TW201002667A - Alicyclic structure-containing compound, (meth)acrylate, (meth)acrylic polymer and positive resist composition containing the (meth)acrylic polymer - Google Patents

Abstract

Disclosed is an alicyclic structure-containing compound represented by the following general formula (I): R1-L-X (I) (wherein R1 represents an alicyclic structure-containing group having 5-20 carbon atoms, which is represented by general formula (i) disclosed in the description; L represents a linking group having an ester bond and an ether bond, which is represented by general formula (ii) disclosed in the description; and X represents a halogen atom or a hydroxyl group), which is useful as a raw material for a monomer for photoresists to be used in semiconductor device production or such a monomer. The alicyclic structure-containing compound has excellent exposure sensitivity, solubility, compatibility, defect reduction, roughness improvement and the like. Also disclosed are a (meth)acrylate represented by general formula (II) (wherein R1 and L are as defined for the alicyclic structure-containing compound and R8 represents a hydrogen or the like), which is derived from the alicyclic structure-containing compound, a method for producing the (meth)acrylate, a (meth)acrylic polymer containing a monomer unit derived from the (meth)acrylate, and a positive resist composition.

Description

201002667 VI. Description of the Invention: [Technical Field] The present invention relates to a novel alicyclic structure-containing compound, (meth) acrylate, a method for producing the same, a (meth)acrylic polymer, a positive type Photoresist composition and photoresist pattern forming method. More specifically, it relates to a compound having an alicyclic structure and having an alicyclic structure and having excellent sensitivity, solubility, compatibility, defect reduction, roughness improvement, etc., which is excellent as a photoresist, ( a methyl (meth) acrylate and a method for producing the same, comprising a (fluorenyl) acrylic polymer based on the monomer unit of the (meth) acrylate, and a positive photoresist containing the (fluorenyl) acrylic polymer A composition and a green pattern forming method including the step of forming a ruthenium film using a ruthenium-type green composition. [Prior Art] In recent years, with the development of miniaturization of semiconductor elements, in the photolithography step of the manufacturing process, it is required to be more refined, and various studies have been conducted on the following methods: use corresponding to KrF, ArI^F2 A photoresist material of short-wavelength illumination light such as excimer laser light is formed into a fine pattern. Further, it is desired to present a new photoresist material which can correspond to short-wavelength illumination light such as excimer laser light. As a photoresist material, a large number of expectant resins have been developed as a substrate. However, these materials have a large absorption due to the inclusion of an aromatic ring, and it is impossible to obtain a pattern precision which can correspond to miniaturization. Therefore, as a photosensitive photoresist for fabricating a semiconductor by ArF excimer laser, it is proposed to have an alicyclic skeleton such as methacrylic acid 2, fluorenyl 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ A polymer obtained by copolymerizing a polymerizable compound (for example, see Patent Document 1). However, with the advancement of microfabrication technology, it is currently desired to achieve a line defect of 32 nm or less, but various properties such as exposure sensitivity, resolution, pattern shape, exposure depth, and surface roughening cannot be fully obtained by the prior art. Specifically, it is called LER (Line Edge R〇ughness), LWR (Line Width R〇Ughness, line width roughness), the roughness (roughness) of the pattern surface, or smoothness such as unevenness. The problem has become apparent. Further, in recent years, in the method of exposure by immersion liquid, development defects such as defects (=defect) caused by the immersion medium are also observed everywhere. Furthermore, it is desirable to develop a higher-sensitivity photoresist using the ultraviolet light of 13.5 nm (EUV, Zhe _ 〇 1 called semiconductor manufacturing step in order to improve production f'. In the above, the use of more carbonyl groups has been used. The glycolate resist material achieves an improvement in LER (refer to Patent Document 2)' or by using a long chain extended alkyl chain from a rigid (fluorenyl) acrylic acid chain to achieve a photoresist solvent. Improvement of the solubility (see Patent Document 3). In addition, it is required to have a special performance for photosensitive photoresists that are not only for ArF but also for Euv (Ref., pp., pp. 9 and 1). However, in Patent Documents 4 to 8, the high sensitivity of the photosensitive photoresist has been achieved. However, the above-mentioned required performance cannot be completely obtained by using only these techniques, and thus the photoresist is further improved. Patent Document 1: Patent Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 4,396. 〇6_96965 Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2007-177016. Patent Document No. Japanese Laid-Open Patent Publication No. Hei. No. 2006-227398 (Patent Document No. JP-A-2006-227074). Next, an object of the present invention is to provide a compound containing a lipophilic structure, a (meth) acrylate, a method for producing the same, a (meth)acrylic polymer, and a composition for a positive resist, the above-described alicyclic structure The compound is useful as a raw material for a photoresist for use in the manufacture of a semiconductor device, or a monomer or the like, and is excellent in exposure sensitivity, solubility, compatibility I" reduction in biodefects, improvement in coarse sugar content, and the like, in particular, although it is usually exposed. The sensitivity and the roughness are opposite (compromise), but the properties of the compound containing the alicyclic structure are excellent. The technical means for solving the problem are repeated by the present inventors. After diligent research, it was found that a (meth) acrylate polymer derived from a compound having a large number of carbonyl or ester bonds and actively introducing an oxy-containing alicyclic structure can improve compatibility or light. The solubility of the resist solution, and the solubility of the alkali developer after exposure also become the same, thus also reducing the defects, and further, although the exposure sensitivity is generally opposite (equivalent) relationship with the roughness 140388.doc 201002667 degrees, By stretching the (indenyl) acrylic acid chain and the terminal group, polymerization control which is not affected by the terminal group can be performed, so that the molecular weight distribution can be narrowed, so that the roughness can be improved and the exposure sensitivity can be improved at the same time. The present invention has been completed based on this finding. That is, the present invention provides: 1. A compound having an alicyclic structure represented by the following formula (1): R - LX (I) (wherein R1 is represented by the following formula (1): a group of an alicyclic structure of 5 to 2 Å, "a linking group represented by the following general formula (8), an lanthanide atom or a meridine), [Chemical 1]

It may contain an alicyclic structure having a carbon number of 5 to 2 G, a substituted or unsubstituted cigarette having a reverse valence of 1 to 5, and a substituted or unsubstituted hetero atom. What is the substituted base and the tooth stand for the second base? Base, (d), pendant oxy or amine group. p and q are the same as the integers above. A plurality of R2 can be phased-TR3 can be the same or different), _ can be different in phase, a plurality of _{(Lm-(Le)n}- (ii) (wherein, La is based on the following formula ( b) The Lianshe, which is represented by the company, is based on the following formula, L, Lb and the above-mentioned formula (4), I40388.doc

Take any key sequence. kAm is independently an integer on W 201002667, η is an integer greater than 0), [Chem. 2]

(In the formula, R4 is a hydrogen atom or an alkyl group, and the silk is represented by the formula (i). The base bond (10) of the oxime forms a cyclic knot to form a ring. Structure, r5~r7 #read one ^ mutual key

2. As described above, the alicyclic structure: hydrogen atom or methyl group), (1) to (4), is not represented by the following formula [Chemical 3J (in the formula r1, 〇

'R is the base of the ring structure of the itit formula (1), R4 is independently a gas containing a carbon number of 5 to 20, and the base bond η of the alicyclic ring structure represented by the above formula 140388.doc 201002667 (1) Forming a cyclic structure, a plurality of R4 groups may be bonded to each other to form a cyclic structure, and R5 to R7 are each independently a germanium atom or a fluorenyl group 'X is a halogen atom or a hydroxyl group); 3. a kind of (meth) acrylate type, It is represented by the general formula (11), [Chemical 4] R1 〇 /

And a trifluoromethyl group having a carbon number of 5 to 20, L (wherein R1 is a group of a ring structure represented by the following formula (1): a R8 hydrogen atom, a methyl group, and the following formula (ii) the linked base represented) [Chemical 5]

(In the formula, the Z system may contain an alicyclic structure in which the carbon number of the hetero atom is 5 to 2 Å, and the carbon number of the two hetero atoms is 1 to 5, substituted or unsubstituted, 2: 'R table may not contain A substituted or unsubstituted alkyl group, a hydrazine atom, a hydrazine group, a ruthenium group, a side oxy group or an amine group, and p and q respectively represent an integer of 0 or more. The number of silver R may be the same or different, and the plural R may be the same or different), double-he a)k-(Lb)m-(I/)n}_ (Η) (wherein I/system is as follows Formula () _ (b), _ . U(4) "The joint base, Lb is based on the following corpse, and the La, Tb, and c soils are linked by the following formula (C) L takes the end of the bond sequence ^ k and the claws are independently 1

14〇388.dOC 201002667 On the sound of the gold, the main enemy 'η is an integer greater than 0), [Chem. 6]

(a) (b)

c (wherein R is a hydrogen atom or & _ containing an alicyclic structure which is carried by Α山/' 乂 The knot represented by the above formula (1) forms an if makeup & ^ ό5 7-shaped structure, a plurality of R4 Mutual bond-like structure, R5~R7 are independent of κ 4 such as Bu / independent of ruthenium atom or methyl); _ said (meth) acrylate, said by the dragon - as follows In the general formulae (5) to (8) [Chemical 7]

(wherein R1 is a group having a ring-containing structure represented by the above formula (1), and R4 is independently a number of 5 to 20 of a fat _ horse 虱 atom or a fluorenyl group, and can be represented by 卜, +, £ 靡The group containing the alicyclic structure is bonded to form a cyclic structure!: R, mutually bonded to form a cyclic structure, r5~r(tetra), plural or f-group, R8 is a hydrogen atom independently a hydrogen atom F group, a sulfonium atom or a trifluoromethyl group; I40388.doc 201002667 5_ a (meth) acrylate such as the above 3 or 4, wherein the above z is an adamantyl ring; 6. a species of (meth) acrylate A method of producing a compound containing an alicyclic structure such as the above hydrazine or 2 and a (meth)acrylic acid, a (meth)acrylic acid halide, a (meth)acrylic acid anhydride, and a (meth)acrylic acid The above-mentioned 3 or 4 (meth) acrylates are obtained in the _2-hydroxyalkyl vinegar derivative, and the (meth)acrylic polymer, (meth) a monomer unit of an acrylate type; 8. a positive type resist composition containing the (meth)acrylic acid polymer as described above 7; 9. A photoresist pattern forming method, comprising: a step of forming a photoresist film on a support using a positive complex as described above; a step of exposing the photoresist film; and selectively exposing The photoresist film is subjected to a step of inspecting the shirt to form a photoresist pattern. EFFECTS OF THE INVENTION Secondly, the (meth)acrylic acid derived from the compound containing an alicyclic structure is singular and sturdy, and has solubility, compatibility, and reduction, roughness improvement, exposure sensitivity, and the like. Excellent. [Embodiment] The compound having an alicyclic structure is represented by the following formula (1). Χ (I) Ring structure J 乂 : The formula (1) indicates that the carbon number is 5 to 2. The base of the lipid, L is a linking group represented by the following formula (ii), and is a letter 140388.doc 10 201002667 Atom or hydroxyl group, [Chemical 8]

(In the formula 7, the Z system may contain a hetero atom having a carbon number of 5 to 20, preferably m 7 to u, and a better number of turns is

The carbon number of the sub-... is just the base ring. The R2 system may contain a divalent hydrocarbon having a carbon number of 1 or 2, a dibasic hydrocarbon group, a preferred or unsubstituted hydrocarbon group, and a cleavage group indicating a substituent or amine which may contain a hetero atom. Base, preferably, element, original:, chaotic, silk, side oxygen independently represent the integer above 〇, #土 or side reduction. p and q respectively, several R2 can be the same, scoop 疋〇 5 is better 〇~2. In addition, a plurality of R3s may be the same or different); {(LV(LW) small(ii) (wherein I/ is a linking group represented by the following formula (8) = a linking group represented by 'Lb' or less The above formula is also a combination of the above-mentioned formula (4), an integer, a preferred order. kAm is independently 1 or 丨), or 2.11 is an integer above ,, preferably 0 [化9]

140388.doc ‘11· 201002667 (b) c (in the formula R4 hydrogenogen)

a sub- or a calcination group, the base bond of the alicyclic ring-containing structure (4) is formed into a ring structure represented by the formula (1), and a ring structure is formed, r5~r7^, Ό structure, and a plurality of bonds 4 can be mutually bonded as the above-mentioned knife 1 Independently a helium atom or a methyl group). The halogen oxime, the atom and the iodine atom in the above formula (I). The alicyclic structure in which the number of carbon atoms which may contain a hetero atom and which has a carbon number of 5 to 20 may be exemplified by a cyclopentyl ring, a ro group ring, a cyclodecyl ring (tetra) ring, Cyclooctyl ring, Fuyi production, #, soil clothing, decahydronaphthalene ring (perhydronaphthalene ring), stagnation 癸 strict production "isocarbyl%, diamond justification ring, three rings [5.2.1. 〇 2 ,6] : ring r.°f'17, twelve-ring ring and other single-ring or multi-ring knot ring, 4-oxa-tricyclic ring 4 2丨3,7 one today he Η.ζ.ι .υ] decane-5-one, 4,8-:^三环卜.2·1.03,7]壬烧,心氧杂-三环 [4.3丄门〗10: Single or multi-ring In the formula, vinegar, tetrachlorine, tetracycline 'made an alkane early ring or polycyclic _ 'and these perfluorinates, etc. 乍 is the upper 逑 formula (1) can contain heteroatoms, the carbon number is Specific examples of the substituted unsubstituted divalent nicotine group include a linear or branched bond-forming group such as a methylene group or an exoethylene group or a total vaporized group thereof. Specific examples of the substituted or unsubstituted I40388.doc 12· 201002667 alkyl group which may contain a hetero atom in the above formula (1) include methyl group, Linear, n-propyl, isopropyl, n-butyl, t-butyl, tert-butyl, n-pentyl, isopentyl, hexyl, heptyl, octyl, decyl, fluorenyl, etc. a branched alkyl group or a total vaporized product. The alicyclic structure which may contain a hetero atom having a carbon number of 5 to 2 Å may be substituted or unsubstituted having a carbon number of 1 to 5 which may contain a hetero atom. The divalent hydrocarbon group and the hetero atom which may be contained in the substituted or unsubstituted alkyl group which may contain a hetero atom may, for example, be a nitrogen atom, a sulfur atom or an oxygen atom.

I, as the alkyl group in the above formula (a), may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl or isodecyl. a linear or branched alkyl group such as a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group. In addition, examples of the cyclic structure in which R4 is bonded to a group containing an alicyclic structure represented by the above formula (1) or a plurality of R4 are bonded to each other include tetrahydrofuran and tetrahydropyran, [1, 4] Residues such as dioxane. ί) The L in the above formula (1) is a divalent linking group represented by the above formula (ii), and is composed of the above-mentioned linking groups I/, Lb and 1/. These linking groups form a linking group L by any bonding sequence. In the case where the linking group [containing at least one of a plurality of linking groups La, Lb & Lc, the linking group. The mutually connecting bases Lb and the connecting bases Le may be the same or different, and the same type of linking groups may be bonded to each other without being adjacent to each other. Specifically, it may be a bonding sequence such as [a·Lb-La. The above-mentioned linking group L is preferably a linking group represented by the following formula (m) or (iv). Μ 140388.doc -13- 201002667 -La-Lb- (iii) -La-Lb-Lc- (iv) (wherein l is a linking group represented by the above formula (a), and Lb is represented by the above formula w The linking group of the above formula "is the "r linkage group of the above formula (4).) Further, the compound of the present invention containing the alicyclic structure is preferably any one of the following general formulae (1) to (4). Said, [10]

(wherein R1 is a group having an alicyclic structure having a carbon number of 5 to 20 represented by the above formula (1), and RV is independently a hydrogen atom or a burnt group, and may be contained in the above formula (1) „The base bond of the structure (4) is a ring structure, and the complex number (10) can be bonded to each other to form a cyclic structure, r5~r, independently a hydrogen atom or a methyl group, and X is a halogen atom or a hydroxyl group, which can be used as R4 to r7 in the above formulae (1) to (4) are the same as those in the formulae (a) to (c), and R4 to r7 in the above formulae (1) to (4) (1) Table: The ring-bonding structure of the % fat-containing structure or the cyclic structure in which a plurality of r4 are bonded to each other, and examples thereof include residues of tetrahydrogenin, tetrahydron-t, and [M] The fluorine atom, the halogen atom in the above formulas (1) to (4), 140388.doc -14- 201002667, a chlorine atom, a bromine atom, and an iodine atom are used as the above formula (1) to (4). Specific examples of the alicyclic structure-containing compound of the present invention represented by the formula include 2-(cyclopentyloxy decyloxy)_2_sideoxyethanol and 2-(cyclohexyloxymethoxy)_ 2 - side oxygen B , 2_(cycloheptyloxymethoxy)_2_sideoxyethanol, 2-(cyclooctyloxymethoxy)-2-oxoethanol, 2-(cyclodecyloxymethoxy)_2_ side Oxyethanol, 2-(cyclodecylmethoxy)_2_sideoxyethanol, 2-(cyclodecalinoxycarbonyloxy)-2. ethoxyethanol, 2-(cyclopentadienyloxy) Oxy)_2_ side oxyethanol, 2-(3⁄4 methoxy methoxy)_2_ pendant oxyethanol, 2-(isodecyloxymethoxy)-2-oxoethanol, 2-(3-three Ring [5.2.1 ·〇2,6]decyloxymethoxy)-2-oxoethanol, 2-(3-tetracyclo[4.4.0.12,5.17,10]dodecyloxymethoxy )-2-oxoethanol, 2-(1-adamantyloxycarbonyl)_2_sideoxyethanol, 2-(2-adamantyloxymethoxy)_2_sideoxyethanol, 2_ (1_Adamantyl methoxymethoxy)-2-oxoethanol, 2-(2-(1-adamantyl)ethoxymethoxy)-2-oxoethanol, 2-( 5-hydroxy-2-adamantanylmethoxy)-2-oxoethanol, 2-(3,5-dihydroxy-1-adamantyloxymethoxy)-2-oxooxy Ethanol, 2-(4-o-oxy-1 adamantyloxymethoxy)-2-oxoethanol, 2-(4-sideoxy-2 _Adamantyloxymethoxy)_2_ pendant oxyethanol, 2-(2-cyanoguanidino-2_adamantyloxymethoxy)_2_sideoxyethanol, 2-(1-γ-butyl Lactamyloxymethoxy)_2_sideoxyethanol, 2_(5-(2,6-norbornanecarbonyl lactone)oxymethoxy)_2_sideoxyethanol, 2-(5 -(7-oxa-2,6-norfosanecarbonyl lactone)oxymethoxy)_2_sideoxyethanol, 2-(8-(4-oxa-tricyclo[4.3.1.13' 8] undecane _5-keto)oxymethoxy)-2-oxoethanol, 2-(perfluorocyclopentyloxy decyloxy)_2_sideoxyethyl 140388.doc •15- 201002667 Alcohol, 2-(perfluorocyclohexyloxycarbonyl)_2_sideoxyethanol, 2_(perfluoro_ι_adamantyloxymethoxy)-2_sideoxyethanol, 2_(perfluoro-丨_Adamantyl methoxy oxime)-2-oxoethanol, 2-(3-hydroxymethyl-perfluoro-fluorenyl-adamantyloxymethoxy)_2-oxoethanol, 2-(1-(1-adamantyloxy)ethoxy)-2-oxoethanol, 2-(1_(2-_adamantyloxy)ethoxy b-2-oxyethanol, 2-( 2-tetrahydrofuranoxymethoxy)_2_sideoxyethanol, 2-(2·tetrahydropyranoxymethoxy)-2- Oxyethanol, 2-(2-(1,4-dioxanyl)oxymethoxy)-2-oxoethanol, 2-(2-(1-adamantyloxycarbonyl) 2-sided lactyl ethoxy)ethanol, 2-(2-(2-adamantyloxymethoxy)_2_sideoxyethoxy)ethanol, 2-(1-adamantyloxymethoxy) Methoxy)-2-oxoethanol, 2-(2-adamantyloxymethoxymethoxyethoxyethanol, 2-(2-(1-adamantyloxymethoxymethoxy)) _2_Sideoxyethoxy)ethanol 2-(2-(2-adamantyloxymethoxymethoxy)_2_sideoxyethoxy)ethanol, 2-(cyclopentyloxymethoxy) ) _ _ _ ethoxyethyl chloride, 2-(cyclohexyloxymethoxy)-2-oxoethyl carboxide, 2-(cycloheptyloxymethoxy) 2 _ oxyethyl Chloride, 2-(cyclooctyloxymethoxy)_2_sideoxyethyl chloride, 2-(cyclomethoxymethoxy)_2_sideoxyethyl vapor, 2_(cyclodecyloxy) Methoxy)-2-oxoethylethyl chloride, 2-(cyclodecahydronaphthalenyloxy)-2-oxoethylethyl chloride, 2·(cyclopentanoxyoxyloxy) )_2_Sideoxyethyl chloride, 2-(3⁄4oxymethoxy)_2_ Oxyethyl oxylate, 2-(isofosoxymethoxy)_2_sideoxyethyl chloride, 2_(3_tricyclo[5_2·1.〇2'6]decyloxymethoxy _2_ side oxyethyl vapor, 2_(3_tetracyclo[4.4·〇·ΐ2,5·ι7, 'dodecyloxymethoxy)_2_sideoxyethyl chlorination 140388.doc 16 201002667, 2-(1-adamantyloxymethoxy)_2_sideoxyethyl vapor, 2_(2_adamantyloxymethoxy)-2-oxoethylethyl chloride, 2_ (1_adamantyloxymethoxymethoxy)-2-oxoethylethyl chloride, 2-(2-(1-adamantyl)ethoxyethoxy)-2-oxoethylethyl chloride , 2_(5-hydroxy_2_adamantyloxycarbonyl)-2-oxoethylethyl chloride, 2_(3,5-di-trans-yl-adamantyloxycarbonyloxyl -2-oxoethylethyl chloride, 2_(4-side-adamantyloxymethoxy)-2-oxoethyl carboxide, 2_(4_sideoxy-2-methanol Oxymethoxy)-2-oxoethyl methoxide, 2-(2-cyanomethyl-2-ethyl-adamantyloxycarbonyl); 2_side oxyethyl vapor, 2_(1 _丫-butyrolactoneoxymethoxy)-2-oxoethylethyl chloride , 2_(5_(2,6_nordecanecarbonyl lactone)oxymethoxy)_2_sideoxyethyl chloride, 2_(5_(7_oxa-2,6-norbornanecarbonyl) Lactone oxy methoxy wide 2_sideoxyethyl vapor, 2-(8-(4-oxa-tricyclo[4.3丄丨3'8]undecane-5-one)oxy Methoxy)_2_ oxoethyl chloride, 2-(perfluorocyclopentyloxymethoxy)_2_sideoxyethyl vapor, 2-(perfluorocyclohexyloxydecyloxy) _2_Sideoxyethyl chloride, 2-(perfluoro-1-adamantyloxymethoxy)_2_sideoxyethyl vapor, 2-(perfluoro-1-adamantylmethoxy) Methoxy)_2_sideoxyethyl vapor, 2-(3-hydroxyindenyl-perfluoro-fluorenyl-adamantylmethoxymethoxy)_2_sideoxyethyl vapor, 2- (1-(1_adamantyloxy)ethoxy)_2_sideoxyethyl chloride, 2-(1-(2-adamantyloxy)ethoxy)_2_sideoxyethyl chloride , 2-(2-tetrahydrofuranoxymethoxy)_2_sideoxyethyl chloride, 2_(2-tetrahydropyranyloxymethoxy)_2_sideoxyethyl chloride, 2_( 2-(1,4-dioxohexyl)oxydecyloxy)_2_sideoxyethyl chloride , 2_(2_140388.doc -17- 201002667 adamantyloxymethoxy)-2-oxoethoxyethoxy) gas, 2_(2_(2_adamantyloxymethoxy)-2·side oxygen Ethoxylated gas, 2 servant alkoxy methoxy methoxy) 2_sideoxy vapor, 2_(2_adamantyloxymethoxymethoxy)_2_sideoxy gas , 2_(2_(1_adamantyloxymethoxymethoxy)-2-oxoethoxyethoxy) chloride, 2_(2_(2_adamantyloxymethoxymethoxy)- 2-sided oxyethoxy) chloride, 2-(cyclopentyloxymethoxy)_2_sideoxyethyl desert, 2-(cyclohexyloxymethoxy)-2-oxoethoxy Base desert, 2_(cycloheptyloxymethoxy side ethoxyethyl desert, 2-(cyclooctyloxymethoxy)-2-oxoethylethylate, 2-(cyclodecyloxy) Methoxy)_2_sideoxyethyl desert, cyclodecyloxymethoxy)_2_sideoxyethyl desert, 2—(cyclodecahydronaphthalenyl)>2-side oxygen m odor, 2_(cyclopentanyloxymethoxy) winterside oxyethyl bromide, 2_(pentoxymethoxy)_2•side oxyethyl evolution, 2-(isofoxylmethoxy) _2_side oxygen Ethyl evolution, 2_(3_tricyclo)^'" methoxy oxy oxime oxime oxyethyl bromide ^ (1) - 4% [4.4.0.1 .1 ] dodecyloxy methoxy Side oxyethyl bromide 2 (1 hexamethyleneoxymethoxy)_2_sideoxyethyl desert, 2 chloropredoxy methoxy methoxy)-2_side oxyethyl evolution, called Adamantyl methoxymethoxy) 2-sided oxyethylaceline, adamantyl) ethoxymethoxy) 2-oxoethyl bromide, 2_(5·hydroxy·2·金刚Alkoxymethoxy)-2-oxoethylethylate, 2_(3,5-di-pyrrolidinylmethyl-methoxy)_2-sideoxyethyl evolution, 2_( 4_Sideoxy xiaojingang oxymethoxy)_2_sideoxyethyl desert, 2_(4_sideoxy_2_adamantyloxymethoxy)_2_sideoxyethyl desertification , 2_M-methyl group_140388.doc -18- 201002667 2-adamantyloxymethoxy)_2_sideoxyethyl bromide, 2_(1_丫·butyrolactoneoxymethoxy)- 2-sided oxyethyl bromide, 2-(5-(2,6-nordecanecarbonyl lactone) fluorenyl decyloxy)_2_ fluorenylethyl bromide, 2-(5-( 7-oxa-2,6-lower Alkylcarbonyl lactone oxymethoxy) 2_side oxyethyl bromide, 2-(8-(4-oxa-tricyclo[4.3.1.ι3,8]undecane-5-one) )oxymethoxy)-2-oxoethyl bromide, 2-(perfluorocyclopentyloxy methoxy)-2-oxoethyl bromide, 2-(perfluorocyclohexoxy oxime) Oxy)_2_ side oxyethyl bromide, 2-(perfluoro_1_adamantyloxy methoxy)_2_side oxyethyl bromide, 2-(perfluoro_ι_adamantyl Oxymethoxyoxy)_2_sideoxyethyl bromide, 2-(3-hydroxymethyl-perfluoroadamantylmethoxymethoxy)-2-oxoethyl bromide, 2_( 1_(1_adamantyloxy)ethoxy)_2-sided oxyethyl bromide, 2-(1-(2-cyanoalkoxy)ethoxy)_2_sideoxyethyl bromide, 2 -(2-tetrahydrofuranoxymethoxy)_2_sideoxyethyl desert, 2-(2-tetrahydropyranyloxycarbonyl)_2_sideoxyethyl bromide, 2-(2 -( 1,4-dioxanyl)oxymethoxy)_2_sideoxyethyl bromide, 2-(2-(1-adamantyloxymethoxy)_2_sideoxy B Oxy) bromide, 2-(2-(2-adamantyloxymethoxy)_2_ side Oxyethoxyethoxy) bromide, 2-(1-adamantyloxymethoxy)_2_sideoxy bromide, 2-(2-adamantyloxymethoxymethoxy)_2_ Side oxybromide, 2_(2_(Bukincalineoxymethoxymethoxy)_2_sideoxyethoxy) bromide, 2_(2_(2-adamantyloxymethoxymethoxy) _2_ side oxyethoxy) bromide and the like. Among the compounds having an alicyclic structure, from the viewpoints of properties and ease of production, 2-(1-adamantyloxymethoxy)> 2-sided oxyethanol, 2-(2- Diamond oxymethoxy)_2_sideoxyethanol, 2_(1_adamantane I40388.doc -19· 201002667 oxymethoxy)-2-oxoethyl chloride, 2-(2- Adamantyloxymethoxy)-2-oxoethyl carboxide, 2-(1-adamantyloxycarbonyl)-2-oxoethyl bromide, 2-(2-adamantane Oxymethoxy)-2-oxoethylethylate, etc. Specific examples of the chemical formula of the alicyclic structure-containing compound of the present invention are shown below, but the present invention is not limited thereto.

140388.doc -20- 201002667 [Chem. 13]

α

^p°^Cl --- "^·〇-^〇-^—CJ^^xr^xr^or31^*χι

-S^o

140388.doc -21 - 201002667 [Chem. 15]

The alicyclic structure-containing compound of the present invention can be produced by various methods, and the following examples are exemplified, but are not limited thereto. a. The alcohol having an alicyclic structure is reacted with a hydrogen peroxide gas in the presence of an aldehyde to esterify the thus obtained oxime etherate with a 2-hydroxycarboxylic acid. b. reacting the alcohol having an alicyclic structure in the presence of an alkyl sulfoxide and an acid anhydride to obtain a sulfur-burning alkyl etherate, and using the chemical agent to make the sulfur-burning alkyl etherate into 140388.doc -22-201002667 The halogenated alkyl ether compound is further esterified with a 2-based base acid. C_ The alcohol having an alicyclic structure is reacted with a functional hydrogen gas in the presence of an aldehyde to esterify the thus obtained tooth methyl etherate with a 2_-carboxylic acid. D_ reacting an alcohol having an alicyclic structure in the presence of an alkyl sulfoxide and an acid anhydride to obtain an alkylthioalkyl etherate, and using a toothing agent to make the thioalkyl etherate a halogenated alkyl etherate, thereby 2 - Halogenated carboxylic acids are esterified.

e. The alicyclic structure-containing compound obtained in the above a or b is etherified with hydrazine, 2-dihaloethane or 2-dentate ethanol (sterol). f. The compound having an alicyclic structure obtained in the above c or d is shouted with 2 - chitosan (-alcohol) or ethylene glycol. Examples of the aldehydes include linear or branched aliphatic aldehydes such as furfural, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, and isobutyraldehyde. / The above-mentioned hydrogen-generating gas' may, for example, be a monomer gas such as hydrogen fluoride gas, hydrogen chloride gas or hydrogen bromide gas or a mixed gas thereof. Examples of the alkyl anthracene include dimethyl sulfoxide, diethyl secondary, di-n-propyl fluorene, diisopropyl hard, di-n-butyl sorbite, and butyl. Symmetrical or asymmetric fats such as sulfone, 2-butyl sulfoxide, di-t-butyl arylene, diisoamyl sulfoxide, methyl ethyl sulfoxide, decyl-t-butyl argon The family is crushed. Examples of the acid anhydride include aliphatic or aromatic carboxylic anhydrides such as acetic anhydride, propionic anhydride, butyric acid-/, butan anhydride, valeric anhydride, pivalic anhydride, benzoic anhydride, gas acetic anhydride, and difluoroacetic anhydride. . / 乍 is the above m, for example, sulphur sulphide gas, gamma chloride, sub-n sulfite gas, desert chloroform, etc. i-generation sulfide 140388.doc -23- 201002667, or phosphorus trichloride Phosphorus compounds such as phosphorus, triiodide, tri-phosphoric acid, tri-phosphoric acid, phosphorus pentoxide, and phosphorus pentabromide. Examples of the above-mentioned 2_subtractive (four) type include, for example, glycolic acid, lactic acid & propylpropionic acid, 2, butylbutyric acid, and the like, and the like, and the acid-hepatic, as the 2-dentate carboxylic acid, for example. For example, 2'------- bromo-acetic acid, 2- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ As the above 1,2-di-generation ho _, &, _ generation 颏 颏 颏 颏 颏 颏 颏 颏 颏 颏 颏 颏 颏 颏 颏 颏 颏 颏 颏 颏 颏 颏 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 臭 臭 1 1己,ρ. 铁乙坑,1-演-2-气乙,^漠- 2-iodoethane, 1-气-2-iodoethane, 丨, 臭# 22_虱propane, 1-bromo a symmetrical or asymmetrical 1,2-halogenated aliphatic hydrocarbon of -2-iodopropane. Examples of the above-mentioned 2-haloethanol (-alcohol)-based ore, hydrazine, and hydrazine are as follows: 2-chloroethanol (虱%) '2-bromoethanol (bromo alcohol), 2-iodoethanol ^ 9 X匕, alcohol) 2 - chaotic-n-propanol, 2-> odor-n-propanol, 2-iodo-n-propanol, 2 惫 2 2 - n-butanol, 2-but-n-butanol, 2 -Iodine-n-butanol, 2-chloroisopropanol, 2 scorpion scorpion 筮 丁 diisoisodol, 2-iodoisopropanol, 2-indole-butanol, 2-bromo-second butanol, A linear or branched 2-ary aliphatic such as iodine-second butanol, 21-butanol, 2-bromo-t-butanol, drunken 2虱-dier, m-butanol alcohol. 〃 X-bonded form As the above-mentioned ethylene glycols, for example, alcohol), 1,2·propylene glycol (propylene glycol), and diethyl hydrazine? , 2_ethylene glycol (Ethylene di- 1,2-di-based aliphatic cigarette. % or the like # or asymmetric of the above-mentioned halogenated metrobenide is obtained by reacting an alcohol of the group with an i hydrogen gas In the lower or non-existent presence of the alicyclic ring-containing structure, it can be carried out in the presence of an organic solvent. The use of organic solvents is as long as the concentration of the matrix of the saturated mellow-containing alcohol-containing alcohol Below the degree, there is no special limit I40388.doc •24- 201002667

Preferably, it is adjusted such that the substrate concentration is about θ"m〇l/L~l() m〇l/L. If the substrate concentration is θ jm〇l/L or more, the necessary amount can be obtained by using the usual reaction benefits, so that it is economically preferable, and if the base exhibitance is 10 m〇l/L or less, the reaction liquid Temperature control is easier and better. Examples of the organic solvent which can be used include hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene, a hydrocarbon solvent such as benzene, diethyl ether monobutyl ether, THF trahydrofuran, tetrahydrofuran. ), dioxane, DME (dimethoxy ethane), etc. (4) solvent, dioxane, tetra-carbonized carbon, etc.

The above is mixed. Preferably, the tooth-based solvent having a higher dissolved amount of the hydrogenated hydrogen gas is preferred. Further, the reaction temperature may be any temperature, but if it is too high, the mass of the hydrogen gas is lowered, and if it is too low, the reaction itself is slowed, so nc is preferable. The M force can take any pressure, but if it is a pressurized condition, it is also necessary to control the side reaction, so it is preferably normal pressure. When the pressure is too high, a special pressure-resistant device is required, which is uneconomical. The above alkylthioalkyl etherate is obtained by reacting an alcohol having an alicyclic structure in the presence of an alkyl group and an acid anhydride. In this case, it can be carried out in the presence or absence of an organic solvent, but usually, a reaction is carried out by using a large amount of an excess of an alkyl sulphate and an acid anhydride as a reaction reagent, and as a reagent. In the case of additionally using an organic solvent, it is preferable to use a ruthenium such that the concentration of the matrix is about 1 mol/L to 10 mol/L or more, and it is more than mol/L. Well, the temperature control of the liquid becomes easy, and the necessary amount can be obtained in the usual reactor, and it is preferable if the base of the base is 1 〇m〇l/L or less. As an organic solvent that can be used, it can be exemplified by a hydrocarbon solvent such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, toluene or xylene, and a double bond or a dibutyl group. Ether, THF (tetrahydrofuran), two p-burning, DME (dimethoxyethane) and other ether-based solvents, two gas-fired, tetrachlorite anti-Team halogen bath, §Hai can use one or two More than one kind of mixture is used. The reaction temperature may be any temperature, but if it is too high, the selectivity is lowered by the side reaction, and if it is too low, the reaction itself is slowed down, so it is preferably room temperature to 60. (: The pressure may take any pressure, but if it is a pressurized condition, it is also necessary to control the side reaction, so it is better to be normal pressure. If the pressure is too high, a special financial device is required, which is uneconomical. The ether group is obtained by reacting an alkylthioalkyl etherate with a halogenating agent. In this case, it may be carried out in the presence or absence of an organic solvent, or a large amount of a reagent may be used as a reaction reagent. When the organic solvent is additionally used, it is preferred to adjust the concentration of the substrate to a concentration of about 0.1 m〇1/L to 10 mol/L. If the substrate concentration is 0.1 m〇1/L or more. 'There is a necessary amount by using a conventional reactor, so it is economically preferable. If the substrate concentration is 1 〇m〇i/L or less, the temperature control of the reaction liquid becomes easy and preferable. Organic solvent: can be listed as: the ancestral solvent of the ancestral home, the Gengyuan, the cyclohexanone, the ethylcyclohexene, the benzene, the jiaben-jiaben, the second screaming, the second screaming, and the (tetrachlorine) , No. 2, DME (dimethoxyethane), etc. A gas such as a gasified carbon such as a gasified carbon, which may be used alone or in combination of two or more. The reaction temperature may be any temperature, but if it is too high, the material may be lowered by the side reaction, and if it is too low, It is slower to carry out, so it is better to use room temperature. The pressure can be any pressure. If it is 140388.doc •26- 201002667, the pressure reaction must also control the side reaction, so it is better to be normal pressure. When the pressure is too high, a special pressure-resistant device is required, which is uneconomical. The above esterification and etherification can also produce a salt in the system by causing a base to act on the alcohol containing the alicyclic structure and the reaction reagent, which can be The water produced by the azeotropic dehydration reaction is forcibly removed to the outside of the system to promote the reaction. The above esterification and etherification can be carried out in the presence or absence of an organic solvent, and in the case of using an organic solvent, it is preferred to The substrate concentration is adjusted in a manner of about 0.1 mol/L to 10 m〇l/L. If the substrate concentration is 0.1 mol/L or more, the necessary amount can be obtained by using a usual reactor, and thus it is economically preferable. If the substrate concentration is 1 When 〇m〇1/L or less, temperature control of the reaction liquid becomes easy, and examples of the usable organic solvent include hexane, heptane, cyclohexane, ethylcyclohexane, benzene, and toluene. A hydrocarbon solvent such as diphenylbenzene, an ether solvent such as diethyl ether, dibutyl ether, THF (tetrahydrofuran), dioxane or DME (dimethoxyethane), methylene chloride or tetrachae fossil. Solvent 'DMF (dimethylformamide, N, N-dimethylformamide), DMSO (dimethylsulfoxide, dimethylsulfoxide), NMP (N-methyl-2-pyrrolidone, N-mercapto-2-pyrrolidone ), HMPA (hexamethyl phosphoric triamine), HMPT (hexamethyl phosphorous triamide), carbon disulfide and other aprotic polar solvents, which may be used alone or in combination of two or more use. Examples of the base include sodium hydride, sodium hydroquinone, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, silver oxide, sodium phosphate, potassium phosphate, disodium hydrogen phosphate, and hydrogen phosphate. Potassium, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium decyl alcohol, tert-butanol 140388.doc -27· 201002667 Potassium, triethylamine, tributylamine, trioctylamine, acridine, n, n _Dimethylaminopyridine, DBN (1,5-diazabicyclo[4,3,〇]decane-5-ene), DBU(1,8-diazabicyclo[5,4,0] Inorganic test and organic amines such as eleven burned _7_ return). In the case of the azeotropic dehydration reaction, as the solvent, (iv) oxime is selected from a flue-based solvent such as cyclohexane, ethylcyclohexane, toluene or xylene. The addition ratio of the reaction reagent to the alcohol having an alicyclic structure is about 1 to 1 〇〇 〇 〇 1 , and preferably K 5 times mG 卜 ( 4 ) is an alcohol having an alicyclic structure, and the amount of the base is (M~H) times the mol or so 'the ideal is w$ times the 丨. The reaction temperature is -200 to 20 (about TC or so, preferably _5 〇 ~1 〇 (Γ. Further, the reaction pressure is about 0.01 to 10 MPa in absolute pressure, preferably atmospheric pressure; When the reaction time is long, the residence time becomes longer, and when the pressure is too high, a special pressure-resistant device is required, which is uneconomical. In the above-mentioned reaction, the reaction liquid after the reaction is separated into an organic layer of the water tray. The product may be extracted from the aqueous layer as needed. The compound containing the alicyclic structure of the present invention may be obtained by subtracting π # ' from the reaction liquid by means of the chlorogen. The purification may be carried out or the reaction may be carried out without purification. The liquid is supplied to the second, and as a purification method, it is possible to consider the purity of the core mold and the purity of the brother mold, and the purification method from the distillation, the decantation, the activated carbon adsorption, the ruthenium column chromatography, etc. It is better to use the extraction cleaning or crystallization because of the extraction and crystallization. The reason is that it can be operated at a relatively low temperature, and the sample is processed. (Methyl) Acrylose citrate members are listed in the following formula (II) 140388.doc -28- I) 201002667 [Chem. 16]

The base of the ring structure, R8 3 is present (wherein R1 is represented by the following formula (1)

5 to 20 of the fluorofluorenyl group, L (wherein the Z system may contain a carbon number structure of a hetero atom, more preferably a diamond _. == the carbon number of the subunit is 1 to 5% of the ,, ' 3 has a sputum gingivitis, silky or unsubstituted hydrocarbon group, preferably

J:: is a divalent hydrocarbon group of 1 or 2. R3 represents a substituted A group which may contain a hetero atom: a thiol group, a fluorenyl group, a thiol group, a cyano group, a sulfhydryl group, a pendant oxygen group, and preferably a south atom, a (tetra) atom or a pendant oxy group. ... each of the integers above, preferably 0 to 5, more preferably 〇~2. The plural numbers may be the same or different, and the plural numbers may be the same), ~((L )k-(Lb)m-(LC)n}- (ii) (wherein the La system is represented by the following formula (4) The linking group, Lb is a linking group represented by the following formula (), Lc is a linking group represented by the following formula (c), and P, 〇 and a wide variety of bonding sequences are available. An integer, preferably 丄 or an integer of 2.4 〇 or more, preferably 140388.doc 禆 below, a f atom, a methyl group, a fluorine atom or a linking group represented by the following formula (li)), — [化17]

•29· 201002667 0 or 1 ), [Chem. 18]

The lipid-containing ring-junction hydrogen atom or the courtyard group may be bonded to the group represented by the above formula (1) to form a cyclic structure, and the complex number 4 may be bonded to each other: a %-like structure 'r5~r7 Separately, they are hydrogen atoms or sulfhydryl groups. The above formula (1) may contain a hetero atom having an alicyclic group having a carbon number of 5 to 2 G, and may be exemplified. A pentyl ring, a cyclohexyl ring, a cycloheptyl ring, a cyclooctane ring Base, cyclodecyl ring, decahydronaphthalene ring (perhydronaphthalene ring), sulphonic H, in the base ring, isofos ring, adamantyl ring, tricyclo[5.2.1.02,6]^ring, four Ring [((4)^巧十^环等单单或多环结等... Buddy internal ring, 4_oxa-tricyclo[4·2丄〇3,7]decane_5·one, 4,8_ ::hetero-tricyclo[4.2丄〇]]decane·5-ketone, 4_oxa-tricyclo[4 3”” 38] 垸: monocyclic or polycyclic lactones such as 5-ketone, tetrahydrofuran, a monocyclic or polycyclic ether such as tetrahydropyran or '4-dioxane, and the number of carbons which may contain a hetero atom in the above formula (1) = a substituted or unsubstituted divalent hydrocarbon group Specific examples thereof include a linear or branched alkyl group such as a methylene group, a stretching group 140388.doc -30-201002667 group or a trimethylene group, or the perfluorinated compounds thereof, etc., as the above formula (1). Specific examples of the substituted or unsubstituted alkyl group which may contain a hetero atom include methyl group, ethyl group, n-propyl group and isobutyl group. a linear or branched alkyl group such as a base, n-butyl group, a second butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group, or the like The perfluorinated compound may be a substituted or unsubstituted divalent hydrocarbon group having a carbon number of 5 to 20 which may contain a hetero atom and a hetero atom having 1 to 5 carbon atoms, and may contain a hetero atom. Specific examples of the hetero atom which may be contained in the substituted or unsubstituted alkyl group include a nitrogen atom, a sulfur atom, and an oxygen atom. Examples of the alkyl group in the above formula (a) include a mercapto group and a Linear, n-propyl, isopropyl, n-butyl, t-butyl, tert-butyl, n-pentyl, isopentyl, hexyl, heptyl, octyl, decyl, decyl, etc. Further, as the cyclic structure in which R4 is bonded to a group containing an alicyclic structure represented by the above formula (1) or a plurality of R4 are bonded to each other, tetrahydrofuran and tetra are mentioned. a residue of hydropyran, hydrazine, 4] dioxane, etc. The divalent group represented by the above formula (Π) is linked to the L group in the above formula (II) The linking group is composed of the bonding group, and the bonding group is configured to form the linking group L. The connecting red has a plurality of links: in the case of at least one of the links, the linking group 1/one, and the linking group 1 are connected to each other. The two types of the same can be different from each other, and the same kind of linking groups can also be bonded to each other without being adjacent to each other. Specifically, it can be 140388.doc 201002667

Bonding order such as Lb-La. The above-mentioned linking group L is preferably a linking group represented by the following general formula (Ui) or (iv), -La-Lb-(iii) - Lb-Le- (iv) (wherein 'L is in the above formula (a) The linking group 'Lb is a linking group represented by the above formula (b), and Le is a linking group represented by the above formula (c)). Further, the (mercapto)acrylic acid S of the present invention is preferably represented by any one of the following general formulae (5) to (8), [Chem. 19]

The intermediate R is a group having a ring structure having a carbon number of 5 to 20 represented by the above formula (1), and each of R4 is independently a derivative of the subcutaneous group and may be bonded to a group having an alicyclic structure containing the above formula. (4) Ring-forming structure R can be bonded to each other to form 稷.. „8, 状, 、, α, R~R are independently nitrogen or methyl, R8 is hydrogen® early ^ Ningfeng atom, methyl The fluorine atom or the trifluoro group is used as the above formula (5) to the medium v, and the cores K to R are the same, and R4 to R7 in the formulas (a) to (c) can be used in the same manner. The R is bonded to each other by the above formula 4 and R4, and as the base bond of the alicyclic structure represented by the above formulas (5) to (8), 140388.doc -32- 201002667 The % structure may be, for example, a residue such as tetrahydrofuran, tetrahydropyran or [丨,4]dioxane. Specific examples of the alicyclic structure-containing compound of the present invention represented by the above general formulae (5) to (8) include methacrylic acid 2-(cyclopentyloxymethoxy)-2-oxo-oxygen Ethyl ethyl ester, methacrylic acid 2-(cyclohexyloxy decyloxy)_2_side oxyacetate, 2-(cycloheptyloxymethoxy)-2. ethoxyethyl methacrylate 2-(cyclooctyloxymethoxy)_2_side oxyethyl methacrylate, 2,2-(cyclomethoxymethoxy)-2-oxoethyl methacrylate, methacrylic acid _ 2-(cyclodecyloxymethoxy)_2_side oxyethyl ester, methacrylic acid 2-(cyclodecahydronamethoxymethoxy)-2-oxoethyl ester, methyl acrylate _2_(cyclopentanyloxymethoxy)-2-oxoethyl ester, methacrylic acid _2_(decyloxydecyloxy)_2-tertiary oxyethyl ester, methacrylic acid _2-( Isophenoxymethoxy)_2_trioxyethyl ester, 2-(3-tricyclo[5.2.1.02'6]decyloxymethoxy) 2-ethyloxy ethoxylate , methacrylic acid-2-(3-tetracyclo[4.4.0.12'5.17,10]dodecyloxymethoxy)-2-oxoethyl ester, methacrylic acid 2-(1 · Adamantyloxymethoxy )-2-oxoethyl ester, methacrylic acid _2 _(2_金刚院 oxymethoxy)-2-oxoethyl ester, methacrylic acid _2-(i-adamantyl methoxy Methoxy)-2-oxoethyl ester, 2-(2-(1-adamantyl)ethoxyethoxy)-2-oxoethyl methacrylate, mercapto propylene Acid 2-(5-hydroxy-2-adamantoxycarbonyl)-2-oxoethyl ester, methacrylic acid-2-(3,5-di-propyl-1-adamantyloxy) 2-oxooxy)-2-oxoethyl ester, methacrylic acid 2-(4-oxo-l-adamantyloxymethoxy)-2-oxoethyl ester, methacrylic acid-2 -(4-Sideoxy-2-adamantyloxycarbonyl)_2_side oxyethyl ester, 2-(2-cyanoguanidino-2-metalamyloxymethoxy) methacrylate _2_Sideoxyethyl 140388.doc -33- 201002667 ester, 2-(1-γ-butyrolactyloxymethoxy)-2-oxoethyl methacrylate, methacrylic acid-2 -(5-(2,6-norbornanecarbonyl lactone)oxymethoxy)_ 2-sided oxyethyl ester, methacrylic acid-2-(5-(7-oxa-2,6) -nordecane-lactone-)oxymethoxy)-2-oxoethyl ester, methacrylic acid-2-(8-(4-oxa-tricyclo[ 4.3.1.13 '8] undecane _5-ketone) oxymethoxy)-2-oxoethyl ester, 2-(perfluorocyclopentyloxymethoxy)-2- methacrylate Oxyethyl ester, methacrylic acid 2 - (perfluorocyclohexyloxy decyloxy) - 2 - pendant oxy ethoxylate, thiol acrylate - 2 - (perfluoro-1-gold sulphuroxy methoxy methoxy Ethyl 2-ethyloxyethyl ester, methacrylic acid 2·(perfluoro-1-adamantyloxycarbonyloxy)-2-oxoacetic acid, methyl acrylate- 2- (3-transyl fluorenyl _ perfluoro-1-adamantyl methoxy methoxy)-2-oxoethyl ester, 2-(1-(1-adamantyloxy) methacrylate 2-oxoethyl ester, 2-(1-(2-adamantyloxy)ethoxy)-2-oxoethyl methacrylate, methyl acrylate-2-(2) - Tetrahydrofuranoxymethoxy) 2_ pendant oxyethyl ester, methacrylic acid-2-(2-tetrahydro). Bis-oxymethoxy)_2_sideoxyethyl ester, mercaptopropionic acid-2-(2-(1,4-dioxanyl)oxymethoxy)_2_sideoxy B Ester, 2-(2-(1-adamantyloxymethoxy)> 2-sided ethoxyethoxy) ethyl methacrylate, 2-(2-(2-adamantyloxy) methacrylate曱 oxy)-2-oxoethoxyethoxy)ethyl ester, methacrylic acid _2·(1·adamantyloxymethoxymethoxy)-2-oxoethyl ester, methacrylic acid _2_(2_adamantyloxymethoxymethoxy)-2-oxoethyl ester, adamantyloxymethoxymethoxy)-2-oxoethoxy ethoxy) Ester, methacrylic acid _2_(2_(2_adamantyloxy methoxy methoxyoxy)-2-oxoethoxyethoxy) ethyl ester, propylene sulfonium adamantyloxy methoxy)-2- side Oxyethyl ester, acrylic acid-2-(2-140388.doc -34· 201002667 adamantyloxy methoxy)-2-oxoethyl ester, 2-trifluoromethyl acrylate-2-(1-gold gang Alkoxymethoxy)-2-oxoethyl ester, 2-trifluoromethyl acrylate-2-(2-adamantyloxymethoxy)-2-oxoethyl ester, and the like. Among the compounds having an alicyclic structure, 2-(1-adamantyloxymethoxy)-2-oxoethyl methacrylate is preferred from the viewpoints of properties and ease of production. , 2-(2-adamantyloxycarbonyl)-2-oxoethyl methacrylate, and the like. Specific examples of the chemical formula of the alicyclic structure-containing compound of the present invention are shown below, but the present invention is not limited thereto. [Chem. 20]

I ^^ One. Jy 〇J^^〇一

Cr 〇c v°~ff~~^χ°°~yifczfcr0-丫o^riK^gL^c^〇lr

140388.doc 35- 201002667 [Chem. 21]

The (mercapto) acrylate of the present invention can be produced by a variety of methods and is particularly limited. Specific examples thereof include a method for producing a (meth) acrylate according to the present invention. The mussel core Iw method of the (meth) acrylate provided by the present invention utilizes the alicyclic structure-containing compound of the present invention and is selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid ii compound, and (methyl). A method for producing an esterification of one or more of an acrylic acid anhydride and a (meth)acrylic acid 2-1-alkylalkyl ester derivative. Examples of the (meth)acrylic acid include acrylic acid, methyl propyl sulfonate, 2-fluoroacrylic acid, and 2-trimethyl fluorenyl acrylic acid. Examples of the (meth)acrylic acid-based compound include acrylonitrile, propylene, propylene, propylene, methacrylium, methacrylium, methacrylium, and methacrylium. Methyl propylene oxime iodine, 2 fluoro propylene fluorene fluoride, 2-fluoro propylene fluorene, 2 fluoro propylene hydrazine, 2 fluoro propylene hydrazine iodine, 2 _ three 140388. doc • 36- 201002667 fluoromethyl propylene fluorene fluoride , 2_trifluoromethyl propylene chloro, 2 | C

Sk > odor, 2-trifluoromethyl propylene oxime iodine, etc., as the above (meth)acrylic anhydride, for example, acrylic acid anhydride, methacrylic anhydride, 2·fluoroacrylic anhydride, and 2-trifluoromethyl group Acrylic acid anhydride, etc. Examples of the (meth)acrylic acid 2-hydroxyalkyl ester derivative include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and methacrylic acid. _2_hydroxypropyl ester and the like.

The above self-deuteration can also be carried out by causing a base to act on the alicyclic structure-containing compound of the present invention and from (meth)acrylic acid, (meth)acrylic acid sulphate, (meth) propyl (tetra) sulphate. And (meth)(tetra)acid_2_ The salt is produced in the system by more than one species in the basal vinegar derivative, and the reaction can be promoted by forcibly removing the water produced by the azeotropic dehydration reaction to the outside of the system. . The above vinegarization can be carried out in the presence or absence of an organic solvent, and in the case of using an organic solvent, it is preferred to have a base f concentration of about q"m〇1/L~U) mol/L. Make adjustments. If the substrate concentration is 〇" mol / L or more, the necessary amount can be obtained by using a conventional reactor, so it is economically preferable. If the substrate concentration is 1 〇 m 〇 1 / L or less, the temperature of the reaction liquid is controlled. It's easier and better. Examples of the organic solvent that can be used include hydrocarbon solvents such as hexane, heptane, cyclohexane, ethylcyclohexane, benzene, methyl bromide, and xylene; diethyl ether, dibutyl ether, and THF (tetrahydrofuran). An ether solvent such as dioxane or DME (dimethoxyethane), a halogen solvent such as dichloromethane or tetrahydrogenated hydride, DMF (N,N-dimercaptocarboxamide), DMSO (dimercapto)飒), NMP (N-methyl-2-pyrrolidinone), HMPA (hexamethylphosphonium diamine), HMPT (hexamethylenephosphonium triamine), carbon disulfide and other aprons 140388.doc •37- 201002667 or a mixture of two or more. As sodium hydroxide, potassium hydroxide, sodium carbonate, or a polar solvent, the above base can be used, and sodium hydride carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, silver oxide, sodium sulphate, potassium silicate, and acid can be used. Disodium hydrogen, (tetra) dipotassium hydrogen, sodium dihydrogen phosphate, potassium dihydrogenate, sodium methoxide, potassium butoxide, monoethylamine, tributylamine, triamine, N,N-dimethyl Inorganic bases such as amines, D-clear, 5-diazabicyclo[4,3,indole], DBU (1,8-diazabicyclo[54]]decane--7-one) Organic amines. The azeotropic dehydration reaction is a solvent, and it is preferred to select a hydrocarbon solvent such as cyclohexene, ethylcyclohexane, hydrazine or dimethyl strepone. The addition ratio of the reaction reagent to the alcohol having an alicyclic structure is preferably about 1 to 1 〇〇 m〇i, more preferably about 0.5 times m. Compared with the alcohol containing the alicyclic structure, the amount of addition is (U~1〇 times m〇丨, preferably 丨~丨5 times m〇i. The reaction temperature is only about -200~200〇C) Preferably, it is preferably _5 〇 〜1 〇〇艽. Further, the reaction pressure is about 0·01 〜1 () Mpa in absolute pressure, preferably atmospheric pressure ~! MPa. The reaction time is longer. In the case of a situation, the residence time becomes longer, and when the Lili is too high, a special pressure-resistant device is required, which is uneconomical. After the reaction, the reaction solution is separated into water and an organic layer, and the product is extracted from the water layer as needed. The solvent may be removed by evaporation under reduced pressure in a liquid to obtain a compound containing an alicyclic structure of the present invention, which may be purified if necessary, or may be supplied to a secondary reaction without purification. As a purification method, a scale of manufacture may be considered. The necessary purity is selected from the usual purification methods such as steaming, extraction washing, crystallization, activated carbon adsorption, and ruthenium column chromatography, preferably by extraction washing or crystallization, because At phase 140388.doc -38- 201002667 operating at lower temperatures Further, a large number of samples can be processed at a time. Further, the present invention also provides a (meth)acrylic polymer comprising a monomer unit of the (meth)acrylic acid s according to the present invention. The acrylic polymer may be a polymer containing a (meth) acrylate of the present invention as long as it contains a monomer unit based on one or more of the above (meth)acrylic vinegars of the present invention. The copolymer 2' of the (meth)acrylic acid vinegar of the present invention may be a copolymer of one or more of the (fluorenyl) acrylates of the present invention and the polymerizable monomer. The (mercapto)acrylic polymer of the present invention is preferably a monomer unit based on the (meth)acrylic acid of the present invention, which is preferably contained in an amount of from 0 to 90 mol%, more preferably Contains 25 to 75 moles. = There is no special rule for the method, and the polymerization method of (4) can be used for the solution polymerization. (Buddha polymerization, non-dwelling point, suspension polymerization, bulk polymerization, etc.) According to the well-known polymerization method, the unreacted monomer remaining in the reaction solution of the human being is not good after the polymerization or after the end of the polymerization, and is better known. The polymerization reaction of the initiator for the early removal of the body. The use of a free radical polymerization using a peroxide chelating agent as a pretreatment agent can be used as a peroxide hydrazine polymerization initiator, etc. , can be oxidized ketone, peroxy (tetra), hydrogen peroxide, ... over-carbon reduction, diterpene, peroxy (peroxidized laurel, η county, peroxide oxide. Also, as Weiben hyperthyroidism) and other organic The starting sword for the polymerization is as follows: 2, 2, azo J40388.doc -39- 201002667 double isobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2, azo double An azo compound such as (a methylvaleronitrile) or 2,2'-azobisisobutyric acid dimethyl ester, etc. Among the above polymerization initiators, depending on the polymerization temperature One or two or more kinds of polymerization initiators are suitably used depending on the reaction conditions. The (meth)acrylic acid vinegar or other copolymerized monomer of the present invention used is removed from the produced polymer after the completion of the polymerization. The method, ^ using various methods 'self-operating or economical considerations, it is better to use the poor solvent of the acrylic polymer to wash the acrylic polymer = poor solvent in the acrylic polymer It is preferred that the boiling point is lower, and representative examples thereof include: methyl amide, ethanol, n-hexane, n-heptane, etc. i 3 The resin composition of the (fluorenyl) acrylic polymer of the present invention can be used for various kinds. The use is, for example, a circuit forming material (photoresist for semiconductor manufacturing, a printed circuit board, etc.), an image forming material (printing plate, uneven image, etc.), etc., and particularly preferably used as a resin composition for photoresist, and is preferable. It is used as a resin composition for a positive resist. Further, the present invention also provides a positive resist composition containing the (fluorenyl) acrylic polymer of the present invention. The positive resist composition of the present invention The (meth)acrylic polymer of the present invention is not particularly limited, and it is preferably contained in an amount of 2 to 5 parts by mass based on 100 parts by mass of the positive resist composition of the present invention. More preferably, the (meth)acrylic polymer contains 5 to 5 parts by mass. In addition to the above (meth)acrylic polymer, the positive resist composition of the present invention may also be added with PAG (ph〇). T〇acid generator, photoacid generator) 140388.doc -40- 201002667 Or organic amines, etc., 丨, tt ±,%> gluten resin (such as phenolic resin, phenolic tree 曰, I subprivate , including a few beautiful sayings ^ hair, want to earth tree, etc.), such as soluble components, colorants (such as dyes, etc.), organic solvents (such as hydrazines, quiet hydrocarbons, alcohols, vinegars, ketones, ethers Class, rayon fiber, carbitol, ethanol ether ester, mixed solvents, etc.). As a photoacid generator, it can be listed as an I* shell compound which can efficiently form an acid by exposure to exposure, such as diazonium _, 虱1 镌 salt (for example, diphenyl sulfonium hexafluorophosphate I), Salt (eg, poorly loaded left 〆 〆 - 本 蜢 /, fluoroantimonate, triphenyl sulphate, triphenyl sulphate, etc.), tartaric acid vinegar [such as phenyl Small (4_f meryloxyoxybenzhydryl H2,3_tris(tetra)oxymethyl, oxadiphenyl-phenyl hydrazinyloxy) stupid, phenyl-H4_methylphenyl醯oxymethyl hydrazine, carbyl benzoyl carbyl ketone, etc., ten sage derivatives, s-triazine derivatives, two stone derivatives (diphenyl sapphire, etc.), quinone imine, Compound, monthly deficient acid _, diazo naphthalene brewing, benzoin toluene vinegar and so on. These photoacid generators may be used singly or in combination of two or more. "The content of the photoacid generator in the positive resist composition of the present invention may be based on the strength of an acid generated by light irradiation or the above (meth)acrylic acid polymerization: based on the above (meth)acrylic acid The content of the monomer unit of the brewing type is appropriately selected. For example, it is preferably contained in an amount of 0.1 part by mass based on 1 part by mass of the above (meth)acrylic polymer. The mass fraction, further preferably 2 to 20 parts by mass, of the photoacid generator. The positive photoresist composition of the present invention can be produced by the following (meth)acrylic polymer and photoacid generator And mixing the above-mentioned organic solvent or the like as needed, and removing the inclusions by using a conventional solid-state separation mechanism such as a filter, such as a filter, etc. The positive-type photoresist composition is applied to the base. After performing the money on the material or the substrate, the light exposure (or the post-exposure baking) of the coating film (photoresist film) is performed through a specific mask to form a latent image pattern, and then development is performed, thereby achieving high precision. The ground forms a fine pattern. The invention also provides a method for forming a photoresist pattern, comprising: a step of forming a photoresist film on a support by using the above-mentioned positive-type photoresist composition; and selecting a light for the photoresist film; (4); The photoresist film is subjected to an alkali development treatment to form a photoresist pattern. Examples of the support include a stone wafer, a metal, a plastic, a glass ceramic, etc. The positive photoresist composition is used to form a photoresist film. The step can be carried out by using a conventional coating mechanism such as a spin coater, a dip coater, or a (four) machine. The light is preferably a thickness of the 100 resist film, for example, preferably 5 〇ηη to 20 μπι nm to 2 μπι 〇 In the step of selective exposure of the photoresist film, light of various wavelengths such as ultraviolet rays, X-rays, or the like can be used, and when used for semiconductor photoresist, g-line, 1-line, and excimer lasers (for example, XeC丨, KrF, and AfF, AW, etc., soft X-ray, etc. The exposure energy is, for example, (7) (9) mJ/cm2, preferably about 1 to 100 mJ/cm2. The above-mentioned (fluorenyl) acrylic acid contained in the above-mentioned positive resist composition The polymer has an acetal structure and therefore has a function of decomposability. Therefore, an acid is generated from the photoacid generator by selective exposure, and the acid (meth)acrylic polymer is based on the above-mentioned (meth) acrylate-based structural unit The cleavage portion is rapidly desorbed to form a carboxyl group or a hydroxyl group which contributes to dissolution. Therefore, by performing development processing using an alkali developing solution, a specific pattern can be formed with high precision 140388.doc -42 - 201002667. The present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited by the examples. Further, the physical properties are measured as follows. (Measurement method) Nuclear magnetic resonance (NMR): The gas-d-d was used as a solvent, and it was measured by JNM-ECA500 (made by Nippon Denshi Co., Ltd., company). Gas chromatograph-mass spectrometer (GC-MS): The measurement was carried out using El (GCMS-QP2010 manufactured by Shimadzu Corporation). Film thickness and normalized film thickness: Film thickness was measured using an optical film thickness meter (FE-3 000 manufactured by Otsuka Electronics Co., Ltd.) and a contact film thickness meter (ET-4000A manufactured by Kosaka Research Institute). The thickness of the film was set to 1 · 〇 and the normalized U film thickness was calculated. Example 1 (Synthesis of a compound containing an alicyclic structure: chloroacetic acid-2-adamantyloxy oxime ester) To a 100 mL two-necked flask, 2-chloroantimony adamantane 5 1 34 mg (molecular weight: 200.7 1,25.6 mmol), 2661 mg of chloroacetic acid (molecular weight: 95.50, 28.2 mmol, 1.1 eq_), 50 mL of tetrahydrogen was added. Furan (THF) was stirred and dissolved. Then, 4.6 mL of triethylamine (molecular weight: 101.19, specific gravity: 0.726, 33.0 mmol, 1.3 eq) was added dropwise, and it was found that the reaction solution was rapidly cloudy and slightly heated. Stirring was continued for 2 hours. 140388.doc -43 - 201002667 After the addition of 50 mL of water, the reaction was stopped. 1 〇〇 mL - diethyl ether was added to the reaction mixture to shake, and the aqueous layer was removed after standing. Add 50 mL of water again, shake and leave to remove the water layer. This operation was further repeated twice. The obtained organic layer was dried with magnesium sulfate, filtered, and the solvent was removed by distillation. After the solvent was completely removed, a white solid of 6288 mg (24.3 mmol, a yield of 95.0 °/, and a purity of 94.4%) was obtained as a target gas. The measurement results of the obtained resin are as follows. GC-MS: 257 (M+-l, 0.01%), 231 (0.2%), 230 (1.3%), 229 (0.6%), 228 (4.0%), 164 (22.3%), 135 (47.4%), 134 (100%), 92 (57.8%), 79 (36.7%), 67 (17.4%) ^-NMR: 1.50 (d, J = 12.2 Hz, 2H), 1.68 (d, 1 = 12.2, 2H), 1.71 (s, 2H), 1.80-1.87 (m, 4H), 2.01 (s, 3H), 2.04 (s, 1H), 3·77 (s, 1H, d), 4.07 (s, 2H, a), 5.47 (s, 2H,c) "C-NMR: 27.02 (g or g'), 27.24 (g' or g), 31.30 (f or f,), 32.40 (e), 36.40 (f or f), 37.36 (h), 40.90 (a), 83.14 (d), 89.55 (c), 166.90 (b) [22]

Chemical formula: Ci3H19CI〇3 Molecular weight: 258.74 Example 2 (Synthesis of (mercapto) acrylates: 2-(2-adamantyloxycarbonyl)-2-oxoethyl methacrylate) Potassium mothoxide 66 mg (molecular weight: 140388.doc • 44-201002667 166.00, 〇·4 mm〇1), potassium carbonate 2〇7 molecular weight: mu, i5 mmol) added to 2 mL of N in a 50 mL two-necked flask , N-dimethyl decylamine (DMF) and start stirring, adding 0 丨 mL of methacrylic acid (molecular weight: 86.09, specific gravity: i 〇15, working 2 mm〇i) to the obtained slurry, using an oil bath The reaction solution was adjusted to 45 C. Then, 258 mg (molecular weight: 258.74, 1. 〇 mmol) of chloroacetic acid-2-adamantyloxymethyl ester dissolved in 1 mL of DMF was added dropwise using a cannula, and then washed twice with i mL of DMF. After 3 hours, 5 mL of water was added to stop the reaction. 20 mL of diethyl ether was added to the reaction mixture, and the mixture was shaken and allowed to stand to remove the aqueous layer. Add 5 mL of water again, shake and let go to remove the water layer. This operation was further repeated twice. The obtained organic layer was dried over magnesium sulfate, filtered, and then evaporated to remove solvent. After completely removing the solvent, 2-(2-adamantyloxymethoxy)-2-oxoethyl methacrylate 304 mg (0.99 mmol, isolated yield) was obtained as the objective compound. It was 98.6% and the GC purity was 88.3%). The measurement results of the obtained resin are as follows. GC-MS : 278 (Μ+-30, 32.9%), 202 (5.2%), 164 (%), 135 (100%), 134 (79.3%), 92 (63.3%), 69 (51.8%), 41 (38.1%) 'H-NMR: 1.49 (d, J=ll·6 Ηζ» 2Η)5 167 (d, J=12.3 Hz, 2H), 1.71 (s, 2H), 1.79~1.86 (m, 4H) ), 1.95-2.04 (m, 4H), 1.98 (s, 3H, c), 3.74 (s, 1H, h), 4.69 (s, 2H, e), 5.46 (s, 2H, g), 5.66 (t , J=1.5 Hz, 1H, a2), 6.22 (s, 1H, a1) 13C-NMR : 18.03 (c), 26.96 (k or k'), 27.17 (K7 or k), 31.23 (joj,), 32.28 (i), 36.31 G' or j), 37.30 (1), 60.73 (e), 82.79 (h), 88.78 (g), 126.65 (a), 135.25 (b), 166.39 (d or f), 140388. Doc -45- 201002667 167.36 (f or d) [化23]

c $学学: CnHM〇s Molecular weight: 308.37 Example 3 (Synthesis of (meth)acrylic polymer) In decyl isobutyl hydrazine, 〇1/·| Λ/1 & θ 乂〇.1 The mass ratio of /1.0/10 was added to 22,_ azobis(isobutyrate) dimethyl ester/monomer A/fluorene oxime + human 丄^ MA/early C, and stirred under heating and reflux for 2 hours. Thereafter, the reaction solution was poured into a mixed solvent of methanol and water in the main body of the main solution, and the reaction was carried out three times to purify the reaction. As a result, (4) A: the copolymerization composition of the monomer C (m〇1) = 52: 48, the weight average molecular weight (Mw) of 73 82, and the dispersion degree (Mw/MnA 13 〇 copolymer η) were obtained. 24]

Synthesis Example 1 (Synthesis of Polymer) Polymerization was carried out in the same manner as in Example 3 using a monomer oxime synthesized separately, and a monomer Β was obtained as a result: a copolymerization composition of the monomer c (m〇1) = 55: 45 The weight average molecular weight (Mw) is 75; 35, and the degree of dispersion (Mw/Mn) is 共聚32 copolymerized P2. One κ 140388.doc • 46- 201002667 [Chem. 25]

Example 4 (Preparation of a positive-type photoresist composition) 5 parts by mass of triphenylsulfonium nonafluorobutanesulfonate was added as a photoacid generator with respect to 100 parts by mass of the copolymer P1 obtained in Example 3. The photoresist composition R1 was prepared by dissolving 90 parts by mass of propylene glycol monomethyl ether acetate with respect to 10 parts by mass of the obtained resin composition. The prepared photoresist composition R1 was coated on a Shi Xi wafer and baked at 11 ° C for 6 seconds to form a photoresist film. The thus obtained wafer is subjected to several open exposures with different exposure amounts using light having a wavelength of 248 nm. Immediately after the exposure, it was heated at 1 lOt: for 60 seconds, and then developed with an aqueous solution of tetramethylammonium hydroxide (2.38 mass%) for 60 seconds. The change in film thickness at this time with respect to the amount of exposure is shown in Table 1 and Fig. 1. Comparative Example 1 (Synthesis of 2-hydroxyethyl 2-(adamantyloxymethoxy)_2_oxyethyl methacrylate); potassium iodide 66 mg (molecular weight: 66·00 (Μ) added to a 5 mL two-necked flask Mm〇i), gas adamantyloxy vinegar 258 (in the molecule 258·74 'K〇_〇1) 'Add 5 mL of THF and start stirring. Add methyl methacrylate to the obtained m material. 〇2 〇 Molecular weight: 86〇9, specific gravity: 1.015' 2.4 _〇1), triethylamine 〇42 called molecular weight: 1.19 specific gravity · 〇.726 ' 3 Q coffee, using the oil bath to the reaction solution U0388.doc -47· 201002667 Adjusted to 60 °C. After 5 hours, 5 mL of water was added to stop the reaction. 20 mL of diethyl ether was added to the reaction mixture, and the mixture was shaken and allowed to stand to remove the aqueous layer. Add 5 mL of water again, shake and let stand to remove the water layer. This operation was further repeated twice. The obtained organic layer was dried over magnesium sulfate, filtered, and then evaporated to remove solvent. After the solvent was completely removed, the target substance was not obtained, and the methacrylic acid _2_adamantyloxy oxime ester 193 obtained by transesterifying the acetic acid 2-adamantyloxymethyl ester of the raw material with methacrylic acid was obtained. Mg(〇77 mmol) ° GC-MS : 220 (M+_CH2〇, 29 9%), 164 (57 5%), 134 (93.50/0), 1 35 (!00〇/〇), 122 (21.4 〇/〇), 92 (68.9〇/„), 79 (43.2〇/〇), 69 (51.5%), 41 (47.6%) •H-NMR: 1.50 (d, J=12.3 Hz, 2H), 1.68 (d, J = 12.3 Hz, 2H), ^ (s, 2H), ~187 (m, 4H), i % (s, wind a), 2.05 (m, 3H), 2.07 (s, 1H), 3.76 (t, J = 3.4 Hz, 1H, f), 5.46 (s, 2H, e), 5.59 (t, J = 1.9 Hz, 1H, b1), 6.13 (s, 1H, b2) 13C-NMR: 18·19 (4),27.u (i or r), 27 33 (i, 〇r υ, 31 4〇(g)' 32.52 (h or h'), 36.50 (h' or h), 37.47 (1), 82 95 (f), 88.61 (e), 125.89 (b), 136.32 (c), 166.88 (d) [Chem. 26]

$ Formula: Ci5H22〇; I Molecular weight: 250.33 140388.doc 201002667 Comparative Example 2 (Preparation of Resin Composition) Except that the copolymer P2 obtained in Synthesis Example 1 was used instead of the copolymer p丨, 4 The photoresist composition R2 was prepared in the same manner, and the change in film thickness with respect to the exposure amount was measured. The results are shown in Table 1 and Figure 1. [Table 1] Example 4 Specific Rate 2 Film Thickness (nm) Normalized Film Thickness (nm) Normalized Film Thickness Exposure (mJ/cm2) 0 250 1.00 246 1.00 2 252 1.01 248 1.01 4 248 0.99 250 1.02 6 250 1.00 250 1.02 8 245 0.98 253 1.03 10 150 0.60 248 1.01 12 15 0.06 246 1.00 14 0 0.00 248 1.01 16 0 0.00 245 1.00 18 0 0.00 245 1.00 20 0 0.00 252 1.02 22 0 0.00 248 1.01 24 0 0.00 240 0.98 26 0 0.00 243 0.99 28 0 0.00 245 1.00 30 0 0.00 248 1.01 32 0 0.00 244 0.99 In the fourth embodiment of the present invention, it was confirmed that the film thickness was changed by the amount of exposure, and it was confirmed that the photoresist composition R1 has a photosensitive resin. Features. Industrial Applicability The alicyclic structure-containing compound and the (meth) acrylate of the present invention are particularly excellent as a photoresist material corresponding to irradiation light of a short wavelength. 140388.doc -49- 201002667 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing changes in film thickness of a photoresist composition R1 obtained in Example 4 and a photoresist composition R2 obtained in Comparative Example 2 with respect to exposure amount. Figure. 140388.doc -50-

Claims (1)

201002667 VII. Patent application scope: 1. A compound containing an alicyclic structure, R'-LX (1) ..., represented by the following general formula (I): (wherein R1 is represented by the following formula (0) The basis of the alicyclic structure, L system or less: not containing a carbon number of 5 to 20, a sulfonate atom or a base group, and a linking group represented by the formula (ii), X [Chemical Formula 1] ^中中Z Z series may contain a heterocyclic ring having an alicyclic structure of 5 to 2G, and R2" may contain a hetero atom having a carbon number of 2 and a substituted or unsubstituted group of '5'. a substituted or unsubstituted alkyl group, a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a pendant oxy group or an amine group; p and q each independently represent an integer above 〇; a plurality of R2 may be the same or different 'A plurality of R3's may be the same or different), '((La)k-(Lb)m-(Lc)n}-(ϋ) (wherein L is a linking group represented by the following formula (a)' Lb is a linking group represented by the following formula (b), and is a linking group represented by the following formula (C), and 'La, !^, and Le are arbitrary bonding sequences; k and m are each independently 1 or more. The integer, η is an integer above )), 140388.doc 201002667 [化2] One (b) (Γ2' fluorene-based hydrogen atom or alkyl group' may be bonded to a group having a structure represented by the above formula (1) to form a cyclic structure, and plural forms to form a ring-shaped knot *~ each independently is a chlorine atom or a 2 The compound having an alicyclic structure according to claim 1, which is represented by any one of the following general formulae (1) to (4) [Chemical 3] 140388.doc 201002667 Structure 'A plurality of R4 can be bonded to each other and form a site. Ί J~ attack %-like structure, which is independently a hydrogen atom or a sulfhydryl group, and X is a halogen atom or a hydroxyl group). 3* A (meth) acrylate which is represented by the formula (11), [Chemical 4] No, R1 - L-R8 (In the formula, Ri is a group represented by the following general formula (1), which has an alicyclic structure having a carbon number of 5 to 2 Å, an R8 hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group 'L system, The linking group represented by the formula (ii), [Chemical 5] (^ slightly one (1) '(R3)q (wherein the z-system may contain a hetero atom having an alicyclic structure of 5 to 2 Å, R2 system ~TS has a substituted or unsubstituted divalent hydrocarbon group of 1 to 5, and R3 represents a substituted or unsubstituted alkyl group, a _ atom, a hydroxyl group, a cyano group which may contain a hetero atom. Carboxy' side oxy or amine group; p and q each independently represent an integer above 〇; plural R2 may be the same or different, and plural R3 may be the same or different), -{(La)k-(Lb)m - (Lc)n}. (ii) wherein La is a linking group represented by the following formula (a), Lb is a linking group represented by the following formula (b), and Le is represented by the following formula (c) For the connected groups, L, L, and Lc take any bonding sequence; let m be independent of an integer of 1 or more, „is an integer above ,, 140388.doc 201002667 [Chem. 6] (wherein R4 is a hydrogen atom or an alkyl group, and may be bonded to a group containing an alicyclic structure represented by the above formula (1) to form a cyclic structure, and a plurality of fluorene may be bonded to each other to form a cyclic structure, R5 to r7 are each independently a hydrogen atom or a methyl group). 4. The (mercapto) acrylate of claim 3, which is represented by any one of the following general formulae (5) to (8), [Chem. 7] (In the formula, R1 is a group having a ring structure represented by the above formula (1) and having a carbon number of 5 to 20: Μ is independently a hydrogen atom or an alkyl group, and can be represented by the above formula (1). The group of the alicyclic ring-containing structure is bonded to form a ring-shaped complex. The plurality of fluorenes can form a ring structure with each other, and r5 to r7 are each independently a hydrogen atom or m is a hydrogen atom, an f group, an I atom or three. 140388.doc 201002667 Fluorinyl). 5. The (meth) acrylate of claim 3 or 4, wherein the above z is an adamantyl ring. A method for producing a hydrazine-based acrylate group, which comprises the compound of the alicyclic structure according to claim i or 2, and a hydrazide-based acrylic acid or a (fluorenyl) acrylate-based compound. One or more of the (mercapto)acrylic anhydrides and the (meth)acrylic acid hydroxyalkyl ester derivatives are esterified to obtain the (meth)acrylates of claim 3 or 4. A (meth)acrylic polymer comprising a monomer unit based on the (meth) acrylate of claim 3 or 4. 8. A positive-type photoresist composition comprising the polymer of the invention of claim 7. A photoresist pattern forming method comprising: a step of forming a photoresist film on a support using a positive-type photoresist composition as claimed in claim 8; a step of selectively exposing the photoresist film; The photoresist film is subjected to a development process to form a photoresist pattern. 140388.doc