JP5133606B2 - Surfactant - Google Patents

Description

  The present invention relates to a novel block copolymer production method and a surfactant containing the block copolymer obtained by the production method.

Fluorine-containing compounds having a fluorine-containing alkyl group as a hydrophobic group have a high ability to reduce surface tension. Therefore, when added to a coating composition as a surfactant, excellent permeability, wettability, and leveling properties Demonstrate such effects. As the fluorine-containing compound, various structures have been proposed so far.
As the fluorine-containing compound, a polymer is also known. For example, the following copolymers are known.
(1) A random copolymer of a fluorine-containing monomer and a monomer having an amphiphilic group.
(2) A block copolymer having a segment composed of a molecular chain containing a unit derived from a fluorine-containing monomer and a segment composed of another molecular chain.

The random copolymer (1) generally has a low ability to reduce the surface tension of the liquid, and in order to sufficiently exert its function as a leveling agent, the content of fluorine in the copolymer is increased. Or it is necessary to increase the amount added to the coating composition or the like.
However, when the fluorine content in the copolymer is increased in order to exert a function as a leveling agent, the solubility of the random copolymer in various solvents decreases. Moreover, when the addition amount to a coating composition is increased in order to exhibit the function as a leveling agent, it is not economical and may adversely affect the obtained coating film.

For the block copolymer (2), several production methods have been proposed. For example, Patent Document 1 describes a method using a nitroxy free radical, and Patent Document 2 describes an ATRP (Atom Transfer Radical Polymerization) method as a suitable technique for block copolymerization.
However, in these techniques, it is essential to use a heavy metal catalyst substantially. Therefore, the block copolymer produced using the heavy metal catalyst cannot be used for applications that require the amount of heavy metals present in the system to be reduced as much as possible, such as photoresists. .

On the other hand, in recent years, concerns have been expressed regarding the safety of compounds containing a perfluoroalkyl group. Among them, those containing a long-chain perfluoroalkyl group having an alkyl chain length of 8 or more are regarded as a problem of accumulation in the human body, and a reduction in the amount of use is desired (Non-patent Document 1). ).
This alkyl chain length of 8 or more is a length required for a perfluoroalkyl group in order to allow a compound containing a perfluoroalkyl group to exhibit sufficient performance in terms of surface modification. However, it has been difficult to develop performance when the alkyl chain length is shorter than that, particularly when the alkyl chain length is 6 or less (Non-patent Document 2).
Japanese Patent Laid-Open No. 10-130348 JP 2006-063132 A U. S. Environmental Protection Agency, “Perfluorooctanoic Acid (PFOA) and Fluorinated Telomers” [online], May 22, 2007 [2007] Search May 28], Internet <URL: http://www.epa.gov/oppt/pfoa/index.htm> “Development of Fluorine-Based Materials”, first edition, CMC Publishing, published on September 10, 1997, pages 135-165

  The present invention has been made in view of the above circumstances, and uses a heavy metal block copolymer that exhibits an excellent ability to reduce the surface tension of a liquid without containing a long-chain perfluoroalkyl group. An object of the present invention is to provide a production method that can be produced without any problem and a surfactant containing a block copolymer obtained by the production method.

As a result of intensive studies on the polymerization method and polymerization composition, the present inventor achieved the above problem by polymerizing a specific monomer using a thiocarbonyl compound having a specific structure in the absence of a solvent or in the presence of a fluorinated solvent. The present invention has been completed by finding that it can be solved.
That is, the first aspect of the present invention is a polymer obtained by polymerizing the monomer represented by the following formula (2) in the state where the thiocarbonylthio compound represented by the following formula (1) is present in the system. The surfactant further contains a block copolymer obtained by polymerizing the monomer represented by the following formula (3) in the absence of a solvent or in the presence of a fluorinated solvent.

［式中、Ｘ^１は水素原子、ハロゲン原子、アミノ基、Ｐ（Ｏ）（ＯＨ）_２基または１価の有機基であり；Ｙ^１は水素原子、ハロゲン原子、アルカリ金属原子、ＮＨ_４基または１価の有機基であり；Ｒ^１は水素原子、ハロゲン原子、炭素数１〜５のアルキル基または炭素数１〜５のフルオロアルキル基であり；Ｒ^２は水素原子または１価の基であり；Ａは−Ｏ−または−ＮＲ^３−（Ｒ^３は水素原子または炭素数１〜５のアルキル基を示す。）であり；Ｒ^４は水素原子、ハロゲン原子、炭素数１〜５のアルキル基または炭素数１〜５のフルオロアルキル基であり；Ｒ^５は単結合または２価の連結基であり；Ｂは−Ｏ−または−ＮＲ^６−（Ｒ^６は水素原子または炭素数１〜５のアルキル基を示す。）であり；Ｒｆは炭素数１〜６のパーフルオロアルキル基である。］

[Wherein, X ¹ is a hydrogen atom, halogen atom, amino group, P (O) (OH) ₂ group or monovalent organic group; Y ¹ is a hydrogen atom, halogen atom, alkali metal atom, NH ₄ group Or R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms; R ² is a hydrogen atom or a monovalent group. Yes; A represents —O— or —NR ³ — (R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms); R ⁴ represents a hydrogen atom, a halogen atom, or an alkyl having 1 to 5 carbon atoms. R ⁵ is a single bond or a divalent linking group; B is —O— or —NR ⁶ — (R ⁶ is a hydrogen atom or a carbon number of 1 to 5; And Rf is a perfume having 1 to 6 carbon atoms. Is a Oroarukiru group. ]

In a second embodiment of the present invention, in the state where the thiocarbonylthio compound represented by the following formula (1) is present in the system, the monomer represented by the following formula (3) is used in the absence of a solvent or a fluorine-containing compound. It is a surfactant containing a block copolymer obtained by polymerizing in the presence of a solvent and further polymerizing a monomer represented by the following formula (2) to the resulting polymer.

［式中、Ｘ^１は水素原子、ハロゲン原子、アミノ基、Ｐ（Ｏ）（ＯＨ）_２基または１価の有機基であり；Ｙ^１は水素原子、ハロゲン原子、アルカリ金属原子、ＮＨ_４基または１価の有機基であり；Ｒ^１は水素原子、ハロゲン原子、炭素数１〜５のアルキル基または炭素数１〜５のフルオロアルキル基であり；Ｒ^２は水素原子または１価の基であり；Ａは−Ｏ−または−ＮＲ^３−（Ｒ^３は水素原子または炭素数１〜５のアルキル基を示す。）であり；Ｒ^４は水素原子、ハロゲン原子、炭素数１〜５のアルキル基または炭素数１〜５のフルオロアルキル基であり；Ｒ^５は単結合または２価の連結基であり；Ｂは−Ｏ−または−ＮＲ^６−（Ｒ^６は水素原子または炭素数１〜５のアルキル基を示す。）であり；Ｒｆは炭素数１〜６のパーフルオロアルキル基である。］

[Wherein, X ¹ is a hydrogen atom, halogen atom, amino group, P (O) (OH) ₂ group or monovalent organic group; Y ¹ is a hydrogen atom, halogen atom, alkali metal atom, NH ₄ group Or R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms; R ² is a hydrogen atom or a monovalent group. Yes; A represents —O— or —NR ³ — (R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms); R ⁴ represents a hydrogen atom, a halogen atom, or an alkyl having 1 to 5 carbon atoms. R ⁵ is a single bond or a divalent linking group; B is —O— or —NR ⁶ — (R ⁶ is a hydrogen atom or a carbon number of 1 to 5; And Rf is a perfume having 1 to 6 carbon atoms. Is a Oroarukiru group. ]

According to the production method of the present invention, it is possible to produce a block copolymer that exhibits an excellent ability to reduce the surface tension of a liquid without containing a long-chain perfluoroalkyl group without using a heavy metal.
Further, the surfactant of the present invention contains the block copolymer and exhibits an excellent ability to reduce the surface tension of a liquid even when added in a small amount. In addition, since the production method does not use a heavy metal catalyst, the block copolymer produced by the production method can be used in applications where it is required to reduce the amount of heavy metal present in the system as much as possible. Furthermore, since it does not contain a long-chain perfluoroalkyl group, it is excellent in safety.

  Hereinafter, in the present specification, the compound represented by the formula (1) is referred to as a compound (1), the monomer represented by the formula (2) is referred to as a monomer (2), and is represented by the formula (4). The group is referred to as group (4). The same applies to other equations.

<Method for producing block copolymer>
[First manufacturing method]
The production method according to the first aspect of the present invention (hereinafter sometimes referred to as the first production method) comprises a polymerization of the monomer (2) in the state where the compound (1) is present in the system. In this method, the monomer (3) is further polymerized in the absence of a solvent or in the presence of a fluorinated solvent.
The compound (1), monomer (2), and monomer (3) will be described in detail later.

In the first production method, first, the monomer (2) is polymerized in a state where the compound (1) is present in the system.
A compound (1) may be used individually by 1 type, and may use 2 or more types together.
The amount of the compound (1) used is preferably 0.01 to 10% by mass, and 0.05 to 5% by mass with respect to the total of the monomer (2) and monomer (3) used in the production of the block copolymer. Is more preferable. When using 2 or more types of compounds (1), it is preferable that those sum total exists in the said range.

A monomer (2) may be used individually by 1 type, and may use 2 or more types together.
Although the usage-amount of a monomer (2) is not specifically limited, It is preferable that it is 10-97 mass% with respect to the sum total of the monomer (2) used for manufacture of a block copolymer, and a monomer (3), 20 More preferably, it is -95 mass%. When using 2 or more types of monomers (2), it is preferable that those sum total exists in the said range.

The polymerization of the monomer (2) may be performed in the absence of a solvent or may be performed in the presence of a solvent.
When the polymerization of the monomer (2) is carried out in the presence of a solvent, the solvent to be used is not particularly limited as long as the raw material dissolves, and a solvent containing no fluorine atom in the structure (hereinafter referred to as a fluorine-free solvent). Or a fluorine-containing solvent, and one or more of these may be used as appropriate.
The fluorine-free solvent is not particularly limited as long as the raw material dissolves, and examples thereof include acetone, methanol, ethanol, 2-propanol, ethyl acetate, toluene, tetrahydrofuran and the like.

The fluorine-containing solvent is not particularly limited as long as the raw material dissolves. For example, perfluorocarbon (PFC), hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), hydrofluoroether (HFE), etc. And a solvent containing a fluorine atom.
Specific examples of fluorine-containing solvents include 3M's HFE series, Fluorinert series, Asahi Glass series, Asahi Glass Co., Ltd., ZEOLA H. Mitsui DuPont Fluorochemicals, Inc. There are series, etc. In addition to these, fluorine-containing aromatic compound derivatives, fluorine-containing alcohols, fluorine-containing ketones, trifluoromethylbenzene and derivatives thereof, hexafluoroxylene and derivatives thereof, and the like can be given.
The fluorine-containing solvent is preferably one that does not have an ozone depletion coefficient, and among them, it has a sufficiently high solubility even for non-fluorinated polymers, so that fluorine-substituted aromatics, fluoroalkyl-substituted aromatics, fluoroalcohols Are preferred.

More specific examples of the fluorine-containing solvent include, but are not limited to, the following.
Benzotrifluoride,
m-xylene hexafluoride (hereinafter referred to as m-XHF),
p-xylene hexafluoride (hereinafter referred to as p-XHF),
CF ₃ CH ₂ CF ₂ CH ₃ ,
CF ₃ CH ₂ CF ₂ H,
C ₆ F ₁₃ OCH ₃ ,
C ₆ F ₁₃ OC ₂ H ₅ ,
C ₃ F ₇ OCH ₃ ,
C ₃ F ₇ OC ₂ H ₅ ,
C ₆ F ₁₃ H,
CF ₂ HCF ₂ CH ₂ OCF ₂ CF ₂ H,
CF ₃ CFHCFHCF ₂ CH _3,
CF ₃ (OCF ₂ CF ₂ ) _q (OCF ₂ ) _r OCF ₂ H (q and r each independently represents 1 to 20),
C ₈ F ₁₇ OCH ₃ ,
C ₇ F ₁₅ CH ₃ ,
C ₄ F ₉ OCH ₃ ,
C ₄ F ₉ OC ₂ H ₅ ,
C ₄ F ₉ CH ₂ CH ₃ ,
CF ₃ CH ₂ OCF ₂ CF ₂ CF ₂ H,
CF ₃ COCF ₃ ,
CF ₃ CH ₂ OH,
HCF ₂ CF ₂ CH ₂ OH,
(CF ₃ ) ₂ CHOH,
HCF ₂ CF ₂ CF ₂ CF ₂ CH ₂ OH

  Polymerization of the monomer (2) in the first production method is performed in the presence of a solvent within a range of 0.5 to 10 times the mass of the monomer (2) or in the absence of a solvent. Is preferred.

A radical polymerization method is used for the polymerization of the monomer (2), and the form thereof may be any of solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.
A polymerization initiator is preferably used for the polymerization of the monomer (2). The polymerization initiator is not particularly limited. For example, 2,2′-azobis-2-methylbutyronitrile, dimethyl-2,2′-azobis-2-methylpropionate, 2,2′-azobisiso Examples thereof include azo compounds such as butyronitrile and organic oxides such as lauroyl peroxide.

The polymerization temperature is preferably 0 to 150 ° C. in terms of ease of control. In particular, when polymerization is performed in the absence of a solvent, it is preferable to perform the polymerization at a temperature equal to or higher than the glass transition temperature of the produced polymer.
The polymerization pressure is preferably normal pressure or, in the case of a closed system, a pressure of about the gas generated by the decomposition of the polymerization initiator from the viewpoint of simplicity.
The atmosphere at the time of polymerization is air, nitrogen atmosphere, argon atmosphere, helium atmosphere or the like. In order not to consume radicals during polymerization, an inert gas atmosphere is preferred.

After the polymerization of the monomer (2), the resulting polymer is polymerized with the monomer (3).
In the first production method, as the monomer (3), one type may be used alone, or two or more types may be used in combination.
Although the usage-amount of a monomer (3) is not specifically limited, It is preferable that it is 3-90 mass% with respect to the sum total of the monomer (2) and monomer (3) used for manufacture of a block copolymer, More preferably, it is 80 mass%. When two or more types of monomers (3) are included, the total of them is preferably in the above range. When the amount of the monomer (3) used is within this range, both the function of the monomer (3) and the function of the monomer (2) can be utilized.
Especially in this invention, the usage-amount of a monomer (3) exists in the range of 5-50 mass% with respect to the sum total of the monomer (2) used for manufacture of a block copolymer, and a monomer (3). Is preferred. Within this range, the resulting block copolymer has excellent solubility in various solvents and can be suitably used as a surfactant.

The polymerization of the monomer (3) is carried out in the absence of a solvent or in the presence of a fluorinated solvent.
When the polymerization of the monomer (2) is performed in the absence of a solvent and the polymerization of the monomer (3) is performed in the absence of a solvent, the polymerization of the monomer (3) is performed as it is after the polymerization of the monomer (2). Can be implemented.
When the polymerization of the monomer (2) is performed in the absence of a solvent and the polymerization of the monomer (3) is performed in the presence of a fluorinated solvent, after the polymerization of the monomer (2), a fluorinated solvent is added. Monomer (3) is polymerized.
When the polymerization of the monomer (2) is performed in the presence of a solvent and the polymerization of the monomer (3) is performed in the absence of a solvent, after the polymerization of the monomer (2), the solvent is removed and then the monomer (3) Is polymerized. As a method for removing the solvent, a known method such as using an evaporator such as an evaporator can be used.
When the polymerization of the monomer (2) is performed in the presence of a solvent and the polymerization of the monomer (3) is performed in the presence of a fluorinated solvent, the solvent used for the polymerization of the monomer (2) includes a fluorinated solvent. In this case, the monomer (3) may be polymerized as it is, and further a fluorine-containing solvent may be added. If the solvent used for the polymerization of the monomer (2) does not contain a fluorinated solvent, the fluorinated solvent is added to carry out the polymerization of the monomer (3).

In the first production method, when the polymerization of the monomer (3) is carried out in the presence of a fluorine-containing solvent, examples of the fluorine-containing solvent include those similar to those mentioned in the polymerization of the monomer (2). These may be used alone or in combination of two or more.
When the polymerization of the monomer (3) is performed in the presence of a fluorine-containing solvent, only the fluorine-containing solvent may be used as the polymerization solvent, or a fluorine-free solvent may be used in combination with the fluorine-containing solvent.
Examples of the fluorine-free solvent include the same ones as mentioned in the polymerization of the monomer (2), and any one of them may be used alone, or two or more may be used in combination.
When the fluorine-containing solvent and the fluorine-free solvent are used in combination, the ratio of the fluorine-containing solvent to the total amount of the fluorine-containing solvent and the fluorine-free solvent is preferably 25% by mass or more, and more preferably 50% by mass or more.

The polymerization of the monomer (3) in the first production method is carried out in the presence of a polymerization solvent in the range of 1 to 20 times the total mass of the monomer (2) and the monomer (3), or the solvent It is preferably performed in the absence.
Here, the polymerization solvent is the total of all solvents present in the system at the time of polymerization. In the polymerization of the monomer (3), the polymerization solvent needs to contain a fluorinated solvent.
That is, in the polymerization of the monomer (3) in the presence of a fluorine-containing solvent, the total amount of the fluorine-containing solvent and the fluorine-free solvent (the amount of the fluorine-containing solvent when a fluorine-free solvent is not used) is the monomer (2 ) And the monomer (3) is preferably within a range of 1 to 20 times the total mass.

  For the polymerization of the monomer (3), a radical polymerization method is used as in the polymerization of the monomer (2). The polymerization conditions such as the polymerization temperature, the polymerization pressure, and the atmosphere during the polymerization are the same as those for the polymerization of the monomer (2). It may be the same.

In the first production method, the polymerization of the monomer (2) is preferably performed until the conversion rate of the monomer (2) becomes 80% or more. The conversion is more preferably 90% or more, and particularly preferably 95% or more. Thus, by polymerizing a certain amount of monomer (2) and then polymerizing monomer (3), the randomness of the block portion in the obtained block copolymer is lowered, and the resulting block copolymer is obtained. Performance (such as the ability to reduce the surface tension of the liquid) is improved.
In the first production method, the polymerization of the monomer (3) is preferably performed until the conversion rate of the monomer (3) becomes 80% or more. The conversion is more preferably 90% or more, and particularly preferably 95% or more. Thereby, the obtained block copolymer will be excellent in performance such as the ability to reduce the surface tension of the liquid.
Here, the conversion rate means the ratio (%) of the monomer actually used for the polymerization reaction among the used monomers (monomer (2) or (3)).
The conversion rate is determined, for example, by measuring the amount of monomer (mole) in the system before the reaction and the amount of monomer in the system after the reaction (that is, the amount of unreacted monomer) using a gas chromatograph or the like. It can ask for.
Conversion (%) = {(monomer amount in the system before reaction−monomer amount in the system after reaction) / monomer amount in the system before reaction} × 100

[Second manufacturing method]
In the production method of the second aspect of the present invention (hereinafter sometimes referred to as the second production method), the monomer (3) is added in the absence of a solvent or in the state where the compound (1) is present in the system. In this method, polymerization is carried out in the presence of a fluorine-containing solvent, and the monomer (2) is further polymerized to the resulting polymer.

In the second production method, first, the monomer (3) is polymerized in the absence of a solvent or in the presence of a fluorinated solvent while the compound (1) is present in the system.
A compound (1) may be used individually by 1 type, and may use 2 or more types together.
The amount of the compound (1) used is preferably 0.01 to 10% by mass, and 0.05 to 5% by mass with respect to the total of the monomer (2) and monomer (3) used in the production of the block copolymer. Is more preferable. When using 2 or more types of compounds (1), it is preferable that those sum total exists in the said range.

A monomer (3) may be used individually by 1 type, and may use 2 or more types together.
Although the usage-amount of a monomer (3) is not specifically limited, It is preferable that it is 3-90 mass% with respect to the sum total of the monomer (2) used for manufacture of a block copolymer, and a monomer (3). More preferably, it is -80 mass%. When using 2 or more types of monomers (3), it is preferable that those sum total exists in the said range. When the amount of the monomer (3) used is within this range, both the function of the monomer (3) and the function of the monomer (2) can be utilized.

The polymerization of the monomer (3) is carried out in the absence of a solvent or in the presence of a fluorinated solvent.
When the polymerization of the monomer (3) is carried out in the presence of a fluorine-containing solvent, examples of the fluorine-containing solvent include the same as those mentioned in the first production method, and any one of them may be used alone. Well, you may use 2 or more types together.
When the polymerization of the monomer (3) is performed in the presence of a fluorine-containing solvent, only the fluorine-containing solvent may be used as the polymerization solvent, or a fluorine-free solvent may be used in combination with the fluorine-containing solvent.
Examples of the fluorine-free solvent include the same solvents as those mentioned in the first production method, and any one of them may be used alone, or two or more may be used in combination.
When the fluorine-containing solvent and the fluorine-free solvent are used in combination, the ratio of the fluorine-containing solvent to the total amount of the fluorine-containing solvent and the fluorine-free solvent is preferably 25% by mass or more, and more preferably 50% by mass or more.

The polymerization of the monomer (3) in the second production method is performed in the presence of a polymerization solvent within a range of 0.5 to 20 times the mass of the monomer (3) or in the absence of a solvent. It is preferable.
Here, the polymerization solvent is the total of all solvents present in the system at the time of polymerization, as described above. In the polymerization of the monomer (3), the polymerization solvent needs to contain a fluorinated solvent.
That is, in the polymerization of the monomer (3) in the presence of a fluorine-containing solvent, the total amount of the fluorine-containing solvent and the fluorine-free solvent (the amount of the fluorine-containing solvent when a fluorine-free solvent is not used) is the monomer (2 ) And the total mass of the monomer (3) is preferably in the range of 0.5 to 20 times.

  For the polymerization of the monomer (3), a radical polymerization method is used as in the polymerization of the monomer (3) in the first production method, and the polymerization conditions such as the polymerization temperature, the polymerization pressure, and the atmosphere during the polymerization are as described above. 1 may be the same as the polymerization of the monomer (3) in the production method.

After the polymerization of the monomer (3), the resulting polymer is polymerized with the monomer (2).
In the second production method, as the monomer (2), one type may be used alone, or two or more types may be used in combination.
Although the usage-amount of a monomer (2) is not specifically limited, It is preferable that it is 10-97 mass% with respect to the sum total of the monomer (2) used for manufacture of a block copolymer, and a monomer (3), 20-20. More preferably, it is 95 mass%. When two or more types of monomers (2) are included, the total of them is preferably in the above range. By using the amount of monomer (2) within this range, both the function of monomer (3) and the function of monomer (2) can be utilized.

The polymerization of the monomer (2) may be performed in the absence of a solvent or may be performed in the presence of a solvent.
When the polymerization of the monomer (2) is performed in the presence of a solvent, the solvent to be used is not particularly limited as long as the raw material dissolves, and may be a fluorine-free solvent or a fluorine-containing solvent. Of these, one or two or more may be appropriately used.
Examples of the fluorine-free solvent and the fluorine-containing solvent are the same as those mentioned in the first production method.

When the polymerization of the monomer (3) is performed in the absence of a solvent and the polymerization of the monomer (2) is performed in the absence of a solvent, the polymerization of the monomer (2) is performed as it is after the polymerization of the monomer (3). Can be implemented.
When the polymerization of the monomer (3) is performed in the absence of a solvent and the polymerization of the monomer (2) is performed in the presence of a solvent, after the polymerization of the monomer (3), the solvent is added and then the monomer (2) Is polymerized.
When the polymerization of the monomer (3) is performed in the presence of a fluorine-containing solvent and the polymerization of the monomer (2) is performed in the absence of a solvent, the monomer (3) is polymerized and then the monomer (3 2) is polymerized. As a method for removing the solvent, a known method such as using an evaporator such as an evaporator can be used.
When the polymerization of the monomer (3) is performed in the presence of a fluorine-containing solvent and the polymerization of the monomer (2) is performed in the presence of a solvent, the polymerization of the monomer (2) is performed as it is after the polymerization of the monomer (3). Or a solvent may be added.

  The polymerization of the monomer (2) in the second production method is performed in the presence of a solvent within a range of 0.5 to 20 times the total mass of the monomer (2) and the monomer (3), or It is preferable to carry out in the absence of a solvent.

  For the polymerization of the monomer (2), a radical polymerization method is used as in the polymerization of the monomer (2) in the first production method. The polymerization conditions such as the polymerization temperature, the polymerization pressure, and the atmosphere during the polymerization are as described above. 1 may be the same as the polymerization of the monomer (2) in the production method.

In the second production method, the polymerization of the monomer (3) is preferably performed until the conversion rate of the monomer (3) becomes 80% or more. The conversion is more preferably 90% or more, and particularly preferably 95% or more.
In the second production method, the polymerization of the monomer (2) is preferably performed until the conversion rate of the monomer (2) becomes 80% or more. The conversion is more preferably 90% or more, and particularly preferably 95% or more.

In the first production method and the second production method of the present invention described above, when the monomer (2) and the monomer (3) are polymerized, the compound (1) is present in the system, and at least the monomer ( The polymerization in 3) is common in that it is carried out in the absence of a solvent or in the presence of a fluorinated solvent.
The polymerization performed in the presence of the compound (1) is polymerization by RAFT (Reversible Addition / Desorption Chain Transfer) method.
By polymerizing the monomer (2) and the monomer (3) in the presence of the compound (1), respectively, and at least polymerizing the monomer (3) in the absence of a solvent or in the presence of a fluorinated solvent, The effect of the present invention can be obtained. This is presumably because the precipitation of the monomer (3) hardly occurs during the polymerization, and the polymerization reaction of the monomer (3) proceeds well.

The block copolymer produced by the first production method or the second production method of the present invention is derived from the monomer (3) and a segment comprising a molecular chain containing a repeating unit derived from the monomer (2). And a segment composed of a molecular chain containing a repeating unit.
As for the molecular weight of the block copolymer, the number average molecular weight (Mn) measured by gel permeation chromatography is preferably 1,000 to 1,000,000, and 2,000 to 500,000. Is more preferable.
When added to various liquids, the block copolymer can reduce the surface tension of the liquid without being limited by the composition of the liquid. Moreover, it is excellent in solubility in various solvents. Therefore, the block copolymer can be suitably used as a surfactant.

[Compound (1)]
Compound (1) is a compound having a thiocarbonylthio group (thiocarbonylthio compound).
In the formula (1), X ¹ is a hydrogen atom, a halogen atom, an amino group, a P (O) (OH) ₂ group or a monovalent organic group.
Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

In the present invention, the “organic group” means a group containing a carbon atom.
The monovalent organic group for X ¹ is not particularly limited. Preferred organic groups include alkyl groups, alkylthio groups, alkoxy groups, dialkylamino groups, saturated hydrocarbon ring groups, unsaturated hydrocarbon ring groups, aromatic hydrocarbon ring groups, aromatic heterocyclic groups and the like.
The carbon atom in each organic group may have a substituent. Here, that a carbon atom has a substituent means that an atom or group other than a hydrogen atom is bonded to the carbon atom. Examples of the substituent include a halogen atom, an alkyl group, a hydroxy group, a carbonyl group, a carboxy group, an alkoxy group, an alkylthio group, a dialkylamino group, an amide group, and a nitro group.

  The alkyl group, alkylthio group, and alkoxy group each preferably have 1 to 10 carbon atoms, and particularly preferably have 1 to 5 carbon atoms. These groups may be linear or branched.

The alkyl group in the dialkylamino group preferably has 1 to 10 carbon atoms, and particularly preferably has 1 to 5 carbon atoms. The alkyl group may be linear or branched, and is preferably linear.
In the dialkylamino group, the two alkyl groups substituted with a nitrogen atom may have the same structure or different structures, and the ends may be bonded to each other to form a ring together.

Among the above organic groups, the ring in the ring group (saturated hydrocarbon ring group, unsaturated hydrocarbon ring group, aromatic hydrocarbon ring group, aromatic heterocyclic group) may be a single ring or 2 It may be a condensed ring in which two or more rings are condensed.
These cyclic groups preferably have 4 to 12 carbon atoms, and particularly preferably have 4 to 10 carbon atoms.
Examples of the saturated hydrocarbon ring group include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
Examples of the unsaturated hydrocarbon ring group include a cyclopentenyl group and a cyclohexenyl group.
Examples of the aromatic hydrocarbon ring group include a phenyl group, a naphthyl group, and an anthranyl group.
Examples of the aromatic heterocyclic group include a pyrrolyl group, a thienyl group, a furyl group, and a pyridyl group.

In the present invention, X ¹ in the formula (1) is a hydrogen atom, a halogen atom, an alkyl group, an alkylthio group, an alkoxy group, a dialkylamino group, a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group, an aromatic carbon It is preferably a hydrogen ring group or an aromatic heterocyclic group (however, the carbon atom in each of the above groups may have a substituent).

In the present invention, the atom bonded to carbon of the thiocarbonyl group in X ¹ is preferably a hetero atom.
Examples of the hetero atom include an oxygen atom, a nitrogen atom, a phosphorus atom, a sulfur atom, and a silicon atom, and among them, an oxygen atom or a nitrogen atom is preferable.

In the present invention, X ¹ is preferably a group represented by the following formula (6) or the following formula (7).

［式中、Ｒ^７は炭素数１〜１０のアルキル基であり；Ｒ^８、Ｒ^９はそれぞれ独立して水素原子または炭素数１〜１０のアルキル基である。］

[Wherein, R ⁷ is an alkyl group having 1 to 10 carbon atoms; R ⁸ and R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]

The alkyl group in R ⁷ , R ⁸ and R ⁹ may be linear or branched. 1-10 are preferable and, as for carbon number of this alkyl group, 1-5 are more preferable.
At least one of R ⁸ and R ⁹ is preferably an alkyl group, and more preferably both are alkyl groups.

Y ^{1 in the} compound (1) is a hydrogen atom, a halogen atom, an alkali metal atom, an NH ₄ group or a monovalent organic group.
Examples of the halogen atom for Y ¹ include the same as those mentioned for X ¹ above.
Examples of the alkali metal atom in Y ¹ include a lithium atom, a sodium atom, and a potassium atom, and a sodium atom is preferable.
When Y ¹ is an alkali metal atom or NH ₄ group, compound (1) exists as a salt.
The monovalent organic group for Y ¹ is not particularly limited, and examples thereof include the same organic groups as those described for X ¹ .
In the present invention, Y ¹ is preferably a monovalent organic group having a thiocarbonyl group, and particularly preferably a group represented by the following formula (4) or the following formula (5).

［式中、Ｘ^２、Ｘ^３はそれぞれ独立して水素原子、ハロゲン原子、アルキル基、アルキルチオ基、アルコキシ基、ジアルキルアミノ基、飽和炭化水素環基、不飽和炭化水素環基、芳香族炭化水素環基または芳香族複素環基（ただし、前記の各基中の炭素原子は置換基を有していてもよい。）を示す。］

[Wherein, X ² and X ³ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkylthio group, an alkoxy group, a dialkylamino group, a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group, or an aromatic hydrocarbon. A cyclic group or an aromatic heterocyclic group (however, the carbon atom in each of the aforementioned groups may have a substituent); ]

As the halogen atom, alkyl group, alkylthio group, alkoxy group, dialkylamino group, saturated hydrocarbon ring group, unsaturated hydrocarbon ring group, aromatic hydrocarbon ring group or aromatic heterocyclic group in X ² and X ³ , the same as those mentioned above for X ¹ can be mentioned.

In the present invention, X ¹ in the formula (1) is a hydrogen atom, a halogen atom, an alkyl group, an alkylthio group, an alkoxy group, a dialkylamino group, a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group, an aromatic carbonization. A hydrogen ring group or an aromatic heterocyclic group (wherein the carbon atom in each group may have a substituent), and Y ¹ is represented by the formula (4) or the formula (5). It is preferable that it is group represented.
That is, the compound (1) is preferably represented by the following formula (1 ′) or the following formula (1 ″).

［式中、Ｘ^１１〜Ｘ^１３はそれぞれ独立して水素原子、ハロゲン原子、アルキル基、アルキルチオ基、アルコキシ基、ジアルキルアミノ基、飽和炭化水素環基、不飽和炭化水素環基、芳香族炭化水素環基または芳香族複素環基（ただし、前記の各基中の炭素原子は置換基を有していてもよい。）を示す。］

[Wherein, X ^{11 to} X ¹³ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkylthio group, an alkoxy group, a dialkylamino group, a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group, or an aromatic hydrocarbon. A cyclic group or an aromatic heterocyclic group (however, the carbon atom in each of the aforementioned groups may have a substituent); ]

Examples of X ^{11 to} X ¹³ include the same as X ² and X ³ .

  Particularly preferred as the compound (1) is a compound represented by the following formula (1-1), the following formula (1-2) or the following formula (1-3).

［式中、Ｒ^７は炭素数１〜１０のアルキル基であり；Ｒ^８、Ｒ^９はそれぞれ独立して水素原子または炭素数１〜１０のアルキル基である。］

[Wherein, R ⁷ is an alkyl group having 1 to 10 carbon atoms; R ⁸ and R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]

^{R 7} in the formula (1-1) is the same as ^{R 7} in the formula (6), the two ^{R 7} may be the same, respectively, may be different.
^R 8, ^{R 9} in the formula (1-2) to (1-3) are each same as ^R 8, ^{R 9} in the formula (7), the two ^R 8, ^{R 9} respectively the same May be different or different.

[Monomer (2)]
The monomer (2) is a polymerizable compound having at least one polymerizable group.
R ¹ in Formula (2) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms.
The halogen atom, the same groups in the X ¹ can be mentioned.
The alkyl group in R ¹ may be linear or branched. 1-4 are preferable and, as for carbon number of this alkyl group, 1 is especially preferable.
The fluoroalkyl group is a group in which one or more hydrogen atoms of the alkyl group are substituted with a fluorine atom.
R ¹ is preferably a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

A in Formula (2) is —O— or —NR ³ — (R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
The alkyl group in —NR ³ — may be linear or branched.
A is preferably -O-.

R ² in the formula (2) is a hydrogen atom or a monovalent group.
The monovalent group is not particularly limited, and for example, a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group, an aromatic hydrocarbon ring group, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, a silyl group (trialkyl) Silyl group, etc.), alkoxy group, isocyanate group and the like.

Examples of the monomer (2) include the following compounds (2-1) to (2-8).
_{CH 2 = C (R) -COO} -R '... (2-1)
_{CH 2 = C (R) -COO-} (Ak) m - (O) l -Cyc ... (2-2)
_{CH 2 = C (R) -COO-} (Ak) m - (AkO) n -R '... (2-3)
_{CH 2 = C (R) -COO-} (Ak) m - (AkO) n -Cyc ... (2-4)
_{CH 2 = C (R) -COO-} (Ak) m - (AkO) n - (Ak) m -OCO-C (R) = CH 2 ... (2-5)
_{CH 2 = C (R) -COO-} (Ak) m -OP (O) (OH) 2 ... (2-6)
_{CH 2 = C (R) -COO-} (Ak) m -Si ((O) p R ') 3 ... (2-7)
_{CH 2 = C (R) -CONR} -R '... (2-8)

In the above formulas (2-1) to (2-8), R and R ′ are each independently a hydrogen atom or a chain aliphatic hydrocarbon group having 1 to 22 carbon atoms.
The aliphatic hydrocarbon group may be linear or branched. The hydrogen atom in the group may be substituted with a hydroxy group, a halogen atom, a carboxy group or an isocyanate group. The carbon atom in the group may be substituted with -O-, -NR- (R is as defined above) or -CO-.
Cyc is a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group or an aromatic hydrocarbon ring group. The carbon atom in each of these groups may be substituted with —O— or —NR— (R is as defined above).
Ak is an alkylene group having 1 to 10 carbon atoms. The alkylene group may be linear or branched. When a plurality of Ak are present in one molecule, each Ak may be the same or different.
l is an integer of 0 or 1.
m is an integer of 0 or 1.
n is an integer of 1-50.
p is an integer of 0 or 1.

  These compounds are commercially available, Kyoeisha Chemical Co., Ltd. light ester, light acrylate, Kojin Co., Ltd. monomer product, Showa Denko Co., Ltd., Nippon Oil & Fat Co., Bremer, Shin-Nakamura Chemical Co., Ltd. NK ester, Chisso Corporation Each brand product such as Silaplane can be used or its equivalent.

Among these, more specifically preferred structures include the following compounds.
Methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, n-stearyl methacrylate, isostearyl methacrylate, behenyl methacrylate, cyclohexyl methacrylate , T-butylcyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, isobornyl methacrylate.

  Acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, isoamyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, lauryl acrylate, isomyristyl acrylate, stearyl acrylate, isostearyl acrylate, behenyl acrylate , Cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, isobornyl acrylate.

  2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, glycerin methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, glycerin acrylate, polyethylene glycol Methacrylate (EO number average 1 to 45), polyethylene glycol acrylate (EO number: average 1 to 45), methoxy polyethylene glycol methacrylate (EO number average 1 to 45), methoxy polyethylene glycol acrylate (EO number average 1 to 45), polypropylene Glycol methacrylate (PO number average 1 to 22), Polypropylene glycol acrylate (PO number average 1 to 1) 2), poly (ethylene glycol-propylene glycol) methacrylate (EO number average 1 to 22, PO number average 1 to 22), poly (ethylene glycol-propylene glycol) acrylate (EO number average 1 to 22, PO number average 1 to 2) 22), polyethylene glycol dimethacrylate (EO number average of 1 to 22), polyethylene glycol diacrylate (EO number average of 1 to 22), poly (ethylene glycol-tetramethylene glycol) methacrylate (EO number average of 1 to 22, BO number average) 1-22), poly (ethylene glycol-tetramethylene glycol) acrylate (EO number average 1-22, BO number average 1-22), poly (propylene glycol-tetramethylene glycol) methacrylate (PO number average 1-22, BO Number average 1-22 , Poly (propylene glycol-tetramethylene glycol) acrylate (PO number average 1-22, BO number average 1-22), ethoxydiethylene glycol monoacrylate octoxypolyethylene glycol polypropylene glycol methacrylate (EO number average 1-22, PO number average 1) -12), octoxy polyethylene glycol polypropylene glycol acrylate (EO number average 1 to 22, PO number average 1 to 12), lauroxy polyethylene glycol methacrylate (EO number average 1 to 22), lauroxy polyethylene glycol acrylate (EO number average) 1 to 22), stearoxy polyethylene glycol methacrylate (EO number average 1 to 22), phenoxy polyethylene glycol acrylate (EO number average 1 to 22), Alkoxy polyethylene glycol methacrylate (EO average number 1-22).

  Glycidyl methacrylate, glycidyl acrylate, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl 2-hydroxypropyl phthalate, 2-acryloyloxyethyl succinic acid, 2-acrylic acid Leuoxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, neopentyl glycol acrylic acid benzoate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate.

  n-butoxyethyl methacrylate, butoxydiethylene glycol methacrylate, phenoxyethyl methacrylate, butoxyethyl acrylate, ethoxy-diethylene glycol acrylate, 2-ethylhexyl-diglycol acrylate phenoxyethyl acrylate, phenoxy polyethylene glycol acrylate (EO number average 1 to 22), 2-hydroxy -3-phenoxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, N, N-dimethylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropylacrylamide , Acryloylmorpholine, N-isopropyl acrylate Amide, N, N-diethylacrylamide, 2-methacryloyloxyethyl isocyanate, methacrylic acid-2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl, diacetone acrylamide, acryloxymethyltrimethylsilane, (3 -Acryloxypropyl) dimethylmethoxysilane, (3-acryloxypropyl) trichlorosilane.

In the above, EO number average, PO number average, and BO number average are an ethylene oxide repeating unit (—CH ₂ CH ₂ O—), a propylene oxide repeating unit, and a butylene oxide repeating contained in one molecule of the compound, respectively. The average number of moles of units.

  The monomer (2) preferably has a molecular weight of less than 10,000, and more preferably less than 5,000. When the molecular weight is less than 10,000, the solubility of the resulting block copolymer in various solvents is improved.

  The monomer (2) can be appropriately selected from known compounds according to the performance required for the block copolymer.

[Monomer (3)]
The monomer (3) is a polymerizable compound having at least one polymerizable group and a perfluoroalkyl group.
Rf in Formula (3) is a C 1-6 perfluoroalkyl group. The perfluoroalkyl group is a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms. The perfluoroalkyl group may be linear or branched, and is preferably linear.
4-6 are preferable and, as for carbon number of Rf, 6 is more preferable.

R ⁴ in the formula (3) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms. Specifically, R 4 in the formula (2) The same thing as ¹ is mentioned.
R ⁴ is preferably a hydrogen atom, a halogen atom, a methyl group, or a trifluoromethyl group, and more preferably a hydrogen atom or a methyl group.

B in the formula (3) is —O— or —NR ⁶ — (R ⁶ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), specifically, in the formula (2) The thing similar to A of A is mentioned.
-B is preferably -O-.

R ⁵ in Formula (3) is a single bond or a divalent linking group.
If R ⁵ is a single bond, it means a B at the left end of the R ⁵ in formula (3), that the Rf at the far right of the R ⁵ are directly bonded.

As the divalent linking group, a divalent chain aliphatic hydrocarbon group, a divalent cyclic aliphatic hydrocarbon group, a divalent aromatic ring group, a divalent heterocyclic group, -O-, —S—, —NH—, —NR ¹⁰ — (wherein R ¹⁰ is an alkyl group having 1 to 5 carbon atoms), —SO ₂ —, —PO ₂ —, —CH═N—, —N Examples include groups such as ═N—, —N (O) ═N—, —CO—, —CH (OH) —, and combinations of these groups.
Moreover, these groups may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a halogen atom, and a cyano group.

R ⁵ is preferably a divalent linking group, and the divalent linking group is preferably a divalent chain aliphatic hydrocarbon group.
The divalent chain aliphatic hydrocarbon group may be linear or branched.
Examples of the divalent chain aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group, but an alkylene group is preferable. As the alkylene group, a linear alkylene group having 1 to 5 carbon atoms is preferable.

Examples of the monomer (3) include, but are not limited to, the following compounds.
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 4 -F,
_{CH 2 = CH-COO- (CH} 2) 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 - (CF 2) 6 -F,
_{CH 2 = CH-COO- (CH} 2) 3 - (CF 2) 4 -F,
_{CH 2 = CH-COO- (CH} 2) 3 - (CF 2) 6 -F,
_{CH 2 = CH-COO-CH} 2 CH (OH) CH 2 - (CF 2) 4 -F,
_{CH 2 = CH-COO-CH} 2 CH (OH) CH 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 3 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 3 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -COO-CH 2 CH (OH) CH 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -COO-CH 2 CH (OH) CH 2 - (CF 2) 6 -F,
_{CH 2 = CH-COO-CH} 2 CH 2 N (CH 3) -SO 2 - (CF 2) 4 -F,
_{CH 2 = CH-COO-CH} 2 CH 2 N (CH 3) -SO 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -COO-CH 2 CH 2 N (CH 3) -SO 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -COO-CH 2 CH 2 N (CH 3) -SO 2 - (CF 2) 6 -F,
_{CH 2 = CH-COO-CH} 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 4 -F,
_{CH 2 = CH-COO-CH} 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -COO-CH 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -COO-CH 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 6 -F,
_{CH 2 = CH-COO- (CH} 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 4 F,
_{CH 2 = CH-COO- (CH} 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 6 F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 4 F,
_{CH 2 = C (CH 3)} -COO- (CH 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 6 F,

_{CH 2 = CH-CONH- (CH} 2) 2 - (CF 2) 4 -F,
_{CH 2 = CH-CONH- (CH} 2) 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -CONH- (CH 2) 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -CONH- (CH 2) 2 - (CF 2) 6 -F,
_{CH 2 = CH-CONH- (CH} 2) 3 - (CF 2) 4 -F,
_{CH 2 = CH-CONH- (CH} 2) 3 - (CF 2) 6 -F,
_{CH 2 = CH-CONH-CH} 2 CH (OH) CH 2 - (CF 2) 4 -F,
_{CH 2 = CH-CONH-CH} 2 CH (OH) CH 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -CONH- (CH 2) 3 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -CONH- (CH 2) 3 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -CONH-CH 2 CH (OH) CH 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -CONH-CH 2 CH (OH) CH 2 - (CF 2) 6 -F,
_{CH 2 = CH-CONH-CH} 2 CH 2 N (CH 3) -SO 2 - (CF 2) 4 -F,
_{CH 2 = CH-CONH-CH} 2 CH 2 N (CH 3) -SO 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -CONH-CH 2 CH 2 N (CH 3) -SO 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -CONH-CH 2 CH 2 N (CH 3) -SO 2 - (CF 2) 6 -F,
_{CH 2 = CH-CONH-CH} 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 4 -F,
_{CH 2 = CH-CONH-CH} 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 6 -F,
_{CH 2 = C (CH 3)} -CONH-CH 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 4 -F,
_{CH 2 = C (CH 3)} -CONH-CH 2 CH 2 N (C 2 H 5) -SO 2 - (CF 2) 6 -F,
_{CH 2 = CH-CONH- (CH} 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 4 F,
_{CH 2 = CH-CONH- (CH} 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 6 F,
_{CH 2 = C (CH 3)} -CONH- (CH 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 4 F,
_{CH 2 = C (CH 3)} -CONH- (CH 2) 2 -N (CH 2 CH 2 CH 3) -SO 2 - (CF 2) 6 F

<Surfactant>
The surfactant of the present invention contains a block copolymer (hereinafter sometimes referred to as a block copolymer (A)) obtained by the production method of the present invention.
The surfactant may contain one type of block copolymer (A) or two or more types.
0.001-80 mass% is preferable with respect to the total mass of the said surfactant, and, as for content of the block copolymer (A) in surfactant, 0.005-70 mass% is more preferable. When the content of the block copolymer (A) is within the above range, effects such as excellent surface tension reducing ability, improved viscosity, and easy handling are obtained.
When using 2 or more types of block copolymers (A), it is preferable that the total amount is in the said range.

The surfactant of the present invention may contain a solvent, other additives and the like in addition to the block copolymer (A).
Examples of the solvent include water and organic solvents.
Examples of the organic solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol and t-butanol, esters such as ethyl acetate, methyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, Polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, glycol ethers such as diethylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, glycols such as ethylene glycol and propylene glycol, diethyl ether, tetrahydrofuran , Ethers such as dioxane, nitrogen-containing solvents such as pyridine and piperazine, paraffins such as hexane, octane, decane and isohexane S, toluene, aromatic hydrocarbons such as xylene, a fluorine-containing solvents. Examples of the fluorinated solvent include the same fluorinated solvents as mentioned in the production method of the present invention.
A solvent may be used individually by 1 type and may use 2 or more types together.
Other additives are not particularly limited, and may be appropriately selected depending on the use of the surfactant.

By adding the surfactant of the present invention to various liquids, the surface tension of the liquid can be lowered without being restricted by the solvent composition of the liquid. Moreover, functions, such as leveling property, permeability, foaming property, washing | cleaning property, and emulsifying property, can be provided to the liquid by the surface tension reducing ability.
The surfactant of the present invention can exhibit a sufficient surface tension reducing ability even when added in a small amount.
Therefore, the surfactant of the present invention can be used for various applications. Examples of the use include penetrants, wettability improvers, leveling agents, paint / pigment additives, emulsifiers, fire extinguishing agents, floor waxes, cleaning agents, foaming agents, and antifoaming agents.

The surfactant of the present invention is suitably used as a leveling agent among the above various uses.
When the surfactant of the present invention is used as a leveling agent, the leveling agent contains the surfactant of the present invention.
The leveling agent may be composed of the surfactant of the present invention, and may contain components other than the surfactant of the present invention, such as a solvent and other additives, if necessary.
As a solvent, the thing similar to what was mentioned as a solvent which the surfactant of this invention may contain is mentioned.
Other additives include various resins, various surfactants other than the surfactant of the present invention, coupling agents, metal oxides, antioxidants, antistatic agents, rust preventives, antifogging agents, and ultraviolet ray preventing agents. And a photosensitizer.

  According to the leveling agent containing the surfactant of the present invention, printing materials, photosensitive materials, paints, optical materials, coating materials such as floor waxes, resists, water glass, cleaning agents, etching solutions, plating solutions, adhesives Leveling properties can be imparted to the various compositions without being affected by other components in the various compositions such as rust preventives and agricultural chemicals.

Further, the surfactant of the present invention is suitably used in a surface tension reducing method for reducing the surface tension of a liquid.
The surface tension reducing method using the surfactant of the present invention can be carried out by performing a step of adding the surfactant of the present invention to a liquid.

As the liquid, water and an organic solvent are preferable, and an organic solvent is more preferable. Examples of the organic solvent include the same solvents as those described above as the solvent that the surfactant of the present invention may contain.
When the surfactant contains a solvent, the solvent and the liquid that lowers the surface tension by the surfactant may be the same or different as long as there is no problem in solubility.

  Liquids include various resins, hydrocarbon surfactants, silicone surfactants, fluorine surfactants excluding the surfactant composition of the present invention, silane coupling agents, titanium coupling agents, metal oxidation Products, antistatic agents, rust preventive agents, antifogging agents, ultraviolet ray preventive agents, photosensitive agents, and the like may be added.

  The amount of the surfactant of the present invention added to the liquid is preferably such that the content of the block copolymer (A) in the surfactant is 0.001 to 10% by mass with respect to 100% by mass of the liquid, 0 An amount of 0.005 to 5% by mass is more preferable.

  According to the surface tension reducing method, the surface tension of the liquid can be reduced by the action of the block copolymer (A) without being restricted by the solvent composition of the liquid. Moreover, functions, such as leveling property, osmosis | permeability, foamability, washing | cleaning property, emulsifying property, can be provided to the liquid by the ability to reduce the surface tension.

Specific examples are shown below.
In the following, the conversion rate was determined using a gas chromatograph.
The solid content concentration of the solution was determined by the volume method.
The molecular weight (number average molecular weight (Mn)) of the polymer was measured using gel permeation chromatography (GPC-101, Showa Denko KK) based on polymethyl methacrylate.

In addition, the reagents used are as follows unless otherwise specified.
2-perfluorohexyl ethyl acrylate: synthesized by a known method from 2-perfluorohexyl ethanol. Hereinafter referred to as C6FA.
2-perfluorohexylethyl methacrylate: synthesized from 2-perfluorohexylethanol by a known method. Hereinafter, it is referred to as C6FMA.
3-perfluorohexyl-2-hydroxypropyl acrylate: manufactured by Daikin Chemicals. Hereinafter, it is referred to as C6FA-OH.
3-perfluorohexyl-2-hydroxypropyl methacrylate: manufactured by Daikin Chemicals. Hereinafter, it is described as C6FMA-OH.

Isoamyl acrylate: manufactured by Kyoei Chemical Co., Ltd.
Octoxy polyethylene glycol polypropylene glycol monoacrylate (EO number average 8, PO number average 6): manufactured by NOF Corporation. Hereinafter, it is described as 50AOEP-800B.
2-Ethylhexyl acrylate: manufactured by Aldrich. Hereinafter, it is described as 2-EHA.
N, N-dimethylaminopropylacrylamide: manufactured by Kojin. Hereinafter, it is referred to as DMAPAA.
2-hydroxypropyl acrylate: manufactured by Kyoeisha Chemical. Hereinafter, it is described as HOP-A.
Polyethylene glycol monoacrylate (EO number average 4.5): manufactured by NOF Corporation. Hereinafter, it is described as AE-200.
Polyethylene glycol monoacrylate (EO number average 10): manufactured by Nippon Oil & Fats. Hereinafter, it is described as AE-400.
Methoxypolyethylene glycol acrylate (EO number average 9): manufactured by Kyoeisha Chemical. Hereinafter, it is described as 130A.

Isopropylxanthic disulfide: manufactured by Wako Pure Chemical Industries. Hereinafter, it is described as IP-DS. IP-DS is a compound in which all R ⁷ in the formula (1-1) are isopropyl groups.
Tetramethylthiuram disulfide: manufactured by Wako Pure Chemical Industries. Hereinafter, it is described as TT-DS. TT-DS is a compound in which R ⁸ and R ⁹ in the formula (1-2) are all methyl groups.
Octanethiol: Wako Pure Chemical Industries

Meta-xylene hexafluoride: Made of Miteni. Hereinafter, it is described as m-XHF.
Ethyl acetate: manufactured by Wako Pure Chemical Industries.
Methyl ethyl ketone: manufactured by Wako Pure Chemical Industries. Hereinafter referred to as MEK.
HCFC-225: Made by Asahi Glass. Hereinafter referred to as AK-225.

  Dimethyl 2,2'-azobis (2-methylpropionate): manufactured by Wako Pure Chemical Industries. Hereinafter referred to as V-601.

[Example 1]
A 100 ml pressure glass bottle was charged with 22.65 g of isoamyl acrylate, 0.34 g of IP-DS, 0.19 g of V-601 and 36.9 g of m-XHF, sealed, and then heated at 70 ° C. for 16 hours. . At this stage, the conversion of isoamyl acrylate in the reaction solution was 99.8%, and the solid content concentration was 38.2%. Further, the molecular weight Mn of the polymer in the reaction solution was 11,376.
15.50 g of this reaction solution, 1.59 g of C6FA, 3.08 g of m-XHF, and 0.038 g of V-601 were charged in a 50 ml pressure-resistant glass bottle, sealed, and then heated at 70 ° C. for 16 hours. In the obtained reaction solution, the conversion of C6FA was over 99%, and the solid content concentration was 37.3%. The molecular weight Mn of the polymer (block copolymer) in the reaction solution was 19,708.

[Example 2]
A 100 ml pressure glass bottle was charged with 22.65 g of 50AOEP-800B, 0.33 g of IP-DS, 36.88 g of m-XHF, and 0.18 g of V-601, and then sealed and heated at 70 ° C. for 16 hours. did. The solid content concentration of the reaction solution at this stage was 38.9%.
18.11 g of this reaction solution, 1.88 g of C6FA, and 0.048 g of V-601 were charged into a 50 ml pressure-resistant glass bottle, sealed, and then heated at 70 ° C. for 16 hours. In the obtained reaction solution, the conversion of C6FA was over 99%, and the solid content concentration was 44.1%. In addition, the molecular weight Mn of the polymer (block copolymer) in the reaction solution was 6,775.

[Example 3]
A 100 ml pressure glass bottle was charged with 15.34 g of 2-EHA, 1.71 g of DMAPAA, 0.23 g of IP-DS, 42.62 g of m-XHF, and 0.13 g of V-601, and sealed. Heated at 70 ° C. for 16 hours. At this stage, the conversion rate of 2-EHA in the reaction solution was 98.5%, and the solid content concentration was 28.7%. Further, the molecular weight Mn of the polymer in the reaction solution was 11,210.
9.65 g of this reaction solution, 0.75 g of C6FA, 9.64 g of m-XHF, and 0.020 g of V-601 were charged into a 50 ml pressure-resistant glass bottle, sealed, and then heated at 70 ° C. for 16 hours. In the obtained reaction solution, the conversion of C6FA was 96.2%, and the solid content concentration was 17.7%. Moreover, the molecular weight Mn of the polymer (block copolymer) in the reaction solution was 13,217.

[Example 4]
A 100 ml glass bottle was charged with 13.28 g of 2-EHA, 13.28 g of HOP-A, 0.18 g of IP-DS, 33.19 g of MEK, and 0.11 g of V-601, and after sealing, 70 Heat at 16 ° C. for 16 hours. The conversion rate of HOP-A in the reaction solution at this stage was 99.4%, the conversion rate of 2-EHA was 98.2%, and the solid content concentration was 45.2%. Further, the molecular weight Mn of the polymer in the reaction solution was 17,553.
12.34 g of this reaction solution, 1.47 g of C6FA, 6.17 g of AK-225, and 0.034 g of V-601 were charged into a 50 ml pressure-resistant glass bottle, sealed, and then heated at 70 ° C. for 16 hours. In the obtained reaction solution, the conversion of C6FA was 97.2%, and the solid content concentration was 37.8%. The molecular weight Mn of the polymer (block copolymer) in the reaction solution was 22,166.

[Example 5]
A 100 ml pressure glass bottle was charged with 8.57 g of 2-EHA, 8.56 g of AE-200, 0.058 g of IP-DS, 42.86 g of MEK, and 0.034 g of V-601, and sealed. Heated at 70 ° C. for 16 hours. At this stage, the conversion rate of 2-EHA in the reaction solution was 95.9%, and the solid content concentration was 29.1%. The molecular weight Mn of the polymer in the reaction solution was 14,692.
The reaction solution (11.02 g), C6FA (1.24 g), m-XHF (10.00 g), and V-601 (0.030 g) were charged in a 50 ml pressure-resistant glass bottle, sealed, and then heated at 70 ° C. for 16 hours. In the obtained reaction solution, the conversion rate of C6FA was 96.5%, and the solid content concentration was 9.67%. The molecular weight Mn of the polymer (block copolymer) in the reaction solution was 22,645.

[Example 6]
A 100 ml pressure glass bottle was charged with 8.51 g of 2-EHA, 8.51 g of AE-400, 0.23 g of IP-DS, 42.69 g of ethyl acetate, and 0.28 g of V-601, and sealed to 70. Heat at 16 ° C. for 16 hours. At this stage, the conversion rate of 2-EHA in the reaction solution was 97.6%, and the solid content concentration was 29.5%. Further, the molecular weight Mn of the polymer in the reaction solution was 9,797.
9.50 g of this reaction solution, 0.75 g of C6FA, 9.64 g of m-XHF, and 0.022 g of V-601 were charged in a 50 ml glass bottle, sealed, and then heated at 70 ° C. for 16 hours. In the obtained reaction solution, the conversion of C6FA was 97.9% and the solid content concentration was 18.4%. The molecular weight Mn of the polymer (block copolymer) in the reaction solution was 11,701.

[Example 7]
A 100 ml pressure-resistant glass bottle was charged with 8.55 g of 2-EHA, 8.59 g of 130A, 0.12 g of IP-DS, 42.68 g of MEK, and 0.14 g of V-601, and sealed at 16O <0> C at 16O <0> C. Heated for hours. At this stage, the conversion of 2-EHA in the reaction solution was 98.0%, and the solid content concentration was 29.34%. Further, the molecular weight Mn of the polymer in the reaction solution was 7,663.
9.63 g of this reaction solution, 0.75 g of C6FA, 9.62 g of m-XHF, and 0.02 g of V-601 were charged into a 50 ml glass bottle, sealed, and then heated at 70 ° C. for 16 hours. In the obtained reaction solution, the conversion of C6FA was 97.9%, and the solid content concentration was 18.2%. Moreover, the molecular weight Mn of the polymer (block copolymer) in the reaction solution was 8,639.

[Example 8]
A 500 ml pressure-resistant glass bottle was charged with 184.3 g of 2-EHA, 2.72 g of IP-DS, 200.5 g of m-XHF, and 1.15 g of V-601, sealed, and then heated at 70 ° C. for 16 hours. did. At this stage, the conversion rate of 2-EHA in the reaction solution was 99.2%, and the solid content concentration was 49.5%. Moreover, the molecular weight Mn of the polymer in the reaction solution was 13,200.
31.91 g of this reaction solution, 4.00 g of C6FMA, 3.99 g of m-XHF, and 0.12 g of V-601 were charged in a 100 ml glass bottle, sealed, and then stirred at 70 ° C. for 16 hours. In the obtained reaction solution, the conversion rate of C6FMA was 95.3%, and the solid content concentration was 48.3%. The molecular weight Mn of the polymer (block copolymer) in the reaction solution was 14,860.

[Example 9]
A 100 ml pressure glass bottle was charged with 8.53 g of 2-EHA, 8.53 g of AE-200, 0.22 g of TT-DS, 42.57 g of MEK, and 0.17 g of V-601, and sealed. Heated at 70 ° C. for 16 hours. Furthermore, 0.18 g of V-601 was added, and after sealing, it was heated at 70 ° C. for 16 hours. At this stage, the conversion of 2-EHA in the reaction solution was 97.6%, and the solid content concentration was 29.2%. Further, the molecular weight Mn of the polymer in the reaction solution was 8,451.
9.63 g of this reaction solution, 0.74 g of C6FA, 9.89 g of m-XHF, and 0.02 g of V-601 were charged in a 100 ml pressure-resistant glass bottle, sealed, and then heated at 70 ° C. for 16 hours. In the obtained reaction solution, the conversion of C6FA was 96.8%, and the solid content concentration was 17.8%. The molecular weight Mn of the polymer (block copolymer) in the reaction solution was 9,729.

[Example 10]
A 100 ml pressure-resistant glass bottle was charged with 17.04 g of 2-EHA, 0.23 g of TT-DS, 42.58 g of MEK, and 0.17 g of V-601, and heated at 70 ° C. for 16 hours after sealing. Furthermore, 0.10 g of V-601 was added, and after sealing, it was heated at 70 ° C. for 16 hours. At this stage, the conversion rate of 2-EHA in the reaction solution was 97.3%, and the solid content concentration was 28.6%. The molecular weight Mn of the polymer in the reaction solution was 8,208.
9.64 g of this reaction solution, 0.73 g of C6FA, 9.66 g of m-XHF, and 0.02 g of V-601 were charged into a 100 ml pressure-resistant glass bottle, sealed, and then heated at 70 ° C. for 16 hours. In the obtained reaction solution, the conversion of C6FA was 97.0%, and the solid content concentration was 18.0%. The molecular weight Mn of the polymer (block copolymer) in the reaction solution was 9,496.

[Example 11]
A 500 ml pressure-resistant glass bottle was charged with 184.3 g of 2-EHA, 2.72 g of IP-DS, 200.5 g of m-XHF, and 1.15 g of V-601, sealed, and then heated at 70 ° C. for 16 hours. did. At this stage, the conversion rate of 2-EHA in the reaction solution was 99.2%, and the solid content concentration was 49.5%. Moreover, the molecular weight Mn of the polymer in the reaction solution was 13,200.
20. The reaction solution (20.78 g), C6FMA-OH (2.60 g), m-XHF (16.56 g), and V-601 (0.07 g) were charged into a 100 ml pressure-resistant glass bottle, sealed, and then heated at 70 ° C. for 16 hours. . In the obtained reaction solution, the conversion rate of C6FMA-OH was 95.2%, and the solid content concentration was 31.9%. The molecular weight Mn of the polymer (block copolymer) in the reaction solution was 13,686.

[Example 12]
A 500 ml pressure-resistant glass bottle was charged with 184.3 g of 2-EHA, 2.72 g of IP-DS, 200.5 g of m-XHF, and 1.15 g of V-601, sealed, and then heated at 70 ° C. for 16 hours. did. At this stage, the conversion rate of 2-EHA in the reaction solution was 99.2%, and the solid content concentration was 49.5%. Moreover, the molecular weight Mn of the polymer in the reaction solution was 13,200.
The reaction solution (22.41 g), C6FA-OH (1.27 g), m-XHF (16.35 g) and V-601 (0.04) were charged into a 100 ml pressure-resistant glass bottle, sealed, and then heated at 70 ° C. for 16 hours. . In the obtained reaction liquid, the conversion rate of C6FA-OH was 96.3%, and the solid content concentration was 30.38%. Moreover, the molecular weight Mn of the polymer (block copolymer) in the reaction solution was 14,917.

[Comparative Example 1]
7.90 g of 2-EHA, 2.08 g of C6FA, 0.12 g of octanethiol, 19.76 g of m-XHF, 0.16 g of V-601 were charged in a 100 ml pressure-resistant glass bottle and sealed, then 70 ° C. For 16 hours. In the obtained reaction solution, the conversion rate of 2-EHA was 99.4%, and C6FA was not detected by gas chromatography. Moreover, the solid content concentration of the reaction solution was 33.6%, and the molecular weight Mn of the obtained polymer was 9,524.

[Comparative Example 2]
2.95 g of 2-EHA, 3.96 g of C6FMA, 0.13 g of octanethiol, 19.79 g of m-XHF, 0.16 g of V-601 were charged into a 100 ml pressure-resistant glass bottle and sealed, then 70 ° C. For 16 hours. In the obtained reaction liquid, the conversion of 2-EHA was 99.0%, and C6FMA was not detected by gas chromatography. Moreover, the solid content concentration of the reaction solution was 33.7%, and the molecular weight Mn of the obtained polymer was 8,870.

[Comparative Example 3]
2.96 g of 2-EHA, 4.00 g of AE-200, 2.10 g of C6FA, 0.12 g of octanethiol, 9.87 g of MEK, 9.87 g of m-XHF, 0.15 g of V-601 Was placed in a 100 ml pressure-resistant glass bottle, sealed, and then heated at 70 ° C. for 16 hours. In the obtained reaction solution, 2-EHA and C6FA were not detected by gas chromatography. Moreover, the solid content concentration of the reaction solution was 33.9%, and the molecular weight Mn of the obtained polymer was 13,294.

[Comparative Example 4]
2.95 g 2-EHA, 3.95 g HOP-A, 2.09 g C6FA, 0.12 g octanethiol, 9.86 g MEK, 9.87 g AK-225, 0.16 g V-601 Was placed in a 100 ml pressure-resistant glass bottle, sealed, and then heated at 70 ° C. for 16 hours. In the obtained reaction solution, the conversion rate of 2-EHA was 98.9%, and C6FA was not detected by gas chromatography. Moreover, the solid content concentration of the reaction solution was 34.3%, and the molecular weight Mn of the obtained polymer was 9,025.

[Comparative Example 5]
2-EHA (7.12 g), DMAPAA (0.80 g), C6FA (2.09 g), Octanethiol (0.12 g), m-XHF (19.75 g), V-601 (0.16 g) were charged into a 100 ml pressure-resistant glass bottle and sealed. And heated at 70 ° C. for 16 hours. In the obtained reaction solution, the conversion rate of 2-EHA was 99.0%, and C6FA was not detected by gas chromatography. Further, the solid content concentration of the reaction solution was 33.9%, and the molecular weight Mn of the obtained polymer was 18,594.

[Comparative Example 6]
50AOEP-800B (7.91 g), C6FA (2.09 g), octanethiol (0.13 g), m-XHF (19.75 g), V-601 (0.15 g) were charged in a 100 ml pressure-resistant glass bottle and sealed, then 70 ° C. For 16 hours. C6FA was not detected by gas chromatography in the obtained reaction solution. Moreover, the solid content concentration of the reaction solution was 33.5%, and the molecular weight Mn of the obtained polymer was 6,597.

[Comparative Example 7]
2-EHA (55.28 g), IP-DS (8.11 g), ethyl acetate (200.00 g), and V-601 (3.45 g) were charged in a 500 ml pressure-resistant glass bottle and heated at 70 ° C. for 16 hours. The obtained solution was evaporated at 70 ° C. to obtain a highly viscous liquid. The molecular weight Mn of the polymer in this viscous liquid was 14,384.
5.00 g of this viscous liquid, 5.02 g of C6FA, and 29.98 g of ethyl acetate were charged into a 100 ml pressure glass bottle and heated at 70 ° C. for 16 hours. As a result, the solution was separated into two layers, and a uniform solution was not obtained.

[Evaluation]
The ethyl acetate solutions of the polymers obtained in Examples 1-12 and Comparative Examples 1-6 were prepared, and the static surface tension of the ethyl acetate solutions was measured. Measurement was performed using an automatic surface tension meter CBVP-A3 type (manufactured by Kyowa Interface Chemical Co., Ltd.). The results are shown in Tables 1-3.
The numbers in the leftmost column in Tables 1 to 3 are the concentration (mass%) of the polymer in the ethyl acetate solution, and each numerical value in the table represents the value of the static surface tension (unit “mN / m”). means.

  From these results, it was confirmed that a block copolymer having excellent surface tension reducing ability could be produced even at a low concentration by the production method of the present invention.

Claims (6)

In the state where the compound represented by the following formula (1) is present in the system, the monomer represented by the following formula (2) is polymerized, and the resulting polymer is further represented by the following formula (3). A surfactant containing a block copolymer obtained by polymerizing a monomer in the absence of a solvent or in the presence of a fluorine-containing solvent.

[Wherein, X ¹ is a hydrogen atom, halogen atom, amino group, P (O) (OH) ₂ group or monovalent organic group; Y ¹ is a hydrogen atom, halogen atom, alkali metal atom, NH ₄ group Or R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms; R ² is a hydrogen atom or a monovalent group. Yes; A represents —O— or —NR ³ — (R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms); R ⁴ represents a hydrogen atom, a halogen atom, or an alkyl having 1 to 5 carbon atoms. R ⁵ is a single bond or a divalent linking group; B is —O— or —NR ⁶ — (R ⁶ is a hydrogen atom or a carbon number of 1 to 5; And Rf is a perfume having 1 to 6 carbon atoms. Is a Oroarukiru group. ] In the state where the compound represented by the following formula (1) is present in the system, the monomer represented by the following formula (3) is polymerized in the absence of a solvent or in the presence of a fluorinated solvent, and the resulting polymer is obtained. Furthermore, a surfactant containing a block copolymer obtained by polymerizing a monomer represented by the following formula (2).

[Wherein, X ¹ is a hydrogen atom, halogen atom, amino group, P (O) (OH) ₂ group or monovalent organic group; Y ¹ is a hydrogen atom, halogen atom, alkali metal atom, NH ₄ group Or R ¹ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms; R ² is a hydrogen atom or a monovalent group. Yes; A represents —O— or —NR ³ — (R ³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms); R ⁴ represents a hydrogen atom, a halogen atom, or an alkyl having 1 to 5 carbon atoms. R ⁵ is a single bond or a divalent linking group; B is —O— or —NR ⁶ — (R ⁶ is a hydrogen atom or a carbon number of 1 to 5; And Rf is a perfume having 1 to 6 carbon atoms. Is a Oroarukiru group. ] X ¹ in the formula (1) is a hydrogen atom, a halogen atom, an alkyl group, an alkylthio group, an alkoxy group, a dialkylamino group, a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group, an aromatic hydrocarbon ring group or an aromatic Group heterocyclic group (however, the carbon atom in each of the aforementioned groups may have a substituent),
The surfactant according to claim 1 or 2, wherein Y ¹ is a group represented by the following formula (4) or the following formula (5).

[Wherein, X ² and X ³ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkylthio group, an alkoxy group, a dialkylamino group, a saturated hydrocarbon ring group, an unsaturated hydrocarbon ring group, or an aromatic hydrocarbon. A cyclic group or an aromatic heterocyclic group (however, the carbon atom in each of the aforementioned groups may have a substituent); ] The surfactant according to any one of claims 1 to 3, wherein an atom bonded to carbon of the thiocarbonyl group of X ¹ in the formula (1) is a hetero atom. The surfactant according to claim 1, wherein X ¹ in the formula (1) is a group represented by the following formula (6) or the following formula (7).

[Wherein, R ⁷ is an alkyl group having 1 to 10 carbon atoms; R ⁸ and R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ] The compound represented by the formula (1) is a compound represented by the following formula (1-1), the following formula (1-2) or the following formula (1-3): The surfactant described in 1.

[Wherein, R ⁷ is an alkyl group having 1 to 10 carbon atoms; R ⁸ and R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]