JP4846267B2 - Silicone copolymer having hydroxyl group and method for producing the same - Google Patents
Silicone copolymer having hydroxyl group and method for producing the same Download PDFInfo
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本発明は、電子材料や微細加工の材料として有用な水酸基を有する新規シリコーン共重合体に関するものである。 The present invention relates to a novel silicone copolymer having a hydroxyl group useful as an electronic material or a material for fine processing.
近年、半導体素子の微細化が進むとともに、その製造に用いられるリソグラフィ工程についていっそうの微細化が求められるようになってきている。微細化が急速に発展してきた背景には、投影レンズの高NA化、レジストの性能向上、短波長化が挙げられる。 In recent years, with the progress of miniaturization of semiconductor elements, further miniaturization of a lithography process used for manufacturing the semiconductor element has been demanded. The background of rapid progress in miniaturization includes higher NA of projection lenses, improved resist performance, and shorter wavelengths.
特に露光波長の短波長化は大きな変革をもたらしてきたが、さらに微細化の要求は大きく、KrF(248nm)露光からArF(193nm)露光への短波長化が進んできている。 In particular, the shortening of the exposure wavelength has brought about a great change, but the demand for further miniaturization is great, and the shortening of the wavelength from KrF (248 nm) exposure to ArF (193 nm) exposure is progressing.
しかし、この波長の短波長化により、従来使用されてきたノボラックやポリビニルフェノール系の樹脂では、ベンゼン環骨格を含有することにより193nm付近に強い吸収を示し透明性が低下するため使用することができないという問題点があった。 However, due to the shortening of this wavelength, conventionally used novolac and polyvinylphenol resins cannot be used because they contain a benzene ring skeleton and exhibit strong absorption near 193 nm, resulting in decreased transparency. There was a problem.
一方、微細パターンを作成するために、中間層を設ける三層レジストプロセスも考案されており、フェノール性水酸基をもつポリオルガノシルセスキオキサンの例は報告されている(特許文献1参照)。しかしながら、それらの共重合体では、側鎖にベンゼン環を有するため、ArF(193nm)のような遠紫外線波長での露光波長には樹脂自体の吸収が大きく、光が透過しないという問題があった。 On the other hand, in order to create a fine pattern, a three-layer resist process in which an intermediate layer is provided has been devised, and an example of a polyorganosilsesquioxane having a phenolic hydroxyl group has been reported (see Patent Document 1). However, since these copolymers have a benzene ring in the side chain, there is a problem that the exposure wavelength at a far ultraviolet wavelength such as ArF (193 nm) has a large absorption of the resin itself and does not transmit light. .
また、樹脂自体の透過性を上げるため、ベンゼン環骨格がなく、フッ素原子により樹脂自体の透過性を上げるシリコーン重合体が提案されている(特許文献2参照)。しかしながら、アルコール部位がフッ素置換基に立体障害のため反応性が悪く、三層レジストプロセスで使用される中間層として使用することができなかった。 In order to increase the permeability of the resin itself, a silicone polymer that has no benzene ring skeleton and increases the permeability of the resin itself by fluorine atoms has been proposed (see Patent Document 2). However, the alcohol moiety has poor reactivity due to steric hindrance to the fluorine substituent, and cannot be used as an intermediate layer used in a three-layer resist process.
このことから、短波長での透過性を上げるためベンゼン環骨格がなく、水酸基を有した新規シリコーン共重合体が求められていた。
本発明者らは、ArF(193nm)のような遠紫外線露光波長でも透明性を良くするため、水酸基を有するシリコーン共重合体について、種々検討を重ねた結果、特定の組成をもつシリコーン共重合体では、遠紫外線露光波長で使用でき、水酸基を有することにより微細加工に使用される中間層材料として好適な新規材料を見出し、この知見に基づいて本発明をなすに至った。 In order to improve transparency even at a far-ultraviolet exposure wavelength such as ArF (193 nm), the present inventors have conducted various studies on a silicone copolymer having a hydroxyl group. As a result, a silicone copolymer having a specific composition is obtained. Then, a novel material suitable as an intermediate layer material that can be used at a far ultraviolet exposure wavelength and has a hydroxyl group and is used for fine processing has been found, and the present invention has been made based on this finding.
すなわち、本発明は、下記一般式 That is, the present invention has the following general formula:
(式中、A、Rは、それぞれ脂肪族炭化水素基を示し、かつA又はRの少なくとも一方が、炭素数5〜20の環状又は架橋環状の炭化水素基である。nは1〜5の整数を示す。a、bはモル%を示し、aは1〜99モル%、bは1〜99モル%、但しa+b=100である) (In the formula, A and R each represent an aliphatic hydrocarbon group, and at least one of A or R is a cyclic or bridged cyclic hydrocarbon group having 5 to 20 carbon atoms. N is 1 to 5) A and b represent mol%, a represents 1 to 99 mol%, b represents 1 to 99 mol%, provided that a + b = 100)
で示される繰り返し単位をもつシリコーン共重合体であって、該シリコーン共重合体のポリスチレン換算の重量平均分子量が500〜100000であることを特徴とする水酸基を有するシリコーン共重合体である。
A silicone copolymer having the repeating units represented in polystyrene-reduced weight average molecular weight of the said silicone copolymer is a silicone copolymer having a hydroxyl group, which is a 500 to 100,000.
本発明のシリコーン共重合体は、ベンゼン環骨格をもたず、水酸基を有している。 The silicone copolymer of the present invention does not have a benzene ring skeleton and has a hydroxyl group.
本発明の水酸基を有するシリコーン共重合体は、ArF露光(193nm)にような250nm以下の遠紫外線領域での短波長の露光波長で透過性が良く、水酸基を有することにより微細加工が可能な中間層材料として好適な材料である。本発明のシリコーン共重合体は水酸基を有しており、遠紫外線領域での短波長露光により、硬化剤と反応して反射防止膜的な役割を果たすため、微細加工プロセスに導入することができる。 The silicone copolymer having a hydroxyl group of the present invention has good transparency at an exposure wavelength of a short wavelength in a far ultraviolet region of 250 nm or less, such as ArF exposure (193 nm), and has a hydroxyl group. It is a material suitable as a layer material. Since the silicone copolymer of the present invention has a hydroxyl group and reacts with a curing agent by short wavelength exposure in the far ultraviolet region, it acts as an antireflection film and can be introduced into a microfabrication process. .
また、本発明のシリコーン共重合体は、側鎖にアルコール性水酸基を有していることから、アルコール性水酸基に様々な置換基の導入が可能となる。よって、本発明のシリコーン共重合体は電子材料分野に限らず、塗料や接着剤等、幅広い分野で応用できる。 Further, since the silicone copolymer of the present invention has an alcoholic hydroxyl group in the side chain, various substituents can be introduced into the alcoholic hydroxyl group. Therefore, the silicone copolymer of the present invention can be applied not only in the field of electronic materials but also in a wide range of fields such as paints and adhesives.
本発明のシリコーン共重合体は、下記一般式 The silicone copolymer of the present invention has the following general formula:
(式中、A、Rは、それぞれ脂肪族炭化水素基を示し、かつA又はRの少なくとも一方が、炭素数5〜20の環状又は架橋環状の炭化水素基である。nは1〜5の整数を示す。a、bはモル%を示し、aは1〜99モル%、bは1〜99モル%、但しa+b=100である) (In the formula, A and R each represent an aliphatic hydrocarbon group, and at least one of A or R is a cyclic or bridged cyclic hydrocarbon group having 5 to 20 carbon atoms. N is 1 to 5) A and b represent mol%, a represents 1 to 99 mol%, b represents 1 to 99 mol%, provided that a + b = 100)
で示される繰り返し単位をもつシリコーン共重合体であって、シリコーン共重合体のポリスチレン換算の重量平均分子量が500〜100000である水酸基を有するシリコーン共重合体である。 A silicone copolymer having the repeating units represented in a silicone copolymer having a weight average molecular weight in terms of polystyrene of the silicone copolymer having a hydroxyl group is 500 to 100,000.
本発明のシリコーン共重合体は、重量平均分子量(ポリスチレン換算)が500〜100000の範囲である。1000〜20000の範囲にあるものが最も好ましい。 The silicone copolymer of the present invention has a weight average molecular weight (polystyrene conversion) in the range of 500 to 100,000 . Those in the range of 1000 to 20000 are most preferred.
本発明のシリコーン共重合体の分散度は、1.0〜10.0の範囲にあるものが好ましく、1.5〜5.0の範囲にあるものが最も好ましい。 The degree of dispersion of the silicone copolymer of the present invention is preferably in the range of 1.0 to 10.0, and most preferably in the range of 1.5 to 5.0.
本発明のシリコーン共重合体の下記骨格は、 The following skeleton of the silicone copolymer of the present invention is:
シルセスキオキサン骨格を示し、各ケイ素原子が3個の酸素原子に結合し、各酸素原子が2個のケイ素原子に結合していることを示し、たとえば、下記一般式 A silsesquioxane skeleton, each silicon atom is bonded to three oxygen atoms, each oxygen atom is bonded to two silicon atoms,
(式中、A、Rは、それぞれ脂肪族炭化水素基を示し、かつA又はRの少なくとも一方が、炭素数5〜20の環状又は架橋環状の炭化水素基である。nは1〜5の整数を示す。a、bはモル%を示し、aは1〜99モル%、bは1〜99モル%、但しa+b=100である)
に示す構造式で示すことができる。
(In the formula, A and R each represent an aliphatic hydrocarbon group, and at least one of A or R is a cyclic or bridged cyclic hydrocarbon group having 5 to 20 carbon atoms. N is 1 to 5) A and b represent mol%, a represents 1 to 99 mol%, b represents 1 to 99 mol%, provided that a + b = 100)
It can be shown by the structural formula shown in
ここで、本発明のシリコーン共重合体の形態である下記一般式
Here, the following formula in the form status of the silicone copolymer of the present invention
(式中、A、Rは、それぞれ脂肪族炭化水素基を示し、かつA又はRの少なくとも一方が、炭素数5〜20の環状又は架橋環状の炭化水素基である。nは1〜5の整数を示す。a、bはモル%を示し、aは1〜99モル%、bは1〜99モル%、但しa+b=100である)
に示す本発明のシリコーン共重合体の繰り返し単位中、A、Rで示される脂肪族炭化水素基は、ベンゼン環で代表される芳香族炭化水素基を含まないものを示す。
(In the formula, A and R each represent an aliphatic hydrocarbon group, and at least one of A or R is a cyclic or bridged cyclic hydrocarbon group having 5 to 20 carbon atoms. N is 1 to 5) A and b represent mol%, a represents 1 to 99 mol%, b represents 1 to 99 mol%, provided that a + b = 100)
In the repeating unit of the silicone copolymer of the present invention, the aliphatic hydrocarbon groups represented by A and R do not contain an aromatic hydrocarbon group represented by a benzene ring.
本発明のシリコーン共重合体の好ましい形態である下記一般式 The following general formula, which is a preferred form of the silicone copolymer of the present invention
(式中、A、Rは、それぞれ脂肪族炭化水素基を示し、かつA又はRの少なくとも一方が、炭素数5〜20の環状又は架橋環状の炭化水素基である。nは1〜5の整数を示す。a、bはモル%を示し、aは1〜99モル%、bは1〜99モル%、但しa+b=100である)
のAで示される炭化水素基としては、炭素数1〜20の直鎖状、分枝状または環状の炭化水素基が好ましく、架橋炭化水素基でも良い。
(In the formula, A and R each represent an aliphatic hydrocarbon group, and at least one of A or R is a cyclic or bridged cyclic hydrocarbon group having 5 to 20 carbon atoms. N is 1 to 5) A and b represent mol%, a represents 1 to 99 mol%, b represents 1 to 99 mol%, provided that a + b = 100)
The hydrocarbon group represented by A is preferably a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, and may be a crosslinked hydrocarbon group.
好ましい炭化水素基として、例えば、炭素数1〜20の直鎖状炭化水素基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基等の炭化水素基が挙げられる。分枝状炭化水素基としては、イソプロピレン基、イソブチレン基等の炭化水素基が好ましい。環状炭化水素基としてはシクロペンチレン基、シクロヘキシレン基、シクロペンタレン基などの環状のアルキレン基が好ましい。また、架橋環状炭化水素基としては、下記構造式のアルキレン基等が好ましい。 Preferable hydrocarbon groups include, for example, hydrocarbon groups such as a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group as the linear hydrocarbon group having 1 to 20 carbon atoms. The branched hydrocarbon group is preferably a hydrocarbon group such as an isopropylene group or an isobutylene group. The cyclic hydrocarbon group is preferably a cyclic alkylene group such as a cyclopentylene group, a cyclohexylene group, or a cyclopentalene group. Moreover, as the crosslinked cyclic hydrocarbon group, an alkylene group having the following structural formula is preferable.
これら炭化水素基は、透明性の観点から、不飽和結合を含まない化合物がより好ましく、炭化水素基に置換基が結合していてもよい。 These hydrocarbon groups are more preferably compounds not containing an unsaturated bond from the viewpoint of transparency, and a substituent may be bonded to the hydrocarbon group.
本発明のシリコーン共重合体の好ましい形態である下記一般式 The following general formula, which is a preferred form of the silicone copolymer of the present invention
(式中、A、Rは、それぞれ脂肪族炭化水素基を示し、かつA又はRの少なくとも一方が、炭素数5〜20の環状又は架橋環状の炭化水素基である。nは1〜5の整数を示す。a、bはモル%を示し、aは1〜99モル%、bは1〜99モル%、但しa+b=100である)
の繰り返し単位中、Rで示される脂肪族炭化水素基としては、炭素数1〜20の直鎖状、分枝状または環状の炭化水素基が好ましく、架橋炭化水素基でも良い。これらの炭化水素基は1価の炭化水素基がより好ましい。
(In the formula, A and R each represent an aliphatic hydrocarbon group, and at least one of A or R is a cyclic or bridged cyclic hydrocarbon group having 5 to 20 carbon atoms. N is 1 to 5) A and b represent mol%, a represents 1 to 99 mol%, b represents 1 to 99 mol%, provided that a + b = 100)
In the repeating unit, the aliphatic hydrocarbon group represented by R is preferably a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, and may be a crosslinked hydrocarbon group. These hydrocarbon groups are more preferably monovalent hydrocarbon groups.
本発明のシリコーン共重合体の好ましい形態である下記一般式 The following general formula, which is a preferred form of the silicone copolymer of the present invention
(式中、A、Rは、それぞれ脂肪族炭化水素基を示し、かつA又はRの少なくとも一方が、炭素数5〜20の環状又は架橋環状の炭化水素基である。nは1〜5の整数を示す。a、bはモル%を示し、aは1〜99モル%、bは1〜99モル%、但しa+b=100である)
の繰り返し単位中、Rで示される好ましい脂肪族炭化水素基の例として、炭素数1〜20の直鎖状飽和炭化水素基としては、メチル基、エチル基、n−プロピル基、n−ブチル基、n−ペンチル基、n−ヘキシル基等の炭化水素基が挙げられる。分枝状炭化水素基としては、イソプロピル機、イソブチル基等の炭化水素基が好ましい。環状炭化水素基として、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等の環状炭化水素基が好ましい。また、架橋環状炭化水素基として、下記構造式の架橋炭化水素基等が好ましい。
(In the formula, A and R each represent an aliphatic hydrocarbon group, and at least one of A or R is a cyclic or bridged cyclic hydrocarbon group having 5 to 20 carbon atoms. N is 1 to 5) A and b represent mol%, a represents 1 to 99 mol%, b represents 1 to 99 mol%, provided that a + b = 100)
In the repeating unit, as a preferred aliphatic hydrocarbon group represented by R, examples of the linear saturated hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. , Hydrocarbon groups such as n-pentyl group and n-hexyl group. The branched hydrocarbon group is preferably a hydrocarbon group such as an isopropyl machine or an isobutyl group. As the cyclic hydrocarbon group, a cyclic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group is preferable. Further, as the crosslinked cyclic hydrocarbon group, a crosslinked hydrocarbon group having the following structural formula is preferred.
これら炭化水素基には透明性の観点から、不飽和結合を含まない化合物が好ましく、炭化水素基に置換基が結合していてもよい。 From the viewpoint of transparency, these hydrocarbon groups are preferably compounds containing no unsaturated bond, and a substituent may be bonded to the hydrocarbon group.
本発明のシリコーン共重合体は、A又はRの少なくとも一方が、炭素数5〜20の環状又は架橋環状の炭化水素基である。A及びRが、直鎖または分枝状のみで構成されたシリコーン共重合体では、分子量が増大し、ガラス転移温度が低下し、ゴム状ポリマーとなることから、製造上取り扱いにくいポリマーとなる。A又はRのどちらか一方が、炭素数5〜20の環状又は架橋環状の炭化水素基を有する。 In the silicone copolymer of the present invention, at least one of A or R is a cyclic or crosslinked cyclic hydrocarbon group having 5 to 20 carbon atoms . A and R are the linear or branched only silicone copolymer comprised of, increasing the molecular weight, the glass transition temperature is lowered, since the rubbery polymer, that Do and difficult to handle on a manufacturing polymer . Either one of A or R, that have a cyclic or bridged cyclic hydrocarbon group having 5 to 20 carbon atoms.
Rを、炭素数5〜20の環状または架橋環状の1価炭化水素基を用いた場合の好ましいシリコーン共重合体例を下記に示す。 Examples of preferable silicone copolymers in the case where R is a cyclic or crosslinked cyclic monovalent hydrocarbon group having 5 to 20 carbon atoms are shown below.
特に、下記一般式 In particular, the general formula
(式中、A、Rは、それぞれ脂肪族炭化水素基を示し、かつA又はRの少なくとも一方が、炭素数5〜20の環状又は架橋環状の炭化水素基である。nは1〜5の整数を示す。a、bはモル%を示し、aは1〜99モル%、bは1〜99モル%、但しa+b=100である)
のシリコーン共重合体では、A、Rで示される脂肪族炭化水素基の炭素数が少ないほうが物性に大きく影響を与えるシリコンの含有率が向上することから、特に好ましい。ノルボルナニル基のような架橋炭化水素基を含むシリコーン重合体は、シリコーン重合体のガラス転移温度が向上し、製造上取り扱いやすくなることから、特に好ましい。このことから、本発明のシリコーン重合体では、Aの炭化水素基の炭素数が少なく、Rにノルボルナニル基を含むシリコーン重合体が最も好ましい。
(In the formula, A and R each represent an aliphatic hydrocarbon group, and at least one of A or R is a cyclic or bridged cyclic hydrocarbon group having 5 to 20 carbon atoms. N is 1 to 5) A and b represent mol%, a represents 1 to 99 mol%, b represents 1 to 99 mol%, provided that a + b = 100)
In the silicone copolymer, it is particularly preferable that the aliphatic hydrocarbon group represented by A or R has a smaller number of carbon atoms because the silicon content that greatly affects the physical properties is improved. A silicone polymer containing a cross-linked hydrocarbon group such as a norbornanyl group is particularly preferred because the glass transition temperature of the silicone polymer is improved and it becomes easy to handle in production. Therefore, the silicone polymer of the present invention is most preferably a silicone polymer in which the hydrocarbon group of A has a small number of carbon atoms and R contains a norbornanyl group.
また、本発明のシリコーン共重合体で、Aとして炭素数5〜20の環状または架橋環状の炭化水素基を用いた場合は、Rとして炭素数1〜20の直鎖状、分枝状の1価炭化水素基を組み合わせたシリコーン共重合体が、物性に大きく影響を与えるシリコン含有率が向上したシリコーン共重合体となる。特に好ましいシリコーン共重合体例を下記に示す。 In the silicone copolymer of the present invention, when A is a cyclic or crosslinked cyclic hydrocarbon group having 5 to 20 carbon atoms, R is a linear or branched 1 having 1 to 20 carbon atoms. A silicone copolymer combined with a valent hydrocarbon group becomes a silicone copolymer with an improved silicon content that greatly affects physical properties. Examples of particularly preferred silicone copolymers are shown below.
下記一般式 The following general formula
(式中、A、Rは、それぞれ脂肪族炭化水素基を示し、かつA又はRの少なくとも一方が、炭素数5〜20の環状又は架橋環状の炭化水素基である。nは1〜5の整数を示す。a、bはモル%を示し、aは1〜99モル%、bは1〜99モル%、但しa+b=100である)
に示されるシリコーン共重合体を製造する場合、例えば、下記で示される合成法で合成することができる。
(In the formula, A and R each represent an aliphatic hydrocarbon group, and at least one of A or R is a cyclic or bridged cyclic hydrocarbon group having 5 to 20 carbon atoms. N is 1 to 5) A and b represent mol%, a represents 1 to 99 mol%, b represents 1 to 99 mol%, provided that a + b = 100)
When the silicone copolymer shown in (2) is produced, for example, it can be synthesized by the synthesis method shown below.
(式中、A、Rは脂肪族炭化水素基を示し、かつA又はRの少なくとも一方が、炭素数5〜20の環状又は架橋環状の炭化水素基である。nは1〜5の整数を示す。Mは炭素数1〜5の炭化水素基、または、下記一般式 (In the formula, A and R represent an aliphatic hydrocarbon group, and at least one of A or R is a cyclic or bridged cyclic hydrocarbon group having 5 to 20 carbon atoms. N represents an integer of 1 to 5) M is a hydrocarbon group having 1 to 5 carbon atoms, or the following general formula
(式中、Bは炭素数1〜5の炭化水素基を示す。)
に示すアルキルカルボニル基を示す。a、bはモル%を示しaは1〜99モル%、bは1〜99モル%、但しa+b=100を満たす。)。
(In the formula, B represents a hydrocarbon group having 1 to 5 carbon atoms.)
The alkylcarbonyl group shown by these is shown. a and b represent mol%, a is 1 to 99 mol%, b is 1 to 99 mol%, provided that a + b = 100 is satisfied. ).
すなわち、下記一般式 That is, the following general formula
(式中、Aは脂肪族炭化水素基を示す。Mは炭素数1〜5の炭化水素基、または、
下記一般式
(In the formula, A represents an aliphatic hydrocarbon group. M represents a hydrocarbon group having 1 to 5 carbon atoms, or
The following general formula
(式中、Bは炭素数1〜5の炭化水素基を示す。)
に示すアルキルカルボニル基を示す。)
に示すアルコキシ基またはアルキルエステル基をもつトリクロロシランモノマーあるいはトリアルコキシシランモノマーと下記一般式
(In the formula, B represents a hydrocarbon group having 1 to 5 carbon atoms.)
The alkylcarbonyl group shown by these is shown. )
A trichlorosilane monomer or trialkoxysilane monomer having an alkoxy group or an alkyl ester group shown in the following general formula
(式中、Rは脂肪族炭化水素基を示す。)
で示される炭化水素基をもつトリクロロシランモノマーあるいはトリアルコキシシランモノマーを加水分解後、重合することにより高分子化し、下記構造式
(In the formula, R represents an aliphatic hydrocarbon group .)
After hydrolyzing a trichlorosilane monomer or trialkoxysilane monomer having a hydrocarbon group represented by
(式中、A、Rは脂肪族炭化水素基を示し、かつA又はRの少なくとも一方が、炭素数5〜20の環状又は架橋環状の炭化水素基である。nは1〜5の整数を示す。Mは炭素数1〜5の炭化水素基、または、下記一般式 (In the formula, A and R represent an aliphatic hydrocarbon group, and at least one of A or R is a cyclic or bridged cyclic hydrocarbon group having 5 to 20 carbon atoms. N represents an integer of 1 to 5) M is a hydrocarbon group having 1 to 5 carbon atoms, or the following general formula
(式中、Bは炭素数1〜5の炭化水素基を示す。)
に示すアルキルカルボニル基を示す。a、bはモル%を示しaは1〜99モル%、bは1〜99モル%、但しa+b=100を満たす。)
のシリコーン共重合体を合成した後、最後にアルコキシ基またはアルキルエステル基を脱保護すれば合成できる。
(In the formula, B represents a hydrocarbon group having 1 to 5 carbon atoms.)
The alkylcarbonyl group shown by these is shown. a and b represent mol%, a is 1 to 99 mol%, b is 1 to 99 mol%, provided that a + b = 100 is satisfied. )
After synthesizing this silicone copolymer, it can be synthesized by finally deprotecting the alkoxy group or alkyl ester group.
また、Xはハロゲンもしくは炭素数1〜5の直鎖状もしくは分枝状のアルコキシ基を示す。 X represents halogen or a linear or branched alkoxy group having 1 to 5 carbon atoms.
この加水分解反応法として、使用するシランモノマーが共にトリクロロシランモノマーの場合は、炭酸水素ナトリウム水溶液のような中性に近い条件で容易に加水分解できる。また、トリアルコキシシランモノマーを使用する場合は、塩酸やリン酸水溶液のような酸性条件で行うほうが好ましい。 As this hydrolysis reaction method, when both silane monomers used are trichlorosilane monomers, they can be easily hydrolyzed under conditions close to neutrality such as an aqueous sodium hydrogen carbonate solution. Moreover, when using a trialkoxysilane monomer, it is more preferable to carry out on acidic conditions, such as hydrochloric acid and phosphoric acid aqueous solution.
次に加水分解で回収した油層を200℃まで加熱することにより、水酸基がアルコキシ基またはアルキルカルボニル基で保護された下記一般式 Next, the oil layer recovered by hydrolysis is heated to 200 ° C., whereby the hydroxyl group is protected with an alkoxy group or an alkylcarbonyl group.
(式中、A、Rは脂肪族炭化水素基を示し、かつA又はRの少なくとも一方が、炭素数5〜20の環状又は架橋環状の炭化水素基である。Mは炭素数1〜5の炭化水素基、または、
下記一般式
(In the formula, A and R represent an aliphatic hydrocarbon group, and at least one of A or R is a cyclic or bridged cyclic hydrocarbon group having 5 to 20 carbon atoms. M is a carbon group having 1 to 5 carbon atoms. A hydrocarbon group, or
The following general formula
(式中、Bは炭素数1〜5の直鎖状、分枝状または環状の1価炭化水素基を示す。)
に示すアルキルカルボニル基を示す。nは1〜5の整数を示す。a、bはモル%を示しaは1〜99モル%、bは1〜99モル%、但しa+b=100を満たす。)
の化合物を得ることができる。
(In the formula, B represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 5 carbon atoms.)
The alkylcarbonyl group shown by these is shown. n shows the integer of 1-5. a and b represent mol%, a is 1 to 99 mol%, b is 1 to 99 mol%, provided that a + b = 100 is satisfied. )
Can be obtained.
シリコーン共重合体の重量平均分子量(ポリスチレン換算)が1000〜100000の範囲にあるものが好ましく、2000〜30000の範囲にあるものが最も好ましい。分散度は1.0〜10.0の範囲にあるものが好ましく、1.5〜5.0の範囲にあるものが最も好ましい。 What has the weight average molecular weight (polystyrene conversion) of the silicone copolymer in the range of 1000-100000 is preferable, and what is in the range of 2000-30000 is the most preferable. The dispersity is preferably in the range of 1.0 to 10.0, and most preferably in the range of 1.5 to 5.0.
次に、シリコーン共重合体のアルキル基またはアルキルカルボニル基で水酸基が保護された部位を脱保護して目的の水酸基を有するシリコーン共重合体を得ることができる。 Next, the silicone copolymer having the target hydroxyl group can be obtained by deprotecting the site where the hydroxyl group is protected by the alkyl group or alkylcarbonyl group of the silicone copolymer.
この脱保護条件として、アルキル基で保護された場合は、酸性条件下が好ましく、トリメチルシリルヨードのような脱保護試薬を使用することが特に好ましい。そして水で加水分解することによりシリコーン共重合体を得ることができる。このトリメチルシリルヨードの代わりにトリメチルシリルクロライドとヨウ化ナトリウムを使用してもかまわない。この脱保護反応の溶媒はアセトニトリルやクロロホルム等が使われるが、シリコーン共重合体の溶解性により使い分けることができる。 As this deprotection condition, when protected with an alkyl group, an acidic condition is preferable, and it is particularly preferable to use a deprotection reagent such as trimethylsilyliodo. And a silicone copolymer can be obtained by hydrolyzing with water. Trimethylsilyl chloride and sodium iodide may be used in place of this trimethylsilyliodide. As the solvent for this deprotection reaction, acetonitrile, chloroform, or the like is used, but it can be properly used depending on the solubility of the silicone copolymer.
アルキルカルボニル基で保護された場合は、塩基性条件が好ましく、炭酸カリウムのような脱保護試薬を使用することが特に好ましい。水酸化ナトリウムのような強塩基性条件ではSi−Oの結合が切断される可能性があるため避けることが好ましい。この脱保護反応の溶媒はメタノール、エタノール、イソプロパノールのようなアルコール系溶媒が反応を進行させることから特に好ましい。 When protected with an alkylcarbonyl group, basic conditions are preferred, and it is particularly preferred to use a deprotecting reagent such as potassium carbonate. In strongly basic conditions such as sodium hydroxide, it is preferable to avoid Si—O bonds because they may be broken. As the solvent for this deprotection reaction, an alcohol solvent such as methanol, ethanol or isopropanol is particularly preferred since the reaction proceeds.
このように脱保護することにより水酸基をもつシリコーン共重合体を合成することができる。 By deprotecting in this manner, a silicone copolymer having a hydroxyl group can be synthesized.
以下、実施例を示して本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
以下の実施例において、測定には下記装置を使用し、原料は試薬メーカーから購入した一般的な試薬を用いた。 In the following examples, the following apparatus was used for the measurement, and a general reagent purchased from a reagent manufacturer was used as a raw material.
測定装置
NMR測定・・・日本電子製400MHz NMR測定器
IR測定・・・島津製IR Prestige-21
GPC測定・・・東ソー製HLC-8220
実施例1
3−ヒドロキシプロピルシルセスキオキサン・2−ノルボルネニルシルセスキオキサン共重合体の合成
撹拌機、環流冷却器、滴下ろう斗及び温度計を備えた1L4つ口フラスコに、水225g仕込み、3−メトキシプロピルトリメトキシシラン100g(0.514モル)と2−ノルボルナニルトリクロロシラン50.4g(0.220モル)のトルエン225g溶液を反応温度10〜20℃で滴下した。滴下終了後、同温度で2時間熟成後に静置後分液を行い、油層を回収した。次いで5%炭酸水素ナトリウム水溶液で洗浄し、トルエン油層を回収した。
measuring device
NMR measurement: JEOL 400MHz NMR measuring instrument
IR measurement ・ ・ ・ IR Prestige-21 made by Shimadzu
GPC measurement: Tosoh HLC-8220
Example 1
Synthesis of 3-hydroxypropylsilsesquioxane / 2-norbornenylsilsesquioxane copolymer 225 g of water was charged into a 1 L four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. A solution of 100 g (0.514 mol) of methoxypropyltrimethoxysilane and 50.4 g (0.220 mol) of 2-norbornanyltrichlorosilane in 225 g of toluene was added dropwise at a reaction temperature of 10 to 20 ° C. After completion of the dropwise addition, the mixture was aged at the same temperature for 2 hours and then allowed to stand, followed by liquid separation to recover the oil layer. Subsequently, it was washed with a 5% aqueous sodium hydrogen carbonate solution to recover a toluene oil layer.
次にそのトルエン溶液を撹拌機、蒸留塔、冷却器及び温度計を備えた1L4つ口フラスコに移し、オイルバスに入れ、徐々に加熱し、トルエンを留去した。トルエン留去後にさらに温度を上げ、200℃で2時間熟成し、GPC分析により、重量平均分子量(Mw:ポリスチレン換算)16900、分散度(Mw/Mn:ポリスチレン換算)3.3の3−メトキシプロピルシルセスキオキサン・2−ノルボルネニルシルセスキオキサン共重合体95.0g合成した。 Next, the toluene solution was transferred to a 1 L four-necked flask equipped with a stirrer, a distillation tower, a cooler, and a thermometer, placed in an oil bath, and gradually heated to distill off the toluene. After the toluene was distilled off, the temperature was further raised, the mixture was aged at 200 ° C. for 2 hours, and 3-methoxypropyl having a weight average molecular weight (Mw: polystyrene conversion) of 16900 and a dispersity (Mw / Mn: polystyrene conversion) of 3.3 by GPC analysis. 95.0 g of a silsesquioxane · 2-norbornenylsilsesquioxane copolymer was synthesized.
得られた共重合体のスペクトルデータを下記に示す。 The spectrum data of the obtained copolymer is shown below.
赤外線吸収スペクトル(IR)データ
1018-1196cm-1(Si-O)
核磁気共鳴スペクトル(NMR)データ(1H-NMR溶媒:CDCl3)
0.577ppm(bs)、0.858-1.613ppm(b)、2.072-2.262ppm(b)、3.289(bs)ppm。
Infrared absorption spectrum (IR) data
1018-1196cm -1 (Si-O)
Nuclear magnetic resonance spectrum (NMR) data ( 1 H-NMR solvent: CDCl 3 )
0.577 ppm (bs), 0.858-1.613 ppm (b), 2.072-2.262 ppm (b), 3.289 (bs) ppm.
次に、撹拌機、環流冷却器、滴下ろう斗及び温度計を備えた500mL4つ口フラスコに、アセトニトリル240gを仕込み、3−メトキシプロピルシルセスキオキサン・2−ノルボルネニルシルセスキオキサン共重合体47.4gとヨウ化ナトリウム113.2g(0.755モル)とトリメチルクロロシラン82.0g(0.755モル)を順次加え、65〜70℃で24時間還流した。還流後、水79.0gを滴下し、65〜70℃で6時間還流後に冷却し、亜硫酸水素ナトリウム水溶液で遊離ヨウ素を還元した後、15%食塩水で2回洗浄し、油層を回収した。さらに、油層を水に落として結晶を回収し、その結晶を乾燥し、GPC分析により、重量平均分子量(Mw:ポリスチレン換算)9400、分散度(Mw/Mn:ポリスチレン換算)3.1の3−ヒドロキシプロピルシルセスキオキサン・2−ノルボルネニルシルセスキオキサン共重合体48.1g合成した。 Next, 240 g of acetonitrile was charged into a 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, and 3-methoxypropylsilsesquioxane / 2-norbornenylsilsesquioxane co-polymerized. 47.4 g of the compound, 113.2 g (0.755 mol) of sodium iodide and 82.0 g (0.755 mol) of trimethylchlorosilane were sequentially added, and the mixture was refluxed at 65 to 70 ° C. for 24 hours. After refluxing, 79.0 g of water was added dropwise, the mixture was refluxed at 65-70 ° C. for 6 hours, cooled, free iodine was reduced with an aqueous sodium hydrogen sulfite solution, and then washed twice with 15% saline to recover the oil layer. Further, the oil layer was dropped into water to recover the crystals, and the crystals were dried and analyzed by GPC analysis with a weight average molecular weight (Mw: converted to polystyrene) of 9400 and a dispersity (Mw / Mn: converted to polystyrene) of 3.1. 48.1 g of hydroxypropylsilsesquioxane / 2-norbornenylsilsesquioxane copolymer was synthesized.
得られた共重合体のスペクトルデータを下記に示す。 The spectrum data of the obtained copolymer is shown below.
赤外線吸収スペクトル(IR)データ
3339cm-1(-OH)、993-1251cm-1(Si-O)
核磁気共鳴スペクトル(NMR)データ(1H-NMR溶媒:CDCl3)
0.07-0.09ppm(b)、0.60ppm(bs)、1.11-1.86ppm(b)、2.21ppm(bs)、3.30ppm(bs)、3.58ppm(bs)、4.03(bs)ppm。
Infrared absorption spectrum (IR) data
3339cm -1 (-OH), 993-1251cm -1 (Si-O)
Nuclear magnetic resonance spectrum (NMR) data ( 1 H-NMR solvent: CDCl 3 )
0.07-0.09ppm (b), 0.60ppm (bs), 1.11-1.86ppm (b), 2.21ppm (bs), 3.30ppm (bs), 3.58ppm (bs), 4.03 (bs) ppm.
実施例2
6−ヒドロキシノルボルナン−2(または3)−イル−シルセスキオキサン・n−プロピルシルセスキオキサン共重合体の合成
撹拌機、環流冷却器、滴下ろう斗及び温度計を備えた1L4つ口フラスコに、水84.8gと炭酸水素ナトリウム67.3g仕込み、6−アセトキシノルボルナン−2(または3)−イル−トリクロロシラン50g(0.155モル)とn−プロピルトリクロロシラン11.8g(0.067モル)のトルエン62.3g溶液を反応温度10〜20℃で滴下した。滴下終了後、同温度で2時間熟成後に静置後分液を行い、トルエン油層を回収した。
Example 2
Synthesis of 6-hydroxynorbornane-2 (or 3) -yl-silsesquioxane / n-propylsilsesquioxane copolymer 1 L 4-neck flask equipped with stirrer, reflux condenser, dropping funnel and thermometer Into this, 84.8 g of water and 67.3 g of sodium hydrogen carbonate were charged, 50 g (0.155 mol) of 6-acetoxynorbornane-2 (or 3) -yl-trichlorosilane and 11.8 g (0.067 mol) of n-propyltrichlorosilane. Mole) of toluene in 62.3 g was added dropwise at a reaction temperature of 10 to 20 ° C. After completion of the dropwise addition, the mixture was aged at the same temperature for 2 hours and then allowed to stand for separation to recover a toluene oil layer.
次に、そのトルエン溶液を撹拌機、蒸留塔、冷却器及び温度計を備えた1L4つ口フラスコに移し、オイルバスに入れ、徐々に加熱し、トルエンを留去した。トルエン留去後にさらに温度を上げ、200℃で2時間熟成し、GPC分析により、重量平均分子量(Mw:ポリスチレン換算)4200、分散度(Mw/Mn:ポリスチレン換算)1.8の6−アセトキシノルボルナン−2(または3)−イル−シルセスキオキサン・n−プロピルシルセスキオキサン共重合体38.3g合成した。 Next, the toluene solution was transferred to a 1 L four-necked flask equipped with a stirrer, a distillation tower, a cooler, and a thermometer, placed in an oil bath, and gradually heated to distill off the toluene. After evaporating the toluene, the temperature was further raised, aging was carried out at 200 ° C. for 2 hours, and 6-acetoxynorbornane having a weight average molecular weight (Mw: converted to polystyrene) of 4200 and a dispersity (Mw / Mn: converted to polystyrene) of 1.8 by GPC analysis. 38.3 g of -2 (or 3) -yl-silsesquioxane / n-propylsilsesquioxane copolymer was synthesized.
得られた共重合体のスペクトルデータを下記に示す。 The spectrum data of the obtained copolymer is shown below.
赤外線吸収スペクトル(IR)データ
1734cm-1(-CO2-)、1018-1246cm-1(Si-O)
核磁気共鳴スペクトル(NMR)データ(1H-NMR溶媒:DMSO-d6)
0.77-2.52ppm(b)、2.02ppm(bs,-CH3)、4.94ppm(bs)。
Infrared absorption spectrum (IR) data
1734cm -1 (-CO 2- ), 1018-1246cm -1 (Si-O)
Nuclear magnetic resonance spectrum (NMR) data ( 1 H-NMR solvent: DMSO-d 6 )
0.77-2.52ppm (b), 2.02ppm (bs, -CH3), 4.94ppm (bs).
次に、撹拌機、環流冷却器、滴下ろう斗及び温度計を備えた500mL4つ口フラスコに、メタノール240gと水240gを仕込み、6−アセトキシノルボルナン−2(または3)−イル−シルセスキオキサン・n−プロピルシルセスキオキサン共重合体35.0gと炭酸カリウム70.7gを順次加え、40℃で6時間撹拌した。反応後、酢酸エチルで抽出し、食塩水で2回洗浄後、油層を濃縮し結晶を得た。その結晶のGPC分析により、重量平均分子量(Mw:ポリスチレン換算)4000、分散度(Mw/Mn:ポリスチレン換算)1.8の6−ヒドロキシノルボルナン−2(または3)−イル−シルセスキオキサン・n−プロピルシルセスキオキサン共重合体32.1g合成した。 Next, 240 g of methanol and 240 g of water were charged into a 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, and 6-acetoxynorbornane-2 (or 3) -yl-silsesquioxane. -35.0 g of n-propylsilsesquioxane copolymer and 70.7 g of potassium carbonate were sequentially added and stirred at 40 ° C. for 6 hours. After the reaction, the mixture was extracted with ethyl acetate, washed twice with brine, and the oil layer was concentrated to obtain crystals. According to GPC analysis of the crystal, 6-hydroxynorbornane-2 (or 3) -yl-silsesquioxane of weight average molecular weight (Mw: polystyrene conversion) 4000 and dispersity (Mw / Mn: polystyrene conversion) 1.8 was obtained. 32.1 g of n-propylsilsesquioxane copolymer was synthesized.
得られた共重合体のスペクトルデータを下記に示す。 The spectrum data of the obtained copolymer is shown below.
赤外線吸収スペクトル(IR)データ
3358cm-1(-OH)、1009-1192cm-1(Si-O)
核磁気共鳴スペクトル(NMR)データ(1H-NMR溶媒:CDCl3)
0.69-2.11ppm(b)、4.00ppm(bs)、4.50ppm(bs)
実施例3
6−ヒドロキシノルボルナン−2(または3)−イル−シルセスキオキサン・n−プロピルシルセスキオキサン・メチルシルセスキオキサン共重合体の合成
撹拌機、環流冷却器、滴下ろう斗及び温度計を備えた1L4つ口フラスコに、水84.8gと炭酸水素ナトリウム67.3g仕込み、6−アセトキシノルボルナン−2(または3)−イル−トリクロロシラン50g(0.155モル)とn−プロピルトリクロロシラン6.6g(0.037モル)とメチルトリクロロシラン 4.5g(0.030モル)のトルエン62.3g溶液を反応温度10〜20℃で滴下した。滴下終了後、同温度で2時間熟成後に静置後分液を行い、トルエン油層を回収した。
Infrared absorption spectrum (IR) data
3358cm -1 (-OH), 1009-1192cm -1 (Si-O)
Nuclear magnetic resonance spectrum (NMR) data ( 1 H-NMR solvent: CDCl 3 )
0.69-2.11ppm (b), 4.00ppm (bs), 4.50ppm (bs)
Example 3
Synthesis of 6-hydroxynorbornane-2 (or 3) -yl-silsesquioxane / n-propylsilsesquioxane / methylsilsesquioxane copolymer Stirrer, reflux condenser, dropping funnel and thermometer A 1 L four-necked flask equipped with 84.8 g of water and 67.3 g of sodium hydrogen carbonate, 50 g (0.155 mol) of 6-acetoxynorbornane-2 (or 3) -yl-trichlorosilane and 6-n-propyltrichlorosilane 6 62.3 g (0.037 mol) and methyltrichlorosilane 4.5 g (0.030 mol) in 62.3 g toluene were added dropwise at a reaction temperature of 10 to 20 ° C. After completion of the dropwise addition, the mixture was aged at the same temperature for 2 hours and then allowed to stand for separation to recover a toluene oil layer.
次に、そのトルエン溶液を撹拌機、蒸留塔、冷却器及び温度計を備えた1L4つ口フラスコに移し、オイルバスに入れ、徐々に加熱し、トルエンを留去した。トルエン留去後にさらに温度を上げ、200℃で2時間熟成し、GPC分析により、重量平均分子量(Mw:ポリスチレン換算)4700、分散度(Mw/Mn:ポリスチレン換算)2.3の6−アセトキシノルボルナン−2(または3)−イル−シルセスキオキサン・n−プロピルシルセスキオキサン・メチルシルセスキオキサン共重合体37.9g合成した。 Next, the toluene solution was transferred to a 1 L four-necked flask equipped with a stirrer, a distillation tower, a cooler, and a thermometer, placed in an oil bath, and gradually heated to distill off the toluene. After evaporating the toluene, the temperature was further raised, aging was carried out at 200 ° C. for 2 hours, and 6-acetoxynorbornane having a weight average molecular weight (Mw: converted to polystyrene) of 4700 and a dispersity (Mw / Mn: converted to polystyrene) of 2.3 by GPC analysis. 27.9 g of -2 (or 3) -yl-silsesquioxane / n-propylsilsesquioxane / methylsilsesquioxane copolymer was synthesized.
得られた共重合体のスペクトルデータを下記に示す。 The spectrum data of the obtained copolymer is shown below.
赤外線吸収スペクトル(IR)データ
1734cm-1(-CO2-)、1018-1246cm-1(Si-O)
核磁気共鳴スペクトル(NMR)データ(1H-NMR溶媒:DMSO-d6)
0.77-2.52ppm(b)、2.05ppm(bs,-CH3)、4.94ppm(bs)。
Infrared absorption spectrum (IR) data
1734cm -1 (-CO 2- ), 1018-1246cm -1 (Si-O)
Nuclear magnetic resonance spectrum (NMR) data ( 1 H-NMR solvent: DMSO-d 6 )
0.77-2.52ppm (b), 2.05ppm (bs, -CH3), 4.94ppm (bs).
次に、撹拌機、環流冷却器、滴下ろう斗及び温度計を備えた500mL4つ口フラスコに、メタノール240gと水240gを仕込み、6−アセトキシノルボルナン−2(または3)−イル−シルセスキオキサン・n−プロピルシルセスキオキサン・メチルシルセスキオキサン共重合体35.0gと炭酸カリウム70.7gを順次加え、40℃で6時間撹拌した。反応後、酢酸エチルで抽出し、食塩水で2回洗浄後、油層を濃縮し結晶を得た。その結晶のGPC分析により、重量平均分子量(Mw:ポリスチレン換算)4000、分散度(Mw/Mn:ポリスチレン換算)1.8の6−ヒドロキシノルボルナン−2(または3)−イル−シルセスキオキサン・n−プロピルシルセスキオキサン・メチルシルセスキオキサン共重合体31.8g合成した。 Next, 240 g of methanol and 240 g of water were charged into a 500 mL four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, and 6-acetoxynorbornane-2 (or 3) -yl-silsesquioxane. -35.0 g of n-propylsilsesquioxane / methylsilsesquioxane copolymer and 70.7 g of potassium carbonate were sequentially added and stirred at 40 ° C for 6 hours. After the reaction, the mixture was extracted with ethyl acetate, washed twice with brine, and the oil layer was concentrated to obtain crystals. According to GPC analysis of the crystal, 6-hydroxynorbornane-2 (or 3) -yl-silsesquioxane of weight average molecular weight (Mw: polystyrene conversion) 4000 and dispersity (Mw / Mn: polystyrene conversion) 1.8 was obtained. 31.8 g of n-propylsilsesquioxane / methylsilsesquioxane copolymer was synthesized.
得られた共重合体のスペクトルデータを下記に示す。 The spectrum data of the obtained copolymer is shown below.
赤外線吸収スペクトル(IR)データ
3358cm-1(-OH)、1009-1192cm-1(Si-O)
核磁気共鳴スペクトル(NMR)データ(1H-NMR溶媒:CDCl3)
0.69-2.11ppm(b)、3.89ppm(bs)、4.50ppm(bs)
Infrared absorption spectrum (IR) data
3358cm -1 (-OH), 1009-1192cm -1 (Si-O)
Nuclear magnetic resonance spectrum (NMR) data ( 1 H-NMR solvent: CDCl 3 )
0.69-2.11ppm (b), 3.89ppm (bs), 4.50ppm (bs)
Claims (5)
で示される繰り返し単位をもつシリコーン共重合体であって、該シリコーン共重合体のポリスチレン換算の重量平均分子量が500〜100000であることを特徴とする水酸基を有するシリコーン共重合体。 The following general formula
A silicone copolymer having a hydroxyl group, wherein the silicone copolymer has a weight average molecular weight in terms of polystyrene of 500 to 100,000.
に示すアルキルカルボニル基を示す。a、bはモル%を示しaは1〜99モル%、bは1〜99モル%、但しa+b=100を満たす。)
で示される繰り返し単位を有するシリコーン共重合体を、脱保護することを特徴とする請求項1から4のいずれかに記載の水酸基を有するシリコーン共重合体の製造方法。 The following general formula
The alkylcarbonyl group shown by these is shown. a and b represent mol%, a is 1 to 99 mol%, b is 1 to 99 mol%, provided that a + b = 100 is satisfied. )
The method for producing a silicone copolymer having a hydroxyl group according to any one of claims 1 to 4 , wherein the silicone copolymer having a repeating unit represented by formula (2) is deprotected.
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