TW200922947A - Photosensitive resin and photosensitive composition - Google Patents

Abstract

Provided is a photosensitive resin and photosensitive composition capable of obtaining well-formed pattern, without accompanying with a problem of an acid-generating agent being difficult to be compatible with a polymer having an acidic dissociation group which is a main component of photo-resist. The photosensitive resin according to the present invention includes a repeated unit represented by the following formula (1), at least one of a repeated unit represented by the following formula (2) and a repeated unit represented by the following formula (3), and a repeated unit represented by the following formula (4), and may further include a repeated unit represented by the following formula (5) if required. (in the formula (1), R1 represents C2 to 9 linear or branched bivalent hydrocarbon group, R2 to R5 respectively independently represent hydrogen atom or C1 to 3 linear or branched hydrocarbon group, R6 and R7 respectively independently represent organic group, R6 and R7 may form a bivalent organic group together. X- represents anion.) (in the formula (2), R8 represents C2 to 9 linear or branched bivalent hydrocarbon group.)

Description

200922947 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to the dissociation of the structure which is susceptible to acid production by irradiation of active ultraviolet radiation such as deep ultraviolet light, electricity, and external light (EUV). The photoresist which is a chemically amplified type is a useful resin, and a photosensitive composition using the resin. [Prior Art] For example, semiconductors such as high-integrated circuit elements represented by DRAMs and the like are expected to have higher density, higher integration, and higher speed. In addition, in the field of manufacturing various electronic devices, the establishment of microfabrication technology of a half micron order, for example, the development of photolithography for forming fine patterns has been tightened. In the technique of miniaturization of the technique, the method of miniaturizing the pattern is to shorten the wavelength of the active radiation (exposure light used) at the time of forming the photoresist (4). Here 'because the resolution of the reduced projection exposure device (8) is from Rayleigh (10) yleigh) R = k • In / NA (wherein, the wavelength of the exposure is shown, the lens aperture is not shown, the process factor (prQcess faetQr) is shown) As shown in the figure, the wavelength λ of the active radiation (exposure light) used for the purpose of forming the photoresist can be shortened to improve the resolution. A photo-resistance system suitable for a short wavelength is proposed to have a chemical amplification type (refer to Patent Document 1, etc.). The chemically amplified photoresist is characterized in that it is irradiated by exposure light, and the photoacid generator belonging to the component contained therein produces a protonic acid which is subjected to heat treatment after exposure and has acid dissociation property. An acid catalyst reaction occurs in a polymer such as a base (dissociated and decomposed by an acid). The 319750 9 200922947 light resistor has been developed and is mostly chemically amplified. A variety of sulfonium salts are known for this chemically amplified photoresist. However, the conventional bismuth salt photoacid generator has disadvantages such as poor mutual solubility with a polymer having an acid dissociation group which is a main component of a photoresist: also: =, in the light containing the photoacid generator When the pattern of the active radiation line ", / is blocked, the resulting pattern shape does not have the problem of adversely affecting the desired shape. [Patent Document 1: U.S. Patent No. 4,491,628, the disclosure of the present invention] [Problems to be Solved by the Invention] The present invention has the above-mentioned circumstances, and provides a photosensitive resin and an inductive composition which are the subject of the present invention, and the photosensitive resin is not There is a problem that the mutual solubility between the product U and the polymer having an acid dissociation group which is a main component of the photoresist is poor, and a pattern of a good shape can be obtained. [Means for Solving the Problem] The first method of the present invention for solving the above problems provides a photosensitive resin having a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and the following formula (8). The repeating unit of the repeating unit and the repeating unit of the following formula (4) 7F may have a repeating unit represented by the following formula (5) if necessary. 319750 10 200922947

Ο) v ^ v 1; r , Κι, 砉子工山也 _ np ^ D, versatile 1 to 9 linear or branched" The hydrocarbon group of the shell, R2 to r5 each 猸 ^ ^ Gas atom or carbon number 1 to

Straight or branched smoke, the bases R p ^ ^ 焱 匕 and 1 ^ each independently represent an organic group, and 匕 and R? may together form a bis-valent | shell & 虿 虿 machine base, X represents an anion)

(Formula (2) base) represents a linear or branched hydrocarbon having a carbon number of 1 to 9 319750 11 1 200922947 (3)

OH

(5) The _ lipid of the present invention, A, the method of the anion of the residual light material X as described in the first method

CkHmFnS〇3- (6) is an anion represented by the following formula (6). (Formula (6)_, 讫, when m is 〇, kmn each independently represents an integer above 〇; a positive number of the alkane sulfonate ion. 1, n is 2k + 1, and the formula (6) is a perfluoro or higher Integer, formula (^λ!Λ'" is an integer from 1 to 15, m is 1 continuous acid ion; acid return, acid residue or benzene to ι〇 integer, independently 1 or more In the case of an integer, k is a 1st generation of a pyridyl benzene-substituted benzene-substituted benzenesulfonate ion, a fluorine-substituted or fluorine-substituted acid salt, which is a method of the first method. The photosensitive tree anion described in the following formula (7) is a double (perfluoroalkyl 319750 12 200922947 sallow) imine ion

(CpF2P+iS〇2) 2N—(In the formula (7), an integer from 1 to 8.) 匕, ^ The fourth method of the invention is as shown in the first method, the photosensitive tree shown in the first method, and the anion shown by X An anion represented by the following formula (8) is used. 88 So2 F2C, JF2. (8) The fifth method of any one of the first to fourth methods, wherein the weight average molecular weight is 2, (10) 0 to 100, OGG fen 'The number of repeating units of the above formula (1) a, the number of repeating units of the above formula (2) b, the number of repeating units of the above formula (3) ^, the number of repeating units of the above formula (4) and the number of repeating units of the above formula (5) a/(a+b+c+d+e) = 〇.谢〇·3 > (b+c)/(a+b+c+d+e) = 〇.1 ^ 〇. 5 > ( d+e)/(a+b+c + d+e) = 0.5 to 〇·8, and e/(d+e) = 〇 to 〇.2.

The sixth method of the present invention is as described in the photosensitive resin, wherein. Any one of the first to fifth methods, wherein the terminal hydrogen atom or the methyl group of the main chain provides a photosensitive composition, which is a species to the sixth method, Seven methods dissolve a solution of the first photosensitive resin in an organic solvent. [Effects of the Invention] 319750 13 200922947 The method of not containing an acid generator alone becomes a chemically amplified photosensitive composition, so that the problem of poor mutual solubility between the acid generator and the polymer having an acid dissociation group is not caused. The effect of a good shape pattern can be obtained. [Embodiment] The present invention will be described below. The photosensitive resin of the present invention has a repeating unit represented by the above formula (1), a repeating unit represented by the above formula (2), and at least one of repeating units represented by the above formula (3), and the above formula (4) The repeating unit shown is a polymer having a repeating unit represented by the above formula (5) and having a structure derived from the photoacid generator function of the mirror salt and an acid dissociation group. Since the photosensitive resin of the present invention has a structure and an acid dissociation group as a function of a photoacid generator, it can be a chemically amplified photosensitive composition by dissolving in a solvent and not necessarily containing an acid generator. Therefore, when used in a photosensitive composition, there is no problem of miscibility between an acid generator and a polymer having an acid dissociation group, and a pattern having a good shape can be obtained. /, the body σ, the repeating unit of the formula (1) has a structure which is exposed to active radiation and produces acid as a function of a photoacid generator, and an acid which can be dissociated by an acid generated by the acid generator Dissociation base. Further, the repeating unit represented by the above formula (2) and the repeating sheet represented by the above formula (3) have a weight expressed by the above formula (4) in a group which can be dissociated by an acid, and the unit I The structure of the system (4). The repeating unit shown in the above formula (4) and the repeating unit in the above (5) are all related to the solubility of the alkali developing solution, and the solubility can be adjusted by adjusting the amount. The photosensitive resin of the present invention itself is insoluble or extremely difficult to dissolve in the test liquid 319750 14 200922947, but the acid is generated from the repeating unit represented by the formula (1) by the exposure of the active radiation, and the acid is produced by the acid. Function, the above formula / Dingzhi Dongfu early production ^ ^ ππ Equation (1) does not repeat the unit, the above formula (2) does not focus on the early position and the above formula (3) w J pounds under the weight The acid dissociation in the early position dissociates and increases its solubility in the alkali imaging solution. In the above formula (1), 'R! is a carbon number 〇 main ... 丄 Retorting the divalent hydrocarbon group of Z to 9 and optionally being a straight chain or a branched form. Each of 1 to r5 independently represents an atom or a linear or branched hydrocarbon group having 1 to 3 carbon atoms.匕 and -t- ( independently of the organic group. =: a base such as a linear, branched or alicyclic structure. Also, the ring (tetra) or heterocyclic aryl. Preferred organic Preferably, the U group, the phenyl group and the tert-butylphenyl group are the same. The enthalpy or heterocyclic aryl group may have a substituted substituent of carbon number i to 30, for example, a carbon number. A hydrocarbon group of 1 to 30 is preferred. The hydrocarbon group having 1 to 30 carbon atoms as a substituent is a thiol group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third mountain. An alkyl group such as a fluorenyl group, a hexyl group, a heptyl group, an octyl group, a third amyl group, a decyl group, a decyl anaalkyl group or a hexadecyl group, ^ m 4 % propyl group, % pentyl group, cyclohexyl group,二i王:::N-alkyl, cyclohexadecyl and adamantyl, etc., as an alkyl group having 1 to 30 carbon atoms as a substituent, such as A. Lacto-based, ethoxylated, propoxy, isopropoxy, ^^j-yl, second butoxy, pentyloxy, hydrazine: hexyloxy, n-octyloxy, n-decyloxy and 1 -The same force can be combined with each other to form a ring 'this time' can be included The bivalent organic m of the wood structure. The organic compound of the divalent form 319750 15 200922947 is an aliphatic cyclic group having a carbon number of 3 to 9 bonded by h and R? having a saturated carbon structure. Preferred examples of the base include a polymethylene group such as a butyl group and a pentyl group. In general, a ring formed of a divalent organic group and m is preferably a ring of 4 to 8 members, particularly The anion represented by X in the formula (1) is not particularly limited, and an anion used in the conventional photoacid generator can be used. Examples of the anion include an anion represented by the formula (8), and an anion. An anion represented by the formula (7) and an anion (cyclo1,3-perfluoropropane disulfonimide ion) represented by the above formula (8). In the 弋(), km and η each independently represent an integer of q or more. When it is 0, an integer of U 1 to 8, η is 2kH, and the formula (8) is a perfluoroalkyl sulfonate ion. Preferably, it is a sb Av # ) Examples include, for example, CF3SO3 (difluoromethane hydrochloride). rp from thousands of CASO3 (nonafluorobutane sulfonate from 8 17 and 3 (heptadecafluorooctanoate), etc. 6) When 1 is 0, k is an integer from 1 to 15, ^ is! The above integer 'Eq. (8) is a correction (tetra) ion, a benzoate acid ion. When the acid ion is burned, m is as. Preferably =: an example of a salt ion For example, (10) salt ion ^ (ethanesulfonate ion), C9HI9sn-ri . 9lli9S 〇 3 (〗-壬 sulfonate salt-like alkane sulfonate ion, such as ϊη #ηκ < w 10- knowing ceramide sulfonate ion, etc. Examples of the besylate ion are exemplified by yttrium triisopropyl benzoate ion. A (4) salt ion or 2, 4, 6-, and (8), each independently The ground is ^, k is an integer from 1 to 10, and the formula is positive ^ ^ b. The formula (6) is a benzene sulfonate ion substituted by fluorine, and a fluorocarbon substituted by a fluorine atom. Alkane sulfonate ion. 319750 16 200922947 Preferred fluorine-substituted besylate ion, 4-fluorobenzene ion, such as 2~fluorobenzenesulfonate, benzoic acid salt, and the like. ; , 4:, fluorobenzene sulfonate ion and fluorine-substituted alkane sulfonate of pentafluoro gamma lanthanide ΓΓ: ΓΓ 4: gas one (10) Α) benzene external oxime and - mouse methyl) benzene yellow Acid ions and 3,5-bis (trifluoromethyl: the second sub-etc. Also, preferably the fluorine-substituted sulfonate ion',, 丨, 2, 3, 3'3 - hexafluoropropane sulfonic acid Salt anion The anion represented by the formula (7) is a bis(perfluorinated phase) imine ion, which is prepared in the first to the whole of the heart. Preferably, the bis (perfluoro) bis(trifluoromethyl) The imide ion and the bis(pentafluoroacetite) are sub-monthly: the photosensitive resin of the present invention preferably has a hydrogen atom or a methyl group at the end of the main chain. The polymerization initiator and the terminating agent in the case of the polymer of the substrate are arbitrarily determined. Further, the photosensitive resin of the present invention preferably has a weight average molecular weight of 2, 〇〇〇 to ip^OOf, wherein The range of 2, _ to 50, _ is preferred. The average molecular weight in the field is small, the exposure sensitivity is lowered and the strength of the cured film is also lowered. When the weight average molecular weight is large, The adhesion of the sheet is lowered and the pattern formation is not easy. X, the above weight average molecular weight refers to the polystyrene exchange weight average molecular weight (MW) obtained by gel permeation chromatography (GPG) of the photosensitive resin of the present invention. The ratio of the average molecular weight (Mw/Mn) of the QMW and the GPC obtained by the GPC is generally from i to 3, and preferably from 1 to 2.5. Further, the repeating unit of the formula (1) The number is &, the number of repeating units of the formula (2) is b, the number of repeating units of the formula (3) is c, the number of repeating units of the formula (4) 319750 17 200922947 is d, and the number of repeating units of the formula (5) For e, to satisfy a/(a+b+c+d+e>〇. 〇〇1 to 〇.3, (b+c)/(a+b+c+d+e>〇.丨 to 〇·5, (d + e) / (a + b + c + d + e) = 0.5 to 0 · 8, and e / (d + e) = 〇 to 〇. 2 is better. Satisfy a / (a +b+c+d+e) = 〇· 〇〇1 to 〇. 3 conditions, the structure of the formula (1) by exposure to acid production becomes the amount of catalyst, and a good acid generator can be achieved. Further, when (b+c)/(a+b + c+d + e) = 〇· i to 〇. 5, the effect of the dissolution inhibiting function on the alkali imaging solution can be achieved. When the foot (d+e)/(a+b+c+d+e)=0.5 to 0·8 and e/(d+e)=〇 to 〇.2, adhesion to a coated object such as a substrate can be achieved. The effect is good and the solubility in the alkali developing solution is good. Further, the photosensitive resin of the present invention does not affect the present invention except for the repeating units represented by the formulas (1) to (5). Within the scope of the effect, there are other architectures. The method for producing the photosensitive resin of the present invention is not particularly limited, for example,

It is produced by the following formulas (13) to (15). \ (P2〇5) is a catalyst, and a compound represented by the formula (9) and a sulfoxide are reacted to obtain a compound represented by the formula (10). The dialkyl sulfoxide can be obtained by hydrogen peroxide oxidation. For example, the repeating unit shown in the formula (1) can be introduced by the following method. First, as shown in the following reaction formula, in methanesulfonic acid (CH3S〇3H)t, with phosphorus pentoxide, the second sulphate (dialkyl compound (methanesulfonate). In addition, oxidized dialkyl sulfide And easy to make 319750 18 (10) 200922947

+ ο II Re~~S—R7

Only 3 > 5 is the amount of phosphorus pentoxide which is a catalyst, relative to the compound 1 of the formula (9), preferably from 1.1 to 3. 〇mole, wherein 〇5 to i ^ Moore is preferred. Further, the amount of the methylic acid is preferably from 1 to 10 mols per mol of the compound of the formula (9), and preferably from 4 to 6 mols. The reaction temperature is generally in the range of 〇 to 5 (rc range, wherein 1 〇 to 3 〇. 〇 is preferred) The reaction time is generally in the range of ! to 15 hours, wherein 3 to 8 hours is preferred. The reaction is terminated by the addition of water. - Secondly, as shown in the following reaction formula, the formazin ion of the compound of the formula <1〇) is substituted (CH3S0O is substituted with a salt of X-. Further, in the following reaction formula In the aqueous solution of the compound of the formula (1〇), in contrast to the compound 1 of the formula (1〇), the enthalpy is added to 2 mol of X, For example, it is preferred to include various acids (Η+χ_) or salts (Μ+Γ) of formula (6), formula (8) or formula (8), wherein U5 to 1.2 mol is preferred. It is preferred to use a chlorine-based solvent such as methylene chloride or chloroform. Further, the reaction temperature is usually in the range of 10 to 5 crc, and preferably 20 to 3 Torr. The reaction is finally carried out, and the water layer is separated and washed with water. The organic layer is cleaned and crystallized by using a suitable recrystallization solvent to obtain a compound of the formula (11). Further, the compound of the formula (10) is synthesized. Adding potassium iodide to the reaction solution, and separating the formula (i(7) 19 319750 200922947 as a solid, and purifying the product, using the sulfonate to replace the compound with the iodide ion, and then replacing it with x, and iodine. It is also possible to carry out salt substitution with ions.

(10)

After OH R6'S+, r7 ch3s〇3, as shown in the following reaction formula, the compound of the formula (1 1 ) is used to carry out the dehydrogenation reaction of the compound of the formula (13) to obtain the formula (13) " Further, in the following reaction formula, γ represents a halogen atom such as chlorine or bromine. Specifically, for example, in a polar solvent, it is achieved by reacting a compound represented by the formula (11) with a compound represented by the formula (12) in the presence of potassium carbonate ([COO or the like). The reaction temperature is generally 60 to 9 (TC range. After the reaction is completed, water is added, and the aqueous layer is washed with a non-polar solvent such as hexane, and then extracted with a chlorine-based solvent. Then, the organic layer is separated, washed with water, and then the chlorine-based solvent is distilled off. Further, a phosphonium salt represented by the formula (13) can be obtained. Further, a compound represented by the formula (9) to the formula (12) can also be used as a commercially available product. 319750 20 (13) 200922947

The compound represented by the formula (13) and the copolymer of polyhydroxystyrene or poly(p-styrene-styrene) are contained in an organic solvent such as 1,3-dioxanane. When reacting under an acidic catalyst, a repeating unit represented by the above formula (1) can be introduced. The repeating unit represented by the formula (2) may be a copolymer of hydroxystyrene or poly(hydroxystyrene-styrene) and a vinyl ether compound represented by the following formula (14) in an organic solvent such as a 1 '3-dioxolane ring. " Addition reaction in the presence of medium and acidic catalysts. (R8 represents a linear or branched hydrocarbon group having 2 to 9 carbon atoms.) The repeating unit represented by the formula (3) can be represented by the following formula (15): di-dibutyl phthalate and poly! A copolymer of styrene or poly(hydroxystyrene-styrene) is produced by reacting in an organic solvent such as hydrazine or 3-oxapentane with a basic catalyst. ^〇Λ〇Λ〇ν (15) Further 5 i A polymer having a repeating unit represented by the formula (1) to (5) is suitable. The 319750 21 200922947 reaction is also carried out to produce the photosensitive resin of the present invention. The monomer of the repeating unit shown in (5) is copolymerized by the formula (1) in the organic solution a, and can also be used to form a polymerization initiator solvent such as tetrahydrogen, and /3 -, photosensitive resin. The organic burning (di◦), etc. n '-ring and 1,3-dioxin, photopolymerization initiator, oxidation two: triggering convenience, reaction speed and easy (10) v 4, can be considered treatment Gu Yi adjusts the molecular weight and so on and chooses it appropriately. Specific manufacturing methods are exemplified below. About the first shown in the list below! The photosensitive resin is prepared by, for example, adding a compound represented by the formula (10) and a compound of the formula (13) to a polyphenylene bromide in the presence of an acidic catalyst in the above organic solvent. Further, the second type of sensitizing resin may be added to the polypyridylbenzene-ene in the presence of an acidic catalyst in the organic solvent in the presence of an acidic catalyst, and then the test catalyst and the formula may be added. (The compound represented by (5) is prepared by reacting. The photosensitive resin of the third type can be added to the compound represented by the formula (14) and the compound represented by the formula (13) in the presence of an acidic catalyst in the above organic solvent. After being formed into polyhydroxystyrene, a basic catalyst and a compound represented by the formula (15) are added and reacted. The photosensitive resin of the fourth type can be present in the above organic solvent in the presence of an acidic catalyst. Next, a compound represented by the formula (14) and a compound of the formula (13) are added to poly(p-styrene-styrene) to prepare a photosensitive resin of the fifth type in the above organic solvent. Adding a compound represented by the formula (13) to poly(hydroxystyrene-styrene) in the presence of an acidic catalyst, and adding a basic catalyst and a compound represented by the formula (丨5) are reacted. Form 6. Type of photosensitive resin, can be used in the above organic solvent, in the organic solvent, 319750 22 200922947 In the presence of the compound of the formula (III) and the compound of the formula (13), the compound is added to the poly(hydroxystyrene-styrene), and the basic catalyst and the compound represented by the formula (丨5) are reacted. And made. [Table 1] ^ ' ------- The presence or absence of repeating units in the resin structure

(There is no indication) If the photosensitive resin of the present invention is dissolved in an organic solvent, it is a pure composition of the invention. Since the photosensitive resin of the present invention has a photoacid generator as the photoacid generator (IV) and an acid dissociation group, when it is dissolved in a solvent, it can be used as an acid generator, and it is a chemically amplified type of composition alone. Therefore, the problem of poor mutual solubility between the acid generating agent and the poly-S material having an acid dissociating group is not caused, and a photosensitive composition of a homogeneous solution can be formed, whereby the desired pattern can be formed. & Sodium citrate is used as an organic solvent for photosensitive compositions, such as ethylene glycol monoterpenoids, ethyl alcohol (tetra) acetazide, diethylene glycol dialkyl ether, ethyl alcohol, alcohol, =: : early, _, propylene glycol monoalkyl bond, acetonide, and propyl urethane acetate. The ratio of the photosensitive resin of the present invention contained in the photosensitive composition of 319750 23 200922947 may be within the range of solubility of the photosensitive resin. It is preferable to use ' generally in the range of 3 to 30% by weight. ... In the photosensitive composition of the present invention, it is preferred to use an acid which can be controlled from the repeating unit represented by the above formula (1) by exposure in the photoresist film. a so-called acid diffusion controlling agent having a diffusion phenomenon and an action of suppressing an unsuitable chemical reaction in an unexposed region, etc. The acid diffusion controlling agent is a nitrogen-containing organic substance which does not change in alkalinity due to exposure or heating. Further, the amount of the acid diffusion controlling agent used is generally 〇 to 5% by weight based on the photosensitive resin. When the amount used is too large, the sensitivity and developability of the resist are lowered. Conversely, when there are too few, as a photoresist Further, in the photosensitive composition of the present invention, various additives such as an interface activator, a sensitizer, and an antifoaming agent may be blended as needed in the photosensitive composition of the present invention. When the photoresist pattern is formed, the photosensitive composition is applied onto a substrate such as a germanium wafer by a suitable coating method such as a spin coating method or a flow casting coating method to form a photoresist film, and if necessary, the heat treatment is performed, and the spacer has a predetermined property. The reticle of the pattern is exposed, and the active radiation used at this time is appropriately selected from deep ultraviolet rays, electron beams, X-rays, or EUV (extreme ultraviolet light) depending on the degree of the fineness of the pattern and the sensitivity of the photosensitive composition. Further, the exposure conditions such as the exposure amount may be appropriately selected depending on the composition of the composition, various types of soiling agents, etc., and heat treatment after exposure: preferably, the heating conditions are determined by the composition of the composition. The composition, various additives, etc. can be appropriately selected. Dogs, secondly, the exposed photoresist film can be imaged by alkali imaging liquid to form 319750 24 200922947 Photoresist pattern. The alkali such as liquid, such as alkali metal hydrogen 4 舲 gas water, mono-, di- or tri-alkyl amines, .., chloroammonium oxychloride, wins and turns The compound is usually dissolved in 1 to 2, and the bile is tested in the V* lining 4/time degree, and the liquid is mixed. Further, it is formed by using the aqueous test solution and then subjected to a water washing treatment. The present invention is illustrated by the following examples, but the present invention is not limited to such examples. Inches (Synthesis Example 1) ^ Compound represented by the following formula (4-vinyloxyethoxyphenyldiphenylfluorene perfluoro) Synthesis of butane sulfonate):

Dissolving 52.2 g of 4-hydroxyphenyldiphenylphosphonium perfluorobutanesulfonate, 18·〇g of potassium carbonate and 1. 〇5g of N, Ν, Ν', Ν'-tetramethylethylene The amine is in 26 lg of dimethyl sulfoxide. Thereafter, 9 g of chloroethyl vinyl ether was added and the temperature was raised to 80 °C. After stirring for 15 hours, the reaction liquid was cooled to 301: or less. After removing the solid matter, 10 Og of water was added, and the aqueous layer was washed 3 times with 10 Og of the hexane. Add 209 g of dioxane and 260 g of water, stir and extract 25 319750 200922947 * Take a private product into the dichloromethane layer. The organic layer was washed repeatedly with distilled water until the separated aqueous layer exhibited p H 7 . The solvent was distilled off by a rotary evaporator to obtain 69. 9 g of an oily substance. The result was determined by ih_nmr and ion chromatography, and it was confirmed that the substance was 4-vinyloxyethoxyphenyldiphenylphosphonium perfluorobutane. NMR 24 (d, J 4 9 (dd , 2H), 7 .

4 4 7 Μ Η z , C D C 1 3) <5 4 . 2.4 Hz, 1 H) , 4. 4,7 · 4 Hz, 1 H), 7 4 (m, 1 2 H)

ί (Synthesis Example 2) Synthesis of a compound of the formula (4-ethoxyoxyethoxy 3, dinonylphenyl bis(4-t-butylphenyl)phosphonium perfluorobutane sulfonate) :

Dissolving 28. 6 g of 4-hydroxy 3,5-dimercaptophenyl bis(4-tert-butylphenyl) mirror perfluorobutanic acid anhydride, 8.10 g of potassium carbonate and 〇.46 g of N, N , N 'N'-tetramethylethylenediamine in i42 g of dimethyl sulfoxide. Then, 6. 0g of ethyl vinyl ether was added, and the temperature was raised to 8 (rc. Stir for 19 hours, and the reaction liquid was cooled to 30. (: The following. After removing the solid matter by filtration, adding 20.9 g of water' using 85.1 g The washed water layer was washed three times. Add 226 g of dichloro 26 319750 200922947 曱 and 141 g of water 'after stirring, extract the target into the chloroform layer. Repeat the washing of the organic layer with distilled water until the separated water is present. The solvent was distilled off by a rotary evacuator to obtain 27.4 g of a brown oil. The product was confirmed to be 4-vinyloxyethoxy 3, 5-. Diphenyl bis(4-tert-butylphenyl)phosphonium perfluorobutane salt. H6mMR4 〇V°. CDCIs) δ1- 35 (s· 18H) > 2· 36 (s 5 ( d 'jil! ;4«〇f (m> 3H) 4· 12-4· 14 (m, 2H) , 4. 2

Hz' 1H) 7 HZ,1H) ' 6> 50 (dd> ^ = 1^. 3, 6. 6

Hz-1H), 7.35 <s, 2H), 7. 5 9 - 7. 7 5 (m, 8 H) (Synthesis Example 3) Compound of the formula: 4-vinyloxyoctyloxyphenyl Synthesis of phenylhydrazine perfluorobutanide):

Η ^Ίο-clo 1.23g of 8-chloro-I-octyl alcohol, sodium carbonate, strontium 47g·## chlorobis[77-cyclooctadiene oxime (1)] and 1.31 § vinyl acetate i 6. In 15 g of toluene, stir at 1 Torr (rc for 4 hours). After cooling to room, the solvent is removed by distillation, and a mixed solvent of hexane and di-methane (hexane) 319750 27 200922947 and a volume of methane are used. Purification by column chromatography of 2:1) gave 1.16 g of 8-chlorooctyl vinyl ether as a colorless transparent liquid. Dissolving 2.67g of 4-hydroxyphenyldiphenylphosphonium perfluorobutanesulfonate, 7878g of potassium carbonate and 0.05g of N,N,N,,N'-tetradecylethylenediamine at 13.3 g in dimethyl sulfoxide. Then, add 1〇5§ of 8_chlorooctyl vinyl ether, and raise the temperature to 8 (TC. After stirring for 15 hours, cool the reaction solution to 3 (rc or less. By using hydrazine, remove the solidification), then add 13· 3 g of water, the aqueous layer was washed three times with 7.96 g of hexane. After adding 1 m. of dichloromethane and water, the target was extracted into the m layer with stirring, and the organic layer was repeatedly washed with steam to the water. The separated water was subjected to ΡΗ7·0. The solvent was distilled off by a rotary evacuator to obtain 2.53 g of a brown oily substance. The material was confirmed to be 4-vinyloxyoctyloxy group by lH_NMR and ion chromatography. Phenyldiphenylphosphonium perfluorobutane sulfonate 1 H-NMR .6 4-1. 6 . 6 Η ζ (t , J = 6 ), 6.46 (4 0 0 6 7 (m, , 2H) , .6 Hz (dd , MHz, - CD C Ls) 2 H) , 1. 7 8-1. 3. 9 6 (dd , J = 6 2H) , 7. 6 5 - 7. 7 6 (m, 1 2H) ^ 1 · 3 6 - 1. 4 7 (m, 8 H: 8 3 (m, 2H), 3. 6 7 ( t , 2H) - 4. 1 6 (dd8'ji'i4. 4Z, 1H) ' 4· J = 14. 4,6.8 Ηζ,ΐΗ), ?., 2 6 0 7

Hz 19 ,1 J = 0 4 1H (m, (Synthesis Example 4) Compound of the formula: 4-vinyloxyethoxyphenyldiphenylfluorene ring (1,3-perfluoropropane disulfonate) Synthesis of imine salts): 319750 28 200922947

〇2fN'so2 f2c, xf2 bath% 4.66g of pentoxide and 13.3g of diphenyl benzoate were harder than 63.1g of methic acid, and 9.26g of benzene was charged and was disturbed for 15 hours at room temperature. 199 g of water was added dropwise at a temperature of 3 ° C or lower, and the aqueous layer was washed 3 times with 66.4 g of the third butyl methyl ether, and then 12 g of dichloromethane and 23.9 g of ring 1 were added. 3-Perfluoropropane disulfonimide potassium salt and allowed to mix for 2 hours. After the stirring was terminated and the separated aqueous layer was removed, 66. 4 g of a 1% by weight aqueous ammonia solution was added and stirred. Then, the organic layer was washed with distilled water to repeat r until the aqueous layer was separated to pH 7.0. The solvent was removed by a rotary evaporator to give a brown oily 4-hydroxyphenyldiphenylsulfonium (1,3-perfluoropropanedisulfonium)imide salt. Dissolving 32. lg of 4-hydroxyphenyldiphenylfluorene ring (1,3-perfluoropropane-stone), imine salt, 11.2 g of carbon-acid_ and 0.67 g of N, N, N, N ,-Tetramethylethylenediamine in 164 g of dimethyl sulfoxide. Then, 8.65 g of chloroethyl vinyl ether was added, and the temperature was raised to 8 (TC. The mixture was stirred for 15 hours, and the reaction liquid was cooled to 30 C or less. After removing the solid matter by filtration, 8 g of water was added, and 40 g of water was used for washing. 3 times of water purification layer. Add 120g of dichlorohydrazine and 260g of 319750 29 200922947, and then scramble the water, then extract the target to diclofenac. Repeat the washing of the organic layer with water to the separated water to pH7. So far, the solvent was removed by steam distillation to obtain 29. g of an oily substance. The substance was subjected to ^r = ion chromatography, and it was confirmed that it was a 4-ethylidene phenylphenyl diphenyl fluorene ring. (1,3-perfluoropropane disulfonium) imine salt. H-NMR (4〇〇2 4 (d, J = 7.4, 49 (dd, J = i4. 2H), 7. 6 4- 7. 0 5-4. 〇8 (m, 3 H) , 4 3 1 - 4 . 3 3 (m, 2 H) 6 7. 24 (d, J = 6. 8 Η ε MHz, CDC 】 3) 5 4 2. 4 Hz, 1H), 4, 4> 7 · 4 Hz, 1 H), 7 4 (m, 1 2 H) (Synthesis Example 5) Compound of the formula: 4-vinyloxyethoxy Synthesis of phenyldiphenylphosphonium bis(perfluoromethanesulfonyl)imide salt: &

02S"NsS〇2 CF3 0F3 dissolves 2.33g of pentoxide and 6.6 5g of diphenyl argon; ε wind after 3·5g of methanesulfonic acid, adds 4.80g of phenol' at room temperature for 15 hours . The water was added dropwise at a temperature below 30 ° C, and the aqueous layer was washed three times with 30 g of t-butyl decyl ether. Then, 6 g of methane and 6 g of bis (perfluoromethanesulfonate) were added. Amine) potassium salt 'and stirred for 2 hours. The mixing was terminated, and after the separated aqueous layer was removed, 1% by weight of aqueous ammonia was added and stirred at 319750 30 200922947. Next, the organic layer was repeatedly washed with distilled water until the separated aqueous layer showed pH 7. The solvent was distilled off by a rotary evacuol to give 16. The brown oily form 4 - the basic diphenyl mirror bis(perfluorosulfonium sulfonate) imide salt. Dissolve 16g of 4-hydroxyphenyldiphenylfluorene bis(perfluorodecanesulfonyl)imide salt, 4.7g of potassium carbonate and 〇.33g of N,N,N,,N,-tetramethylethylene The amine is in 8Og of disulfoxide. Then, <66 g of chloroethyl vinyl ether was added and the temperature was raised to 80 °C. After stirring for 15 hours, the reaction liquid was cooled to the following. After removing the solid matter by filtration, 4 g of water was added, and the aqueous layer was washed 3 times with 3 g of the hexane. 60 g of dichloromethane and 12 g of water were added, and the target was extracted into a dioxane layer with stirring. The organic layer was washed with distilled water and repeated until the separated water appeared to pH 7. The solvent was distilled off by a rotary evaporator to give a red oily substance. The substance was identified by iH_NMR and ion chromatography to be 4-ethyloxyethoxyphenyldiphenylphosphonium (perfluorodecanesulfonyl)imide salt. .. H-NMR (4〇〇2 4 (d, J = 7. 4, 49 (dd, J = 1 4 ' 2 Η), 7. 6 4-7. ΜΗ ζ , CDC 1 3) <5 4. 0 5 2· 4 Η ζ , 1 Η) , 4. 31 4, 7. 4 Hz, 1Η) , 7. 7 4 (m, 1 2 Η) ~ 4 · 〇8 (ιη, 3 Η) — 4. 3 3 (m, 2Η) 2 4 (d, J = 6 8 , 4., 6. Η ζ, (synthesis example β) a j-vinyloxyethoxy phenyl di(4_third butyl) Synthesis of phenyl 2,4,6-diisopropylbenzenesulfonate 319750 31 200922947

〇的的的。 Ig, 5-hydroxyphenyl bis(4-t-butylphenyl) fluorene 2, 4,6-triisopropylbenzenesulfonate, 28.28g of potassium carbonate and 0. l〇g N, N, N, N, - tetramethylethylenediamine in 15 g of dimethyl sulfoxide. Then, add 83 g of chloroethyl vinyl ether, and raise the temperature to 8 (TC. Stir for 15 hours, cool the reaction solution to below 30 ° C. After filtration to remove the solid matter, add 75 g of water and 44 g of dichloromethane. The target is poured into a methylene chloride layer, and the organic layer is repeatedly washed with distilled water until the separated water is at pH 7. The solvent is removed by rotary evacuol, and the obtained oil is dissolved in 2Og of acetonitrile, and 15 g is used. The acetonitrile layer was washed five times with hexane, and the solvent was evaporated to give 4.46 g of brown oily material. The material was determined by lH_NMR and ion chromatography to confirm that it was 4-ethyloxy ethoxylate. Phenyl phenyl bis(4_t-butylphenyl) fluorene 2, 4, 6-triisopropylbenzene sulfonate. H-NMR Η), 1. 3 2 2-4. 0 8 • 2 9 — 4.3 〇 (dd , J = • 2 6 (m, 2

I T_J — kt W Dish 3) <5 1 · 2 1 (d, (sep, J = 6 . ( P» J = 6 . .7.02 1 0 H) i, J = 6. 8 Hz, 18 8 Hz , 1 H) , 4. 〇 2.4 Hz, 1 H) , 4 8 Hz, 2 H) , 6. 5 (s , 2 H) , 7,24 — 7 319750 32 200922947 (Synthesis Example 7) 4-Vinyl Oxygen Synthesis of ethoxylated phenyldiphenyl sulfonium 2,4,6-triisopropylbenzenesulfonate:

Dissolving 8·00g of 4-pyridyldiphenyl vegetable 2,4,6-triisopropylbenzenesulfonate, 2.46g of potassium carbonate and cesium. 16g of Ν, Ν, Ν', Ν' - Tetradecylethylenediamine in 24.00 g of disulfoxide. Then, 1.59 g of gaseous ethyl vinyl ether was added, and the temperature was raised to 8 (TC. Stir for 15 hours, and the reaction liquid was cooled to 301: or less. After the transition to remove the solid matter, 160 g of water and 64 g of methylene chloride were added to extract the target. To the dichloromethane layer, the organic layer was washed repeatedly with distilled water until the separated aqueous layer appeared to be pjj7. The solvent was distilled off by a rotary distiller to dissolve the obtained oil in 32 g of acetonitrile using 24 g of hexane. The net acetonitrile layer was removed 5 times. The solvent was evaporated to give a white oily substance of 9.84 g. The material was determined by iH_NMR and ion chromatography to confirm that it was 4-vinyloxyethoxyphenyl Phenylhydrazine 2,4,6-triisopropylbenzene hydrochloride. 319750 33 200922947 ... NMR ( 4 Ο Ο ΜΗ z sep,1 Η) , 4. 0 2 — 4 -4. 3 1 (m, 2 Η) , 4. 2 (s, 2 Η) , 7. 2 4-7

(Synthesis Example 8) Synthesis of 4-vinyloxy salt: oxyphenyldiphenylphosphonium 2-trifluorodecylbenzenesulfonic acid

- Dissolving 3. OOg of phosphorus pentoxide and .8· Olg of diphenylarsin after 38. llg of methanesulfonic acid ‘5·75 g of phenol was added and allowed to accumulate at room temperature for 15 hours. Stay at 3〇. (: Add 120g of water below, wash the water layer with 4〇g of _ butyl methyl ether 3 times, then add 80g of dichloromethane and 2 of 2 difluorononylbenzene benzoic acid clock salt and give it 2 hours. Termination is granted, g, after separating the separated aqueous layer, adding 28 g of 0.1% by weight aqueous ammonia solution and mixing. Ending the stirring and removing the separated aqueous layer, repeating this step until the separated aqueous layer is present. The solvent was distilled off by a rotary evaporator to obtain 10.33 g of a white powder of 4-hydroxyphenyldiphenylphosphonium 2~trifluoromethylbenzene$xamate. Dissolving 8· Olg of 4-carbyl group Phenyl diphenyl vegetable trifluoromethyl stupid 319750 34 200922947 salt, 2. 74g of potassium carbonate and cesium. I8g of N, N, N, N,-tetramethylethylenediamine in 36g of two Then, add 5. 3 ig of chloroethyl vinyl ether, raise the temperature to 8 (TC. Stir for 15 hours, cool the reaction solution to 3 (TC or less. After filtering to remove the solid matter, add 4 〇g of water, The aqueous layer was washed three times with 30 g of hexane, 30 g of dichloromethane and 6 g of water were added, and the target was extracted into a dichlorof-ane layer by stirring. The organic layer was washed repeatedly with distilled water. The water layer is pH 7. The oil is used to obtain 3. 7g of oily substance. The substance is known as 4-ethyloxyethoxy bromide by distillation to remove the solvent by twirl and t is 1H-NMR And ion chromatography to determine the acid salt. Diphenyl hydrazine 2-trifluoromethyl stupid

(4 0 0 MHz, 1 Η), 4. 2 7 (d, 2Η), . 1 〇H), 7.

' CD CI 3) (d, 1H), 7. 4 1 (t, .8 5 (d, I 〇9 - 4 . 0 5 (n 6(t, 2H), 6. , 7. 5 0 ( t , 1 i 8· 4 1 (d, 2 H) (m, 2H), 6· 5 3 (q, 1H), 7, ((ethyleneoxyethoxyphenyl) dimethane methyl sulfonic acid Synthesis of salt: dibutylphenyl) 铳2-three 〇t°

44. 51g of 4-hydroxyphenyl bis(4-t-butylphenyl) 毓2~ 319750 35 200922947 Two said methyl benzoate, 5. 30g of potassium carbonate and cesium. 53 , N, N,, N,-tetramethylethylenediamine in 3 〇g of disulfoxide. Then, 10. g of ethylene vinyl ether was added and the temperature was raised to 80 °C. Stir for 15 hours and cool the reaction to below 30 °C. After the solid matter was removed by filtration, i5 g of water and 93 g of one chlorodecane were added, and the target was extracted into a dichloromethane layer. The organic layer was washed repeatedly with distilled water until the separated aqueous layer appeared to pH 7. The solvent was removed by rotary distillation to give a red powder of 8.7 g. This material was identified as a 4-vinyloxyethoxyphenyl bis(4-t-butylphenyl)phosphonium 2-trifluoromethyl benzene phleoate by the results of the analysis by ion chromatography and ion chromatography. (ή, 一▲·〇厶, S, 丄on;,, 7 2 8 // t' 27 (d' 1H) ' 4·; 6 4 Z f,, 2H), 7. 4 1 (t, 1H 6 4 (m, 8H), 7.85 (d, 2H), 0 9 - (t, 7 · 5 4 1 (H-NMR (4 0 0 MHz, 4 · 0 5 (m, 2 Η) , 4. 2 3 2Η), 6 · 5 3 (q, 1 Η), 〇 (t, 1H), 7. 6 9-7. d, 2H) (Example 1) The sensitization shown in the following formula (A) Synthesis of photosensitive resin) (ie, type 1 in Table 1)

31975〇 36 200922947

OH (A) In a nitrogen atmosphere, the molecular weight (Mw) in terms of polystyrene is 50,400, and the molecular weight distribution (Mw/Mn) is 1. 聚9 of polypyridyl styrene in 350 ml of 1,3 - After the dioxapentane ring, the 1,3- oxalo- pentane is removed by steaming under normal pressure, and the water in the reaction system is reduced to 1 〇〇ppm (below. Cooling the reaction solution to below 20 °C) 6重量的含乙乙含的1,3-二oxacyclo ring solution, in the case of adding 6 2 /z L of 5% by weight of hydrochloric acid. The mixture was stirred at 30 ° C for 2 hours. Cooling / glutamic solution to 15 C ' at 30 minutes. Into 8. 8 g of the 4-methyloxyethoxyphenyldiphenylphosphonium perfluorobutane obtained in Synthesis Example 1. After the 63.8 wt% 1,3-dioxolane solution of the alkanesulfonate was stirred for 2 hours at 3 Torr: neutralized with aqueous ammonia, and the solution was dropped into 17 Torr at room temperature. g. In the pure water of 'pure the solid matter. After filtering and taking the solid matter, use acetonitrile and pure water to give the sulphide' at 35. (: drying under 24 hours to obtain 53.5 g of resin. The tree 37 319750 200922947 Lipid measurement by 1Η-plane It is confirmed that the ethoxyethylation ratio of the hydrogen atom of the perylene group of the acetophenone used is 3.6%, and the unit represented by the formula (1) is a photosensitive resin composed of "%". The composition is a: b: d = l6: 3〇6: 67. 8 (mol%). (Example 2) Synthesis of the photosensitive resin 2 represented by the above formula (A) (i.e., the first in Table i) i type photosensitive resin) A polyhydroxy styrene having a molecular weight (Mw) of 16400 and a molecular weight distribution (Mw/Mn) of 1.09 in a nitrogen atmosphere was dissolved in 350 mL of 1,3- After the dioxapentane ring, distilling under normal pressure to remove i,3_oxathiam, the water content in the reaction system is reduced to less than 1 〇〇卯m. Cool the reaction solution to 2 (TC below, add 62/zL) 35% by weight of hydrochloric acid. Next, 27.9 g of a 1,3-dioxolane solution containing 35 4 wt% of ethyl vinyl ether was added dropwise over 1 hour, and stirred at 3 (rc for 2 hours). 8% by weight of 1,3- ethoxyethoxy phenyl diphenyl fluorene perfluorobutane sulfonate obtained in Synthesis Example 1. After dioxolane, stir at 3 (TC for 2 hours) The mixture was neutralized with aqueous ammonia, and the solution was added dropwise to 2000 g of pure water at room temperature to precipitate a solid. The solid matter was collected by filtration and reprecipitated using acetonitrile and pure water, and dried at 35 ° C for 24 hours. The resin of 52. 〇g. The resin was determined by 1H-NMR, and it was confirmed that the ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the polyhydroxystyrene used was 3 /. 8 ° /. The photosensitive resin represented by the formula (1) is 〇. 6〇%. That is, the composition is a : b : d = 0.6: 30. 8 : 68. 6 (% by mole). (Example 3) 38 319750 200922947 Synthesis of photosensitive resin 3 represented by the following formula (B) (that is, photosensitive resin of the third type in Table 1)

ΟΗ (Β) C4F9S〇3'

V in a nitrogen atmosphere, dissolved in 50. 〇g in polystyrene conversion molecular weight (Mw) of 16400, molecular weight distribution (Mw / Mn; ^ 丨 〇 9 polyhydroxy styrene in 350mL of 1, 3 _ After the oxapenic ring, the 1,3-dioxolane was distilled off under normal pressure, and it was confirmed that the water content in the reaction system was reduced to 100 ppm or less. The reaction liquid was cooled to 2 (r or less, and 35 wt% of 63/^ was added. Hydrochloric acid. Next, 26.0 g of a solution containing 281% by weight of ethyl b, ether 1 ^-dioxolane was added dropwise over 1 hour, and stirred at 3 (rc for 2 hours. Cooling the solution to 15 C, using 30 8.8 g of the mixture containing the synthesis example 2 ethyleneoxyethoxy group "phenyl di("tributylphenyl;; 63.8 wt% L3-dioxa compound After the pentacyclic solution, it was stirred at 30 C for 2 hours. Then, 2 ng of nn-monoamidopyridine was added, and the temperature was increased to 4 (rc. 19.5% by weight of bismuth carbonic acid was added dropwise for 1 hour. The third butyl vinegar is dissolved in dioxopentane ring, and the phase is 319750 39 200922947 at the same temperature (four) for 1 hour. The solution is dropped into 17GGg of pure water at room temperature to precipitate solid matter. After the solid matter was collected by filtration, reprecipitation was carried out using dioxane and hexane, and dried at 35 ° C for 24 hours to obtain a resin of 53. ig. The resin was confirmed by 1 H-NMR to confirm the polyhydroxybenzene used. The hydroxyethylation ratio of the hydrogen group is 21.4%, the unit of the formula (1) is 1.7%, and the third butoxycarbonylation ratio is 9.2%. That is, each composition is a: b: c: d = 1.7: 2L4: 9.2: 67.7 (mol%). (Example 4) Synthesis of photosensitive resin 4 represented by the following formula (C) (ie, table The photosensitive resin of the type II in i)

Under a nitrogen atmosphere, 50. 〇g of polystyrene-converted molecular weight (Mw) of 16400, molecular weight distribution of 09.09 polyhydroxystyrene after 350 mL of 1,3-dioxolane, at atmospheric pressure Distillation to remove 319750 40 200922947

For each of α, it was confirmed that the water content in the reaction system was reduced to 100 ppm to 20 t: or less, and 62/zL of 35 wt% hydrochloric acid was added. 'J, when 27.8 wt% of ethyl vinyl ether was added dropwise, and the dioxolane solution was stirred, and the mixture was stirred at 3 (TC for 2 hours. The solution was cooled to 丨5 C' and dropped into 4 for 30 minutes. 2g of the 4_vinylmercaptooxyphenyldiphenylfluorene perfluorobutane sulfonate obtained in Synthesis Example 3, 63.8% by weight of the plant 3 - dioxapentane solution, at 3 ( The mixture was stirred for 2 hours at rc, neutralized with aqueous ammonia, and the solution was dropped into 2 〇〇〇g of pure water at room temperature to precipitate a solid matter. After solid matter was collected by filtration, acetonitrile and pure water were applied thereto. The precipitate was dried at 35 Torr for 24 hours to obtain a resin of 52.0 g. The resin was confirmed by ^-NMR to confirm that the ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the polyhydroxystyrene used was 30.2%. A photosensitive resin composed of the formula (1) and having a unit of 1% by weight. That is, each composition is a: b: d = i. 〇: 3〇2: 68% by ear) . . . . Example 5) Synthesis of the photosensitive resin 5 represented by the following formula (D) (that is, the photosensitive resin of the first type in the table) 319750 41 200922947

〇2宁/, 宁〇2 F2C, c/CF2 f2 dissolved in a nitrogen atmosphere, 50. Og of polystyrene-converted molecular weight (Mw) of 9000, molecular weight distribution (Mw / Mn) of 1.11 polyhydroxystyrene In 400 mL of the 1,3-dioxolane, it was confirmed that the water content in the reaction system was reduced to 100 ppm or less. The solution was cooled to 15 ° C, and 63 wt% of 35 wt% hydrazine hydrochloride was added. Next, '2. 4g of 1,3-dioxolane containing 3.5.5% by weight of ethyl vinyl ether was added dropwise in 15 minutes, stirred at 151 for 6 minutes, followed by stirring at 30 ° C. 5 hours. The solution was cooled to 15 bp, and 8.4 g of the 4-vinyloxyethoxyphenyldiphenyl fluorenyl ring (1,3-perfluoropropane disulfonate) obtained in Synthesis Example 4 was added dropwise. % of amine salt. 丨% by weight of 一3 dioxolane solution in minutes, followed by 3 generations for half an hour. Adding "28% by weight of ammonia water, and neutralizing (4) or more for neutralization", the solution was dropped into 1 700 g of pure water at room temperature for 1 hour to make a solid matter. Reprecipitation was carried out with a nitrile and pure water of B 319750 42 200922947, and dried for 24 hours at 35 ° C to obtain 53 7 g of a resin. The resin was determined by W-NMR, and the polyhydroxyl group used in the market was confirmed. The ethoxyethylation rate of the argon atom of the hydroxy group of the styrene is 31.8%, and the unit represented by the formula (1) is a photosensitive resin composed of 1.1%. The composition of g 1 'is a. : b : d = l. 1 : 31. 8 : 67. 1 (mole %). (Example 6) The first synthetic formula 6 of the following formula (E), & i _ type Photosensitive resin)

In a nitrogen atmosphere, after dissolving 50. Og of polystyrene, the molecular weight is 16400, and the molecular weight distribution (Mw/Mn) is 1.09, and the molecular weight distribution (Mw/Mn) is 1.39 after the 1,3-dioxolane The hydrazine and 3 to dioxolane were distilled off under normal pressure, and it was confirmed that the water content in the reaction system was reduced to less than 10 ppm. Lengjin 31975〇 43 200922947 The reaction solution was cooled to below 20 °C, and 62//L of 35 wt% hydrochloric acid was added. Next, 27.9 g of a 1,3__ dioxapentane solution containing 35.4 wt% of ethyl vinyl ether was added dropwise over 1 hour, and the mixture was stirred at 30 ° C for 2 hours. The weight of the 4-ethyleneoxyethoxyphenyldiphenylphosphonium bis(perfluoromethanesulfonate) imide salt obtained in Synthesis Example 5 was dropped into 3.5 g of the mixture. After the % 1,3-dioxolane solution, it was stirred at 3 Torr for 2 hours. The lipid is a photosensitive resin composed of an ethoxy group of a hydrogen atom as a result of H-NMR measurement. ! 68. 4 (% by mole). (Example 7) - Neutralization was carried out with aqueous ammonia, and the solution was dropped into 2 g of pure water at room temperature to precipitate a solid matter. After taking the solid matter, the secret chamber was applied with acetonitrile and pure water, and dried under the muscle for 24 hours to obtain a resin of 52. The tree

Synthesis of a photosensitive resin type 7 photosensitive resin represented by the following formula (F) (i.e., the first 319750 44 200922947 trli in Table 1)

OH (F) in a nitrogen atmosphere 'dissolved 50. Og of polystyrene in terms of molecular weight of 16400, molecular weight distribution (heart ^ ^ is 丨 · 〇 9 of polyhydroxybenzene ethyl) 3j0mL of 1,3-dioxine After the penta ring, the hydrazine and t-dioxolane were distilled off under normal pressure, and it was confirmed that the water in the reaction system was reduced to 1 〇〇 ppm or less. The cold P reaction solution was cooled to 20 ° C or lower, and 62//L of 35 wt% hydrochloric acid was added. Next, 27.2 g of 1,3 wt% of ethyl vinyl ether was added dropwise over 1 hour. 3-dioxolane solution at 3 Torr. Stir under the arm for 2 hours. The solution was cooled to 15 C, and 1 g of the 4-vinyloxyethoxyphenyl bis(4__t-butylphenyl) ruthenium 2,4,6 obtained in Synthesis Example 6 was added dropwise over 30 minutes. Triisopropyl 319750 45 200922947 '19.9% by weight of benzoate, i.3-dioxalanyl solution, then mixed at 3 °C for 2 hours' Then, neutralized with ammonia water The solution was dropped into 2500 g of pure water at room temperature to precipitate a solid matter. After the solid matter was taken, it was reprecipitated with acetonitrile and pure water, and dried at 35 for 24 hours to obtain a resin of 7 g. As a result of 1H-NMR measurement, it was confirmed that the ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the polyphenylene styrene used was 32 3%, and the unit represented by the formula (1) was 0.6%. Resin. That is, each level becomes a : b : d = 0.6: 32. 3 : 67. 1 (mole %). (Example 8) Synthesis of photosensitive resin 8 represented by the following formula (G)

In a nitrogen atmosphere, 'dissolve 2 〇. 〇〇g's melon is converted to a molecular weight of 319,750 46 200922947 (Mw) is 16400, 士士θ^ Knife 1 distribution (Mw/Mn) is 1.09 polyhydroxy stupid Above 200mL, after d-doping pentane ring, distilling off oxygen under normal pressure is only possible. It is known that the water in the reaction system is reduced to less than 10Oppm and the cold reaction liquid is below 2〇°c, and 25/zL is added. 35 wt% of salt mash. Next, 11.89 g of a solution containing 37,2% by weight of ethyl ethoxide 1,3-dioxolane was added dropwise over 1 hour, at 3 (Γ(:2), cooling = / combined The solution was added to 15 C, and a solution of 46 g of 4-vinyloxyethoxyphenyldiphenylphosphonium 2,4,6-triisopropylbenzenesulfonate I was added dropwise over 30 minutes. 63. 8% by weight of hydrazine, after the 3 dioxolane solution, was mixed for 3 hours under 3 Torr. Neutralize with ammonia water, and the solution was dropped into the room temperature at room temperature. In the pure water, the solid matter is precipitated. After the solid matter is filtered, it is reprecipitated with acetonitrile and pure water, and dried at 35 t for 24 hours to obtain a resin of the coffee. The resin is determined according to the result of 1H-biliary determination. The ethoxyethylation ratio of the hydrogen atom of the hydroxyl group of the styrene-based styrene used is 33 〇%, and the unit represented by the formula (1) is 〇.6%. The composition is a · b : I 6 : 33. 0 : 66. 4 (mole %). ' (Example 9) Synthesis of photosensitive resin 9 shown by the following formula (Η) 319750 47 200922947

In a nitrogen atmosphere, 'dissolved 20.0 g of polystyrene-converted molecular weight (μ is 16400, molecular weight distribution. Then it is 1〇9 of poly-phenylene 2 〇〇mL of 1,3-dioxolane) Distilling and removing hydrazine and dioxapentane under normal pressure, and confirming that the water content in the reaction system is reduced to less than 1 〇〇 ppm. 'Colding the reaction solution to 2 (below TC, adding 35 wt% of 25/zL) Hydrochloric acid. Next, 12.02 g of a dioxolane solution containing 37.8% by weight of ethyl vinyl ether was added dropwise over 1 hour, and stirred at 3 (rc for 2 hours. The solution was cooled to 15 =, and dropped for 30 minutes). 1.45 g of 66.0% by weight of Synthesis Example 8 4-vinyloxyethoxyphenyl dipyridyl 2 -trifluorodecylbenzenesulfonic acid 1 1 - bis-oxopentane ring solution Thereafter, the mixture was stirred at 3 (TC for 2 hours. Neutralization with feng shui') The solution was dropped into 100 mL of pure water at room temperature to precipitate a solid matter. After the solid matter was collected by filtration, acetonitrile was used. And pure water is applied to the temple again, at q Rτ

The resin was dried by drying at W (10) L for 24 hours. The resin is characterized by the fact that the hydrogen atom of the hydroxyl group of ethylene of 1H-Li R 48 319750 200922947 is 1.4%, and the sense is d=l. 4 : 31. 5 : 67. 1 (Moer measurement result 'is sure The polyacetoxy group having a polyethylation ratio of 31.5% is a compound of the formula (1), that is, each composition is a: b. 0/〇). (Embodiment 10)

Synthesis of photosensitive resin 1 下 represented by the following formula (I)

()

In a helium environment, 'dissolved 20. lg of polystyrene-converted molecular weight (Mw) of 1,600,400, molecular weight distribution (Mw/Mn) g 1〇9 of polyhydroxystyrene in 2j0mL of 1,3 - dioxa After the penta ring, the hydrazine and the 3 dioxolane were distilled off under normal pressure, and it was confirmed that the water content in the reaction system was reduced to 1 〇〇 ppm or less. The reaction solution was cooled to 20 t or less, and 25 wt% of 35 wt% hydrochloric acid was added. The solution was dropwise added to 11.84 g of a 13-dioxolane solution containing 36.4% by weight of ethyl vinyl ether in 1 hour, and stirred at 3 (rc for 2 hours. The solution was cooled to 319750 49 200922947 15 ° C, The Ug was added dropwise to Ug for 30 minutes, containing 68.8 wt% of the [ethyleneoxyethoxy/amp; phenyl n-butylphenyl) vegetable 2_tris-f-benzenesulfonate obtained in Synthesis Example 9. After the dioxolane solution, it was at 3 Torr. Underarm, mix for 2 hours. Neutralization was carried out with aqueous ammonia, and the solution was dropped in 100 mL of pure water at room temperature to precipitate a solid matter. After the solid matter was collected by filtration, it was dried with acetonitrile and pure water and dried at 35 Torr for 24 hours to obtain a resin. The resin was confirmed by the MMR measurement, and it was confirmed that the ethoxyethylation ratio of the hydrogen atom of the phenyl sulfonate group was 35.2%, and the unit represented by the formula (1) was 0.6%. .艮p, each composition is a:b: (four) 6: 35. 2: 64. 2 (mole%). <Evaluation of Exposure Using Xenon Lamp> (Modulating Photoresist and Measuring Breaking Time) θ Dissolving 1 part by weight of the photosensitive resin i obtained in Example 、, and 24 parts by weight of triethanolamine in 5-25 parts by weight In a portion of propylene glycol monomethyl acetate vinegar, a liquid positive resist (photosensitive composition) was prepared by filtration through a filter (PTFE filter). The photoresist was coated on a tantalum wafer (diameter: 4 inches) using a spin coater to pre-bake for 9 seconds at 11 (r, and a film of 5 〇 was obtained). (The wavelength is 248 nm), the photoresist film is exposed, followed by baking at noc (post-exposure heating) for 9 sec. Then, under 23, using a developing solution (2.38% by weight of tetramethyl hydroxide) Ammonium aqueous solution), the failure time is measured. Among them, the failure time refers to the number of seconds required to make the residual film disappear after irradiation with a certain energy. As a result, the failure time is 12 seconds when the exposure amount is 100 mJ, when 5 〇〇 The mJ was 3 seconds. Therefore, the photosensitive resin obtained in Example 1 1 319 750 50 200922947 was exposed to a xenon lamp, and an acid was generated from the photosensitive resin of the present invention, and the acid hydrolysis of the resin was not caused by the acid. The points ^ _ fat 丞邛 丞邛 脱离 , , , 对于 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖 胖According to Zhao Bu, +, Shi Menshi W, all know, ", the same method as above, modulation of the positive photoresist film, after exposure, Pre-bake 卩獍 卩獍 卩獍 里 里 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士In the range of 1 second, it is understood that the photosensitive resin 2 is also exposed to a lamp, and an acid is generated from the photosensitive tree of the present invention (1), and the acid dissociation portion of the polymer is partially separated by the acid. For 29 image liquids, 'from poor solubility to solubility. <Evaluation by exposure to extreme ultraviolet light (EUV)> (Preparation and coating of photoresist) Eight 100 parts by weight of the photosensitive resin obtained in Example 1 3% by weight of triphenyl sulfonamide in 2 parts by weight of propylene glycol military acetic acid test, filtered with a 0.2/zm crucible (PTFE filter) to prepare positive photoresist ° spin coating The photoresist solution was coated on a 4 inch crucible wafer treated with hexamethyldisilazane, and heated by a heating plate for about 9 G seconds before and after liGt to prepare a film thickness of 〇1. a film of uniformity of βπι. Using the same method, photosensitive resins 2 to 1 obtained in Examples 2 to 1 were used. A positive-type photoresist is separately modulated to form a film. (Measurement of sensitivity) Acceleration electrons of lGeV incident from a linear accelerator of Spr i ng_8 of a large-scale radiant light device, polarized electrons in the New SUBARU storage ring 319750 51 200922947 The generated synchronous accelerated radiant light is monochromatically converted into a light having a wavelength of 13.5 nm by using a molybdenum/niobium multilayer film as an exposure light. The liver is irradiated onto the photoresist film formed as described above. After 9 (rc was heat treated up and down for about 6 sec, it was subjected to a 2.38 wt% aqueous solution of 30 sec of tetramethylammonium hydroxide at 23 ° C). Next, the film thickness was measured by a non-contact type film thickness measurement after washing with water and drying. Various operations were performed by diversifying the exposure level, and the exposure amount at which the photoresist residual film thickness was zero was determined as the Eth sensitivity. As a result, with respect to the photoresists of Examples 1 to 1 , Eth was 〇 9 to 6 mJ/cm 2 , respectively. Therefore, it is understood that the photosensitive resin of the present invention is excellent in sensitivity. Further, the result of measuring the amount of gas generated from the photoresist in the exposure by the quadrupole mass spectrometer is less than that of the conventional ESCAP type chemical amplification photoresist having a small amount of gas. It is only about 1/2 to w. Among them, the smaller the amount of gas generated, the less the effect of the mask or the optical system, and the like. <Evaluation by Electron Tracing Apparatus> (Preparation and Coating of Photoresist) Density / gluten solution _ parts by weight of the photosensitive resin U 4 obtained in Example 1 to the triphenyl amide amine in 2 parts by weight of propylene glycol Monomethyl test = vinegar, prepared by filtration using a 0.2... filter (PTFE filter): t photoresist. The photoresist solution was rubbed by a spin coater on a 4 inch wafer to be added; the plate was heated to a film thickness of 〇1/zm for 90 seconds, and Examples 2 to 1 were used. () The obtained photosensitive resin 2 to \=^ 319750 52 200922947 was formed into a positive resist to form a film. The electron beam drawing device was used to accelerate the voltage of 3 〇 keV and the current value τ, in the above-mentioned photoresist film. On the top, the pattern of the line and the gap (Hne and space) of w〇nm is expected to be irradiated. After the irradiation, it is baked at 9 ° C for 60 seconds 'dip at tetrazolium hydroxide at 23 ° C. The aqueous solution was applied in a 2.38 wt% aqueous solution for 3 sec, and then 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 using a scanning electron microscope (SEM). 100. The minimum illumination energy of the line (line and gap 1: 丨) is used as the sensitivity. ~ (line edge roughness) The scanning line electron microscope (SEM) is used to observe the line pattern made under the above sensitivity. Line end roughness (LER). Further, the line end roughness was obtained by multiplying the standard deviation of the dispersion of each point at intervals of 1 〇 nm by three times along the line pattern of the obtained SEM image at a length of 1.5/z m. The smaller the roughness value, the smoother it is. As a result, with respect to the photoresists of Examples 1 to 10, when the sensitivity was 6 4 to 20/zC/cm2, the LER showed 2.0 to 6.0 nm, forming a good pattern. Further, with respect to the photoresists of Examples 1 to ί, an electron beam drawing device having an acceleration voltage of 50 keV was used, and it was confirmed that the resolution of 1 〇〇 ηη or less was obtained. In particular, in the photoresist of Example 7, it was confirmed that the resolution of 25 nm was obtained. Therefore, it was confirmed that the use of the photosensitive resin of the present invention can form a good pattern. 319750 53 200922947 [Simple description of the diagram] M. t »»&gt; [Main component symbol description]

Claims (1)

200922947 X. Patent application scope: 1. A photosensitive resin with the following formula [1, self! ς _ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 4) The heavy weights shown in the early position, if necessary, have the repeating unit shown in the following formula (5). (1) »VS+, r7 x~ : a hydrocarbon group of a valence, ... each independently;; a linear or branched tobacco group, each independently of the table 3 base '...7 can form a divalent organic group, r represents Overcast (2) 319750 55 4 200922947 (in the formula (2), 'R8 represents a linear or branched hydrocarbon group having 2 to 9 carbon atoms) OH (5) 2. The photosensitive resin according to the ninth aspect of the invention, wherein the anion represented by i is an anion represented by the following formula (6), and is not represented by the number of CkHmFnSOs' (6). An integer greater than 0, when m is 〇, k is an integer from 1 to 8 and the number n is 2k+l, and the formula π) is a perfluoroalkyl sulfonate ion; n A is flying (eight)) m., horse 0 In the case of 1 to 15, let m be an integer of 1 or more, and the formula (6) ^the integer ' when the salt ion or the alkylbenzenesulfonate is separated from the S group of the acid salt or the benzoic acid , k is from 1 to 10 mn, each independently is 1 with a besylate ion, substituted with a fluorine (6) is a fluorine-substituted elemental sulfonate ion or a fluorine is used for 319750 56 200922947 alkyl sulfonate Acid salt). 3. The photosensitive resin according to the first aspect of the patent application, wherein the anion represented by Γ is a bis(perfluoroalkylsulfonyl)imide ion represented by the following formula (7), C CpF 2p + l S〇 2) 2N (7) (where p represents an integer from 1 to 8). 4. The photosensitive resin according to item 1 of the patent application, wherein the anion represented by Γ is an anion represented by the following formula (8), 〇 2 N / N, S02 〇 2. (8) ^ 2 Ο 5. The photosensitive resin of claim 1, wherein the weight average molecular weight is 2,000 to 100, 〇〇〇, the number of repeating units a of the above formula (1), the number of repeating units b of the above formula (2), and the above formula ( 3) The number of repetition units c, the number of repetition units d of the above formula (4), and the number of repetition units e of the above formula (5) satisfy a/(a+b+c+d+e)= 0. 001 to 〇. 3, (b+c)/(a+b+c+d+e) = 〇. 1 to 0·5, (d+e)/(a+b+c+d+e) = 〇. 5至〇·8, and e/(d+e) =〇 to 0. 2. 6. The photosensitive resin of claim 3, wherein the terminal group of the main chain is a hydrogen atom or a fluorenyl group. A photosensitive composition which is a solution in which the photosensitive resin of any one of the above items (i) to (6) is dissolved in an organic solvent. 319750 57 200922947 VII. Designated representative map: None (1) The representative representative of the case is: (). (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 8 319750