. On the other hand, it has been suggested that benzenesulfonic acid esters of cyclopentanol and cyclohexanol are autocatalytically decomposed by heating to form benzenesulfonic acid and cyclopentene or cyclohexene (CD Nenitzescu, V. Ioan and L. Teodo).
rescu, Chem. Ber., 90, 585 (1957)). That is,
These can function as acid proliferating agents. However, it has been reported that since cycloalkene and benzenesulfonic acid cause an addition reaction, this reaction proceeds reversibly in a solution and reaches a certain equilibrium state. Therefore, the acid generation efficiency is reduced.

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the thermal decomposition behavior of cyclopentyl sulfonate and cyclohexyl sulfonate in the absence or presence of sulfonic acid. As a result, the rate of thermal decomposition reaction accompanied by elimination of sulfonic acid is significantly affected by the type and position of the substituent of cyclohexane, and the addition reaction between the corresponding cycloalkene and sulfonic acid is also the same. Have been found to undergo significant substituent effects. That is, when an electron-withdrawing substituent such as a hydroxyl group, an acyloxy group, an alkoxycarbonyloxy group, an alkanesulfonyloxy group, or an alensulfonyloxy group is introduced into the cyclohexane ring, the substituent is included at the 3- and / or 4-position with respect to the substituent. It has been found that a sulfonic acid having a fluorine-alkanesulfonyloxy group bonded is remarkably thermally stable. Furthermore, in the presence of a strong acid, a decomposition reaction occurs to generate a fluorinated alkanesulfonic acid which is a super strong acid, so that an autocatalytic acid multiplication reaction occurs. That is, it has been found that a fluorinated alkanesulfonic acid ester having a large desorbing ability is thermally stable and also has a super-acid-proliferating ability.

[0007]

SUMMARY OF THE INVENTION The present invention provides an organic superacid generator, a composition containing the same, and a method for forming a polymer pattern using the composition. Is the subject.

[0008]

According to the present invention, the following general formula (1)

Embedded image (Wherein, X represents a hydrogen atom or a fluorine atom, R ¹ represents a substituent having an aromatic substituent constant σ ₁ of 0.00 to +0.70, and a substituent —OSO ₂ [CX ₂ ] _t CF ₃ And R ² is a substituent having an aromatic substituent constant σ ₁ of −0.03 to +0.70, and t 2
Represents an integer of 0 or 1, n represents an integer of 1 or 2,
m represents an integer of 0 to 4, and n + m represents an integer of 1 to 5). Further, according to the present invention, there is provided an active energy ray-curable composition comprising the organic superacid generator, an acid generator that generates an acid by an active energy ray, and a cationic polymerizable compound. . Further, according to the present invention, the organic superacid generator,
There is provided a pattern forming composition comprising an acid generator that generates an acid by an active energy ray and an acid-catalyzed reactive substance. Furthermore, according to the present invention,
There is provided a method for forming a polymer pattern, which comprises a step of irradiating a pattern composed of the composition for forming a pattern with active energy rays.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The superacid generator according to the present invention is represented by the general formula (1) and comprises a cyclohexane derivative having a fluorine-containing alkanesulfonic acid ester group. The super strong acid generator of the present invention decomposes in the presence of an acid to generate a super strong acid, and the amount of the generated super strong acid increases with time. That is, it has the property of proliferatingly decomposing. In the general formula (1), R ¹ has an aromatic substituent constant σ ₁ of 0.00 to +0.70, preferably +0.
And 05 to +0.60. When σ _{1 of} R ¹ is smaller than the above range, the compound becomes thermally unstable. On the other hand, when σ _{1 of} R ¹ is larger than the above range, the acid growth reaction rate of the compound becomes low. The aromatic substituent constant σ ₁ is described, for example, in the literature “Kozo Tabe and Tsuneichi Takeshita,“ Acid-Base Catalyst ”, Sangyo Tosho (1965), Nos. 301-30.
It is described in detail on page 4.

The substituent R ¹ includes an organic sulfonyloxy group represented by the following general formula (2).

Embedded image —OSO ₂ —R ₃ (2) In the above formula, R ³ represents an aromatic group or an aliphatic group. The aromatic groups include those in which the aromatic ring comprises a carbon ring or a heterocyclic ring. In addition, the aromatic group consisting of the carbon ring includes a single (benzene ring), a condensed polycyclic (a naphthalene ring, a pyrene ring, an azulene ring, a fluorene ring, an anthracene ring,
Chrysene ring etc.) and chain polycycles (biphenyl ring, terphenyl ring etc.). An aromatic group consisting of a heterocyclic ring is
It is a heteroaromatic group containing at least one heteroatom such as a nitrogen atom, an oxygen atom, and a sulfur atom. Such aromatic groups include those having 4 to 20, preferably 5 to 10 ring atoms. Examples of the heterocyclic ring include a thiophene ring, a benzothiophene ring, a thianthrene ring, a furan ring, a benzofuran ring, a carbazole ring, a pyridine ring, a pyrazine ring, and a pyrrolidine ring.
A substituent may be bonded to the aromatic group. Such a substituent includes a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a naphthyl group and the like.

Specific examples of the aromatic group include a phenyl group, a naphthyl group, a biphenylyl group, a terphenylyl group,
Pyrenyl group, fluorenyl group, 9,9-dimethyl-2-
Fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, benzyl group, 4-chlorobenzyl group, 4-
Examples include a methylbenzyl group, a naphthylmethyl group, a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group, a carbazolyl group, a pyridyl group, a pyraridinyl group, a pyrrolidyl group, and an oxazolyl group.

The aliphatic group has 1 to 1 carbon atoms.
20, preferably 1 to 10. The aliphatic group includes linear and cyclic ones. The chain includes an alkyl group and an alkenyl group, and a preferred chain aliphatic group is an alkyl group having 1 to 20, preferably 1 to 4 carbon atoms. The cycloaliphatic group includes a cycloalkyl or bicycloalkyl group having 5 to 20, preferably 6 to 10 carbon atoms. A substituent may be bonded to the aliphatic group. Such substituents include halogen atoms,
An alkoxy group having 1 to 6 carbon atoms is included.

Specific examples of the aliphatic group include an allene group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a sec-butyl group,
-Butyl group, iso-butyl group, trifluoromethyl group and the like.

In addition, R ¹ represents an aromatic group, a halogen atom, a hydroxyl group, a hydrocarbon oxy group, a hydrocarbon thio group, an acyloxy group, a hydrocarbon group, in addition to the substituent represented by the general formula (2). Oxycarbonyloxy groups are included.
In this case, the aromatic groups include those described for R ³ above. The halogen atom includes fluorine, chlorine and bromine.

[0015] The hydrocarbon oxy group (RO-) includes
An aliphatic hydrocarbon oxy group and an aromatic hydrocarbon oxy group are included. Aliphatic hydrocarbon oxy groups have 1 to 1 carbon atoms.
20, preferably 1 to 10 chain alkoxy groups and 3 to 20 carbon atoms, preferably 4 to 10 cyclic alkoxy groups. The aromatic hydrocarbon oxy group has 6 to 6 carbon atoms.
18, preferably an aryloxy group having 6 to 12 carbon atoms and an arylalkoxy group having 7 to 18 carbon atoms, preferably 7 to 12 carbon atoms. A substituent may be bonded to the hydrocarbon oxy group. Such substituents include halogen atoms and the like.

Specific examples of the hydrocarbon oxy group include:
Methoxy, ethoxy, n-propoxy, iso-
Propoxy group, n-butoxy group, iso-butoxy group,
sec-butoxy group, tert-butoxy group, 2-hydroxyethoxy group, benzyloxy group, 4-methylbenzyloxy group, trifluoromethoxy group and the like.

The hydrocarbon thio group (RS-) includes an aliphatic hydrocarbon thio group and an aromatic hydrocarbon thio group. The aliphatic hydrocarbon thio group includes a linear alkylthio group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and 3 to 5 carbon atoms.
Twenty, preferably four to ten, cyclic alkylthio groups are included. The aromatic hydrocarbon thio group has 6 to 18 carbon atoms,
Preferably an arylthio group having 6 to 12 and a carbon number of 7 to 1
8, preferably 7 to 12 arylalkylthio groups are included. A substituent may be bonded to the hydrocarbon thio group. Such substituents include a halogen atom and the like.

The acyloxy group (RCOO-) includes
Aliphatic and aromatic ones are included. The aliphatic acyloxy group has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
10 chains and 3-20 carbon atoms, preferably 4-carbon atoms
Ten annular ones are included. The aromatic acyloxy group includes an arylcarbonyloxy group having 6 to 18 carbon atoms, preferably 6 to 12 carbon atoms, and an arylalkylcarbonyloxy group having 7 to 18 carbon atoms, preferably 7 to 12 carbon atoms. A substituent may be bonded to the acyloxy group. Such substituents include halogen atoms and the like. Specific examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

The hydrocarbon oxycarbonyloxy group (ROCOO-) includes aliphatic and aromatic ones. The aliphatic alkoxycarbonyloxy group includes a linear one having 1 to 20, preferably 1 to 10 carbon atoms and a cyclic one having 3 to 20, preferably 4 to 10 carbon atoms. Aromatic ones have 6 to 1 carbon atoms.
8, preferably 6 to 12 aryloxycarbonyloxy groups and 7 to 18 carbon atoms, preferably 7 to 12 arylalkyloxycarbonyloxy groups.
A substituent may be bonded to the hydrocarbon oxycarbonyloxy group. Such substituents include halogen atoms and the like. Specific examples of the hydrocarbon oxycarbonyloxy group include a t-butoxycarbonyloxy group and a benzyloxycarbonyloxy group.

In the general formula (1), specific examples of R ² include methyl, ethyl, phenyl, substituted phenyl, hydroxyl, chloro, bromo, acetoxy,
Examples include a benzenesulfonyloxy group, a p-toluenesulfonyloxy group, a trifluoromethanesulfonyloxy group, and a trifluoroethanesulfonyloxy group.

In the general formula (1), n is 1 or 2
Indicates an integer. m represents an integer of 0 to 4, preferably 0 to 2. The sum of n and m (n + m) is 1 to 5, preferably 1
整数 2. In the general formula (1), X represents a hydrogen atom or a fluorine atom. t indicates an integer of 0 or 1, and when t is 0, it indicates that CX ₂ does not exist. When t is 1, it indicates that CX ₂ exists. In the general formula (1), the substituent R ¹ bonded to the cyclohexane ring is bonded to the 3- and / or 4-position with respect to —OSO ₂ [CX ₂ ] _t CF ₃ . This allows
A thermally stable superacid generator can be obtained. Also,
When two substituents R ¹ are attached to the cyclohexane ring,
The two R ¹ may be the same or different.

Specific examples of the super strong acid generator of the present invention include:
The following can be mentioned.

Embedded image

The superacid generator of the present invention can be used in the presence of an acid.
Understand super strong acid (HOSO_Two[CX_Two] _tCF_ThreeGenerate)
You. In this case, the decomposition occurs quantitatively and over time
Decomposition rate is higher, and super strong acids are generated proliferatively
You. In this case, one mole of the acid is dissolved in one liter of water.
PH is 2.0 or less, preferably 1.0 or less
What is shown may be sufficient.

The active energy ray-curable composition of the present invention comprises (i) a super strong acid generator, (ii) an acid generator that generates an acid by an active energy ray, and (iii) a cationic polymerizable compound. . The acid generator in this case generates an acid by ultraviolet light, visible light, electron beam, X-ray, or the like, and the acid causes the super strong acid generator of the present invention to be catalytically decomposed to produce a fluorinated alkane sulfone which is a super strong acid. Generates acids. As a result, the super-strong acid generator is decomposed in a self-catalytic manner to generate a fluorinated alkanesulfonic acid which is a super-strong acid one after another.

As the active energy ray acid generator, various conventionally known ones can be used. As such a material, for example, a compound used for a chemically amplified photoresist or a cationic photopolymerization is suitably used (Organic Materials Research Society, “Organic Materials for Imaging”, Bunshin Publishing (1993)). 187-192). That is, diazonium, iodonium,
Examples include PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , and CF ₃ SO ₃ ⁻ salts of aromatic onium compounds such as sulfonium and phosphonium. Further, there may be mentioned a sulfonated compound which generates sulfonic acid and an iron allene complex. In order to expand the photosensitive wavelength range of these photoacid generators, a photosensitizer can be appropriately used. For specific examples of the photosensitizer, see, for example, JP-A-12-35665.
The details are described in Japanese Patent Publication No.

As the cationically polymerizable compound used in the present invention, conventionally known various compounds can be used. Such compounds include alkenyl, alkynyl or diene compounds represented by α-methylstyrene; oxygen, nitrogen or sulfur atoms having unpaired electrons having C が C
Vinyl ether conjugated to the bond, propenyl ether,
Unsaturated compounds such as vinyl sulfide and N-vinylamine; compounds having a residue such as epoxy, oxetane and spiro orthoester having a cyclic structure containing an oxygen atom, a nitrogen atom and a sulfur atom having an unpaired electron; Can be.

A commonly used cationic polymerization initiator is an aprotic Lewis acid, and a protic acid such as sulfonic acid is rarely used. This is due to the fact that the sulfonate ion has a weak nucleophilic reactivity but reacts with a cation site as a growing species. The acid generated from the super-strong acid generator of the present invention is a fluorinated sulfonic super-acid, and the nucleophilic reactivity of its counter anion is significantly reduced. It can be polymerized well. Further, in order to effectively perform curing by active energy rays, compounds in which these molecules are substituted with at least two or more cationically polymerizable groups are more preferable. Further, linear aliphatic epoxides such as epoxidized soybean oil and the like can be mentioned.
Examples of the epoxy resin that is solid at room temperature include triglycidyl ether triphenylmethane and tetraglycidyl ether tetraphenylethane, bisphenol S diglycidyl ether, cresol novolac glycidyl ether, triglycidyl isocyanurate, and tetrabromobisphenol A diglycidyl. .

The method for preparing the active energy ray-curable composition of the present invention is described below. The composition of the present invention contains 0.1 to 20 parts by weight, more preferably 0.5 to 5 parts by weight, of an energy ray-sensitive cationic polymerization initiator based on 100 parts by weight of a cationically polymerizable organic compound, and a super strong acid generator. To 0.1
To 20 parts by weight, more preferably 0.1 to 10 parts by weight. If the weight part of the energy ray-sensitive cationic polymerization initiator is less than this range, the productivity is inferior because the active ray irradiation time becomes extremely long, and if it is more than this range, further addition effect is recognized. There is no meaning because there is no. When the weight part of the acid-proliferating super-strong acid generator is smaller than the above range, the effect of accelerating the curing by the addition thereof is not remarkable, and the blending above the range is not preferable because the physical properties of the cured product are inferior. Further, since the curable composition is in a liquid or semi-solid state, the acid multiplication reaction of the super-strong acid generator causes the acid to propagate in an uncured part while chain-growing similarly to the solution. .
As a result, for example, the strong acid diffuses to a portion where the ultraviolet light does not reach due to the presence of the coloring or scattering filler, and the curing can be completed.

The composition for pattern formation of the present invention comprises (i)
It is composed of a super strong acid generator, (ii) an acid generator that generates an acid by an active energy ray, and (iii) an acid reactive substance. The acid-reactive substance includes a high-molecular substance and a low-molecular substance that solidify or oxidize (insolubilize) by reacting in the presence of an acid.

Examples of the acid-reactive substance suitably used in the present invention are shown below (edited by the Research Group for Organic Electronics Materials,
"Organic Materials for Imaging", Bunshin Publishing (1993
Year), see pages 199-201. Supervised by Tadahiro Omi, "New semiconductor manufacturing processes and materials", CMC,
(2000), pp. 50-67). Many utilize the reaction of deprotection groups in synthetic organic chemistry (T.
W. Greene, Protective Groups in Organic Synthesis,
John Wiley & Sons (1981)) gives a specific example below.

First, a high molecular substance having an acid-reactive residue in a side chain or a main chain can be mentioned. Examples of the acid-reactive residue include carboxylic acid secondary and tertiary esters, tetrahydropyranyl esters, carbonic acid tertiary esters, phenolic compounds protected with trialkylsilyl and tetrahydropyranyl groups, and N-methylol compounds. A hydroxyl group is preferably used. In these, a deprotection reaction occurs by the action of an acid to generate a carboxylic acid or phenol having a high polarity, so that the exposed portion is solubilized in a polar solvent or an aqueous alkaline solution.

Second, there is a polymer compound containing an acid-reactive low-molecular compound. Here, the acid-reactive low-molecular compound has an effect of reducing the solubility of the resin compound, and is called a dissolution inhibitor. Examples of the dissolution inhibitor include acetal compounds, ketal compounds, tertiary esters of carboxylic acids, tetrahydropyranyl esters, tertiary carbonates, phenols protected with trialkylsilyl groups and tetrahydropyranyl groups, pinacol derivatives, and the like. be able to. As resin compounds containing these dissolution inhibitors, for example, novolak resins, poly (p
-Hydroxystyrene), methacrylic acid copolymer, N-
Methylol maleimide copolymer and the like can be mentioned. The low molecular weight compound has an effect of inhibiting the solubility of these resins in an aqueous alkali solution. However, when decomposed by the action of an acid, the effect of inhibiting the dissolution is lost, and the polymer becomes alkali-soluble.

Third, a condensation-reactive high-molecular substance produced by an acid-catalyzed reaction can be used. Residues which form cations by an acid catalyst and cause a condensation reaction include benzyl alcohol derivatives, melamine derivatives, N-methylolimide derivatives,
Acetal derivatives, vinyl ether derivatives and the like can be mentioned. Examples of the residue that reacts with the generated cation include phenol and alcohol. Polymers having these residues, such as a polymer of p-hydroxystyrene, a novolak resin, and hydroxyethyl methacrylate may be used. Is preferably used. Further, the polymer having both the condensable residue and the phenyl residue causes cross-linking by the acid catalyst itself.

Fourth, a polymer having a residue which is polymerized by an acid catalyst can be mentioned. Examples of the cationic polymerizable residue include an epoxy group, an oxetane residue, a vinyl ether group, an isopropenylphenyl group, and a cyclic orthoester. Fifth, a composition comprising a cationically polymerizable monomer or prepolymer is also used. As the cationic monomer unit, an epoxy group, an oxetane group, a vinyl ether residue, a cyclic orthoester, or the like is used.

In the composition for pattern formation of the present invention,
The ratio of the photoacid generator is 0.5 to 20 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the acid-reactive substance. The ratio of the super strong acid generator is 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight.

In order to form a pattern using the composition for pattern formation of the present invention, the composition of the present invention is dissolved in an appropriate solvent to form a uniform solution, which is applied onto a substrate. Next, the coating film formed on the substrate is irradiated with active energy rays in a pattern. Thereby, a pattern made of a polymer is formed on the substrate. By using the composition for pattern formation of the present invention, a fine pattern can be formed. The composition of the present invention is formed as a thin film on a substrate such as a silicon wafer by spin coating or the like, and is exposed through a mask to generate an acid as a latent image. As a radiation source, visible light that generates an acid from an acid generator,
Active energy rays such as ultraviolet rays, far ultraviolet rays, X-rays, and electron beams can be used. Then, a heating (post-baking) treatment is performed to promote the chain decomposition of the proliferating super strong acid generator of the present invention, and to cause a structural change of the acid-reactive substance by an acid-catalyzed reaction. The conditions of the heat treatment vary depending on the exposure energy, the type of the residue active in the acid used, the glass transition temperature of the polymer, and the like, and the heating temperature is in the range of 60 to 150 degrees, more preferably 80 to 130 degrees. Range of degrees. The heating time is 10 seconds to 10 minutes,
More preferably, it is 30 seconds to 5 minutes. If the heating time is shorter than this, the acid-catalyzed reaction is not sufficiently caused. If the time exceeds this range, the acid-proliferating super-strong acid generator may cause a side reaction, and the resolution of the pattern deteriorates due to excessive diffusion of acid molecules. After performing these processes, a pattern is obtained with a developing solution. When a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group is generated by a deprotection reaction by an acid-catalyzed reaction, development can be performed with an aqueous alkali solution. These operations are essentially the same as those applied to the chemically amplified resist, but the addition of the proliferative superacid generator of the present invention not only improves the sensitivity but also improves the resolution and other properties. Is also improved. This is presumably because the generated acid is easily trapped in a predetermined atomic group in the polymer film due to the super-strong acid called fluorine-substituted sulfonic acid, and excessive diffusion and migration are suppressed.

[0037]

(1) The superacid generator of the present invention has high storage stability, and the sensitivity of the photosensitive material is greatly improved due to the generated superacid, so that high sensitivity and high resolution can be obtained. It can be used as a material for forming a conductive pattern. (2) The composition of the present invention can be used effectively in ultraviolet-curable paints, inks, surface coating agents, etc. because the combination of light irradiation and heat treatment greatly improves the crosslinking efficiency of the photocurable resin. Can be. In a coating film composed of a pigment-dispersed photo-curing agent, the photo-absorption occurs only in the surface layer, so that the curing is insufficient or does not occur at all inside. However, according to the present invention, the curing is completed by the heat treatment after light irradiation. Can be (3) Since the amount of generated acid is greatly increased by the proliferative superacid generator, the amount of the photoacid generator used can be reduced. As a result, light can sufficiently penetrate into the inside of the photosensitive layer, so that the thickness of the photosensitive layer can be greatly increased. (4) A photosensitive material with high sensitivity can be produced by adding a photosensitizer to the composition of the present invention.

[0038]

Example 1 5.0 g of 1,4-cyclohexanediol was dissolved in 80 ml of pyridine, 8.21 g of p-toluenesulfonyl chloride was added to the solution under ice cooling, and the mixture was stirred at room temperature for 24 hours. . The reaction was poured into ice-cold water and the organic layer was extracted twice with dichloromethane and washed with water, dilute hydrochloric acid and brine.
After drying over magnesium sulfate, the solvent was distilled off, and the product was purified by silica gel column chromatography. 1-Hydroxy-4- (p-toluenesulfonyloxy) cyclohexane having a melting point of 72-73 ° C was obtained in a yield of 64.9%. 1.0 g of this compound was dissolved in 20 ml of pyridine, and 1.15 g of trifluoromethanesulfonic anhydride was added under ice cooling, followed by stirring at room temperature for 24 hours. The product was poured into ice water, the organic layer was extracted with dichloromethane, washed with water, dried, and the solvent was removed. Then, the product was purified by silica gel column chromatography. Yield 3
1- (p-Toluenesulfonyloxy) -4-trifluoromethanesulfonyloxycyclohexane having a melting point of 34-35 ° C at 9.6% was obtained. ¹ H-NMR (CDCl ₃ ,
200 MHz) [delta] (ppm): 1.17-1.88
(M, 3H), 2.03-2.38 (m, 5H), 2.
45 (s, 3H), 4.68-4.82 (m, 1H),
5.61-5.73 (m, 1H), 7.33 (d, 2
H, J = 8.4 Hz), 7.80 (d, 2H, J = 8.
4 Hz). Elemental analysis: C42.09%, H4.10.
%, S15.77%, F13.97%. Calculated value (C ₁₄ H
₁₇ S ₂ O ₆ F ₃ : C 41.80%, H 4.26%, S1
5.90%, F14.10%.

Example 2 1-Hydroxy-4- (p-toluenesulfonyloxy) cyclohexane obtained in Example 1 was reacted with 3,3,3-trifluoroethanesulfonyl chloride in the same manner as in Example 1. With a yield of 97.4% and a melting point of 68-70 ° C.
(P-toluenesulfonyloxy) -4- (3,3,3
-Trifluoroethanesulfonyloxy) cyclohexane was obtained. ¹ H-NMR (CDCl ₃ , 200 MHz) δ
(Ppm): 1.60-1.99 (m, 8H), 2.4
6 (s, 3H), 3.86 (q, 2H, J = 8.6H)
z) 4.53-4.68 (m, 1H), 4.81-
5.04 (m, 1H), 7.34 (d, 2H, J = 8.
4 Hz), 7.78 (d, 2H, J = 8.4 Hz). Elemental analysis: C 43.47%, H 4.67%, S15.2
0%, F13.87%. Calculated value (C ₁₅ H ₁₉ S ₂ O ₆ F ₃ :
C43.26%, H4.60%, S15.40%, F1
3.69%.

Example 3 1.0 g of 1,4-cyclohexanediol was dissolved in 40 ml of pyridine, and 1.48 g of 3,3
Reacted with 3-trifluoroethanesulfonyl chloride. By the same operation as in the first embodiment, the target 1,4
-Bis (3,3,3-trifluoroethanesulfonyloxy) cyclohexane was obtained in a yield of 76.6%. 110-111 ° C. ¹ H-NMR (CDCl ₃ ), 200 MHz) δ (pp
m): 1.54-2.20 (m, 8H), 4.10
(Q, 4H, J = 8.4 Hz), 4.82-5.01
(M, 2H). Elemental analysis: C 29.74%, H 3.6
3%, S 15.44%, F 27.62%. Calculated value (C _{15
H 19 S 2 O 6 F 3} : C29.42%, H3.46%, S1
5.70%, F27.92%.

Comparative Example 1 5.97 g of cis- (1S, 2S, 3R, 5S) -pinanediol, 1.05 of 4- (dimethylamino) pyridine
g and 3.55 ml of triethylamine were dissolved in 80 ml of dichloromethane, and 5.55 g of 3,3 was added thereto.
Add 3-trifluoroethanesulfonyl chloride to add 4
The mixture was stirred at room temperature for two days, and 2-hydroxy-3-
(3,3,3-trifluoroethanesulfonyloxy)
Attempt to synthesize pinan. The organic layer was washed with dilute hydrochloric acid, water and aqueous sodium hydrogen carbonate, dried, and the solvent was distilled off. When the oily residue was left at room temperature, it turned black and decomposed.

Comparative Example 2 Under the same reaction conditions as in Comparative Example 1, pinanediol was reacted with trifluoromethanesulfonic anhydride to try to synthesize 2-hydroxy-3-trifluoromethanesulfonyloxypinane as a growth agent. The decomposition progressed rapidly during the process of distilling off the solvent from the organic layer, and an acidic dark black oily product was obtained.

Example 3 70 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Union Carbide Co., product name ERL-4221), bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd.) 30 parts of product name Epicoat 828), 4 parts of diphenyl- (p-phenylthiophenyl) sulfonium hexafluoroantimonate, and 2 parts of 1- (p-toluenesulfonyloxy) -4-trifluoromethanesulfonyloxycyclohexane were stirred. Make a uniform liquid, and add 20
Irradiation with ultraviolet light from a 0WXe-Hg lamp yielded a tack-free transparent cured film. The irradiation light amount is 1- (p-
It was about half as compared with the case where no toluenesulfonyloxy) -4-trifluoromethanesulfonyloxycyclohexane was added.

Example 4 Poly (tert-butyl methacrylate) (Mw = 3
6,000, Mw · Mn = 1.20) and triphenylsulfonium triflate in an amount of 5 w
Then, 1- (p-toluenesulfonyloxy) -4-trifluoromethanesulfonyloxycyclohexane obtained in Example 1 was added to obtain a resist solution. This is spin-coated on a silicon wafer to form a thin film,
After heating at 100 ° C for 1 minute, irradiate with 254 nm light,
Heated at 100 ° C. for 1 minute. This was developed with a 2.5% aqueous solution of tetramethylammonium, and the remaining film was measured to obtain a sensitivity curve. Table 1 summarizes the results obtained by estimating the minimum exposure energy at which the film is completely removed by the alkaline water as the sensitivity. Similarly, 1- (p-
The results for toluenesulfonyloxy) -4-trifluoromethanesulfonyloxycyclohexane and 1- (p-toluenesulfonyloxy) -4- (3,3,3-trifluoroethanesulfonyloxy) cyclohexane are also shown in Table 1. .

[0045]

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 (72) Inventor Koji Arimitsu 2-1 Narusegaoka, Machida, Tokyo 3 Naruse 33 Heim 203 F term (reference) 2H025 AA01 AA02 AB20 AC01 AD01 AD03 BE00 BG00 CC20 4H006 AA03 AB76 TB03 TB36 4J002 BC091 BE041 BL001 CD001 CH011 EB107 EV216 EV297 EW177

Claims (4)

[Claims] [Claim 1] The following general formula (1) (Wherein, X represents a hydrogen atom or a fluorine atom, R ¹ represents a substituent having an aromatic substituent constant σ ₁ of 0.00 to +0.70, and a substituent —OSO ₂ [CX ₂ ] _t CF ₃ And R ² is a substituent having an aromatic substituent constant σ ₁ of −0.03 to +0.70, and t 2
Represents an integer of 0 or 1, n represents an integer of 1 or 2,
m represents an integer of 0 to 4, and n + m represents an integer of 1 to 5). 2. An active energy ray-curable composition comprising the organic superacid generator according to claim 1, an acid generator that generates an acid by an active energy ray, and a cationic polymerizable compound. 3. A pattern-forming composition comprising the organic superacid generator according to claim 1, an acid generator that generates an acid by an active energy ray, and an acid-catalyzed reactive substance. 4. A method for forming a polymer pattern, comprising a step of irradiating an active energy ray in a pattern on a film made of the composition according to claim 3.