JP2006206649A - Heat-decomposable block copolymer composed of ketene and aldehyde copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a block copolymer enabling easy removal of a decomposed polymer chain generated by the breakage and decomposition of the main chain of a specific repeating unit of the block copolymer. <P>SOLUTION: The heat-decomposable block copolymer contains a decomposable chain composed of a structure decomposable with acid or heat as at least one phase of the block copolymer. Especially, the heat-decomposable block copolymer contains a repeating unit expressed by formula (I) as a decomposable chain having a structure decomposable with heat. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel block polymer and graft copolymer comprising a thermally decomposable unit and a non-thermally decomposable resin. More specifically, the present invention relates to a thermally decomposable chain-containing block copolymer and graft copolymer in which at least one phase is composed of degradable units in the block copolymer, and the main chain of the degradable unit is cleaved by heat to decompose to a low molecular weight.

  Various block copolymers have been known so far. As a method for forming a molded article having a nanometer-order microstructure using this block copolymer, a method using block copolymer or microphase separation of the block copolymer is known. This method selectively removes one specific phase of the microphase separation structure to form a molded body having a fibrous structure, a thin film structure, or a porous structure, or a microphase separation film formed on a substrate. As the dots arranged in a porous film or array by selectively removing one phase of the film, the substrate is finely processed using the porous film or the dot array as an etching mask.

  At this time, since each polymer chain constituting the block copolymer or graft copolymer is chemically bonded to each other, in order to selectively remove one specific phase, the main chain of the polymer chain constituting the phase Break and break chains. The polymer chain that has been cut and decomposed is removed by heating to volatilize or by elution with an organic solvent or water.

  However, there was a problem in the heating operation necessary for removing the above-described cleaved and decomposed polymer chains and the elution operation with an organic solvent or water.

  That is, the heating operation usually needs to be performed at a high temperature of 200 ° C. or higher in order to thermally decompose and volatilize the polymer. Therefore, there is a possibility that the fine processing remaining during the heating operation is thermally deteriorated due to oxidation or the like, or becomes higher than the glass transition temperature, and is thermally deformed. For this reason, the molded object which can be manufactured by heating operation is restricted to the form of the heat resistant polymer which has high glass transition temperature, such as a polyimide, and does not have the versatility of a material.

In addition, the elution operation has an advantage that a polymer chain that has been cut and decomposed can be obtained at a relatively low temperature. However, there is a problem that elution often requires a long time of one day or more and the throughput is low.
On the other hand, in the pamphlet of International Publication No. 03/069412, it is described that the block polymer of ketene and aldehyde copolymer represented by Chemical Formula 1 is decomposed with an acid.
International Publication No. 03/069412 Pamphlet

  An object of the present invention is to provide a block copolymer capable of easily removing, decomposing and decomposing a polymer chain of a specific repeating unit of the block copolymer.

  As a result of intensive studies to solve the above problems, the present inventors have determined that a specific combination of polymers having an ester bond in the main chain, which can be easily synthesized from ketene and aromatic aldehyde, is part of the block copolymer. It was found that the above-mentioned problems can be solved by introducing it in this phase, and the present invention has been completed.

（式中、Ｒ₁、Ｒ₂はそれぞれ独立に、水素原子、ハロゲン原子、Ｃ１〜Ｃ２０の炭化水素基、ヘテロ環基、シアノ基、ニトロ基、Ｃ（＝Ｏ）Ｒ₄基、Ｓ（０）_pＲ₄基、Ｐ（＝Ｏ）（Ｒ₄）₂基、Ｍ（Ｒ₄）₃基を表し、Ｒ₃はＣ１〜Ｃ２０の炭化水素基、ヘテロ環基を表し、Ｒ₄はＣ１〜Ｃ２０の炭化水素オキシ基、Ｃ１〜Ｃ２０の炭化水素基、Ｃ１〜Ｃ２０の炭化水素チオ基、モノもしくはジＣ１〜Ｃ２０の炭化水素アミノ基を表し、Ｍは、ケイ素原子、ゲルマニウム原子、スズ原子、鉛原子を表し、ｐは０、１、または２のいずれかを表す。）で表される繰り返し単位を有することを特徴とする（１）に記載の熱分解性ブロックコポリマー。
（３）式（Ｉ）で表される化合物中、Ｒ₃が、式（II）

（式中、Ｘは、酸素原子、硫黄原子を表し、Ｒ₅は、水素原子、Ｃ１〜Ｃ２０の炭化水素基、または熱で分解・脱離する基を表し、Ｒ₆は、ハロゲン原子、Ｃ１〜Ｃ２０の炭化水素基を表し、ｍは１〜３のいずれかの整数を表し、ｎは０または１〜３のいずれかの整数を表し、ｍ＋ｎ≦５を表し、ｍが２以上の場合、Ｒ₅は同一または相異なっていてもよく、ｎが２以上の場合、Ｒ₆は同一または相異なっていてもよい。）で表される置換基であることを特徴とする（２）に記載の熱分解性ブロックコポリマー。
（４）重合体の数平均分子量が、２，０００〜９００，０００であることを特徴とする（１）〜（３）のいずれかに記載の熱分解性ブロックコポリマー。
（５）重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が、１．０１〜３．００の範囲であることを特徴とする（１）〜（４）のいずれかに記載の熱分解性ブロックコポリマー及び熱分解性グラフトコポリマー。
（６）ブロックコポリマーがグラフトコポリマーであることを特徴とする（１）〜（５）のいずれかに記載の熱分解性ブロックコポリマー。
（７）（１）〜（６）記載の熱分解性ブロックコポリマーを含有する樹脂組成物を、酸非存在下で加熱して分解することを特徴とする樹脂組成物の分解方法。 That is, the present invention is as follows.
(1) A thermally decomposable block copolymer in which at least one phase of the block copolymer contains a degradable chain having a structure decomposable by acid or heat.
(2) As a degradable chain having a structure decomposable by acid or heat as described in (1) above, formula (I)

(In the formula, R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, a heterocyclic group, a cyano group, a nitro group, a C (═O) R ₄ group, S (0 ) _P R ₄ group, P (═O) (R ₄ ) ₂ group, M (R ₄ ) ₃ group, R ₃ represents a C1-C20 hydrocarbon group or heterocyclic group, and R ₄ represents C1— C20 represents a hydrocarbon oxy group, C1 to C20 hydrocarbon group, C1 to C20 hydrocarbon thio group, mono or di C1 to C20 hydrocarbon amino group, and M represents a silicon atom, a germanium atom, a tin atom, (1) represents a lead atom, and p represents any one of 0, 1, or 2. The heat decomposable block copolymer according to (1), which has a repeating unit represented by
(3) In the compound represented by the formula (I), R ₃ represents the formula (II)

(In the formula, X represents an oxygen atom or a sulfur atom, R ₅ represents a hydrogen atom, a C1 to C20 hydrocarbon group, or a group that decomposes and desorbs by heat, R ₆ represents a halogen atom, C1 C represents a hydrocarbon group of C20, m represents an integer of 1 to 3, n represents an integer of 0 or 1 to 3, m + n ≦ 5, and when m is 2 or more, R ₅ may be the same or different, and when n is 2 or more, R ₆ may be the same or different.) Thermally decomposable block copolymer.
(4) The thermally decomposable block copolymer according to any one of (1) to (3), wherein the polymer has a number average molecular weight of 2,000 to 900,000.
(5) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 1.01 to 3.00, any of (1) to (4) Thermally decomposable block copolymers and thermally decomposable graft copolymers as described above.
(6) The thermally decomposable block copolymer according to any one of (1) to (5), wherein the block copolymer is a graft copolymer.
(7) A method for decomposing a resin composition comprising heating and decomposing a resin composition containing the thermally decomposable block copolymer according to (1) to (6) in the absence of an acid.

  The block copolymer refers to a copolymer (copolymer) having a plurality of single polymer chains as partial constituent components (blocks). A typical example of the block copolymer is in the form of a linear molecular chain, in which an A polymer chain having a repeating unit A and a B polymer chain having a repeating unit B are chemically bonded at the ends. It is an AB type diblock copolymer having a structure of (AA ·· AA)-(BB ·· BB)-. Moreover, the block copolymer which 3 or more types of polymer chains couple | bonded may be sufficient. In the case of a triblock copolymer, any of ABA type, BAB type, and ABC type may be used. It may be in the form of a star-shaped molecular chain. As the star type, block copolymer chains may extend radially from the center, or different polymer chains may extend from the center. A block copolymer such as (AB) t or (ABA) t type having four or more blocks may be used. In addition to the above, for example, a block copolymer in which at least one block is a polymer chain made of a random copolymer, such as-(AA ·· AA)-(BCBBBCBCCBCB ·· CBB)-, may be used.

  The graft copolymer has a structure in which another polymer chain is suspended as a side chain in the main chain of a certain polymer. In the graft copolymer, several types of polymers can be hung on the side chain. Further, a combination of a block copolymer and a graft copolymer in which a C polymer chain is suspended from a block copolymer such as an AB type, an ABA type, or a BAB type may be used.

  The block copolymer of the present invention can easily cleave, decompose, and remove the main chain of a specific repeating unit, and is excellent in operability.

In the repeating unit represented by the formula (I) used in the present invention, R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, a heterocyclic group, a cyano group, or a nitro group. , C (═O) R ₄ group, S (0) _p R ₄ group, P (═O) (R ₄ ) ₂ group, M (R ₄ ) ₃ group, and R ₃ is a C1-C20 hydrocarbon. R ₄ represents a C1-C20 hydrocarbon oxy group, a C1-C20 hydrocarbon group, a C1-C20 hydrocarbon thio group, a mono- or di-C1-C20 hydrocarbon amino group. , M represents a silicon atom, a germanium atom, a tin atom, or a lead atom, and p represents any of 0, 1, or 2. Specific examples of R ₁ and R ₂ include a hydrogen atom, a fluorine atom, a chromium atom, a bromine atom, a halogen atom that is an iodine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, t -Butyl group, s-butyl group, isobutyl group, n-pentyl group, s-pentyl group, isopentyl group, neopentyl group, n-hexyl group, s-hexyl group, s-hexyl group, 1,1-dimethyl-n -Hexyl group, n-heptyl group, n-decyl group, n-dodecyl group, etc. C1-C20 alkyl group, vinyl group, allyl group, 2-butenyl group, 1-methyl-2-propenyl group, 4-octenyl C2-C20 alkenyl group such as a group, ethynyl group, propargyl group, C2-C20 alkynyl group such as 1-methyl-propynyl group, cyclopropyl group, cyclobutyl group, cyclo C3 to C20 alicyclic rings such as nyl, 1-methylcyclopentyl, 1-methylcyclohexyl, 1-adamantyl, 1-methyladamantyl, 2-adamantyl, 2-methyl-2-adamantyl, norbornyl C6-C20 aromatic hydrocarbon group such as formula hydrocarbon group, phenyl group, 1-naphthyl group, 9-anthracenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-furanyl group, 2 -Thienyl group, 3-thienyl group, 1-pyrrolo group, 2-oxazolyl group, 3-isoxazolyl group, 2-thiazolyl group, 3-isothiazolyl group, 1-pyrazolyl group, 4-pyrazolyl group, 2-imidazolyl group, 1 , 3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-triazol-2-yl, 1,2,3-thiadiazol-5-yl, 1,2,3-triazol-4-yl, 1, 2,3,4-tetrazol-5-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrazin-2-yl, pyridazin-3-yl, 1,2,4-triazin-6-yl, 1, Heterocyclic groups such as 3,5-triazin-2-yl, 1-pyrrolidinyl group, 1-piperidyl group, 4-morpholinyl group, 2-tetrahydrofuranyl group, 4-tetrahydropyranyl group, methoxycarbonyl group, ethoxycarbonyl group A C1-C20 alkoxycarbonyl group such as n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, etc. C1-C20 alkylthiocarbonyl group such as thiocarbonyl group, substituted or unsubstituted carbamoyl group such as N, N-dimethylcarbamoyl group, methylsulfenyl group, phenylsulfenyl group, methylsulfinyl group, phenylsulfinyl group, methylsulfonyl group , Phenylsulfonyl group, methylsulfuryl group, substituted or unsubstituted sulfamoyl group such as N, N-dimethylsulfamoyl group, dimethylphosphoryl group, bismethylthiophosphonyl group, phosphonyl group such as tetramethylaminophosphonyl group, trimethylsilyl group , T-butyldimethylsilyl group, phenyldimethylsilyl group, trimethylstannyl group, triphenylplanbanyl group, and the like.

R ₃ represents a C1-C20 hydrocarbon group or heterocyclic group, and specific examples thereof include the same substituents as exemplified for R ₁ and R ₂ .
As described above, each of the substituents represented by R _{1 to} R ₃ can have a substituent at an appropriate carbon position. As the substituent, fluorine atom, chloro atom, bromine atom, halogen atom which is iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group , Fluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluoroethyl group, cyclopropyl group, cyclohexyl group, vinyl group, allyl group, phenyl group, 4-chlorophenyl group, 4-methoxyphenyl group, 3,4- Substituted phenyl group such as dimethylphenyl group, propargyl group, 2-hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl group, 2- (ethoxymethoxy) -1,1,1,3 , 3,3-hexafluoro-2-propyl group, etc., methoxy group, ethoxy group, n-propoxy group, isopropoxy group, -Butoxy group, s-butoxy group, isobutoxy group, t-butoxy group, fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, phenoxy group, 4-chlorophenoxy group, benzyloxy group, phenethyloxy group, t-butoxy Alkoxy groups such as carbonyloxy group, tetrahydropyranyloxy group, phenoxyethoxy group, ethoxyethoxy group, trimethylsilyloxy group, t-butoxycarbonylmethoxy group, amino group, methylamino group, dimethylamino group, t-butoxycarbonylamino group Such as amino group, methylthio group, phenylthio group, 2-pyridylthio group, methylsulfinyl group, methylsulfonyl group, etc., alkyl, aryl, or heterocyclic thio group or its oxidized form, methoxycarbonyl group, ethoxycarboni Group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, C1-C20 alkoxycarbonyl group such as t-butoxycarbonyl group, acetyl group, propanoyl group, benzoyl group, 2-pyridylcarbonyl group, etc. Examples include C2-C20 acyl groups, cyano groups, nitro groups and the like.

Specific examples of R _{1 to} R ₃ having these substituents include chloromethyl group, fluoromethyl group, bromomethyl group, dichloromethyl group, difluoromethyl group, dibromomethyl group, trichloromethyl group, trifluoromethyl group, tribromo Methyl group, trichloromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3,3,3-trifluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group Haloalkyl groups such as tetrafluoroethenyl group, haloalkenyl groups such as 2,2-difluoroethenyl group, alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, phenoxymethyl group, methylthiomethyl group, phenylthiomethyl group, etc. Alkylthioalkyl group or arylthioalkyl group, benzyl group, diphenyl Rumechiru group, trityl group, aralkyl groups such as phenethyl group, benzoyl methyl group, an acyl group such as acetyl group, there can be exemplified a cyanomethyl group.

In addition, a substituent represented by the formula (II) can be preferably exemplified as R ₃ . In the substituent represented by the formula (II), R ₅ represents a hydrogen atom, a C1-C20 hydrocarbon group, an acid elimination / decomposition group or a thermal elimination / decomposition group, and m is any one of 1 to 3 When m is 2 or more, R ₅ may be the same or different. Here, the acid leaving / decomposing group means a group that can be eliminated and / or decomposed by an acid, and the thermal leaving / decomposing group means a group that can be eliminated and / or decomposed by heat. Specifically, methoxymethyl group, 2-methoxyethoxymethyl group, bis (2-chloroethoxy) methyl group, tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, tetrahydrofuranyl group, triphenylmethyl group, trimethylsilyl group , 2- (trimethylsilyl) ethoxymethyl group, t-butyldimethylsilyl group, trimethylsilylmethyl group, or a substituent as shown in the following formula.

  (Wherein k represents 0 or 1). Furthermore, the following formula

Wherein R ₁₄ represents a C1-C20 unsubstituted or alkoxy-substituted alkyl group, a C5-C10 cycloalkyl group, or a C6-C20 unsubstituted or alkoxy-substituted aryl group, and R ₁₅ represents hydrogen or A C1-C3 alkyl group, and R ₁₆ represents a hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group). Specific examples include 1-methoxyethyl group, 1-ethoxyethyl group, 1-methoxypropyl group, 1-methyl-1-methoxyethyl group, 1- (isopropoxy) ethyl group and the like. The substitution position of the hydroxyl group or alkoxy group (OR ₅ group) is not particularly limited, but the meta position or para position is preferred.
R ₆ represents a halogen atom or a C1-C20 hydrocarbon group. Specifically, among the substituents exemplified for R ₁ and R ₂ , the same substituents as the corresponding examples can be exemplified. .
Specific examples of the substituent represented by the formula (II) include 4-hydroxyphenyl group, 4-hydroxy-3-methylphenyl group, 4-t-butoxyphenyl group, 4-tetrahydropyranyloxyphenyl group, 4 -Phenoxyethoxyphenyl group, 4-trimethylsilyloxyphenyl group, 4-t-butoxycarbonyloxyphenyl group, 4-t-butoxycarbonylmethoxyphenyl group, 2,3-difluoro-4-hydroxyphenyl group, 2,3-difluoro -4-t-butoxyphenyl group, 2,6-difluoro-4-hydroxyphenyl group, 2,6-difluoro-4-t-butoxyphenyl group, 3,5-difluoro-4-hydroxyphenyl group, 3,5 -Difluoro-4-t-butoxyphenyl group, 2,3,5,6-tetrafluoro-4-hydroxy Phenyl group, 2,3,5,6-tetrafluoro-4-t-butoxyphenyl group, 2-trifluoromethyl-4-hydroxyphenyl group, 2-trifluoromethyl-4-t-butoxyphenyl group, 2- Trifluoromethyl-6-fluoro-4-hydroxyphenyl group, 2-trifluoromethyl-6-fluoro-4-t-butoxyphenyl group, 3-trifluoromethyl-5-fluoro-4-hydroxyphenyl group, 3-trimethyl Fluoromethyl-5-fluoro-4-t-butoxyphenyl group, 4- (1-ethoxyethoxy) phenyl group, 4- (2-hydroxy-1,1,1,3,3,3-hexafluoro-2- (Propyl) phenyl group, 4- (2-ethoxymethoxy-1,1,1,3,3,3-hexafluoro-2-propyl) phenyl group, etc. You can.
Further, the substituent represented by the formula (II) exemplified as a preferred embodiment of R ₃ can be preferably exemplified as the substituent of R ₁ and R ₂ .

In addition, the substituents represented by R _{1 to} R ₃ do not have to be the same in all the repeating units represented by the formula (I), and two or more kinds can be appropriately mixed and used. For example, as a substituent for R ₃ , a p-methoxyphenyl group and a p- (1-ethoxyethoxy) phenyl group can be mixed at a molar ratio of 1/99 to 99/1.

  The block copolymer containing a degradable chain represented by the formula (I) in the present invention is a polymerization site consisting only of a repeating unit represented by the formula (I) and a repeating unit other than the repeating unit represented by the formula (I). It is a block copolymer consisting of polymerization sites consisting of repeating units of

  Specific examples of the repeating unit other than the repeating unit represented by the formula (I) include a repeating unit represented by the formula (III).

In the formula, R ₃₁ , R ₃₂ and R ₃₃ each independently represents a hydrogen atom, a fluorine atom, a C1-C20 linear, branched or cyclic alkyl group or a fluorinated alkyl group, and R ₃₄ It represents a hydroxyl group or an aromatic hydrocarbon group having an alkoxy group may be substituted C6~C20 or represents CO ₂ R ₃₅ group, R _35,, represents a C1~C20 hydrocarbon group.

  In this case, the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms includes methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, A cyclopentyl group, a cyclohexyl group, a 2-ethylcyclohexyl group, an n-octyl group and the like can be exemplified, and those having 1 to 12 carbon atoms, particularly 1 to 10 carbon atoms are preferable. The fluorinated alkyl group is one in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and includes a trifluoromethyl group, a 2,2,2-trifluoroethyl group, 3, Examples include 3,3-trifluoropropyl group and 1,1,2,3,3,3-hexafluoropropyl group.

R ₃₄ is a hydroxyl group or a C6-C20 aromatic hydrocarbon group which may be substituted with hydrogen or a substituted hydrogen group, specifically, a substituent represented by the following formula (IV): It can be illustrated.

In the formula, R ₄₀ represents a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms or a fluorinated alkyl group, and specific examples thereof are the same substitutions as the specific examples illustrated for R ₃₁ above. Group may be exemplified, X represents a fluorine atom, and R ₄₁ represents a C1-C20 hydrocarbon group. a, b, c and d each represents 0 or an integer of 1 to 5, and a + b + c + d is 0 to 5.

In R ₄₁ , examples of the C1-C20 hydrocarbon group include the same substituents as those exemplified for R ₁ . Various heat labile groups are selected, and specifically, a group represented by the following formula (V), (VI), or (VII), or a trialkylsilyl group having 1 to 6 carbon atoms of each alkyl group And an oxoalkyl group having 4 to 20 carbon atoms.

In the formulas (V) and (VI), R ₅₁ and R ₅₄ are monovalent hydrocarbon groups such as linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, oxygen atom, sulfur atom, nitrogen atom And may contain a hetero atom such as a fluorine atom.

R ₅₂ and R ₅₃ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom or a fluorine atom. R ₅₂ and R ₅₃ , R ₅₂ and R ₅₄ , and R ₅₃ and R ₅₄ may be bonded to each other to form a ring. a represents 0 or an integer of 1 to 10.

More preferably, R _{51 to} R ₅₄ are the following groups. R ₅₁ is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the above general formula ( VII), and specific examples of the tertiary alkyl group include tert-butyl group, tert-amyl group, 1,1-diethylpropyl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1 -Ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group, etc. Specifically, a trimethylsilyl group, a triethylsilyl group, a dimethyl-tert-butylsilyl group, and the like can be given as an oxoalkyl group. The body, the 3-oxo-cyclohexyl group, 4-methyl-2-oxooxan-4-yl group, and 5-methyl-5-oxo-dioxolane-4-yl group. a is an integer of 0-6.

R ₅₂ and R _{53 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically a methyl group, an ethyl group, a propyl group or an isopropyl group. N-butyl group, s-butyl group, t-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylcyclohexyl group, n-octyl group and the like. R ₉ represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and is a linear, branched or cyclic alkyl group, Examples include those in which a part of hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like. Specifically, a 4-hydroxybutyl group, a 2-butoxyethyl group, 4 Examples thereof include substituted alkyl groups such as -hydroxymethyl-1-cyclohexylmethyl group, 2-hydroxyethoxy-2-ethyl group, 6-hydroxyhexyl group and 1,3-dioxolan-2-one-4-methyl group.

R ₅₂ and R ₅₃ , R ₅₂ and R ₅₄ , R ₅₃ and R ₅₄ may be combined to form a ring, and in the case of forming a ring, R ₅₂ , R ₅₃ and R ₅₄ each have 1 carbon atom. Represents a linear or branched alkylene group of -18, preferably 1-10.

  Specific examples of the formula (V) include a t-butoxycarbonyl group, a t-butoxycarbonylmethyl group, a t-amyloxycarbonyl group, a t-amyloxycarbonylmethyl group, a 1,1-diethylpropyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethoxyethoxycarbonylmethyl group, 2- Examples thereof include a tetrahydropyranyloxycarbonylmethyl group and a 2-tetrahydrofuranyloxycarbonylmethyl group.

  Specific examples of the linear or branched ones represented by the above formula (VI) include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, n-butoxymethyl group, 1 -Ethoxy-ethyl group, 1-methoxy-propyl group, 1-methoxy-butyl group, 1-ethoxy-propyl group, 1-n-propoxy-ethyl group, 1-n-propoxy-propyl group, 1-n-butoxy -Butyl group, 1-n-propoxy-butyl group, 1-cyclopentyloxy-ethyl group, 1-cyclohexyloxy-ethyl group, 2-methoxy-2-propyl group, 2-ethoxy-2-propyl group, etc. be able to.

  Among the thermally labile groups represented by the above formula (VI), specific examples of the cyclic group include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2 -A methyltetrahydropyran-2-yl group etc. can be illustrated. As the formula (4), a 1-ethoxy-ethyl group, a 1-n-butoxy-ethyl group, and a 1-ethoxy-n-propyl group are preferable.

In the formula (VII), R ₅₅ , R ₅₆ , and R ₅₇ are monovalent hydrocarbon groups such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom. Hetero atoms, fluorine atoms and the like, and R ₅₅ and R ₅₆ , R ₅₅ and R ₅₇ , and R ₅₆ and R ₅₇ may be bonded to each other to form a ring.

  The tertiary alkyl group represented by the formula (VII) includes a t-butyl group, 1,1-diethyl-n-propyl group, 1-ethylnorbornyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, 2 -(2-Methyl) adamantyl group, 2- (2-ethyl) adamantyl group, tert-amyl group and the like can be mentioned.

  Moreover, as a tertiary alkyl group represented by Formula (VII), the functional group shown below can be illustrated concretely.

Here, R ₆₁ and R ₆₄ represent a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group. , Sec-butyl group, n-pentyl group, n-hexyl group, cyclopropyl group, cyclopropylmethyl group and the like. R ₆₂ represents a monovalent hydrocarbon group such as a hydrogen atom or an alkyl group which may be bonded via a hetero atom having 1 to 6 carbon atoms. Examples of the hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom, and —OH, —OR (R is an alkyl group having 1 to 20 carbon atoms, particularly 1 to 16 carbon atoms, the same shall apply hereinafter), —O—, — S-. -S (= O) -, - NH 2, -NHR, -NR 2 -, - NH -, - can contain or intervening as NR-.

Examples of R ₆₃ include a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, particularly 1 to 16 carbon atoms, a hydroxyalkyl group, an alkoxy group, or an alkoxyalkyl group. These are linear, branched, and cyclic. Either of these may be used. Specifically, methyl group, hydroxymethyl group, ethyl group, hydroxyethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, methoxy group, methoxymethoxy Group, ethoxy group, tert-butoxy group and the like.

Examples of the trialkylsilyl group in which each alkyl group used as the heat labile group for R ₄₁ has 1 to 6 carbon atoms include a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, and the like.

  Examples of the oxoalkyl group having 4 to 20 carbon atoms include a 3-oxocyclohexyl group and a group represented by the following formula.

Further, the heat-insecure group of R ₄₁ may be an acetal bridging group represented by the following formula (VIII) or (IX).

In formula, _R71 , _R72 shows a hydrogen atom or a C1-C8 linear, branched, or cyclic alkyl group. Alternatively, R ₇₁ and R ₇₂ may combine to form a ring, and in the case of forming a ring, R ₇₁ and R ₇₂ represent a linear or branched alkylene group having 1 to 8 carbon atoms. Show. R ₇₃ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, e is an integer of 1 to 7, and f and g are 0 or an integer of 1 to 10. A represents an (e + 1) -valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may intervene a hetero atom, Alternatively, a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group, or a fluorine atom. B represents —CO—O—, —NHCO—O— or —NHCONH—.

  Specific examples of the crosslinked acetal represented by the formulas (VIII) and (IX) include the following formulas.

  Specific examples of the repeating unit (III) having a functional group represented by the formula (IV) include styrene, α-methylstyrene, chlorostyrene, 1,1-diphenylethylene, stilbene, 4-hydroxystyrene, 4- Hydroxy-α-methylstyrene, 4-hydroxy-3-methyl-styrene, 4-tert-butoxy-styrene, 4-tetrahydropyranyloxy-styrene, 4-phenoxyethoxy-styrene, 4-trimethylsilyloxy-styrene, 4- Trimethylsilyloxy-styrene, 4-t-butoxycarbonyloxy-styrene, 4-t-butoxycarbonylmethoxy-styrene, 2,3-difluoro-4-hydroxystyrene, 2,3-difluoro-4-t-butoxy-styrene, 2,6-difluoro-4-hydroxy-styrene 2,6-difluoro-4-t-butoxy-styrene, 3,5-difluoro-4-hydroxy-styrene, 3,5-difluoro-4-t-butoxy-styrene, 2,3,5,6-tetrafluoro -4-hydroxy-styrene, 2,3,5,6-tetrafluoro-4-t-butoxy-styrene, 2-trifluoromethyl-4-hydroxy-styrene, 2-trifluoromethyl-4-t-butoxy- Styrene, 2-trifluoromethyl-6-fluoro-4-hydroxy-styrene, 2-trifluoromethyl-6-fluoro-4-tert-butoxy-styrene, 3-trifluoromethyl-5-fluoro-4-hydroxy- Styrene, 3-trifluoromethyl-5fluoro-4-t-butoxystyrene, 4- (1-ethoxyethoxy) -styrene, 4- (2 -Hydroxy-1,1,1,3,3,3-hexafluoro-2-propyl) -styrene, 4- (2-ethoxymethoxy-1,1,1,3,3,3-hexafluoro-2- Propyl) -styrene, 2,3-difluoro-4-hydroxystyrene, 2,3-difluoro-4-tert-butoxy-α-fluoro-styrene, 2,6-difluoro-4-hydroxy-α-fluoro-styrene, 2,6-difluoro-4-t-butoxy-α-fluoro-styrene, 3,5-difluoro-4-hydroxy-α-fluoro-styrene, 3,5-difluoro-4-t-butoxy-α-fluoro- Styrene, 2,3,5,6-tetrafluoro-4-hydroxy-α-fluoro-styrene, 2,3,5,6-tetrafluoro-4-tert-butoxy-α-fluoro-styrene, -Trifluoromethyl-4-hydroxy-α-fluoro-styrene, 2-trifluoromethyl-4-t-butoxy-α-fluoro-styrene, 2-trifluoromethyl-6-fluoro-4-hydroxy-α-fluoro -Styrene, 2-trifluoromethyl-6-fluoro-4-t-butoxy-α-fluoro-styrene, 3-trifluoromethyl-5-fluoro-4-hydroxy-α-fluoro-styrene, 3-trifluoromethyl -5-fluoro-4-t-butoxy-α-fluoro-styrene, 4- (1-ethoxyethoxy) -α-methyl-styrene, 4- (2-hydroxy-1,1,1,3,3,3) -Hexafluoro-2-propyl) -α-fluoro-styrene, 4- (2-ethoxymethoxy-1,1,1,3,3,3-hexafluoro-2- Propyl)-.alpha.-fluoro - can be exemplified styrene.

Furthermore, when R ₃₄ is a CO ₂ R ₃₅ group, R ₃₅ can be exemplified by the same substituents as those exemplified for R ₄ . In this case, as a combination of R _{31 to} R _33, a combination as shown in the following formula can be preferably used. (Represents a repeating unit obtained by polymerizing the following compounds.)

As the repeating unit having a CO ₂ R ₃₅ group, specifically, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethyl cyclohexyl acrylate, octyl acrylate, acrylic acid-t- Octyl, chloroethyl acrylate, 2-ethoxyethyl acrylate, 2,2-dimethyl-3-ethoxypropyl acrylate, 5-ethoxypentyl acrylate, 1-methoxyethyl acrylate, 1-ethoxyethyl acrylate, 1-methoxypropyl acrylate, 1- Methyl-1-methoxyethyl acrylate, 1- (isopropoxy) ethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate Acrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-ethoxyethyl methacrylate, 4-methoxybutyl methacrylate, 5 -Methoxypentyl methacrylate, 2,2-dimethyl-3-ethoxypropyl methacrylate, 1-methoxyethyl methacrylate, 1-methyl-1-methoxyethyl methacrylate, 1- (isopropoxy) ethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate Methacrylic acid esters such as

  Methyl crotonate, ethyl crotonate, propyl crotonate, amyl crotonate, cyclohexyl crotonate, ethyl hexyl crotonate, octyl crotonate, crotonate-t-octyl, chloroethyl crotonate, 2-ethoxyethyl crotonate, 2,2 -Dimethyl-3-ethoxypropyl crotonate, 5-ethoxypentyl crotonate, 1-methoxyethyl crotonate, 1-ethoxyethyl crotonate, 1-methoxypropyl crotonate, 1-methyl-1-methoxyethyl crotonate, 1 -(Isopropoxy) ethyl crotonate, benzyl crotonate, methoxybenzyl crotonate, furfuryl crotonate, tetrahydrofurfuryl crotonate, crotonates, dimethyl itaconate, diitaconate Til, dipropyl itaconate, diamyl itaconate, dicyclohexyl itaconate, bis (ethylhexyl) itaconate, dioctyl itaconate, di-t-octyl itaconate, bis (chloroethyl) itaconate, bis (2-ethoxyethyl) itaconate, bis (2,2-dimethyl-3-ethoxypropyl) itaconate, bis (5-ethoxypentyl) itaconate, bis (1-methoxyethyl) itaconate, bis (1-ethoxyethyl) itaconate, bis (1-methoxypropyl) itaconate, Bis (1-methyl-1-methoxyethyl) itaconate, bis (1- (isopropoxy) ethyl) itaconate, dibenzyl itaconate, bis (methoxybenzyl) itaconate, diflufuriritaconate, ditetrahydro It can be exemplified repeating units derived from Le furyl itaconate itaconic acid esters such like. Furthermore, the repeating unit represented by a following formula can be illustrated.

  Furthermore, the compound represented by Formula (VII) can be illustrated as repeating units other than the repeating unit represented by Formula (I).

In the formula, each of R ₈₁ and R ₈₂ independently represents a hydrogen atom, a halogen atom, a C1 to C20 hydrocarbon group, a heterocyclic group, a cyano group, a nitro group, a C (═O) R ₄ group, or S (= O) represents a pR ₄ group, a P (═O) (R ₄ ) ₂ group, and an M (R ₄ ) ₃ group, and specifically, the same substituents as those exemplified for R ₁ may be exemplified. it can.

  As described above, the degradable chain-containing block copolymer having a repeating unit represented by the formula (I) in the present invention includes a polymerization site consisting of only the repeating unit represented by the formula (I), and the formula (I ) Is a polymer composed of a repeating unit other than the repeating unit represented by formula (I), and the bonding order of the repeating unit represented by formula (I) and the other repeating unit is not particularly limited. The mixing ratio of the repeating unit represented by the above formula and other repeating units is not particularly limited, and can be arbitrarily set within a range of 99/1 to 1/99 in terms of molar ratio.

  The number average molecular weight of the degradable chain-containing block copolymer having a repeating unit represented by the formula (I) is not particularly limited. However, in view of finding a significant difference in physical properties before and after decomposition, 2,000 A range of ˜900,000 is preferred. The molecular weight distribution, which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is not particularly limited, but is in the range of 1.01 to 3.00, more preferably in the range of 1.01 to 1.50. preferable.

  As a method for producing a degradable chain-containing block copolymer having a repeating unit represented by the formula (I), specifically, a ketene represented by the following formula (X) and an aldehyde represented by the formula (XI), After anionic polymerization in the presence of an anionic polymerization initiator, the monomer constituting the non-degradable unit is added and polymerized, or after the monomer constituting the non-degradable unit is polymerized in the presence of the anionic polymerization initiator Examples of the polymerization method include adding a ketene represented by the following formula (X) and an aldehyde represented by the formula (XI).

In the formula, R ₉₁ corresponds to R ₁ , R ₉₂ corresponds to R ₂ , and R ₉₃ corresponds to R ₃ , respectively, and a substituent that hinders anionic polymerization, such as a substituent having an active hydrogen atom, The substituent which excluded the substituent etc. which are reactive with an anionic polymerization initiator is represented.
The solvent used for anionic polymerization is not particularly limited as long as it is a polar solvent that does not participate in the polymerization reaction and is compatible with the polymer. Specifically, aliphatic solvents such as n-hexane and n-heptane are used. Hydrocarbons, alicyclic hydrocarbons such as cyclohexane and cyclopentane, aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether, tetrahydrofuran (THF) and dioxane, as well as anisole and hexamethyl phosphor The organic solvent normally used in anionic polymerization, such as amide, can be mentioned. Moreover, these solvent can be used individually by 1 type or as a 2 or more types of mixed solvent.

  Examples of the anionic polymerization initiator include alkali metals or organic alkali metals. Examples of the alkali metals include lithium, sodium, potassium, cesium, sodium-potassium alloys, and the like. Alkylated products, allylated products, arylated products and the like of the above alkali metals can be used. Specifically, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, ethylsodium, lithium biphenyl, lithium Naphthalene, lithium triphenyl, sodium naphthalene, potassium naphthalene, α-methylstyrene sodium dianion, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, 1,1-diphenylmethyl potassium 1,4-dilithio-2-butene, 1,6-dilithiohexane, polystyryllithium, cumylpotassium, cumylcesium and the like. These compounds may be used alone or in combination of two or more. Can be used.

  The reaction is usually performed by adding the compounds represented by (X) and (XI) to the anionic polymerization initiator and polymerizing the site constituting the non-degradable unit after the anionic living polymerization, or the anionic polymerization initiator. In addition, the compounds represented by (X) and (XI) are added, and after anionic living polymerization, polymerization of the site constituting the non-degradable unit is performed. These series of reactions are carried out in the range of inert gas such as argon or nitrogen, or high vacuum, -100 ° C to 0 ° C, preferably -70 ° C to -20 ° C. The molar ratio of the ketene represented by the formula (X) to be used and the aldehyde represented by the formula (XI) is not particularly limited, but is preferably in the range of 99/1 to 50/50. In addition, as described above, the ketene represented by the formula (III) and the aldehyde represented by the formula (IV) can be used singly or in combination of two or more.

In the polymer in which R ₃ is a substitution represented by the formula (II), the compound in which R ₅ is a hydrogen atom is polymerized in a compound having a functional group other than a hydrogen atom, and the functional group is It can be obtained by desorption, and at that time, only a part of the functional group can be desorbed by controlling the reaction. For example, the reaction for removing part or all of the protecting group of the phenolic hydroxyl group that is unstable to acid includes the solvents exemplified in the polymerization reaction, alcohols such as methanol, ethanol, ketones such as acetone and methyl ethyl ketone. , Polyhydric alcohol derivatives such as methyl cellosolve, ethyl cellosolve, one or more kinds of mixed solvents such as water, hydrochloric acid, sulfuric acid, hydrogen chloride gas, hydrobromic acid, p-toluenesulfonic acid, Usually, an acid reagent such as bisulfate represented by trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, general formula XHSO ₄ (wherein X represents an alkali metal such as Li, Na, K) is used as a catalyst. The reaction is performed in the range of room temperature to 150 ° C.

The amount of the acidic reagent to be used is sufficient as the catalyst amount, but usually the average molecular weight of the whole polymer is obtained from the molar fraction of each unit and the molecular weight of each unit, and each of the total weight, average molecular weight, and molar fraction of each polymer is determined. The number of moles of the unit is determined and is in the range of 0.1 to 1 equivalent with respect to the number of moles of the alkoxy group (OR ₅ group).

Moreover, another functional group can also be introduce | transduced into the hydroxyl part obtained as mentioned above. The above-described operation has been described by taking the substituent of R ₃ as an example, but can also be performed on the same substituent as OR ₅ on R ₁ and R ₂ .

  The polymer having a repeating unit represented by the formula (I) can be used as a thermally decomposable chain because the main chain is easily cleaved by heat as described in Examples. The component resulting from the decomposition of the degradable resin of the present invention has a structure represented by the following formula (XII). Therefore, the decomposed component can utilize a double bond or the like.

式中、Ｒ₁₀₁はＲ₁、Ｒ₁₀₂はＲ₂、Ｒ₁₀₃はＲ₃にそれぞれ対応しており、Ｒ₁、Ｒ₂、Ｒ₃で例示したのと同様の置換基を例示することができる。

In the formula, R ₁₀₁ corresponds to R ₁ , R ₁₀₂ corresponds to R ₂ , and R ₁₀₃ corresponds to R ₃ , respectively, and examples thereof are the same as those exemplified for R ₁ , R ₂ , and R _3. .

  As the solvent used in the decomposable chain-containing block copolymer composition of the present invention, a decomposable chain-containing block copolymer having a repeating unit represented by the formula (I), or an ultraviolet absorber used as necessary, Although it will not restrict | limit especially if it can melt | dissolve additives, such as an acidic compound and surfactant, Usually, the thing with favorable film formability is preferable. Specifically, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, 2-ethoxyethyl acetate, methyl pyruvate, ethyl pyruvate, 3-methoxypropion Acid methyl, ethyl 3-methoxypropionate, ethyl 2-hydroxybutanoate, ethyl 3-hydroxybutanoate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, γ-propiolactone, cyclohexanone, methyl ethyl ketone, 2-heptanone, 1,4-dioxane, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, ethylene Recall isopropyl ether, toluene, can be exemplified and tetrahydrofuran, the solvent is used in combination usually alone, or two or more kinds.

  The amount of the solvent in the decomposable chain-containing block copolymer composition according to the present invention is such that the block copolymer composition obtained as a result of dissolving the polymer and the acid generator and other additives is coated on the substrate. Although it will not specifically limit if it is the quantity which does not cause trouble on the occasion, Usually, it is 1-20 weight part with respect to 1 weight part of this polymer, Preferably it is 1.5-10 weight part.

  The block copolymer composition of the present invention comprises a degradable chain-containing block copolymer having a repeating unit represented by formula (I) and a solvent as main components, but in addition to this, an acid generator, a basic compound, an ultraviolet ray Absorbers, surfactants, and plasticizers may be used.

  The block copolymer composition of the present invention may be used after the solvent is volatilized to form a thin film. For example, a thin film can be formed as follows. A composition comprising the block copolymer of the present invention and a solvent is spin-coated on a semiconductor substrate so as to have a thickness of about 0.1 to 2 μm, and this is applied in an oven at 70 to 150 ° C. for 1 to 30 minutes, or A good thin film is formed by prebaking at 70 to 100 ° C. for 1 to 2 minutes on a hot plate.

  After decomposing the degradable chain represented by the formula (I) in the block copolymer of the present invention, it can be removed by developing the decomposed product or by heating and volatilizing the decomposed product.

  The developer is not particularly limited as long as it does not dissolve the non-degradable unit and dissolves the low molecular weight compound generated by decomposing the degradable chain represented by the formula (I), but it is preferably NaOH. Examples thereof include aqueous solutions containing inorganic alkalis such as KOH, aqueous solutions containing organic amines such as TMAH, choline, and triethanolamine, alcohols, and the like.

  As long as the decomposable resin of the present invention is used as it is or does not impair the effects of the present invention, a general-purpose thermoplastic resin such as a polyester resin, an acrylic resin, a vinyl chloride resin, or a polyvinyl ether resin is mixed with the decomposable resin of the present invention. Can also be used.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, the scope of the present invention is not limited to an Example.

The method for purifying the reagents used in the examples of the present invention will be described below.
Ketenes were distilled under reduced pressure after reacting acid chloride with triethylamine in THF at room temperature. Aldehydes were distilled under reduced pressure after adding CaH ₂ .
As n-butyllithium (n-BuLi), a commercially available n-BuLi hexane solution (1.6 mol / l) was used as it was. For tetrahydrofuran, a commercially available dehydrated solvent was used.

Synthesis Example 1 (Synthesis of ethyl phenyl ketene (EPK))
Under a nitrogen atmosphere, a THF solution of 55 g (0.3 mol) of 2-phenylbutyryl chloride was dropped into a mixed solution of 91 g (0.9 mol) of triethylamine in tetrahydrofuran (THF). One hour later, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was distilled under reduced pressure to obtain EPK (60 to 70 ° C./4 mmHg). Yield 30 g (70% yield).

Synthesis Example 2 (Synthesis of 4- (1′-ethoxyethoxy) benzaldehyde (EEBA))
In a nitrogen atmosphere, 100 g (0.82 mol) of 4-hydroxybenzaldehyde was dissolved in THF (500 ml), and then 236 g (3.3 mol) of vinyl ethyl ether and 4 ml (16 mmol) of 4M HCl dioxane solution were added overnight at room temperature. Stir. After neutralization by adding an aqueous Na ₂ CO ₃ solution, the solution was separated, and the upper layer was washed with water until pH = 7. The organic layer was dehydrated and filtered with MgSO ₄ and then concentrated under reduced pressure. The obtained residue was distilled under reduced pressure to obtain EEBA (83 to 85 ° C., 0.04 mmHg) as a colorless oily substance. Yield 129 g (81% yield).
Example 1

(Synthesis of polystyrene-bp (EEBA / EPK))
Under a nitrogen atmosphere, 18.73 g (0.18 mol) of styrene was dissolved in 148 g of THF, and then cooled to −40 ° C. n-Butyllithium was added to proceed the polymerization. After stirring for 10 minutes, EEBA 5.7 g (29.3 mmol), EPK 4.17 g (28.5 mmol), and lithium chloride 0.78 g (18.41 mmol) were dissolved in THF 37.86 g, and this solution was reacted. The solution was added dropwise over 3 minutes. After stirring at −40 ° C. for 10 minutes, 2 ml of methanol was added to inactivate the reaction. After washing with water until the reaction solution became neutral, the organic layer was concentrated under reduced pressure. The obtained residue was dissolved in THF (60 g), added dropwise to water (1 L), and purified by reprecipitation. As a result of GPC analysis, a block copolymer having Mn = 12600 and Mw / Mn = 1.3 was obtained as a colorless solid.

The thermally decomposable block copolymer of the present invention can form a molded article having a microstructure on the order of nanometers. That is, the thermally decomposable block copolymer of the present invention uses a microphase separation of the block copolymer to selectively remove one specific phase of the microphase separation structure, thereby forming a fibrous structure, a thin film structure, a porous structure. The porous film or dot array is formed as dots formed in a porous film or array by forming a molded body having a structure or selectively removing one phase of the microphase separation film formed on the substrate. The substrate can be finely processed as an etching mask. In addition, although it has stability, the main chain is cleaved by heat, it can be easily removed by decomposing to low molecular weight, and it is excellent in operability. , This is mixed and pyrolyzed, the resin is removed, and the desired product is manufactured (for porous film, ceramic firing, plasma display panel use), the thermal decomposable resin is layered and thermally decomposed to remove the resin, It can also be used to decompose and foam a thermally decomposable resin.

Claims (7)

A thermally decomposable block copolymer in which at least one phase of the block copolymer contains a degradable chain composed of a thermally decomposable structure. The decomposable chain having a heat-decomposable structure according to claim 1,

(In the formula, R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, a heterocyclic group, a cyano group, a nitro group, a C (═O) R ₄ group, S (0 ) _P R ₄ group, P (═O) (R ₄ ) ₂ group, M (R ₄ ) ₃ group, R ₃ represents a C1-C20 hydrocarbon group or heterocyclic group, and R ₄ represents C1— C20 represents a hydrocarbon oxy group, C1 to C20 hydrocarbon group, C1 to C20 hydrocarbon thio group, mono or di C1 to C20 hydrocarbon amino group, and M represents a silicon atom, a germanium atom, a tin atom, 2. The thermally decomposable block copolymer according to claim 1, wherein the thermally decomposable block copolymer has a repeating unit represented by a lead atom, and p represents 0, 1, or 2. In the compound represented by the formula (I), R ₃ represents the formula (II)

(In the formula, X represents an oxygen atom or a sulfur atom, R ₅ represents a hydrogen atom, a C1 to C20 hydrocarbon group, or a group that decomposes and desorbs by heat, R ₆ represents a halogen atom, C1 C represents a hydrocarbon group of C20, m represents an integer of 1 to 3, n represents an integer of 0 or 1 to 3, m + n ≦ 5, and when m is 2 or more, R ₅ may be the same or different, and when n is 2 or more, R ₆ may be the same or different. Thermally decomposable block copolymer. The heat-decomposable block copolymer according to any one of claims 1 to 3, wherein the polymer has a number average molecular weight of 2,000 to 900,000. 5. The heat according to claim 1, wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 1.01 to 3.00. Degradable block copolymer. The thermally decomposable block copolymer according to any one of claims 1 to 5, wherein the block copolymer is a graft copolymer. A method for decomposing a resin composition, wherein the resin composition containing the thermally decomposable block copolymer according to claim 1 is decomposable by heating in the absence of an acid.