TW201120063A - Sugar derivative having a polymerizable group, and resist material using said sugar derivative - Google Patents

Abstract

Provided are pyranose derivatives and furanose derivatives, depicted in formulas (I) through (V), of glucose, mannose, psicose, sorbose, tagatose, allose, altrose, gulose, idose, or talose. (In the formulas, M1 represents a specific polymerizable group.)

Description

[Technical Field] The present invention relates to a piperanose derivative and a furanose derivative which can be used for a polymerizable resin such as a photosensitive resin, a method for producing the same, and the like. [Prior Art] In the semiconductor manufacturing using photolithography technology using ArF excimer laser, in terms of photosensitive photoresist, it can be used to have 2-methyl-2-adamantyl methacrylate A polymer obtained by copolymerizing a polymerizable compound of an alicyclic skeleton (Patent Document 1). However, with the progress of the semiconductor manufacturing technology and the remarks of the refinement of the circuit, the smoothness of the surface roughness or wave bulge of the pattern called LER (line edge roughness) and LWR (line width roughness) is made. The problem is more significant. In the 'in recent years' method of immersion exposure, the main use of water as a liquid immersion medium 'in this water' is dissolved in a photoresist material, and thus the defect of the photoresist pattern is not good. Scattered, I hope to resolve these defects as soon as possible. In liquid immersion exposure, in order to prevent the photoresist film from directly contacting the liquid during exposure, a method of forming a protective film (hereinafter referred to as "top layer coating") on the photoresist film and performing liquid immersion exposure from above the top layer is reviewed. (Patent Document 2). On the other hand, from the viewpoint of reducing the step of forming the top layer coating, the method of whether or not the top layer is covered even if the surface of the photoresist film is directly immersed is also examined. In any of these methods, in order to perform the exposure well and to increase the scanning speed of the liquid immersion head of the exposure machine, the top layer coating or photoresist is desired to be hydrophobic on the surface of the film. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei-4-39665 (Patent Document 2) JP-A-2005-158 A sugar derivative of a material and a polymer compound thereof. The present inventors have found that a substrate in which a (cyclic) aliphatic hydrocarbon group is introduced into a monosaccharide has high hydrophobicity and a high glass transition point, and when used as a photoresist material, the hydrophobicity of the photoresist material is enhanced. It is difficult to dissolve in the liquid immersion medium, and further, the defects are reduced, and the roughness can be improved, and the present invention is completed. According to the present invention, the following monosaccharide derivatives, methods for producing the same, and the like can be provided. 1. The following glucose (mannose, psicose, sorbose, tagatose, allose, altrose, gulose, idose, represented by the formulas (I) to (V) , a glucopyranose derivative of trehalose and a furanose derivative. 201120063 【化1】

(IV) (V) wherein R丨~R4 independently represent hydrogen, may contain a haiku heteroatom; or an aliphatic hydrocarbon group of a substituent, or an aliphatic group which may contain a hetero atom and/or an A fluorenyl group A cyclic hydrocarbon group, and Ri and R2 and/or R_3 and 114 can also be used to form a ring. However, in the formulas (II) and (V), when R1 to R4 are not all methyl groups, M represents a group represented by the following formula. [Chemical 2]

(wherein R6 and R7 each independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, and R6 and R7 may together m and η are independently represented by an integer of 0 or more and 4 or less. 201120063 When η and/or m are 2 or more, 'the plural R6 and R·7 may be the same or different, and S represents 0 or 1. X represents The polymerizable group represented by any one of the formulas (1) to (3) is hereinafter referred to as 〇Re -C—C=CH2 (1) valence CH\7H2 (2) r9 I -CH,- CH-CH, CH2-0 (3) (wherein R8 represents a hydrogen atom, a halogen atom, a methyl group or a halogenated methyl group, and R9 represents a hydrocarbon group having 1 to 5 carbon atoms))]. 2. A galactose-paraffinose derivative and a carraghalose derivative represented by the following formula (VI), a pipose derivative represented by the formula (V), or a formula (VII) or The galactose furanose derivative shown by IV) and the fructose derivative represented by the formula (VIII). 201120063 【化4】

[In the formula, Ri to R/t and Rii to Ri4 independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent. And 1 and 112, ^ and! ^, Ri^Ri2 and/or the ruler door and Rm may also be joined to form a ring. However, the case where Ri~^ and Rn~R14 of the formula (V) are not all methyl groups. The base represented by the following formula is shown. 【化5】

(wherein R6 and R7 independently represent an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, and 116 together with R7 The carbonyl group is formed by an integer of 0 or more and 4 or less. -9 - 201120063 When η and/or m are 2 or more, 'R6 and R7 of the plural number may be the same or different, and s represents 0 or 1. X The polymerizable group represented by any one of the following formulas (1) to (3) is shown. [Chemical 6] 〇ReII I-~ 〇-CH2 valence—/(3) 2 (1) (2) R9 I -CH2_CH -ch2 ch2-o (3) (wherein r8 represents a gas atom, a halogen atom, a methyl group or a halogenated methyl group, and R9 represents a hydrocarbon group having 1 to 5 carbon atoms))]. 3. The derivative according to 1 or 2, wherein R1 and R2 and R3 and R4, or R11 and R12 and Rl3 are bonded to RM to form adamantane which may contain a hetero atom and/or a substituent. 4. The derivative according to 1 or 2, wherein Ri and R2 and R3 and R4, or a ruthenium & 12 and R13 are bonded to Rm to form adamantyl alcohol or adamantane. 5. The derivative according to any one of 1 to 4, wherein X is a polymerizable group represented by formula (1). 6. The derivative according to any one of 1 to 5, wherein ' m = 0. 7. Glucose, mannose, aldose oxime, sorbose, tagatose, represented by the following formula (IX), formula (X), formula (XI), formula (XXX), and formula (XXXI), Allose, altrose, gulose, idose, a pentose sugar-halfose derivative and a furanose derivative. -10- 201120063 【化7】

(XXXI) [wherein, 1^~114 and Rn~R|4 each independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic group which may contain a hetero atom and/or a substituent The cyclic hydrocarbon group 'and r@r2, Rii and Ri2 and/or R13 and R!4 may also be bonded to form a ring. However, in the case of allose, altrose, glucose, glucomannan, and a furanose derivative, R, t~Rm are not all methyl. Further, in the formula (XXXI), when ^^~~ is all methyl, there is no case where the rule 1 and 112 are joined to each other to form a ring-yard ring, and r3 and R4 are bonded to each other to form a cyclohexane ring. M3 represents a group represented by the following formula. 【化8】

Wherein 'R·6, R? independently represents hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or -11 - 201120063 or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, And R6 and R7 may together form a carbonyl group. m and η independently represent an integer of 4 or more in 〇. When η and/or m is 2 or more, the plural Re and R7 may be the same or different 〇 s represents 0 or 1. L represents a hydroxyl group or a halogen atom. However, in the formula (XXX), when S and m are 0 and L is a hydroxyl group, r, and R4& are not all methyl groups)]. 8. A fruit pipetose derivative represented by the following formula (ΧΠ) and (XXXI) and a fructofuran derivative represented by the formula (XIII). 【化9】

(XII)

Wherein R, R, R4 independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, and R! and R2 R3 and R4 may also be joined to form a ring.

Roi to R34 each independently represent hydrogen, an aliphatic hydrocarbon group having 2 or more carbon atoms which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, and 1131 and 1132 And/or R33 and r34 may form a ring having a carbon number of 4, 5 or 7 or more bonded by a carbon chain. Further, in the formula (XXXI) -12 to 201120063, when all of the methyl groups are present, there is no case where the ring is bonded to the group 112 to form a ring-grafted ring, and R3 and R4 are bonded to each other to form a cyclohexane ring. M3 represents a group represented by the following formula. [化1 0]

Lithium or aryl, a group of R7 hydrocarbons, a group, a 6 R fatty group ’ aliphatic hydrocarbon

R and 6 R contain and can be used, and the original ammonia is shown to have a subtropical or heterogeneous carbonyl formation: m and m η 猸 are heterogeneous or in phase. The number of J-4 can be arbitrarily R7 and 6 times R, and 〇 or 1 is represented by 2 S on the table. L represents a trans-base, a _ atom)). A derivative according to 7 or 8, wherein ' Ri and R2 and R3_r ^ 4, or 1131 and 1132 and R33 and R34 are bonded to form adamantane. The derivative according to any one of 7 to 9 wherein 'm' is a hydroxy group. The method for producing a derivative according to any one of 1 to 6, which is based on any one of the following formulas (1) to (3) Reaction of a compound having a polymerizable group as shown. -13- 201120063 oo=c

H2 c8 II RIC

2HVCH -C H2 CH 2 r9 I -CH2-CH-CH2I I ch2-o (3) (wherein R8 represents a hydrogen atom, a halogen atom, a methyl group or a halogenated methyl group, and represents a hydrocarbon group having 1 to 5 carbon atoms) . 12. A method for producing a monosaccharide derivative represented by the following formulas (XX) to (XXII) which is attached to adamantanone to form galactose, glucose, mannose, psicose, sorbose, and tartar Glycemic, allose, altrose, gulose, idose, teraloose, fructose. [1 2]

[Ms represents a group represented by the following formula]. 【化1 3】

(wherein R6 and R7 independently represent hydrogen, an aliphatic smog group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent] and Han 6 and r7 -14- 201120063 m, η series independently represent an integer of 4 or more in 〇. s represents 〇 or 1. When η and / or m is 2 or more, the plural r6, R7 may be the same or phase The isoindole L represents a hydroxyl group or a halogen atom)]. 1 3 - A polymer compound obtained by polymerizing a derivative according to any one of 1 to 6. 1 . A semiconductor photoresist material and a semiconductor base film which are obtained by using the derivative described in any one of 1 to 6 or the polymer compound described in 丨3. A method for forming a photoresist pattern, comprising the step of using a photoresist composition comprising the derivative according to any one of 1 to 6 or the polymer compound described in 13; a step of forming a photoresist film on the body, a step of exposing the photoresist film, and a step of developing the photoresist film to form a photoresist pattern. (16) A cured product obtained by curing the light-emitting or light-emitting polymer of the derivative according to any one of 1 to 6 or the polymer compound described in 13. A color resist and a black matrix material obtained by using the derivative described in any one of 1 to 6 or the polymer compound described in 13. And a photoresist material for forming a printed circuit board and a solder resist material which are obtained by using the derivative described in any one of the items 1 to 6 or the polymer compound described in the above. A bottom hydrating agent obtained by using the derivative described in any one of 1 to 6 or the polymer compound described in 13. -15-201120063 2 0. An optical recording material obtained by using the derivative described in any one of 1 to 6 or the polymer compound described in 丨3. An optical adhesive or a sealant obtained by using the derivative described in any one of 1 to 6 or the polymer compound described in 13. A material for a nanoimprint using the derivative described in any one of 1 to 6 or the polymer compound described in 13. According to the present invention, a sugar derivative which can be used as a photoresist material and a polymer compound thereof can be provided. [Embodiment] [Form of the invention] Glucose, mannose, psicose, sorbose, tagatose, allose, altrose, gulose, idose, talose in the present invention The vinylidose derivative and the furanose derivative are represented by the following formulas (I) to (V). [化1 4]

(III)

(II)

-16- (IV) 201120063 wherein R, R, R4 independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent. 'and 111 and 112 and/or 113 and 114 may also be joined to form a ring. However, in the formula (π)' (v), Ri~ "is not all methyl. Preferably, R1 and R2 are bonded to 1 and 114 to form adamantane which may contain a hetero atom and/or a substituent. More preferably, each of them is formed with adamantyl alcohol or adamantane, and it is particularly preferable to form a diamond ruthenium each. The formula is represented by the following formula: [Chem. 1 5]

In the formula, 'R6' R7 independently represents hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent. ^ can form a carbonyl group. m and π are independent integers representing 〇 or more*. When η and/or m is 2 or more, the plural scales 6 and R7 may be the same or different from each other. 〇 s is not 0 or 1. X represents the polymerizable property shown by any one of the following formulas (1) to (3) -17- 201120063 [Chemical 1 6] T9 〇r8 II ι_ - CH2 - CH-CH2 \ / -ch2-ch- -ch2 1 C-C-CH2 0 ch2- -0 (1) (2) (3) where r8 represents a hydrogen atom, a halogen atom, a methyl group or a halogenated methyl group, and R9 represents a hydrocarbon group having 1 to 5 carbon atoms. . In terms of a halogen atom, a fluorine atom or a halogenated methyl group may, for example, be a trifluoromethyl group. Further, the galactooligosaccharide derivative and the fruit pipechose derivative of the present invention have the following formula (v I ). The flutose derivative is represented by the formula (V), the galactofuran derivative is represented by the formula (V11) or (IV), and the fructose derivative is represented by the formula (VIII). Show. [化1 7]

(IV) (V) wherein Rh~Ri4 independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or a fat which may contain a hetero atom and/or a substituent -18- 201120063 A cyclic hydrocarbon group, and 11|1 and 1^|2 and/or R|3 and R14 may be bonded to form a ring. However, R, R, and R are not all methyl. Preferably, Rh and R12 and R13 are bonded to Rl4 to form adamantane which may contain a hetero atom and/or a substituent, and it is more preferred that each of them forms an adamantyl alcohol or a diamond. It is the same as the above formulas (I) to (V). In the formulae (I) to (VIII), examples of the substituent include a hydroxyl group, an amine group, an ether bond-containing substituent, a ketone group, an ester bond-containing substituent, a guanamine bond-containing substituent, and a lactone-containing ester. a substituent of a ring, a substituent containing an indoleamine ring, and the like. The derivatives represented by the formulae (I) to (V111) may, for example, be the following compounds. [化1 8]

19- 201120063 [Chem. 1 9]

-20- 201120063 【化2 0】

-21 - 201120063 [Chem. 2 1]

-22- 201120063 【化2 2】

-23- 201120063 【化2 3】

-24- 201120063

-25- 201120063 [Chem. 2 5]

-26 201120063 [Chem. 2 6]

-27- 201120063 [Chem. 2 7]

-28- 201120063 【化2 8】

29- 201120063 [Chem. 2 9]

-30- 201120063

201120063 【化3 1】

-32- 201120063 [Chem. 3 2]

33- 201120063 【化3 3】

Further, the glucose, mannose, psicose, sorbose, tagatose, allose, altrose, gulose, idose, glucopyranose derivative and furanose of the present invention The derivative is represented by the following formula (IX), (X), (XI), (XXX) or (XXXI). [化3 4]

-34 201120063

In the formula, R1 to R4 and R11 to Rl4 each independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, and 1^ And 112, R3 and R4, and R12 and / or R13 and Rl4 may also be joined to form a ring. However, in the case of allose, altrose, glucose, pentose, and a furanose derivative, Rh to R14 are not all methyl groups. Further, in the formula (XXXI), when all are methyl groups, there is no case where 1 is bonded to R2 to form a cyclohexane ring, and R3 and R4 are bonded to form a cyclohexane ring. Preferably, R丨 and R2 and R3 and R4, or Ru and R丨2 and 11丨3 and R丨4 are bonded to form adamantane. M3 represents a group represented by the following formula. [化3 5]

In the formula, R6 and 117 each independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, and R6 and r7 may together A carbonyl group is formed. -35- 201120063 m, η series independently represent an integer of 0 or more and 4 or less. m is preferably 〇. When η and/or m is 2 or more, the plural R6 and R7 may be the same or different 〇 s represents 0 or 1. L represents a hydroxyl group or a halogen atom, and is preferably a hydroxyl group. Examples of the halogen atom include a chlorine group and a bromine group. However, in the formula (XXX), when s and m are 0 and L is a hydroxyl group, r, ~r4& are not all methyl. Further, the pistylene derivative of the present invention is represented by the following formulas (XII) and (XXXI), and the furfuran derivative is represented by the formula (XIII). [Chem. 3 6]

(XII)

R31 to r34 are each independently represent hydrogen, an aliphatic hydrocarbon group having 2 or more carbon atoms which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, and 1131 and 1132 And/or R33 and R34 may form a ring having a carbon number of 4, 5 or 7 or more bonded by a carbon chain. Preferably, the ruler 31 and R32 and R33 are bonded to R34 to form adamantane. R丨~R4 are the same as the above formula (XXXI), and the M3 system is the same as M3 of the above formula (IX). Next, a method for producing the derivative of the present invention will be described. -36-201120063 The derivatives of the formulae (I) to (VIII) are obtained by reacting each of the corresponding intermediates with a compound having a polymerizable group represented by any one of the above formulas (1) to (3). The derivatives of the above (IX) to (XIII), (XXX) and (XXXI) can be used as an intermediate. When the esterification reaction is carried out, an azeotropic dehydration method, a mercapto chloride method, an acid anhydride method, or the like can be used. Examples of the compound having a polymerizable group of an ester include acrylic acid, methacrylic acid, α-trifluoromethacrylic acid, α-fluoroacrylic acid, acrylic acid chloride, methacrylic acid chloride, and trifluoromethyl acrylate chloride. , α-fluoroacrylic acid chloride, acrylic anhydride, methacrylic anhydride, and the like. Preferred are acrylic acid, methacrylic acid, acrylic acid chloride, methacrylic acid chloride, acrylic acid anhydride, and methacrylic anhydride. In the azeotropic dehydration method, the reaction temperature is usually 50 to 200 ° C, preferably 100 to 180 ° C. If the temperature is too low, the reaction rate will decrease and the reaction time may become longer. If the temperature is too high, there will be side reactions, and there is a fear of intense color. The pressure is 0.01 to 10 MPa in a general absolute pressure, preferably at a normal pressure of ~1 MPa. When the pressure is too high, there will be safety problems, and there must be special equipment that is difficult to use in the industry. A general acid catalyst can be used for the catalyst system. For example, sulfuric acid, P-toluenesulfonic acid, trifluoroacetic acid or the like can be mentioned. For the raw material alcohol, the catalyst is usually used in an amount of from 0. 0 1 m 〇丨% to 2 0 m ο 1 %, preferably 0·0 5 to 1 0 m 〇丨%. The solvent is preferably used in an amount of 0.5% or more, preferably 5% or more, based on the solubility of the monosaccharide derivative. The amount used is preferably such that the concentration of the monosaccharide derivative is 0.5% or more, preferably 5% or more. At this time, the derivative may be in a suspended state from -37 to 201120063, but it is preferably dissolved. Examples of the solvent include alkane, undecane, cyclohexane, methylcyclohexane, ethylcycloxylene, and the like. As the polymerization inhibiting agent, p-phenol, phenothiazine, methoxymorphthiazine or the like may be added as needed. When the monosaccharide-based inhibiting agent is usually used in an amount of 10 to 100 wtppm, 5 000 wtppm of the indenyl chloride method or the acid anhydride method, the reaction temperature is usually preferably 0 to 50 °C. If the temperature is too low, it will need to be used in the industry. If the temperature is too high, there will be a fierce reaction. The pressure is 0.01 to 10 MPa to IMP a in general absolute pressure. When the pressure is too high, there is a safety problem, so it is difficult to use it in the industry. The scavenger for the acid generated by the reaction may be organic, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate or phosphorus base such as tributylamine, pyridine or dimethylaminopyridine. The ratio of the use of the base of the monosaccharide derivative to the ratio of the abused derivative is usually about 0.5 to 20 (mole ratio). The solvent is preferably a solvent having a solubility of a monosaccharide derivative of preferably 5% or more. The amount of the monosaccharide is preferably 0.5% or more, preferably 5% or more. In this case, although it may be in a suspended state, it is preferably dissolved. The solvent is decane, decane, toluene, diphenol, methoxybenzene, and the device is preferably 50 to -50 to 100 ° C, which is difficult to handle, and is preferable. For normal pressure, it is necessary to use an inorganic cerium/fluorinated adamantane t such as triethylamine, an amine or potassium NaOH, preferably 1 to 0.5% or more, and the concentration of the organism is a monosaccharide derivative. Examples thereof include hexane-38-201120063, heptane, cyclohexane, toluene, DMF, NMP, DMAc, DMSO, diethyl ether, THF, ethyl acetate, dichloromethane, chloroform and the like. As the polymerization inhibiting agent, hydroquinone, methoxybenzoquinone, phenothiazine, methoxymorphothiazine, and the like may be added as needed. For the monosaccharide derivative, the polymerization inhibiting agent is usually used in an amount of 10 to 100 wtppm, preferably 50 to 5 000 wtppm of the acrylate produced by the reaction. The purification method may be distillation, crystallization, column separation, etc. The purification method can be selected depending on the nature of the product and the type of the impurity. When a compound having a polymerizable group represented by the formulas (2) and (3) is used for the reaction, the derivatives represented by the formulae (IX) to (XIII), (XXX), and (XXXI) are used. The compound having a polymerizable group represented by the formulae (2) and (3) is reacted in the presence of a basic catalyst to synthesize a monosaccharide derivative for the purpose of introducing a cyclic ether group into the derivative. Examples of the compound having a polymerizable group represented by the formulas (2) and (3) include a cyclic ether compound represented by the following formula (XIV) or (XV).

(XIV) (XV) wherein 'Q' represents Cl, Br, I or F, Q2 represents Cl, Br, 1'F, OTs, and R9 represents a hydrocarbon group having 1 to 5 carbon atoms. In the case of a cyclic ether compound represented by the formula (XIV) or (XV), epichlorohydrin, epibromohydrin, 3-chloromethyl-3-methyloxetane, and 3 may be mentioned in the range of -39-201120063. - chloromethyl-3-ethyloxetane and the like. In the reaction of a derivative represented by the formulae (IX) to (XIII), (XXX) and (XXXI) with a compound having a polymerizable group represented by the formula (2) or (3), the reaction temperature is usually 0. ~200 °C, preferably 50~150 °C. If the temperature is too low, the reaction rate will decrease, which may delay the reaction time. When the temperature is too high, there is a fear of intense coloration. The pressure is usually 0.01 to 10 MPa in absolute pressure, preferably atmospheric pressure to IMP a. When the pressure is too high, there are safety problems, and special equipment is required and it is difficult to use it in the industry. The reaction time is usually from 1 minute to 24 hours, preferably from 1 hour to 10 hours, and the basic catalyst includes sodium decylamine, triethylamine, tributylamine, trioctylamine, and pyridine. , N,N-dimethylaniline, 1,5-diazabicyclo[4,3,0]nonene-5 (DBN), 1,8-diazabicyclo[5,4,0] Undecene-7 (DBU), tetramethylammonium chloride, tetraethylammonium chloride, sodium hydroxide, potassium hydroxide, sodium hydride, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, silver acid sulfate, Sodium oxide, t-butoxide, and the like. The solvent is preferably a solvent having a solubility of a monosaccharide derivative of 0.5% or more, preferably 5% or more. The amount is preferably 0.5% or more, preferably 5% or more, based on the concentration of the monosaccharide derivative. In this case, the monosaccharide derivative may be in a suspended state, but it is preferably dissolved. Examples of the solvent include hexane, Gengyuan 'toluene, DMF, DMAc, DMSO, ethyl acetate, diethyl ether, tetrahydrofuran, and the like. It is also possible to use a halogenated alkyl group-containing -40-201120063 ether compound as a solvent. The purification method of the monosaccharide derivative into which the cyclic ether group is introduced may be distillation, crystallization, column separation, etc., but the purification method may be selected depending on the nature of the product and the type of the impurity. Next, a method for producing a monosaccharide derivative containing the above-described derivatives represented by the formulae (IX) to (XIII), (XXX) and (XXXI) of the present invention will be described. The monosaccharide derivative can be produced by subjecting a corresponding monosaccharide to an organic compound having a carbonyl group by a ketalization reaction. Examples of the monosaccharide include galactose, glucose, fructose, mannose, psicose, sorbose 'tagugose' allose, altrose, gulose, idose, and talose. Preferred are glucose, fructose, and mannose. Examples of the organic compound having a carbonyl group include 2-adamantanone, 5-hydroxy-2-adamantanone, 2,4-adamantanedione, 4-hydroxy-2-adamantanone, and α-ethenyl group. - γ-butyrolactone, ethyl acetoacetate, ethyl cyclopentanone-2-carboxylate, 2-cyclohexanonecarboxylic acid ethyl 'camphor, and the like. Preferred are 2-adamantanone, 5-hydroxy-2-adamantane and the like. For example, adamantone is reacted on a monosaccharide to produce a monosaccharide derivative represented by the following formula (XX) to (XXII). -41 - 201120063 [Chem. 3 8]

The M3 system is the same as the above formula (IX). The reaction temperature of the ketalization reaction is usually from 〇 to 200. (:, preferably 20 to 150 ° C. If the temperature is too low, the reaction rate will decrease, and the reaction time may be prolonged. If the temperature is too high, the coloring may be intense. The pressure is usually measured by absolute pressure. It is 0.01 to 10 MPa, preferably atmospheric pressure to 1 MPa. When the pressure is too high, there is a problem that safety may require a special device, and it is difficult to use it in the industry. The reaction time is usually 1 minute to 2 hours, preferably 1 hour to 15 hours of citrate may be an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, or an organic acid such as P-toluenesulfonic acid, xylenesulfonic acid or methanesulfonic acid, aluminum chloride or zinc chloride. And Lewis acid such as copper sulfate, etc. These may be used alone or as a mixture of mineral acid and Lewis acid, organic acid and Lewis acid. The solvent may not be used, but the organic sugar or organic compound having a carbonyl group may be used. The solvent having a solubility of the compound of 0.5% or more, preferably 10% or more is preferred. The amount is preferably such that the concentration of the monosaccharide or the organic compound having a carbonyl group is 0.5% or more, preferably 10% or more. Monosaccharide or organic with carbonyl Although the compound may be in a suspended state, it is preferably dissolved. In the case of solvent-42-201120063, it can be cited as a hospital, Gengyuan, toluene, DMF, DMAc, DMSO, ethyl acetate, ethyl ether, Tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. These may be used singly or in combination, preferably tetrahydrofuran, DMF, DMSO. In terms of purification method of the reaction product, distillation may be used as needed. , crystallization, column separation, etc., but the purification method can be selected depending on the nature of the product and the type of impurities. Next, the monosaccharide derivative obtained by the ketalization reaction and the carboxylic acid derivative are halogenated. By reacting an alcohol, a halogen compound or the like, a derivative of the formula (IX) to (XIII), (XXX) and (XXXI) wherein m and η are 1 or more can be obtained. Examples of the reaction include an esterification reaction or an etherification reaction. The carboxylic acid derivative may, for example, be the following compound: -43- 201120063 [Chem. 3 9]

ΑΑ^ΟΗ C|A/CI b"X^〇h b"A^B" h〇A/OH

aApH Cl person, CI &person# person, H.人/〇H BrAL〇H hoA^ci H〇vJ^〇人/OH c\^X〇X^c\

Br

Preferred are diol acid, 2-hydroxyisobutyric acid, 2-chloroisobutyric acid, bromoethene chloride, and chloroacetic chloride. The halogenated alcohol may, for example, be the following compounds. [化4 0]

Preferred are 2-chloroethanol, 2-bromoethanol, 1-chloro-2-methyl-2-propanol, and 1-bromo-2-methyl-2-propanol. As the halogen compound, for example, the following compounds can be mentioned. -44- 201120063 [Chem. 4 1]

Preferred is 1,2-dichloroethane, I,2-dibromoethane. When the monosaccharide derivative obtained by the above ketalization reaction is subjected to an esterification reaction with a carboxylic acid derivative, an azeotropic dehydration method, a mercapto chloride method, an acid hydrazine method or the like can be used. The reaction conditions and the like are the same as those of the above esterification reaction. When the monosaccharide derivative obtained by the above ketalization reaction is subjected to etherification reaction with a hydroxyl group or a halogen compound, the reaction temperature is usually from 0 to 200 ° C, preferably from 50 to 150 ° C. If the temperature is too low, the reaction rate will decrease, which may cause the reaction time to prolong. When the temperature is too high, there is a fear of intense coloration. The pressure is usually 0.01 to 10 MPa in absolute pressure, preferably at normal pressure 〜1 Μ P a . When the pressure is too high, there are safety problems that require special equipment and are difficult to use in the industry. The reaction time is usually from 1 minute to 24 hours, preferably from 1 hour to 1 hour. 触 The catalyst side is preferably used to determine the reaction speed of the tube. The solvent is preferably a solvent having a solubility of the monosaccharide derivative of 0.5% or more, preferably 5% or more. The amount is preferably such that the concentration of the monosaccharide derivative -45 to 201120063 is 0.5% or more, preferably 5% or more. In this case, the monosaccharide derivative may be in a suspended state, but it is preferably dissolved. The solvent may, for example, be hexane, heptane, toluene, DMF, NMP, DMAc, DMSO, ethyl acetate, diethyl ether or tetrahydrofuran. The halogen-containing compound can also be used as a solvent. Although the purification method of the reaction product may be distillation, crystallization, column separation, etc., the purification method may be selected depending on the properties of the product and the type of the impurities. The above derivatives (I) to (VIII) can be polymerized to form a polymer compound by a known method. The polymer compound may be a single polymer or a copolymer. In the case of a copolymer, other monomers may, for example, be 3-hydroxy-1-adamantyl methacrylate, 3-hydroxy-1-adamantyl acrylate, 2-methyl-2-adamantyl group Acrylate, 2-methyl-2-adamantyl acrylate, t-butyl methacrylate, t-butyl acrylate, methyl methacrylate, methacrylate, 2-hydroxyethyl methyl The weight average molecular weight of the fluorene polymer compound such as acrylate or 2-hydroxyethyl acrylate is preferably 1, 〇〇〇 100,000. It is preferably 3,000 to 15,000. The above-mentioned derivatives (I) to (VIII) and the polymer compound may be a solution obtained by adding a digested product such as PAG (photoacid generator) or an organic amine or a solvent, and may be used as a resist. The derivatives (I) to (VIII) and the polymer compound have high hydrophobicity and high glass transition point, and the photoresist thus obtained is excellent in reducing defects and improving coarse sugar content. -46- 201120063 Examples of the solvent to be added to the photoresist include propylene glycol methyl ether, cyclohexane, and propylene glycol monomethyl ether acetate. Further, the derivatives (I) to (VIII) and the composition in which the polymer compound and the polymer are mixed can be cured. For example, the formed model is either formed by coating to form the desired shape. At this time, other polymerizable monomers are contained without adverse effects such as heat resistance and mechanical properties. The compounding surface having a polymerizable unsaturated group may, for example, be a methyl (meth) acrylate, an ethyl (meth) acrylate, a propyl (meth) acrylate or a butyl (meth) acrylate adamantane. (meth) acrylate, benzyl (meth) acrylate ethylene di(meth) acrylate, I, 3 · propylene glycol bis (methyl enoate, I, 4-butanediol di (A) Acrylate, tricyclodecanol di(meth)acrylate, adamantane-1,3-diol di()acrylate, adamantane-1,3-dimethanoldi(methyl)acrylic acid adamantane- I,3-diethanol di(meth)acrylate, pentaerythritol acrylate, dipentaerythritol hexaacrylate, etc. Polymerization initiator, when hardened by heat, is initiated by thermal polymerization when light is used When it is hardened, a photopolymerization initiator is used. Examples of the thermal polymerization starting surface include benzammonium peroxide, methyl ethyl ketone peroxide isobutyl peroxide, and cumene hydroperoxide. An azo initiator such as t-butyl peroxy organic peracid or azobisisobutyronitrile. Acetylbenzene, diphenyl ketone, benzo, benzoin ether, benzyl ketal, thioxanthone, mercaptooxy, decylphosphonate, aromatic diazo iron salt, Aromatic sulfonium salts and aryl ketones are combined to inject their hard aryl acrylates, esters, propane dimethyl esters, four doses, agents, methyl hydrogen and other photopolymers of phosphines -47- 201120063 Town Salt, aromatic oxygen iodide salt, aromatic oxonium salt, metal aromatic compound, and the like. The addition amount of the polymerization initiator is 0.01 to 10% by weight, preferably 5% to 5% by weight based on the total composition, and these may be used singly or in combination. Further, the composition may also contain a binder polymer. Examples of the binder polymer include an acrylic resin, a styrene resin, an epoxy resin, a guanamine resin, a guanamine epoxy resin, an alkyd resin, and a phenol resin. From the viewpoint of alkali developability, an acrylic resin is preferred. These may be used alone or in combination of two or more. The binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives such as styrene, vinyl toluene, a-methylstyrene, p-methylstyrene, and p-ethylstyrene, and acrylamide. An ester of a vinyl alcohol such as acrylonitrile or vinyl-η-butyl ether, an alkyl (meth)acrylate, a (meth)propionic acid tetrakiltitol, or a (meth)acrylic acid- Methylaminoethyl vinegar diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth)acrylic acid, α-bromo (meth)acrylic acid, α-chloro(meth)acrylic acid, β-furanyl (methyl) Acrylic acid, β·styryl (meth)acrylic acid, maleic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monoethyl, maleic acid A maleic acid monoester such as monoisopropyl, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid or the like. These can be used alone or in combination of two or more types. 48 - 201120063 The above (meth)acrylic acid alkyl ester may, for example, be (methyl acrylate, ethyl (meth) acrylate, (meth) propyl ester, butyl (meth) acrylate, ( Methyl)acrylic acid, hexyl (meth)acrylate, octyl (meth)acrylate) octyl acrylate, 2-ethylhexyl (meth) acrylate isomer, and the like. These may be used singly or in combination of two or more types, and the temperature is usually 30 to 200 ° C, preferably 50 Å. In the case of calender curing, for example, the curing intensity can be obtained by irradiation of ultraviolet rays. The type of the polymerization initiator and the film of the cured product are arbitrary, but usually 100 to 5 000 m J/cm 2 , more preferably 4000 mJ/cm 2 °. The optical properties of the cured product in transparency, (long-term) light resistance, and the like It is excellent in heat and has good mechanical properties, while the linear expansion hardening shrinkage rate is low. Therefore, it can be applied to various coating agents, lens mirrors, film capacitors, pattern forming bodies by nanoimprint method, and the like. The composition containing the derivatives (I) to (VIII) and the high compound of the present invention is excellent in characteristics, so that it can be applied to a light semi-LED or the like, a flat panel display (organic EL device, etc.), electricity, and optoelectronics. Resin for optical circuit (optical waveguide) (optical electronic component such as sealing agent, adhesive communication lens, and optical film. The above composition can be used for semiconductor device/integrated circuit), individual semiconductor (diode, Transistors, thermal resistors, etc.) Methyl) pentyl acrylate, (A, etc. -1 50 °C. Depending on the thickness, 5 00 ~ sex, resistance coefficient or micro-permeable molecules Conductor (sub-circuit), light (1C other aspects - -49- 201120063 LED (LED lamp 'wafer LED, light-receiving element, optical semiconductor lens), sensor (temperature sensor, light sensor, magnetic sensor) , passive parts (high-frequency devices, resistors, capacitors, etc.), mechanical parts (connectors, switches, relays, etc.), automotive parts (circuits, control systems, sensors, light stickers, etc.), adhesives (optical Parts, light The film, the photographic lens, etc. can also be used for surface coating of an optical film or the like. Further, the derivatives (I) to (VIII) of the present invention and the polymer compound have heat resistance and adhesion due to the adamantane skeleton. It is excellent in the above-mentioned performance, and it can be used as a semiconductor forming material such as a semiconductor sealing agent or an antireflection film for a semiconductor. Therefore, the composition can be used for a sealing agent for an optical semiconductor or a sealing for an electronic circuit. A stopper, an optical waveguide, a lens for optical communication, a sealing agent for an organic EL device, and an optical film. The sealing agent for an optical semiconductor (LED or the like) is applied to a bullet type or a surface mount (SMT) type. The element can be well adhered to a semiconductor such as GaN formed on a metal or polyimide, and a fluorescent pigment such as YAG can be dispersed and used. Further, it can be used on the surface of a bullet-type LED. For the organic EL, the anode/cavity injection layer/light-emitting layer/electron is provided on a light-transmissive substrate such as a general glass or a transparent resin. An organic EL device having a structure of an in-layer/cathode. In the case of a sealing material for an organic EL device, an adhesive agent for coating a resin film such as a metal can or a metal foil or SiN on an EL element, or an application to the present invention The inorganic gas material for the gas barrier of the invention is dispersed, and the EL element-50-201120063 can be directly sealed. The display method is now applicable to the mainstream bottom emission type, but it is suitable for use in the future. The top emission type which is expected from the viewpoint of light extraction efficiency, etc., and the effect of transparency or heat resistance of the composition described above can be utilized for the configuration of the optical circuit, and can be applied to single mode or multimode. A thermal optical switch or an array of waveguide type grids, a combiner/demultiplexer, a wavelength variable filter, or a nuclear material or cladding material of an optical fiber. Further, it is applied to a mirror of a microlens array or a MEMS type optical switch that collects light on a waveguide. Further, it is also applicable to a pigment binder such as a photoelectric conversion element. When it is used as a film for optical use, it can be applied to a display for liquid crystal film, a film substrate for organic EL, or the like, or a light-transmissive film, an anti-reflection film, or a color conversion by dispersing a fluorescent dye. When a composition such as a derivative (I) to (v 111 ) and a polymer compound of the present invention is used for a substrate for circuit formation, it is possible to maintain both the adhesion and the peeling property of the substrate at a high level. Therefore, when wiring is formed, occurrence of disconnection and short circuit of the wiring can be avoided. The semiconductor industry has been continually demanding smaller shapes, and recently there have been technologies for manufacturing devices with 193111111 lithography and 31115_1〇〇11111. For the use of such shorter wavelengths of light, a bottom anti-reflective film (BARC) is required. This B ARC reduces reflection on the substrate and suppresses hardening due to photoresist vibration by absorbing light passing through the photoresist. Commercially available antireflection film (ARC) is made of both organic materials and inorganic materials. In general, inorganic ARC, which exhibits good uranium resistance, is easily and completely connected based on CVD. -51 - 201120063 is disadvantageous due to the formation of extremely fine structures (topography). The organic ARC material is coated according to the Spin-on process. It has excellent charging characteristics and flattening characteristics, and because of the large number of adamantane skeletons, the etching resistance is good, and the etching property can be changed at the introduction rate. In recent years, miniaturization of LSI devices has been demanded. Therefore, new packages such as CSP or BGA are becoming more and more popular. The wire-free wafer carrier, in general, is formed from a ceramic-containing package which is intended to form a substrate on which the wafer is mounted. A package containing a wafer is mounted on a larger printed circuit board (PCB) or the like. Specifically, the contact portion of the package and the contact portion in the mirror image relationship are formed on the PCB, and after the two are matched, electrical and mechanical connection is performed by reflow soldering or the like, and the surface is mounted. . When the package is soldered to the PCB by solder, it is common to use solder paste or solder bumps. A gap between the substrate and the PCB substrate due to solder bumps is generally applied to an epoxy resin or the like (bottom charge material). Further, one of the methods for reducing the area when the wafer is packaged or mounted on the PCB is a flip chip bonding method. At this time, the gap between the wafer substrate surface and the wafer carrier substrate or the wafer substrate surface and the PCB substrate due to the solder bumps is generated, and the underlying chelating material can be injected in the same manner. The bottom splicing material not only embeds the gap or space in the splicing portion, but also protects the package substrate and the PCB substrate, and has small mechanical properties while sealing the electrical contacts and protecting from the periphery. The purpose of preventing excessive force on the solder bump joint of the joint. The composition using the derivatives (I) to (V111) of the present invention and the polymer compound-52-201120063 is a bottom entangled material which can be used for sealing two or more substrates with a gap, and the bottom sputum can be used. It exhibits short-time hardening, excellent adhesion, and high heat resistance. As a result of this, it is possible to achieve improved reliability and productivity of electronic components. [Examples] Hereinafter, the present invention shows examples and comparative examples to explain more specifically, but the present invention is not limited thereto. Moreover, various analytical methods are implemented as follows. [Glass Transfer Point (Tg): Differential Scanning Thermal Analysis (DSC)] The measurement was carried out using EXSTAR D S C 7 0 2 0 manufactured by SII NanoTechnology Co., Ltd. [Molecular weight, molecular weight distribution: colloidal permeation chromatography (GPC)] The measurement was carried out using HLC-8220GPC manufactured by TOSOH Co., Ltd. Example 1 Synthesis of 1,2: 3,4-di-O-(2,2-adamantyl)-D-galacto-pentanose A 2000 mL 3-golate type containing a dropping funnel and a reflux tube To the flask, 2-adamantanone l〇〇g, D-(+)-galactose 60 g, zinc chloride 90 g, and tetrahydrofuran (THF) 100 mL were added. Heat to 40 ° C 'drop Η 2 S Ο 4 1 5 m L, at 40 t: stir for 6 hours. Thereafter, after cooling to room temperature, the resulting salt was filtered off through a membrane filter. In the filtrate, a potassium carbonate aqueous solution was added for neutralization. Dilute with ethyl acetate l〇〇〇mL 'after removing the aqueous layer' -53- 201120063 Wash with saturated saline. The organic layer was dried with magnesium sulfate to distill off the solvent. The title compound (136.2 g, yield: 92%) was obtained by recrystallised from white solids. [化4 2]

OH

Nuclear Magnetic Resonance Spectroscopy (Solvent: Chloroform-d) JNM-EC A500 'H-NMR (500MHz) : 1.55-2.20 ( m, 28H ) , 4.73- 4.80 ( m, 2H ) , 4.86-4.92 ( m , 2H ) , 4.28 ( dd, 1H, J = 7.9, 1.5Hz) , 4.37 ( dd, 1H, J = 4.9, 2.5Hz ) , 4.65 ( dd, 1H, J = 7.9, 2.5Hz) , 5.59 ( d, 1H, J = 5.2 Hz) 1 3 C-NMR (125MHz): 26.65, 26. 82, 26. 90, 26. 95, 34. 12, 34 • 42, 34.61, 34.64, 34.89, 34. 96, 35 • 00, 35. 02, 3 5 . .06, 35 .35, 36.95, 37.02, 37.14, 37. 32, 62 • 77, 68. 06, 70. .23, 70. 58, 7 1.45, 95.93, 1 1 1.70, 1 112.56 Example 2 1, 2 : 3,4· Di-anthracene - (2,2-Adamantry) -6- 0-methylpropanone 1 fluorenyl-D-galactose It was synthesized in a 2000 mL 3-port eggplant type flask equipped with a dropping funnel and a reflux tube. 201120063, and 1,2:3,4-di-indole-(2,2-adamantyl)-D obtained in Example 1 was added. - galactose 2g, triethylamine 0.82g, N,N-dimethylaminopyridine 165mg, toluene l〇m L. 1.34 mL of anhydrous methacrylic acid was added dropwise at room temperature with stirring, and the mixture was stirred for 1 hour. Thereafter, the force [I was added to 50 mL of toluene and distilled water, and the organic layer was washed. Then, it was washed once with 100 mL of each of a 3% K3P〇4 aqueous solution and a saturated saline solution. The organic layer was dried over magnesium sulfate, and the solvent was evaporated to give the objective compound (2 g, yield: 7%).

Nuclear Magnetic Resonance Spectroscopy (Solvent: Chloroform-d) JNM-EC A500 manufactured by JEOL Ltd. *H-NMR (500MHz): 1.60-2. 1 Ο ( m, 3 1 Η ) , 4.08( ddd, 1 H, J = 6.1, 4.3, 1.9 Hz), 4.21 - 4.3 0 ( im, 2H ) ^ t 4.36 (< dd, 1H, J = 4.9, 2.5 Hz), 4.00 ( dd , 1 H, J — 11.3, 4. 3 Hz ): , 4.66 ( dd, 1H, J = 7.9, 2. 7Hz) , 5 .55 (d, 1H, J = 4. 9Hz ): , 5.56 ( s, 1 H ) , 6.12 ( s, 1H ) 1 : 3c-nmr (1 25MHz): 18.19, 26. 62, 26 .84, 26 .90' 26. .92, 34 .09, 34. 41, 34.57, 34.63, 34. 85, 34 .88, 34 .93 , 34. .92, 3 5 .17, 35. 48, 36.96, 37.04, 37. 13, 37 .43 , 63 .99, 6 6. .17, 70. 21, 70.47, 70.71, 95.77, 11 1.65, 1 12. 57, 1 25 .62, -55- 201120063 136.24, 167.35 Example 3 1,2 : 5,6-di-indole 2,2-adamantyl)-D-glucofuranose synthesis The target product (i3i.8 g, yield 89%) was obtained by the use of glucose to s|μ galactose. [4 4]

Nuclear Magnetic Resonance Spectroscopy (Solvent: Chloroform_d) JNM-ECA500 manufactured by JEOL Ltd. 'H-NMR (500 MHz): 1.50-2.40 (m, 28H), 3.95 (dd, 1H, J=8.7, 5.4Hz), 4.〇5(dd, 1H, J=7.6, 2.8Hz), 4.17 (dd, 1H, J=8.6, 6.1HZ) ? 4.30-4.38 (m, 2H) , 4.54 (d, J = 3.7Hz), 5.97 ( d, J = 3.7 Hz, 1H) 13 C-NMR (125MHz ): 26. 68, 26. 73, 26. 84, 26. ,88, 3 1 .84, 34.3 0, 34.63, 34 .68, 34 .90, 34, ,96, 35, .05, 35. '10, 35, .75, 3 6.7 8, 3 6.9 8, 37 .91, 3 8 .05, 39 '24, 67 .45, 74 , .53, 75 .78, 81.33, 84.3 8, 104. 84, 112 .67, 11 4 .91 Example 4 1,2 : 5,6-di-O-( 2,2-adamantyl) -3_〇_methacrylofluorene-56- 201120063 base-D-grape furanose alkyl)-D-glucosyl)-D-galactosylate to obtain the target except for 1,2:5,6- 2--0-(2,2-Adamantane sucrose to replace 1,2 ··3,4 -di- Ο- (2,2-a ruthenium hexose), the rest is the same as in the second embodiment Real formula (1.7g, yield 74%). [Chemical 4 5]

Nuclear Magnetic Resonance Spectroscopy (Solvent: Chloroform-d) Japan JNM-EC A5 00 1 H.-NMR (500MH z ) : 1.54 -2.34 ( m, dd, 1H, J = 8.7, 5.4Hz ) , 4.12 ( dd, 1H, J - 4.1 5 ( dd, 1 H, J = 8.4, 6.3 Hz ), 4.2 1 - 4.27 ( (d 1, J = : 3.7 Hz, 1H), 5 _ 57 ( s, 1H ) , 5.97 1 H ), 6.14 ( s,: IH) 13C-NMR ( 125MHz ) : 18 .3 1 , 26. 68, 26. 88, 31.84, 3 4.30, 34 .63, 34 • 68, 34.90, 3 5. 10, 35.75 , 3 6.78, 36 .98, 37 • 91, 3 8. 05, 74. 53, 75.78, 8 1.33 ,: 34.38, 104. 84, 1 125 ;.34, 136.83, 167.2 1 Example 5 2,3 : 5,6-di-0-( 2,2-ardamantyl:)- D-— [3H, manufactured by Subsidiary Co., Ltd., 3.95 (= 7.4, 3.1 Hz), m, 2 Η ) , 4.55 (d , J = 3.7 Hz, 26.73, 26.84, 34.96, 35.05, 39.24, 68.94, 12.67, 114.91, Synthesis of sucrose-57-201120063 The same procedure as in Example 1 was carried out except that mannose was used instead of galactose. The target product (1 12.5 g, yield 76%) was obtained.

NMR spectrum of OH (solvent: chloroform-d) JNM-EC A500 manufactured by JEOL Ltd. 1H-NMR (500MHz): 1.60-2.05 ( m, 28H ) , 4.00- 4.10 ( m, 2H ) , 4.33 ( t, 1 H, J = 4.6 Hz), 4.44 (dd, 1 H, J = 11.3, 6.1 Hz), 4.60 (d, 1H, J = 5.8 Hz), 4.76 (dd, 1H, J = 5.8, 3.7 Hz), 5.40 (d, 1H, J = 2.1 Hz) 1 3 lC-NMR (125MHz): 26. 77, 26. 85, 26. 90, 27. 00, 34. .50, 34 • 5 7, 3 4.70, 34.87, 35 .00, 35. 03, 3 5 ' .04, 3 5. 05, 35. .28, 3 5 .71, 3 Ί .02, 37.16, 3 7 .3 1, 37. 40, 65 .54, 73 . 17, 79. .3 8, 80. 60, 85 • 00, 1 01.63, 111 .3 8, 115 • 79 Example 6 2, 3 : 5,6- • 2-0-( 2,2- Aradamantyl) -1 - 0-methylpropanone: Synthesis of decyl-D-mannose except 2,3: 5,6-di-fluorenyl-(2,2-adamantyl)-D The same procedure as in Example 2 was carried out except that mannose was substituted for 1,2:3,4-di-#-(2,2-adamantyl)-D-galactose. (-58- 201120063 2.〇g, yield 87%). [化 4 7]

Nuclear Magnetic Resonance Spectroscopy (Solvent: Chloroform-d) JNM-EC A500 'H-NMR (500MHz): 1.59-2. 1 3 ( m, 3 1 Η ) , 4.2 1-4.18 ( m, 2H ) , 4.33 (t, 1 H, J = 4.6Hz ) , 4.44 ( dd, 1 H, J = 11.3, 6.1Hz) , 4.60 (d, 1H, J=5.8Hz) , 4.76 (dd, J = 5.8 , 3 .7 Hz ), 5 • 40 ( d, 1H, J = 2.Π Hz ) , 5 .58 (s, 1 H ), 6.1 1 ( s, 1H ) 1 : JC-NMR ( 125MHz )·' 18 32, 26. 65 , 26. .97, 26. 91, 27. 00, 34.5 1 , 3 4.54, 34 .61 , 34 .65 , 34. , 87, 3 5 . .01, 3 5 . 03, 3 5. 07, 3 5.3 1 , 3 5.89, 36 .83, 3 7 • 19, 37. 43 , 3 7. .76, 65 . 35, 15. 04, 79.3 8, 80.60, 85.00, 10 1. 63, 11 1 . 3 8, 1 15. 79, 1 2 5.1 9, 1 3 6.3 2, 1 67.22 Example 7 1,2: 4,5 -di-O-(2,2-ardamantyl) The synthesis of -D-fructofuran was carried out in the same manner as in Example 1 except that fructose was used instead of galactose, and the objective compound (1 2 5 · 8 g, yield: 85 %) was obtained. -59- 201120063 [Chem. 4 8]

Nuclear Magnetic Resonance Spectroscopy (Solvent: Chloroform-d) JNM-EC A500 1H-NMR (500 MHz): 1.50-2.3 2 ( m, 28H ) , 3.64 ( t, 1H, J = 7.7Hz ) , 3.96 ( d, 1H, J = 8.6 Hz) , 4.04 ( d, 1H, J =1 3 . 1 Hz ) , 4.1 0-4.24 ( m, 4H ) 1 3 'C-NMR ( 125MHz ): 26. 60 , 26. 70, 26. .84, 26. .87, 34. .05, 34 .48, 3 4.75, 34 .79, 34 .96, 34. 99, 3 5 . .03, 3 5. ,22 , 36. .29, 36 • 96, 3 7.06, 37 • 10, 3 7 • 11, 39. 21, 6 1 , .28, 70. .95, 7 1 . .79, 72. 92, 77 • 00 , 104. 26, 112 .50, 114 .89 Example 8 1,2:4,5-di-O-(2,2-adamantyl)-3-0-methylpropenyl-D- The pistylene is replaced by 1,2:4,5-di-indole-(2,2-adamantyl)-D-fructofuran, 2:3,4-di--0-( The objective compound (2.17 g, yield 94%) was obtained in the same manner as in Example 2 except for the 2,2-y-adamantyl)-D-galactose. -60- 201120063 [Chem. 4 9]

Nuclear Magnetic Resonance Spectroscopy (Solvent: Chloroform-d) JNM-EC A500

1 H-NMR ( 5 00 MHz ) : 1. . . . . . ( d, 1H, J — 13.1Hz) , 4..1 3-4.24 ( m, 4H ) , 5. 4 9 ( s, 1H) , 6. 15 (s, 1 Η ) 1 3c-nmr ( 125MHz ) :18. .24, 26. 60, 26. 70, 26. 84, 26 • 8 7, 3 4. 05, 34.48, 34 .75, 34.79, 34. 96, 34. 99, 35. .03, 35 .22, 3 6. 29, 3 6.96, 37 .06, 37 .10, 37. 11, 39. 21, 62. .67, 70 .95, 71 • 79, 72.92, 77.00, 104, .26, 11 2.50, 1 14. 89, 125.77, 13 6.65 5 167.54 Example 9 1,2 : 3,4-di-O-( 2,2-adamantyl)-6-0-propenyl-D- The synthesis of the lactose was carried out in the same manner as in Example 2 except that acryloyl chloride was used in place of anhydrous methacrylic acid (1.9 g, yield 88%) -61 - 201120063

Nuclear Magnetic Resonance Spectroscopy (Solvent: Chloroform-d) JNM-ECA500 manufactured by JEOL Ltd. 1 H-NMR (500MHz) : 1.54-2.07 ( m, 28H ) , 4.11 ( ddd, 1H, J = 6.2, 4.3, 1.8Hz) , 4.20-4.32 ( m, 2Η) , 4.32 (dd, 1 Η, J = 4.9, 2.5Hz ) , 4.01 ( dd, 1 Η, J = 1 1.2, 4.3Ηζ ), 4.63 ( dd, 1 Η, J = 7.7, 2·7Ηζ), 5.98 ( dd, J = 9.7, 2.0Hz, 1Η), 6.01 ( dd, J= 10.1Hz, J= 16.3Hz, 1H) , 6.47 (dd, J = 1 6. 1 , 1 , 4Hz, 1 H ) 1 3 C-NMR (125MHz ): 26. 59, 26. 57, 26. ,65, 26, ,87, 34. .15, 34.34, 34.76, 34.79, 34 • 8 1, 34 .88, 34 91, 34. .93, 35. , 33, 35.48, 36.95, 37.01, 37 .15, 37. .27, 63 .89, 6 6. .11, 70. ,19, 70.33, 70.65 , 95.47, 111. 21, 11 2.36, 125. .22, 136.56,167,67. Example 1 〇 [Synthesis of (meth)acrylic acid alone polymer] Methyl ethyl ketone 8 4 ml was bubbled with nitrogen gas at room temperature for 1 hour. After adding '1,2: 5,6-di-anthracene-(2,2-aradamantyl)--62- 201120063 3-0-methyl propylene-based-D-Guandian 1 〇 8g ( 211mm 〇 1) and ν· 601 (Dimethyl 2, 2'-AZ〇bis ( is〇 butyrate ) 4g5 gmg ( 2.1 mmol ), heated to 8 ° C, nitrogen gas i〇mL / min The mixture was stirred for 6 hours while bubbling. After cooling the reaction solution to room temperature, it was added dropwise to 84 mL of methanol while stirring. The resulting white solid was filtered, and the obtained white solid was dried under reduced pressure. The polymer of the following formula i,2 _· 5,6_di·〇_(2,2-adamantyl)-3-0-methylpropenyl-D_glucofuranose l〇g (weight average molecular weight (Mw) 18,6〇0, degree of dispersion (Mw/Mn) = 1.4). The results are shown in Table j. [Chem. 5 1]

The number of η repeats in the formula. Comparative Example 1 The following polymer bodies were made in accordance with Havard, Vladimirov, Ν.

Frechet, J. M. Macromolecules 1 999, 32, 86_ was synthesized. The results are shown in Table 1. [化5 2] 201120063 The number of η-system repeats in the formula. [Table η

Mw Mw/Mn Tg (°C) Comparative Example 1 20,200 1.42 157 Example 10 18,600 1.40 >250 Example 1 1 [Synthesis of (meth)acrylic copolymer] In methyl isobutyl ketone, weight ratio 0.1/1.0/1.0/1.0 was placed in 2,2'-azobis(isobutyric acid) dimethyl/monomer oxime/monomer oxime/monomer C, and stirred under heating for 2 hours. In the case of monomer C, I, 2: 3,4-di-0-(2,2-adamantyl)-6-0-methylpropenyl hydrazine-hydrazine-half-pipeper obtained in Example 2 was used. Brown sugar. Thereafter, the operation of precipitating the reaction solution with a large amount of methanol and water was carried out three times to purify it. As a result, a copolymer of monomer Α: monomer Β: monomer C having a copolymerization composition (mol) = 28:42:30, a weight average molecular weight (Mw) of 7 542, and a degree of dispersion (Mw/Mn) of 1.56 was obtained.

-64- 201120063 Example 1 2 [Formation of Photoresist Film] To the copolymer of Example 11, 5 wt% of triphenylsulfonium nonafluorobutanesulfonate as a photoacid generator was added to propylene glycol monomethyl ether B. The ester is dissolved so that it becomes 10% by weight to modulate the photoresist composition. The prepared photoresist composition was coated on a sand wafer and baked at 1 1 〇 ° C for 60 seconds to form a photoresist film. The wafer thus obtained was subjected to a number of open exposures with different exposure amounts by light having a wavelength of 248 nm. Immediately after the exposure, the mixture was heated at 110 ° C for 60 seconds, and then developed with an aqueous solution of tetramethylammonium hydroxide (2.3 8 mass%) for 60 seconds. The film thickness change of the exposure amount at this time is shown in Fig. 1. As a result of this, it was confirmed that the film thickness was changed by the amount of exposure, and the function as a photosensitive resin was exhibited. [Industrial Applicability] The derivatives (I) to (VIII) and the polymer compound of the present invention can be used as a photoresist material for a semiconductor, a color resist material, a photoresist material for forming a printed circuit board, and an anti-resistance. A photoresist material such as a flux material. Further, the derivatives (I) to (VIII) and the polymer compound of the present invention can be used as a base film for a semiconductor, a black matrix material, a bottom entangler, an optical recording material, an optical adhesive and a sealant, and a nano Material for embossing (nanoimprint). The derivatives (IX) to (X111) (XXX) and (XXXI) of the present invention can be used as intermediates for the production of the derivatives (I) to (VIII). Although the embodiments of the present invention and/or the -65-201120063 embodiment have been described in detail above, those skilled in the art can readily at the same time without departing from the novel teachings and effects of the present invention. Many variations are added to these exemplary embodiments and/or embodiments. Therefore, many such changes are intended to be included within the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing changes in film thickness of a photoresist film produced in Example 12. -66 -

Claims (1)

201120063 VII. Patent application scope: 1. A kind of glucose, mannose, psicose, sorbose, tagatose, allose, altogether, gulo, represented by the formula (D~(V) Sugar, idose, glucopyranose derivatives and furanose derivatives, [5, 5] (IV) (V) [wherein, independently represents hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, and Ri and R·2 And/or R·3 and R4 may be bonded to each other to form a ring; however, in the case where the formulas (11) and (V) are not all methyl groups, the group represented by the following formula; 5] R7-67-201120063 (wherein R6 and R·7 are independently an aliphatic hydrocarbon group which may not contain hydrogen, may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent And R6 and R? may together form a carbonyl group; m and η independently represent an integer of 4 or less in 〇; and when η and/or m are 2 or more, 'R6 and R·7 of plural numbers may be the same or different 1 s. 0 or 1; X represents a polymerizable group represented by any one of the following formulas (1) to (3): lit 5 6) Rg I 0 Re II I ru. -c-C-CH2 • CH2 CH—CH2 \j —ch2-ch—ch2 ch2-o (1) (2) (3) (wherein R8 represents a gas atom, a dentate atom, a methyl group or a halogenated methyl group, and R9 represents a carbon number of 1~ 5 of the hydrocarbon group))]. 2 - a galactose-halfose derivative and a carraghalose derivative represented by the formula (VI), a peptidose derivative represented by (V), or a formula (v π ) or a galactose furanose derivative represented by (IV), and a fructofuran derivative represented by the formula (VIII) '-68- 201120063 [Chem. 5 7 (IV) wherein R1 to R4 and Rl1 to RM each independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic ring of a 3 J 雑 雑 atom and/or a substituent a hydrocarbon group, and R丨 and r2, p D 2 core and R4, Rn and R and/or R13 and R14 may also be bonded to form a ring; however, R1 to R4 Rn~Rm of the formula (V) are not all methyl The case; represents a base represented by the following formula; [Chem. 5 8] (wherein R6 and R7 each independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, and R 6 and R 7 The carbonyl group may be formed together; -69-201120063 m, η is an integer representing 0 or more and 4 or less; and when η and/or m is 2 or more, the plural R6 and R7 may each represent 0 or 1; X represents the following Any one of the formulas (1) to (3) [化5 9] | ^8 —ch2-ch-ch2 a c—c==ch2 , 〇 / (1) (2) (wherein R8 represents A hydrogen atom, a halogen atom, a methyl group, and R9 represents a hydrocarbon group having 1 to 5 carbon atoms))]. The derivative according to claim 1 or 2, wherein R3 and R4, or Ru and R12 and R13 and R14 are bonded to form adamantane of a sub-and/or a substituent. 4. The derivative according to claim 1 or 2, wherein R3 and R4, or Rm and R12 and Rl3 are bonded to Rm to form adamantane. 5. The derivative according to claim 1 or 2, wherein the polymerizable group represented by 1). 6. The derivative according to claim 1 or 2, wherein the glucose, mannose, and the following formula (IX), formula (X), formula (XXX), and formula (XXXI) are used. Polymeric R9 I of the same or different properties of sorbose, tagatose, allose, altrose, gulose, CH2-CH-CH; ch2-o (3) or halogenated methyl 'R1 and May contain miscellaneous, Ri and R2 and amantadine or X-based formula ( m = 0 〇 XI), formula ( , psicose, idose, -70- 201120063 thaoseose peptose derivative And furanose derivatives, [chemical 60] [wherein, Ri to R4 and Rii to Ri4 each independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero substituent, and 1 and R2; R3 and R4, 11 and R!2 and/or R! 3 and Rl4 may also be linked to form a ring; however, among allose, altrose, glucose, pentose pistose derivatives and furanose derivatives, When RU to R丨4 are not all methyl groups; in the formula (XXXI), when Ri to R4 are all methyl groups, there is no case where a ring is formed by linking R2 to R2 and R3 and R4 are formed. a case where a cyclohexane ring is formed by linking; m3 represents a group represented by the following formula; -71 - 201120063 [Chem. 6 1] (In the formula, Re and R7 independently represent an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, and R·6 and & 7 may form a sulfhydryl group; m and η independently represent an integer of 4 or more 〇; when η and/or m are 2 or more, 'the plural r6 and r7 may each be the same or the different s represents 0 or 1; L represents a hydroxyl group or a halogen atom; however, in the formula (XXX), when s and m are 0 and L is a hydroxyl group, 1^ to 114 are not all methyl groups). 8. The following: a fruit-pentane sugar derivative represented by the formula (XII) or (XXXI) and a furfuran derivative represented by the formula (XIII), [Chem. 6 2] [wherein, Ri to R4 each independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and /72-201120063 or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, and R1 R2 to Rb may be bonded to each other to form a ring; and Rm to R34 each independently represent hydrogen, may contain a hetero atom, and/or a substituent having an aliphatic hydrocarbon group having 2 or more carbon atoms, or may contain a hetero atom and/or a substituent. Base of aliphatic cyclic hydrocarbon groups, and Hanmen and ruler 32 and / or! ^3 and R34 can form a ring having a carbon number of 4, 5 or more, which is linked by a carbon chain; and, in the formula (χχχι), when 'R!~R4 are all methyl groups', there is no 1^ and R2 a case where a cyclohexane ring is formed to form a ring, and a case where R3 and R4 are bonded to form a cyclohexane ring; M3 represents a group represented by the following formula; [Chem. 6 3] (wherein R6 and R? independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and/or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, and R6 and R7 may The carbonyl group is formed together; m ' η is independently an integer of 0 or more and 4 or less; when η and/or m is 2 or more, the plural R 6 and R 7 may be the same or different each other » s represents 0 or 1; L represents a hydroxyl group, Halogen atom)] 9. The derivative described in the claim 7 or 8 wherein R' and R2 and 113 and 114, or r3I and R32 and R33 and R34 are bonded to form adamantane. 10. The method of producing a derivative according to any one of claims 1 to 8 wherein the derivative is described in the item 7 or 8 wherein the 'm=0, L-73-201120063 is a hydroxyl group. It is obtained by reacting a compound having a polymerizable group represented by any one of the following formulas (1) to (3) on a derivative described in any one of the claims 7 to i, (Chem. 6 4) Rg I -CH2~CH-CH2 CH2~ο (3) II I —ch2-ch—CH 2 —C—C=CH 2 (1) (2) (wherein R 8 represents a hydrogen atom, a halogen atom, a methyl group or a halogenated methyl group And R9 represents a hydrocarbon group having 1 to 5 carbon atoms). 12. A method for producing a monosaccharide derivative represented by the following formula (XX) to (XXII), which is based on adamantanone to impart galactose, glucose, mannose, psicose, sorbose, Tagatose, allose, altrose, gulose, idose, telose, fructose reaction [Chem. 6 5] (XX) Base shown] [Μ 3 indicates the following -74- 201120063 [Chem. 6 6] (In the formula, Re and R·7 each independently represent hydrogen, an aliphatic hydrocarbon group which may contain a hetero atom and y or a substituent, or an aliphatic cyclic hydrocarbon group which may contain a hetero atom and/or a substituent, and 116 and R7 The carbonyl group may be formed together; m and η independently represent an integer of 0 or more and 4 or less; s represents 0 or 1; and when η and/or m is 2 or more, the plural R·6, R·7 may be the same or different. t L represents a hydroxyl group, a halogen atom)]. A polymer compound obtained by polymerizing a derivative described in any one of claims 1 to 6. I. A photoresist film for a semiconductor and a base film for a semiconductor, which is the derivative according to any one of claims 1 to 6, or the polymer compound described in claim 1 1 . A resist pattern forming method comprising forming a photoresist on a support by using a photoresist composition containing the derivative according to any one of claims 1 to 6 or the polymer compound described in claim 13 a step of forming a film, a step of exposing the photoresist film, and a step of developing the photoresist film to form a photoresist pattern. -75- 201120063 16 'A hardened material which is obtained by subjecting the derivative of any one of claims 1-6 to the polymer compound of claim 13 to hardening by heating. 17. A color resist and a black matrix material, wherein the derivative described in any one of items 1 to 6 or the high compound described in claim 13 is used. (1) A photoresist material for forming a printed circuit board and a solder resist, which is the derivative according to any one of claims 1 to 6, or the polymer compound described in the above. 1 . A bottom tamping agent, which is the use of the derivative described in any of claims 1-6, or the polymer compound described in claim 13 of the invention. The derivative according to any one of the above-mentioned items, or the polymer compound according to claim 1 of the invention, wherein the optical adhesive and the sealant are used as the derivative or the claim described in any one of the claims. The polymer described in 1 3 is a polymer. 22. A material for nanoimprint, which is described in any one of claims 1 to 6, or a polymer compound in claim 1 or as claimed in the optical product. Item-item-item 0 1~6 combined use: 76-