WO2020116161A1 - Block copolymer - Google Patents
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- WO2020116161A1 WO2020116161A1 PCT/JP2019/045411 JP2019045411W WO2020116161A1 WO 2020116161 A1 WO2020116161 A1 WO 2020116161A1 JP 2019045411 W JP2019045411 W JP 2019045411W WO 2020116161 A1 WO2020116161 A1 WO 2020116161A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
Definitions
- the present invention relates to a block copolymer.
- Patent Document 1 discloses that a hydrophilic polymer portion obtained by polymerizing a monomer mixture containing N,N-dimethylacrylamide and N-methylolacrylamide and methylmethacrylate (methacrylic acid). Block copolymers comprising a hydrophobic polymer portion obtained by polymerizing a monomer mixture containing (methyl acid)) (Examples, etc.). Patent Document 1 describes that the N-methylolacrylamide is dehydrated and condensed by heating to form a crosslinked structure.
- an object of the present invention is to provide a block copolymer having excellent fast curability.
- the present inventors have found that the above problems can be solved by introducing a repeating unit having an alkoxysilyl group, and have reached the present invention. That is, the present inventors have found that the above problems can be solved by the following configurations.
- the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
- each component may be used alone or in combination of two or more.
- the content of the component means the total content unless otherwise specified.
- the block copolymer of the present invention is A polymer block A having a repeating unit A1 represented by the following formula (A1) or a repeating unit A2 represented by the following formula (A2), A polymer block B having a repeating unit represented by the following formula (B1), At least one of the polymer block A and the polymer block B is a block copolymer (hereinafter, also referred to as “polymer of the present invention”) having a repeating unit C1 represented by the following formula (C1). is there.
- R represents a hydrogen atom or a methyl group.
- R A1 represents a hydrogen atom or a hydrocarbon group. The two R A1 may be the same or different.
- R A2 represents a hydrogen atom or a hydrocarbon group.
- p represents an integer of 1 or more.
- R B1 represents a hydrocarbon group.
- L represents a single bond or a divalent linking group.
- R C11 and R C12 each independently represent a hydrocarbon group.
- m represents an integer of 1 to 3.
- n is an integer of 2 or more, a plurality of R C11 existing may be the same or different.
- n is 2, the two R C12 may be the same or different.
- the polymer of the present invention has such a constitution, it can be considered that the above-mentioned effects can be obtained. Although the reason is not clear, it is presumed that the alkoxysilyl group contained in the repeating unit C1 has high reactivity.
- the polymer of the present invention may be a diblock copolymer of one polymer block A and one polymer block B, or a multiblock copolymer in which at least one of each polymer block is present in plural. Good. Further, the polymer of the present invention may have a polymer block that does not correspond to either the polymer block A or the polymer block B.
- the polymer of the present invention is excellent in quick-curing property, and when formed into a cured film, it is excellent in antifogging property, adhesion property, durability, water resistance, warm water resistance and appearance. It is preferably a diblock copolymer of A and one polymer block B.
- the polymer of the present invention "excellent in quick-curing property, and when formed into a cured film, it is excellent in antifogging property, adhesiveness, durability, water resistance, warm water resistance and appearance” Is more effective.”
- the shape of the polymer of the present invention include a linear shape, a graft shape, and a star shape. Among them, the linear shape is preferable because the effects of the present invention are more excellent.
- the polymer block A is generally more hydrophilic than the polymer block B, and the polymer block B is relatively more hydrophobic than the polymer block A.
- the polymer block A has the repeating unit A1 represented by the above formula (A1) or the repeating unit A2 represented by the above formula (A2).
- the polymer block A may have a repeating unit other than the repeating unit A1 and the repeating unit A2.
- the repeating unit is not particularly limited.
- at least one of the polymer block A and the polymer block B has the repeating unit C1 represented by the above formula (C1).
- the polymer block A has a repeating unit A1 represented by the following formula (A1) or a repeating unit A2 represented by the following formula (A2).
- R represents a hydrogen atom or a methyl group.
- R A1 represents a hydrogen atom or a hydrocarbon group. The two R A1 may be the same or different.
- R A1 represents a hydrogen atom or a hydrocarbon group.
- the above-mentioned hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group combining these.
- the aliphatic hydrocarbon group may be linear, branched or cyclic.
- Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (especially 1 to 30 carbon atoms), a linear or branched alkenyl group (especially 2 to 30 carbon atoms), Examples thereof include a linear or branched alkynyl group (in particular, having 2 to 30 carbon atoms).
- aromatic hydrocarbon group examples include an aromatic hydrocarbon group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
- R A1 is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group, and further preferably a linear alkyl group, for the reason that the effects of the present invention are more excellent.
- a linear alkyl group having 1 to 5 carbon atoms is particularly preferable.
- R represents a hydrogen atom or a methyl group.
- R A2 represents a hydrogen atom or a hydrocarbon group.
- p represents an integer of 1 or more.
- R A2 represents a hydrogen atom or a hydrocarbon group. Specific examples and preferred embodiments of the R A2 is the same as R A1 in the formula (A1).
- p represents an integer of 1 or more.
- the upper limit of p is not particularly limited, but is preferably 10 or less because the effects of the present invention are more excellent.
- the total content of the repeating unit A1 and the repeating unit A2 in the polymer block A is preferably 50 mol% or more, and more preferably 70 mol% or more from the reason that the effects of the present invention are more excellent. It is preferably 90 mol% or more, and more preferably 90 mol% or more.
- the upper limit of the total content of the repeating unit A1 and the repeating unit A2 in the polymer block A is not particularly limited and is 100 mol%.
- the “total content of the repeating unit A1 and the repeating unit A2 in the polymer block A” (mol %) means the repeating unit A1 and the repeating unit A2 with respect to all the repeating units (the number of moles) of the polymer block A. It means the ratio (mol %) of the total (number of moles).
- the content of the polymer block A is preferably 20 to 95 mol %, more preferably 30 to 90 mol %, for the reason that the effects of the present invention are more excellent. It is more preferably 40 to 80 mol %.
- the “content of the polymer block A” means the ratio (mol %) of all the repeating units (mol number) of the polymer block A to all the repeating units (mol number) of the block copolymer. means.
- the content of the polymer block A is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, for the reason that the effects of the present invention are more excellent. It is more preferably 40 to 80% by mass.
- the polymer block B has the repeating unit B1 represented by the above formula (B1).
- the polymer block B may have a repeating unit other than the repeating unit B1.
- the repeating unit is not particularly limited.
- at least one of the polymer block A and the polymer block B has the repeating unit C1 represented by the above formula (C1).
- the polymer block B has a repeating unit B1 represented by the following formula (B1).
- R represents a hydrogen atom or a methyl group.
- R B1 represents a hydrocarbon group.
- R B1 represents a hydrocarbon group. Specific examples and preferred embodiments of the above hydrocarbon group are the same as R A1 in formula (A1).
- the content of the repeating unit B1 in the polymer block B is preferably 50 mol% or more, more preferably 70 mol% or more, and 90 mol% or more for the reason that the effects of the present invention are more excellent. Is more preferable.
- the upper limit of the content of the repeating unit B1 in the polymer block B is not particularly limited and is 100 mol%.
- the “content of the repeating unit B1 in the polymer block B” (mol %) means the ratio (mol%) of the repeating unit B1 (mol number) to all the repeating units (mol number) of the polymer block B. means.
- the content of the polymer block B is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, for the reason that the effects of the present invention are more excellent. It is more preferably 20 to 60 mol %.
- the “content of the polymer block B” (mol %) means the ratio (mol %) of all the repeating units (mol number) of the polymer block B to all the repeating units (mol number) of the block copolymer. means.
- the content of the polymer block B is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, for the reason that the effects of the present invention are more excellent. It is more preferably 20 to 60% by mass.
- the ratio of the content of the polymer block A to the content of the polymer block B is a molar ratio because the effects of the present invention are more excellent. And is preferably 0.25 to 19, more preferably 0.42 to 9.0, and further preferably 0.67 to 4.0.
- the total content of the polymer block A and the polymer block B is preferably 50 mol% or more, and 70 mol% or more for the reason that the effects of the present invention are more excellent. More preferably, it is more preferably 90 mol% or more.
- the upper limit of the total content of the polymer block A and the polymer block B is not particularly limited and is 100 mol%.
- the “total content of the polymer block A and the polymer block B” (mol %) means all the repeating units of the polymer block A and the polymer blocks with respect to all the repeating units (the number of moles) of the block copolymer. It means the ratio (mol %) of the total (mol number) of all repeating units of B.
- the total content of the polymer block A and the polymer block B is preferably 50% by mass or more, and 70% by mass or more, for the reason that the effects of the present invention are more excellent. Is more preferable, and 90% by mass or more is further preferable.
- the upper limit of the total content of the polymer block A and the polymer block B is not particularly limited and is 100% by mass.
- At least one of the polymer block A and the polymer block B has the repeating unit C1 represented by the following formula (C1). From the reason that the effects of the present invention are more excellent, it is preferable that at least the polymer block B has the repeating unit C1, and it is more preferable that both the polymer block A and the polymer block B have the repeating unit C1.
- L represents a single bond or a divalent linking group.
- R C11 and R C12 each independently represent a hydrocarbon group.
- m represents an integer of 1 to 3.
- m is an integer of 2 or more, a plurality of R C11 existing may be the same or different.
- n is 2, the two R C12 may be the same or different.
- L represents a single bond or a divalent linking group.
- the divalent linking group include linear, branched or cyclic divalent aliphatic hydrocarbon groups (eg, alkylene groups such as methylene group, ethylene group, propylene group) and divalent aromatic groups.
- Hydrocarbon group (eg phenylene group), —O—, —S—, —SO 2 —, —NR L —, —CO—, —NH—, —COO—, —CONR L —, —O—CO— O—, —SO 3 —, —NHCOO—, —SO 2 NR L —, —NH—CO—NH— or a group combining two or more thereof (eg, alkyleneoxy group, alkyleneoxycarbonyl group, alkylenecarbonyloxy) Group) and the like.
- R L represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
- the above L is preferably an alkyleneoxycarbonyl group for the reason that the effects of the present invention are more excellent.
- R C11 and R C12 each independently represent a hydrocarbon group.
- Specific examples and preferred embodiments of the above hydrocarbon group are the same as R A1 in formula (A1).
- n represents an integer of 0 to 2.
- the content of the repeating unit C1 in the polymer block A is preferably 0.1 to 20 mol% and more preferably 0.2 to 10 mol% for the reason that the effects of the present invention are more excellent. It is preferably 0.5 to 5 mol% and more preferably 0.5 to 5 mol %.
- the content of the repeating unit C1 in the polymer block B is preferably 0.1 to 20 mol% and more preferably 0.2 to 10 mol% for the reason that the effects of the present invention are more excellent. It is preferably 0.5 to 5 mol% and more preferably 0.5 to 5 mol %.
- the “content of the repeating unit C1 in the polymer block A” (mol %) means the ratio (mol%) of the repeating unit C1 (mol number) to all the repeating units (mol number) of the polymer block A.
- the “content of the repeating unit C1 in the polymer block B” means the ratio (mol%) of the repeating unit C1 (the number of moles) to all the repeating units (the number of moles) of the polymer block B.
- the content of the repeating unit C1 is preferably 0.1 to 20 mol% with respect to all the repeating units of the block copolymer for the reason that the effects of the present invention are more excellent. , 0.2 to 10 mol% is more preferable, and 0.3 to 5 mol% is further preferable.
- At least one of the polymer block A and the polymer block B preferably has a repeating unit C2 represented by the following formula (C2) for the reason that the effects of the present invention are more excellent. .. From the reason that the effects of the present invention are more excellent, it is preferable that at least the polymer block B has the repeating unit C2, and it is more preferable that both the polymer block A and the polymer block B have the repeating unit C2.
- R represents a hydrogen atom or a methyl group.
- R C2 represents a hydrogen atom or a hydrocarbon group having a hydroxy group.
- R C2 represents a hydrogen atom or a hydrocarbon group having a hydroxy group.
- Specific examples and preferred embodiments of the hydrocarbon group in the hydrocarbon group having a hydroxy group are the same as R A1 in formula (A1).
- Examples of the hydrocarbon group having a hydroxy group include a 2-hydroxyethyl group.
- the content of the repeating unit C2 in the polymer block A is preferably 0.1 to 20 mol% and more preferably 0.2 to 10 mol% for the reason that the effects of the present invention are more excellent. It is preferably 0.5 to 5 mol% and more preferably 0.5 to 5 mol %.
- the content of the repeating unit C2 in the polymer block B is preferably 0.1 to 20 mol% and more preferably 0.2 to 10 mol% for the reason that the effects of the present invention are more excellent. It is preferably 0.5 to 5 mol% and more preferably 0.5 to 5 mol %.
- the “content of the repeating unit C2 in the polymer block A” (mol %) means the ratio (mol %) of the repeating unit C2 (mol number) to all the repeating units (mol number) of the polymer block A.
- the “content of the repeating unit C2 in the polymer block B” means the ratio (mol%) of the repeating unit C2 (the number of moles) to all the repeating units (the number of moles) of the polymer block B.
- the content of the repeating unit C2 is preferably 0.1 to 20 mol% based on all the repeating units of the block copolymer, for the reason that the effects of the present invention are more excellent. , 0.2 to 10 mol% is more preferable, and 0.3 to 5 mol% is further preferable.
- the total content of the repeating unit C1 and the repeating unit C2 is 0.1 to 20 mols based on the total repeating units of the block copolymer for the reason that the effects of the present invention are more excellent. %, preferably 0.2 to 10 mol %, more preferably 0.3 to 5 mol %.
- the ratio of the content of the repeating unit C1 to the content of the repeating unit C2 is a molar ratio of 0. It is preferably 1 to 10, more preferably 0.2 to 5, and further preferably 0.3 to 3.
- the number average molecular weight (Mn) of the polymer of the present invention is not particularly limited, but is preferably 1,000 to 1,000,000, and preferably 10,000 to 100, for the reason that the effects of the present invention are more excellent. It is more preferably 000, and even more preferably 20,000 to 80,000.
- the weight average molecular weight (Mw) of the polymer of the present invention is not particularly limited, but is preferably 1,000 to 1,000,000, and preferably 10,000 to 100, for the reason that the effects of the present invention are more excellent. It is more preferably 000, and even more preferably 20,000 to 80,000.
- the molecular weight distribution (Mw/Mn) of the polymer of the present invention is not particularly limited, but is preferably 10 or less, more preferably 5 or less for the reason that the effect of the present invention is more excellent.
- the lower limit of the molecular weight distribution is not particularly limited, but is usually 1.0 or more.
- Mn and Mw are standard polystyrene conversion values obtained by gel permeation chromatography (GPC) measurement under the following conditions.
- GPC gel permeation chromatography
- the method for producing the polymer of the present invention is not particularly limited, and a conventionally known method can be used. Among them, the method using the living radical polymerization method is preferable, and the method using the RAFT method (reversible addition fragmentation chain transfer polymerization method) (particularly the method using a trithiocarbonate compound as a chain transfer agent) is more preferable. ..
- a monomer that becomes the repeating unit B1 for example, methyl methacrylate
- a monomer that becomes the repeating unit C1 for example, 3-methacryloxypropyltrimethoxysilane
- a monomer eg, 2-hydroxyethyl methacrylate
- a monomer eg, N,N-dimethylacrylamide
- a monomer for example, 3-methacryloxypropyltrimethoxysilane
- a monomer for example, 2-hydroxyethyl methacrylate
- the polymer block A and A method for producing a block copolymer containing the united block B in this case, both the polymer block A and the polymer block B have the repeating unit C1 and the like can be mentioned.
- composition of the present invention is a composition containing the above-mentioned polymer of the present invention.
- the composition may contain components other than the polymer of the present invention. Examples of the components include a leveling agent, a phosphate ester monomer, a solvent (for example, alcohol), and the like.
- the composition of the present invention is useful, for example, as an anti-fog coating agent (coating agent for preventing fogging).
- the cured film of the present invention is not particularly limited as long as it is formed from the composition of the present invention described above.
- the method for producing the cured film of the present invention is not particularly limited, but for example, the composition of the present invention described above is applied onto a substrate (preferably a (meth)acrylate resin substrate) and heated (preferably 50 to 200). °C) and the like. By heating, the alkoxysilyl groups in the repeating unit C1 react (crosslink) with each other to form a cured film.
- the polymer of the present invention has the repeating unit C2
- the alkoxysilyl group in the repeating unit C1 and the —OH group in the repeating unit C2 are combined.
- crosslinking Upon reaction (crosslinking), a cured film is formed.
- the cured film of the present invention is useful, for example, as an anti-fog film (a film for preventing fogging).
- Example 4 Methyl methacrylate (Tokyo Kasei: 16 mL), 2-hydroxyethyl methacrylate (Tokyo Kasei: 0.4 mL), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Silicone: 0.4 mL), azobisiso Butyronitrile (manufactured by Tokyo Chemical Industry: 10 mg), 4-cyano-4-(((dodecylthio)carbothioyl)thio)pentanoic acid (manufactured by Boron Molecular: 0.12 g) and N,N-dimethylformamide (manufactured by Kanto Kagaku: 50 mL) were mixed, heated to 70° C., and stirred.
- the resulting block copolymer had a repeating unit derived from N,N-dimethylacrylamide (corresponding to the repeating unit A1 described above) (97 mol %) and a repeating unit derived from 3-methacryloxypropyltrimethoxysilane (described above.
- Polymer block A (corresponding to polymer block A described above) consisting of (1 mol%) and 2-hydroxyethyl methacrylate (corresponding to repeating unit C2 described above) (2 mol%) And methyl methacrylate (corresponding to the repeating unit B1 described above) (97 mol %), a repeating unit derived from 3-methacryloxypropyltrimethoxysilane (corresponding to the repeating unit C1 described above) (1 mol %), and methacrylic acid A block copolymer (straight chain) containing a polymer block B (corresponding to the polymer block B described above) consisting of 2-hydroxyethyl (corresponding to the repeating unit C2 described above) (2 mol %).
- the content of the polymer block A in the block copolymer is 50 mol%
- the content of the polymer block B in the block copolymer is 50 mol%.
- ⁇ Fast curability> Each of the obtained block copolymers is dissolved in a solvent, and this is coated on a methyl methacrylate resin substrate by a spray coating method so that the thickness of the coating film (cured film) after curing becomes 3 to 5 ⁇ m. After drying at 30° C. for 1 minute, heat curing was performed at 100° C. Then, the rapid curing property was evaluated according to the following 5 grades. In addition, if the evaluation is ⁇ or more, there is no practical problem, and ⁇ is more preferable, and ⁇ + is more preferable. ⁇ + : Cured within 4 minutes. ⁇ : Hardens within more than 4 minutes and within 5 minutes. ⁇ : Cured in more than 5 minutes and less than 10 minutes. (Triangle
- ⁇ Warm water resistance> Each of the obtained block copolymers is dissolved in a solvent, and this is coated on a methyl methacrylate resin substrate by a spray coating method so that the thickness of the coating film (cured film) after curing becomes 3 to 5 ⁇ m. After drying at 30° C. for 1 minute, heat curing was performed at 100° C. until it was sufficiently cured. The obtained cured film was immersed in warm water of 40° C. for 240 hours, the water was removed by a blower, and the appearance of the cured film after drying at room temperature for 1 hour was visually evaluated. In addition, when the evaluation is ⁇ or more, there is no practical problem, and when ⁇ , it is more preferable. A: No whitening is observed. ⁇ : A slight whitening is observed. ⁇ : Remarkable whitening is observed. X: Elution of the cured film is observed.
- Examples 1 to 5 in which at least one of the united block A and the polymer block B had the repeating unit C1 showed excellent fast curability and hot water resistance showed excellent fast curability and hot water resistance. From the comparison of Examples 1 to 5, Examples 1 and 3 to 5 in which the polymer block A has the repeating unit C1 showed more excellent fast curability. Further, from the comparison of Examples 1 to 5, Examples 2 to 5 in which the polymer block B has the repeating unit C1 showed more excellent hot water resistance. Further, from the comparison of Examples 1 to 5, Examples 4 to 5 in which at least one of the polymer block A and the polymer block B has the repeating unit C2 showed more excellent fast curability.
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Abstract
The purpose of the present invention is to provide a block copolymer having excellent fast curability. This block copolymer includes polymer block A having a (meth)acrylamide-based repeating unit and the like, and polymer block B having a (meth)acrylate-based repeating unit, wherein the polymer block A and/or the polymer block B has a repeating unit C1 having an alkoxysilyl group.
Description
本発明は、ブロック共重合体に関する。
The present invention relates to a block copolymer.
自動車のヘッドランプ等の車両灯具において、灯室内に高湿度の空気が入り込み、外気や降雨等によってレンズが冷やされ、レンズ内面に水分が結露することにより、曇りが生じることがある。その結果、車両灯の輝度が低下し、またレンズ面の美観が損なわれることにより、ユーザーの不快感を引き起こす場合がある。このようなレンズ内面の曇りを防ぐために、レンズ内面に防曇剤組成物を塗布し、防曇塗膜を形成させる方法が知られている。
In vehicle lamps such as automobile headlamps, high humidity air may enter the lamp room, the lens may be cooled by outside air or rainfall, and water may condense on the inner surface of the lens, resulting in fogging. As a result, the brightness of the vehicle light is reduced, and the aesthetic appearance of the lens surface is impaired, which may cause user discomfort. In order to prevent such fog on the inner surface of the lens, a method is known in which an antifog composition is applied to the inner surface of the lens to form an antifog coating film.
このような防曇組成物に使用されるポリマーとして、特許文献１には、Ｎ，Ｎ－ジメチルアクリルアミド及びＮ－メチロールアクリルアミドを含む単量体混合物を重合した親水性重合体部分とメチルメタクリレート（メタクリル酸メチル）を含む単量体混合物を重合した疎水性重合体部分とからなるブロック共重合体が開示されている（実施例等）。
特許文献１には、加熱により上記Ｎ－メチロールアクリルアミドが脱水縮合して架橋構造を形成する旨が記載されている。 As a polymer used for such an antifogging composition, Patent Document 1 discloses that a hydrophilic polymer portion obtained by polymerizing a monomer mixture containing N,N-dimethylacrylamide and N-methylolacrylamide and methylmethacrylate (methacrylic acid). Block copolymers comprising a hydrophobic polymer portion obtained by polymerizing a monomer mixture containing (methyl acid)) (Examples, etc.).
Patent Document 1 describes that the N-methylolacrylamide is dehydrated and condensed by heating to form a crosslinked structure.
特許文献１には、加熱により上記Ｎ－メチロールアクリルアミドが脱水縮合して架橋構造を形成する旨が記載されている。 As a polymer used for such an antifogging composition, Patent Document 1 discloses that a hydrophilic polymer portion obtained by polymerizing a monomer mixture containing N,N-dimethylacrylamide and N-methylolacrylamide and methylmethacrylate (methacrylic acid). Block copolymers comprising a hydrophobic polymer portion obtained by polymerizing a monomer mixture containing (methyl acid)) (Examples, etc.).
Patent Document 1 describes that the N-methylolacrylamide is dehydrated and condensed by heating to form a crosslinked structure.
このようななか、本発明者らが特許文献１の実施例に記載のブロック共重合体を合成し、評価したところ、硬化速度が昨今要求されているレベルを必ずしも満たしていない（速硬化性が不十分である）ことが明らかになった。
Under these circumstances, the inventors of the present invention synthesized and evaluated the block copolymers described in Examples of Patent Document 1, and found that the curing rate does not always meet the level currently required (the rapid curing property is unsatisfactory). Suffices).
そこで、本発明は、上記実情を鑑みて、速硬化性に優れるブロック共重合体を提供することを目的とする。
Therefore, in view of the above circumstances, an object of the present invention is to provide a block copolymer having excellent fast curability.
本発明者らは、上記課題について鋭意検討した結果、アルコキシシリル基を有する繰り返し単位を導入することで上記課題が解決できることを見出し、本発明に至った。
すなわち、本発明者らは、以下の構成により上記課題が解決できることを見出した。 As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by introducing a repeating unit having an alkoxysilyl group, and have reached the present invention.
That is, the present inventors have found that the above problems can be solved by the following configurations.
すなわち、本発明者らは、以下の構成により上記課題が解決できることを見出した。 As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by introducing a repeating unit having an alkoxysilyl group, and have reached the present invention.
That is, the present inventors have found that the above problems can be solved by the following configurations.
（１） 後述する式（Ａ１）で表される繰り返し単位Ａ１、又は、後述する式（Ａ２）で表される繰り返し単位Ａ２を有する重合体ブロックＡと、
後述する式（Ｂ１）で表される繰り返し単位を有する重合体ブロックＢとを含み、
上記重合体ブロックＡ及び上記重合体ブロックＢのうち少なくとも一方が、後述する式（Ｃ１）で表される繰り返し単位Ｃ１を有する、ブロック共重合体。
（２） 上記重合体ブロックＡ及び上記重合体ブロックＢのうち少なくとも一方が、後述する式（Ｃ２）で表される繰り返し単位Ｃ２を有する、上記（１）に記載のブロック共重合体。
（３） 上記重合体ブロックＢが、上記式（Ｃ１）で表される繰り返し単位を有する、上記（１）又は（２）に記載のブロック共重合体。
（４） 上記重合体ブロックＡの含有量が、３０～９０質量％である、上記（１）又は（２）に記載のブロック共重合体。 (1) A polymer block A having a repeating unit A1 represented by the formula (A1) described below or a repeating unit A2 represented by the formula (A2) described below,
A polymer block B having a repeating unit represented by the formula (B1) described later,
A block copolymer in which at least one of the polymer block A and the polymer block B has a repeating unit C1 represented by the formula (C1) described later.
(2) The block copolymer according to (1) above, wherein at least one of the polymer block A and the polymer block B has a repeating unit C2 represented by the formula (C2) described later.
(3) The block copolymer as described in (1) or (2) above, wherein the polymer block B has a repeating unit represented by the formula (C1).
(4) The block copolymer as described in (1) or (2) above, wherein the content of the polymer block A is 30 to 90% by mass.
後述する式（Ｂ１）で表される繰り返し単位を有する重合体ブロックＢとを含み、
上記重合体ブロックＡ及び上記重合体ブロックＢのうち少なくとも一方が、後述する式（Ｃ１）で表される繰り返し単位Ｃ１を有する、ブロック共重合体。
（２） 上記重合体ブロックＡ及び上記重合体ブロックＢのうち少なくとも一方が、後述する式（Ｃ２）で表される繰り返し単位Ｃ２を有する、上記（１）に記載のブロック共重合体。
（３） 上記重合体ブロックＢが、上記式（Ｃ１）で表される繰り返し単位を有する、上記（１）又は（２）に記載のブロック共重合体。
（４） 上記重合体ブロックＡの含有量が、３０～９０質量％である、上記（１）又は（２）に記載のブロック共重合体。 (1) A polymer block A having a repeating unit A1 represented by the formula (A1) described below or a repeating unit A2 represented by the formula (A2) described below,
A polymer block B having a repeating unit represented by the formula (B1) described later,
A block copolymer in which at least one of the polymer block A and the polymer block B has a repeating unit C1 represented by the formula (C1) described later.
(2) The block copolymer according to (1) above, wherein at least one of the polymer block A and the polymer block B has a repeating unit C2 represented by the formula (C2) described later.
(3) The block copolymer as described in (1) or (2) above, wherein the polymer block B has a repeating unit represented by the formula (C1).
(4) The block copolymer as described in (1) or (2) above, wherein the content of the polymer block A is 30 to 90% by mass.
以下に示すように、本発明によれば、速硬化性に優れるブロック共重合体を提供することができる。
As shown below, according to the present invention, it is possible to provide a block copolymer having excellent quick-curing properties.
以下に、本発明のブロック共重合体について説明する。
なお、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
また、各成分は、１種を単独でも用いても、２種以上を併用してもよい。ここで、各成分について２種以上を併用する場合、その成分について含有量とは、特段の断りが無い限り、合計の含有量を指す。 The block copolymer of the present invention will be described below.
In the present specification, the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
In addition, each component may be used alone or in combination of two or more. Here, when two or more kinds of each component are used in combination, the content of the component means the total content unless otherwise specified.
なお、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
また、各成分は、１種を単独でも用いても、２種以上を併用してもよい。ここで、各成分について２種以上を併用する場合、その成分について含有量とは、特段の断りが無い限り、合計の含有量を指す。 The block copolymer of the present invention will be described below.
In the present specification, the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
In addition, each component may be used alone or in combination of two or more. Here, when two or more kinds of each component are used in combination, the content of the component means the total content unless otherwise specified.
［ブロック共重合体］
本発明のブロック共重合体は、
下記式（Ａ１）で表される繰り返し単位Ａ１、又は、下記式（Ａ２）で表される繰り返し単位Ａ２を有する重合体ブロックＡと、
下記式（Ｂ１）で表される繰り返し単位を有する重合体ブロックＢとを含み、
上記重合体ブロックＡ及び上記重合体ブロックＢのうち少なくとも一方が、下記式（Ｃ１）で表される繰り返し単位Ｃ１を有する、ブロック共重合体（以下、「本発明の重合体」とも言う）である。 [Block copolymer]
The block copolymer of the present invention is
A polymer block A having a repeating unit A1 represented by the following formula (A1) or a repeating unit A2 represented by the following formula (A2),
A polymer block B having a repeating unit represented by the following formula (B1),
At least one of the polymer block A and the polymer block B is a block copolymer (hereinafter, also referred to as “polymer of the present invention”) having a repeating unit C1 represented by the following formula (C1). is there.
本発明のブロック共重合体は、
下記式（Ａ１）で表される繰り返し単位Ａ１、又は、下記式（Ａ２）で表される繰り返し単位Ａ２を有する重合体ブロックＡと、
下記式（Ｂ１）で表される繰り返し単位を有する重合体ブロックＢとを含み、
上記重合体ブロックＡ及び上記重合体ブロックＢのうち少なくとも一方が、下記式（Ｃ１）で表される繰り返し単位Ｃ１を有する、ブロック共重合体（以下、「本発明の重合体」とも言う）である。 [Block copolymer]
The block copolymer of the present invention is
A polymer block A having a repeating unit A1 represented by the following formula (A1) or a repeating unit A2 represented by the following formula (A2),
A polymer block B having a repeating unit represented by the following formula (B1),
At least one of the polymer block A and the polymer block B is a block copolymer (hereinafter, also referred to as “polymer of the present invention”) having a repeating unit C1 represented by the following formula (C1). is there.
式（Ａ１）、（Ａ２）、（Ｂ１）及び（Ｃ１）中、Ｒは、水素原子又はメチル基を表す。
式（Ａ１）中、ＲＡ１は、水素原子又は炭化水素基を表す。２つのＲＡ１は同一であっても異なってもよい。
式（Ａ２）中、ＲＡ２は、水素原子又は炭化水素基を表す。ｐは、１以上の整数を表す。
式（Ｂ１）中、ＲＢ１は、炭化水素基を表す。
式（Ｃ１）中、Ｌは、単結合又は２価の連結基を表す。ＲＣ１１及びＲＣ１２は、それぞれ独立に、炭化水素基を表す。ｍは１～３の整数を表す。ｎは、０～２の整数を表す。ただし、ｍ＋ｎ＝３である。ｍが２以上の整数である場合に複数存在するＲＣ１１は同一であっても異なってもよい。ｎが２である場合の２つのＲＣ１２は同一であっても異なってもよい。 In formulas (A1), (A2), (B1) and (C1), R represents a hydrogen atom or a methyl group.
In formula (A1), R A1 represents a hydrogen atom or a hydrocarbon group. The two R A1 may be the same or different.
In formula (A2), R A2 represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 or more.
In formula (B1), R B1 represents a hydrocarbon group.
In formula (C1), L represents a single bond or a divalent linking group. R C11 and R C12 each independently represent a hydrocarbon group. m represents an integer of 1 to 3. n represents an integer of 0 to 2. However, m+n=3. When m is an integer of 2 or more, a plurality of R C11 existing may be the same or different. When n is 2, the two R C12 may be the same or different.
式（Ａ１）中、ＲＡ１は、水素原子又は炭化水素基を表す。２つのＲＡ１は同一であっても異なってもよい。
式（Ａ２）中、ＲＡ２は、水素原子又は炭化水素基を表す。ｐは、１以上の整数を表す。
式（Ｂ１）中、ＲＢ１は、炭化水素基を表す。
式（Ｃ１）中、Ｌは、単結合又は２価の連結基を表す。ＲＣ１１及びＲＣ１２は、それぞれ独立に、炭化水素基を表す。ｍは１～３の整数を表す。ｎは、０～２の整数を表す。ただし、ｍ＋ｎ＝３である。ｍが２以上の整数である場合に複数存在するＲＣ１１は同一であっても異なってもよい。ｎが２である場合の２つのＲＣ１２は同一であっても異なってもよい。 In formulas (A1), (A2), (B1) and (C1), R represents a hydrogen atom or a methyl group.
In formula (A1), R A1 represents a hydrogen atom or a hydrocarbon group. The two R A1 may be the same or different.
In formula (A2), R A2 represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 or more.
In formula (B1), R B1 represents a hydrocarbon group.
In formula (C1), L represents a single bond or a divalent linking group. R C11 and R C12 each independently represent a hydrocarbon group. m represents an integer of 1 to 3. n represents an integer of 0 to 2. However, m+n=3. When m is an integer of 2 or more, a plurality of R C11 existing may be the same or different. When n is 2, the two R C12 may be the same or different.
本発明の重合体はこのような構成をとるため、上述した効果が得られるものと考えらえる。その理由は明らかではないが、繰り返し単位Ｃ１が有するアルコキシシリル基の反応性が高いためと推測される。
Since the polymer of the present invention has such a constitution, it can be considered that the above-mentioned effects can be obtained. Although the reason is not clear, it is presumed that the alkoxysilyl group contained in the repeating unit C1 has high reactivity.
本発明の重合体は、１つの重合体ブロックＡと１つの重合体ブロックＢとのジブロック共重合体でもいいし、各重合体ブロックの少なくとも一方が複数存在するマルチブロック共重合体であってもよい。また、本発明の重合体は、重合体ブロックＡ及び重合体ブロックＢのいずれにも該当しない重合体ブロックを有していてもよい。
本発明の重合体は、速硬化性により優れ、また、硬化皮膜にしたときに、防曇性、密着性、耐久性、耐水性、耐温水性及び外観により優れる理由から、１つの重合体ブロックＡと１つの重合体ブロックＢとのジブロック共重合体であることが好ましい。以下、本発明の重合体について「速硬化性により優れ、また、硬化皮膜にしたときに、防曇性、密着性、耐久性、耐水性、耐温水性及び外観により優れる」ことを「本発明の効果等がより優れる」とも言う。
本発明の重合体の形状としては、直鎖状、グラフト状及び星型等が挙げられ、なかでも、本発明の効果等がより優れる理由から、直鎖状であることが好ましい。 The polymer of the present invention may be a diblock copolymer of one polymer block A and one polymer block B, or a multiblock copolymer in which at least one of each polymer block is present in plural. Good. Further, the polymer of the present invention may have a polymer block that does not correspond to either the polymer block A or the polymer block B.
The polymer of the present invention is excellent in quick-curing property, and when formed into a cured film, it is excellent in antifogging property, adhesion property, durability, water resistance, warm water resistance and appearance. It is preferably a diblock copolymer of A and one polymer block B. Hereinafter, regarding the polymer of the present invention, "excellent in quick-curing property, and when formed into a cured film, it is excellent in antifogging property, adhesiveness, durability, water resistance, warm water resistance and appearance" Is more effective.”
Examples of the shape of the polymer of the present invention include a linear shape, a graft shape, and a star shape. Among them, the linear shape is preferable because the effects of the present invention are more excellent.
本発明の重合体は、速硬化性により優れ、また、硬化皮膜にしたときに、防曇性、密着性、耐久性、耐水性、耐温水性及び外観により優れる理由から、１つの重合体ブロックＡと１つの重合体ブロックＢとのジブロック共重合体であることが好ましい。以下、本発明の重合体について「速硬化性により優れ、また、硬化皮膜にしたときに、防曇性、密着性、耐久性、耐水性、耐温水性及び外観により優れる」ことを「本発明の効果等がより優れる」とも言う。
本発明の重合体の形状としては、直鎖状、グラフト状及び星型等が挙げられ、なかでも、本発明の効果等がより優れる理由から、直鎖状であることが好ましい。 The polymer of the present invention may be a diblock copolymer of one polymer block A and one polymer block B, or a multiblock copolymer in which at least one of each polymer block is present in plural. Good. Further, the polymer of the present invention may have a polymer block that does not correspond to either the polymer block A or the polymer block B.
The polymer of the present invention is excellent in quick-curing property, and when formed into a cured film, it is excellent in antifogging property, adhesion property, durability, water resistance, warm water resistance and appearance. It is preferably a diblock copolymer of A and one polymer block B. Hereinafter, regarding the polymer of the present invention, "excellent in quick-curing property, and when formed into a cured film, it is excellent in antifogging property, adhesiveness, durability, water resistance, warm water resistance and appearance" Is more effective.”
Examples of the shape of the polymer of the present invention include a linear shape, a graft shape, and a star shape. Among them, the linear shape is preferable because the effects of the present invention are more excellent.
なお、通常、重合体ブロックＡは相対的に重合体ブロックＢよりも親水性であり、重合体ブロックＢは相対的に重合体ブロックＡよりも疎水性である。
Incidentally, the polymer block A is generally more hydrophilic than the polymer block B, and the polymer block B is relatively more hydrophobic than the polymer block A.
以下各重合体ブロックについて詳述する。
Details of each polymer block are given below.
〔重合体ブロックＡ〕
上述のとおり、重合体ブロックＡは、上記式（Ａ１）で表される繰り返し単位Ａ１、又は、上記式（Ａ２）で表される繰り返し単位Ａ２を有する。
重合体ブロックＡは、繰り返し単位Ａ１及び繰り返し単位Ａ２以外の繰り返し単位を有していてもよい。そのような繰り返し単位としては特に制限されない。
上述のとおり、重合体ブロックＡ及び重合体ブロックＢのうち少なくとも一方は、上記式（Ｃ１）で表される繰り返し単位Ｃ１を有する。 [Polymer block A]
As described above, the polymer block A has the repeating unit A1 represented by the above formula (A1) or the repeating unit A2 represented by the above formula (A2).
The polymer block A may have a repeating unit other than the repeating unit A1 and the repeating unit A2. The repeating unit is not particularly limited.
As described above, at least one of the polymer block A and the polymer block B has the repeating unit C1 represented by the above formula (C1).
上述のとおり、重合体ブロックＡは、上記式（Ａ１）で表される繰り返し単位Ａ１、又は、上記式（Ａ２）で表される繰り返し単位Ａ２を有する。
重合体ブロックＡは、繰り返し単位Ａ１及び繰り返し単位Ａ２以外の繰り返し単位を有していてもよい。そのような繰り返し単位としては特に制限されない。
上述のとおり、重合体ブロックＡ及び重合体ブロックＢのうち少なくとも一方は、上記式（Ｃ１）で表される繰り返し単位Ｃ１を有する。 [Polymer block A]
As described above, the polymer block A has the repeating unit A1 represented by the above formula (A1) or the repeating unit A2 represented by the above formula (A2).
The polymer block A may have a repeating unit other than the repeating unit A1 and the repeating unit A2. The repeating unit is not particularly limited.
As described above, at least one of the polymer block A and the polymer block B has the repeating unit C1 represented by the above formula (C1).
＜繰り返し単位Ａ１及びＡ２＞
<Repeating units A1 and A2>
重合体ブロックＡは、下記式（Ａ１）で表される繰り返し単位Ａ１、又は、下記式（Ａ２）で表される繰り返し単位Ａ２を有する。
The polymer block A has a repeating unit A1 represented by the following formula (A1) or a repeating unit A2 represented by the following formula (A2).
式（Ａ１）中、Ｒは、水素原子又はメチル基を表す。ＲＡ１は、水素原子又は炭化水素基を表す。２つのＲＡ１は同一であっても異なってもよい。
In formula (A1), R represents a hydrogen atom or a methyl group. R A1 represents a hydrogen atom or a hydrocarbon group. The two R A1 may be the same or different.
上述のとおり、式（Ａ１）中、ＲＡ１は、水素原子又は炭化水素基を表す。
上記炭化水素基としては、例えば、脂肪族炭化水素基、芳香族炭化水素基、またはこれらを組み合わせた基などが挙げられる。
上記脂肪族炭化水素基は、直鎖状、分岐鎖状、環状のいずれであってもよい。上記脂肪族炭化水素基の具体例としては、直鎖状または分岐状のアルキル基（特に、炭素数１～３０）、直鎖状または分岐状のアルケニル基（特に、炭素数２～３０）、直鎖状または分岐状のアルキニル基（特に、炭素数２～３０）などが挙げられる。
上記芳香族炭化水素基としては、例えば、フェニル基、トリル基、キシリル基、ナフチル基などの炭素数６～１８の芳香族炭化水素基などが挙げられる。
上記ＲＡ１は、本発明の効果等がより優れる理由から、炭化水素基であることが好ましく、脂肪族炭化水素基であることがより好ましく、直鎖状のアルキル基であることがさらに好ましく、炭素数１～５の直鎖状のアルキル基であることが特に好ましい。 As described above, in the formula (A1), R A1 represents a hydrogen atom or a hydrocarbon group.
Examples of the above-mentioned hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group combining these.
The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (especially 1 to 30 carbon atoms), a linear or branched alkenyl group (especially 2 to 30 carbon atoms), Examples thereof include a linear or branched alkynyl group (in particular, having 2 to 30 carbon atoms).
Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
R A1 is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group, and further preferably a linear alkyl group, for the reason that the effects of the present invention are more excellent. A linear alkyl group having 1 to 5 carbon atoms is particularly preferable.
上記炭化水素基としては、例えば、脂肪族炭化水素基、芳香族炭化水素基、またはこれらを組み合わせた基などが挙げられる。
上記脂肪族炭化水素基は、直鎖状、分岐鎖状、環状のいずれであってもよい。上記脂肪族炭化水素基の具体例としては、直鎖状または分岐状のアルキル基（特に、炭素数１～３０）、直鎖状または分岐状のアルケニル基（特に、炭素数２～３０）、直鎖状または分岐状のアルキニル基（特に、炭素数２～３０）などが挙げられる。
上記芳香族炭化水素基としては、例えば、フェニル基、トリル基、キシリル基、ナフチル基などの炭素数６～１８の芳香族炭化水素基などが挙げられる。
上記ＲＡ１は、本発明の効果等がより優れる理由から、炭化水素基であることが好ましく、脂肪族炭化水素基であることがより好ましく、直鎖状のアルキル基であることがさらに好ましく、炭素数１～５の直鎖状のアルキル基であることが特に好ましい。 As described above, in the formula (A1), R A1 represents a hydrogen atom or a hydrocarbon group.
Examples of the above-mentioned hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group combining these.
The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (especially 1 to 30 carbon atoms), a linear or branched alkenyl group (especially 2 to 30 carbon atoms), Examples thereof include a linear or branched alkynyl group (in particular, having 2 to 30 carbon atoms).
Examples of the aromatic hydrocarbon group include an aromatic hydrocarbon group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
R A1 is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group, and further preferably a linear alkyl group, for the reason that the effects of the present invention are more excellent. A linear alkyl group having 1 to 5 carbon atoms is particularly preferable.
式（Ａ２）中、Ｒは、水素原子又はメチル基を表す。ＲＡ２は、水素原子又は炭化水素基を表す。ｐは、１以上の整数を表す。
In formula (A2), R represents a hydrogen atom or a methyl group. R A2 represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 or more.
上述のとおり、式（Ａ２）中、ＲＡ２は、水素原子又は炭化水素基を表す。
上記ＲＡ２の具体例及び好適な態様は、式（Ａ１）中のＲＡ１と同じである。 As described above, in the formula (A2), R A2 represents a hydrogen atom or a hydrocarbon group.
Specific examples and preferred embodiments of the R A2 is the same as R A1 in the formula (A1).
上記ＲＡ２の具体例及び好適な態様は、式（Ａ１）中のＲＡ１と同じである。 As described above, in the formula (A2), R A2 represents a hydrogen atom or a hydrocarbon group.
Specific examples and preferred embodiments of the R A2 is the same as R A1 in the formula (A1).
上述のとおり、式（Ａ２）中、ｐは、１以上の整数を表す。
上記ｐの上限は特に制限されないが、本発明の効果等がより優れる理由から、１０以下であることが好ましい。 As described above, in the formula (A2), p represents an integer of 1 or more.
The upper limit of p is not particularly limited, but is preferably 10 or less because the effects of the present invention are more excellent.
上記ｐの上限は特に制限されないが、本発明の効果等がより優れる理由から、１０以下であることが好ましい。 As described above, in the formula (A2), p represents an integer of 1 or more.
The upper limit of p is not particularly limited, but is preferably 10 or less because the effects of the present invention are more excellent.
重合体ブロックＡ中の繰り返し単位Ａ１及び繰り返し単位Ａ２の合計の含有量は、本発明の効果等がより優れる理由から、５０モル％以上であることが好ましく、７０モル％以上であることがより好ましく、９０モル％以上であることがさらに好ましい。重合体ブロックＡ中の繰り返し単位Ａ１及び繰り返し単位Ａ２の合計の含有量の上限は特に制限されず、１００モル％である。
なお、「重合体ブロックＡ中の繰り返し単位Ａ１及び繰り返し単位Ａ２の合計の含有量」（モル％）とは、重合体ブロックＡの全繰り返し単位（モル数）に対する繰り返し単位Ａ１及び繰り返し単位Ａ２の合計（モル数）の割合（モル％）を意味する。 The total content of the repeating unit A1 and the repeating unit A2 in the polymer block A is preferably 50 mol% or more, and more preferably 70 mol% or more from the reason that the effects of the present invention are more excellent. It is preferably 90 mol% or more, and more preferably 90 mol% or more. The upper limit of the total content of the repeating unit A1 and the repeating unit A2 in the polymer block A is not particularly limited and is 100 mol%.
The “total content of the repeating unit A1 and the repeating unit A2 in the polymer block A” (mol %) means the repeating unit A1 and the repeating unit A2 with respect to all the repeating units (the number of moles) of the polymer block A. It means the ratio (mol %) of the total (number of moles).
なお、「重合体ブロックＡ中の繰り返し単位Ａ１及び繰り返し単位Ａ２の合計の含有量」（モル％）とは、重合体ブロックＡの全繰り返し単位（モル数）に対する繰り返し単位Ａ１及び繰り返し単位Ａ２の合計（モル数）の割合（モル％）を意味する。 The total content of the repeating unit A1 and the repeating unit A2 in the polymer block A is preferably 50 mol% or more, and more preferably 70 mol% or more from the reason that the effects of the present invention are more excellent. It is preferably 90 mol% or more, and more preferably 90 mol% or more. The upper limit of the total content of the repeating unit A1 and the repeating unit A2 in the polymer block A is not particularly limited and is 100 mol%.
The “total content of the repeating unit A1 and the repeating unit A2 in the polymer block A” (mol %) means the repeating unit A1 and the repeating unit A2 with respect to all the repeating units (the number of moles) of the polymer block A. It means the ratio (mol %) of the total (number of moles).
＜含有量＞
本発明の重合体において、重合体ブロックＡの含有量は、本発明の効果等がより優れる理由から、２０～９５モル％であることが好ましく、３０～９０モル％であることがより好ましく、４０～８０モル％であることがさらに好ましい。
なお、「重合体ブロックＡの含有量」（モル％）とは、ブロック共重合体の全繰り返し単位（モル数）に対する重合体ブロックＡの全繰り返し単位（モル数）の割合（モル％）を意味する。 <Content>
In the polymer of the present invention, the content of the polymer block A is preferably 20 to 95 mol %, more preferably 30 to 90 mol %, for the reason that the effects of the present invention are more excellent. It is more preferably 40 to 80 mol %.
The “content of the polymer block A” (mol %) means the ratio (mol %) of all the repeating units (mol number) of the polymer block A to all the repeating units (mol number) of the block copolymer. means.
本発明の重合体において、重合体ブロックＡの含有量は、本発明の効果等がより優れる理由から、２０～９５モル％であることが好ましく、３０～９０モル％であることがより好ましく、４０～８０モル％であることがさらに好ましい。
なお、「重合体ブロックＡの含有量」（モル％）とは、ブロック共重合体の全繰り返し単位（モル数）に対する重合体ブロックＡの全繰り返し単位（モル数）の割合（モル％）を意味する。 <Content>
In the polymer of the present invention, the content of the polymer block A is preferably 20 to 95 mol %, more preferably 30 to 90 mol %, for the reason that the effects of the present invention are more excellent. It is more preferably 40 to 80 mol %.
The “content of the polymer block A” (mol %) means the ratio (mol %) of all the repeating units (mol number) of the polymer block A to all the repeating units (mol number) of the block copolymer. means.
本発明の重合体において、重合体ブロックＡの含有量は、本発明の効果等がより優れる理由から、２０～９５質量％であることが好ましく、３０～９０質量％であることがより好ましく、４０～８０質量％であることがさらに好ましい。
In the polymer of the present invention, the content of the polymer block A is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, for the reason that the effects of the present invention are more excellent. It is more preferably 40 to 80% by mass.
〔重合体ブロックＢ〕
上述のとおり、重合体ブロックＢは、上記式（Ｂ１）で表される繰り返し単位Ｂ１を有する。
重合体ブロックＢは、繰り返し単位Ｂ１以外の繰り返し単位を有していてもよい。そのような繰り返し単位としては特に制限されない。
上述のとおり、重合体ブロックＡ及び重合体ブロックＢのうち少なくとも一方は、上記式（Ｃ１）で表される繰り返し単位Ｃ１を有する。 [Polymer block B]
As described above, the polymer block B has the repeating unit B1 represented by the above formula (B1).
The polymer block B may have a repeating unit other than the repeating unit B1. The repeating unit is not particularly limited.
As described above, at least one of the polymer block A and the polymer block B has the repeating unit C1 represented by the above formula (C1).
上述のとおり、重合体ブロックＢは、上記式（Ｂ１）で表される繰り返し単位Ｂ１を有する。
重合体ブロックＢは、繰り返し単位Ｂ１以外の繰り返し単位を有していてもよい。そのような繰り返し単位としては特に制限されない。
上述のとおり、重合体ブロックＡ及び重合体ブロックＢのうち少なくとも一方は、上記式（Ｃ１）で表される繰り返し単位Ｃ１を有する。 [Polymer block B]
As described above, the polymer block B has the repeating unit B1 represented by the above formula (B1).
The polymer block B may have a repeating unit other than the repeating unit B1. The repeating unit is not particularly limited.
As described above, at least one of the polymer block A and the polymer block B has the repeating unit C1 represented by the above formula (C1).
＜繰り返し単位Ｂ１＞
重合体ブロックＢは、下記式（Ｂ１）で表される繰り返し単位Ｂ１を有する。 <Repeating unit B1>
The polymer block B has a repeating unit B1 represented by the following formula (B1).
重合体ブロックＢは、下記式（Ｂ１）で表される繰り返し単位Ｂ１を有する。 <Repeating unit B1>
The polymer block B has a repeating unit B1 represented by the following formula (B1).
式（Ｂ１）中、Ｒは、水素原子又はメチル基を表す。
式（Ｂ１）中、ＲＢ１は、炭化水素基を表す。 In formula (B1), R represents a hydrogen atom or a methyl group.
In formula (B1), R B1 represents a hydrocarbon group.
式（Ｂ１）中、ＲＢ１は、炭化水素基を表す。 In formula (B1), R represents a hydrogen atom or a methyl group.
In formula (B1), R B1 represents a hydrocarbon group.
上述のとおり、式（Ｂ１）中、ＲＢ１は、炭化水素基を表す。
上記炭化水素基の具体例及び好適な態様は、式（Ａ１）中のＲＡ１と同じである。 As described above, in the formula (B1), R B1 represents a hydrocarbon group.
Specific examples and preferred embodiments of the above hydrocarbon group are the same as R A1 in formula (A1).
上記炭化水素基の具体例及び好適な態様は、式（Ａ１）中のＲＡ１と同じである。 As described above, in the formula (B1), R B1 represents a hydrocarbon group.
Specific examples and preferred embodiments of the above hydrocarbon group are the same as R A1 in formula (A1).
重合体ブロックＢ中の繰り返し単位Ｂ１の含有量は、本発明の効果等がより優れる理由から、５０モル％以上であることが好ましく、７０モル％以上であることがより好ましく、９０モル％以上であることがさらに好ましい。重合体ブロックＢ中の繰り返し単位Ｂ１の含有量の上限は特に制限されず、１００モル％である。
なお、「重合体ブロックＢ中の繰り返し単位Ｂ１の含有量」（モル％）とは、重合体ブロックＢの全繰り返し単位（モル数）に対する繰り返し単位Ｂ１（モル数）の割合（モル％）を意味する。 The content of the repeating unit B1 in the polymer block B is preferably 50 mol% or more, more preferably 70 mol% or more, and 90 mol% or more for the reason that the effects of the present invention are more excellent. Is more preferable. The upper limit of the content of the repeating unit B1 in the polymer block B is not particularly limited and is 100 mol%.
The “content of the repeating unit B1 in the polymer block B” (mol %) means the ratio (mol%) of the repeating unit B1 (mol number) to all the repeating units (mol number) of the polymer block B. means.
なお、「重合体ブロックＢ中の繰り返し単位Ｂ１の含有量」（モル％）とは、重合体ブロックＢの全繰り返し単位（モル数）に対する繰り返し単位Ｂ１（モル数）の割合（モル％）を意味する。 The content of the repeating unit B1 in the polymer block B is preferably 50 mol% or more, more preferably 70 mol% or more, and 90 mol% or more for the reason that the effects of the present invention are more excellent. Is more preferable. The upper limit of the content of the repeating unit B1 in the polymer block B is not particularly limited and is 100 mol%.
The “content of the repeating unit B1 in the polymer block B” (mol %) means the ratio (mol%) of the repeating unit B1 (mol number) to all the repeating units (mol number) of the polymer block B. means.
＜含有量＞
本発明の重合体において、重合体ブロックＢの含有量は、本発明の効果等がより優れる理由から、５～８０モル％であることが好ましく、１０～７０モル％であることがより好ましく、２０～６０モル％であることがさらに好ましい。
なお、「重合体ブロックＢの含有量」（モル％）とは、ブロック共重合体の全繰り返し単位（モル数）に対する重合体ブロックＢの全繰り返し単位（モル数）の割合（モル％）を意味する。 <Content>
In the polymer of the present invention, the content of the polymer block B is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, for the reason that the effects of the present invention are more excellent. It is more preferably 20 to 60 mol %.
The “content of the polymer block B” (mol %) means the ratio (mol %) of all the repeating units (mol number) of the polymer block B to all the repeating units (mol number) of the block copolymer. means.
本発明の重合体において、重合体ブロックＢの含有量は、本発明の効果等がより優れる理由から、５～８０モル％であることが好ましく、１０～７０モル％であることがより好ましく、２０～６０モル％であることがさらに好ましい。
なお、「重合体ブロックＢの含有量」（モル％）とは、ブロック共重合体の全繰り返し単位（モル数）に対する重合体ブロックＢの全繰り返し単位（モル数）の割合（モル％）を意味する。 <Content>
In the polymer of the present invention, the content of the polymer block B is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, for the reason that the effects of the present invention are more excellent. It is more preferably 20 to 60 mol %.
The “content of the polymer block B” (mol %) means the ratio (mol %) of all the repeating units (mol number) of the polymer block B to all the repeating units (mol number) of the block copolymer. means.
本発明の重合体において、重合体ブロックＢの含有量は、本発明の効果等がより優れる理由から、５～８０質量％であることが好ましく、１０～７０質量％であることがより好ましく、２０～６０質量％であることがさらに好ましい。
In the polymer of the present invention, the content of the polymer block B is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, for the reason that the effects of the present invention are more excellent. It is more preferably 20 to 60% by mass.
〔重合体ブロックＡ／重合体ブロックＢ〕
本発明の重合体において、重合体ブロックＢの含有量に対する重合体ブロックＡの含有量の割合（重合体ブロックＡ／重合体ブロックＢ）は、本発明の効果等がより優れる理由から、モル比で、０．２５～１９であることが好ましく、０．４２～９．０であることがより好ましく、０．６７～４．０であることがさらに好ましい。 [Polymer Block A/Polymer Block B]
In the polymer of the present invention, the ratio of the content of the polymer block A to the content of the polymer block B (polymer block A/polymer block B) is a molar ratio because the effects of the present invention are more excellent. And is preferably 0.25 to 19, more preferably 0.42 to 9.0, and further preferably 0.67 to 4.0.
本発明の重合体において、重合体ブロックＢの含有量に対する重合体ブロックＡの含有量の割合（重合体ブロックＡ／重合体ブロックＢ）は、本発明の効果等がより優れる理由から、モル比で、０．２５～１９であることが好ましく、０．４２～９．０であることがより好ましく、０．６７～４．０であることがさらに好ましい。 [Polymer Block A/Polymer Block B]
In the polymer of the present invention, the ratio of the content of the polymer block A to the content of the polymer block B (polymer block A/polymer block B) is a molar ratio because the effects of the present invention are more excellent. And is preferably 0.25 to 19, more preferably 0.42 to 9.0, and further preferably 0.67 to 4.0.
〔重合体ブロックＡ＋重合体ブロックＢ〕
本発明の重合体において、重合体ブロックＡ及び重合体ブロックＢの合計の含有量は、本発明の効果等がより優れる理由から、５０モル％以上であることが好ましく、７０モル％以上であることがより好ましく、９０モル％以上であることがさらに好ましい。本発明の重合体において、重合体ブロックＡ及び重合体ブロックＢの合計の含有量の上限は特に制限されず、１００モル％である。
なお、「重合体ブロックＡ及び重合体ブロックＢの合計の含有量」（モル％）とは、ブロック共重合体の全繰り返し単位（モル数）に対する重合体ブロックＡの全繰り返し単位及び重合体ブロックＢの全繰り返し単位の合計（モル数）の割合（モル％）を意味する。 [Polymer block A+polymer block B]
In the polymer of the present invention, the total content of the polymer block A and the polymer block B is preferably 50 mol% or more, and 70 mol% or more for the reason that the effects of the present invention are more excellent. More preferably, it is more preferably 90 mol% or more. In the polymer of the present invention, the upper limit of the total content of the polymer block A and the polymer block B is not particularly limited and is 100 mol%.
The “total content of the polymer block A and the polymer block B” (mol %) means all the repeating units of the polymer block A and the polymer blocks with respect to all the repeating units (the number of moles) of the block copolymer. It means the ratio (mol %) of the total (mol number) of all repeating units of B.
本発明の重合体において、重合体ブロックＡ及び重合体ブロックＢの合計の含有量は、本発明の効果等がより優れる理由から、５０モル％以上であることが好ましく、７０モル％以上であることがより好ましく、９０モル％以上であることがさらに好ましい。本発明の重合体において、重合体ブロックＡ及び重合体ブロックＢの合計の含有量の上限は特に制限されず、１００モル％である。
なお、「重合体ブロックＡ及び重合体ブロックＢの合計の含有量」（モル％）とは、ブロック共重合体の全繰り返し単位（モル数）に対する重合体ブロックＡの全繰り返し単位及び重合体ブロックＢの全繰り返し単位の合計（モル数）の割合（モル％）を意味する。 [Polymer block A+polymer block B]
In the polymer of the present invention, the total content of the polymer block A and the polymer block B is preferably 50 mol% or more, and 70 mol% or more for the reason that the effects of the present invention are more excellent. More preferably, it is more preferably 90 mol% or more. In the polymer of the present invention, the upper limit of the total content of the polymer block A and the polymer block B is not particularly limited and is 100 mol%.
The “total content of the polymer block A and the polymer block B” (mol %) means all the repeating units of the polymer block A and the polymer blocks with respect to all the repeating units (the number of moles) of the block copolymer. It means the ratio (mol %) of the total (mol number) of all repeating units of B.
また、本発明の重合体において、重合体ブロックＡ及び重合体ブロックＢの合計の含有量は、本発明の効果等がより優れる理由から、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。本発明の重合体において、重合体ブロックＡ及び重合体ブロックＢの合計の含有量の上限は特に制限されず、１００質量％である。
In the polymer of the present invention, the total content of the polymer block A and the polymer block B is preferably 50% by mass or more, and 70% by mass or more, for the reason that the effects of the present invention are more excellent. Is more preferable, and 90% by mass or more is further preferable. In the polymer of the present invention, the upper limit of the total content of the polymer block A and the polymer block B is not particularly limited and is 100% by mass.
〔繰り返し単位Ｃ１〕
上述のとおり、重合体ブロックＡ及び重合体ブロックＢのうち少なくとも一方は、下記式（Ｃ１）で表される繰り返し単位Ｃ１を有する。
なお、本発明の効果等がより優れる理由から、少なくとも重合体ブロックＢが繰り返し単位Ｃ１を有するのが好ましく、重合体ブロックＡ及び重合体ブロックＢの両方が繰り返し単位Ｃ１を有するのがより好ましい。 [Repeating unit C1]
As described above, at least one of the polymer block A and the polymer block B has the repeating unit C1 represented by the following formula (C1).
From the reason that the effects of the present invention are more excellent, it is preferable that at least the polymer block B has the repeating unit C1, and it is more preferable that both the polymer block A and the polymer block B have the repeating unit C1.
上述のとおり、重合体ブロックＡ及び重合体ブロックＢのうち少なくとも一方は、下記式（Ｃ１）で表される繰り返し単位Ｃ１を有する。
なお、本発明の効果等がより優れる理由から、少なくとも重合体ブロックＢが繰り返し単位Ｃ１を有するのが好ましく、重合体ブロックＡ及び重合体ブロックＢの両方が繰り返し単位Ｃ１を有するのがより好ましい。 [Repeating unit C1]
As described above, at least one of the polymer block A and the polymer block B has the repeating unit C1 represented by the following formula (C1).
From the reason that the effects of the present invention are more excellent, it is preferable that at least the polymer block B has the repeating unit C1, and it is more preferable that both the polymer block A and the polymer block B have the repeating unit C1.
式（Ｃ１）中、Ｌは、単結合又は２価の連結基を表す。ＲＣ１１及びＲＣ１２は、それぞれ独立に、炭化水素基を表す。ｍは１～３の整数を表す。ｎは、０～２の整数を表す。ただし、ｍ＋ｎ＝３である。ｍが２以上の整数である場合に複数存在するＲＣ１１は同一であっても異なってもよい。ｎが２である場合の２つのＲＣ１２は同一であっても異なってもよい。
In formula (C1), L represents a single bond or a divalent linking group. R C11 and R C12 each independently represent a hydrocarbon group. m represents an integer of 1 to 3. n represents an integer of 0 to 2. However, m+n=3. When m is an integer of 2 or more, a plurality of R C11 existing may be the same or different. When n is 2, the two R C12 may be the same or different.
上述のとおり、式（Ｃ１）中、Ｌは、単結合又は２価の連結基を表す。
上記２価の連結基としては、例えば、直鎖状、分岐状若しくは環状の２価の脂肪族炭化水素基（例えば、メチレン基、エチレン基、プロピレン基などのアルキレン基）、２価の芳香族炭化水素基（例えば、フェニレン基）、－Ｏ－、－Ｓ－、－ＳＯ２－、－ＮＲＬ－、－ＣＯ－、－ＮＨ－、－ＣＯＯ－、－ＣＯＮＲＬ－、－Ｏ－ＣＯ－Ｏ－、－ＳＯ３－、－ＮＨＣＯＯ－、－ＳＯ２ＮＲＬ－、－ＮＨ－ＣＯ－ＮＨ－またはこれらを２種以上組み合わせた基（例えば、アルキレンオキシ基、アルキレンオキシカルボニル基、アルキレンカルボニルオキシ基など）などが挙げられる。ここで、ＲＬは、水素原子またはアルキル基（好ましくは炭素数１～１０）を表す。
上記Ｌは、本発明の効果等がより優れる理由から、アルキレンオキシカルボニル基であることが好ましい。 As described above, in the formula (C1), L represents a single bond or a divalent linking group.
Examples of the divalent linking group include linear, branched or cyclic divalent aliphatic hydrocarbon groups (eg, alkylene groups such as methylene group, ethylene group, propylene group) and divalent aromatic groups. Hydrocarbon group (eg phenylene group), —O—, —S—, —SO 2 —, —NR L —, —CO—, —NH—, —COO—, —CONR L —, —O—CO— O—, —SO 3 —, —NHCOO—, —SO 2 NR L —, —NH—CO—NH— or a group combining two or more thereof (eg, alkyleneoxy group, alkyleneoxycarbonyl group, alkylenecarbonyloxy) Group) and the like. Here, R L represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
The above L is preferably an alkyleneoxycarbonyl group for the reason that the effects of the present invention are more excellent.
上記２価の連結基としては、例えば、直鎖状、分岐状若しくは環状の２価の脂肪族炭化水素基（例えば、メチレン基、エチレン基、プロピレン基などのアルキレン基）、２価の芳香族炭化水素基（例えば、フェニレン基）、－Ｏ－、－Ｓ－、－ＳＯ２－、－ＮＲＬ－、－ＣＯ－、－ＮＨ－、－ＣＯＯ－、－ＣＯＮＲＬ－、－Ｏ－ＣＯ－Ｏ－、－ＳＯ３－、－ＮＨＣＯＯ－、－ＳＯ２ＮＲＬ－、－ＮＨ－ＣＯ－ＮＨ－またはこれらを２種以上組み合わせた基（例えば、アルキレンオキシ基、アルキレンオキシカルボニル基、アルキレンカルボニルオキシ基など）などが挙げられる。ここで、ＲＬは、水素原子またはアルキル基（好ましくは炭素数１～１０）を表す。
上記Ｌは、本発明の効果等がより優れる理由から、アルキレンオキシカルボニル基であることが好ましい。 As described above, in the formula (C1), L represents a single bond or a divalent linking group.
Examples of the divalent linking group include linear, branched or cyclic divalent aliphatic hydrocarbon groups (eg, alkylene groups such as methylene group, ethylene group, propylene group) and divalent aromatic groups. Hydrocarbon group (eg phenylene group), —O—, —S—, —SO 2 —, —NR L —, —CO—, —NH—, —COO—, —CONR L —, —O—CO— O—, —SO 3 —, —NHCOO—, —SO 2 NR L —, —NH—CO—NH— or a group combining two or more thereof (eg, alkyleneoxy group, alkyleneoxycarbonyl group, alkylenecarbonyloxy) Group) and the like. Here, R L represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
The above L is preferably an alkyleneoxycarbonyl group for the reason that the effects of the present invention are more excellent.
上述のとおり、式（Ｃ１）中、ＲＣ１１及びＲＣ１２は、それぞれ独立に、炭化水素基を表す。
上記炭化水素基の具体例及び好適な態様は、式（Ａ１）中のＲＡ１と同じである。 As described above, in the formula (C1), R C11 and R C12 each independently represent a hydrocarbon group.
Specific examples and preferred embodiments of the above hydrocarbon group are the same as R A1 in formula (A1).
上記炭化水素基の具体例及び好適な態様は、式（Ａ１）中のＲＡ１と同じである。 As described above, in the formula (C1), R C11 and R C12 each independently represent a hydrocarbon group.
Specific examples and preferred embodiments of the above hydrocarbon group are the same as R A1 in formula (A1).
上述のとおり、式（Ｃ１）中、ｍは１～３の整数を表す。ｎは、０～２の整数を表す。ただし、ｍ＋ｎ＝３である。
上記ｍ及びｎは、本発明の効果等がより優れる理由から、ｍ＝３であり、ｎ＝０であることが好ましい。 As described above, m represents an integer of 1 to 3 in the formula (C1). n represents an integer of 0 to 2. However, m+n=3.
It is preferable that m and n are m=3 and n=0, for the reason that the effects of the present invention are more excellent.
上記ｍ及びｎは、本発明の効果等がより優れる理由から、ｍ＝３であり、ｎ＝０であることが好ましい。 As described above, m represents an integer of 1 to 3 in the formula (C1). n represents an integer of 0 to 2. However, m+n=3.
It is preferable that m and n are m=3 and n=0, for the reason that the effects of the present invention are more excellent.
＜含有量＞
重合体ブロックＡ中の繰り返し単位Ｃ１の含有量は、本発明の効果等がより優れる理由から、０．１～２０モル％であることが好ましく、０．２～１０モル％であることがより好ましく、０．５～５モル％であることがさらに好ましい。
重合体ブロックＢ中の繰り返し単位Ｃ１の含有量は、本発明の効果等がより優れる理由から、０．１～２０モル％であることが好ましく、０．２～１０モル％であることがより好ましく、０．５～５モル％であることがさらに好ましい。
なお、「重合体ブロックＡ中の繰り返し単位Ｃ１の含有量」（モル％）とは、重合体ブロックＡの全繰り返し単位（モル数）に対する繰り返し単位Ｃ１（モル数）の割合（モル％）を意味し、「重合体ブロックＢ中の繰り返し単位Ｃ１の含有量」とは、重合体ブロックＢの全繰り返し単位（モル数）に対する繰り返し単位Ｃ１（モル数）の割合（モル％）を意味する。 <Content>
The content of the repeating unit C1 in the polymer block A is preferably 0.1 to 20 mol% and more preferably 0.2 to 10 mol% for the reason that the effects of the present invention are more excellent. It is preferably 0.5 to 5 mol% and more preferably 0.5 to 5 mol %.
The content of the repeating unit C1 in the polymer block B is preferably 0.1 to 20 mol% and more preferably 0.2 to 10 mol% for the reason that the effects of the present invention are more excellent. It is preferably 0.5 to 5 mol% and more preferably 0.5 to 5 mol %.
The "content of the repeating unit C1 in the polymer block A" (mol %) means the ratio (mol%) of the repeating unit C1 (mol number) to all the repeating units (mol number) of the polymer block A. The "content of the repeating unit C1 in the polymer block B" means the ratio (mol%) of the repeating unit C1 (the number of moles) to all the repeating units (the number of moles) of the polymer block B.
重合体ブロックＡ中の繰り返し単位Ｃ１の含有量は、本発明の効果等がより優れる理由から、０．１～２０モル％であることが好ましく、０．２～１０モル％であることがより好ましく、０．５～５モル％であることがさらに好ましい。
重合体ブロックＢ中の繰り返し単位Ｃ１の含有量は、本発明の効果等がより優れる理由から、０．１～２０モル％であることが好ましく、０．２～１０モル％であることがより好ましく、０．５～５モル％であることがさらに好ましい。
なお、「重合体ブロックＡ中の繰り返し単位Ｃ１の含有量」（モル％）とは、重合体ブロックＡの全繰り返し単位（モル数）に対する繰り返し単位Ｃ１（モル数）の割合（モル％）を意味し、「重合体ブロックＢ中の繰り返し単位Ｃ１の含有量」とは、重合体ブロックＢの全繰り返し単位（モル数）に対する繰り返し単位Ｃ１（モル数）の割合（モル％）を意味する。 <Content>
The content of the repeating unit C1 in the polymer block A is preferably 0.1 to 20 mol% and more preferably 0.2 to 10 mol% for the reason that the effects of the present invention are more excellent. It is preferably 0.5 to 5 mol% and more preferably 0.5 to 5 mol %.
The content of the repeating unit C1 in the polymer block B is preferably 0.1 to 20 mol% and more preferably 0.2 to 10 mol% for the reason that the effects of the present invention are more excellent. It is preferably 0.5 to 5 mol% and more preferably 0.5 to 5 mol %.
The "content of the repeating unit C1 in the polymer block A" (mol %) means the ratio (mol%) of the repeating unit C1 (mol number) to all the repeating units (mol number) of the polymer block A. The "content of the repeating unit C1 in the polymer block B" means the ratio (mol%) of the repeating unit C1 (the number of moles) to all the repeating units (the number of moles) of the polymer block B.
本発明の重合体において、繰り返し単位Ｃ１の含有量は、本発明の効果等がより優れる理由から、ブロック共重合体の全繰り返し単位に対して、０．１～２０モル％であることが好ましく、０．２～１０モル％であることがより好ましく、０．３～５モル％であることがさらに好ましい。
In the polymer of the present invention, the content of the repeating unit C1 is preferably 0.1 to 20 mol% with respect to all the repeating units of the block copolymer for the reason that the effects of the present invention are more excellent. , 0.2 to 10 mol% is more preferable, and 0.3 to 5 mol% is further preferable.
〔繰り返し単位Ｃ２〕
本発明の重合体は、本発明の効果等がより優れる理由から、重合体ブロックＡ及び重合体ブロックＢのうち少なくとも一方が、下記式（Ｃ２）で表される繰り返し単位Ｃ２を有するのが好ましい。
なお、本発明の効果等がより優れる理由から、少なくとも重合体ブロックＢが繰り返し単位Ｃ２を有するのが好ましく、重合体ブロックＡ及び重合体ブロックＢの両方が繰り返し単位Ｃ２を有するのがより好ましい。 [Repeating unit C2]
In the polymer of the present invention, at least one of the polymer block A and the polymer block B preferably has a repeating unit C2 represented by the following formula (C2) for the reason that the effects of the present invention are more excellent. ..
From the reason that the effects of the present invention are more excellent, it is preferable that at least the polymer block B has the repeating unit C2, and it is more preferable that both the polymer block A and the polymer block B have the repeating unit C2.
本発明の重合体は、本発明の効果等がより優れる理由から、重合体ブロックＡ及び重合体ブロックＢのうち少なくとも一方が、下記式（Ｃ２）で表される繰り返し単位Ｃ２を有するのが好ましい。
なお、本発明の効果等がより優れる理由から、少なくとも重合体ブロックＢが繰り返し単位Ｃ２を有するのが好ましく、重合体ブロックＡ及び重合体ブロックＢの両方が繰り返し単位Ｃ２を有するのがより好ましい。 [Repeating unit C2]
In the polymer of the present invention, at least one of the polymer block A and the polymer block B preferably has a repeating unit C2 represented by the following formula (C2) for the reason that the effects of the present invention are more excellent. ..
From the reason that the effects of the present invention are more excellent, it is preferable that at least the polymer block B has the repeating unit C2, and it is more preferable that both the polymer block A and the polymer block B have the repeating unit C2.
式（Ｃ２）中、Ｒは、水素原子又はメチル基を表す。ＲＣ２は、水素原子、又は、ヒドロキシ基を有する炭化水素基を表す。
In formula (C2), R represents a hydrogen atom or a methyl group. R C2 represents a hydrogen atom or a hydrocarbon group having a hydroxy group.
上述のとおり、式（Ｃ２）中、ＲＣ２は、水素原子、又は、ヒドロキシ基を有する炭化水素基を表す。
上記ヒドロキシ基を有する炭化水素基中の炭化水素基の具体例及び好適な態様は、式（Ａ１）中のＲＡ１と同じである。
上記ヒドロキシ基を有する炭化水素基としては、例えば、２－ヒドロキシエチル基が挙げられる。 As described above, in the formula (C2), R C2 represents a hydrogen atom or a hydrocarbon group having a hydroxy group.
Specific examples and preferred embodiments of the hydrocarbon group in the hydrocarbon group having a hydroxy group are the same as R A1 in formula (A1).
Examples of the hydrocarbon group having a hydroxy group include a 2-hydroxyethyl group.
上記ヒドロキシ基を有する炭化水素基中の炭化水素基の具体例及び好適な態様は、式（Ａ１）中のＲＡ１と同じである。
上記ヒドロキシ基を有する炭化水素基としては、例えば、２－ヒドロキシエチル基が挙げられる。 As described above, in the formula (C2), R C2 represents a hydrogen atom or a hydrocarbon group having a hydroxy group.
Specific examples and preferred embodiments of the hydrocarbon group in the hydrocarbon group having a hydroxy group are the same as R A1 in formula (A1).
Examples of the hydrocarbon group having a hydroxy group include a 2-hydroxyethyl group.
＜含有量＞
重合体ブロックＡ中の繰り返し単位Ｃ２の含有量は、本発明の効果等がより優れる理由から、０．１～２０モル％であることが好ましく、０．２～１０モル％であることがより好ましく、０．５～５モル％であることがさらに好ましい。
重合体ブロックＢ中の繰り返し単位Ｃ２の含有量は、本発明の効果等がより優れる理由から、０．１～２０モル％であることが好ましく、０．２～１０モル％であることがより好ましく、０．５～５モル％であることがさらに好ましい。
なお、「重合体ブロックＡ中の繰り返し単位Ｃ２の含有量」（モル％）とは、重合体ブロックＡの全繰り返し単位（モル数）に対する繰り返し単位Ｃ２（モル数）の割合（モル％）を意味し、「重合体ブロックＢ中の繰り返し単位Ｃ２の含有量」とは、重合体ブロックＢの全繰り返し単位（モル数）に対する繰り返し単位Ｃ２（モル数）の割合（モル％）を意味する。 <Content>
The content of the repeating unit C2 in the polymer block A is preferably 0.1 to 20 mol% and more preferably 0.2 to 10 mol% for the reason that the effects of the present invention are more excellent. It is preferably 0.5 to 5 mol% and more preferably 0.5 to 5 mol %.
The content of the repeating unit C2 in the polymer block B is preferably 0.1 to 20 mol% and more preferably 0.2 to 10 mol% for the reason that the effects of the present invention are more excellent. It is preferably 0.5 to 5 mol% and more preferably 0.5 to 5 mol %.
The “content of the repeating unit C2 in the polymer block A” (mol %) means the ratio (mol %) of the repeating unit C2 (mol number) to all the repeating units (mol number) of the polymer block A. The "content of the repeating unit C2 in the polymer block B" means the ratio (mol%) of the repeating unit C2 (the number of moles) to all the repeating units (the number of moles) of the polymer block B.
重合体ブロックＡ中の繰り返し単位Ｃ２の含有量は、本発明の効果等がより優れる理由から、０．１～２０モル％であることが好ましく、０．２～１０モル％であることがより好ましく、０．５～５モル％であることがさらに好ましい。
重合体ブロックＢ中の繰り返し単位Ｃ２の含有量は、本発明の効果等がより優れる理由から、０．１～２０モル％であることが好ましく、０．２～１０モル％であることがより好ましく、０．５～５モル％であることがさらに好ましい。
なお、「重合体ブロックＡ中の繰り返し単位Ｃ２の含有量」（モル％）とは、重合体ブロックＡの全繰り返し単位（モル数）に対する繰り返し単位Ｃ２（モル数）の割合（モル％）を意味し、「重合体ブロックＢ中の繰り返し単位Ｃ２の含有量」とは、重合体ブロックＢの全繰り返し単位（モル数）に対する繰り返し単位Ｃ２（モル数）の割合（モル％）を意味する。 <Content>
The content of the repeating unit C2 in the polymer block A is preferably 0.1 to 20 mol% and more preferably 0.2 to 10 mol% for the reason that the effects of the present invention are more excellent. It is preferably 0.5 to 5 mol% and more preferably 0.5 to 5 mol %.
The content of the repeating unit C2 in the polymer block B is preferably 0.1 to 20 mol% and more preferably 0.2 to 10 mol% for the reason that the effects of the present invention are more excellent. It is preferably 0.5 to 5 mol% and more preferably 0.5 to 5 mol %.
The “content of the repeating unit C2 in the polymer block A” (mol %) means the ratio (mol %) of the repeating unit C2 (mol number) to all the repeating units (mol number) of the polymer block A. The "content of the repeating unit C2 in the polymer block B" means the ratio (mol%) of the repeating unit C2 (the number of moles) to all the repeating units (the number of moles) of the polymer block B.
本発明の重合体において、繰り返し単位Ｃ２の含有量は、本発明の効果等がより優れる理由から、ブロック共重合体の全繰り返し単位に対して、０．１～２０モル％であることが好ましく、０．２～１０モル％であることがより好ましく、０．３～５モル％であることがさらに好ましい。
In the polymer of the present invention, the content of the repeating unit C2 is preferably 0.1 to 20 mol% based on all the repeating units of the block copolymer, for the reason that the effects of the present invention are more excellent. , 0.2 to 10 mol% is more preferable, and 0.3 to 5 mol% is further preferable.
〔繰り返し単位Ｃ１＋繰り返し単位Ｃ２〕
本発明の重合体において、繰り返し単位Ｃ１及び繰り返し単位Ｃ２の合計の含有量は、本発明の効果等がより優れる理由から、ブロック共重合体の全繰り返し単位に対して、０．１～２０モル％であることが好ましく、０．２～１０モル％であることがより好ましく、０．３～５モル％であることがさらに好ましい。 [Repeating unit C1+Repeating unit C2]
In the polymer of the present invention, the total content of the repeating unit C1 and the repeating unit C2 is 0.1 to 20 mols based on the total repeating units of the block copolymer for the reason that the effects of the present invention are more excellent. %, preferably 0.2 to 10 mol %, more preferably 0.3 to 5 mol %.
本発明の重合体において、繰り返し単位Ｃ１及び繰り返し単位Ｃ２の合計の含有量は、本発明の効果等がより優れる理由から、ブロック共重合体の全繰り返し単位に対して、０．１～２０モル％であることが好ましく、０．２～１０モル％であることがより好ましく、０．３～５モル％であることがさらに好ましい。 [Repeating unit C1+Repeating unit C2]
In the polymer of the present invention, the total content of the repeating unit C1 and the repeating unit C2 is 0.1 to 20 mols based on the total repeating units of the block copolymer for the reason that the effects of the present invention are more excellent. %, preferably 0.2 to 10 mol %, more preferably 0.3 to 5 mol %.
〔繰り返し単位Ｃ１／繰り返し単位Ｃ２〕
本発明の重合体において、繰り返し単位Ｃ２の含有量に対する繰り返し単位Ｃ１の含有量の割合（繰り返し単位Ｃ１／繰り返し単位Ｃ２）は、本発明の効果等がより優れる理由から、モル比で、０．１～１０であることが好ましく、０．２～５であることがより好ましく、０．３～３であることがさらに好ましい。 [Repeating unit C1/Repeating unit C2]
In the polymer of the present invention, the ratio of the content of the repeating unit C1 to the content of the repeating unit C2 (repeating unit C1/repeating unit C2) is a molar ratio of 0. It is preferably 1 to 10, more preferably 0.2 to 5, and further preferably 0.3 to 3.
本発明の重合体において、繰り返し単位Ｃ２の含有量に対する繰り返し単位Ｃ１の含有量の割合（繰り返し単位Ｃ１／繰り返し単位Ｃ２）は、本発明の効果等がより優れる理由から、モル比で、０．１～１０であることが好ましく、０．２～５であることがより好ましく、０．３～３であることがさらに好ましい。 [Repeating unit C1/Repeating unit C2]
In the polymer of the present invention, the ratio of the content of the repeating unit C1 to the content of the repeating unit C2 (repeating unit C1/repeating unit C2) is a molar ratio of 0. It is preferably 1 to 10, more preferably 0.2 to 5, and further preferably 0.3 to 3.
〔分子量〕
[Molecular weight]
＜数平均分子量＞
本発明の重合体の数平均分子量（Ｍｎ）は特に制限されないが、本発明の効果等がより優れる理由から、１，０００～１，０００，０００であることが好ましく、１０，０００～１００，０００であることがより好ましく、２０，０００～８０，０００であることがさらに好ましい。 <Number average molecular weight>
The number average molecular weight (Mn) of the polymer of the present invention is not particularly limited, but is preferably 1,000 to 1,000,000, and preferably 10,000 to 100, for the reason that the effects of the present invention are more excellent. It is more preferably 000, and even more preferably 20,000 to 80,000.
本発明の重合体の数平均分子量（Ｍｎ）は特に制限されないが、本発明の効果等がより優れる理由から、１，０００～１，０００，０００であることが好ましく、１０，０００～１００，０００であることがより好ましく、２０，０００～８０，０００であることがさらに好ましい。 <Number average molecular weight>
The number average molecular weight (Mn) of the polymer of the present invention is not particularly limited, but is preferably 1,000 to 1,000,000, and preferably 10,000 to 100, for the reason that the effects of the present invention are more excellent. It is more preferably 000, and even more preferably 20,000 to 80,000.
＜重量平均分子量＞
本発明の重合体の重量平均分子量（Ｍｗ）は特に制限されないが、本発明の効果等がより優れる理由から、１，０００～１，０００，０００であることが好ましく、１０，０００～１００，０００であることがより好ましく、２０，０００～８０，０００であることがさらに好ましい。 <Weight average molecular weight>
The weight average molecular weight (Mw) of the polymer of the present invention is not particularly limited, but is preferably 1,000 to 1,000,000, and preferably 10,000 to 100, for the reason that the effects of the present invention are more excellent. It is more preferably 000, and even more preferably 20,000 to 80,000.
本発明の重合体の重量平均分子量（Ｍｗ）は特に制限されないが、本発明の効果等がより優れる理由から、１，０００～１，０００，０００であることが好ましく、１０，０００～１００，０００であることがより好ましく、２０，０００～８０，０００であることがさらに好ましい。 <Weight average molecular weight>
The weight average molecular weight (Mw) of the polymer of the present invention is not particularly limited, but is preferably 1,000 to 1,000,000, and preferably 10,000 to 100, for the reason that the effects of the present invention are more excellent. It is more preferably 000, and even more preferably 20,000 to 80,000.
＜分子量分布＞
本発明の重合体の分子量分布（Ｍｗ／Ｍｎ）は特に制限されないが、本発明の効果等がより優れる理由から、１０以下であることが好ましく、５以下であることがより好ましい。分子量分布の下限は特に制限されないが、通常、１．０以上である。 <Molecular weight distribution>
The molecular weight distribution (Mw/Mn) of the polymer of the present invention is not particularly limited, but is preferably 10 or less, more preferably 5 or less for the reason that the effect of the present invention is more excellent. The lower limit of the molecular weight distribution is not particularly limited, but is usually 1.0 or more.
本発明の重合体の分子量分布（Ｍｗ／Ｍｎ）は特に制限されないが、本発明の効果等がより優れる理由から、１０以下であることが好ましく、５以下であることがより好ましい。分子量分布の下限は特に制限されないが、通常、１．０以上である。 <Molecular weight distribution>
The molecular weight distribution (Mw/Mn) of the polymer of the present invention is not particularly limited, but is preferably 10 or less, more preferably 5 or less for the reason that the effect of the present invention is more excellent. The lower limit of the molecular weight distribution is not particularly limited, but is usually 1.0 or more.
なお、上記Ｍｎ及びＭｗは、以下の条件のゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定により得られる標準ポリスチレン換算値とする。
・溶媒：テトラヒドロフラン
・検出器：ＲＩ検出器 The Mn and Mw are standard polystyrene conversion values obtained by gel permeation chromatography (GPC) measurement under the following conditions.
・Solvent: Tetrahydrofuran ・Detector: RI detector
・溶媒：テトラヒドロフラン
・検出器：ＲＩ検出器 The Mn and Mw are standard polystyrene conversion values obtained by gel permeation chromatography (GPC) measurement under the following conditions.
・Solvent: Tetrahydrofuran ・Detector: RI detector
〔製造方法〕
本発明の重合体を製造する方法は特に制限されず、従来公知の方法を用いることができる。なかでも、リビングラジカル重合法を用いた方法が好ましく、ＲＡＦＴ法（可逆的付加開裂連鎖移動重合法）を用いた方法（特に、トリチオカーボナート化合物を連鎖移動剤として用いた方法）がより好ましい。 〔Production method〕
The method for producing the polymer of the present invention is not particularly limited, and a conventionally known method can be used. Among them, the method using the living radical polymerization method is preferable, and the method using the RAFT method (reversible addition fragmentation chain transfer polymerization method) (particularly the method using a trithiocarbonate compound as a chain transfer agent) is more preferable. ..
本発明の重合体を製造する方法は特に制限されず、従来公知の方法を用いることができる。なかでも、リビングラジカル重合法を用いた方法が好ましく、ＲＡＦＴ法（可逆的付加開裂連鎖移動重合法）を用いた方法（特に、トリチオカーボナート化合物を連鎖移動剤として用いた方法）がより好ましい。 〔Production method〕
The method for producing the polymer of the present invention is not particularly limited, and a conventionally known method can be used. Among them, the method using the living radical polymerization method is preferable, and the method using the RAFT method (reversible addition fragmentation chain transfer polymerization method) (particularly the method using a trithiocarbonate compound as a chain transfer agent) is more preferable. ..
より具体的には、例えば、リビングラジカル重合法により、繰り返し単位Ｂ１となるモノマー（例えば、メタクリル酸メチル）と繰り返し単位Ｃ１となるモノマー（例えば、３－メタクリロキシプロピルトリメトキシシラン）と繰り返し単位Ｃ２となるモノマー（例えば、メタクリル酸２－ヒドロキシエチル）とを重合して重合体ブロックＢを製造してから、繰り返し単位Ａ１となるモノマー（例えば、Ｎ，Ｎ－ジメチルアクリルアミド）と繰り返し単位Ｃ１となるモノマー（例えば、３－メタクリロキシプロピルトリメトキシシラン）と繰り返し単位Ｃ２となるモノマー（例えば、メタクリル酸２－ヒドロキシエチル）とを重合して重合体ブロックＡを製造して、重合体ブロックＡと重合体ブロックＢとを含むブロック共重合体を製造する方法（この場合、重合体ブロックＡ及び重合体ブロックＢの両方が繰り返し単位Ｃ１を有する）等が挙げられる。
More specifically, for example, by a living radical polymerization method, a monomer that becomes the repeating unit B1 (for example, methyl methacrylate) and a monomer that becomes the repeating unit C1 (for example, 3-methacryloxypropyltrimethoxysilane) and the repeating unit C2. After polymerizing a monomer (eg, 2-hydroxyethyl methacrylate) to produce a polymer block B, a monomer (eg, N,N-dimethylacrylamide) that becomes the repeating unit A1 and a repeating unit C1 become A monomer (for example, 3-methacryloxypropyltrimethoxysilane) and a monomer (for example, 2-hydroxyethyl methacrylate) that becomes the repeating unit C2 are polymerized to produce a polymer block A, and the polymer block A and A method for producing a block copolymer containing the united block B (in this case, both the polymer block A and the polymer block B have the repeating unit C1) and the like can be mentioned.
［組成物］
本発明の組成物は、上述した本発明の重合体を含有する組成物である。
上記組成物は、本発明の重合体以外の成分を含有してもよい。
上記成分としては、例えば、レベリング剤、リン酸エステルモノマー及び溶剤（例えば、アルコール）等が挙げられる。
本発明の組成物は、例えば、防曇コーティング剤（曇りを防止するためのコーティング剤）として有用である。 [Composition]
The composition of the present invention is a composition containing the above-mentioned polymer of the present invention.
The composition may contain components other than the polymer of the present invention.
Examples of the components include a leveling agent, a phosphate ester monomer, a solvent (for example, alcohol), and the like.
The composition of the present invention is useful, for example, as an anti-fog coating agent (coating agent for preventing fogging).
本発明の組成物は、上述した本発明の重合体を含有する組成物である。
上記組成物は、本発明の重合体以外の成分を含有してもよい。
上記成分としては、例えば、レベリング剤、リン酸エステルモノマー及び溶剤（例えば、アルコール）等が挙げられる。
本発明の組成物は、例えば、防曇コーティング剤（曇りを防止するためのコーティング剤）として有用である。 [Composition]
The composition of the present invention is a composition containing the above-mentioned polymer of the present invention.
The composition may contain components other than the polymer of the present invention.
Examples of the components include a leveling agent, a phosphate ester monomer, a solvent (for example, alcohol), and the like.
The composition of the present invention is useful, for example, as an anti-fog coating agent (coating agent for preventing fogging).
［硬化皮膜］
本発明の硬化皮膜は、上述した本発明の組成物から形成されたものであれば特に制限されない。
本発明の硬化皮膜を製造する方法は特に制限されないが、例えば、基板（好ましくは、（メタ）アクリレート樹脂基板）上に上述した本発明の組成物を塗布し、加熱（好ましくは、５０～２００℃）する方法等が挙げられる。
加熱することで、繰り返し単位Ｃ１中のアルコキシシリル基同士が反応して（架橋して）硬化皮膜が形成される。また、本発明の重合体が繰り返し単位Ｃ２を有する場合は、繰り返し単位Ｃ１中のアルコキシシリル基同士の反応に加えて、繰り返し単位Ｃ１中のアルコキシシリル基と繰り返し単位Ｃ２中の－ＯＨ基とが反応して（架橋して）硬化皮膜が形成される。
本発明の硬化皮膜は、例えば、防曇皮膜（曇りを防止するための皮膜）として有用である。 [Cured film]
The cured film of the present invention is not particularly limited as long as it is formed from the composition of the present invention described above.
The method for producing the cured film of the present invention is not particularly limited, but for example, the composition of the present invention described above is applied onto a substrate (preferably a (meth)acrylate resin substrate) and heated (preferably 50 to 200). ℃) and the like.
By heating, the alkoxysilyl groups in the repeating unit C1 react (crosslink) with each other to form a cured film. When the polymer of the present invention has the repeating unit C2, in addition to the reaction between the alkoxysilyl groups in the repeating unit C1, the alkoxysilyl group in the repeating unit C1 and the —OH group in the repeating unit C2 are combined. Upon reaction (crosslinking), a cured film is formed.
The cured film of the present invention is useful, for example, as an anti-fog film (a film for preventing fogging).
本発明の硬化皮膜は、上述した本発明の組成物から形成されたものであれば特に制限されない。
本発明の硬化皮膜を製造する方法は特に制限されないが、例えば、基板（好ましくは、（メタ）アクリレート樹脂基板）上に上述した本発明の組成物を塗布し、加熱（好ましくは、５０～２００℃）する方法等が挙げられる。
加熱することで、繰り返し単位Ｃ１中のアルコキシシリル基同士が反応して（架橋して）硬化皮膜が形成される。また、本発明の重合体が繰り返し単位Ｃ２を有する場合は、繰り返し単位Ｃ１中のアルコキシシリル基同士の反応に加えて、繰り返し単位Ｃ１中のアルコキシシリル基と繰り返し単位Ｃ２中の－ＯＨ基とが反応して（架橋して）硬化皮膜が形成される。
本発明の硬化皮膜は、例えば、防曇皮膜（曇りを防止するための皮膜）として有用である。 [Cured film]
The cured film of the present invention is not particularly limited as long as it is formed from the composition of the present invention described above.
The method for producing the cured film of the present invention is not particularly limited, but for example, the composition of the present invention described above is applied onto a substrate (preferably a (meth)acrylate resin substrate) and heated (preferably 50 to 200). ℃) and the like.
By heating, the alkoxysilyl groups in the repeating unit C1 react (crosslink) with each other to form a cured film. When the polymer of the present invention has the repeating unit C2, in addition to the reaction between the alkoxysilyl groups in the repeating unit C1, the alkoxysilyl group in the repeating unit C1 and the —OH group in the repeating unit C2 are combined. Upon reaction (crosslinking), a cured film is formed.
The cured film of the present invention is useful, for example, as an anti-fog film (a film for preventing fogging).
以下、実施例により、本発明についてさらに詳細に説明するが、本発明はこれらに限定されるものではない。
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
〔ブロック共重合体の合成〕
以下のとおり、各ブロック共重合体を合成した。 [Synthesis of block copolymer]
Each block copolymer was synthesized as follows.
以下のとおり、各ブロック共重合体を合成した。 [Synthesis of block copolymer]
Each block copolymer was synthesized as follows.
＜実施例４＞
メタクリル酸メチル（東京化成工業製：１６ｍＬ）、メタクリル酸２－ヒドロキシエチル（東京化成工業製：０．４ｍＬ）、３－メタクリロキシプロピルトリメトキシシラン（信越シリコーン製：０．４ｍＬ）、アゾビスイソブチロニトリル（東京化成工業製：１０ｍｇ）、４－シアノ－４－（（（ドデシルチオ）カルボチオイル）チオ）ペンタン酸（Ｂｏｒｏｎ Ｍｏｌｅｃｕｌａｒ製：０．１２ｇ）及びＮ，Ｎ－ジメチルホルムアミド（関東化学製：５０ｍＬ）を混合し、７０℃に加熱して、攪拌した。２０時間後、Ｎ，Ｎ－ジメチルアクリルアミド（東京化成工業製：１５．４ｍＬ）、メタクリル酸２－ヒドロキシエチル（東京化成工業製：０．４ｍＬ）及び３－メタクリロキシプロピルトリメトキシシラン（信越シリコーン製：０．４ｍＬ）を投入し、７０℃に加熱して、攪拌した。４０時間後室温に冷却し、重合を停止した。得られたポリマー溶液を取り出し、減圧下で濃縮した。その結果、ブロック共重合体（３１．０ｇ，Ｍｎ＝４０，０００，Ｍｗ＝４８，０００，ＰＤＩ＝１．２）を９９％の収率で得た。
得られたブロック共重合体は、Ｎ，Ｎ－ジメチルアクリルアミドに由来する繰り返し単位（上述した繰り返し単位Ａ１に該当）（９７モル％）と３－メタクリロキシプロピルトリメトキシシランに由来する繰り返し単位（上述した繰り返し単位Ｃ１に該当）（１モル％）とメタクリル酸２－ヒドロキシエチル（上述した繰り返し単位Ｃ２に該当）（２モル％）とからなる重合体ブロックＡ（上述した重合体ブロックＡに該当）と、メタクリル酸メチル（上述した繰り返し単位Ｂ１に該当）（９７モル％）と３－メタクリロキシプロピルトリメトキシシランに由来する繰り返し単位（上述した繰り返し単位Ｃ１に該当）（１モル％）とメタクリル酸２－ヒドロキシエチル（上述した繰り返し単位Ｃ２に該当）（２モル％）とからなる重合体ブロックＢ（上述した重合体ブロックＢに該当）とを含むブロック共重合体（直鎖状）である。ブロック共重合体中の重合体ブロックＡの含有量は５０モル％、ブロック共重合体中の重合体ブロックＢの含有量は５０モル％である。 <Example 4>
Methyl methacrylate (Tokyo Kasei: 16 mL), 2-hydroxyethyl methacrylate (Tokyo Kasei: 0.4 mL), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Silicone: 0.4 mL), azobisiso Butyronitrile (manufactured by Tokyo Chemical Industry: 10 mg), 4-cyano-4-(((dodecylthio)carbothioyl)thio)pentanoic acid (manufactured by Boron Molecular: 0.12 g) and N,N-dimethylformamide (manufactured by Kanto Kagaku: 50 mL) were mixed, heated to 70° C., and stirred. After 20 hours, N,N-dimethylacrylamide (manufactured by Tokyo Chemical Industry: 15.4 mL), 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry: 0.4 mL) and 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone) : 0.4 mL) was added, and the mixture was heated to 70° C. and stirred. After 40 hours, it was cooled to room temperature to terminate the polymerization. The obtained polymer solution was taken out and concentrated under reduced pressure. As a result, a block copolymer (31.0 g, Mn=40,000, Mw=48,000, PDI=1.2) was obtained with a yield of 99%.
The resulting block copolymer had a repeating unit derived from N,N-dimethylacrylamide (corresponding to the repeating unit A1 described above) (97 mol %) and a repeating unit derived from 3-methacryloxypropyltrimethoxysilane (described above. Polymer block A (corresponding to polymer block A described above) consisting of (1 mol%) and 2-hydroxyethyl methacrylate (corresponding to repeating unit C2 described above) (2 mol%) And methyl methacrylate (corresponding to the repeating unit B1 described above) (97 mol %), a repeating unit derived from 3-methacryloxypropyltrimethoxysilane (corresponding to the repeating unit C1 described above) (1 mol %), and methacrylic acid A block copolymer (straight chain) containing a polymer block B (corresponding to the polymer block B described above) consisting of 2-hydroxyethyl (corresponding to the repeating unit C2 described above) (2 mol %). The content of the polymer block A in the block copolymer is 50 mol%, and the content of the polymer block B in the block copolymer is 50 mol%.
メタクリル酸メチル（東京化成工業製：１６ｍＬ）、メタクリル酸２－ヒドロキシエチル（東京化成工業製：０．４ｍＬ）、３－メタクリロキシプロピルトリメトキシシラン（信越シリコーン製：０．４ｍＬ）、アゾビスイソブチロニトリル（東京化成工業製：１０ｍｇ）、４－シアノ－４－（（（ドデシルチオ）カルボチオイル）チオ）ペンタン酸（Ｂｏｒｏｎ Ｍｏｌｅｃｕｌａｒ製：０．１２ｇ）及びＮ，Ｎ－ジメチルホルムアミド（関東化学製：５０ｍＬ）を混合し、７０℃に加熱して、攪拌した。２０時間後、Ｎ，Ｎ－ジメチルアクリルアミド（東京化成工業製：１５．４ｍＬ）、メタクリル酸２－ヒドロキシエチル（東京化成工業製：０．４ｍＬ）及び３－メタクリロキシプロピルトリメトキシシラン（信越シリコーン製：０．４ｍＬ）を投入し、７０℃に加熱して、攪拌した。４０時間後室温に冷却し、重合を停止した。得られたポリマー溶液を取り出し、減圧下で濃縮した。その結果、ブロック共重合体（３１．０ｇ，Ｍｎ＝４０，０００，Ｍｗ＝４８，０００，ＰＤＩ＝１．２）を９９％の収率で得た。
得られたブロック共重合体は、Ｎ，Ｎ－ジメチルアクリルアミドに由来する繰り返し単位（上述した繰り返し単位Ａ１に該当）（９７モル％）と３－メタクリロキシプロピルトリメトキシシランに由来する繰り返し単位（上述した繰り返し単位Ｃ１に該当）（１モル％）とメタクリル酸２－ヒドロキシエチル（上述した繰り返し単位Ｃ２に該当）（２モル％）とからなる重合体ブロックＡ（上述した重合体ブロックＡに該当）と、メタクリル酸メチル（上述した繰り返し単位Ｂ１に該当）（９７モル％）と３－メタクリロキシプロピルトリメトキシシランに由来する繰り返し単位（上述した繰り返し単位Ｃ１に該当）（１モル％）とメタクリル酸２－ヒドロキシエチル（上述した繰り返し単位Ｃ２に該当）（２モル％）とからなる重合体ブロックＢ（上述した重合体ブロックＢに該当）とを含むブロック共重合体（直鎖状）である。ブロック共重合体中の重合体ブロックＡの含有量は５０モル％、ブロック共重合体中の重合体ブロックＢの含有量は５０モル％である。 <Example 4>
Methyl methacrylate (Tokyo Kasei: 16 mL), 2-hydroxyethyl methacrylate (Tokyo Kasei: 0.4 mL), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Silicone: 0.4 mL), azobisiso Butyronitrile (manufactured by Tokyo Chemical Industry: 10 mg), 4-cyano-4-(((dodecylthio)carbothioyl)thio)pentanoic acid (manufactured by Boron Molecular: 0.12 g) and N,N-dimethylformamide (manufactured by Kanto Kagaku: 50 mL) were mixed, heated to 70° C., and stirred. After 20 hours, N,N-dimethylacrylamide (manufactured by Tokyo Chemical Industry: 15.4 mL), 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry: 0.4 mL) and 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone) : 0.4 mL) was added, and the mixture was heated to 70° C. and stirred. After 40 hours, it was cooled to room temperature to terminate the polymerization. The obtained polymer solution was taken out and concentrated under reduced pressure. As a result, a block copolymer (31.0 g, Mn=40,000, Mw=48,000, PDI=1.2) was obtained with a yield of 99%.
The resulting block copolymer had a repeating unit derived from N,N-dimethylacrylamide (corresponding to the repeating unit A1 described above) (97 mol %) and a repeating unit derived from 3-methacryloxypropyltrimethoxysilane (described above. Polymer block A (corresponding to polymer block A described above) consisting of (1 mol%) and 2-hydroxyethyl methacrylate (corresponding to repeating unit C2 described above) (2 mol%) And methyl methacrylate (corresponding to the repeating unit B1 described above) (97 mol %), a repeating unit derived from 3-methacryloxypropyltrimethoxysilane (corresponding to the repeating unit C1 described above) (1 mol %), and methacrylic acid A block copolymer (straight chain) containing a polymer block B (corresponding to the polymer block B described above) consisting of 2-hydroxyethyl (corresponding to the repeating unit C2 described above) (2 mol %). The content of the polymer block A in the block copolymer is 50 mol%, and the content of the polymer block B in the block copolymer is 50 mol%.
＜その他の実施例及び比較例＞
重合体ブロックＡ中の各モノマーに由来する各繰り返し単位の含有量（モル％）、及び、重合体ブロックＢ中の各モノマーに由来する各繰り返し単位の含有量（モル％）、並びに、ブロック共重合体中の重合体ブロックＡの含有量（モル％）、及び、ブロック共重合体中の重合体ブロックＢの含有量（モル％）が、表１に記載のとおりになるように各モノマーの混合量を変更した以外は実施例４と同様の手順に従って、各ブロック共重合体を合成した。各ブロック共重合体のＭｎ及びＭｗを表１に示す。 <Other Examples and Comparative Examples>
Content (mol%) of each repeating unit derived from each monomer in the polymer block A, content (mol%) of each repeating unit derived from each monomer in the polymer block B, and block The content (mol %) of the polymer block A in the polymer and the content (mol %) of the polymer block B in the block copolymer are as shown in Table 1. Each block copolymer was synthesized according to the same procedure as in Example 4 except that the mixing amount was changed. Table 1 shows Mn and Mw of each block copolymer.
重合体ブロックＡ中の各モノマーに由来する各繰り返し単位の含有量（モル％）、及び、重合体ブロックＢ中の各モノマーに由来する各繰り返し単位の含有量（モル％）、並びに、ブロック共重合体中の重合体ブロックＡの含有量（モル％）、及び、ブロック共重合体中の重合体ブロックＢの含有量（モル％）が、表１に記載のとおりになるように各モノマーの混合量を変更した以外は実施例４と同様の手順に従って、各ブロック共重合体を合成した。各ブロック共重合体のＭｎ及びＭｗを表１に示す。 <Other Examples and Comparative Examples>
Content (mol%) of each repeating unit derived from each monomer in the polymer block A, content (mol%) of each repeating unit derived from each monomer in the polymer block B, and block The content (mol %) of the polymer block A in the polymer and the content (mol %) of the polymer block B in the block copolymer are as shown in Table 1. Each block copolymer was synthesized according to the same procedure as in Example 4 except that the mixing amount was changed. Table 1 shows Mn and Mw of each block copolymer.
〔評価〕
得られた各ブロック共重合体について以下の評価を行った。 [Evaluation]
The following evaluations were performed on each of the obtained block copolymers.
得られた各ブロック共重合体について以下の評価を行った。 [Evaluation]
The following evaluations were performed on each of the obtained block copolymers.
＜速硬化性＞
得られた各ブロック共重合体を溶剤に溶かして、これをメチルメタクリレート樹脂基板に、硬化後の塗膜（硬化皮膜）の膜厚が３～５μｍとなるようにスプレーコート法にて塗装を行い、３０℃で１分間乾燥を行った後、１００℃で加熱硬化を行った。そして、速硬化性を次の５段階で評価した。なお、評価が○以上であれば実用上問題なく、◎であればより好ましく、◎＋であればさらに好ましい。
◎＋：４分以内に硬化する。
◎：４分超５分以内に硬化する。
○：５分超１０分未満で硬化する。
△：１０分超２０分未満で硬化する。
×：硬化するのに２０分以上かかる。 <Fast curability>
Each of the obtained block copolymers is dissolved in a solvent, and this is coated on a methyl methacrylate resin substrate by a spray coating method so that the thickness of the coating film (cured film) after curing becomes 3 to 5 μm. After drying at 30° C. for 1 minute, heat curing was performed at 100° C. Then, the rapid curing property was evaluated according to the following 5 grades. In addition, if the evaluation is ◯ or more, there is no practical problem, and ◎ is more preferable, and ⊚ + is more preferable.
⊚ + : Cured within 4 minutes.
⊚: Hardens within more than 4 minutes and within 5 minutes.
◯: Cured in more than 5 minutes and less than 10 minutes.
(Triangle|delta): It hardens in more than 10 minutes and less than 20 minutes.
X: It takes 20 minutes or more to cure.
得られた各ブロック共重合体を溶剤に溶かして、これをメチルメタクリレート樹脂基板に、硬化後の塗膜（硬化皮膜）の膜厚が３～５μｍとなるようにスプレーコート法にて塗装を行い、３０℃で１分間乾燥を行った後、１００℃で加熱硬化を行った。そして、速硬化性を次の５段階で評価した。なお、評価が○以上であれば実用上問題なく、◎であればより好ましく、◎＋であればさらに好ましい。
◎＋：４分以内に硬化する。
◎：４分超５分以内に硬化する。
○：５分超１０分未満で硬化する。
△：１０分超２０分未満で硬化する。
×：硬化するのに２０分以上かかる。 <Fast curability>
Each of the obtained block copolymers is dissolved in a solvent, and this is coated on a methyl methacrylate resin substrate by a spray coating method so that the thickness of the coating film (cured film) after curing becomes 3 to 5 μm. After drying at 30° C. for 1 minute, heat curing was performed at 100° C. Then, the rapid curing property was evaluated according to the following 5 grades. In addition, if the evaluation is ◯ or more, there is no practical problem, and ◎ is more preferable, and ⊚ + is more preferable.
⊚ + : Cured within 4 minutes.
⊚: Hardens within more than 4 minutes and within 5 minutes.
◯: Cured in more than 5 minutes and less than 10 minutes.
(Triangle|delta): It hardens in more than 10 minutes and less than 20 minutes.
X: It takes 20 minutes or more to cure.
＜耐温水性＞
得られた各ブロック共重合体を溶剤に溶かして、これをメチルメタクリレート樹脂基板に、硬化後の塗膜（硬化皮膜）の膜厚が３～５μｍとなるようにスプレーコート法にて塗装を行い、３０℃で１分間乾燥を行った後、十分に硬化するまで１００℃で加熱硬化を行った。
得られた硬化皮膜を４０℃の温水に２４０時間浸漬後、ブローワーで水分を除去し、室温にて１時間乾燥した後の硬化皮膜の外観を目視によって評価した。なお、評価が○以上であれば実用上問題なく、◎であればより好ましい。
◎：白化が全く見られない。
○：かすかな白化が見られる。
△：著しい白化が見られる。
×：硬化皮膜の溶出が見られる。 <Warm water resistance>
Each of the obtained block copolymers is dissolved in a solvent, and this is coated on a methyl methacrylate resin substrate by a spray coating method so that the thickness of the coating film (cured film) after curing becomes 3 to 5 μm. After drying at 30° C. for 1 minute, heat curing was performed at 100° C. until it was sufficiently cured.
The obtained cured film was immersed in warm water of 40° C. for 240 hours, the water was removed by a blower, and the appearance of the cured film after drying at room temperature for 1 hour was visually evaluated. In addition, when the evaluation is ◯ or more, there is no practical problem, and when ⊚, it is more preferable.
A: No whitening is observed.
○: A slight whitening is observed.
Δ: Remarkable whitening is observed.
X: Elution of the cured film is observed.
得られた各ブロック共重合体を溶剤に溶かして、これをメチルメタクリレート樹脂基板に、硬化後の塗膜（硬化皮膜）の膜厚が３～５μｍとなるようにスプレーコート法にて塗装を行い、３０℃で１分間乾燥を行った後、十分に硬化するまで１００℃で加熱硬化を行った。
得られた硬化皮膜を４０℃の温水に２４０時間浸漬後、ブローワーで水分を除去し、室温にて１時間乾燥した後の硬化皮膜の外観を目視によって評価した。なお、評価が○以上であれば実用上問題なく、◎であればより好ましい。
◎：白化が全く見られない。
○：かすかな白化が見られる。
△：著しい白化が見られる。
×：硬化皮膜の溶出が見られる。 <Warm water resistance>
Each of the obtained block copolymers is dissolved in a solvent, and this is coated on a methyl methacrylate resin substrate by a spray coating method so that the thickness of the coating film (cured film) after curing becomes 3 to 5 μm. After drying at 30° C. for 1 minute, heat curing was performed at 100° C. until it was sufficiently cured.
The obtained cured film was immersed in warm water of 40° C. for 240 hours, the water was removed by a blower, and the appearance of the cured film after drying at room temperature for 1 hour was visually evaluated. In addition, when the evaluation is ◯ or more, there is no practical problem, and when ⊚, it is more preferable.
A: No whitening is observed.
○: A slight whitening is observed.
Δ: Remarkable whitening is observed.
X: Elution of the cured film is observed.
表１から分かるように、重合体ブロックＡ及び重合体ブロックＢのいずれも繰り返し単位Ｃ１を有さない（Ｎ－メチロールアクリルアミドに由来する繰り返し単位を有する）比較例１～３と比較して、重合体ブロックＡ及び重合体ブロックＢのうち少なくとも一方が繰り返し単位Ｃ１を有する実施例１～５は、優れた速硬化性及び耐温水性を示した。
実施例１～５の対比から、重合体ブロックＡが繰り返し単位Ｃ１を有する実施例１及び３～５は、より優れた速硬化性を示した。
また、実施例１～５の対比から、重合体ブロックＢが繰り返し単位Ｃ１を有する実施例２～５は、より優れた耐温水性を示した。
また、実施例１～５の対比から、重合体ブロックＡ及び重合体ブロックＢのうち少なくとも一方が繰り返し単位Ｃ２を有する実施例４～５は、より優れた速硬化性を示した。 As can be seen from Table 1, as compared with Comparative Examples 1 to 3 in which neither polymer block A nor polymer block B has a repeating unit C1 (having a repeating unit derived from N-methylolacrylamide), Examples 1 to 5 in which at least one of the united block A and the polymer block B had the repeating unit C1 showed excellent fast curability and hot water resistance.
From the comparison of Examples 1 to 5, Examples 1 and 3 to 5 in which the polymer block A has the repeating unit C1 showed more excellent fast curability.
Further, from the comparison of Examples 1 to 5, Examples 2 to 5 in which the polymer block B has the repeating unit C1 showed more excellent hot water resistance.
Further, from the comparison of Examples 1 to 5, Examples 4 to 5 in which at least one of the polymer block A and the polymer block B has the repeating unit C2 showed more excellent fast curability.
実施例１～５の対比から、重合体ブロックＡが繰り返し単位Ｃ１を有する実施例１及び３～５は、より優れた速硬化性を示した。
また、実施例１～５の対比から、重合体ブロックＢが繰り返し単位Ｃ１を有する実施例２～５は、より優れた耐温水性を示した。
また、実施例１～５の対比から、重合体ブロックＡ及び重合体ブロックＢのうち少なくとも一方が繰り返し単位Ｃ２を有する実施例４～５は、より優れた速硬化性を示した。 As can be seen from Table 1, as compared with Comparative Examples 1 to 3 in which neither polymer block A nor polymer block B has a repeating unit C1 (having a repeating unit derived from N-methylolacrylamide), Examples 1 to 5 in which at least one of the united block A and the polymer block B had the repeating unit C1 showed excellent fast curability and hot water resistance.
From the comparison of Examples 1 to 5, Examples 1 and 3 to 5 in which the polymer block A has the repeating unit C1 showed more excellent fast curability.
Further, from the comparison of Examples 1 to 5, Examples 2 to 5 in which the polymer block B has the repeating unit C1 showed more excellent hot water resistance.
Further, from the comparison of Examples 1 to 5, Examples 4 to 5 in which at least one of the polymer block A and the polymer block B has the repeating unit C2 showed more excellent fast curability.
Claims (4)
- 下記式（Ａ１）で表される繰り返し単位Ａ１、又は、下記式（Ａ２）で表される繰り返し単位Ａ２を有する重合体ブロックＡと、
下記式（Ｂ１）で表される繰り返し単位を有する重合体ブロックＢとを含み、
前記重合体ブロックＡ及び前記重合体ブロックＢのうち少なくとも一方が、下記式（Ｃ１）で表される繰り返し単位Ｃ１を有する、ブロック共重合体。
式（Ａ１）、（Ａ２）、（Ｂ１）及び（Ｃ１）中、Ｒは、水素原子又はメチル基を表す。
式（Ａ１）中、ＲＡ１は、水素原子又は炭化水素基を表す。２つのＲＡ１は同一であっても異なってもよい。
式（Ａ２）中、ＲＡ２は、水素原子又は炭化水素基を表す。ｐは、１以上の整数を表す。
式（Ｂ１）中、ＲＢ１は、炭化水素基を表す。
式（Ｃ１）中、Ｌは、単結合又は２価の連結基を表す。ＲＣ１１及びＲＣ１２は、それぞれ独立に、炭化水素基を表す。ｍは１～３の整数を表す。ｎは、０～２の整数を表す。ただし、ｍ＋ｎ＝３である。ｍが２以上の整数である場合に複数存在するＲＣ１１は同一であっても異なってもよい。ｎが２である場合の２つのＲＣ１２は同一であっても異なってもよい。 A polymer block A having a repeating unit A1 represented by the following formula (A1) or a repeating unit A2 represented by the following formula (A2),
A polymer block B having a repeating unit represented by the following formula (B1),
A block copolymer in which at least one of the polymer block A and the polymer block B has a repeating unit C1 represented by the following formula (C1).
In formulas (A1), (A2), (B1) and (C1), R represents a hydrogen atom or a methyl group.
In formula (A1), R A1 represents a hydrogen atom or a hydrocarbon group. The two R A1 may be the same or different.
In formula (A2), R A2 represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 or more.
In formula (B1), R B1 represents a hydrocarbon group.
In formula (C1), L represents a single bond or a divalent linking group. R C11 and R C12 each independently represent a hydrocarbon group. m represents an integer of 1 to 3. n represents an integer of 0 to 2. However, m+n=3. When m is an integer of 2 or more, a plurality of R C11 existing may be the same or different. When n is 2, the two R C12 may be the same or different. - 前記重合体ブロックＡ及び前記重合体ブロックＢのうち少なくとも一方が、下記式（Ｃ２）で表される繰り返し単位Ｃ２を有する、請求項１に記載のブロック共重合体。
式（Ｃ２）中、Ｒは、水素原子又はメチル基を表す。ＲＣ２は、水素原子、又は、ヒドロキシ基を有する炭化水素基を表す。 The block copolymer according to claim 1, wherein at least one of the polymer block A and the polymer block B has a repeating unit C2 represented by the following formula (C2).
In formula (C2), R represents a hydrogen atom or a methyl group. R C2 represents a hydrogen atom or a hydrocarbon group having a hydroxy group. - 前記重合体ブロックＢが、前記式（Ｃ１）で表される繰り返し単位を有する、請求項１又は２に記載のブロック共重合体。 The block copolymer according to claim 1 or 2, wherein the polymer block B has a repeating unit represented by the formula (C1).
- 前記重合体ブロックＡの含有量が、３０～９０質量％である、請求項１又は２に記載のブロック共重合体。 The block copolymer according to claim 1 or 2, wherein the content of the polymer block A is 30 to 90% by mass.
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| JP2002060449A (en) * | 2000-08-11 | 2002-02-26 | Kanegafuchi Chem Ind Co Ltd | Curable composition containing block copolymer |
| JP2002338625A (en) * | 2001-05-14 | 2002-11-27 | Kanegafuchi Chem Ind Co Ltd | Block copolymer |
| JP2017008217A (en) * | 2015-06-23 | 2017-01-12 | 日油株式会社 | Antifogging agent composition |
| JP2017179174A (en) * | 2016-03-31 | 2017-10-05 | 日油株式会社 | Catalyst for antifogging agent composition |
| JP2017179112A (en) * | 2016-03-30 | 2017-10-05 | Dic株式会社 | Block polymer, coating agent and coated film containing the same |
| WO2018067284A1 (en) * | 2016-10-06 | 2018-04-12 | Johnson & Johnson Vision Care, Inc. | Tri-block prepolymers and their use in silicone hydrogels |
| WO2018181251A1 (en) * | 2017-03-31 | 2018-10-04 | 東亞合成株式会社 | Curable resin composition and production method therefor |
| JP2018188627A (en) * | 2017-05-05 | 2018-11-29 | ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド | Epilamization agent and epilamization method using such epilamization agent |
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| JP2002060449A (en) * | 2000-08-11 | 2002-02-26 | Kanegafuchi Chem Ind Co Ltd | Curable composition containing block copolymer |
| JP2002338625A (en) * | 2001-05-14 | 2002-11-27 | Kanegafuchi Chem Ind Co Ltd | Block copolymer |
| JP2017008217A (en) * | 2015-06-23 | 2017-01-12 | 日油株式会社 | Antifogging agent composition |
| JP2017179112A (en) * | 2016-03-30 | 2017-10-05 | Dic株式会社 | Block polymer, coating agent and coated film containing the same |
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