JP6157837B2 - ABXBA type block copolymer - Google Patents

Description

  The present invention relates to an ABXBA type block copolymer. Specifically, the present invention relates to an ABXBA block copolymer having an atomic group X derived from a bifunctional initiator, a block A that is a hydrophobic block, and a block B that is a hydrophilic block.

  In general, resin materials are easily charged with static electricity, and the inherent function of the resin may be deteriorated due to the adhesion of dust or dust. Therefore, a method of applying an antistatic agent to the surface of the resin material is taken. Also, there are cases where a charge control agent is applied to the surface of a resin material for the purpose of surface modification of the resin material, and the antistatic agent and charge control agent (hereinafter referred to as “charge control agent”) to be used. ) Is required to maintain a stable charge control effect over a long period of time.

  As the charge control agent, a substance such as a metal-containing compound, a surfactant or a polymer is used. Among them, the polymer-based charge control agent has an advantage that a stable effect can be obtained with a small amount of addition without being eluted during use. In addition, since the ratio of anionic sites or cationic sites in the molecular design can be adjusted, there is also an advantage that a charge control agent having a desired charge amount can be easily obtained.

  As a polymer charge control agent, a polymer having a quaternary ammonium cation as a cationic site has been proposed.

  For example, an antistatic agent comprising a polymer obtained by random copolymerization of a quaternary cationic (meth) acrylamide monomer and an acrylate ester or a polyfunctional acrylate is disclosed (see Patent Document 1). Also disclosed is an antistatic agent comprising an AB type block copolymer having a block B in which repeating units having a quaternary ammonium cation are continuous and a block A in which (meth) acrylic acid ester units are continuous (patent). Reference 2).

JP 2010-229187 A Japanese Patent Laid-Open No. 10-10673

  However, since these polymers have low adhesion to the resin surface and are inferior in durability (peeling resistance), it has not been possible to solve the problem of maintaining a stable charge control effect over a long period of time. .

  The present invention has been made to solve the above-described problems of the prior art, has high adhesion to the resin surface, excellent durability, and can maintain a stable charge control effect over a long period of time. It is an object of the present invention to provide a polymer-based charge control agent.

  As a result of intensive studies to solve the above problems, the present inventors have found that an ABA type block copolymer in which a hydrophobic block A expressing adhesiveness is bonded to both ends of a block B having a cationic site. More precisely, the present inventors have found that the above problem can be solved by an ABXBA type block copolymer in which the block B and the block A are sequentially polymerized through a hydrophilic atomic group X. It came to be completed.

  That is, according to the present invention, the following ABXBA type block copolymer is provided.

[1] A ABXBA type block copolymer represented by the following general formula (1) selected atomic group X is represented by the following general formula (2) to (4), (2 ') - (4') Any one kind of atomic group having a quaternary ammonium cation, wherein the block A is a hydrophobic block composed of a hydrophobic repeating unit a, and the block B is composed of a repeating unit b having a quaternary ammonium cation. An ABXBA type block copolymer, which is a hydrophilic block.

〔一般式（１）中、ｌ、ｍ、ｎ、ｏは、それぞれが繰返し単位ａまたは繰返し単位ｂの平均繰返し数を示す整数であり、１５≦（ｌ＋ｏ）≦１０５、２０≦（ｍ＋ｎ）≦１０５の条件を満たす。〕

[In general formula (1), l, m, n, and o are integers each representing the average number of repeating units a or b, and 15 ≦ (l + o) ≦ 105, 20 ≦ (m + n) ≦. The condition of 105 is satisfied. ]

〔一般式（２）〜（４）、（２’）〜（４’）中、Ｒ¹は、炭素数１〜４のアルキル基を示す。Ｒ²およびＲ³は、それぞれが炭素数１〜４のアルカンジイル基を示す。Ｒ⁴は、炭素数１〜２０のアルキル基を示す。〕

[In General Formulas (2) to (4) and (2 ′) to (4 ′), R ¹ represents an alkyl group having 1 to 4 carbon atoms. R ² and R ³ each represent an alkanediyl group having 1 to 4 carbon atoms. R ⁴ represents an alkyl group having 1 to 20 carbon atoms. ]

[2] The ABXBA block copolymer according to claim 1, wherein the repeating unit a is one selected from the group consisting of a (meth) acrylic acid ester unit, a vinyl carboxylate unit and an aromatic vinyl unit.

[3] The repeating unit b has a skeleton as one selected from the group consisting of a (meth) acrylic acid ester unit having an amine structure, a (meth) acrylamide unit, and an N-vinylamide unit, and an N atom in the skeleton The ABXBA type block copolymer according to claim 1, which has a quaternary ammonium cation obtained by alkylation of

[4] The atomic group X is an atomic group having a quaternary ammonium cation represented by the general formula (2), (3) or (2 ′), and the repeating unit a is an alkyl (meth) acrylate unit. 2. The ABXBA block copolymer according to claim 1, wherein the repeating unit b has a quaternary ammonium cation obtained by alkylating a N atom in the skeleton with a dialkylaminoalkyl (meth) acrylate unit as a skeleton. .

[5] The polydispersity Mw / Mn calculated from the number average molecular weight Mn and the weight average molecular weight Mw measured by the gel permeation method is in the range of 1.0 to 1.2. ABXBA type block copolymer.

  The block copolymer according to the present invention has high adhesion to the resin surface and is excellent in durability. Accordingly, it is possible to maintain a stable charge control effect over a long period of time.

  Hereinafter, although embodiment of this invention is described, this invention is not limited to the following embodiment. The “unit” in the text means a repeating unit obtained by polymerizing a monomer unless otherwise specified.

[1] Block copolymer:
The ABXBA block copolymer according to the present invention is a polymer represented by the following general formula (1).

  This polymer is composed of an atomic group X having a quaternary ammonium cation, a hydrophobic block A comprising a hydrophobic repeating unit a, and a hydrophilic block B comprising a repeating unit b having a quaternary ammonium cation. Further, since the block B and then the block A are sequentially polymerized at both ends of the atomic group X, the structure substantially has an ABA type structure. When the block A is adhered to the resin surface by chemical modification, there is no significant difference in adhesive strength between the AB type (tail type) in which the block A is only at one end and the ABA type (loop type) having the block A at both ends. However, when the block A adheres to the resin surface by electrostatic interaction or adsorption by van der Waals force as in the present invention, the ABA type is preferable because it exhibits higher adhesion.

[1-1] Block A:
As shown in the general formula (1), the block A is a hydrophobic block composed of a hydrophobic repeating unit a, and functions as a site that exhibits adhesion to a resin material.

  The hydrophobic repeating unit is a repeating unit obtained by polymerizing a hydrophobic monomer having a hydrophobic functional group in the side chain. Examples of the hydrophobic functional group include an aliphatic hydrocarbon group such as an alkyl group; an alicyclic hydrocarbon group such as a cycloalkyl group; an aromatic hydrocarbon group such as a phenyl group; The aliphatic hydrocarbon group may be not only linear but also branched. The aliphatic hydrocarbon group or the alicyclic hydrocarbon group includes not only a saturated hydrocarbon group but also an unsaturated hydrocarbon group. These hydrophobic functional groups preferably do not contain a hydrophilic functional group such as a hydroxyl group, an amino group, or a carboxyl group.

  The hydrophobic repeating unit a is preferably one selected from the group consisting of a (meth) acrylic ester unit, a vinyl carboxylate unit and an aromatic vinyl unit.

[1-1A] (Meth) acrylic acid ester unit:
Examples of the (meth) acrylic acid ester unit include (meth) acrylic acid alkyl units, (meth) acrylic acid alkoxyalkyl units, (meth) acrylic acid cycloalkyl units, and (meth) acrylic acid aryl units.

  Specific examples of alkyl (meth) acrylate units include (meth) methyl acrylate units, (meth) ethyl acrylate units, (meth) acrylic acid n-propyl units, (meth) isopropyl acrylate units, (meth). N-butyl acrylate unit, isobutyl (meth) acrylate unit, tert-butyl (meth) acrylate unit, n-pentyl unit (meth) acrylate, n-hexyl unit (meth) acrylate, (meth) acrylic acid n-heptyl unit, n-octyl (meth) acrylate unit, 2-ethylhexyl (meth) acrylate unit, nonyl unit (meth) acrylate, decyl (meth) acrylate unit, dodecyl (meth) acrylate unit, Examples thereof include a stearyl acrylate unit.

  Specific examples of the alkoxyalkyl unit (meth) acrylate include 2-methoxyethyl unit (meth) acrylate, 3-methoxypropyl unit (meth) acrylate, and the like.

  Specific examples of the (meth) acrylate cycloalkyl unit include cyclohexyl (meth) acrylate units. Specific examples of the aryl (meth) acrylate unit include a phenyl (meth) acrylate unit, a toluyl (meth) acrylate unit, a benzyl (meth) acrylate unit, and the like.

[1-1B] Vinyl carboxylate unit:
Examples of vinyl carboxylate units include aliphatic vinyl carboxylate units and aryl carboxylate vinyl units. Specific examples of the aliphatic vinyl carboxylate unit include a vinyl propionate unit, a vinyl pivalate unit, a vinyl neodecanoate unit, a vinyl decanoate unit, and a vinyl stearate unit. Specific examples of vinyl arylcarboxylate units include vinyl benzoate units.

[1-1C] Aromatic vinyl unit:
Specific examples of the aromatic vinyl unit include a styrene unit and a repeating unit obtained by polymerizing a styrene derivative.

  Among the repeating units, (meth) acrylic acid ester units are preferable, alkyl (meth) acrylate units are more preferable, ethyl (meth) acrylate units, (meth) acrylate n-propyl units, ( Particularly preferred are n-butyl acrylate units.

Number of [1-1D] unit repeats:
It is preferable that the average repeating numbers l and o of the repeating unit a in the block A are integers, and l + o is in the range of 15 to 105. By setting l + o to 15 or more, adhesion to a resin material can be exhibited. On the other hand, by setting l + o to 105 or less, synthesis can be performed in a short time, and the viscosity of the obtained polymer can be kept low, so that handling becomes easy.

[1-2] Block B:
As shown in the general formula (1), the block B is a hydrophilic block composed of a repeating unit b having a quaternary ammonium cation, and functions as a site that develops chargeability.

  The structure of the repeating unit b is not particularly limited as long as it is a repeating unit having a quaternary ammonium cation. However, the repeating unit b has a skeleton of one selected from the group consisting of a (meth) acrylic acid ester unit having an amine structure, a (meth) acrylamide unit, and an N-vinylamide unit, and the N atom in the skeleton is an alkyl group. It preferably has a quaternary ammonium cation obtained by conversion.

[1-2A] (Meth) acrylate unit having an amine structure:
Having an amine structure means having an amine structure in a functional group bonded to a (meth) acryloyl group. The amine structure includes primary amine, secondary amine, and tertiary amine structures.

  The (meth) acrylic acid ester unit having an amine structure is assumed to have a primary amine structure, the (meth) acrylic acid aminoalkyl unit or the like as a secondary amine structure, and a (meth) acrylic acid monoalkyl Examples of the aminoalkyl unit having a tertiary amine structure include a (meth) acrylic acid dialkylaminoalkyl unit.

  Specific examples of the aminoalkyl (meth) acrylate unit include 2-aminoethyl (meth) acrylate units.

  Specific examples of the (meth) acrylic acid monoalkylaminoalkyl unit include 2- (N-methylamino) ethyl unit of (meth) acrylic acid.

  Specific examples of the (meth) acrylic acid dialkylaminoalkyl unit include (meth) acrylic acid 2- (dimethylamino) ethyl unit, (meth) acrylic acid 3- (dimethylamino) propyl unit, (meth) acrylic acid 4- (Dimethylamino) butyl unit, (meth) acrylic acid 2- (diethylamino) ethyl unit, (meth) acrylic acid 2- (diethylamino) propyl unit, (meth) acrylic acid 2- (diisopropylamino) ethyl unit, etc. Can do.

[1-2B] (Meth) acrylamide unit:
Specific examples of the (meth) acrylamide unit include N- (3- (dimethylamino) propyl) acrylamide unit and 4-acryloylmorpholine unit.

[1-2C] N-vinylamide unit:
Specific examples of the N-vinylamide unit include an N-vinylformamide unit and an N-methyl-N-vinylacetamide unit.

  The repeating unit b has a skeleton derived from a monomer having a vinyl group and an amine structure, such as an N, N-dimethylvinylbenzylamine unit, in addition to the repeating unit, and is obtained by alkylating an N atom in the skeleton. It may have a quaternary ammonium cation.

  Among these repeating units, those having a (meth) acrylic acid ester unit having an amine structure as a skeleton and having a quaternary ammonium cation obtained by alkylating an N atom in the skeleton are preferred. The (meth) acrylic acid ester unit is preferably a (meth) acrylic acid dialkylaminoalkyl unit, particularly a (meth) acrylic acid 2- (dimethylamino) ethyl unit or a (meth) acrylic acid 3- (dimethylamino) propyl unit. preferable.

Number of [1-2D] unit repeats:
The average repeating numbers m and n of the repeating unit b in the block B are each an integer, and m + n is in the range of 20 to 105. By setting m + n to 20 or more, the charging property can be efficiently expressed. On the other hand, by setting m + n to 105 or less, synthesis can be performed in a short time, and the viscosity of the obtained polymer can be kept low, so that handling becomes easy.

[1-3] Atomic group X:
The atomic group X is an atomic group having any one quaternary ammonium cation selected from the following general formulas (2) to (4) and (2 ′) to (4 ′). General formulas (2) and (2 ′) are tertiary amine types, general formulas (3) and (3 ′) are amide types, and general formulas (4) and (4 ′) are imide type quaternary ammonium cations. . Since the atomic group X is similar to the block B and has a cationic property, the function (providing charging property) of the block B is not hindered.

In the general formulas (2) to (4) and (2 ′) to (4 ′), R ¹ represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. . Among these, a methyl group and an n-butyl group are preferable, and a methyl group is more preferable.

In general formulas (2) to (4) and (2 ′) to (4 ′), R ² and R ³ each represent an alkanediyl group having 1 to 4 carbon atoms. Examples of the alkanediyl group having 1 to 4 carbon atoms include those obtained by removing one H atom from the alkyl group described in the section of R ¹ . Among these, a methylene group, an ethylene group, and an n-butylene group are preferable, and an ethylene group is more preferable. R ² and R ³ may be the same group or different groups.

In general formulas (2) to (4) and (2 ′) to (4 ′), R ⁴ represents an alkyl group having 1 to 20 carbon atoms. For example, in addition to the alkyl group having 1 to 4 carbon atoms described in the section of R ¹ ; n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, and an alkyl group having 5 to 20 carbon atoms such as an n-undecyl group and an n-dodecyl group. Among these, a C6-C12 alkyl group is preferable and n-octyl group is still more preferable.

[1-4] Preferred combinations of X, a, and b:
Considering the above contents, the block copolymer according to the present invention is an atomic group in which the atomic group X has a quaternary ammonium cation represented by the general formula (2), (3) or (2 ′), The repeating unit a is an alkyl (meth) acrylate unit, and the repeating unit b is a quaternary ammonium obtained by alkylating a N atom in the skeleton with a (meth) acrylate dialkylaminoalkyl unit as a skeleton. It preferably has a cation.

[1-5] Polydispersity (Mw / Mn):
The block copolymer according to the present invention has a polydispersity Mw / Mn calculated from the number average molecular weight Mn and the weight average molecular weight Mw measured by the gel permeation method in the range of 1.0 to 1.2. Is preferred. A polymer having a polydispersity of 1.2 or less has a sharp molecular weight distribution, and when used as a charge control agent, has a good orientation control effect because of good orientation. Furthermore, since the polymer having a polydispersity of 1.2 or less has high symmetry, the adhesiveness of the blocks A at both ends becomes uniform and is thermodynamically stable, so that it has excellent durability.

[1-6] Usage method:
The ABXBA type block copolymer according to the present invention may be used as it is as a charge control agent, or may be diluted with a solvent and mixed with a binder resin.

  The kind of the binder resin is not particularly limited. However, polyester, polyamide, acrylic resin, urethane resin, phenol resin, epoxy resin, or the like can be suitably used.

  The mixing ratio of the ABXBA type block copolymer and the binder resin is not particularly limited, but in order to sufficiently exhibit the function as a charge control agent and to improve the compatibility with the binder resin, 5: 1 to A range of 1: 5 is preferable.

[2] Manufacturing method:
The block copolymer according to the present invention may be produced by any production method as long as the structure can be obtained. However, it is preferable to produce by the atom transfer radical polymerization method (ATRP method) using the bifunctional initiator x having a structure corresponding to the atomic group X. According to the method, since the polymerization proceeds symmetrically, the symmetry is high (that is, l and o in the general formula (1), m and n are substantially equal), and the polydispersity (Mw / Mn) is close to 1. A polymer can be obtained (about 1.0 to 1.2). In the following, after synthesizing the synthesis procedure in the above production method, each item will be specifically described.

[2-1] Synthesis procedure:
First, the monomer b ^{1 used} as the raw material of the block B is polymerized with the bifunctional initiator x to form the block B ′ composed of the repeating unit b ² . Thus, a B′X′B ′ type diblock body having a structure in which the block B ′ is bonded to the atomic group X ′ is obtained (the following general formula (8)).

  The atomic group X ′ is an atomic group derived from the bifunctional initiator x, and is a precursor of the atomic group X represented by the general formula (1). In the atomic group X ′, the N atom in the structure is not quaternized. The block B ′ is a precursor of the block B in the ABXBA type block copolymer. Also in the block B ', the N atom in the structure is not quaternized.

Next, the monomer a ¹ as the raw material of the block A is polymerized by the B′X′B ′ type diblock body which is a living radical, and the block A composed of the repeating unit a is formed. Thus, an AB′X′B′A type tetrablock body having a structure in which the block A is bonded to the B′X′B ′ type diblock body is obtained (the following general formula (9)). The block A has the same structure as the block A in the ABXBA type block copolymer.

Finally, the N atom in the structure of the AB′X′B′A type tetrablock body is quaternized. Specifically, the N atom in the structure of the repeating unit b ² (and hence the block B ′) is quaternized by alkylation to form the repeating unit b (and thus the block B). Further, the N atom in the structure of the atomic group X ′ is quaternized by alkylation to form the atomic group X. Thereby, the ABXBA type block copolymer which concerns on this invention can be obtained (the following general formula (1)).

〔一般式（５）〜（７）中、Ｒ⁰は、Ｈ原子または炭素数１〜４のアルキル基を示す。Ｒ²およびＲ³は、一般式（２）〜（４）に示すＲ²およびＲ³と同義である。Ｚは、それぞれがＣｌ原子、Ｂｒ原子またはＩ原子を示す。〕 [2-2] Bifunctional initiator x:
The bifunctional initiator x is a polymerization initiator and a substance that will later constitute the atomic group X. Therefore, the structure corresponding to the atomic group X is used. For example, an organic dihalide having an N atom that can be quaternized and having two halogen atoms as reaction sites, more specifically, a structure represented by any one of the following general formulas (5) to (7) The organic dihalide can be used.

[In General Formulas (5) to (7), R ⁰ represents an H atom or an alkyl group having 1 to 4 carbon atoms. R ² and R ³ are synonymous with R ² and R ³ shown in the general formulas (2) to (4). Z represents a Cl atom, a Br atom or an I atom, respectively. ]

Since the bifunctional initiator has an N atom that can be quaternized and has a structure similar to that of the monomer b ¹ that is a raw material monomer of the repeating unit b (and hence the block B), it is compatible with the monomer b ^1. And the reactivity with the monomer b ¹ is good. Therefore, a B′X′B ′ type diblock body having a sharp molecular weight distribution and excellent symmetry can be synthesized. Such a B′X′B ′ type diblock body facilitates uniform polymerization of the block A, and the polydispersity (Mw / Mn) of the AB′X′B′A type copolymer (and thus the ABXBA type copolymer) Can be controlled in the range of 1.0 to 1.2.

  In addition, after the polymerization, the chargeability similar to that of the block B can be imparted to the atomic group X by quaternizing (cationizing) the N atom. Therefore, the chargeability as a function of the block B is not inhibited by the atomic group X located at the center of the ABXBA type block copolymer.

R ² and R ³ are preferably the same group (for example, both R ² and R ³ are ethylene groups). By making R ² and R ^{3 the} same group, it becomes difficult for the chemical properties of the two reaction points (the halogen atom represented by Z) to differ, and the reaction easily proceeds uniformly.

  Z may be an I atom, but is preferably a Cl atom or a Br atom. The Cl-forming reagent and the Br-forming reagent are easier to obtain than the I-forming reagent, and the synthesis of the bifunctional initiator is facilitated. Z may be a different type of halogen atom, but is preferably the same type of halogen atom. By using the same type of halogen atom, the reaction can easily proceed uniformly at the two reaction points. Further, it is easier to synthesize a bifunctional initiator than to introduce different types of halogen atoms.

[2-2A] Tertiary amine type initiator:
The bifunctional initiator represented by the general formula (5) is a tertiary amine type initiator having a structure corresponding to the atomic group X represented by the general formulas (2) and (2 ′).

  The tertiary amine type initiator can be synthesized, for example, by a halogen substitution reaction. Examples of the halogen substitution reaction include a method in which a compound having a reactive functional group (such as a hydroxyl group) at the Z position in the general formula (5) is used as a raw material and the reactive functional group is substituted with a halogen atom. For example, a diol having a hydroxyl group at the Z position in the general formula (5) may be used as a raw material, and the hydroxyl group may be substituted with a halogen atom with a halogenating agent.

  Examples of the diol include bis (hydroxyalkyl) amines such as diethanolamine and N-methyldiethanolamine.

  As the halogenating agent, conventionally known halogenating agents such as thionyl chloride, sulfuryl chloride, phosphorus tribromide, hydrogen bromide and the like can be used. Of these, thionyl chloride is preferred because it is highly versatile and easy to handle. The amount of the halogenating agent used is preferably at least 2 molar equivalents relative to the diol, and more preferably in the range of 2.5 to 4.0 molar equivalents.

  There are no particular limitations on the reaction temperature and reaction solvent in the halogen substitution reaction. What is necessary is just to select suitably according to the kind of diol or a halogenating agent, and it can also make it react without a solvent depending on the kind of diol or a halogenating agent. Further, DMF may be added as a catalyst.

  The tertiary amine type initiator may be synthesized by reductive amination. As the reductive amination reaction, an aldehyde having a halogen atom (or a reactive functional group that can be substituted with a halogen atom) in its structure and a reactive functional group that can be substituted with a halogen atom (or a halogen atom) in its structure. And a method of reducing the imine with a reducing agent.

  The aldehyde is chloroacetaldehyde, and the amine is 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1- Examples include hexanol.

  The amount of the amine used is preferably at least 1 molar equivalent relative to the aldehyde, and more preferably in the range of 1.1 to 1.5 molar equivalents.

  As the reducing agent, conventionally known reducing agents such as formic acid, sodium borohydride, sodium triacetoxyborohydride, 2-picoline-borane can be used. The amount used is not particularly limited. However, it is preferable to set it as the range of 0.3-1 molar equivalent with respect to an amine. There are no particular limitations on the reaction temperature or reaction solvent in the reductive amination reaction. However, the reaction is preferably carried out under ice cooling.

[2-2B] Amide type initiator:
The bifunctional initiator represented by the general formula (6) is an amide type initiator having a structure corresponding to the atomic group X represented by the general formulas (3) and (3 ′).

  The amide-type initiator can be synthesized, for example, by a method in which a halogenocarboxylic acid halide is reacted with an amine having a halogen atom in the structure thereof to amidate.

  Examples of the halogenocarboxylic acid halide include chloroacetyl chloride, 3-chloropropionyl chloride, 4-chlorobutyryl chloride, 5-chlorovaleric acid chloride and the like. These carboxylic acid halides may be synthesized by halogenating the corresponding halogenocarboxylic acid, or commercially available products may be used. For the halogenation, the halogenating agents exemplified in the above-mentioned halogen substitution reaction can be preferably used.

  Examples of the amine having a halogen atom in the structure include 2-chloroethylamine and 3-chloropropylamine. Secondary amines in which the N atom of these amines is further alkylated may be used. The amine is preferably used in an amount of at least 1 molar equivalent, more preferably 1.1 to 1.5 molar equivalent, based on the halogenocarboxylic acid halide.

  There are no particular limitations on the reaction temperature and reaction solvent in the amidation reaction. What is necessary is just to select suitably according to the kind of the said halogenocarboxylic acid halide or the said amine.

[2-2C] imide type initiator:
The bifunctional initiator represented by the general formula (7) is an imide-type initiator having a structure corresponding to the atomic group X represented by the general formulas (4) and (4 ′).

  The imide type initiator can be synthesized, for example, by a method of reacting a halogenocarboxylic acid halide with ammonia or a primary amine to imidize (diacylate) it.

  Examples of the halogenocarboxylic acid halide include the compounds exemplified in the amidation section. Examples of the primary amine include methylamine, ethylamine, propylamine, and butylamine. The amount of ammonia or primary amine used is preferably at least 2 molar equivalents relative to the halide, more preferably in the range of 2.5 to 4.0 molar equivalents.

  The imide type initiator may be synthesized by a method in which halogenocarboxylic acid and ammonia or primary amine are condensed and imidized.

  Examples of the halogenocarboxylic acid include chloroacetic acid, 3-chloropropionic acid, 4-chlorobutyric acid, and 5-chlorovaleric acid. Examples of the primary amine include primary amines exemplified in the section of imidization using a halide. The amount of ammonia or the primary amine used is preferably at least 2 molar equivalents relative to the carboxylic acid, and more preferably in the range of 2.5 to 4.0 molar equivalents.

  Since the halogenocarboxylic acid is less reactive than the halogenocarboxylic acid halide described above, it is preferable to carry out the reaction by adding a condensing agent and a catalyst. Examples of the condensing agent include dicyclohexylcarbodiimide (DCC), and examples of the catalyst include bases such as pyridine. The amount used is not particularly limited. However, it is preferable that the condensing agent is 1.0 to 3.0 molar equivalents and the catalyst is 0.1 to 0.5 molar equivalents relative to the primary amine.

  There is no restriction | limiting in particular also about the reaction temperature and reaction solvent of the said imidation reaction. What is necessary is just to select suitably according to the kind of raw material compound.

  It is preferable to use any of tertiary amine type, amide type and imide type initiators after purification. Examples of the purification method include conventionally known purification methods such as alkali washing, water washing, distillation under reduced pressure of a reaction solvent, and the like.

  The molecular structure of the synthesized bifunctional initiator can be confirmed using NMR (nuclear magnetic resonance apparatus), FT-IR (Fourier transform infrared spectroscopy apparatus), or the like.

[2-3] Polymerization reaction:
The raw material monomer, catalyst, ligand, reaction solvent, and reaction temperature in the polymerization reaction are as follows. These conditions apply to both the formation of a B′X′B ′ type diblock body and the formation of an AB′X′B′A type tetrablock body.

[2-3A] Raw material monomer:
Starting monomer a ¹ block A, using a monomer corresponding to the repeating unit illustrated in the section of the raw material monomer b ¹ both block copolymer block B '. These monomers are preferably used after removing the polymerization inhibitor by a method such as passing an adsorbent before polymerization.

[2-3B] Catalyst:
In the ATRP method, a transition metal of Group 7 to Group 11 is used as a catalyst. Among these, monovalent copper is preferably used when the block copolymer according to the present invention is synthesized. Monovalent copper has the advantage of being readily available and inexpensive. Examples thereof include copper (I) halides such as copper (I) chloride, copper (I) bromide, and copper (I) iodide. The amount of catalyst used is not particularly limited. What is necessary is just to add in the range of the general catalyst amount.

[2-3C] Ligand:
In the ATRP method, it is preferable to use a ligand (hereinafter referred to as “ligand”) in combination in order to increase the activity of the catalyst.

  As the ligand, a conventionally known ligand can be used. For example, polyamine compounds such as N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (PMDT); pyridine compounds such as 2,2′-dipyridyl derivatives; and the like can be used. The amount of ligand used is not particularly limited. However, it is preferably 1.0 molar equivalent or more with respect to the catalyst.

[2-3D] Reaction solvent:
The kind of reaction solvent is not particularly limited. What is necessary is just to select suitably from general purpose solvents according to a raw material monomer. For example, alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; aliphatic hydrocarbons such as n-hexane; aromatic hydrocarbons such as benzene and toluene; non-dimethylsulfoxide, dimethylformamide and the like A protic polar solvent or the like can be used. These solvent can be used individually by 1 type or in mixture of 2 or more types.

[2-3E] Reaction temperature:
The reaction temperature is not particularly limited. What is necessary is just to set suitably according to the kind of raw material monomer or a bifunctional initiator. However, it is preferable to be in the range of room temperature to 200 ° C. Considering an appropriate reaction rate, boiling point of the reaction solvent, suppression of thermal polymerization (side reaction) of raw material monomers, ease of control of the reaction, etc., it is more preferable to set the temperature within the range of 40 ° C to 120 ° C.

[2-4] Quaternization of repeating unit b ² (block B ′) and atomic group X ′:
Examples of the quaternizing agent (alkylating agent) used for quaternizing the N atom include alkyl halides having 1 to 20 carbon atoms. Among them, an alkyl halide having 1 to 12 carbon atoms and a halogen atom being a Br atom or an I atom is preferable in that it is highly reactive and easily available.

  Examples of the alkyl halide include 1-bromoethane, 1-bromopropane, 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bronooctane, 1-bromononane, 1-bromodecane, 1-bromo. Bromoalkyl such as undecane, 1-bromododecane;

  Iodomethane, 1-iodoethane, 1-iodopropane, 1-iodobutane, 1-iodopentane, 1-iodohexane, 1-iodoheptane, 1-iodooctane, 1-iodononane, 1-iododecane, 1-iodoundecane, 1- And iodoalkyl such as iodododecane; Of these, alkyl halides having 6 to 12 carbon atoms are particularly preferable.

The amount of quaternizing agent used is not particularly limited. However, it is preferably at least 1.5 molar equivalents relative to the quaternized N atom, and more preferably in the range of 2.0 to 3.0 molar equivalents. For example, the number of moles of the quaternizing agent used is determined as shown in the following calculation formula (1).
Number of moles of quaternizing agent = [number of moles of B′X′B ′ type diblock body] × [m + n] × 2: (1)

  The reaction solvent for quaternization is not particularly limited. What is necessary is just to select suitably from the solvent illustrated by the term of the reaction solvent for superposition | polymerization, for example, aprotic polar solvents, such as a dimethylformamide, etc. can be used. The reaction temperature is not particularly limited. However, it is preferable to set it as the range of room temperature (25 degreeC) -120 degreeC.

In addition, the quaternization rate of the block B ′ and the atomic group X ′ is an integral value before quaternization, an integral value after quaternization, and a quaternary in a chemical shift in which an alkyl group is observed by ¹ H-NMR. It can be calculated from the theoretical value of the integral value that increases due to conversion (introduction of an alkyl group). Specifically, it can be calculated by the following calculation formula (2).
Quaternization ratio (%) = {(α−β) / γ} × 100: (2)
α: Integral value after quaternization in the chemical shift β: Integral value before quaternization in the chemical shift γ: Theoretical value of the integral value increased by quaternization (introduction of an alkyl group) in the chemical shift

Regarding the alkyl group introduced by quaternization, the H atom bonded to the C atom adjacent to the N atom is affected by the cationic property of the N atom, and therefore the chemical shift in ¹ H-NMR is different from that of the other H atom. Different. Therefore, α, β, and γ in the calculation formula (2) do not include 2H bonded to the C atom. For example, when 1-bromooctane (C ₈ H ₁₇ Br) is used as a quaternizing agent and N-alkylation is carried out, 2H bonded to the C atom adjacent to the N atom is excluded, and γ is converted to 15H. Calculate as That is, if α-β is 15H, the quaternization rate is 100%.

  The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. In the text, “parts” and “%” are based on mass unless otherwise specified.

[1] Synthesis examples 1 to 8 (synthesis of initiator):
Hereinafter, synthesis examples of the initiator will be shown. The molecular structure of the synthesized initiator was confirmed using NMR (trade name: ECA400, manufactured by JEOL Ltd.) and FT-IR (trade name: IR Prestige-21, manufactured by Shimadzu Corporation).

(Synthesis Example 1)
11.92 parts (0.10 mol) of N-methyldiethanolamine, 35.69 parts (0.30 mol) of thionyl chloride, and 0.10 parts (0.001 mol) of pyridine are charged into a nitrogen-substituted eggplant type flask. Then, the halogen substitution reaction was carried out by refluxing at 100 ° C. for 1 hour. After confirming that the generation of HCl was stopped, the remaining thionyl chloride was distilled off under reduced pressure to obtain N, N-bis (2-chloroethyl) methylamine represented by the following formula (A) (initiator 1). Initiator 1 is a tertiary amine type bifunctional initiator.

(Synthesis Example 2)
A solution of 11.60 parts (0.10 mol) of 2-chloroethylamine hydrochloride / 15.00 parts (0.20 mol) of diethyl ether was charged into a nitrogen-substituted eggplant type flask. To the solution, a solution of 12.70 parts (0.10 mol) of 3-chloropropionyl chloride / 15.00 parts (0.20 mol) of diethyl ether was slowly added dropwise under ice cooling, and at room temperature (25 ° C.). Amidation was carried out by stirring for 1 hour. Thereafter, the reaction product was washed with alkali, washed with water to remove acid and the like, and the solvent was distilled off under reduced pressure to obtain a concentrate.

To 17.00 parts (0.10 mol) of the concentrate, 28.39 parts (0.20 mol) of iodomethane and 13.82 parts (0.10 mol) of potassium carbonate were added, and the N atom in the molecule was converted to methyl. And N-methyl- (2-chloroethyl) -3-chloropropanamide represented by the following formula (B) was obtained (initiator 2). Initiator 2 is an amide type bifunctional initiator.

(Synthesis Example 3)
In a eggplant-type flask purged with nitrogen, 7.77 parts (0.10 mol) of methylamine (40% methanol solution), 40.00 parts (0.54 mol) of diethyl ether and 0.10 parts of pyridine (0. 001 mol) was added and mixed with stirring. To this mixture, 38.09 parts (0.30 mol) of 3-chloropropionic acid was slowly added dropwise under ice cooling, and the mixture was stirred at room temperature (25 ° C.) for 3 hours for imidization. Thereafter, the reaction product was washed with alkali, washed with water to remove acid and the like, and the solvent was distilled off under reduced pressure to obtain N-methyl- (2-chloroethyl) -3-chloropropanimide represented by the following formula (C). (Initiator 3). Initiator 3 is an imide-type bifunctional initiator.

(Synthesis Example 4)
N, N-bis (2-chloroethyl) amine represented by the following formula (D) is the same as Synthesis Example 1 except that 0.10 mol of N-methyldiethanolamine was changed to 0.10 mol of diethanolamine. (Initiator 4). Initiator 4 is a tertiary amine type bifunctional initiator.

(Synthesis Example 5)
In the same manner as in Synthesis Example 1, except that 0.10 mol of N-methyldiethanolamine was changed to 0.10 mol of 2- (hydroxy (methyl) amino) ethanol, N- Chloromethyl-2-chloroethylamine was obtained (initiator 5). Initiator 5 is a tertiary amine type bifunctional initiator.

(Synthesis Example 6)
N, N-bis (N) represented by the following formula (F) is the same as in Synthesis Example 1 except that 0.10 mol of N-methyldiethanolamine is changed to 0.10 mol of N-butyldibutanolamine. 4-Chlorobutyl) butylamine was obtained (initiator 6). Initiator 6 is a tertiary amine type bifunctional initiator.

(Synthesis Example 7)
In an eggplant-type flask purged with nitrogen, 28.35 parts (0.30 mol) of monochloroacetic acid, 6.21 parts (0.10 mol) of ethylene glycol, 0.95 parts of p-toluenesulfonic acid monohydrate ( 0.005 mol) and 50.00 parts (0.54 mol) of toluene were added. These were refluxed at 130 ° C. for 6 hours with stirring to carry out esterification. Thereafter, the reaction product was washed with alkali, washed with water to remove acid and the like, and the solvent was distilled off under reduced pressure to obtain ethylene glycol bis (monochloroacetate) represented by the following formula (G) (initiator 7). Initiator 7 is a bifunctional initiator having no N atoms.

(Synthesis Example 8)
In an eggplant-type flask purged with nitrogen, 11.72 parts (0.10 mol) of 6-amino-1-hexanol, 13.81 parts (0.30 mol) formic acid and 20.00 parts (0.62 mol) of methanol ). To these, 39.25 parts (0.20 mol) of chloroacetaldehyde (40% aqueous solution) was slowly added dropwise under ice cooling. After confirming that the exotherm had subsided, reductive amination was carried out by stirring at room temperature (25 ° C.) for 2 hours and then stirring at 60 ° C. for an additional 4 hours.

Thereafter, the reaction product was washed with alkali, washed with water to remove acid and the like, and the solvent was distilled off under reduced pressure to obtain a concentrate. This concentrate was halogenated by the same method as in Synthesis Example 1 to obtain N-methyl-2-chloroethyl-6-chlorohexylamine represented by the following formula (H) (Initiator 8). Initiator 8 is a tertiary amine type bifunctional initiator.

The structures and yields of the initiators 1 to 8 are summarized in Table 1.

The “type” in Table 1 is “tertiary amine” for the structure shown in the following general formula (5), “amide” for the structure shown in the following general formula (6), and the following general formula (7). The structure having the structure shown in FIG.

In Comparative Example 11 described later, (1-chloroethyl) benzene represented by the following formula (I) was used as an initiator (Initiator 9). Initiator 9 is a monofunctional initiator that does not have an N atom in its structure.

[2] Examples 1 to 18 and Comparative Examples 1 to 10 (polymer synthesis):
Hereinafter, synthesis examples of the ABXBA block copolymer using the initiator will be shown.

Example 1
In Example 1, first, a B′X′B ′ type diblock body was synthesized using the initiator, an AB′X′B′A type tetrablock body was synthesized from the diblock body, and the tetra The N atom in the block structure was quaternized to synthesize an ABXBA type block copolymer.

(1) Synthesis of B′X′B ′ type diblock body:
In Example 1, N-dimethylaminoethyl methacrylate was used as the raw material monomer b ² of the block B, N, N-bis (2-chloroethyl) methylamine (the initiator 1) was used as the catalyst, and x as the initiator. Copper (I) was used as a ligand and N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine was used as a ligand.

  In an eggplant-type flask purged with nitrogen, 66.81 parts (85 mol) of N-dimethylaminoethyl methacrylate, 0.78 parts (0.005 mol) of N, N-bis (2-chloroethyl) methylamine, copper chloride ( I) 0.50 part (0.005 mol), N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine 1.73 parts (0.01 mol), methyl ethyl ketone 50 parts (0.69 mol) The polymerization reaction was carried out at 80 ° C. with stirring.

  The polymerization reaction was performed while monitoring the molecular weight by GPC. As GPC, the brand name “HLC8220” (manufactured by Tosoh Corporation) was used. When the molecular weight reached the target value, the reaction solution was cooled with ice water to stop the reaction, and a crude diblock body was obtained. The crude diblock body was purified by a dialysis method to obtain a B′X′B ′ type diblock body.

For the diblock body, the molecular weight and the average number of repetitions (m + n) of the repeating unit b ² in the block B ′ were measured by NMR and GPC. As NMR, a trade name “ECA400” (manufactured by JEOL Ltd.) was used. The molecular weight of the diblock body was 8331, and (m + n) was 52.

(2) Synthesis of AB′X′B′A type tetrablock body:
In Example 1, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine was used as a raw material monomer a ¹ of block A using n-butyl methacrylate as a catalyst, copper (I) chloride as a ligand, and Was used.

  In an eggplant-type flask purged with nitrogen, 85.32 parts (120 mol) of n-butyl methacrylate, 41.65 parts (0.005 mol) of the B′X′B ′ type diblock body, copper (I) 0 .50 parts (0.005 mol), N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine 1.73 parts (0.01 mol) and methyl ethyl ketone 80.00 parts (1.11 mol) are added. The polymerization reaction was carried out at 80 ° C. with stirring.

  The polymerization reaction was performed while monitoring the molecular weight by GPC, as in the synthesis of the diblock body. When the molecular weight reached the target value, the reaction solution was cooled with ice water to stop the reaction, and a crude tetrablock body was obtained. The crude tetrablock body was purified by a dialysis method to obtain an AB′X′B′A type tetrablock body.

For the tetrablock body, the molecular weight and the average number of repetitions (l + o) of the repeating unit a ¹ in the block A were measured by NMR and GPC. The molecular weight of the tetrablock body was 18854, and (l + o) was 74.

(3) Synthesis of ABXBA type block copolymer:
In Example 1, 1-bromooctane was used as a quaternizing agent (alkylating agent).

  In a solution obtained by dissolving 18.85 parts (0.001 mol) of the AB′X′B′A type tetrablock body in 30.00 parts (0.41 mol) of dimethylformamide, 20.08 parts of 1-bromooctane (0.10 mol) was added and mixed. While stirring the mixed solution, the mixture was refluxed at 120 ° C. for 6 hours to quaternize N atoms in the structure of the tetrablock body to obtain a crude block copolymer. The crude block copolymer was purified by a dialysis method to obtain an ABXBA type block copolymer.

The ABXBA block copolymer confirmed the quaternization rate of block B by ¹ H-NMR. Further, when the molecular weight was measured by ¹ H-NMR and GPC, the quaternization ratio of the block copolymer was 98%, and the molecular weight was 28695.

(Examples 2-18, Comparative Examples 1-10)
An ABXBA type block copolymer was synthesized in the same manner as in Example 1 except that the kinds of the initiator, the monomer a ¹ , the monomer b ² and the quaternizing agent were changed.

However, the polymer of Comparative Example 2 is an A ¹ AXAA ¹ type polymer formed only from the hydrophobic blocks A and A ^1, and the polymer of Comparative Example 8 has the positions of the hydrophobic block and the hydrophilic block reversed. The BAXAB type polymer, the polymer of Comparative Example 10 is a B ¹ BXBB ¹ type polymer formed only from the hydrophilic blocks B and B ¹ .

Tables 2 and 3 show the types of the initiator and the raw material monomer and the types of the hydrophobic monomer and the hydrophilic monomer. In addition, the symbol in a table | surface shows the following monomers.
nBMA: butyl methacrylate EMA: ethyl methacrylate Vtol: vinyl toluene BzMA: benzyl methacrylate MEEMA: 2-methoxyethoxyethyl methacrylate DMA: 2-dimethylaminoethyl methacrylate DEAA: diethyl acrylamide IPAA: isopropylacrylamide

Further, the molecular weight of the B′X′B ′ type diblock body, the number of repeating units b ² in the block B ′ (m + n), the molecular weight of the AB′X′B′A type tetrablock body, and the repeating unit a in the block A 1 Tables 4 and 5 show the number of ¹ repeats (l + o), the molecular weight of the ABXBA block copolymer, the type of quaternizing agent used in the synthesis, and the quaternization rate. The “target value” in the table is the target number of repeating units.

〔一般式（１０）中、ｌ、ｍ、ｏは、それぞれ繰返し単位ａまたは繰返し単位ｂの平均繰返し数を示す整数である。〕 [3] Comparative Example 11 (Synthesis of polymer):
Hereinafter, synthesis examples of the X ¹ ABA type block copolymer using the initiator 9 will be shown. The X ¹ ABA type block copolymer is represented by the following general formula (10). The atomic group X ¹ is an atomic group derived from the initiator 9 ((1-chloroethyl) benzene), the block A is a hydrophobic block composed of a hydrophobic repeating unit a, and the block B is a quaternary ammonium. It is a hydrophilic block composed of a repeating unit b having a cation.

[In the general formula (10), l, m and o are integers indicating the average number of repeating units of the repeating unit a or the repeating unit b, respectively. ]

In Comparative Example 11, first, by using the initiator 9 to synthesize X ¹ A type monobloc body synthesizes X ¹ AB 'type diblock body from the mono-block body, X ¹ from the diblock body An AB′A type triblock was synthesized, and the N atom in the structure of the triblock was quaternized to synthesize an XABA type block copolymer.

(1) Synthesis of X ¹ A type monoblock body:
In Comparative Example 11, n-butyl methacrylate was used as the raw material monomer a ¹ of block A, initiator x, (1-chloroethyl) benzene (initiator 9) as the catalyst, copper (I) chloride as the ligand, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine was used.

  In an eggplant-type flask purged with nitrogen, 42.66 parts (0.30 mol) of n-butyl methacrylate, 0.70 parts (0.005 mol) of (1-chloroethyl) benzene, 0.50 of copper (I) chloride Parts (0.005 mol), N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine 1.73 parts (0.001 mol) and methyl ethyl ketone 50.00 parts (0.69 mol) The polymerization reaction was carried out at 80 ° C. with stirring.

The polymerization reaction was carried out in the same manner as in Example 1 while monitoring the molecular weight by GPC. When the molecular weight reached the target value, the reaction solution was cooled with ice water to stop the reaction to obtain a crude monoblock body. The crude monoblock body was purified by a dialysis method to obtain an X ¹ A type monoblock body.

  About the said monoblock body, it carried out similarly to Example 1, and measured molecular weight and the average repeating frequency (l) of the unit by NMR and GPC. The molecular weight of the monoblock body was 5118, and (l) was 35.

(2) Synthesis of X ¹ AB ′ type diblock:
In Comparative Example 11, as raw material monomer b ² of block B, 2-dimethylaminoethyl methacrylate was used as a catalyst, copper (I) chloride was used as a ligand, and N, N, N ′, N ″, N ″ — Pentamethyldiethylenetriamine was used.

In an eggplant-type flask purged with nitrogen, 66.81 parts (0.43 mol) of N-dimethylaminoethyl methacrylate, 29.14 parts (0.005 mol) of the X ¹ A type monoblock body, copper chloride (I ) 0.50 parts (0.005 mol), N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine 1.73 parts (0.01 mol) and methyl ethyl ketone 80.00 parts (1.11 mol) The polymerization reaction was carried out at 80 ° C. with stirring.

The polymerization reaction was performed while monitoring the molecular weight by GPC in the same manner as the monoblock body. When the molecular weight reached the target value, the reaction solution was cooled with ice water to stop the reaction, and a crude X ¹ AB ′ type diblock was obtained. The crude X ¹ AB ′ type diblock body was purified by dialysis to obtain an X ¹ AB ′ type diblock body.

  For the diblock body, the molecular weight and the average number of repeating units (m) were measured by NMR and GPC in the same manner as in Example 1. The molecular weight of the diblock body was 12664, and (m) was 48.

(3) Synthesis of X ¹ AB′A type triblock:
In Comparative Example 11, as raw material monomer a ¹ of block A bonded to the diblock body, n-butyl methacrylate was used as a catalyst, copper (I) chloride as a ligand, N, N, N ′, N “, N” -pentamethyldiethylenetriamine was used.

  In an eggplant-type flask purged with nitrogen, 42.66 parts (0.30 mol) of n-butyl methacrylate, 66.87 parts (0.005 mol) of the diblock body, 0.50 parts of copper (I) chloride (0 0.005 mol), N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (1.73 parts (0.01 mol)) and methyl ethyl ketone (100.00 parts, 1.39 mol) were added and stirred. The polymerization reaction was performed at 80 ° C.

The polymerization reaction was performed while monitoring the molecular weight by GPC, as in the synthesis of the monoblock body. When the molecular weight reached the target value, the reaction solution was cooled with ice water to stop the reaction, and a crude X ¹ AB′A type triblock was obtained. The crude triblock body was purified by a dialysis method to obtain an X ¹ AB′A type triblock body.

  For the triblock body, the molecular weight and the average number of repeating units (o) were measured by NMR and GPC. The molecular weight of the triblock body was 16645, and (o) was 28.

(4) Synthesis of X ¹ ABA type block copolymer:
In Comparative Example 11, 1-bromooctane was used as a quaternizing agent (alkylating agent), and the N atom in the B ′ block of the triblock was quaternized in the same manner as in Example 1, and crude X ^{1 An} ABA type block copolymer was obtained. The crude block copolymer was purified by a dialysis method to obtain an X ¹ ABA type block copolymer.

X ¹ ABA type block copolymer confirmed the quaternization rate of block B by ¹ H-NMR. Further, when the molecular weight was measured by ¹ H-NMR and GPC, the quaternization ratio of the block copolymer was 99%, and the molecular weight was 25882.

Table 6 shows the types of the initiator and the raw material monomer and the classification of the hydrophobic monomer and the hydrophilic monomer. Further, the molecular weight of the X ¹ A type monoblock body and the number of repeating units (l), the molecular weight of the X ¹ AB ′ type diblock body and the number of repeating units (m), the molecular weight of the X ¹ AB′A type triblock body Table 7 shows the number of repeating units (o), the molecular weight of the X ¹ ABA type block copolymer, the type of quaternizing agent used in the synthesis, and the quaternization rate. The “target value” in the table is the target number of repeating units.

〔一般式（１１）中、ｌ、ｍは、それぞれ繰返し単位ａまたは繰返し単位ｂの平均繰返し数を示す整数である。〕 [4] Comparative Example 12 (Synthesis of polymer):
Hereinafter, synthesis examples of the X ¹ AB type block copolymer using the initiator 9 will be shown. The X ¹ AB type block copolymer is represented by the following general formula (11). The atomic group X ¹ is an atomic group derived from the initiator 9 ((1-chloroethyl) benzene), the block A is a hydrophobic block composed of a hydrophobic repeating unit a, and the block B is a quaternary ammonium. It is a hydrophilic block composed of a repeating unit b having a cation.

[In general formula (11), l and m are integers indicating the average number of repeating units a or b, respectively. ]

In Comparative Example 12, an X ¹ A type monoblock body was synthesized using the initiator 9 in the same manner as in Comparative Example 11, and an X ¹ AB ′ type diblock body was synthesized from the monoblock body. An XAB type block copolymer was synthesized by quaternizing N atoms in the structure of the X ¹ AB ′ type diblock.

Table 8 shows the types of the initiator and the raw material monomer and the classification of the hydrophobic monomer and the hydrophilic monomer. Further, the molecular weight of the X ¹ A type monoblock and the number of repeats in block A (l), the molecular weight of the X ¹ AB ′ type diblock and the number of repeats in block B ′ (m), the X ¹ AB type block copolymer Table 9 shows the molecular weight and the type of quaternizing agent used in the synthesis and the quaternization rate. The “target value” in the table is the target number of repeating units.

[5] Evaluation:
The performance of the initiator, the symmetry of the synthesized block copolymer, the adhesiveness and the charging property were evaluated according to the following criteria.

(1) Initiator performance:
Examples 1 to 18 and Comparative Examples 1 to 10 were evaluated based on the difference between the target number of repeating units and the actually measured number of repeating units in the synthesis of the B′X′B ′ type diblock body. Further, Comparative Examples 11 and 12 were evaluated based on the difference between the target number of repeating units and the actually measured number of repeating units in the synthesis of the X ¹ A type monoblock body. The results are shown in Tables 10 and 11.
○: The difference between the target value of the number of repeat units and the measured value is within ± 3 △: The difference between the target value of the number of repeat units and the measured value exceeds ± 3 and within ± 6 ×: The target value of the repeat unit number and the measured value Value difference exceeds ± 6

(2) Symmetry of the copolymer:
The polydispersity Mw / Mn calculated from the number average molecular weight Mn and the weight average molecular weight Mw measured by the GPC method was evaluated. The results are shown in Table 10 and Table 11. Since the diblock copolymer of Comparative Example 12 had no symmetry, it was not evaluated (denoted as “−” in the table), but the polydispersity was measured. The copolymer of Comparative Example 12 had Mw / Mn of 1.36.
○: Mw / Mn is 1.0 to 1.20
Δ: Mw / Mn exceeds 1.20 and within 1.40 ×: Mw / Mn exceeds 1.40

(3) Coatability / durability of copolymer:
The copolymers of Examples and Comparative Examples were diluted with methyl ethyl ketone to prepare a copolymer solution having a concentration of 30%. Separately, polyurethane was diluted with methyl ethyl ketone to prepare a binder solution having a concentration of 30%. The copolymer liquid and the binder liquid were mixed at the following blending ratio.
Polymer dilution: 10 g (solid content conversion)
Binder resin liquid: 30g (solid content conversion)

This mixture was applied to the surface of a PET film (trade name “Lumirror T60 # 100”, manufactured by Toray Industries, Inc.) so that the coating area was 100 cm ² or more and the film thickness was 0.1 mm to 5 mm. This was heated at 140 ° C. for 60 minutes to form a thin film.

The formed thin film was observed visually and with an optical microscope. Moreover, the peeling test based on JISK5600 was done using the commercially available adhesive tape. However, instead of making a grid-like scratch on the surface of the thin film, an arbitrary 10 points of the thin film were selected and a 5 mm square square-shaped scratch was made. The state of the film surface before and after the peel test was observed visually and with an optical microscope. Based on the results of the observation and the tape peeling test, the coatability and durability (strength, peel resistance) of the copolymer were evaluated. Tables 10 and 11 show.
○: A uniform film is formed, and peeling does not occur in the tape peeling test. Δ: A uniform film is formed, but peeling occurs in the tape peeling test. ×: A uniform film is not formed (bubbles on the film surface) Oil droplet aggregation is observed)

(4) Chargeability:
The surface resistivity of the thin film formed by the adhesive evaluation was measured according to the method of JIS K6911, and the chargeability of the thin film made of the copolymer was evaluated. The results are shown in Table 10 and Table 11.
○: The surface resistivity of the thin film is 5.0 × 10 ⁹ Ω / □ or more. Δ: The surface resistivity of the thin film is 5.0 × 10 ⁸ Ω / □ or more and less than 5.0 × 10 ⁹ Ω / □. The surface resistivity of the thin film is less than 5.0 × 10 ⁸ Ω / □

  As is clear from the results shown in Table 10 and Table 11, initiators 1 to 6 showed good performance. Among them, the initiators 1, 2, 4 to 6 showed particularly good performance. Moreover, the copolymers of Examples 1 to 18 were excellent in symmetry, and Examples 1 to 7 and 9 to 18 were particularly excellent in symmetry.

  Furthermore, the copolymers of Examples 1 to 18 were excellent in durability (strength). Among them, the copolymers of Examples 1 to 6, 8, 10, 15, and 16 showed particularly good durability. Furthermore, the copolymers of Examples 1 to 18 were excellent in chargeability. Among them, the copolymers of Examples 1 to 5, 7, 8, 10, 11, 13, 15, and 16 showed particularly good chargeability.

  The ABXBA type block copolymer according to the present invention has high adhesiveness to the resin surface, is excellent in durability, and can maintain a stable charge control effect over a long period of time. Therefore, it can be suitably used as an antistatic agent for preventing deterioration of the original function of the resin or a charge control agent for modifying the surface of the resin material.

Claims (5)

An ABXBA type block copolymer represented by the following general formula (1),
The atomic group X is an atomic group having any one quaternary ammonium cation selected from the following general formulas (2) to (4) and (2 ′) to (4 ′):
A hydrophobic block in which block A consists of a hydrophobic repeating unit a;
An ABXBA type block copolymer, wherein the block B is a hydrophilic block comprising a repeating unit b having a quaternary ammonium cation.

[In general formula (1), l, m, n, and o are integers each representing the average number of repeating units a or b, and 15 ≦ (l + o) ≦ 105, 20 ≦ (m + n) ≦. The condition of 105 is satisfied. ]

[In General Formulas (2) to (4) and (2 ′) to (4 ′), R ¹ represents an alkyl group having 1 to 4 carbon atoms. R ² and R ³ each represent an alkanediyl group having 1 to 4 carbon atoms. R ⁴ represents an alkyl group having 1 to 20 carbon atoms. ]   The ABXBA type block copolymer according to claim 1, wherein the repeating unit a is one selected from the group consisting of a (meth) acrylic acid ester unit, a vinyl carboxylate unit, and an aromatic vinyl unit.   The repeating unit b has a skeleton of one selected from the group consisting of a (meth) acrylic acid ester unit having an amine structure, a (meth) acrylamide unit, and an N-vinylamide unit, and an N atom in the skeleton is alkylated. The ABXBA type block copolymer according to claim 1, which has a quaternary ammonium cation obtained in this manner. The atomic group X is an atomic group having a quaternary ammonium cation represented by the general formula (2), (3) or (2 ′),
The repeating unit a is an alkyl (meth) acrylate unit;
2. The ABXBA block copolymer according to claim 1, wherein the repeating unit b has a quaternary ammonium cation obtained by alkylating a N atom in the skeleton having a (meth) acrylic acid dialkylaminoalkyl unit as a skeleton. Gel permeation degree of distribution (Mw / Mn) is calculated from the measured number-average molecular weight Mn and the weight average molecular weight Mw by molecular weight distribution method according to claim 1 in the range of 1.0 to 1.2 ABXBA type block copolymer.