KR101350717B1 - Photosensitive resin, and photosensitive composition - Google Patents

Abstract

Provided are a photosensitive resin and a photosensitive composition capable of obtaining a pattern having a good shape without accompanying a problem of poor compatibility between an acid generator and a polymer having an acid dissociation group as a main component of the photoresist.

At least one of the repeating unit represented by following formula (1), the repeating unit represented by following formula (2), and the repeating unit represented by following formula (3), and the repeating unit represented by following formula (4), It is set as the photosensitive resin characterized by having a repeating unit represented by following formula (5) as needed.

(In formula (1), R <_1> is a C2-C9 linear or branched bivalent hydrocarbon group, R <_2> -R <_5> is a hydrogen atom or a C1-C3 linear or branched hydrocarbon group each independently, R <_6>. And R ₇ are each independently an organic group, and R ₆ and R ₇ may be combined to form a divalent organic group. X ⁻ represents an anion.)

(In formula (2), R <_8> represents a C2-C9 linear or branched hydrocarbon group.)

Photosensitive, Resin, Photoresist, Acid Generator, Repeating Unit, Acid Dissociation, Chemical Amplification

Description

Photosensitive resin and photosensitive composition {PHOTOSENSITIVE RESIN, AND PHOTOSENSITIVE COMPOSITION}

 The present invention has a structure that easily generates an acid by irradiation of active radiation such as deep UV, electron beam, X-ray or EUV (extreme ultraviolet), and acid dissociation group in the structure, and is useful as a chemically amplified photoresist material. It relates to a photosensitive composition using the same.

In the highly integrated circuit devices represented by semiconductor devices such as DRAMs, there is a high demand for higher density, higher integration or higher speed. Accordingly, in the field of manufacturing various electronic devices, there is an increasing demand for establishing microfabrication technology for half micron order, for example, developing a photolithography technology for forming a fine pattern. As one of means for miniaturizing a pattern in the photolithography technique, there is a method of shortening the wavelength of active radiation (exposure light) used in forming a pattern of a photoresist. Here, the resolution R of the reduced projection exposure apparatus is represented by Rayleigh's formula (R = k · λ / NA (where λ is the wavelength of the exposure light, NA is the numerical aperture of the lens and k is the process factor). The resolution can be improved by shortening the wavelength? Of the active radiation (exposure light) used at the time of pattern formation.

As photoresists suitable for short wavelengths, chemically amplified ones have been proposed (see Patent Document 1 and the like). A characteristic of the chemically amplified photoresist is that a polymer having protonic acid is generated by irradiation of exposure light from a photoacid generator as a containing component, and the protonic acid has an acid dissociable group (group dissociated and decomposed into acid) by heat treatment after exposure. And an acid catalyzed reaction. Most of the photoresists currently being developed are chemically amplified. Various sulfonium salts are known as photoacid generators for such chemically amplified photoresists.

However, conventional sulfonium salt-based photoacid generators have problems such as poor compatibility with a polymer having an acid dissociation group as a main component of the photoresist. Naturally, due to the problem, when the patterned photoresist containing the photoacid generator is subjected to pattern exposure with activating radiation, there arises a problem that the resulting pattern shape does not become a desired shape and adversely affects it.

[Patent Document 1] U.S. Patent 4449216

In view of such circumstances, the present invention provides a photosensitive resin and a photosensitive composition which can obtain a pattern having a good shape without accompanying a problem of poor compatibility between an acid generator and a polymer having an acid dissociating group as a main component of a photoresist. Let's make it a task.

The 1st aspect of this invention for solving the said subject is at least 1 of the repeating unit represented by following formula (1), the repeating unit represented by following formula (2), and the repeating unit represented by following formula (3). And a repeating unit represented by the following formula (4) and, if necessary, a repeating unit represented by the following formula (5).

(In formula (1), R <_1> is a C2-C9 linear or branched bivalent hydrocarbon group, R <_2> -R <_5> is a hydrogen atom or a C1-C3 linear or branched hydrocarbon group each independently, R <_6>. And R ₇ are each independently an organic group, and R ₆ and R ₇ may be combined to form a divalent organic group. X ⁻ represents an anion.)

(In formula (2), R <_8> represents a C2-C9 linear or branched hydrocarbon group.)

The 2nd aspect of this invention is the photosensitive resin as described in the 1st aspect whose negative ion represented by X <^-> is negative ion represented by following formula (6).

_{C k H m F n SO 3} - (6)

(In formula (6), k, m, and n each independently represent an integer of 0 or more. When m is 0, k is an integer of 1 to 8, n is 2k + 1, and formula (6) is perfluoro. When n is 0, k is an integer of 1-15, m is an integer of 1 or more, Formula (6) is an alkylsulfonate ion, benzenesulfonate ion, or alkylbenzenesulfonate ion. When m and n are each independently an integer of 1 or more, k is an integer of 1 to 10, and formula (6) is a fluorine-substituted benzenesulfonate ion, a fluorine-substituted alkylbenzenesulfonate ion or a fluorine-substituted alkylsulfonate ion.)

A third aspect of the present invention is the photosensitive resin according to the first aspect, wherein the negative ion represented by X ⁻ is a bis (perfluoroalkylsulfon) imide ion represented by the following formula (7).

_{(C p F 2p +1 SO 2} ) 2 N - (7)

(In formula, p represents the integer of 1-8.)

A fourth aspect of the present invention is the photosensitive resin according to the first aspect, wherein the negative ion represented by X ⁻ is a negative ion represented by the following formula (8).

5th aspect of this invention is a weight average molecular weight 2,000-100,000, the repeating unit number a of said Formula (1), the repeating unit number b of said Formula (2), the repeating unit number c of said Formula (3), The repeating unit number d of the formula (4) and the repeating unit number e of the formula (5) are a / (a + b + c + d + e) = 0.001 to 0.3, (b + c) / (a + b + c + d + e) = 0.1 to 0.5, (d + e) / (a + b + c + d + e) = 0.5 to 0.8 and e / (d + e) = 0 to 0.2 It exists in the photosensitive resin in any one of the 1st-4th aspect to set as it.

A sixth aspect of the present invention is the photosensitive resin according to any one of the first to fifth aspects, wherein the terminal group of the main chain is a hydrogen atom or a methyl group.

A 7th aspect of this invention is a photosensitive composition characterized by being the solution which melt | dissolved the photosensitive resin in any one of 1st-6th aspect in the organic solvent.

According to this invention, the photosensitive resin which has a structure which has a function as a photo-acid generator, and an acid dissociation group can be provided. Since the photosensitive resin can be formed into a chemically amplified photosensitive composition alone without containing an acid generator by dissolving it in a solvent, it is not accompanied by a problem of poor compatibility with an acid generator and a polymer having an acid dissociation group. The effect is that a pattern of shapes can be obtained.

Hereinafter, the present invention will be described in detail.

The photosensitive resin of this invention is a repeating unit represented by the said Formula (1), the repeating unit represented by the said Formula (2), and the repeating unit represented by the said Formula (3), and said Formula (4) It is a polymer which has a repeating unit represented by the above, and the repeating unit represented by said Formula (5) as needed, and has a structure and an acid dissociation group which have a function as a photo-acid generator derived from a sulfonium salt. Thus, since the photosensitive resin of this invention has a structure which has a function as a photo-acid generator, and an acid dissociation group, it can be made into chemically amplified photosensitive composition independently, without containing an acid generator by dissolving in a solvent. Therefore, when used as a photosensitive composition, the pattern of a favorable shape can be obtained, without accompanying the problem that the compatibility of an acid generator and the polymer which has an acid dissociation group is bad.

Specifically, the repeating unit represented by the formula (1) has a structure having a function as a photoacid generator that generates an acid by exposure to active radiation and a group capable of dissociating into an acid generated from the acid generator (acid dissociation group). Has

In addition, the repeating unit represented by the said Formula (2) and the repeating unit represented by the said Formula (3) have the structure which modified the phenolic hydroxyl group of the repeating unit represented by said Formula (4) with the group which can dissociate with an acid. Has Both the repeating unit represented by the said Formula (4) and the repeating unit represented by the said Formula (5) are involved in solubility to alkaline developing solution, and solubility can be adjusted by adjustment of those quantities.

The photosensitive resin of the present invention is insoluble or very poorly soluble in alkaline developing solution by itself, but when exposed to active radiation, an acid composed of a repeating unit represented by formula (1) is generated, and the action of the acid causes the above formula (1). The acid dissociation group of the repeating unit represented by), the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) is dissociated to increase the solubility in the alkaline developer.

In said Formula (1), R <_1> is a C2-C9 divalent hydrocarbon group, and may be linear or branched. R <_2> -R <_5> is a hydrogen atom or a C1-C3 linear or branched hydrocarbon group each independently. R ₆ and R ₇ are each independently an organic group. Examples of the organic group include linear, branched or alicyclic alkyl groups. Examples of the organic group include carbocyclic aryl groups and heterocyclic aryl groups. Preferred organic groups are carbocyclic aryl groups, and particularly preferred organic groups are phenyl group, methylphenyl group and t-butylphenyl group. Said carbocyclic aryl group or heterocyclic aryl group may have a C1-C30 substituent. As a C1-C30 substituent, a C1-C30 hydrocarbon group or an alkoxy group is preferable. Examples of the hydrocarbon group having 1 to 30 carbon atoms as a substituent include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group and t Alkyl groups such as amyl, decanyl, dodecanyl and hexadecanyl groups; cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecanyl, cyclohexadecanyl and adamantyl groups Aryl groups, such as an alicyclic alkyl group and a phenyl group and a naphthyl group, are mentioned. Moreover, as a C1-C30 alkoxy group which is a substituent, a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentyloxy group , t-amyloxy group, n-hexyloxy group, n-octyloxy group, n-dodecaneoxy group and 1-adamantyloxy group.

Moreover, R <_6> and R <_7> may combine with each other and form a ring, In this case, it becomes bivalent organic group containing the said carbon skeleton: -R <_6> -R <_7> -. As such a bivalent organic group, C3-C9 alicyclic alkyl group with which R <_6> and R <_7> has the saturated carbon skeleton is connected, for example is mentioned. Polymethylene groups, such as a tetramethylene group and a pentamethylene group, etc. are mentioned as an example of a preferable thing in this alicyclic alkyl group. In general, the ring formed by the divalent organic group -R ₆ -R ₇ -with S is preferably a 4-membered to 8-membered ring, more preferably a 5-membered to 6-membered ring.

In formula (1), the negative ion represented by X <^-> is not specifically limited, It can be set as the negative ion conventionally used for the photo-acid generator. Examples of the negative ions are negative ions represented by formula (6), negative ions represented by formula (7) and negative ions represented by formula (8) (cyclo 1,3-perfluoropropanedisulfonimide Ions).

In formula (6), k, m, and n each independently represent an integer of 0 or more. When m is 0, k is an integer of 1-8, n is 2k + 1, and Formula (6) is a perfluoroalkylsulfonate ion. Examples of preferred perfluoroalkylsulfonate ions include CF ₃ SO ₃ ⁻ (trifluoromethanesulfonate ion), C ₄ F ₉ SO ₃ ⁻ (nonafluorobutanesulfonate ion) and C ₈ F ₁₇ SO ₃ ⁻ ( Heptadecafluorooctanesulfonate ions); and the like.

In the formula (6), when n is 0, k is an integer of 1 to 15, m is an integer of 1 or more, and formula (6) is an alkylsulfonate ion, benzenesulfonate ion or alkylbenzenesulfonate ion. . In the case of alkylsulfonate ions, m is represented by 2k + 1. Examples of preferred alkylsulfonate ions include CH ₃ SO ₃ ⁻ (methanesulfonate ion), C ₂ H ₅ SO ₃ ⁻ (ethanesulfonate ion), C ₉ H ₁₉ SO ₃ ⁻ (1-nonansulfonate ion), and the like. And crosslinked cyclic alkylsulfonate ions such as 10-camphorsulfonate ion. Examples of preferred alkylbenzenesulfonate ions include 4-methylbenzenesulfonate ions and 2,4,6-triisopropylbenzenesulfonate ions.

Furthermore, in formula (6), when m and n are each independently an integer of 1 or more, k is an integer of 1 to 10, and formula (6) is a fluorine-substituted benzenesulfonate ion, a fluorine-substituted alkylbenzenesulfonate ion or fluorine Substituted alkylsulfonate ions. Examples of preferred fluorine-substituted benzenesulfonate ions include 2-fluorobenzenesulfonate ions, 4-fluorobenzenesulfonate ions, 2,4-difluorobenzenesulfonate ions, pentafluorobenzenesulfonate ions, and the like. have. In addition, examples of preferred fluorine-substituted alkylbenzenesulfonate ions include 2-trifluoromethylbenzenesulfonate ions, 4-trifluoromethylbenzenesulfonate ions, and 2,4-bis (trifluoromethyl) benzenesulfonate ions. And 3,5-bis (trifluoromethyl) benzenesulfonate ions. Furthermore, examples of preferred fluorine-substituted alkylsulfonate ions include 1,1,2,3,3,3-hexafluoropropanesulfonate ions.

The negative ion represented by Formula (7) is a bis (perfluoroalkyl sulfone) imide ion, and p is an integer of 1-8 in a formula. Examples of preferred bis (perfluoroalkylsulfon) imide ions include bis (trifluoromethanesulfon) imide ions and bis (pentafluoroethanesulfon) imide ions.

It is preferable that the terminal group of a principal chain of the photosensitive resin of this invention is a hydrogen atom or a methyl group. The terminal group can be arbitrarily determined depending on the polymerization initiator and the reagent to stop when synthesizing the polymer to be the base.

Moreover, it is preferable that the weight average molecular weights of the photosensitive resin of this invention are 2,000-100,000, More preferably, it is 2,000-50,000. It is because when a weight average molecular weight is small, exposure sensitivity will become low and cured film intensity | strength will fall, and when it is large, adhesiveness to a board | substrate falls and it becomes difficult to form a pattern. In addition, said weight average molecular weight means the polystyrene conversion weight average molecular weight (Mw) by the gel permeation chromatography (GPC) of the photosensitive resin of this invention. The ratio (Mw / Mn) of the polystyrene reduced number average molecular weight (Mn) by Mw and GPC is usually 1 to 3, preferably 1 to 2.5. In addition, the repeating unit number a of Formula (1), the repeating unit number b of Formula (2), the repeating unit number c of Formula (3), the repeating unit number d of Formula (4), and the repeating unit number of Formula (5) e is a / (a + b + c + d + e) = 0.001-0.3, (b + c) / (a + b + c + d + e) = 0.1-0.5, (d + e) / (a It is preferable to satisfy + b + c + d + e) = 0.5 to 0.8 and e / (d + e) = 0 to 0.2. When a / (a + b + c + d + e) = 0.001 to 0.3 is satisfied, the structure in which acid is generated by the exposure of formula (1) becomes a catalytic amount, and functions well as an acid generator. Moreover, when (b + c) / (a + b + c + d + e) = 0.1-0.5, the effect of the dissolution inhibiting ability with respect to alkaline developing solution will be brought. When (d + e) / (a + b + c + d + e) = 0.5 to 0.8 and e / (d + e) = 0 to 0.2 are satisfied, the adhesion to the coating target such as the substrate and the solubility in the alkaline developer This brings about the effect of being good.

Moreover, the photosensitive resin of this invention may have a structure other than each repeating unit represented by Formula (1)-Formula (5) in a structure in the range which does not impair the effect of this invention.

Although the manufacturing method of the photosensitive resin of this invention is not specifically limited, For example, it can manufacture by adding following formula (13)-(15) to the copolymer of polyhydroxy styrene or poly (hydroxy styrene styrene).

The repeating unit represented by Formula (1) can be introduced, for example, by the following method. First, as shown in the following reaction scheme, a dialkyl sulfoxide is reacted with a compound represented by the formula (9) using diphosphorous pentaoxide (P ₂ 0 ₅ ) as a catalyst in methanesulfonic acid (CH ₃ SO ₃ H), The compound (methanesulfonate) represented by Formula (10) is obtained. In addition, dialkyl sulfoxide can be easily obtained by oxidizing dialkyl sulfide with hydrogen peroxide.

Diphosphorine pentaoxide, which is a catalyst, is used in an amount of 0.1 to 3.0 mol, preferably 0.5 to 1.5 mol, based on 1 mol of the compound represented by the formula (9). The methanesulfonic acid is used in an amount of 1 to 10 mol, preferably 4 to 6 mol, based on 1 mol of the compound represented by the formula (9). The reaction temperature is usually 0 to 50 ° C, preferably 10 to 30 ° C, and the reaction time is usually 1 to 15 hours, preferably 3 to 8 hours. After completion of the reaction, the reaction is stopped by adding water.

Next, as shown in the following reaction scheme, CH ₃ SO ₃ ^- which is a compound represented by the formula (10) is subjected to salt exchange with X ⁻ . In addition, M <^+> represents monovalent metal ion in following reaction formula. Specifically, the formula (10) in an aqueous solution of a compound represented by X ^- a ^- or salts M ⁺ X ^-, for example, the formula (6), equation (7) or (8), various acid H ⁺ X, which comprises a 1-92 mol, Preferably 1.05-1.2 mol is added with respect to 1 mol of compounds represented by Formula (10). It is preferable to use a chlorine solvent such as dichloromethane, chloroform as the reaction solvent. Moreover, reaction temperature is 10-50 degreeC normally, Preferably it is 20-30 degreeC. After completion of the reaction, the aqueous layer is separated, and the organic layer is washed with water. After completion of washing, the compound represented by the formula (11) can be obtained by crystallizing with a suitable recrystallization solvent. Furthermore, after the compound represented by Formula (10) was produced, potassium iodide was added to the reaction solution, and the compound represented by Formula (10) was taken out as a solid by salt-exchanging with iodine ions. ^It is also possible to exchange salts with-and to exchange salts with iodine ions using sulfonic acid esters.

Thereafter, as shown in the following reaction formula, the sulfonium salt represented by the formula (13) can be obtained by performing a dehalogenated hydrogen reaction using the compound represented by the formula (11) and the compound represented by the formula (12). . In addition, in the following reaction formula, Y represents halogen atoms, such as Cl and Br. Specifically, the compound represented by the formula (11) and the compound represented by the formula (12) are reacted in the presence of a basic catalyst such as potassium carbonate (K ₂ CO ₃ ) in a polar solvent. The reaction temperature is usually 60 to 90 ° C. After completion of the reaction, water is added, the aqueous layer is washed with a nonpolar solvent such as hexane, and then extracted with a chlorine solvent. Thereafter, the organic layer is separated, washed with water, and then chlorinated solvent is distilled off to obtain a sulfonium salt represented by the following formula (13). Moreover, what is marketed can also be used for the compound of Formula (9)-Formula (12).

When the copolymer of the compound represented by this Formula (13), and polyhydroxy styrene or poly (hydroxy styrene-styrene) is made to react in an organic solvent, such as 1, 3- dioxolane, under an acidic catalyst, it will become said Formula (1) The repeating unit displayed can be introduced.

The repeating unit represented by the formula (2) is an acidic catalyst in a copolymer of hydroxystyrene or poly (hydroxystyrene-styrene) with vinyl ether represented by the following formula (14) in an organic solvent such as 1,3-dioxolane. It can introduce | transduce by addition reaction in presence of.

(R ₈ represents a straight or branched hydrocarbon group having 2 to 9 carbon atoms.)

The repeating unit represented by Formula (3) is a copolymer of di-t-butyldicarbonate and polyhydroxy styrene or poly (hydroxy styrene-styrene) represented by the following formula (15): 1,3-dioxolane, etc. It can be prepared by reacting in the presence of a basic catalyst in an organic solvent.

Moreover, the photosensitive resin of this invention can also be manufactured by making the polymer which has a repeating unit represented by Formula (1)-(5) react suitably. Moreover, the photosensitive resin of this invention can also be manufactured by copolymerizing the monomer of each repeating unit represented by Formula (1)-(5) using a polymerization initiator in an organic solvent. As the organic solvent, for example, ethers such as tetrahydrofuran (THF), 1,3-dioxolane and 1,3-dioxane, and propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether acetate are preferable. As a polymerization initiator, well-known things, such as a thermal polymerization initiator, a photoinitiator, and a redox-type initiator, may be used, but what is necessary is just to select suitably in consideration of the ease of handling, reaction rate, molecular weight control, etc.

Examples of specific manufacturing methods are described below. The photosensitive resin of type 1 shown in Table 1 below adds a compound of formula (14) and a compound of formula (13) to, for example, polyhydroxystyrene in the presence of an acid catalyst in the organic solvent. In addition, the photosensitive resin of type 2 is added to the compound of formula (13) in polyhydroxystyrene in the presence of an acid catalyst in the organic solvent, followed by addition of the basic catalyst and the compound of formula (15). The photosensitive resin of type 3 is reacted by adding a compound of formula (14) and a compound of formula (13) to polyhydroxystyrene in the presence of an acid catalyst in the organic solvent, followed by addition of a basic catalyst and a compound of formula (15). Let's do it. Type 4 photosensitive resins add a compound of formula (14) and a compound of formula (13) to poly (hydroxy styrene-styrene) in the presence of an acid catalyst in the organic solvent. Type 5 photosensitive resin is added to a poly (hydroxystyrene-styrene) in the presence of an acid catalyst in the organic solvent, followed by addition of a compound of formula (13), followed by addition of a basic catalyst and a compound of formula (15). Type 6 photosensitive resins are obtained by adding a compound of formula (14) and a compound of formula (13) to poly (hydroxystyrene-styrene) in the presence of an acid catalyst in the organic solvent, followed by a basic catalyst and a compound of formula (15) It is added and reacted.

It is the photosensitive composition of this invention which melt | dissolved the photosensitive resin of the said invention in the organic solvent. Since the photosensitive resin of this invention has a structure which acts as a photo-acid generator, and an acid dissociation group, it can be made into chemically amplified photosensitive composition independently, without containing an acid generator by dissolving in a solvent. Therefore, it becomes a photosensitive composition of a uniform solution, without accompanying the problem that compatibility with an acid generator and the polymer which has an acid dissociation group is bad, and can use it and can form a desired pattern.

Examples of the organic solvent of the photosensitive composition include ethylene glycol monoalkyl ethers, ethylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates and propylene glycol di. Alkyl ether acetates are mentioned. Although the ratio of the photosensitive resin of this invention to be contained in a photosensitive composition can be suitably selected in the range in which photosensitive resin can melt | dissolve, Usually, 3-30 weight% is preferable.

The photosensitive composition of the present invention has the effect of controlling the diffusion phenomenon in the resist film of the acid generated from the repeating unit represented by the formula (1) by exposure, and suppressing undesired chemical reaction in the unexposed region. Preference is given to using so-called acid diffusion control agents. As an acid diffusion control agent, the nitrogen containing organic compound which basicity does not change by exposure or heating is preferable. In addition, the usage-amount of an acid diffusion control agent is 0.005 to 5 weight% normally with respect to the photosensitive resin. This is because when the amount is large, the sensitivity and developability as a resist tend to be lowered, and when the amount is small, improvement effects such as resolution and process stability as a resist become insufficient.

Moreover, various additives, such as surfactant, a sensitizer and an antifoamer, can also be mix | blended with the photosensitive composition of this invention as needed.

When forming a resist pattern with the photosensitive composition of this invention, a resist film is formed by apply | coating a photosensitive composition on board | substrates, such as a silicon wafer, for example by suitable coating means, such as spin coating and cast | coating, and heat-processing previously as needed. Then, it exposes through the mask which has a predetermined pattern. What is necessary is just to select a deep UV, an electron beam, an X-ray, EUV (extreme ultraviolet-ray), etc. suitably according to the fineness of a pattern, the sensitivity of a photosensitive composition, etc. to be used at that time. Moreover, what is necessary is just to select exposure conditions, such as an exposure amount, suitably according to the compounding composition of a composition, the kind of each additive, etc. It is preferable to perform heat processing after exposure, and the heating conditions may be suitably selected according to the compounding composition of a composition, the kind of each additive, etc.

Subsequently, a predetermined resist pattern can be formed by developing the pattern exposed resist film with an alkaline developer. As an alkaline developing solution, alkaline aqueous solution which melt | dissolved alkaline compounds, such as alkali metal hydroxide, aqueous ammonia, mono, di or tri-alkylamines, tetraalkylammonium hydroxides, and choline, so that it may become the density | concentration of 1-5 weight% normally is mentioned. . In addition, when the developing solution which consists of such alkaline aqueous solution is used, washing with water is generally performed after image development.

<Examples>

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited at all by these examples.

(Synthesis Example 1)

Synthesis of Compound (4-Vinyloxyethoxyphenyldiphenylsulfonium perfluorobutanesulfonate) represented by the following formula:

52.2 g of 4-hydroxyphenyldiphenylsulfoniumperfluorobutanesulfonate, 18.0 g of potassium carbonate and 1.05 g of N, N, N ', N'-tetramethylethylenediamine were dissolved in 26.1 g of dimethyl sulfoxide. Then, 13.9g of chloroethyl vinyl ether was added and it heated up to 80 degreeC. It stirred for 15 hours and cooled the reaction liquid to 30 degrees C or less. After the solid content was removed by filtration, 100 g of water was added, and the aqueous layer was washed three times using 100 g of hexane. 209 g of dichloromethane and 260 g of water were added and stirred, and the target material was extracted to the dichloromethane layer. The organic layer was washed with distilled water until the pH of the separated aqueous layer became 7. 69.9 g of oily material was obtained by distilling off the solvent with a rotary evaporator. This substance was confirmed to be 4-vinyloxyethoxyphenyl diphenylsulfonium perfluorobutane sulfonate from the measurement result by ¹ H-NMR and ion chromatography.

(Synthesis Example 2)

Synthesis of Compound (4-Vinyloxyethoxy 3,5-dimethylphenyldi (4-t-butylphenyl) sulfoniumperfluorobutanesulfonate) represented by the following formula:

4-hydroxy 3,5-dimethylphenyldi (4-t-butylphenyl) sulfoniumperfluorobutanesulfonate 28.6 g, potassium carbonate 8.10 g and N, N, N ', N'-tetramethylethylenediamine 0.46 g was dissolved in 142 g of dimethylsulfoxide. Then, 6.08g of chloroethyl vinyl ether was added and it heated up to 80 degreeC. It stirred for 19 hours and cooled the reaction liquid below 30 degreeC. After removing solid content by filtration, 20.9g of water was added and the water layer was wash | cleaned 3 times using 85.1g of hexane. 226 g of dichloromethane and 141 g of water were added and stirred, and the target product was extracted to the dichloromethane layer. The organic layer was washed with distilled water until the pH of the separated aqueous layer became 7. The solvent was distilled off by a rotary evaporator to obtain 27.4 g of a brown oily substance. This substance was confirmed to be 4-vinyloxyethoxy 3,5-dimethylphenyldi (4-t-butylphenyl) sulfonium perfluorobutanesulfonate from the measurement results by ¹ H-NMR and ion chromatography. .

(Synthesis Example 3)

Synthesis of Compound (4-Vinyloxyoctoxyphenyldiphenylsulfonium perfluorobutanesulfonate) represented by the following formula:

1.23 g of 8-chloro-1-octanol, 0.47 g of sodium carbonate, 0.47 g of di-μ-chlorobis [η-cyclooctadieneiridium (I)] and 1.31 g of vinyl acetate were added to 6.15 g of toluene and 4 at 100 ° C. Stirred for time. After cooling to room temperature, the solvent was distilled off and purified by column chromatography using a mixed solvent of hexane and dichloromethane (volume ratio of hexane and dichloromethane as the solvent was 2: 1) to give a colorless transparent liquid, 8-chlorooctylvinyl ether 1.16. g was obtained.

2.67 g of 4-hydroxyphenyldiphenylsulfonium perfluorobutanesulfonate, 0.78 g of potassium carbonate and 0.05 g of N, N, N ', N'-tetramethylethylenediamine were dissolved in 13.3 g of dimethyl sulfoxide. Then, 1.05 g of 8-chlorooctyl vinyl ether was added, and it heated up to 80 degreeC. It stirred for 15 hours and cooled the reaction liquid to 30 degrees C or less. After removing solid content by filtration, 13.3g of water was added and the aqueous layer was wash | cleaned 3 times using 7.96g of hexane. 10.6 g of dichloromethane and g of water were added and stirred, and the target substance was extracted to the dichloromethane layer. The organic layer was washed with distilled water until the pH of the separated aqueous layer became 7. 2.53 g of a brown oily substance was obtained by distilling off the solvent by a rotary evaporator. This substance was confirmed to be 4-vinyloxyoctoxyphenyl diphenylsulfonium perfluorobutane sulfonate from the measurement result by <^1> H-NMR and ion chromatography.

(Synthesis Example 4)

Synthesis of Compound (4-Vinyloxyethoxyphenyldiphenylsulfoniumcyclo (1,3-perfluoropropanedisulfone) imide salt) represented by the following formula:

After dissolving 4.66 g of dipentoxide and 13.3 g of diphenyl sulfoxide in 63.1 g of methanesulfonic acid, 9.26 g of phenol was added and stirred at room temperature for 15 hours. 199 g of water was added dropwise keeping the temperature below 30 ° C., and the aqueous layer was washed three times with 66.4 g of t-butyl methyl ether, followed by 120 g of dichloromethane and cyclo 1,3-perfluoropropanedisulfonimide potassium salt 23.9. g was added and stirred for 2 hours. After stirring was stopped and the separated aqueous layer was removed, 66.4 g of 0.1% by weight aqueous ammonia solution was added and stirred. Next, the organic layer was washed with distilled water and repeated until the pH of the separated aqueous layer became 7. The solvent was distilled off by the rotary evaporator and 32.1 g of 4-hydroxyphenyl diphenylsulfonium cyclo (1, 3- perfluoro propane disulfone) imide salt of the brown oil was obtained.

32.1 g of 4-hydroxyphenyldiphenylsulfoniumcyclo (1,3-perfluoropropanedisulfone) imide salt, 11.2 g of potassium carbonate and 0.67 g of N, N, N ', N'-tetramethylethylenediamine were dimethyl It was dissolved in 164 g of sulfoxide. Then, 8.65g of chloroethyl vinyl ether was added and it heated up to 80 degreeC. It stirred for 15 hours and cooled the reaction liquid to 30 degrees C or less. After removing solid content by filtration, 80g of water was added and the aqueous layer was wash | cleaned 3 times using 40g of hexane. 120 g of dichloromethane and 260 g of water were added and stirred, and the target material was extracted to the dichloromethane layer. The organic layer was washed with distilled water until the pH of the separated aqueous layer became 7. The solvent was distilled off with a rotary evaporator to obtain 29.1 g of an oily substance. This substance was confirmed to be 4-vinyloxyethoxyphenyl diphenylsulfonium cyclo (1, 3- perfluoro propane disulfone) imide salt from the measurement result by <^1> H-NMR and ion chromatography.

(Synthesis Example 5)

Synthesis of Compound (4-Vinyloxyethoxyphenyldiphenylsulfonium bis (perfluoromethanesulfon) imide salt) represented by the following formula:

After dissolving 2.33 g of dipentoxide and 6.65 g of diphenyl sulfoxide in 31.5 g of methanesulfonic acid, 4.80 g of phenol was added and stirred at room temperature for 15 hours. 100 g of water was added dropwise while maintaining the temperature below 30 ° C., and the aqueous layer was washed three times with 30 g of t-butyl methyl ether. Then, 60 g of dichloromethane and 11.6 g of bis (perfluoromethanesulfonimide) potassium salt were added thereto. Stir for 2 hours. After stirring was stopped and the separated aqueous layer was removed, 30 g of 0.1% by weight aqueous ammonia solution was added and stirred. Next, the organic layer was washed with distilled water and repeated until the pH of the separated aqueous layer became 7. The solvent was distilled off by the rotary evaporator and 16.1 g of 4-hydroxyphenyl diphenylsulfonium bis (perfluoromethanesulfon) imide salt of the brown oil was obtained. 16 g of 4-hydroxyphenyldiphenylsulfonium bis (perfluoromethanesulfon) imide salt, 4.7 g of potassium carbonate and 0.33 g of N, N, N ', N'-tetramethylethylenediamine were dissolved in 80 g of dimethyl sulfoxide. . Then, 3.66g of chloroethyl vinyl ether was added and it heated up to 80 degreeC. It stirred for 15 hours and cooled the reaction liquid to 30 degrees C or less. After removing solid content by filtration, 40g of water was added and the water layer was wash | cleaned 3 times using 30g of hexane. 60 g of dichloromethane and 120 g of water were added and stirred, and the target product was extracted to the dichloromethane layer. The organic layer was washed with distilled water until the pH of the separated aqueous layer became 7. 144 g of oily material was obtained by distilling off the solvent with a rotary evaporator. This substance was confirmed to be 4-vinyloxyethoxyphenyl diphenylsulfonium bis (perfluoromethanesulfon) imide salt from the measurement result by <^1> H-NMR and ion chromatography.

(Synthesis Example 6)

Synthesis of 4-vinyloxyethoxyphenyldi (4-t-butylphenyl) sulfonium 2,4,6-triisopropylbenzenesulfonate:

5.0 g of 4-hydroxyphenyldi (4-t-butylphenyl) sulfonium 2,4,6-triisopropylbenzenesulfonate, 1.28 g of potassium carbonate and N, N, N ', N'-tetramethylethylenediamine 0.10 g was dissolved in 15 g of dimethyl sulfoxide. Thereafter, 0.83 g of chloroethyl vinyl ether was added, and the temperature was raised to 80 ° C. It stirred for 15 hours and cooled the reaction liquid to 30 degrees C or less. After removing solid content by filtration, 75g of water and 44g of dichloromethane were added, and the target object was extracted to the dichloromethane layer. The organic layer was washed with distilled water until the pH of the separated aqueous layer became 7. The solvent was distilled off by the rotary evaporator, the oil-like substance obtained was dissolved in 20 g of acetonitrile, and the acetonitrile layer was washed five times using 15 g of hexane. 4.64 g of a brown oily substance was obtained by distilling off the solvent with a rotary evaporator. The substance was confirmed to be 4-vinyloxyethoxyphenyldi (4-t-butylphenyl) sulfonium 2,4,6-triisopropylbenzenesulfonate from the measurement results by ¹ H-NMR and ion chromatography. It became.

Synthesis Example 7 Synthesis of 4-vinyloxyethoxyphenyldiphenylsulfonium 2,4,6-triisopropylbenzenesulfonate:

8.00 g of 4-hydroxyphenyldiphenylsulfonium 2,4,6-triisopropylbenzenesulfonate, 2.46 g of potassium carbonate and 0.16 g of N, N, N ', N',-tetramethylethylenediamine were dimethyl sulfoxide Dissolved in 24.00 g. Then, 1.59 g of chloroethyl vinyl ether was added, and it heated up to 80 degreeC. It stirred for 15 hours and cooled the reaction liquid to 30 degrees C or less. After removing solid content by filtration, 160g of water and 64g of dichloromethane were added, and the target object was extracted to the dichloromethane layer. The organic layer was washed with distilled water until the pH of the separated aqueous layer became 7. The solvent was distilled off by the rotary evaporator, the obtained oily substance was dissolved in 32 g of acetonitrile, and the acetonitrile layer was washed five times using 24 g of hexane. 9.84 g of a brown oily substance was obtained by distilling off a solvent by the rotary evaporator. This substance was confirmed to be 4-vinyloxyethoxyphenyl diphenylsulfonium 2,4,6-triisopropylbenzenesulfonate from the measurement result by <^1> H-NMR and ion chromatography.

(Synthesis Example 8)

Synthesis of 4-vinyloxyethoxyphenyldiphenylsulfonium 2-trifluoromethylbenzenesulfonate:

After dissolving 3.00 g of dipentoxide and 8.01 g of diphenylsulfoxide in 38.11 g of methanesulfonic acid, 5.75 g of phenol was added and stirred at room temperature for 15 hours. 120 g of water was added dropwise keeping the temperature below 30 ° C., and the aqueous layer was washed three times with 40 g of t-butyl methyl ether. Then, 80 g of dichloromethane and 11.79 g of 2-trifluoromethylbenzenesulfonate potassium salt were added thereto for 2 hours. Stirred. After stirring was stopped and the separated aqueous layer was removed, 28 g of 0.1% by weight aqueous ammonia solution was added and stirred. After stirring was stopped, the separated aqueous layer was removed, and this was repeated until the pH of the separated aqueous layer became 7. The solvent was distilled off by the rotary evaporator to obtain 10.33 g of 4-hydroxyphenyldiphenylsulfonium 2-trifluoromethylbenzenesulfonate as a white powder.

8.01 g of 4-hydroxyphenyldiphenylsulfonium 2-trifluoromethylbenzenesulfonate, 2.74 g of potassium carbonate and 0.18 g of N, N, N ', N',-tetramethylethylenediamine were dissolved in 36 g of dimethyl sulfoxide. It was. Then, 5.31 g of chloroethyl vinyl ether was added, and it heated up to 80 degreeC. It stirred for 15 hours and cooled the reaction liquid to 30 degrees C or less. After removing solid content by filtration, 40g of water was added and the water layer was wash | cleaned 3 times using 30g of hexane. 30 g of dichloromethane and 60 g of water were added and stirred, and the target material was extracted to the dichloromethane layer. The organic layer was washed with distilled water until the pH of the separated aqueous layer became 7. The solvent was distilled off with a rotary evaporator to obtain 3.7 g of an oily substance. This substance was confirmed to be 4-vinyloxyethoxyphenyl diphenylsulfonium 2-trifluoromethylbenzenesulfonate from the measurement result by <^1> H-NMR and ion chromatography.

(Synthesis Example 9)

Synthesis of 4-vinyloxyethoxyphenyldi (4-t-butylphenyl) sulfonium 2-trifluoromethylbenzenesulfonate:

4.51 g of 4-hydroxyphenyldi (4-t-butylphenyl) sulfonium 2-trifluoromethylbenzenesulfonate, 5.30 g of potassium carbonate and 1.53 g of N, N, N ', N',-tetramethylethylenediamine Was dissolved in 30 g of dimethyl sulfoxide. Then, 10.03 g of chloroethyl vinyl ether was added, and it heated up to 80 degreeC. It stirred for 15 hours and cooled the reaction liquid to 30 degrees C or less. After removing solid content by filtration, 150g of water and 93g of dichloromethane were added, and the target object was extracted to the dichloromethane layer. The organic layer was washed with distilled water until the pH of the separated aqueous layer became 7. 8.57 g of red powder was obtained by distilling a solvent off on the rotary evaporator. This material was confirmed to be 4-vinyloxyethoxyphenyldi (4-t-butylphenyl) sulfonium 2-trifluoromethylbenzenesulfonate from the measurement results by ¹ H-NMR and ion chromatography.

(Example 1)

Synthesis of Photosensitive Resin 1 represented by Formula (A) below (Photosensitive Resin of Type 1 of Table 1)

50.0 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw / Mn) of 1.09 in polystyrene was dissolved in 350 mL of 1,3-dioxolane under nitrogen atmosphere, and then 1,3-dioxolane was distilled off at atmospheric pressure. It was confirmed that the water content in the system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C. or lower and 62 μL of 35% by weight hydrochloric acid was added. Next, 28.4 g of a 1,3-dioxolane solution of 34.6 wt% ethyl vinyl ether was added dropwise over 1 hour, and stirred at 30 ° C. for 2 hours. The solution was cooled to 15 ° C, and 8.8 g of a 63.8% by weight 1,3-dioxolane solution of 4-vinyloxyethoxyphenyldiphenylsulfoniumperfluorobutanesulfonate obtained in Synthesis Example 1 was added dropwise over 30 minutes. It stirred at 30 degreeC for 2 hours. The solution was neutralized with ammonia water, and the solution was added dropwise to 1700 g of pure water at room temperature to precipitate a solid. The solids were separated by filtration, reprecipitated using acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain 53.5 g of a resin. This resin is a photosensitive resin having a structure in which the ethoxyethylation rate of the hydrogen atom of the hydroxyl group of the used polyhydroxystyrene is 30.6% and the unit represented by the formula (1) is 1.6% from the measurement result by ¹ H-NMR. It was confirmed. That is, each composition is a: b: d = 1.6: 30.6: 67.8 (mol%).

(Example 2)

Synthesis of Photosensitive Resin 2 represented by Formula (A) above (Photosensitive Resin of Type 1 of Table 1)

50.0 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw / Mn) of 1.09 in polystyrene was dissolved in 350 mL of 1,3-dioxolane under nitrogen atmosphere, and then 1,3-dioxolane was distilled off at atmospheric pressure. It was confirmed that the water content in the system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C. or lower and 62 μL of 35% by weight hydrochloric acid was added. Next, 27.9 g of a 1,3-dioxolane solution of 35.4 wt% ethyl vinyl ether was added dropwise over 1 hour, and stirred at 30 ° C. for 2 hours. The solution was cooled to 15 ° C., and 2.8 g of a 63.8 wt% 1,3-dioxolane solution of 4-vinyloxyethoxyphenyldiphenylsulfoniumperfluorobutanesulfonate obtained in Synthesis Example 1 was added dropwise over 30 minutes. It stirred at 30 degreeC for 2 hours. The solution was neutralized with ammonia water, and the solution was added dropwise to 2000 g of pure water at room temperature to precipitate a solid. The solid was filtered off, reprecipitated using acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain 52.0 g of resin. This resin is a photosensitive resin having a structure in which the ethoxyethylation rate of the hydrogen atom of the hydroxyl group of the used polyhydroxystyrene is 30.8% and the unit represented by the formula (1) is 0.60% from the measurement result by ¹ H-NMR. It was confirmed. That is, each composition is a: b: d = 0.6: 30.8: 68.6 (mol%).

Example 3 Synthesis of Photosensitive Resin 3 Represented by the Following Formula (B) (Photosensitive Resin of Type 3 of Table 1)

50.0 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw / Mn) of 1.09 in polystyrene was dissolved in 350 mL of 1,3-dioxolane under nitrogen atmosphere, and then 1,3-dioxolane was distilled off at atmospheric pressure. It was confirmed that the water content in the system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C. or lower and 63 μL of 35% by weight hydrochloric acid was added. Next, 26.0 g of a 1,3-dioxolane solution of 28.1 wt% ethyl vinyl ether was added dropwise over 1 hour, and stirred at 30 ° C. for 2 hours. The solution was cooled to 15 ° C., and 63.8% by weight of 1,3-dioxyl of 4-vinyloxyethoxy 3,5-dimethylphenyldi (4-t-butylphenyl) sulfoniumperfluorobutanesulfonate obtained in Synthesis Example 2 8.8 g of solan solutions were added dropwise over 30 minutes, followed by stirring at 30 ° C for 2 hours. Thereafter, 0.21 g of N, N-dimethylaminopyridine was added and heated to 40 ° C. 19.5 g of a 1,3-dioxolane solution of 70.0 wt% di-tert-butyldicarbonate was added dropwise over 1 hour, and stirred at the same temperature for 1 hour. This solution was added dropwise to 1700 g of pure water at room temperature to precipitate a solid. The solid was separated by filtration, reprecipitated using dichloromethane and hexane, and dried at 35 ° C for 24 hours to obtain 53.1 g of resin. This resin was a ¹ from the measurement result by the H-NMR, with a 21.4% ethoxyethyl rate to the hydrogen atom of the hydroxyl group of polyhydroxystyrene, formula (1) is 1.7% units represented by, t- butoxycarbonyl It was confirmed that it was a photosensitive resin with a structure of 9.2% of paintability. That is, each composition is a: b: c: d = 1.7: 21.4: 9.2: 67.7 (mol%).

(Example 4)

Synthesis (photosensitive resin of type 1 of Table 1) of photosensitive resin 4 represented by following formula (C)

50.0 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw / Mn) of 1.09 in polystyrene was dissolved in 350 mL of 1,3-dioxolane under nitrogen atmosphere, and then 1,3-dioxolane was distilled off at atmospheric pressure. It was confirmed that the water content in the system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C. or lower and 62 μL of 35% by weight hydrochloric acid was added. Next, 27.9 g of a 1,3-dioxolane solution of 35.4 wt% ethyl vinyl ether was added dropwise over 1 hour, and stirred at 30 ° C. for 2 hours. The solution was cooled to 15 ° C, and 4.2 g of a 63.8% by weight 1,3-dioxolane solution of 4-vinyloxyoctoxyphenyldiphenylsulfonium perfluorobutanesulfonate obtained in Synthesis Example 3 was added dropwise over 30 minutes. It stirred at 30 degreeC for 2 hours. The solution was neutralized with ammonia water, and the solution was added dropwise to 2000 g of pure water at room temperature to precipitate a solid. The solid was filtered off, reprecipitated using acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain 52.0 g of resin. This resin is a photosensitive resin having a structure in which the ethoxyethylation rate of the hydrogen atom of the hydroxyl group of the used polyhydroxystyrene is 30.2% and the unit represented by the formula (1) is 1.0% from the measurement result by ¹ H-NMR. It was confirmed. That is, each composition is a: b = d = 1.0: 30.2: 68.8 (mol%).

(Example 5)

Synthesis (photosensitive resin of type 1 of Table 1) of photosensitive resin 5 represented by following formula (D)

In polystyrene conversion, 50.0 g of polyhydroxystyrene having a molecular weight (Mw) of 9000 and a molecular weight distribution (Mw / Mn) of 1.11 was dissolved in 400 mL of 1,3-dioxolane under a nitrogen atmosphere to confirm that water content in the system was reduced to 100 ppm or less. The solution was cooled to 15 ° C. and 63 μL of 35% by weight hydrochloric acid was added. Next, 28.4 g of a 1,3-dioxolane solution of 35.5% by weight of ethyl vinyl ether was added dropwise for 15 minutes, and stirred at 15 ° C. for 60 minutes and at 30 ° C. for 1.5 hours. This solution was cooled to 15 ° C, and 35.1% by weight of 1,3-dioxolane of the 4-vinyloxyethoxyphenyldiphenylsulfoniumcyclo (1,3-perfluoropropanedisulfone) imide salt obtained in Synthesis Example 4 After dropping 8.4 g of the solution over 15 minutes, the solution was stirred at 15 ° C for 30 minutes and at 30 ° C for 2 hours. Neutralization was performed by adding 172 µL of 28 wt% aqueous ammonia and stirring for 10 minutes or more. The solution was added dropwise to 1700 g of pure water at room temperature over 1 hour to precipitate a solid. This was filtered, reprecipitated using acetonitrile and pure water, and dried at 35 degreeC for 24 hours, and 53.7 g of resin was obtained. From the measurement results by ¹ H-NMR, the resin was a photosensitive resin having a structure in which the ethoxyethylation rate of the hydroxyl group hydrogen atom of the used polyhydroxystyrene was 31.8% and the unit represented by the formula (1) was 1.1%. Confirmed. That is, each composition is a: b: d = 1.1: 31.8: 67.1 (mol%).

Example 6 Synthesis of Photosensitive Resin 6 Represented by the Following Formula (E) (Photosensitive Resin of Type 1 of Table 1)

50.0 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw / Mn) of 1.09 in polystyrene was dissolved in 350 mL of 1,3-dioxolane under nitrogen atmosphere, and then 1,3-dioxolane was distilled off at atmospheric pressure. It was confirmed that the water content in the system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C. or lower and 62 μL of 35% by weight hydrochloric acid was added. Next, 27.9 g of a 1,3-dioxolane solution of 35.4 wt% ethyl vinyl ether was added dropwise over 1 hour, and stirred at 30 ° C. for 2 hours. The solution was cooled to 15 ° C., and 3.4 g of a 63.8 wt% 1,3-dioxolane solution of the 4-vinyloxyethoxyphenyldiphenylsulfonium bis (perfluoromethanesulfon) imide salt obtained in Synthesis Example 5 was stirred for 30 minutes. After dripping over, it stirred at 30 degreeC for 2 hours. The solution was neutralized with ammonia water, and the solution was added dropwise to 2000 g of pure water at room temperature to precipitate a solid. The solid was filtered off, reprecipitated using acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain 52.0 g of resin. This resin is a photosensitive resin having a structure in which the ethoxyethylation rate of the hydrogen atom of the hydroxyl group of the used polyhydroxystyrene is 30.8% and the unit represented by the formula (1) is 0.8% from the measurement result by ¹ H-NMR. It was confirmed. That is, each composition is a: b: d = 0.8: 30.8: 68.4 (mol%).

Example 7 Synthesis of Photosensitive Resin 7 Represented by the Following Formula (F) (Photosensitive Resin of Type 1 of Table 1)

50.0 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw / Mn) of 1.09 in polystyrene was dissolved in 350 mL of 1,3-dioxolane under nitrogen atmosphere, and then 1,3-dioxolane was distilled off at atmospheric pressure. It was confirmed that the water content in the system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C. or lower and 62 μL of 35% by weight hydrochloric acid was added. Next, 27.2 g of a 1,3-dioxolane solution of 31.3 wt% ethyl vinyl ether was added dropwise over 1 hour, followed by stirring at 30 ° C. for 2 hours. The solution was cooled to 15 ° C. and 19.9% by weight of 4-vinyloxyethoxyphenyldi (4-t-butylphenyl) sulfonium 2,4,6-triisopropylbenzenesulfonate obtained in Synthesis Example 1 1,3- 10.1 g of dioxolane solution was dripped over 30 minutes, and it stirred at 30 degreeC for 2 hours. The solution was neutralized with ammonia water, and the solution was added dropwise to 2500 g of pure water at room temperature to precipitate a solid. The solids were filtered off, reprecipitated using acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain 53.7 g of a resin. This resin is a photosensitive resin having a structure in which the ethoxyethylation rate of the hydrogen atom of the hydroxyl group of the used polyhydroxystyrene is 32.3% and the unit represented by the formula (1) is 0.6% from the measurement result by ¹ H-NMR. It was confirmed. That is, each composition is a: b: d = 0.6: 32.3: 67.1 (mol%).

Example 8 Synthesis of Photosensitive Resin 8 Represented by Formula (G)

After dissolving 20.00 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw / Mn) of 1.09 in polystyrene, the solution was dissolved in 200 mL of 1,3-dioxolane under nitrogen atmosphere, and then 1,3-dioxolane was distilled off at atmospheric pressure. It was confirmed that the water content in the system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C. or lower and 25 μL of 35% by weight hydrochloric acid was added. Next, 11.89 g of a 1,3-dioxolane solution of 37.2 wt% ethyl vinyl ether was added dropwise over 1 hour, and stirred at 30 ° C. for 2 hours. The solution was cooled to 15 ° C., and 1.46 g of a 63.8 wt% 1,3-dioxolane solution of 4-vinyloxyethoxyphenyldiphenylsulfonium 2,4,6-triisopropylbenzenesulfonate obtained in Synthesis Example 7 was dissolved in 30 After dripping over minutes, it stirred at 30 degreeC for 2 hours. The solution was neutralized with ammonia water, and the solution was added dropwise to 1000 g of pure water at room temperature to precipitate a solid. After filtration-separating a solid, reprecipitation was carried out using acetonitrile and pure water, and 18.32 g of resin was obtained by drying at 35 degreeC for 24 hours. This resin is a photosensitive resin having a structure in which the ethoxyethylation rate of the hydrogen atom of the hydroxyl group of the used polyhydroxystyrene is 33.0% and the unit represented by formula (1) is 0.6% from the measurement result by ¹ H-NMR. It was confirmed. That is, each composition is a: b: d = 0.6: 33.0: 66.4 (mol%).

(Example 9) Synthesis of photosensitive resin 9 represented by the following formula (H)

In polystyrene, 20.0 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw / Mn) of 1.09 was dissolved in 200 mL of 1,3-dioxolane under nitrogen atmosphere, and then 1,3-dioxolane was distilled off at atmospheric pressure. It was confirmed that the water content in the system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C. or lower and 25 μL of 35% by weight hydrochloric acid was added. Next, 12.02 g of a 1,3-dioxolane solution of 37.8 wt% ethyl vinyl ether was added dropwise over 1 hour, and stirred at 30 ° C. for 2 hours. The solution was cooled to 15 ° C., and 1.45 g of a 66.0 wt% 1,3-dioxolane solution of 4-vinyloxyethoxyphenyldiphenylsulfonium 2-trifluoromethylbenzenesulfonate obtained in Synthesis Example 8 over 30 minutes. After dripping, it stirred at 30 degreeC for 2 hours. The solution was neutralized with ammonia water, and the solution was added dropwise to 1000 mL of pure water at room temperature to precipitate a solid. The solid was filtered off, reprecipitated using acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain a resin. This resin is a photosensitive resin having a structure in which the ethoxyethylation rate of the hydrogen atom of the hydroxyl group of the used polyhydroxystyrene is 31.5% and the unit represented by the formula (1) is 1.4% from the measurement result by ¹ H-NMR. It was confirmed. That is, each composition is a: b: d = 1.4: 31.5: 67.1 (mol%).

(Example 10) Synthesis of photosensitive resin 10 represented by the following formula (1)

20.1 g of polyhydroxystyrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw / Mn) of 1.09 in polystyrene was dissolved in 200 μL of 1,3-dioxolane under nitrogen atmosphere, and then 1,3-dioxolane was distilled off at atmospheric pressure. It was confirmed that the water content in the system was reduced to 100 ppm or less. The reaction solution was cooled to 20 ° C. or lower and 25 μL of 35% by weight hydrochloric acid was added. Next, 11.84 g of a 1,3-dioxolane solution of 36.4 wt% ethyl vinyl ether was added dropwise over 1 hour, and stirred at 30 ° C. for 2 hours. The solution was cooled to 15 ° C. and a 68.8% by weight 1,3-dioxolane solution of 4-vinyloxyethoxyphenyldi (4-t-butylphenyl) sulfonium 2-trifluoromethylbenzenesulfonate obtained in Synthesis Example 9 1.46 g was dripped over 30 minutes, and it stirred at 30 degreeC for 2 hours. The solution was neutralized with ammonia water, and the solution was added dropwise to 1000 mL of pure water at room temperature to precipitate a solid. The solid was filtered off, reprecipitated using acetonitrile and pure water, and dried at 35 ° C for 24 hours to obtain a resin. This resin is a photosensitive resin having a structure in which the ethoxyethylation rate of the hydrogen atom of the hydroxyl group of the used polyhydroxystyrene is 35.2% and the unit represented by formula (1) is 0.6% from the measurement result by ¹ H-NMR. It was confirmed. That is, each composition is a: b: d = 0.6: 35.2: 64.2 (mol%).

<Evaluation by Exposure Using Xenon Lamp>

(Preparation of photoresist and breakthrough time measurement)

100 parts by weight of the photosensitive resin 1 obtained in Example 1 and 0.24 parts by weight of triethanolamine were dissolved in 525 parts by weight of propylene glycol monomethyl acetate, and filtered through a filter (PTFE filter) to prepare a liquid positive photoresist (photosensitive composition). It was. This resist was applied to a silicon wafer (diameter: 4 inches) using a spinner, and prebaked at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 500 nm. This resist film was exposed by the xenon lamp (wavelength: 248 nm), and post-baking (post exposure heating) was performed at 110 degreeC for 90 second. Then, breakthrough time was measured at 23 degreeC using the developing solution (2.38 weight% of aqueous solution of tetramethylammonium hydroxide). In addition, the break-through time is the number of seconds after which the residual film is completely absent due to the phenomenon after irradiating a constant energy.

As a result, the breakthrough time was 12 seconds at an exposure dose of 100 mJ and 3 seconds at 500 mJ. Therefore, in the photosensitive resin 1 obtained in Example 1, an acid generate | occur | produces from the structural part represented by Formula (1) of the photosensitive resin of this invention by exposure by a xenon lamp, and this acid produces the part of the acid dissociation group of resin. It turned out that it became solubility to solubility with respect to the developing solution.

In addition, a positive photoresist was prepared in the same manner as above using each photosensitive resin 2-10 obtained in Examples 2-10 instead of the photosensitive resin 1, a resist film was obtained, exposure, post-baking, and development were carried out, and the breakthrough was carried out. The time was measured. As a result, the break-through time was in a range of 12 ± 2 seconds at an exposure dose of 100 mJ and in a range of 3 ± 1 second at a 500 mJ. Accordingly, an acid is generated from the structural portion represented by formula (1) of the photosensitive resin of the present invention by exposure to the photosensitive resin 2 to 10 degrees, and the acid dissociates part of the polymer by the acid. It was found that the developer became poorly soluble to soluble.

<Evaluation by exposure of extreme ultraviolet (EUV)>

(Preparation and Application of Photoresist)

100 parts by weight of the photosensitive resin 1 obtained in Example 1 and 4 parts by weight of triphenylsilylamine were dissolved in 2000 parts by weight of propylene glycol monomethyl ether acetate, and filtered through a 0.2 μm filter (PTFE filter) to prepare a positive photoresist. It was. This resist solution was spin-coated on a 4 inch silicon wafer subjected to hexamethyldisilazane treatment, and heated back and forth at 110 ° C for about 90 seconds using a hot plate to prepare a uniform film having a thickness of 0.1 m. Using the photosensitive resins 2-10 obtained in Examples 2-10 by the same method, the positive type photoresist was prepared and formed into a film, respectively.

(Sensitivity measurement)

Ultraviolet (EUV) monochromatic synchrotron radiation generated at deflection electromagnet of NewSUBARU accumulation ring using 1GeV accelerating electrons incident from linear accelerator of large radiation facility SPring-8 with wavelength of 13.5nm by Mo / Si multilayer film reflection It was used for exposure light. This EUV was irradiated to the above-mentioned photoresist thin film, and after heat-processing about 90 second at 90 degreeC, it was immersed at 23 degreeC for 30 second in 2.38 weight% aqueous tetramethylammonium hydroxide (TMAH). Next, the thickness after water washing and drying was measured by non-contact thickness measurement. This operation was carried out in various ways with the setting level of the exposure dose as the various levels, and the exposure dose when the resist residual film thickness became zero was determined as the Eth sensitivity.

As a result, for the resists of Examples 1 to 10, Eth was 0.9 to 6 mJ / cm ^2, respectively. Therefore, it turned out that the sensitivity of the photosensitive resin of this invention is very favorable.

In addition, as a result of measuring the amount of gas generated from the resist during exposure with a quadrupole mass spectrometer, in all cases of Examples 1 to 10, the amount of gas generated in the case of the conventional ESCAP-type chemically amplified resist having a relatively small amount of gas was generated. Was about 1/2 to 3/5. In addition, the smaller the amount of gas generated, the smaller the influence on the mask, the optical system, and the like.

<Evaluation in Electronic Drawing Device>

(Preparation and Application of Photoresist)

100 parts by weight of the photosensitive resin 1 obtained in Example 1 and 4 parts by weight of triphenylsilylamine were dissolved in 2000 parts by weight of propylene glycol monomethyl ether acetate, and filtered through a 0.2 μm filter (PTFE filter) to prepare a positive photoresist. It was. This resist solution was spin-coated on a 4-inch silicon wafer subjected to hexamethyldisilazane treatment, and heated at 110 ° C. for 90 seconds using a hot plate to prepare a uniform film having a thickness of 0.1 μm. Similarly, positive photoresist was prepared and formed into a film using the photosensitive resins 2-10 obtained in Examples 2-10, respectively.

The photoresist thin film formed above was irradiated using the electron drawing apparatus so that the pattern of 100 nm of line-and-space was obtained on the conditions before and behind an acceleration voltage of 30 keV and a current value of 50 pA. After irradiation, baking was carried out at 90 ° C. for 60 seconds, immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C. for 30 seconds, rinsed with pure water, and dried. The obtained pattern was evaluated by the following method.

(Sensitivity)

The cross section of the obtained pattern was observed with a scanning electron microscope (SEM). The minimum irradiation energy which can resolve a 100 nm line (line and space 1: 1) was made into the sensitivity.

(Line Edge Roughness)

The line pattern created under the said sensitivity was observed by SEM, and the line edge roughness (LER) was calculated | required. In addition, the line edge roughness was obtained by three times the standard deviation of the nonuniformity of each point at 10 nm intervals along the line pattern on the obtained SEM at 1.5 μm in length. The smaller this roughness value, the smoother it is.

As a result, with respect to the resists of Examples 1 to 10, 6.4 to 20 µC / cm ² and LER having a sensitivity of 2.0 nm to 6.0 nm showed good patterns. Moreover, it confirmed that it had the resolution performance of 100 nm or less with the electron beam drawing apparatus of the acceleration voltage of 50 keV with respect to the resist of Examples 1-10. In particular, it was confirmed that the resist of Example 7 had a resolution performance of 25 nm.

Therefore, it was confirmed that a good pattern could be formed by using the photosensitive resin of the present invention.

Claims (7)

At least one of the repeating unit represented by following formula (1), the repeating unit represented by following formula (2), and the repeating unit represented by following formula (3), and the repeating unit represented by following formula (4), It has a repeating unit represented by following formula (5) as needed, The photosensitive resin characterized by the above-mentioned.

(In formula (1), R <_1> is a C2-C9 linear or branched bivalent hydrocarbon group, R <_2> -R <_5> is a hydrogen atom or a C1-C3 linear or branched hydrocarbon group each independently, R <_6>. And R ₇ are each independently an organic group, and R ₆ and R ₇ may be combined to form a divalent organic group. X ⁻ represents an anion.)

(In formula (2), R <_8> represents a C2-C9 linear or branched hydrocarbon group.)

The negative ion represented by X <^-> is negative ion represented by following formula (6), The photosensitive resin of Claim 1 characterized by the above-mentioned. _{C k H m F n SO 3} - (6) (In formula (6), k, m, and n each independently represent an integer of 0 or more. When m is 0, k is an integer of 1 to 8, n is 2k + 1, and formula (6) is perfluoro. When n is 0, k is an integer of 1-15, m is an integer of 1 or more, Formula (6) is an alkylsulfonate ion, benzenesulfonate ion, or alkylbenzenesulfonate ion. When m and n are each independently an integer of 1 or more, k is an integer of 1 to 10, and formula (6) is a fluorine-substituted benzenesulfonate ion, a fluorine-substituted alkylbenzenesulfonate ion or a fluorine-substituted alkylsulfonate ion.) The photosensitive resin of Claim 1 whose negative ion represented by X <^-> is bis (perfluoroalkyl sulfone) imide ion represented by following formula (7). _{(C p F 2p +1 SO 2} ) 2 N - (7) (In formula, p represents the integer of 1-8.) The negative ion represented by X <^-> is negative ion represented by following formula (8), The photosensitive resin of Claim 1 characterized by the above-mentioned.

The weight average molecular weight is 2,000-100,000, the repeating unit number a of said Formula (1), the repeating unit number b of said Formula (2), the repeating unit number c of said Formula (3), and said Formula The repeating unit number d of (4) and the repeating unit number e of the formula (5) are a / (a + b + c + d + e) = 0.001 to 0.3, (b + c) / (a + b + c + d + e) = 0.1 to 0.5, (d + e) / (a + b + c + d + e) = 0.5 to 0.8 and e / (d + e) = 0 to 0.2, characterized by The photosensitive resin of Claim 1. The photosensitive resin of Claim 1 whose terminal group of a principal chain is a hydrogen atom or a methyl group. It is a solution which melt | dissolved the photosensitive resin in any one of Claims 1-6 in the organic solvent, The photosensitive composition characterized by the above-mentioned.