JP2000035665A - Acid multiplication agent and photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acid multiplication agent excellent in thermal stability over a long period or time by incorporating a specified crosslinked carbocyclic compd. having a crosslinked carbocyclic skelton, a hydroxyl group on the crosslinked carbon ring and a specified group at a carbon atom adjacent to the carbon to which the hydroxyl group is bonded. SOLUTION: The acid multiplication agent comprises a crosslinked carbocyclic compd. having a crosslinked carbocyclic skeleton and having a hydroxyl group on he crosslinked carbon ring and a sulfonate group represented by the formula -OSO2-R on a carbon atom in a position adjacent to the carbon atom two which the hydroxyl group is bonded. In the formula, R is an aliphatic group or the like. The acid multiplier is characterized by the crosslinked carbocyclic skeleton structure and a crosslinked carbon ring having plural carbon rings, usually 2-6, preferably 2-3 carbon rings is contained in the structure. A substituent, e.g. a 1-6C, preferably 1-3C lower alkyl group such as methyl or ethyl or a lower alkoxy group may bond to the crosslinked carbon ring. The presence of the intramolecular cross linkage enhances thermal stability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acid proliferating agent comprising a crosslinked carbocyclic compound having a hydroxyl group and a sulfonate group, and a photosensitive composition containing the same and a photoacid generator.

[0002]

2. Description of the Related Art Photosensitive compositions are used in various fields, such as being used as an image forming material for optically detecting a chemical structural change caused by a photoreaction, or used for surface coating treatment by photo-curing of a monomer or a prepolymer. Has been put to practical use. The photosensitive speed, photosensitive wavelength range, and resolution of the photosensitive composition are various, and these characteristics are appropriately selected according to the purpose, and a photosensitive composition suitable for it is selected. However, each had the following essential problems. As in photoengraving technology, a large amount of a photosensitive resin mainly composed of a polymer material is widely used as a photosensitive material exhibiting high resolution (Aio Yamaoka, Mototaro Nagamatsu, " Photopolymer Technology ", Nikkan Kogyo Shimbun (1988)). The polymer-based photosensitive material has not only excellent resolution but also many advantages such that a wide range of photosensitive wavelength can be set by selecting a photoreaction, 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. It is. Until now, various attempts have been made to improve the photospeed of the high-molecular photosensitive material. 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. An 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 an acid multiplying agent having such properties is added to a chemically amplified photoresist, the acid rapidly increases,
It is possible to suppress the termination of the acid catalyzed reaction due to the basic substance, prevent the disappearance of the acid by the side reaction, further greatly accelerate the acid catalyzed reaction, and improve the sensitivity. The acid proliferating agent itself is a compound which is easily decomposed by an acid. In order to put a photographic material containing the same into practical use, it is essential that the material be thermally stable and not deteriorate during long-term storage. 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. As the acid proliferating agent, acetoacetic ester derivatives (K. Arimitsu et al., JA)
m. Chem. Soc. , 120, 37 (19
98)), ketal sulfonate derivatives (K. Kud)
o et al. , Mol. Cryst. Liq.
Cryst. , 280, 307 (199
6)), 1,2-diol monosulfonate derivative (S. Noguchi et al., J. Ph.
otopolym. Sci. Technol. ,
10, 315 (1997)). However, none of these is guaranteed sufficient storage stability. It is said that preservation in cold places is essential. 1,2-diol sulfonate derivatives, for example,
Cyclohexane 1,2-diol monosulfonates have good thermal stability among the acid propellants reported so far, but are inferior in long-term thermal stability and decompose when stored at room temperature for a long time. Have a problem.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an acid multiplying agent having excellent long-term heat stability and a photosensitive composition containing the same and a photoacid generator.

[0004]

The present inventors have conducted various studies on conventional acid proliferating agents. As a result, in general, 1,2-diol monosulfonate has a problem that a hydroxy group may be involved in neighboring group participation. In addition, we thought that it lacked thermal stability. Therefore, it has been found that the thermal stability can be improved by making the 1,2-diol monosulfonate skeleton a crosslinked carbocyclic structure and making the molecular structure rigid in order to suppress such participation of adjacent groups. Was. The present invention has been completed based on such findings.
That is, according to the present invention, a cross-linked carbocyclic skeleton is provided, and a hydroxyl group and a carbon atom adjacent to the carbon atom to which the hydroxyl group is bonded on the cross-linked carbon ring are represented by the following general formula (1):

Embedded image —OSO ₂ —R (1) (wherein, R represents an aliphatic group, an aromatic group, or a heterocyclic group)
An acid proliferating agent comprising a crosslinked carbocyclic compound having a sulfonate group represented by the formula: According to the present invention,
There is provided a photosensitive composition comprising the acid proliferating agent and a photoacid generator.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The acid proliferating agent of the present invention is characterized by having a crosslinked carbocyclic skeleton structure. Such include bridged carbocycles having multiple carbocycles, usually 2 to 6, preferably 2 to 3 carbocycles. Further, the bridged carbocycle has a substituent, for example, a methyl group or an ethyl group,
A lower alkyl group or lower alkoxy group having 1 to 6, preferably 1 to 3 carbon atoms such as a propyl group may be bonded, or may have an unsaturated bond such as a double bond. Such a cross-linked carbocycle has a cross-linked bond in the molecule, and has a rigidified molecule, and provides an acid proliferating agent with improved thermal stability.

The acid proliferating agent of the present invention comprises a hydroxyl group on the crosslinked carbon ring and a sulfonate group represented by the following general formula (1) at a carbon atom adjacent to the carbon atom to which the hydroxyl group is bonded. Have.

Embedded image —OSO ₂ —R (1) In the above formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Aliphatic groups include linear or cyclic (including cross-linked carbocyclic) alkyl and alkenyl groups. The number of carbon atoms of the aliphatic group is usually 1 to 12, preferably 1 to 8
It is. The aromatic group may have a monocyclic or polycyclic structure, and the aromatic group includes an aryl group and an arylalkyl group. The heterocyclic group may have a monocyclic or polycyclic structure, and the heterocyclic group includes those derived from various conventionally known heterocyclic compounds.
The aliphatic group, the aromatic group, and the heterocyclic group may have a substituent such as a halogen, a hydrocarbon oxy group, an amino group, and a substituted amino group. Specific examples of the aliphatic group and the aromatic group include, for example, methyl, ethyl, propyl, butyl, acyl, hexyl, vinyl, propylene, allyl,
Examples include cyclohexyl, cyclooctyl, bicyclo hydrocarbon group, tricyclo hydrocarbon group, phenyl, tolyl, benzyl, phenethyl, naphthyl, naphthylmethyl and substituted products thereof. Examples of the heterocyclic group include various heterocyclic compounds, for example, a five-membered ring compound containing one hetero atom such as furan, thiophene, pyrrole, benzofuran, thionaphthene, indole, carbazole and the like, a fused ring compound thereof, oxazole, thiazole, 5-membered ring compound containing two heteroatoms such as pyrazole and a condensed ring compound thereof, pyran, pyrone, coumarin, pyridine, quinoline, isoquinoline, a 6-membered ring compound containing one heteroatom such as acridine and a condensed ring compound thereof, Various compounds derived from a six-membered ring compound containing two heteroatoms such as pyridazine, pyrimidine, pyrazine, phthalazine and the like and a condensed ring compound thereof are exemplified.

[0007] The structural examples of preferred acid-proliferating agents according to the present invention are shown below.

Embedded image

In the above formula, R has the same meaning as described above, and R ¹ represents a hydrogen atom, an aliphatic group or an aromatic group. The aliphatic group includes a chain or cyclic (including a crosslinked cyclic) alkyl group or alkenyl group, and the aromatic group includes an aryl group or an arylalkyl group. These aliphatic groups and aromatic groups may have a substituent such as a halogen atom, an alkoxy group, an amino group, and a substituted amino group.
The aliphatic group has 1 to 12, preferably 1 to 8 carbon atoms. The aromatic group can have a monocyclic or polycyclic structure. R ¹ is preferably an aliphatic group or an aromatic group.

The bicyclo compound (decalin) (a)
Has a cross-link at the 1,6-position, the bicyclo compound (b) has a cross-link at the 1,3-position, and the bicyclo compounds (c) and (d) have Has cross-linking. Therefore, in these bicyclo compounds, the conformational change of the cyclohexane ring is highly suppressed, and the ring structure shows rigidity.

[0010] Specific examples of the acid proliferating agent of the present invention are shown below.

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The acid multiplying agent of the present invention is decomposed by an acid-catalyzed reaction to generate an acid (RSO ₃ H) again. One acid increases in one reaction, and the reaction accelerates with the progress of the reaction. Since the generated acid itself induces self-decomposition,
The strength of the acid generated here is desirably 3 or less, particularly 2 or less, as the acid dissociation constant, pKa. If the acid is weaker than this, self-decomposition cannot be caused. The acid released by such a reaction (RSO
₃ H) as methanesulfonic acid, ethanesulfonic acid,
Propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, cyclohexanesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, 2,
2,2-trifluoroethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-bromobenzenesulfonic acid, p-nitrobenzenesulfonic acid, 2-thiophenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid And so on. The acid proliferating agent of the present invention can be decomposed in a chain by heating.

The compounds of the present invention are easily synthesized by reacting the corresponding diol compound with the corresponding sulfonic acid halide. The diol compound has two isomers, cis and trans. The cis isomer is more thermally stable and is preferably used. The compound of the present invention can be stably stored as long as no acid is present.

The acid multiplying agent of the present invention can be used as a photosensitive composition by using it in combination with a photoacid generator. When this photosensitive composition is irradiated with light,
The acid is liberated from the photoacid generator, which degrades the acid proliferating agent, and the free acid generated by the decomposition decomposes the acid proliferating agent to produce a free acid. In this way, in this composition, upon irradiation with light, the acid proliferating agent contained therein is decomposed in a chain, and a large number of free acid molecules are generated.

As the photoacid generator, any one can be used as long as it generates an acid upon irradiation with light. In general, chemical amplification type photoresists and compounds used for cationic photopolymerization are preferably used (Organic Materials Research Society, “Organic Materials for Imaging”, Bunshin Publishing (1993), 187-192).
Page). Examples of the photoacid generator suitable for the present invention are shown below. In order to expand the photosensitive wavelength range of these photoacid generators, a photosensitizer can be appropriately used.

(1) Aromatic onium compounds Aromatic onium compounds such as diazonium, iodonium, sulfonium, and phosphonium, such as PF ₆₋ , AsF ₆₋ ,
Salts of SbF ₆₋ and CF ₃ SO ₃₋ can be mentioned. Specific examples are shown below.

Embedded image

(2) Sulfonate A sulfonate which generates sulfonic acid can be mentioned. Specific compounds are exemplified below.

Embedded image

(3) Iron allene complexes can be mentioned.

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The photosensitive composition of the present invention may contain an acid-reactive substance. Such acid-reactive substances are conventionally well-known, and there are various kinds (Organic Materials Research Society, “Organic Materials for Imaging”, Bunshin Publishing (1993), pp. 199-201). reference). Many of them make use of the reaction of deprotection groups in synthetic organic chemistry (TW Greene,
ProtectiveGroups in Organ
ic Synthesis, John Wiley
& Sons (1981)), a specific example is shown below. First, a polymer substance having an acid-reactive residue in a side chain or a main chain can be given. 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 highly polar carboxylic acid or phenol, so that the polymer in the exposed portion is solubilized in a polar solvent or an aqueous alkaline solution. The photosensitive composition of the present invention containing the polymer having the acid-reactive residue in a side chain or a main chain can be used as a coating material, and a polymer film (film) formed by the composition can be used as a coating material. When the polymer film is exposed to light, the exposed portion is converted into a soluble portion.

Second, high molecular compounds containing an acid-reactive low molecular compound can be mentioned. 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 dissolution inhibitors 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. Examples of resin compounds containing these dissolution inhibitors include novolak resins, poly (p-hydroxystyrene), methacrylic acid copolymers, and N-methylolmaleimide copolymers. Low molecular compounds have the effect of inhibiting the solubility of these resins in aqueous alkaline solutions,
By decomposing by the action of an acid, this dissolution inhibiting effect is lost and the polymer becomes alkali-solubilized. The photosensitive composition of the present invention containing the polymer compound containing the acid-reactive low-molecular compound can be used as a coating material, and a polymer film (film) formed by the composition has a photosensitivity. When the polymer film is exposed, the exposed portion is converted into a soluble portion.

Thirdly, there may be mentioned a crosslinking agent-containing polymer which causes a condensation reaction by an acid catalyst. As a crosslinking agent that forms a cation by an acid catalyst and causes a condensation reaction,
Compounds containing two condensable reaction residues, for example, an alcohol residue, a melanin residue, an N-methylolimide residue, an acetal residue, a vinyl ether residue and the like can be mentioned. Examples of the polymer that reacts with the generated cation include a polymer having a hydroxyl group, for example, a polymer of p-hydroxystyrene, a novolak resin, a polymer of hydroxyethyl methacrylate, and the like. Further, the polymer having both the condensation-reactive group and the phenol group causes crosslinking by an acid catalyst by itself, which is convenient for the present invention.

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

Next, a method for preparing the photosensitive composition of the present invention will be described below. A resin containing a low-molecular substance having an acid-reactive unit or a polymer compound which is itself acid-reactive, and a photoacid generator in an amount of 0.5 to 20% by weight based on the resin; Add the acid proliferating agent by weight. Since most of the above-mentioned photoacid generators generate radical species together with an acid, a radical polymerizable monomer or prepolymer can be mixed with the acid-reactive substance. Further, pigments, dyes, and the like may be appropriately added. (1)-
Many of the photoacid generators listed in (3) generate an acid only by the action of ultraviolet rays, but by adding an appropriate photosensitizer, the acid can be generated by irradiation with light of a longer wavelength. it can. Therefore, a photosensitive material having high sensitivity can be produced by adding a photosensitizer for the photoacid generator to the photosensitive composition comprising the photoacid generator and the acid multiplying agent according to the present invention. . Conventionally known photosensitizers used for this purpose, for example, when the photoacid generator is an aromatic iodonium salt, pyrene, anthracene, 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9 In addition to polycyclic aromatic compounds such as 1,10-bis (phenylethynyl) anthracene and 9,10-bis (phenylethynyl) -1,8-dimethoxyanthracene, dye compounds substituted with a dialkylamino group may be used. it can. These are exemplified below. A photosensitive composition to which such a photosensitizer has been added exhibits photosensitivity due to light absorbed by the photosensitizer.

Embedded image

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In order to uniformly disperse the respective components in the composition, it is preferable to dissolve the respective components in a liquid state. These compositions are formed into a film and then exposed to generate an acid as a latent image. Then heating (post bake)
Treatment to promote chain degradation of the acid proliferating agent,
The acid-catalyzed reaction causes a structural change of the acid-reactive substance. The condition of the heat treatment for causing the chain decomposition of the acid proliferating agent varies depending on the exposure energy, the type of the residue active in the acid used, the type of the polymer, and the like. In the range of 150 degrees, more preferably 8
It ranges from 0 degrees to 130 degrees. The heating time is from 10 seconds to 10 minutes, more preferably from 30 seconds to 5 minutes. If the heating time is shorter than this, the acid-catalyzed reaction is not sufficiently caused. If the heating time is longer than this range, the acid-proliferating agent may cause a side reaction and the productivity is lacking. A change in physical properties, such as solubility, hardness, film thickness, and viscosity, before and after exposure and heat treatment accompanying a structural change of a resin containing an acid-reactive substance or a resin itself being acid-reactive is used.

[0024]

The acid multiplying agent of the present invention and the photosensitive composition containing the same have the following features. (1) Since the storage stability is high and the sensitivity of the photosensitive material is greatly improved, it can be used as a high-sensitivity image forming material. (2) By combining light irradiation and heat treatment,
Since the crosslinking efficiency of the photocurable resin is greatly improved, it can be effectively used for ultraviolet curable paints, inks, surface coating agents and the like. 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 acid multiplying agent, 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 having high sensitivity can be produced by adding a photosensitizer.

[0025]

Next, the present invention will be described in more detail with reference to examples.

COMPARATIVE EXAMPLE 1 1-phenyl-1-hydroxy-2- (p-toluenesulfonyloxy) cyclohexane, a monocyclic acid proliferating agent having no cross-linked structure, was dissolved in deuterated chloroform and subjected to NMR.
It was sealed in a tube and heated to 100 ° C. Decomposition started rapidly after 250 minutes, and the decomposition reaction was completely terminated in 350 minutes.

Example 1 cis-2,3-pinanediol (1.00 g, 5.9 mm)
ol), 1.5 ml of triethylamine and 20 mg of 4-dimethylaminopyridine were dissolved in 6 ml of dichloromethane and stirred in an ice bath. 5 ml of dichloromethane there
1.25 g of 1-octanesulfonyl chloride dissolved in water
(5.9 mmol) was added dropwise. The solution was stirred at room temperature for one day, and after confirming that the raw materials had almost disappeared from the ¹ H-NMR spectrum, crushed ice was added and the mixture was stirred for 1 hour. This solution was extracted with dichloromethane, and the organic layer was washed with 2.4N hydrochloric acid and subsequently with a saturated aqueous solution of sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained liquid is subjected to column chromatography (filler: silica gel (Wakogel C-20)
0), eluent: hexane: ethyl acetate = 4: 1) to give 1.63 g of cis-3- (octanesulfonyloxy) -2-pinanol (10) as a colorless liquid. Yield 80%.

¹ H-NMR (200 MHz, CDCl ₃ )
δ (ppm): 0.89 (t, J = 7 Hz, 3H, CH
_{2 -CH 3), 0.99 (s} , 3H, C (OH) -C
_{H 3), 1.2-27 (m,} 25H, CH, CH 2, C-
_{(CH 3) 2 andOH),} 3.1-3.3 (m, 2H,
_{S-CH 2), 5.03 (} dd, J = 6,10Hz, 1
H, O-CH) IR (NaCl) (cm ^-1 ): 3541 (OH), 1
_{334,1160 (S = O) C 18} H 34 O 4 Calculated as S: C, 62.39; H,
9.89; S, 9.25%. Analytical value: C, 61.84;
H, 9.55; S, 9.02%. This compound was dissolved in deuterated chloroform, sealed in an NMR tube, and heated to 100 ° C., but no change was observed even after 20 hours.

Example 2 1.00 g of cis-2,3-pinanediol (5.9 mm
ol) was dissolved in 1.5 ml of triethylamine and 20 mg of 4-dimethylaminopyridine in 6 ml of dichloromethane and stirred in an ice bath. There 5m dichloromethane
A solution of 1.47 g (5.9 mmol) of (+)-10-camphorsulfonyl chloride dissolved in 1 was added dropwise.
The solution was stirred at room temperature for two days. This solution was extracted with dichloromethane, and the organic layer was washed with 2.4N hydrochloric acid and subsequently with a saturated aqueous solution of sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained liquid was subjected to column chromatography (filler: silica gel (Wakogel C-200), developing solvent: hexane: ethyl acetate =
4: 1) yielded 0.73 g of cis-3.
-((+)-10-camphorsulfonyloxy) -2
-Pinanol (9) was obtained as colorless crystals. Yield 32% Melting point 92.5-94 ° C. ¹ H-NMR (200 MHz, CDCl ₃ ) δ (pp
m): 0.92 (s, 3H , C (OH) -CH 3),
0.99 (s, 3H, C- ( CH 3) 2), 1.12
(S, 3H, C- (CH 3) 2), 1.2-2.6 (m,
_{19H, CH, CH 2 andC- (} CH 3) 2), 2.93
(S, 1H, OH), 3.41 (AX, J = 15 Hz,
_{2H, S-CH 2),} 5.09 (dd, J = 6,10H
z, 1H, O-CH) IR (KBr) (cm- ¹ ): 3527 (OH), 17
45 (C = O), 130,114 (S = O) Elementary analysis: calculated for _{C 20 H 32 O 5 S:} C, 62.
47; H, 8.39; S, 8.34%. Analytical value: C, 6
2.20; H, 7.85; S, 8.43%. This compound was dissolved in deuterated chloroform, sealed in an NMR tube, and
Heating to 0 ° C. showed no change after 20 hours.

Example 3 cis-2,3-pinanediol (1.00 g, 5.9 mm)
ol) was dissolved in 1.5 ml of triethylamine and 20 mg of 4-dimethylaminopyridine in 6 ml of dichloromethane and stirred in an ice bath. There 5m dichloromethane
p-toluenesulfonyl chloride 1.12 dissolved in
g (5.9 mmol) was added dropwise. The solution was stirred at room temperature for one day, crushed ice was added and stirred for one hour. This was extracted with dichloromethane, and the organic layer was extracted with 2.4N.
After washing with hydrochloric acid and subsequently with a saturated aqueous solution of sodium hydrogen carbonate, the solution was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained liquid is subjected to column chromatography (filler; silica gel (Wakogel C-200), developing solvent;
Purification with hexane: ethyl acetate = 4: 1) gave 1.46 g of cis-3- (p-toluenesulfonyloxy) -2-pinanol (13) as colorless crystals. ¹ H-NMR (200 MHz, CDCl ₃ ) (ppm):
0.93 (s, 3H, C ( OH) -CH 3), 1,22
(S, 3H, C (CH ₃ ) ₂ ), 1, 26 (s, 3H, C
(CH ₃ ) ₂ ), 1.4-2.4 (m, 7H, CH, CH ₂
andOH), 2.46 (s, 3H , Ar-CH 3),
4.88 (dd, J = 6, 10 Hz, 1H, OC)
H), 7.36 (d, J = 8 Hz, 2H, Ar-H),
7.84 (d, J = 8 Hz, 2H, Ar-H) IR (KBr) (cm ^-1 ): 3556 (OH), 13
62,75 (S = O) Elementary analysis: C ₁₇ H ₂ O ₄ Calculated as S: C, 63.72; H, 6.30; S, 10.0
0 Analysis values: C, 63.82; H, 6.52; S, 9.92.
% Yield 80% Melting point 74-75.5 ° C This compound was dissolved in deuterated chloroform, sealed in an NMR tube and heated to 100 ° C, but no change was observed after 20 hours.

Example 4 In exactly the same manner as in Example 3, a dichloromethane solution of benzenesulfonyl chloride was added dropwise to a dichloromethane solution of cis-2,3-pinanediol, triethylamine and 4-dimethylaminopyridine on ice cooling. By the same treatment, 1.35 g of cis-3- (benzenesulfonyloxy) -2-pinanol (11) was obtained as colorless crystals. Yield 80% Melting point 65 ° C Calculated for C ₁₆ H ₁₈ O ₄ S: C, 62.72; H,
5.93; S, 1045% Analytical value: C, 62.88; H, 5.82; S, 10.6
2%. This compound was dissolved in deuterated chloroform, sealed in an NMR tube, and heated to 100 ° C., but no change was observed even after 20 hours.

Example 5 In exactly the same manner as in Example 3, a dichloromethane solution of 2-thiophenesulfonyl chloride was added dropwise to a dichloromethane solution of cis-2,3-pinanediol, triethylamine and 4-dimethylaminopyridine on ice cooling. Then, by the same treatment, 1.49 g of cis-3- (2-thienylsulfonyloxy) -2-pinanol (12) was obtained as colorless crystals. Calculated for _{C 14 H 2 O 4 S2:} C, 53.22; H,
6.37S, 20.21% Analysis: C, 53.03; H, 6.59; S, 19.8.
7%. ¹ H-NMR (200 MHz, CDCl ₃ ): δ (pp
m) 0.94 (s, 3H, C (OH) -CH 3), 1.
21 (s, 3H, C- ( CH 3) 2), 1.27 (s, 3
_{H, C- (CH 3) 2} ), 1.5-2.4 (m, 7H, C
H, CH ₂ , OH), 4.92 (dd, J = 5.9,
9.6 Hz, 1H, O-CH), 7.16 (dd, J =
3.7, 5.1 Hz, 1H, Ar-H), 7.72 (d
d, J = 1.4, 5.1 Hz, 1H, Ar-H), 7.
78 (dd, J = 1.4, 3.7 Hz, 1H, Ar-
H) IR (KBr, cm ^-1 ): 3544 (OH liberated), 34
12 (OH association), 3106 (ArC-H), 1368
(S = O), 1173 (S = O) Yield 85% Melting point 86.5-87.5 ° C This compound was dissolved in heavy chloroform, sealed in an NMR tube and heated to 100 ° C, but for 20 hours. No changes were observed later.

Example 6 In exactly the same manner as in Example 3, a dichloromethane solution of 2-naphthalenesulfonyl chloride was added dropwise to a dichloromethane solution of cis-2,3-pinanediol, triethylamine and 4-dimethylaminopyridine on ice cooling. In the same manner, 1.85 g of cis-3- (2-naphthalenesulfonyloxy) -2-pinanol (14) was obtained.
Was obtained as colorless crystals. Yield 85% C ₂₀ H ₂₃ O ₄ Calculated as S: C, 66.65; H,
6.43; S, 8.88% Analytical value: C, 66.83; H, 6.59; S, 8.57
%. ¹ H-NMR (200 MHz, CDCl ₃ ) δ (pp
m): 0.91 (s, 3H , C (OH) -CH 3),
1.22 (s, 6H, C- ( CH 3) 2), 1.4-2.
4 (m, 6H, CH, CH 2), 2.43 (s, 1H,
OH), 4.96 (dd, J = 6, 10 Hz, 1H, O
-CH), 7.6-8.1 (m, 6H, Ar-H),
8.53 (s, 1H, Ar-H) IR (KBr, cm ^-1 ): 3544 (OH release), 34
17 (OH association, 3109 (ArC-H), 1355
(S = O), 1178 (S = O) Melting point: 100.5-101.5 ° C. This compound was dissolved in deuterated chloroform, sealed in an NMR tube and heated to 100 ° C., but completely changed after 20 hours. Was not observed.

Example 7 A dichloromethane solution of p-toluenesulfonyl chloride was ice-cooled in a dichloromethane solution of cis-2,3-norbornanediol, triethylamine and 4-dimethylaminopyridine in exactly the same manner as in Example 3. It was added dropwise, and 1.85 g of cis-3- (p-
Toluenesulfonyloxy) -2-norbornane (1
7) was obtained as colorless crystals. Calculated for _{C 14 H 18 O 4 S:} C, 59.56; H,
6.43; S, 11.34% Analytical value: C, 59.82; H, 6.59; S, 11.2
3%. ¹ H-NMR (200 MHz, CDCl ₃ ) δ (pp
m): 0.9-2.0 (m, 6H, CHandC
_{H 2), 2.2-2.3 (m,} 2H, C-CH 2), 2.
38 (d, J = 4 Hz, 1H, OH), 2.46 (s,
_{3H, Ar-CH 3),} 3.79 (dt, J = 2,5H
z, 1H, (OH) -CH), 4.34 (dd, J =
2,5 Hz, 1H, (OTs) -CH), 7.35
(D, J = 8 Hz, 2H, Ar-H), 7.81 (d,
J = 8 Hz, 2H, Ar-H) IR (KBr) (cm ^-1 ): 3545, 3373 (O-
H), 1355, 1189 (S = O) Yield 85% Melting point 66-68 ° C This compound was dissolved in deuterated chloroform, sealed in an NMR tube, and heated to 100 ° C. Not observed.

Examples 8 to 25 Poly (tert-butyl methacrylate) was used as an acid-reactive polymer, and this polymer and 2 mol% of a photoacid generator based on monomer units in the polymer (4) −
A cyclohexane solution containing (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate was prepared. This poly (tert-butyl methacrylate)
Was prepared by dissolving 400 mg of the polymer in 10 mL of cyclohexane. The acid proliferating agent shown in Example 1 to Example 7 was added to this polymer solution in 5,
Each of 10 and 15 mol% was added to obtain a solution of the photosensitive composition. This solution was spin-coated on a silicon wafer under the conditions of 1000 rpm and 30 seconds, and heated at 100 ° C. for 30 seconds to perform prebaking. After irradiating the coating film with light of 313 nm, the coating film was subjected to a post-baking treatment at 100 ° C., and this was treated with 2% by weight of tetramethylammonium hydroxide.
It was immersed in an aqueous solution for 1 minute and developed. After washing with water and drying, the film thickness was measured to obtain a sensitivity curve. Table 1 summarizes the thus obtained sensitivity characteristics. The relative sensitivity is a value when the sensitivity in the absence of an acid proliferating agent is set to 1.
In addition, a γ value representing a contrast characteristic is also shown from the sensitivity curve.

[Photosensitive properties of poly (tert-butyl methacrylate) to which acid proliferating agent is added]

[Table 1]

Example 26 Poly (tert-butyl methacrylate) was used as an acid-reactive polymer, and this polymer and 10 mol% of a photoacid generator, diphenyliodonium triflate, based on monomer units in the polymer were used. A cyclohexane solution was prepared. A solution of poly (tert-butyl methacrylate) was prepared by dissolving 500 mg of the polymer in 10 mL of cyclohexane. To this solution, 15 wt% of the acid proliferating agent shown in Example 3 and 5 wt% of 9,10-bis (phenylethynyl) anthracene as a photosensitizing dye were respectively added to prepare a solution of the photosensitive composition. This solution was spin-coated on a silicon wafer under the conditions of 1000 rpm and 30 seconds, and heated at 100 ° C. for 30 seconds to perform prebaking. After the coating film was irradiated with light of 436 nm, it was subjected to a post-baking treatment at 100 ° C. for 90 seconds. In this coating film, the tert-butyl group is eliminated by the acid-catalyzed reaction, and the film thickness is reduced by about 35%. The effect of the amount of exposure energy on the reduction of the film thickness was determined and used as a sensitivity curve.
In the absence of the photosensitizing dye, no decrease in film thickness was observed after irradiation with light at 436 nm. Further, when the acid proliferating agent is not present, 50 m is used even in the presence of the photosensitizing dye.
13% at an exposure energy of J / cm ² , 600 mJ / c
Even at an exposure energy of m ² , the film thickness was reduced by only 25%. In contrast, when the acid breeding agent was present, the film thickness reduction was completed at an exposure energy of 10 mJ / cm ² .

Example 27 A photosensitive composition was prepared in exactly the same manner as in Example 26, except that 9,10-bis (phenylethynyl) -1,8-dimethoxyanthracene was used as a photosensitizing dye. A curve was determined. The film thickness reduction was completed at an exposure energy of 6 mJ / cm ² .

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Claims (8)

[Claims] 1. A crosslinked carbocyclic skeleton, wherein a hydroxyl group and a carbon atom adjacent to the carbon atom to which the hydroxyl group is bonded on the crosslinked carbon ring have the following general formula (1): —OSO ₂ —R (1) (wherein, R represents an aliphatic group, an aromatic group, or a heterocyclic group)
An acid proliferating agent comprising a crosslinked carbocyclic compound having a sulfonate group represented by the formula: 2. The acid proliferating agent according to claim 1, wherein said bridged carbocycle is a bicyclo carbocycle. 3. The bicyclocarbon ring is 2,7,7-trimethylbicyclo [3.1.1] heptane.
Acid proliferating agent. 4. The method according to claim 1, wherein the bicyclo carbon ring is bicyclo [2.
2.1] The acid proliferating agent according to claim 2, which is heptane. 5. An acid proliferating agent comprising a bicyclo carbocyclic compound having a hydroxyl group bonded to the 2-position carbon atom and a sulfonate group bonded to the 3-position carbon atom. 6. A photosensitive composition comprising the acid proliferating agent according to claim 1 and a photoacid generator. 7. The photosensitive composition according to claim 6, further comprising a sensitizer for the photoacid generator. 8. The method according to claim 6, which comprises an acid-reactive substance.
Photosensitive composition.