JP2014098112A5 - - Google Patents

Description

Aluminum-containing copolymer resin and method for producing the same

  The present invention can be used for charge control applications, an aluminum-containing copolymer resin in which a part of a unit obtained from a specific styrene derivative is metal-complexed or salified with aluminum, and the resin as an active ingredient It relates to a charge control agent.

  Conventionally, styrenic resins are widely used because they have a good balance between price, transparency, mechanical strength, and moldability. For example, home appliances, office equipment, household goods, food containers, packaging materials Used for toys. Various molding methods can be used. For example, the molding is performed by methods such as injection molding, extrusion molding, hollow molding, vacuum molding, and injection molding. In general, styrenic resins are mainly produced by thermal polymerization or radical polymerization using an initiator. The main production processes include a bulk polymerization method and a suspension polymerization method, but the bulk polymerization method has become mainstream because impurities such as a dispersant are difficult to be mixed and it is advantageous in terms of cost.

  Styrene monomers, which are raw materials for styrene resins, are widely used as raw materials for many synthetic resins and are industrially important monomers. For example, as a binder resin for toner used in the field of electrophotography, polystyrene; poly-p-chlorostyrene; polyvinyltoluene; styrene-p-chlorostyrene copolymer; styrene-vinyltoluene copolymer; styrene-vinyl. Naphthalene copolymer; Styrene-acrylic acid ester copolymer; Styrene-methacrylic acid ester copolymer; Styrene-α-chloromethyl methacrylate copolymer; Styrene-acrylonitrile copolymer; Styrene-vinyl methyl ether copolymer Styrene-vinyl ethyl ether copolymer; styrene-vinyl methyl ketone copolymer; styrene-butadiene copolymer; styrene-isoprene copolymer; styrene-acrylonitrile-indene copolymer; styrene monomer and acrylamide, vinyl chloride , Acetic acid Alkenyl, vinyl benzoic acid, ethylene, propylene, butylene, vinyl methyl ether, and styrenic copolymer of at least one comonomer selected from vinyl isobutyl ether and the like are used.

  Furthermore, for electrophotographic toners, the rising speed of charging of the toner is increased, the toner is sufficiently charged and stabilized while appropriately controlling the amount of charge, and the charging characteristics are improved. In order to form a clear image while speeding up, a charge control agent is added to the toner in advance. Currently, charge control agents known in the art include negative triboelectric charge control agents including metal complexes of monoazo dyes, metal complexes such as hydroxycarboxylic acids, dicarboxylic acids, and aromatic diols, and acid components. Resins are known. Further, as a positive triboelectric charge control agent, nigrosine dyes, azine dyes, triphenylmethane dyes and pigments, polymers having a quaternary ammonium salt or a quaternary ammonium salt in the side chain are known. The above charge control agent is difficult to balance the image density and fog, it is difficult to obtain a sufficient image density in a high humidity environment, the dispersibility in the resin is poor, the storage stability, the fixability and the anti-resistance. There is a problem that the offset property is adversely affected, and there is room for improvement.

  As an attempt for such improvement, efforts have been made to use a resin having charge control characteristics as a toner for developing an electrostatic charge image with improved compatibility with the toner resin.

  As an attempt to make a resin, Patent Document 1 describes a toner for developing an electrostatic image containing a copolymer composed of at least a styrene derivative and a styrene derivative having a carboxyl group and a hydroxyl group. Further, Patent Document 2 discloses a negatively chargeable toner containing a negatively chargeable charge adjusting agent comprising a polymer of a polymerizable composition containing a radical polymerizable monomer having a diphenyl group optionally substituted with a carboxyl group. Is described. Patent Document 3 discloses a charge control agent comprising 1 to 30% by weight of sulfoalkyl (meth) acrylic acid monomers and 99 to 70% by weight of other vinyl monomers copolymerizable therewith, An electrophotographic negatively charged toner containing 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder is described.

  As an attempt of a metallized resin, Patent Document 4 discloses a carboxyl group-containing acrylic having a weight average molecular weight maximum value of 13,000, a weight molecular weight of 14,000, Mw / Mn = 2.1, and an acid value of 4.0. 50 parts by weight of a resin and 50 parts by weight of a carboxyl group-containing acrylic resin having a weight average molecular weight maximum value of 72,600, a weight molecular weight of 9760,000, an Mw / Mn = 2.1, and an acid value of 4.0 A toner for developing an electrostatic image is described by melting, kneading, cooling, pulverizing, and classifying an ionomer resin metallized with an aluminum chelate, carbon black, a charge control agent, and a wax. Patent Document 5 discloses a crosslinked polyester resin obtained by crosslinking at least a linear polyester resin and a polyester resin containing a trivalent or higher polyvalent carboxylic acid or a trivalent or higher polyhydric alcohol with a metal alkoxide or a metal chelate compound. A resin for an electrophotographic toner characterized in that it contains is described. Patent Document 6 discloses a toner containing a binder resin, a colorant, and a wax, in which the binder resin is obtained by copolymerizing an addition-polymerizable unsaturated carboxylic acid and another copolymerizable monomer. A polyvalent metal chlorinated polymer obtained by polychlorinating a containing polymer, wherein the wax is an ester of a carboxylic acid and an alcohol, and has a chain hydrocarbon group having 12 to 40 carbon atoms in a part of the molecule. An electrostatic charge image developing toner characterized by a structure is described.

  Accompanying higher performance such as improved resolution of copiers and printers in recent years, and the expansion of applications such as low-speed development as well as high-speed development in electrophotographic systems, the toner charge rise is further adjusted and further improved. Therefore, there has been a demand for a charge control agent that can express the charging characteristics, can form a clear and high-resolution image, and has improved compatibility with the binder resin. In addition, there has been a demand for a charge control agent that can be used in powder coatings used in electrostatic powder coating that attracts and charges an electrostatically charged powder coating to the charge on the surface of the structure.

Japanese Patent Laid-Open No. 04-016858 JP 2000-298379 A Japanese Patent Laid-Open No. 08-179564 Japanese Patent Application Laid-Open No. 07-120973 JP 09-244299 A Japanese Patent Laid-Open No. 2001-305798

  The present invention has been made in order to solve the above-mentioned problems, the compatibility with the binder resin is improved, the rise of charging is quick, the excellent charging characteristics are expressed, and a part thereof is metallized. It is an object of the present invention to provide an aluminum-containing copolymer resin having a unit obtained from a styrene derivative, which has good environmental stability, and a charge control agent containing the resin and used for charge control.

  The inventors of the present invention have studied a charge control resin that has a quick rise in charge, exhibits excellent chargeability, and is partially metallized and has good environmental stability. It has a unit obtained from a styrene derivative having a structure having both a phenyl skeleton having a —COOM group and a hydroxyl group (—OH), and a part of the unit is metal complexed or metal chlorided with aluminum. The present inventors have found that an aluminum-containing copolymer resin is good as a charge control agent, solved the above problems, and completed the present invention.

（式中、Ｒ^１はそれぞれ独立して同一または異なり、水素原子、水酸基、ハロゲン原子、炭素数１〜１８で直鎖若しくは分岐鎖のアルキル基、または炭素数１〜１８で直鎖若しくは分岐鎖のアルコキシ基であり、Ｒ^２は水素原子、水酸基、ハロゲン原子、炭素数１〜１８で直鎖若しくは分岐鎖のアルキル基、または炭素数１〜１８で直鎖若しくは分岐鎖のアルコキシ基であり、ｈは１〜３であり、Ｍは水素原子、アルカリ金属、アンモニウム原子団及びそれらの混合物から選ばれる何れかである）で示されるユニットＡを有する共重合体を含み、前記ユニットＡの少なくとも一部が、アルミニウムで金属錯体化または金属塩化されていることを特徴とする。 The aluminum-containing copolymer resin made to achieve the above object is represented by the following chemical formula (1):

(In the formula, each R ¹ is independently the same or different and is a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or a linear or branched chain having 1 to 18 carbon atoms. R ² is a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or a linear or branched alkoxy group having 1 to 18 carbon atoms, h is 1 to 3, and M is any one selected from a hydrogen atom, an alkali metal, an ammonium atom group, and a mixture thereof), and includes at least one of the units A The part is characterized by being metal complexed or metal chlorided with aluminum.

  In the aluminum-containing copolymer resin, the aluminum content is preferably 0.1 to 8.0% by weight.

（式中、Ｒ^３、Ｒ^４、Ｒ^５は、それぞれ同一または異なり、水素原子、アルキル基、ハロゲン原子、及びアルコキシ基から選ばれる何れかである）で示されることが好ましい。 In the aluminum-containing copolymer resin, the copolymer includes a unit B obtained from a vinyl group-containing monomer,
At least one of the units B has the following chemical formula (2)

(Wherein R ³ , R ⁴ and R ⁵ are the same or different and are each selected from a hydrogen atom, an alkyl group, a halogen atom and an alkoxy group).

In the aluminum-containing copolymer resin, the vinyl group-containing monomer represented by the chemical formula (2) is preferably styrene.

（式中、Ｒ ^６ はメチル基または水素原子であり、Ｒ ^７ は置換基を有してもよいアルコキシ基または水酸基である）で示されるものであることが好ましい。 Examples of other vinyl group-containing monomers include vinyl monomers such as acrylonitrile, methacrylonitrile, methacrylic acid, methyl methacrylate, and vinyl acrylate, and maleic anhydride and maleimide. The unit obtained from the vinyl group-containing monomer has the following chemical formula (10)

(Wherein R ⁶ represents a methyl group or a hydrogen atom, and R ⁷ represents an alkoxy group or a hydroxyl group which may have a substituent).

  In the aluminum-containing copolymer resin, it is preferable that 0.1 to 15 mol% of the unit A is contained in the copolymer.

The glass transition temperature of the aluminum-containing copolymer resin is preferably 60 ° C to 150 ° C.

In the differential thermothermal gravimetric analysis of the aluminum-containing copolymer resin, it is preferable that the weight loss is measured at 200 ° C. to 450 ° C.

It is preferable that the volume resistivity of the aluminum-containing copolymer resin is 0.5 × 10 ^{16 to} 7.0 × 10 ¹⁷ Ωcm.

  The crystallinity of the aluminum-containing copolymer resin is preferably 0.0 to 20.0%.

  Similarly, a charge control agent made to achieve the above object is characterized by containing the aluminum-containing copolymer resin as an active ingredient.

  In addition, the method for producing an aluminum-containing copolymer resin of the present invention, which has been made to achieve the above object, includes a styrene derivative that is unit A represented by the chemical formula (1) and a vinyl group-containing monomer that is different from the styrene derivative. And a metallization step of reacting with a metallizing agent containing aluminum to form a metal complex or metal chloride.

  In the method for producing the aluminum-containing copolymer resin, it is preferable that the polymerization reaction step includes a polymerization initiator.

  In the method for producing the aluminum-containing copolymer resin, after the polymerization reaction step, the obtained polymer and the metallizing agent containing aluminum are reacted to form a metal complex or metal chloride. It is preferable.

  The aluminum-containing copolymer resin of the present invention is partly metallized with aluminum, so it has good environmental stability and improved compatibility with the binder resin for toner, and is used for charge control applications. It acts as a charge control resin and can be used as an active ingredient of a charge control agent.

  The charge control agent of the present invention has good charge controllability, in particular, has a fast charge rise, and can be stably charged for a long time while being charged with a negative charge and uniform and high charge amount. Moreover, environmental stability is good because a part is metallized. Therefore, it is effectively used for a wide range of toner applications from low-speed copying to high-speed copying with a stable, clear and high resolution image. It can also be used for powder coatings used for electrostatic powder coating.

  According to the method for producing an aluminum-containing copolymer resin of the present invention, an aluminum-containing copolymer resin having a charge control function can be easily produced.

It is a figure which shows the chart of the nuclear magnetic resonance spectrum of the styrene derivative of Example 1-A used for the aluminum containing copolymer resin to which this invention is applied. It is a figure which shows the chart of the nuclear overhauser effect by the nuclear magnetic resonance spectrum of the styrene derivative of Example 1-A used for the aluminum containing copolymer resin to which this invention is applied. It is a figure which shows the chart of the infrared absorption spectrum of the styrene derivative of Example 1-A used for the aluminum containing copolymer resin to which this invention is applied. It is a figure which shows the chart of the differential thermal-thermogravimetric analysis of the styrene derivative of Example 1-A used for the aluminum containing copolymer resin to which this invention is applied. It is a figure which shows the chart of the liquid chromatograph-mass spectrometry of the styrene derivative of Example 1-A used for the aluminum containing copolymer resin to which this invention is applied. It is a figure which shows the chart of the nuclear magnetic resonance spectrum of the copolymer of Example 1-B used for the aluminum containing copolymer resin to which this invention is applied. It is a figure which shows the chart of the infrared absorption spectrum of the copolymer of Example 1-B used for the aluminum containing copolymer resin to which this invention is applied. It is a figure which shows the chart of the differential thermal-thermogravimetric analysis of the copolymer of Example 1-B used for the aluminum containing copolymer resin to which this invention is applied. It is a figure which shows the chart of the molecular weight distribution of the copolymer of Example 1-B used for the aluminum containing copolymer resin to which this invention is applied. It is a figure which shows the chart of the glass transition temperature of the metallized copolymer of Example 1-C which is an aluminum containing copolymer resin to which this invention is applied. It is a figure which shows the chart of the infrared absorption spectrum of the metallized copolymer of Example 1-C which is an aluminum containing copolymer resin to which this invention is applied. The chart of the differential thermal-thermogravimetric analysis of the metallized copolymer of Example 1-C, which is an aluminum-containing copolymer resin to which the present invention is applied, is shown. It is a figure which shows the charge amount in the charging property test A of each charge control agent obtained from the aluminum containing copolymer resin to which this invention is applied, and a comparative polymer. It is a figure which shows the charge amount in the charging property test B of each charge control agent obtained from the aluminum containing copolymer resin to which this invention is applied, and a comparative polymer.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

  The aluminum-containing copolymer resin of the present invention comprises a unit A having a structure having both a phenylethylene skeleton derived from a styrene structure and a phenyl skeleton having a —COOM group and a hydroxyl group (—OH) (that is, a skeleton of an aromatic oxycarboxylic acid). And at least a part of the unit A is a metal complex or metal chloride with aluminum, exhibits a charge control function, and functions as a charge control agent. Show.

  Unit A is represented by the following chemical formula (1).

The substituents R ¹ are independently the same or different, for example, a hydrogen atom; a hydroxyl group; a halogen atom such as F, Cl, or Br; a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, or an n-butyl group. , Iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, hexyl group, heptyl group, octyl group, etc. Methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, iso-pentoxy group, hexyloxy group , A heptoxy group, an octyloxy group, a 2-ethylhexyloxy group, etc., and a C1-C18 linear or branched alkoxy group. Of these, a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso -A pentyl group, a hexyl group, a heptyl group, and an octyl group are mentioned.

Similarly, the substituent R ² is, for example, a hydrogen atom; a hydroxyl group; a halogen atom such as F, Cl or Br; an alkali metal salt such as COOH, COONa or COOK; a carbooxy-containing group such as COONH ₄ or a mixture thereof; a methyl group, an ethyl Group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, hexyl group, heptyl group, octyl group A linear or branched alkyl group having 1 to 18 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert- 1 carbon number such as butoxy group, n-pentoxy group, iso-pentoxy group, hexyloxy group, heptoxy group, octyloxy group, 2-ethylhexyloxy group It is a -18 or linear or branched alkoxy group. Of these, a hydrogen atom is preferable.
h is preferably 1 in consideration of reactivity such as steric hindrance and cost.
M is a bonding site with a metal in metal complexation or metal chloride, and when not bonded to a metal, an alkali metal such as a hydrogen atom (H), Li, Na, or K, or an ammonium atom such as NH ₄ Any one selected from a group and mixtures thereof.

  Specific examples of the unit A represented by the chemical formula (1) include a unit A ′ represented by the following chemical formula (3). The scope of the present invention is not limited to these.

In the chemical formula (3), R ¹ , R ² , h and M are the same as those exemplified in the chemical formula (1).

  The unit A can be obtained from, for example, a styrene derivative represented by the following chemical formula (4).

In the chemical formula (4), R ¹ , R ² , h and M are the same as those exemplified in the chemical formula (1).

  This styrene derivative has both a phenyl skeleton having a vinyl group in the same molecule (that is, a styrene skeleton) and a phenyl skeleton having a —COOM group and a hydroxyl group in the same molecule (that is, an aromatic oxycarboxylic acid skeleton). It is.

The phenyl skeleton having a vinyl group of the styrene derivative is an important skeleton exhibiting the polymerization function of the styrene derivative. Further, a combination of a phenyl skeleton having a —COOM group and a hydroxyl group and —CH ₂ —O— is an important skeleton for expressing a charge imparting function. Furthermore, a phenyl skeleton having a —COOM group and a hydroxyl group is a skeleton having intramolecular and intermolecular hydrogen bonds presumed to contribute to charging and a function of a ligand.

  Therefore, the unit A represented by the chemical formula (1) constituting the copolymer contained in the aluminum-containing copolymer resin of the present invention has a phenyl skeleton derived from a styrene structure and a phenyl skeleton having a -COOM group and a hydroxyl group. Both are functional units for charge application and charge control applications. This unit A can be used as a charge control agent by using the above functions alone or in combination, and to synthesizing the substituent effect of the styrene derivative and the similarity of the structure to the resin. The dispersibility of is improved.

The unit A represented by the chemical formula (1) has the performance that the higher the alkyl group in R ¹ is, the higher the hydrophobicity is, so that the longer the carbon chain is, the higher the saturation chargeability and the better the environmental stability. The aluminum-containing copolymer resin in which R ¹ is a butyl group, particularly a tert-butyl group, can exhibit better chargeability.

  In unit A, the —OH group (hydroxyl group) represented by the chemical formula (1) is in the ortho position with respect to the —COOM group, so the synergistic effect of the —COOM group and the —OH group is strong, contributing to the charging effect. In addition, a function of complexing with metal or metal chloride as a ligand is developed.

Among all the units A constituting the copolymer contained in the aluminum-containing copolymer resin, at least a part of the units A is a metal complex or metal chloride. As shown in the following chemical formulas (a), (b), and (c), the unit A is formed into a metal complex or metal chloride by trivalent aluminum and the -COOM group and / or -OH group of the unit A. Guessed. Moreover, the carboxy group of several units A and aluminum may comprise a complex.
Among the structures shown above, the aluminum-containing copolymer resin may contain only one kind or may contain a plurality of kinds. The scope of the present invention is not limited to these.

R ¹ , R ² , h and M shown in the chemical formulas (a), (b) and (c) are the same as those exemplified in the chemical formula (1). Y is a monovalent or divalent anion, z is 2 when Y is monovalent, and z is 1 when Y is divalent.
In addition, the dotted line in the said chemical formula shows a covalent bond or an ionic bond.

  In the aluminum-containing copolymer resin, the aluminum content is 0.1 to 8.0% by weight, preferably 0.5 to 5% by weight, and more preferably 1 to 3% by weight.

The aluminum-containing copolymer resin of the present invention is a step of polymerizing a monomer containing a styrene derivative to be unit A (preferably, styrene to be unit A represented by the chemical formula (1) in the presence of a polymerization initiator). A monomer containing a derivative and a vinyl group-containing monomer different from the derivative is polymerized.), And can be produced by a metal complexation or metal chloride step. The method for producing an aluminum-containing copolymer resin of the present invention includes at least the two reaction steps, of which two methods can be mentioned.
The method (I) is a method in which a monomer containing a styrene derivative is polymerized to obtain a polymer, which is then converted into a metal complex or metal chloride to obtain an aluminum-containing copolymer resin.
The method (II) is a method of obtaining an aluminum-containing copolymer resin by synthesizing a polymer by forming a metal complex or metal chloride of a styrene derivative and polymerizing it. That is, the step of producing the aluminum-containing copolymer resin of the present invention can include a polymerization reaction step for obtaining a polymer and a metallization step for metal complexation or metal chloride in any order.

  Hereinafter, the production method of the present invention will be specifically described by exemplifying the method (I). Similarly, in the method (II), the polymerization reaction step and the metallization are appropriately adjusted according to the physical properties of each compound. A process can be performed.

  The polymerization reaction step in the method for producing an aluminum-containing copolymer resin of the present invention is a polymerization reaction in a reaction system having at least a styrene derivative serving as unit A as a monomer. Preferably, in the presence of a polymerization initiator, a monomer containing a styrene derivative that is unit A represented by the chemical formula (1) and a vinyl group-containing monomer different from the styrene derivative is polymerized to obtain a copolymer. Get.

The styrene derivative used as the unit A is not limited to a compound having a structure having both a styrene skeleton and a phenyl skeleton having a —COOM group and a hydroxyl group in advance as shown in the chemical formula (4). The compound which has only a part may be sufficient. As the styrene derivative having only a part of the structure of unit A, for example, —CH ₂ —X (X is a halogen atom) bonded to a styrene skeleton, and phenyl having a —COOM group and a hydroxyl group after the polymerization reaction. It may be such that a skeleton is introduced.

  The synthesis of the styrene derivative represented by the chemical formula (4) among the styrene derivatives to be unit A will be described in detail below.

  The styrene derivative represented by the chemical formula (4) is easily synthesized by using a known method, for example, using the Williamson reaction described in page 187 of Experimental Chemistry Course 4th edition (edited by Chemical Society of Japan, published by Maruzen Co., Ltd.). can do. The synthesis step of the styrene derivative includes, for example, a vinylphenyl halogenated alkylene having or not having a substituent, a dihydroxy aromatic carboxylic acid having or without a substituent and an alkyl ester thereof, preferably hydroxysalicylic acid, in a solvent. A styrene derivative is synthesized by reacting the alkyl ester. One example is shown in the following reaction formula (5). In addition, a vinyl phenyl halogenated alkylene having or not having a substituent and a dihydroxy aromatic carboxylic acid having or not having a substituent may be reacted by selecting one type of each component or by converting each component to 2 More than one type can be combined and mixed to react.

In the reaction formula (5), R ¹ , R ² , M, and h are the same as described above, and X is, for example, a halogen atom such as F, Cl, or Br.

Specific examples of the vinyl phenyl halogenated alkylene group with or without a substituent include 4- (chloromethyl) styrene, 4- (bromomethyl) styrene, 3-methoxy-4- (chloromethyl) styrene, and 3-methoxy-4. -(Bromomethyl) styrene, 2-hydroxy-4- (chloromethyl) styrene, 2-hydroxy-4- (bromomethyl) styrene, 3-bromo-4- (chloromethyl) styrene, 3-bromo-4- (bromomethyl) Styrene, 2-methoxy-4- (chloromethyl) styrene, 2-methoxy-4- (bromomethyl) styrene, 2-chloro-4- (chloromethyl) styrene, 2-chloro-4- (bromomethyl) styrene, 3- Fluoro-4- (chloromethyl) styrene, 3-fluoro-4- (bromomethyl) styrene, 2-butyl Mo-4- (chloromethyl) styrene, 2-bromo-4- (bromomethyl) styrene, 3-tert-butyl-4- (chloromethyl) styrene, 3-tert-butyl-4- (bromomethyl) styrene, 3- Isooctyl-4- (chloromethyl) styrene, 3-isooctyl-4- (bromomethyl) styrene, 3-isopropyl-4- (chloromethyl) styrene, 3-isopropyl-4- (bromomethyl) styrene, 3-methyl-4- (Chloromethyl) styrene, 3-methyl-4- (bromomethyl) styrene, 3-ethoxy-4- (chloromethyl) styrene, 3-ethoxy-4- (bromomethyl) styrene, 3-carboxy-4- (chloromethyl) P-halogenated methylstyrene derivatives such as styrene and 3-carboxy-4- (bromomethyl) styrene;
3- (chloromethyl) styrene, 3- (bromomethyl) styrene, 5-methyl-3- (chloromethyl) styrene, 5-methyl-3- (bromomethyl) styrene, 5-isopropyl-3- (chloromethyl) styrene, 5-isopropyl-3- (bromomethyl) styrene, 5-isooctyl-3- (chloromethyl) styrene, 5-isooctyl-3- (bromomethyl) styrene, 5-methoxy-3- (chloromethyl) styrene, 5-methoxy- 3- (bromomethyl) styrene, 4-ethoxy-3- (chloromethyl) styrene, 4-ethoxy-3- (bromomethyl) styrene, 4-carboxy-3- (chloromethyl) styrene, 4-carboxy-3- (bromomethyl) ) Styrene, 5-hydroxy-3- (chloromethyl) styrene, 5-hydroxy- -(Bromomethyl) styrene, 4-hydroxy-3- (chloromethyl) styrene, 4-hydroxy-3- (bromomethyl) styrene, 4-methoxy-3- (chloromethyl) styrene, 4-methoxy-3- (bromomethyl) Styrene, 5-chloro-3- (chloromethyl) styrene, 5-chloro-3- (bromomethyl) styrene, 4-bromo-3- (chloromethyl) styrene, 4-bromo-3- (bromomethyl) styrene, 2- M such as bromo-3- (chloromethyl) styrene, 2-bromo-3- (bromomethyl) styrene, 5-tert-butyl-3- (chloromethyl) styrene, 5-tert-butyl-3- (bromomethyl) styrene, etc. A halogen-containing methylstyrene derivative;
2- (chloromethyl) styrene, 2- (bromomethyl) styrene, 3-tert-butyl-2- (chloromethyl) styrene, 3-tert-butyl-2- (bromomethyl) styrene, 4-chloro-2- (chloro O-halogen-containing methylstyrene derivatives such as methyl) styrene, 4-chloro-2- (bromomethyl) styrene;
4- (2′-bromoethyl) styrene, 4- (2′-chloroethyl) styrene, 3-methoxy-4- (2′-bromoethyl) styrene, 3-methoxy-4- (2′-chloroethyl) styrene, 2- Hydroxy-4- (2′-bromoethyl) styrene, 2-hydroxy-4- (2′-chloroethyl) styrene, 3-ethoxy-4- (2′-bromoethyl) styrene, 3-ethoxy-4- (2′- Chloroethyl) styrene, 3-bromo-4- (2′-bromoethyl) styrene, 3-bromo-4- (2′-chloroethyl) styrene, 3-tert-butyl-4- (2′-bromoethyl) styrene, 3- p-halogenated ethylstyrene derivatives such as tert-butyl-4- (2′-chloroethyl) styrene;
3- (2′-bromoethyl) styrene, 3- (2′-chloroethyl) styrene, 5-isopropyl-3- (2′-bromoethyl) styrene, 5-isopropyl-3- (2′-chloroethyl) styrene, 5- Chloro-3- (2′-bromoethyl) styrene, 5-chloro-3- (2′-chloroethyl) styrene, 5-hydroxy-3- (2′-bromoethyl) styrene, 5-hydroxy-3- (2′- Chloroethyl) styrene, 4-hydroxy-3- (2′-bromoethyl) styrene, 4-hydroxy-3- (2′-chloroethyl) styrene, 4-bromo-3- (2′-bromoethyl) styrene, 4-bromo- M-halogenated ethylstyrene derivatives such as 3- (2′-chloroethyl) styrene;
2- (2′-bromoethyl) styrene, 2- (2′-chloroethyl) styrene, 3-tert-butyl-2- (2′-bromoethyl) styrene, 3-tert-butyl-2- (2′-chloroethyl) O-halogen-containing ethylstyrene derivatives such as styrene;
4- (3′-bromopropyl) styrene, 4- (3′-chloropropyl) styrene, 2-methoxy-4- (3′-bromopropyl) styrene, 2-methoxy-4- (3′-chloropropyl) Styrene, 2-isopropyl-4- (3′-bromopropyl) styrene, 2-isopropyl-4- (3′-chloropropyl) styrene, 2-isooctyl-4- (3′-bromopropyl) styrene, 2-isooctyl P-Halogen-containing propylstyrene derivatives such as 4- (3'-chloropropyl) styrene, 3-methoxy-4- (3'-bromopropyl) styrene, 3-methoxy-4- (3'-chloropropyl) styrene ;
3- (3′-bromopropyl) styrene, 3- (3′-chloropropyl) styrene, 5-isooctyl-3- (3′-bromopropyl) styrene, 5-isooctyl-3- (3′-chloropropyl) M-halogenated propyl styrene such as styrene, 5-methoxy-3- (3′-bromopropyl) styrene, 5-methoxy-3- (3′-chloropropyl) styrene, 2- (3′-bromopropyl) styrene, etc. Derivatives;
And o-halogenated propylstyrene derivatives such as 2- (3′-chloropropyl) styrene.

Dihydroxy aromatic carboxylic acids with or without substituents are specifically 2,3-dihydroxybenzoic acid, 5-methyl-2,3-dihydroxybenzoic acid, 5-ethyl-2,3-dihydroxybenzoic acid, 5-isopropyl-2,3-dihydroxybenzoic acid, 5-n-butyl-2,3-dihydroxybenzoic acid, 5-tert-butyl-2,3-dihydroxybenzoic acid, 5-sec-butyl-2,3- Dihydroxybenzoic acid, 5-isoheptyl-2,3-dihydroxybenzoic acid, 5-isohexyl-2,3-dihydroxybenzoic acid, 5-isooctyl-2,3-dihydroxybenzoic acid, 5-fluoro-2,3-dihydroxybenzoic acid Acid, 5-chloro-2,3-dihydroxybenzoic acid, 5-bromo-2,3-dihydroxybenzoic acid, 5-fluoro-4-methoxy Cis-2,3-dihydroxybenzoic acid, 4-ethyl-2,3-dihydroxybenzoic acid, 4-methoxy-2,3-dihydroxybenzoic acid, 4-ethoxy-2,3-dihydroxybenzoic acid, 2,3, 2, such as 4-trihydroxybenzoic acid, 4-fluoro-5-methoxy-2,3-dihydroxybenzoic acid, 6-isopropyl-2,3-dihydroxybenzoic acid, 6-butoxy-2,3-dihydroxybenzoic acid 3-dihydroxybenzoic acid derivatives;
2,4-dihydroxybenzoic acid, 6-methyl-2,4-dihydroxybenzoic acid, 6-ethyl-2,4-dihydroxybenzoic acid, 6-isopropyl-2,4-dihydroxybenzoic acid, 6-tert-butyl- 2,4-dihydroxybenzoic acid, 6-sec-butyl-2,4-dihydroxybenzoic acid, 6-isohexyl-2,4-dihydroxybenzoic acid, 6-isoheptyl-2,4-dihydroxybenzoic acid, 6-isooctyl- 2,4-dihydroxybenzoic acid, 5-methoxy-2,4-dihydroxybenzoic acid, 6-butoxy-2,4-dihydroxybenzoic acid, 6-chloro-2,4-dihydroxybenzoic acid, 6-bromo-2, 4-dihydroxybenzoic acid, 6-iodo-2,4-dihydroxybenzoic acid, 5-n-propyl-2,4-dihydroxybenzoic acid, 5-d Toxi-2,4-dihydroxybenzoic acid, 5-chloro-2,4-dihydroxybenzoic acid, 5-bromo-2,4-dihydroxybenzoic acid, 6-methyl-2,4,5-trihydroxybenzoic acid, 5 , 6-Di-tert-butyl-2,4-dihydroxybenzoic acid, 3-tert-butyl-2,4-dihydroxybenzoic acid, 3-isooctyl-2,4-dihydroxybenzoic acid, 3-chloro-2,4 -2,4-dihydroxybenzoic acid derivatives such as dihydroxybenzoic acid, 3-fluoro-2,4-dihydroxybenzoic acid, 3-bromo-2,4-dihydroxybenzoic acid;
2,5-dihydroxybenzoic acid, 3-methyl-2,5-dihydroxybenzoic acid, 3-ethyl-2,5-dihydroxybenzoic acid, 3-isopropyl-2,5-dihydroxybenzoic acid, 3-tert-butyl- 2,5-dihydroxybenzoic acid, 3-sec-butyl-2,5-dihydroxybenzoic acid, 3-isohexyl-2,5-dihydroxybenzoic acid, 3-isoheptyl-2,5-dihydroxybenzoic acid, 3-isooctyl- 2,5-dihydroxybenzoic acid, 3-tert-butoxy-2,5-dihydroxybenzoic acid, 3-chloro-2,5-dihydroxybenzoic acid, 3-bromo-2,5-dihydroxybenzoic acid, 3-iodo- 2,5-dihydroxybenzoic acid, 3-fluoro-2,5-dihydroxybenzoic acid, 6-methoxy-2,5-dihydroxybenzoic acid, 6- Toxi-2,5-dihydroxybenzoic acid, 3-methyl-2,5,6-trihydroxybenzoic acid, 6-fluoro-4-methoxy-2,5-dihydroxybenzoic acid, 3,4-diisopropyl-2,5 -Dihydroxybenzoic acid, 3,4-di-tert-butyl-2,5-dihydroxybenzoic acid, 4-chloro-3-tert-butyl-2,5-dihydroxybenzoic acid, 4-fluoro-2,5-dihydroxy 2,5-dihydroxybenzoic acid derivatives such as benzoic acid;
2,6-dihydroxybenzoic acid, 3-bromo-2,6-dihydroxybenzoic acid, 4-bromo-2,6-dihydroxybenzoic acid, 5-bromo-2,6-dihydroxybenzoic acid, 3-chloro-2, 6-dihydroxybenzoic acid, 4-chloro-2,6-dihydroxybenzoic acid, 5-chloro-2,6-dihydroxybenzoic acid, 3-isopropyl-2,6-dihydroxybenzoic acid, 4-tert-butyl-2, Examples include 2,6-dihydroxybenzoic acid derivatives such as 6-dihydroxybenzoic acid and 5-methyl-2,6-dihydroxybenzoic acid. These dihydroxybenzoic acids may be used alone or in combination of two or more.

  Specific examples of the reaction solvent include methanol, ethanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), ethylene glycol diethyl ether, triglyceride. Alcohol-based, ether-based, and glycol-based organic solvents such as ethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), ethylene glycol, propylene glycol, etc .; N, N-dimethylformamide, N, N-dimethyl Non-pro such as acetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide Polar solvents; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, ethyl propionate, cellosolve acetate; hexane, octane, petroleum ether, cyclohexane, benzene, toluene, xylene, etc. Hydrocarbons; organic solvents such as halogenated hydrocarbons such as trichloroethylene, dichloromethane, and chloroform.

  In the synthesis reaction of a styrene derivative, it is preferable to add a base in order to accelerate the reaction and capture hydrogen halide produced as a by-product during ether bond formation.

  The base that can be used in this synthesis is not particularly limited as long as it reacts with a solvent or a substrate and does not complicate the reaction system. For example, an alkali metal such as lithium hydroxide, sodium hydroxide, or potassium hydroxide is used. And alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, and rubidium carbonate, and alkali metal hydrides such as lithium hydride, sodium hydride, and potassium hydride. . M in the chemical formula (5) may be an alkali metal in the synthesis of Williamson, may be liberated, or may be a cation exchanged.

  The styrene derivative thus obtained is used as a polymer monomer, and is useful as a styrene monomer capable of controlling charge control.

  Specific examples of the styrene derivative represented by the chemical formula (4) include the following chemical formulas (4-a) to (4-c). The scope of the present invention is not limited to these.

In Table 1-9, the case where the substituent R ¹ is only hydrogen atoms is expressed as H, if it contains a non-hydrogen atoms, it is denoted a substituent other than hydrogen atom. In addition, the numerical value of h is ¹ when the substituent R ¹ is only a hydrogen atom, and is otherwise described without counting the hydrogen atoms that are substituents.
The synthesized styrene derivative can be polymerized as a monomer regardless of the presence or absence of a polymerization initiator and a solvent, whereby a polymer having unit A can be obtained. These styrene derivatives may be used alone as a monomer, or may be used as a mixture of plural kinds.

  The polymerization reaction step in the method for producing an aluminum-containing copolymer resin of the present invention may contain a vinyl group-containing monomer as a monomer in addition to the styrene derivative. Preferably, in the presence of a solvent, the styrene derivative represented by the chemical formula (4), one or more other vinyl group-containing monomers, and a polymerization initiator are mixed and polymerized. The obtained polymer is a copolymer having unit A obtained from a styrene derivative and unit B obtained from a vinyl group-containing monomer. An example of this reaction system is shown in the following reaction formula (6).

  In the reaction formula (6), the monomers α, β, and γ are monomers other than the styrene derivative represented by the chemical formula (4), and are different vinyl group-containing monomers.

  Examples of vinyl group-containing monomers include vinyl aromatic hydrocarbon monomers such as styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, and p-chlorostyrene; (meth) acrylic Methyl methacrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid-tert -Butyl, (meth) acrylate-n-pentyl, isopentyl (meth) acrylate, neopentyl (meth) acrylate, 3- (methyl) butyl (meth) acrylate, hexyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, noni (meth) acrylate (Meth) such as ruthenium, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, β-methacryloyloxyethyl hydrogen phthalate Monofunctional vinyl group-containing monomers such as vinyl chloride, vinyl acetate, vinyl benzoate, vinyl methyl ethyl ketone, vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl toluene; divinylbenzene And bifunctional vinyl group-containing monomers such as diethylene glycol (meth) acrylate; monomers having three or more reactive vinyl groups. These monomers can be used alone or in combination of two or more. In addition, (meth) acrylic acid shows acrylic acid or methacrylic acid (α-methylacrylic acid which is an α-methyl derivative of acrylic acid). These acids (salts) refer to these free acids or metal salts of these acids. Similarly, (meth) acrylate represents acrylate or methyl acrylate.

  Examples of the vinyl group-containing monomer include vinyl aromatic hydrocarbon monomers. As a vinyl aromatic hydrocarbon type monomer, the compound shown by following Chemical formula (7) is mentioned, for example.

In said chemical formula (7), R < ³ >, R < ⁴ >, R < ⁵ > is the same or different, for example, a hydrogen atom; a methyl group, an ethyl group, a propyl group, iso-propyl group, n-butyl group, iso-butyl group , Sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, hexyl group, heptyl group, octyl group, etc., and a linear or branched alkyl group having 1 to 8 carbon atoms; methoxy group, ethoxy group Group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, iso-pentoxy group, hexyloxy group, heptoxy group, octyl Examples thereof include linear or branched alkoxy groups having 1 to 8 carbon atoms such as an oxy group; and halogen atoms such as F, Cl and Br.
The substituents R ³ , R ⁴ , and R ⁵ may have a substituent such as an alkyl group, an alkoxy group, a halogen atom, a nitro group, or a hydroxyl group as a substituent.

  A unit obtained from a vinyl aromatic hydrocarbon monomer is represented by the following chemical formula (2).

In the chemical formula (2), R ³ , R ⁴ and R ⁵ are the same as described above.

  Examples of the vinyl aromatic hydrocarbon include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, and 2-propyl. Styrene, 3-propylstyrene, 4-propylstyrene, 2-isopropylstyrene, 3-isopropylstyrene, 4-isopropylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2-methyl-α-methylstyrene 3-methyl-α-methylstyrene, 4-methyl-α-methylstyrene, 2-ethyl-α-methylstyrene, 3-ethyl-α-methylstyrene, 4-ethyl-α-methylstyrene, 2-propyl- α-methylstyrene, 3-propyl-α-methylstyrene, 4-propyl-α-me Styrene, 2-isopropyl-α-methylstyrene, 3-isopropyl-α-methylstyrene, 4-isopropyl-α-methylstyrene, 2-chloro-α-methylstyrene, 3-chloro-α-methylstyrene, 4-chloro -Α-methylstyrene, 2,3-dimethylstyrene, 3,4-dimethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 2,3-diethylstyrene, 3,4-diethylstyrene, 2, 4-diethylstyrene, 2,5-diethylstyrene, 2-methyl-3-ethylstyrene, 2-methyl-4-ethylstyrene, 2-chloro-4-methylstyrene, 2,3-dimethyl-α-methylstyrene, 3,4-dimethyl-α-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethyl-α-methylstyrene, 2,3 -Diethyl-α-methylstyrene, 3,4-diethyl-α-methylstyrene, 2,4-diethyl-α-methylstyrene, 2,5-diethyl-α-methylstyrene, 2-ethyl-3-methyl-α -Methylstyrene, 2-methyl-4-propyl-α-methylstyrene, 2-chloro-4-ethyl-α-methylstyrene, 2-methoxystyrene, 3-ethoxystyrene, 4-ethoxystyrene, 2-isoproxystyrene Etc. These vinyl aromatic hydrocarbons may be used alone or in combination of two or more.

  Moreover, styrene is mentioned as a vinyl group containing monomer. A unit obtained from this styrene is represented by the following chemical formula (8).

  Further, examples of vinyl group-containing monomers include hydrophilic unsaturated monomers. Examples of the hydrophilic unsaturated monomer include (meth) acrylic acid (salt); hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid-2-hydroxypropyl, and the like ( (Meth) acrylic acid alkyl esters; (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethyl (Meth) acrylamides such as aminopropyl (meth) acrylamide and N, N-dimethyl (meth) acrylamide; ethyl (meth) acrylamide sulfonic acid (salt), propyl (meth) acrylamide sulfonic acid (salt), tert-butyl ( (Meth) acrylamide sulfonic acid (salt) Any alkyl (meth) acrylamide sulfonic acid or ester thereof; styrene sulfonic acid (salt), methallyl sulfonic acid (salt), acryloylmorpholine, acrylonitrile, monobutyl maleate, isobutyl maleate, itaconic acid, fumaric acid and the like. These monomers may be used alone or in combination of two or more. Of these monomers, (meth) acrylic acid (salt), (meth) acrylic acid alkyl esters, tert-butylacrylamide sulfonic acid (salt), styrene sulfonic acid (salt), and the like are preferable. In addition, (meth) acrylic acid shows acrylic acid or methacrylic acid (α-methylacrylic acid which is an α-methyl derivative of acrylic acid). These acids (salts) refer to these free acids or metal salts of these acids.

  The (meth) acrylic acid alkyl esters, acrylic acid and salts thereof, methacrylic acid (α-methylacrylic acid which is an α-methyl derivative of acrylic acid) and salts thereof, and hydrophilic group-substituted alkyl esters thereof are vinyl groups. It can be used as a containing monomer. These compounds are represented by the following chemical formula (9).

In the chemical formula (9), R ⁶ represents a methyl group or a hydrogen atom, and R ⁷ represents a hydroxyl group or an alkoxy group which may have a substituent. Examples of the alkoxy group that may have a substituent include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a sec-butoxy group, and a tert-butoxy group. N-pentoxy group, iso-pentoxy group, hexyl group, heptoxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, stearyloxy group and the like. Examples of the substituent for the alkoxy group include a hydroxyl group, a carboxyl group, and an alkoxy group.

  A unit obtained from the compound represented by the chemical formula (9) is represented by the following chemical formula (10).

In the chemical formula (10), R ⁶ and R ⁷ are the same as described above.

  Each unit constituting the copolymer obtained in the polymerization reaction step includes a unit A represented by the chemical formula (1) and / or a unit A ′ represented by the chemical formula (3), and a vinyl group-containing monomer. Among the units B obtained from the above, the unit represented by the chemical formula (2) is preferable. Table 10 shows specific combinations of examples of copolymers having units represented by the chemical formulas (1), (2), (3), (8), and (10) obtained from the respective monomers. . The scope of the present invention is not limited to these examples.

  In Table 10, monomers α, β, and γ are different vinyl group-containing monomers. Moreover, Formula (1), Formula (1 ′), Formula (2), Formula (2 ′), Formula (3), Formula (3 ′), Formula (10), and Formula (10 ′) are respectively Compounds represented by the chemical formula (1), the formula (2), the formula (3), and the formula (10), in which the substituents of each chemical structure are different.

  As these polymerization methods, any known methods such as solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization, and bulk polymerization can be used, and are not particularly limited.

  Solution polymerization is one of the methods used for radical polymerization of a monomer having a vinyl group such as the styrene derivative used in the present invention. In this method, a monomer and an initiator are dissolved in a solvent in which the polymer to be produced is soluble, and polymerization is performed by heating. As the initiator, benzoyl peroxide or azobisisobutyronitrile soluble in a monomer or a solvent is used. The characteristics of solution polymerization are that the degree of polymerization and the polymerization rate are small compared to bulk polymerization, and the polymerization heat generated in the polymerization system is absorbed by the surrounding solvent, so that the polymerization temperature can be easily adjusted. Solution polymerization is extremely useful when used as a polymer solution as it is after completion of polymerization, but in order to take out the polymer as a solid, it is necessary to remove the solvent and recover the polymer.

  Bulk polymerization is one of the methods used for radical polymerization of a monomer having a vinyl group such as the styrene derivative used in the present invention. In this method, polymerization is carried out by heating only vinyl monomers as they are or adding a small amount of an initiator without using a solvent. As the initiator, benzoyl peroxide or azobisisobutyronitrile soluble in the monomer is used. Bulk polymerization is characterized by a high polymerization rate and a relatively pure polymer obtained in bulk. The problems of this reaction are that it is difficult to remove the heat of polymerization, so it is difficult to control the polymerization temperature, such as local heating, and the post-treatment is troublesome, such as solidifying the produced polymer and adhering to the container. There are drawbacks. Industrially, molding of polystyrene pellets by continuous bulk polymerization from styrene monomer, which is the styrene derivative used in the present invention, preparation of polymethylmethacrylate organic glass, curing of glass fiber reinforced unsaturated polyester, mold Bulk polymerization is used for polymerization in the inside-molding (cast polymerization).

  The precipitation polymerization is one of the methods used for radical polymerization of a monomer having a vinyl group such as the styrene derivative in the present invention. In this method, polymerization is carried out by heating using a solvent in which the monomer and the initiator are soluble, the polymer to be produced is not dissolved in the solvent, and hardly swells. As the initiator, benzoyl peroxide or azobisisobutyronitrile soluble in a monomer or a solvent is used. When polymerization starts and a polymer is formed, it is precipitated because it is insoluble in the solvent. The characteristics of precipitation polymerization are that polymerization starts and the precipitated polymer is essentially close to bulk polymerization, so the degree of polymerization and the polymerization rate are higher than those of solution polymerization, but the polymerization heat generated in the polymerization system is affected by the surrounding solvent. Therefore, it is relatively easy to adjust the polymerization temperature. Precipitation polymerization can be obtained after the completion of polymerization by isolation and drying to obtain a single polymer, without using a suspension stabilizer or emulsifier such as suspension polymerization or emulsion polymerization, and only the desired polymer is precipitated. Therefore, a pure polymer can be obtained.

  Suspension polymerization is one of the methods used for radical polymerization of a monomer having a vinyl group such as the styrene derivative in the present invention. When a monomer insoluble in the medium (mainly water) is vigorously stirred in the medium, the monomer is dispersed and suspended to form droplets having a size of 0.01 to 1 mm. Polymerization performed by adding an initiator (eg, benzoyl peroxide, azobisisobutyronitrile, etc.) soluble in the monomer to this is suspension polymerization. In addition, a polyaddition reaction such as polyurethane may be performed in a suspended state. In this polymerization method, it proceeds in the droplets of the monomer, and a particulate polymer is obtained. For example, when spherical polymerization is performed using vinyl acetate, styrene, methyl methacrylate, or the like as a monomer, spherical particles are obtained. In such a case, this is called pearl polymerization. The polymerization in the droplets is essentially the same as the bulk polymerization, and the polymerization rate and degree of polymerization are large. In the suspension polymerization, as the polymerization proceeds, the monomer droplets become a concentrated solution of the polymer using the monomer as a solvent, and the droplets easily adhere to each other. Therefore, it is necessary to carry out the polymerization with vigorous stirring so as to disperse well, and in order to stabilize the droplets, water-soluble polymers such as gelatin, starch, polyvinyl alcohol, carboxymethylcellulose, calcium carbonate, magnesium carbonate Add insoluble powder such as. In addition, the size of the polymer particles produced varies depending on the stirring speed. Further, since the heat of polymerization generated during the polymerization is removed by the surrounding medium, local overheating does not occur, and the temperature can be easily adjusted. In the suspension polymerization, a polymer having a high degree of polymerization is obtained, and the resulting polymer can be easily isolated, so that a polymer for molding material such as polystyrene, polymethyl methacrylate, polyvinyl acetate, polyvinyl chloride, etc. is obtained. For this purpose, it is widely used as an industrial production method. As the polymerization method used in the present application, solution polymerization, precipitation polymerization, and bulk polymerization are preferable.

  As a post-treatment step after the polymerization reaction, a known purification step or separation / extraction step can be performed. For example, it is preferable to provide a purification step such as separation using organic solvent or filtration, solvent purification, or reprecipitation. Moreover, bulk polymerization can be illustrated without adding a solvent.

  Various polymerization initiators such as peroxide polymerization initiators, azo polymerization initiators, and redox initiators can be used as appropriate as polymerization initiators that can be used for polymerizing each component of the monomer. Further, polymerization (natural polymerization) may be performed by heating without adding a polymerization initiator.

  Examples of peroxide polymerization initiators include organic compounds such as peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, and diacyl peroxides. Examples include persulfate and hydrogen peroxide. Specifically, tert-butyl peroxyacetate, tert-butyl peroxylaurate, tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-butylperoxyneodecanoate, tert-hexylperoxyacetate, tert-hexylperoxylaurate, tert-hexylperoxypivalate, tert-hexylperoxy-2-ethylhexanoate, tert-hexylper Oxyisobutyrate, tert-hexylperoxyneodecanoate, tert-butylperoxybenzoate, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1, 3,3-tetramethylbutylperoxy-2-ethylhexano 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, 2,5-dimethyl-2,5-bis (2- Ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, tert-hexylperoxyisopropylmonocarbonate, tert-butylperoxyisopropylmonocarbonate, tert-butylper-2-ethylhexyl Oxymonocarbonate, tert-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, tert-butylperoxy-m-toluoylbenzoate, bis (tert-butylperoxy) iso Phthalate, tert-butylperoxymale Peroxyesters such as quasid, tert-butylperoxy-3,5,5-trimethylhexanoate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane; benzoyl peroxide, lauroyl Diacyl peroxides such as peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane-3, isobutyryl peroxide; diisopropyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) Peroxydicarbonates such as peroxydicarbonate; 1,1-di-tert-butylperoxycyclohexane, 1,1-di-tert-hexylperoxycyclohexane, 1,1-di-tert-butylperoxy-3 , 3,5-trimethylcyclohexane, 2,2-di-tert-butyl Peroxy ketals such as peroxy butane; di -tert- butyl peroxide, dicumyl peroxide, dialkyl peroxides such as tert- butyl cumyl peroxide; and other as tert- butylperoxy allyl monocarbonate and the like.

  As the azo polymerization initiator, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) ), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile and the like.

  Redox initiators include combinations of persulfate initiators such as potassium persulfate, sodium persulfate, and ammonium persulfate with reducing agents such as sodium metabisulfite and sodium bisulfite; organic peroxides and tertiary Combinations with amines such as benzoyl peroxide and dimethylaniline, combinations of cumene hydroperoxide and anilines; combinations of organic peroxides and transition metals, such as combinations of cumene hydroperoxide and cobalt naphthate Etc.

  These polymerization initiators may be used alone or in combination of two or more as required. It is preferable that the usage-amount of a polymerization initiator is 0.1-20 mass parts with respect to 100 mass parts of monomers.

  Solvents used for the polymerization reaction include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, ethyl propionate and cellosolve acetate; hexane, octane, petroleum ether, cyclohexane, benzene, toluene, Hydrocarbons such as xylene; Halogenated hydrocarbons such as trichloroethylene, dichloromethane and chloroform; Ethers such as ethyl ether, dimethyl glycol, trioxane and tetrahydrofuran; Acetals such as methylal and diethyl acetal; Methyl cellosolve, cellosolve and isopropyl cellosolve , Ether alcohols such as butyl cellosolve, diethylene glycol, monobutyl ether; N, N-dimethylformamide, N, N- Examples include aprotic polar solvents such as methylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide, and sulfur- and / or nitrogen-containing organic compounds such as nitropropene and nitrobenzene. These may be used alone or in combination of two or more. It can be used by mixing.

  Specific examples of polymerization reactions by combinations of the styrene derivative represented by the chemical formula (4), monomers α, β, γ, which are different vinyl group-containing monomers, a polymerization initiator, and a solvent are shown in Tables 11 to 11. It is shown in FIG. The scope of the present invention is not limited to these examples.

  In Tables 11-13, the styrene derivative is the compound example illustrated in the said Tables 1-9. Further, tert- is abbreviated as t-, tetrahydrofuran is abbreviated as THF, and N, N-dimethylformamide is abbreviated as DMF.

  The polymer obtained in these polymerization reaction steps can be converted into a metal complex or metal chloride to obtain an aluminum-containing copolymer resin. The metallization step is preferably performed by reacting the polymer obtained in the polymerization reaction step with a metallizing agent containing aluminum in a solvent under known conditions, so that at least a part of the unit A is made of aluminum. This is a step of producing an aluminum-containing copolymer resin containing a complexed or metallated copolymer.

  Specific examples of suitable metallating agents include aluminum chloride, aluminum sulfate, basic aluminum sulfate, aluminum acetate, basic aluminum acetate, aluminum nitrate, aluminum lactate, aluminum n-propoxide, aluminum isopropoxide, and t-butoxy. An aluminizing agent such as aluminum may be used. This metallizing agent is used in an amount of 1-5 to 5 atomic equivalents, preferably 1/3 to 3 atomic equivalents, with respect to the unit A represented by the chemical formula (1) serving as a ligand. As the metallizing agent to be used, one kind may be selected and reacted, or two or more kinds of each component may be combined and reacted.

  Any solvent that can dissolve the polymer and the metallizing agent can be used as the solvent for the metallization reaction. Examples of the organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether (monoglyme), ethylene glycol diethyl ether. , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), alcohols such as ethylene glycol and propylene glycol, ethers, or glycols Organic solvents; tetrahydrofuran, Examples include organic solvents such as aromatic solvents such as chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, styrene, toluene and xylene. These solvents may be used alone or in combination of two or more.

  Although the usage-amount of this organic solvent is not specifically limited, It is 5-30 times amount by weight ratio with respect to the unit A shown by the said Chemical formula (1) used as the said ligand.

  If the reaction product obtained in the metallization reaction in an organic solvent is dissolved in the solvent, disperse it in an appropriate amount of water or an organic solvent that is poorly soluble in the reaction product. Or an appropriate amount of the solvent is distilled off under reduced pressure to precipitate the reaction product. The precipitate can be collected by filtration, washed and dried. Further, when the reaction product is precipitated in the reaction solution, the precipitate can be directly collected by filtration, washed and dried. If the reaction product contains a large amount of impurities, its charge control function decreases, and therefore the reaction product can be used after solvent purification or reprecipitation purification.

  By being metallized by the above method, at least a part of the unit A constituting the polymer becomes a metal complexed or metallized copolymer, and the aluminum-containing copolymer resin of the present invention can be obtained. Although the example of the metallization step in which the polymer obtained by the polymerization reaction step is metal-complexed or metal-chlorinated is exemplified, the case where the polymerization reaction step is performed after metallization of the styrene derivative to be unit A is also as described above. Similarly, an aluminum-containing copolymer resin can be produced.

  The aluminum-containing copolymer resin of the present invention contains 0.1 to 15 mol% of the unit A represented by the chemical formula (1) in the copolymer. 0 to 9.5 mol% is preferable, and 2.0 to 7.5 mol% is more preferable.

  The aluminum-containing copolymer resin of the present invention preferably has a glass transition temperature of 60 ° C to 150 ° C. Furthermore, 70 to 130 degreeC is more preferable. When creating an electrostatic image developing toner or polymer compound containing this aluminum-containing copolymer resin by melt-kneading, by melt-kneading at or above the glass transition temperature at which the fluidity of the aluminum-containing copolymer resin increases, The compatibility with the binder resin becomes higher, the aluminum-containing copolymer resin can be uniformly dispersed, and the charging ability can be exhibited more efficiently.

  The aluminum-containing copolymer resin of the present invention has a number average molecular weight (Mn) of 3000 to 50000, a weight average molecular weight (Mw) of 4000 to 50000, and a weight average molecular weight (Mw) of a number average molecular weight (Mn). Mw / Mn, which is a standard for the molecular weight distribution divided by (1), is preferably 1 to 25. Further, the number average molecular weight (Mn) is in the range of 4000 to 50000, the weight average molecular weight (Mw) is in the range of 5000 to 40000, and the molecular weight distribution (Mw / Mn) is more preferably 1 to 20. If the value of Mw / Mn is close to 1.0, the dispersion is more monodispersed, the compatibility with the binder resin is higher, the aluminum-containing copolymer resin of the present invention can be uniformly dispersed, and the charging ability is improved. It can be exhibited more efficiently.

  The aluminum-containing copolymer resin of the present invention is preferably measured for exotherm and weight loss in the range of 200 ° C. to 450 ° C. in differential thermothermal gravimetric analysis (TG-DTA) measurement. Furthermore, it is preferable that exotherm and weight loss are measured in the range of 250 ° C to 400 ° C. The temperature at which heat generation and weight loss are simultaneously observed is a temperature at which the aluminum-containing copolymer resin is combusted and decomposed, and needs to be equal to or higher than the temperature at the time of heat dispersion treatment after addition to the binder resin.

The volume resistivity of the aluminum-containing copolymer resin of the present invention is preferably 0.5 × 10 ^{16 to} 7.0 × 10 ¹⁷ Ωcm. If the volume resistivity is smaller than this range, the binder resin containing the aluminum-containing copolymer resin will leak the generated charges, while if the volume resistivity is larger than this range, it will be generated. The accumulated charge accumulates too much and lacks stability. More preferably, the volume resistivity is 0.6 × 10 ^{16 to} 5.0 × 10 ¹⁶ Ωcm. The binder resin made of an aluminum-containing copolymer resin having such a volume resistivity is sufficiently charged and exhibits excellent charge rise and excellent temporal stability. The volume resistivity value is measured based on JIS standard (K6911).

  The crystallinity of the aluminum-containing copolymer resin of the present invention is preferably 0.0 to 20.0%. When the crystallinity of the binder resin containing the aluminum-containing copolymer resin is within this range, the compatibility with the binder resin (for example, toner resin) becomes higher, and the aluminum-containing copolymer resin is uniformly dispersed. Therefore, the charging ability can be exhibited more efficiently.

  The aluminum-containing copolymer resin of the present invention has a charge control function, functions as a charge control resin, and has a use as a charge control agent. In particular, since it is metallized, the rising of the charge is fast, and it can be stably charged for a long time while maintaining a uniform and high charge amount with a negative charge. Further, since the heat resistance is increased, for example, the toner can be prevented from being decomposed during kneading with the binder resin, and a stable quality toner can be obtained. Furthermore, environmental stability, which is regarded as important in recent toner evaluation, is also improved. The charge control agent is a polymerization reaction step (preferably a polymerization reaction step using a polymerization initiator) in which a monomer containing a styrene derivative that becomes the unit A represented by the chemical formula (1) is polymerized. And peroxide-based polymerization initiators, azo-based polymerization initiators, redox-based initiators, etc. Among these, peroxide-based polymerization initiators are preferred.), And a metallizing agent containing aluminum It can be obtained by a method for producing a charge control agent comprising an aluminum-containing copolymer resin obtained in a step including a metallization step in which a metal complexation or metallization is performed as an active ingredient.

  The charge control resin as the charge control agent is contained in an electrostatic charge image developing toner or a powder paint. The charge control resin is desirably blended in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin used. Furthermore, a more preferable blending amount of the charge control resin is 0.5 to 7 parts by weight with respect to 100 parts by weight of the resin used.

Examples of the toner resin include the following known toner resins (binder resins). That is, it is a thermoplastic resin such as styrene resin, styrene-acrylic resin, styrene-butadiene resin, styrene-maleic acid resin, styrene-vinyl methyl ether resin, styrene-methacrylic acid ester copolymer, polyester resin, and polypropylene resin. . These resins can be used alone or in combination of several kinds.
In addition, the charge control agent (charge control resin) of the present invention can be used for controlling (enhancing) the charge of the resin powder by being contained in the electrostatic powder paint. In this case, examples of the resin for paint include thermoplastic resins such as acrylic resins, polyolefin resins, polyester resins, and polyamide resins, and thermosetting resins such as phenol resins, epoxy resins, and polyester resins. Can be mentioned, and these can be used alone or in admixture of two or more.

  Various dyes and pigments can be used alone or in combination of two or more as colorants that can be used in the toner. Specific examples of colorants that can be used include, for example, monoazo yellow, disazo yellow, azomethine yellow, quinophthalone yellow, quinoline yellow, isoindolinone yellow, perinone oleidine, perinone red, perylene maroon, rhodamine 6G lake, quinacridone red, anthanthrone red, Organic pigments such as rose bengal, copper phthalocyanine blue, copper phthalocyanine green, and diketopyrrolopyrrole pigments; inorganic pigments and metal powders such as carbon black, titanium white, titanium yellow, ultramarine, cobalt blue, red rice, aluminum powder, and bronze; Various oil-soluble dyes and dispersions such as azo dyes, quinophthalone dyes, anthraquinone dyes, phthalocyanine dyes, indophenol dyes, indoaniline dyes Fee other, rosin, rosin-modified phenol, etc. triarylmethane dyes and xanthene dyes modified with resins such as rosin-modified maleic acid can be exemplified. These can be used alone or in admixture of two or more.

  For example, the toner can be manufactured as follows. Resin for toner, colorant, charge control agent of the present invention, magnetic material (for example, fine powder made of ferromagnetic material such as iron, cobalt, ferrite, etc.), fluidity modifier (For example, silica, aluminum oxide, titanium oxide), anti-offset agent (for example, wax, low molecular weight olefin wax), etc., are thoroughly mixed by a ball mill or other mixer, and then the mixture is heated by a roll, kneader, extruder, etc. A toner having an average particle size of 5 to 20 μm can be obtained by melt-kneading using a thermal kneader, cooling and solidifying the kneaded product, and then pulverizing and classifying the solidified product.

  The aluminum-containing copolymer resin of the present invention can be provided as an enhancer for the purpose of charge control or enhancement, or as a powder coating for electrostatic coating comprising the enhancer and the resin. One type of the enhancer may be included, or a plurality of types may be included. A preferable blending amount of the enhancer is 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin, and a more preferable blending amount is 0.5 to 5 parts by weight with respect to 100 parts by weight of the resin. Examples of the resin and the colorant that can be used in the powder coating for electrostatic coating include those described for the toner.

  This powder coating for electrostatic coating is excellent in environmental resistance and durability. According to this powder coating, the coating efficiency is nearly 100%, the coating film performance is improved, and there is no coating film defect. A thick film can be formed. Since the enhancer is colorless or light-colored, the color tone of the coating film hardly occurs.

  This powder coating for electrostatic coating can be manufactured as follows, for example. Add the colorant, fluidity modifier, filler, curing agent, plasticizer, etc. according to the above-mentioned enhancer and resin, and their applications and purposes, and mix uniformly with a ball mill or other mixer. The mixture is melt-kneaded using a heat kneader such as a heating roll, a kneader, or an extruder, cooled and solidified, and then pulverized and classified to obtain a powder for electrostatic coating having a required particle size range of 10 to 250 μm. Body paint can be obtained.

  The electrostatic powder coating can be applied by using a general electrostatic powder coating method such as a corona imprinting method, a friction charging method, and a hybrid method.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

Example 1-A
100.0 g of 2,5-dihydroxybenzoic acid was dissolved in 2 L of methanol while stirring, 88.3 g of potassium carbonate was added, and the mixture was heated to 67 ° C. To this reaction solution, 102.0 g of 4- (chloromethyl) styrene was added dropwise over 22 minutes and reacted at 67 ° C. for 12 hours. After cooling the reaction solution, methanol was distilled off under reduced pressure, washed with hexane and filtered. The residue was dissolved in methanol and further dropped into water for reprecipitation, and the precipitate was filtered. This reprecipitation operation was repeated twice, and the residue was dried at 80 ° C. for 48 hours to obtain 48.7 g of a styrene derivative (Compound Example a-1) represented by the following chemical formula (A1).

The purity of the obtained styrene derivative (A1) was determined by high performance liquid chromatography (HPLC manufactured by Shimadzu Corporation detector: SPD-M20A, column oven: CTO-20A, pump: LC-20AT, degasser: DGU-20A ₃ ). Was measured under the following measurement conditions, and a purity of 94.6% was confirmed.
HPLC measurement conditions: 3 mg of a sample was dissolved in 10 mL of tetrahydrofuran (THF), sonicated for 30 minutes, filtered through a solvent-resistant membrane filter having a pore diameter of 0.5 μm to obtain a sample solution, and measurement was performed under the following conditions.
Column: L-Column ODS (4.6 × 250 mm), column oven temperature: 40 ° C., flow rate: 1.0 mL / min, sample injection amount: 3 μL, detection wavelength: 254 nm,
Eluent- (1): THF: 0.05M-CH ₃ COONH ₄ aqueous solution = 4: 6
Eluent- (2): THF: 0.05M-CH ₃ COONH ₄ aqueous solution = 6: 4
Eluent- (1): Eluent- (2) = 100: 0 → (20 minutes) → 0: 100

About the obtained styrene derivative (A1), ¹ H-nuclear magnetic resonance apparatus (NMR JEOL Ltd. FT-NMR JNM-AL300) was used, resonance frequency: 300 MHz, measurement nuclide: ¹ H, solvent used: heavy DMSO Measurement temperature: measured at room temperature. ¹ H-NMR spectrum data is as follows and supports the structure represented by the chemical formula (A1). The measurement result of ¹ H-NMR is shown in FIG.
δ (ppm) = 5.06 (2H, s, —CH ₂ —), 5.27 (1H, d, C—H), 5.84 (1H, d, C—H), 6.74 (1H) , Dd, -CH =), 6.91 (1H, d, Ar-H), 7.23 (1H, dd, Ar-H), 7.35 (1H, d, Ar-H) 7.41 (1H, d, Ar-H), 7.49 (2H, d, Ar-H)
In the ¹ H-NMR, irradiation with 5.06 ppm (2H, s, —OCH ₂ —) protons revealed that 22.35 (1H, d, Ar—H) aromatic protons had 22.3% nuclei. Oberhauser effect (NOE) was observed. The measurement result of NOE is shown in FIG.

The weight ratio of carbon (C), hydrogen (H), and nitrogen (N) was measured for the obtained styrene derivative (A1) using an elemental analyzer (Perkin Elmer 2400II fully automatic elemental analyzer CHNS / O analysis). It was measured. The theoretical values and actual measurement values of elemental analysis are shown below.
Actual value C: 71.61 H: 4.90 N: 0.00
Theoretical value C: 71.10 H: 5.22 N: 0.00

When the obtained styrene derivative (A1) was measured by the KBr method using a Fourier transform infrared spectrophotometer (FT-IR JIR-SPX60S manufactured by JEOL Ltd.),
ν (cm ⁻¹ ) = 3132, 3088, 3005, 2924, 2877, 1680, 1614, 1593, 1516, 1487, 1471, 1443, 1408, 1379, 1250, 1196, 1011, 906, 860, 831, 808, 789 , 775, 744, 715, 675, 559, 492, 472 were observed. The measurement result of FT-IR is shown in FIG.

  The obtained styrene derivative (A1) was subjected to temperature differential conditions: 30 ° C. to 550 ° C., temperature increase rate: 10 ° C. using a differential thermothermal gravimetric simultaneous measurement apparatus (TG-DTA6200 EXSTAR6000, manufactured by SII Nano Technology Co., Ltd.). Measured at / min. The measurement results of thermogravimetric analysis-differential thermal analysis (TG-DTA) are shown in FIG. As a result of the measurement, melting point: 168 ° C., exothermic temperature: 551 ° C., weight loss temperature: 210 ° C., 404 ° C., 521 ° C. were observed.

The obtained styrene derivative (A1) was measured with a liquid chromatograph mass spectrometer (LC / 3DQMS system M-8000 manufactured by Hitachi High-Technologies Corporation) under the following conditions.
LC / MS measurement conditions:
Ionization source: ESI ionization source (measured by FI method)
Carrier: Preparation method of methanol sample for electronic industry: 1 mg of each sample was dissolved in methanol for electronic industry. For samples that did not dissolve completely, tetrahydrofuran was added until dissolved.
First pore temperature: 120 ° C, second pore temperature: 100 ° C, solvent removal temperature: 150 ° C, auxiliary gas temperature: 150 ° C, focus voltage: 20V, drift voltage: 20V
The measurement result of liquid chromatograph mass spectrometry is shown in FIG. In addition, theoretical values and actual measurement values of mass spectrometry are shown below.
Found: LC / MS m / z = 269.00 [M−H] ⁻
Theoretical value: m / z = 270.09

(Example 1-B)
(Styrene derivative (A1): styrene = 5.0: 95.0 molar ratio preparation)
8.41 g of styrene derivative (A1) and 61.60 g of styrene were dispersed in 42 mL of N, N-dimethylformamide and heated to 110 ° C. under a nitrogen stream (50 mL / min). To this solution, a mixed solution of 42 mL of N, N-dimethylformamide and 4.62 g of tert-butyl peroxyisopropyl monocarbonate (trade name: Perbutyl I, manufactured by NOF Corporation) was added dropwise over 24 minutes. The reaction was further carried out at 110 ° C. for 4 hours, and then cooled. A mixture of the obtained reaction solution and 300 mL of tetrahydrofuran was added to 3.5 L of methanol to cause reprecipitation, followed by filtration. The residue was washed twice with 200 mL of methanol and dried under reduced pressure at 90 ° C. for 30 hours to obtain 59.19 g of copolymer (B1).

For the obtained copolymer (B1), ¹ H-NMR was measured under the same conditions as in Example 1-A. As a result, styrene before the copolymerization reaction and the styrene derivative (A1) represented by the chemical formula (A1) A peak derived from a vinyl group as a raw material was not observed, a broad aromatic proton and an alkyl chain were observed, a broad hydroxyl group derived from a styrene derivative (A1), and δ (ppm) = 4.9 (—CH ₂ — A broad proton of O-) was observed. It was confirmed that the unit obtained from the styrene derivative (A1) in the obtained copolymer was 4.73% from the integral value of the peak. The measurement result of ¹ H-NMR is shown in FIG.

About the obtained copolymer (B1), when FT-IR was measured on the same conditions as Example 1-A,
ν (cm ⁻¹ ) = 3433, 3082, 3059, 3026, 2922, 2848, 1944, 1873, 1801, 1741, 1678, 1616, 1601, 1493, 1452, 1265, 1215, 1155, 1070, 1028, 906, 758 , 698, 540 were observed. The measurement result of FT-IR is shown in FIG.

  TG-DTA was measured for the obtained copolymer (B1) under the same conditions as in Example 1-A. The measurement result of TG-DTA is shown in FIG. As a result of the measurement, weight loss temperatures: 329 ° C., 394 ° C., 520 ° C., and exothermic temperatures: 347 ° C. and 542 ° C. were observed.

The molecular weight distribution of the obtained copolymer (B1) was determined by GPC (Shimadzu Corporation detector: RID-10A, column oven: CTO-20A, pump: LC-20AT, degasser: DGU-20A ₅ ). Measurement was performed under the following measurement conditions, and molecular weight distribution, number average molecular weight, and weight average molecular weight were confirmed.
As GPC measurement conditions, 5 mg of a sample to be measured was dissolved in 5 mL of tetrahydrofuran, filtered through a solvent-resistant membrane filter having a pore diameter of 0.5 μm to obtain a sample solution, and measurement was performed under the following conditions.
Column: Ultra-high speed SEC (size exclusion) semi-micro GPC column Exclusion limit molecular weight: Polystyrene 4 × 10 ⁶ (TSKgel SuperHM-M, manufactured by Tosoh Corporation),
In calculating the molecular weight of the sample, standard polystyrene (Shodex STANDARD SM-105 (S-3730, S-2480, S-1230, S-579, S-197, S-551, S-551, manufactured by Showa Denko KK) was used. 31.4, S-12.8, S-3.95, S-1.20)) were used.

  The measurement results of the molecular weight distribution of the copolymer (B1) measured under the above conditions are shown in FIG. As a result of the measurement, it was confirmed that the copolymer (B1) had a number average molecular weight (Mn) of 12068, a weight average molecular weight (Mw) of 55593, and a molecular weight distribution (Mw / Mn) = 4.6. .

In the elemental analysis, the abundance ratio of the specific monomer in the copolymer can be estimated from the measurement result of the elemental analysis of the raw material monomer and the measurement result of the elemental analysis of the copolymer. About the obtained copolymer (B1), the elemental analysis was measured on the conditions as described in Example 1-A. The measured values of elemental analysis are shown below.
Found C: 89.55 H: 7.40 N: 0.00 O: 2.76
Theoretical value C: 89.70 H: 7.45 N: 0.00 O: 2.85
Here, oxygen (O) was calculated by dividing from the total value of 100% of the values of carbon (C), hydrogen (H) and nitrogen (N). The measurement result agreed with the estimated theoretical value when 5% of the styrene derivative (A1) was contained in the copolymer.

Example 1-C
To a mixed solution of 180 mL of N, N-dimethylformamide and 30 mL of methanol, 5.34 g of a 20.0 wt% sodium hydroxide solution was added. This solution was added dropwise over 26 minutes to a solution in which 30 g of copolymer (B1) was dissolved in 90 mL of N, N-dimethylformamide and heated to 65 ° C. In this solution, 3.22 g of aluminum chloride hexahydrate was dissolved in a mixed solution of 90 mL of N, N-dimethylformamide and 10 mL of water and added dropwise over 18 minutes. The reaction solution was stirred at 65 ° C. for 15 minutes and then filtered at 65 ° C. The residue was sprinkled with 200 mL of N, N-dimethylformamide twice, dispersed in 1 L of water, and stirred for 1 hour. After filtering the dispersion, sprinkled and washed until the electrical conductivity of the filtrate reached 300 μS / cm or less, and the residue was dried at 80 ° C. under reduced pressure (0.1 MPa) for 12 hours to obtain the copolymer (B1). 15.55g of aluminum containing copolymer resin (C1) which is the reaction material of aluminum was obtained.

  The obtained aluminum-containing copolymer resin (C1) did not dissolve in N, N-dimethylformamide, tetrahydrofuran, chloroform, ethyl acetate, water, cyclohexane, acetone, methanol, or dimethyl sulfoxide.

The glass transition temperature of the obtained aluminum-containing copolymer resin (C1) is measured with a differential scanning calorimeter (DSC6200 EXSTAR6000, manufactured by SII Nano Technology Co., Ltd.) under the following measurement conditions to confirm the glass transition temperature. did.
As the glass dislocation measurement conditions, the sample to be measured was heated to 170 ° C. and then rapidly cooled, and then measured under conditions of temperature increase: 30-170 ° C. and temperature increase rate: 10 ° C./min. As a result of the measurement, the glass transition temperature of the aluminum-containing copolymer resin (C1) was 122.0 ° C. The measurement result of the glass transition temperature is shown in FIG.

  As a result of measuring the aluminum content (%) of the obtained aluminum-containing copolymer resin (C1) with an atomic absorption measuring device (SpectraAA-220FS manufactured by Varian), the aluminum content (%) was 1.26%. The sodium content (%) was 0.24%.

About the obtained aluminum containing copolymer resin (C1), when FT-IR was measured on the same conditions as Example 1-A,
ν (cm ⁻¹ ) = 3440, 3082, 3059, 3026, 2922, 2848, 1651, 1601, 1583, 1493, 1452, 1367, 1252, 1201, 1153, 1068, 1028, 906, 829, 758, 698, 665 540 was observed. The measurement result of FT-IR is shown in FIG.

  About the obtained aluminum containing copolymer resin (C1), TG-DTA was measured on the conditions as described in Example 1-A. The measurement result of TG-DTA is shown in FIG. As a result of the measurement, exothermic temperatures: 356 ° C., 392 ° C., 506 ° C., weight loss temperatures: 331 ° C., 487 ° C. were observed.

The volume specific resistivity of the obtained aluminum-containing copolymer resin (C1) was measured under the following measurement conditions using a digital ultrahigh resistance: microammeter R8340A manufactured by Advantest Corporation, and the volume specific resistivity was confirmed. .
The measurement conditions for the volume resistivity were measured under the following conditions based on JIS standard (K6911).
Applied voltage and time: 500 V, 1 minute, electrode: main electrode 38 mmφ, load: 2000 kg, test atmosphere: temperature 23 ± 2 ° C., humidity 50 ± 5 RH. As a result of the measurement, the volume resistivity of the copolymer (B1) was confirmed to be 2.72 × 10 ¹⁶ Ωcm.

About the obtained aluminum containing copolymer resin (C1), it measured on condition of the following with the X-ray-diffraction apparatus (Rigaku Co., Ltd. sample horizontal type strong X-ray-diffraction apparatus RINT-TTRIII). Preparation of measurement sample sample: The sample was placed on a glass stand dedicated to an X-ray diffractometer, and the sample was flattened with another glass plate to prepare a sample.
Measurement range: 2θ = 5 ° -40 °
Method for obtaining crystallinity: The obtained aluminum-containing copolymer resin was subjected to X-ray diffraction measurement under the above conditions, and then the obtained X-ray diffraction spectrum was subjected to smoothing treatment. Further, the obtained data was analyzed using the analysis software “JADE XRD Pattern Processing Identification & Quantification ver. 7.5.2” manufactured by Materials Data under the following conditions to determine the crystallinity. Profiling fitting conditions: PSF; pseudo-voice, background: horizontal, current profile update: yes, Kα2 peak: yes, initial half-width curve specified value = 0.5, peak search: yes.
About the obtained aluminum containing copolymer resin (C1), the X-ray diffraction was measured on the said conditions, and the result of having computed the crystallinity degree is shown. Crystallinity = 0.12%

(Example 2-A)
100 g of 2,5-dihydroxybenzoic acid and 1441 g of 80% sulfuric acid were heated and mixed at 50 ° C., 144 g of tert-butanol was added to this dispersion, and the mixture was stirred at 50 ° C. for 30 minutes. Thereafter, 144 g of tert-butanol was added to the dispersion and stirred for 30 minutes three times. The reaction solution was cooled to room temperature, poured slowly into 1 kg of ice water, the precipitate was filtered, washed with water, and further washed with hexane. The obtained precipitate was dissolved in 200 mL of methanol and reprecipitated in 3.6 L of water. After filtration, the resulting precipitate was dried at 80 ° C. for 24 hours to obtain 74.9 g of a tert-butylated salicylic acid intermediate.
25.0 g of the obtained salicylic acid intermediate was dissolved in 150 mL of methanol with stirring, 36.9 g of potassium carbonate was added, and the mixture was heated to 65 ° C. To this reaction solution, a solution obtained by mixing and dissolving 18.7 g of 4- (chloromethyl) styrene and 100 mL of methanol was added dropwise and reacted at 65 ° C. for 3 hours. The obtained reaction solution was cooled and then filtered, and methanol in the filtrate was distilled off under reduced pressure to obtain a precipitate.
The obtained precipitate was dispersed in 1.5 L of water at pH = 2, and extracted by adding ethyl acetate. Thereafter, the mixture was washed with water, and the ethyl acetate layer was separated and dried over magnesium sulfate, and the ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The obtained precipitate was washed with hexane, filtered, recrystallized using a mixed solution of toluene and ethyl acetate, dried at 80 ° C. for 40 hours, and then a styrene derivative represented by the following chemical formula (A2) (Compound Example a- 20.1 g of 21) was obtained.

  With respect to the obtained styrene derivative (A2), the HPLC purity was measured under the conditions described in Example 1-A, and it was 98.6%.

About the obtained styrene derivative (A2), ¹ H-NMR was measured under the same conditions as in Example 1-A, except that the measurement solvent was changed to CDCl ₃ . ¹ H-NMR spectrum data is as follows and supports the structure represented by the chemical formula (A2).
δ (ppm) = 1.41 (9H, s, —C (CH ₃ ) ₃ ), 5.00 (2H, s, —OCH ₂ —), 5.26 (1H, d, C—H), 5 .76 (1H, d, C—H), 6.73 (1H, dd, —CH═), 7.25 (1H, d, Ar—H), 7.31 (1H, d, Ar—) H), 7.40 (1H, d, Ar-H), 7.44 (1H, d, Ar-H)
In the ¹ H-NMR, irradiation with a proton of 5.00 (2H, s, —OCH ₂ —) resulted in an aromatic proton of 7.25 (1H, d, Ar—H) having 8.1% nuclei. Oberhauser effect was observed.

For the obtained styrene derivative (A2), FT-IR was measured under the same conditions as in Example 1-A.
ν (cm ⁻¹ ) = 3419, 3093, 3005, 2964, 2866, 2710, 2619, 1894, 1819, 1788, 1774, 1753, 1660, 1630, 1608, 1570, 1514, 1483, 1470, 1429, 1406, 1394 , 1373, 1362, 1331, 1290, 1277, 1225, 1200, 1180, 1117, 1066, 1016, 985, 970, 958, 908, 889, 850, 833, 818, 806, 795, 721, 681, 658, 606 528, 515, 494, 465, 428, 420 were observed.

  About the obtained styrene derivative (A2), TG-DTA was measured on the conditions as described in Example 1-A. As a result of the measurement, melting point: 183 ° C., weight loss temperature: 161 ° C., 386 ° C., 489 ° C., 553 ° C., exothermic temperature: 517 ° C., 563 ° C. were observed.

About the obtained styrene derivative (A2), elemental analysis was measured on the conditions as described in Example 1-A. The theoretical values and actual measurement values of elemental analysis are shown below.
Actual value C: 74.29 H: 6.71 N: 0.00
Theoretical value C: 73.60 H: 6.79 N: 0.00

About the obtained styrene derivative (A2), the liquid chromatograph mass spectrometry was measured on the conditions as described in Example 1-A. The theoretical value and the actual measurement value of mass spectrometry are shown.
Found: LC / MS m / z = 324.86 [M−H] ⁻
Theoretical value: m / z = 326.15

(Example 2-B)
(Styrene derivative (A2): styrene = 5.0: 95.0 molar ratio preparation)
9.91 g of styrene derivative (A2) obtained in Example 2-A and 60.09 g of styrene were dissolved in 42 mL of toluene and stirred for 1 hour. Then, it heated to 110 degreeC under nitrogen stream (50 mL / min). To this solution, a mixed solution of 42 mL of toluene and 4.62 g of tert-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, trade name: Perbutyl I) was added dropwise over 22 minutes. Furthermore, after reacting at 110 degreeC for 4 hours, it cooled, and it was dripped at methanol 1L, and the white deposit was obtained. The reaction mixture was filtered, and the resulting precipitate was dissolved in 300 mL of tetrahydrofuran. This solution was added dropwise to 1.5 L of methanol to precipitate a white precipitate and filtered. The obtained residue was dried at 90 ° C. under reduced pressure to obtain 57.56 g of a copolymer (B2) obtained from a styrene derivative and styrene.

About the obtained copolymer (B2), ¹ H-NMR was measured under the same conditions as in Example 1-A.

Peaks derived from vinyl groups as raw materials of styrene before copolymerization and the styrene derivative (A2) represented by the chemical formula (A2) were not observed, broad aromatic protons and alkyl chains were observed, and styrene derivatives ( A broad hydroxyl group derived from A2) and a broad proton of δ (ppm) = 4.9 (—CH ₂ —O—) were observed. It was confirmed that the unit obtained from the styrene derivative (A2) was contained in the obtained copolymer by 4.69% from the integrated value of the peak.

When the obtained copolymer (B2) was measured by the KBr method using FT-IR under the same conditions as in Example 1-A,
ν (cm ⁻¹ ) = 3455, 3082, 3061, 3026, 2922, 2850, 1942, 1867, 1799, 1741, 1674, 1601, 1493, 1452, 1362, 1265, 1201, 1155, 1030, 906, 798, 756 , 698, 540 were observed.

  The obtained copolymer (B2) is composed of the following unit C obtained from the compound example (A2) and corresponding to the unit A, and the following unit D corresponding to the unit B.

  TG-DTA was measured under the conditions described in Example 1-A. As a result of the measurement, weight loss temperature: 345 ° C., 513 ° C., exothermic temperature: 337 ° C., 535 ° C. were observed.

  About the obtained copolymer (B2), GPC was measured on the conditions as described in Example 1-B. As a result of the measurement, it was confirmed that the number average molecular weight (Mn) of the copolymer (B2) was 16160, the weight average molecular weight (Mw) was 66496, and further the molecular weight distribution (Mw / Mn) = 4.1. .

About the obtained copolymer (B2), the elemental analysis was measured on the conditions as described in Example 1-A. The measured values of elemental analysis are shown below.
Found C: 89.45 H: 7.69 N: 0.00 O: 2.84
Theoretical value C: 89.60 H: 7.62 N: 0.00 O: 2.78
Here, oxygen (O) was calculated by dividing from the total value of 100% of the values of carbon (C), hydrogen (H) and nitrogen (N). The said measurement result corresponded with the presumed theoretical value in case 5% of styrene derivatives (A2) are contained in a copolymer.

(Example 2-C)
To a mixed solution of 180 mL of N, N-dimethylformamide and 30 mL of methanol, 5.21 g of a 20.0 wt% sodium hydroxide solution was added. This solution was added dropwise over 40 minutes to a solution in which 30 g of copolymer (B2) was dissolved in 90 mL of N, N-dimethylformamide and heated to 65 ° C. To this solution, 3.14 g of aluminum chloride hexahydrate was dissolved in a mixture of 90 mL of N, N-dimethylformamide and 10 mL of water, and added dropwise over 19 minutes. The reaction solution was stirred at 65 ° C. for 15 minutes, filtered at 65 ° C., the residue was washed with 200 mL of N, N-dimethylformamide, washed twice, dispersed in 1 L of water, and stirred for 1 hour. The dispersion was filtered, washed with water until the electrical conductivity of the filtrate reached 300 μS / cm or less, washed, and then the residue was dried at 80 ° C. under reduced pressure (0.1 MPa) for 12 hours to obtain a copolymer (B2 24.03 g of an aluminum-containing copolymer resin (C2), which is a reaction product of an aluminum) and aluminum.

  The obtained aluminum-containing copolymer resin (C2) did not dissolve in N, N-dimethylformamide, tetrahydrofuran, chloroform, ethyl acetate, water, cyclohexane, acetone, methanol, or dimethyl sulfoxide.

  About the obtained aluminum containing copolymer resin (C2), the glass transition temperature was measured on the conditions as described in Example 1-C. As a result of the measurement, it was confirmed that the glass transition temperature of the aluminum-containing copolymer resin (C2) was 124.7 ° C.

  About aluminum containing copolymer resin (C2), as a result of measuring aluminum content (%) on the same conditions as Example 1-C, the content rate (%) of aluminum is 0.96% and the content rate of sodium (%) Was 0.07%.

  For the aluminum-containing copolymer resin (C2), TG-DTA was measured under the conditions described in Example 1-A. As a result of the measurement, an exothermic temperature: 362, 391, 497 and a weight reduction temperature: 331 ° C., 479 ° C. were observed.

The volume resistivity of the aluminum-containing copolymer resin (C2) was measured under the conditions described in Example 1-C. As a result of the measurement, the volume resistivity of the aluminum-containing copolymer resin (C2) was confirmed to be 2.46 × 10 ¹⁶ Ωcm.

  About the obtained aluminum containing copolymer resin (C2), the X-ray diffraction was measured on the conditions as described in Example 1-C, and the result of having computed crystallinity is shown. Crystallinity = 4.03%

Example 3-A
78.63 g of 2,4-dihydroxybenzoic acid was dissolved in 400 mL of methanol while stirring, 152.03 g of potassium carbonate was added, and the mixture was heated to 60 ° C. To this reaction solution, a solution obtained by mixing and dissolving 87.88 g of 4- (chloromethyl) styrene and 100 mL of methanol was added dropwise and reacted at 60 ° C. for 2.5 hours. After cooling the obtained reaction solution, the precipitate was filtered and washed with methanol.
The residue was dispersed with hydrochloric acid in 1 L of water at pH = 1. Thereafter, the filtrate was washed with water and dried at 80 ° C. to obtain 55.71 g of a white styrene derivative (Compound Example b-1) represented by the following chemical formula (A3).

  With respect to the obtained styrene derivative (A3), the HPLC purity was measured under the conditions described in Example 1-A, which was 97.7%.

About the obtained styrene derivative (A3), ¹ H-NMR was measured under the conditions described in Example 1-A. ¹ H-NMR spectrum data is as follows and supports the structure represented by the chemical formula (A3).
δ (ppm) = 5.09 (2H, s, —CH ₂ —), 5.27 (1H, d, C—H), 5.85 (1H, d, C—H), 6.38-6 .41 (2H, m, Ar-H), 6.74 (1H, dd, C = H), 7.41 (2H, d, Ar-H), 7.49 (2H, d, Ar- H), 7.61 (1H, d, Ar-H)
In the H-NMR, when the proton of 5.09 (2H, s, —OCH ₂ —) was irradiated, the aromatic proton of 6.38-6.41 (2H, m, Ar—H) was 17. A 2% nuclear overhauser effect was observed.

When FT-IR was measured under the conditions described in Example 1-A for the obtained styrene derivative (A3),
ν (cm ⁻¹ ) = 3086, 3005, 1639, 1589, 1514, 1502, 1450, 1379, 1288, 1254, 1182, 1157, 1105, 1095, 1014, 904, 827, 779, 729, 698, 649, 596 532 and 471 were observed.

  For the obtained styrene derivative (A3), TG-DTA was measured under the conditions described in Example 1-A. As a result of the measurement, melting point: 184 ° C., weight loss temperature: 216 ° C., 430 ° C., 554 ° C. Exothermic temperature: 571 ° C. was observed.

About the obtained styrene derivative (A3), the elemental analysis was measured on the conditions as described in Example 1-A. The theoretical values and actual measurement values of elemental analysis are shown below.
Actual value C: 64.65 H: 4.23 N: 0.00
Theoretical value C: 71.10 H: 5.22 N: 0.00

About the obtained styrene derivative (A3), the liquid chromatograph mass spectrometry was measured on the conditions of Example 1-A. The theoretical values and actual measurement values of mass spectrometry are shown below.
Found: LC / MS m / z = 269.07 [M−H] ⁻
Theoretical value: m / z = 270.09

(Example 3-B)
(Styrene derivative (A3): styrene = 10.0: 90.0 molar ratio preparation)
26.86 g of styrene derivative (A3) and 93.14 g of styrene were dissolved in 72 mL of N, N-dimethylformamide. To this solution, 7.92 g of tert-butyl peroxyisopropyl monocarbonate (Nippon Yushi Co., Ltd., trade name: Perbutyl I) was added and stirred at room temperature under a nitrogen stream (100 mL / min). This mixed solution was added dropwise to 72 mL of N, N-dimethylformamide heated to 110 ° C. under a nitrogen stream (100 mL / min) over 27 minutes. After further reacting at 110 ° C. for 4 hours, the mixture was cooled and added dropwise to 800 mL of methanol to precipitate a rubbery pale yellow product. After removing the supernatant by decantation, the residue was dissolved in 300 mL of tetrahydrofuran, precipitated in 4 L of methanol, filtered, and dried under reduced pressure at 80 ° C. for 16 hours to obtain 96.50 g of copolymer (B3).

When ¹ H-NMR was measured for the obtained copolymer (B3) under the conditions described in Example 1-B, styrene before the copolymerization reaction and the styrene derivative (A3) represented by the chemical formula (A3) A peak derived from a vinyl group as a raw material was not observed, a broad aromatic proton and an alkyl chain were observed, a broad hydroxyl group derived from a styrene derivative (A3), and δ (ppm) = 4.97 (—CH ₂ — A broad proton of O-) was observed. From the integrated value of the peak, it was confirmed that the styrene derivative (A3) was contained in the obtained copolymer by 7.84%.

About the obtained copolymer (B3), when FT-IR was measured on the conditions as described in Example 1-B,
ν (cm ⁻¹ ) = 3432, 3083, 3059, 3027, 3002, 2922, 2851, 1943, 1870, 1802, 1742, 1673, 1654, 1623, 1601, 1584, 1493, 1453, 1376, 1243, 1183, 1150 1094, 1029, 1017, 979, 961, 907, 840, 820, 759, 699, 645, 622, 601, 541, 458, 415 were observed.

  About the obtained copolymer (B3), TG-DTA was measured on the conditions as described in Example 1-B, and as a result of the measurement, weight loss temperature: 207 ° C., 334 ° C., 517 ° C., exothermic temperature: 358 ° C. and 540 ° C. were observed.

  About the obtained copolymer (B3), GPC was measured on the conditions as described in Example 1-B. As a result of measuring the molecular weight distribution of the copolymer (B3) measured under the above conditions, the number average molecular weight (Mn) of the copolymer (B3) is 4887, the weight average molecular weight (Mw) is 12413, and the molecular weight distribution ( Mw / Mn) = 2.5.

Example 3-C
35.0 g of copolymer (B3) was dissolved in 105 mL of N, N-dimethylformamide. Add 11.6 g of 20 wt% aqueous sodium hydroxide solution to a mixed solvent of 105 mL of N, N-dimethylformamide and 35 mL of methanol, add to the copolymer solution over 28 minutes, heat to 65 ° C., and add 105 mL of N, N-dimethylformamide. added. A solution obtained by adding 7.0 g of aluminum chloride hexahydrate to a mixed solvent of 12 mL of water and 105 mL of N, N-dimethylformamide was added to this solution over 10 minutes, and the mixture was heated and stirred at 65 ° C. for 15 minutes. Thereafter, it is filtered, washed with tap water until the electric conductivity of the filtrate is 300 μS / cm or less, dried at 80 ° C. for 24 hours, and a white aluminum-containing copolymer which is a reaction product of the copolymer (B3) and aluminum. 30.3g of polymerization resin (C3) was obtained.

  About the obtained aluminum containing copolymer resin (C3), the weight% of the metal to contain was measured on the conditions as described in Example 1-C. The measured values of atomic absorption are shown below. Al = 2.20%, Na = 0.05%

About the obtained aluminum containing copolymer resin (C3), when FT-IR was measured on the conditions as described in Example 1-B,
ν (cm ⁻¹ ) = 3431, 3082, 3059, 3026, 3001, 2922, 2850, 1942, 1873, 1803, 1601, 1512, 1493, 1452, 1377, 1263, 1180, 1155, 1101, 1070, 1028, 1016 , 906, 840, 820, 758, 698, 667, 629, 540 were observed.

  The obtained aluminum-containing copolymer resin (C3) was measured for TG-DTA under the conditions described in Example 1-A. As a result, weight loss temperatures: 340 ° C., 473 ° C. exothermic temperature: 370 ° C., 477 ° C. were observed. did.

  About the obtained aluminum containing copolymer resin (C3), the X-ray diffraction was measured on the conditions as described in Example 1-C, and the result of having computed crystallinity is shown. Crystallinity = 0.03%

  About the obtained aluminum containing copolymer resin (C3), the glass transition temperature was measured on the conditions as described in Example 1-C. As a result of the measurement, it was confirmed that the glass transition temperature of the aluminum-containing copolymer resin (C3) was 154.8 ° C.

Example 4-A
A styrene derivative (A3) was synthesized in the same manner as in Example 3-A.

(Example 4-B)
(Styrene derivative (A3): styrene = 10.0: 90.0 molar ratio preparation)
The copolymer (B4) was polymerized in the same manner as in Example 3-B.

(Example 4-C)
9.0 g of copolymer (B4) was dissolved in 27 mL of N, N-dimethylformamide. To a mixed solvent of 27 mL of N, N-dimethylformamide and 9 mL of methanol is added 3.0 g of a 20 wt% aqueous sodium hydroxide solution, added to the copolymer solution over 15 minutes, heated to 65 ° C., and added to 9 mL of N, N-dimethylformamide. A solution containing 4.98 g of aluminum sulfate was added over 32 minutes, and then 27 mL of N, N-dimethylformamide was added. The mixture was heated and stirred at 65 ° C. for 15 minutes, filtered, and the residue was washed with 60 mL of N, N-dimethylformamide by shaking twice and dispersed in 300 mL of water. After filtration, the residue was washed with 150 mL of water three times and dried at 80 ° C. for 24 hours to obtain 6.45 g of a white aluminum-containing copolymer resin (C4) that is a reaction product of the copolymer (B4) and aluminum. It was.

  About the obtained aluminum containing copolymer resin (C4), the weight% of the metal to contain was measured on the conditions as described in Example 1-C. The measured values of atomic absorption are shown below. Al = 1.92%, Na = 0.30%

About the obtained aluminum containing copolymer resin (C4), when FT-IR was measured on the conditions as described in Example 1-B,
ν (cm ⁻¹ ) = 3431, 3082, 3059, 3026, 3001, 2922, 2850, 1942, 1873, 1803, 1601, 1512, 1493, 1452, 1377, 1263, 1180, 1155, 1101, 1070, 1028, 1016 , 906, 840, 820, 758, 698, 667, 629, and 540, the same spectrum as that of the copolymer metal compound (C3) was observed.

  About the obtained aluminum containing copolymer resin (C4), as a result of measuring TG-DTA on the conditions as described in Example 1-A, exothermic temperature: 368 degreeC, 489 degreeC, weight reduction temperature: 338 degreeC, 472 degreeC Observed and showed TG-DTA similar to the aluminum-containing copolymer resin (C3).

  About the obtained aluminum containing copolymer resin (C4), the X-ray diffraction was measured on the conditions as described in Example 1-C, and the result of having computed crystallinity is shown. Crystallinity = 16.29%

(Example 5-B)
(4-chloromethylstyrene: styrene = 5.0: 95.0 molar ratio preparation)
4.63 g of 4-chloromethylstyrene and 60.09 g of styrene were dissolved in 36.3 g of toluene and heated to 110 ° C. under a nitrogen stream (50 mL / min). To this solution, a fully nitrogen-substituted mixture of 33.7 g of toluene and 4.27 g of tert-butyl peroxyisopropyl monocarbonate (trade name: Perbutyl I, manufactured by NOF Corporation) was added dropwise over 20 minutes. The reaction was further carried out at 110 ° C. for 4 hours, and then cooled. Thereafter, the reaction solution was added to 1 L of methanol and decanted. The polymerization reaction product was dissolved in 150 mL of tetrahydrofuran, and the solution was added to cause precipitation in 1 L of methanol, followed by filtration. The residue was washed 4 times with 100 mL of methanol and dried under reduced pressure at 60 ° C. for 10 hours to obtain 64.1 g of a copolymer intermediate.

About the obtained copolymer intermediate, ¹ H-NMR was measured under the conditions described in Example 1-A, and the peaks of vinyl groups of styrene and 4-chloromethylstyrene as raw materials before the copolymerization reaction were observed. Instead, a broad aromatic proton, an alkyl chain and a benzyl proton δ (ppm) derived from 4-chloromethylstyrene = 4.5 (—CH ₂ —Cl) were observed. It was confirmed that 4.3% of 4-chloromethylstyrene was contained in the obtained copolymer intermediate from the integral value of the peak.

About the obtained copolymer intermediate, FT-IR was measured under the conditions described in Example 1-A.
ν (cm ⁻¹ ) = 3103, 3082, 3059, 3026, 3001, 2976, 2924, 2848, 1942, 1869, 1801, 1741, 1601, 1583, 1506, 1493, 1452, 1423, 1385, 1373, 1363, 1352 , 1329, 1313, 1263, 1182, 1155, 1105, 1070, 1028, 1003, 980, 964, 943, 906, 839, 758, 698, 621, 540 were observed.

  The obtained copolymer intermediate has the following unit E and unit D.

  About the obtained copolymer intermediate, GPC was measured on the conditions as described in Example 1-B. As a result of the measurement, it was confirmed that the copolymer intermediate had a number average molecular weight (Mn) of 8287, a weight average molecular weight (Mw) of 20482, and a molecular weight distribution (Mw / Mn) = 2.5.

  10.0 g of the copolymer intermediate was dissolved in 60 mL of tetrahydrofuran, dispersed by adding 4.3 g of sodium hydride, and stirred at 70 ° C. for 1 hour. Thereafter, 3.3 g of 2,5-dihydroxybenzoic acid was added, reacted at 70 ° C. for 5 hours, cooled to room temperature, gradually added and dispersed in 1 kg of ice water, and extracted with chloroform. Thereafter, it was washed with water, the chloroform layer was separated and dried over magnesium sulfate, and chloroform was distilled off under reduced pressure. The precipitate was dried under reduced pressure at 80 ° C. for 24 hours to obtain 7.6 g of a copolymer (B5).

When ¹ H-NMR was measured on the obtained copolymer (B5) under the conditions described in Example 1-A, benzyl proton δ (ppm) as a raw material before the reaction = 4.5 (—CH ₂ -Cl) was confirmed to be 0.90% from the integration ratio of the peaks. Furthermore, a broad hydroxyl group and a broad proton in the vicinity of δ (ppm) = 4.9 (—CH ₂ —O—) were observed, and the dihydroxybenzoic acid unit in the resulting copolymer was determined from the integrated value of the peak. It was confirmed that 4.02% was contained.

About the obtained copolymer (B5), when FT-IR was measured on the conditions as described in Example 1-A,
ν (cm ⁻¹ ) = 3435, 3060, 3027, 2922, 2848, 1944, 1873, 1800, 1741, 1678, 1616, 1601, 1577, 1493, 1455, 1265, 1215, 1155, 1069, 1028, 906, 758 , 698, 540 were observed.

  The obtained copolymer (B5) is composed of the following unit F corresponding to the unit A, the following unit D corresponding to the unit B, and a unit E derived from the copolymer intermediate.

  As for the obtained copolymer (B5), TG-DTA was measured under the conditions described in Example 1-B. As a result, weight loss temperature: 317 ° C., 389 ° C., 512 ° C., exothermic temperature: 345 ° C., 539 ° C. Was observed.

  About the obtained copolymer (B5), GPC was measured on the conditions as described in Example 1-B. As a result of the measurement, it was confirmed that the copolymer (B5) had a number average molecular weight (Mn) of 8157, a weight average molecular weight (Mw) of 19775, and a molecular weight distribution (Mw / Mn) = 2.4.

  About the obtained copolymer (B5), the glass transition temperature was measured on the conditions as described in Example 1-B. As a result of the measurement, it was confirmed that the glass transition temperature of the copolymer (B5) was 101.6 ° C.

(Example 5-C)
9.0 g of copolymer (B5) was dissolved in 27 mL of N, N-dimethylformamide. To a mixed solvent of 27 mL of N, N-dimethylformamide and 9 mL of methanol is added 3.0 g of a 20 wt% aqueous sodium hydroxide solution, added to the copolymer solution over 15 minutes, heated to 65 ° C., and added to 9 mL of N, N-dimethylformamide. A solution containing 4.98 g of 25.7% purity aluminum sulfate was added over 30 minutes, followed by 27 mL of N, N-dimethylformamide. The mixture was heated and stirred at 65 ° C. for 15 minutes, filtered, and the residue was washed with 60 mL of N, N-dimethylformamide by shaking twice and dispersed in 300 mL of water. After filtration, the residue was washed with 150 mL of water three times and dried at 80 ° C. for 24 hours to obtain 6.02 g of a white aluminum-containing copolymer resin (C5) that is a reaction product of the copolymer (B5) and aluminum. It was.

  About the obtained aluminum containing copolymer resin (C5), the weight% of the metal to contain was measured on the conditions as described in Example 1-C. The measured values of atomic absorption are shown below. Al = 1.41%, Na = 0.06%

About the obtained aluminum containing copolymer resin (C5), when FT-IR was measured on the conditions as described in B1 of Example 1,
ν (cm ⁻¹ ) = 3431, 3082, 3059, 3026, 3001, 2922, 2850, 1942, 1873, 1803, 1601, 1512, 1493, 1452, 1377, 1263, 1180, 1155, 1101, 1070, 1028, 1016 , 906, 840, 820, 758, 698, 667, 629, and 540, the same spectrum as that of the aluminum-containing copolymer resin (C3) was observed.

  With respect to the obtained aluminum-containing copolymer resin (C5), TG-DTA was measured under the conditions described in Example 1-A. As a result, weight loss temperature: 329 ° C., 467 ° C., exothermic temperature: 365 ° C., 469 ° C. Observed.

  About the obtained aluminum containing copolymer resin (C5), the X-ray diffraction was measured on the conditions as described in Example 1-C, and the result of having computed crystallinity is shown. Crystallinity = 10.6%

(Comparative Example 1)
90.0 g of 2,5-dihydroxybenzoic acid was dissolved in 1200 mL of methanol, 159.0 g of potassium carbonate was added, and the mixture was heated to 50 ° C. To this reaction solution, 72.6 g of allyl bromide was added dropwise over 90 minutes and reacted at 60 ° C. for 12 hours. After cooling the reaction solution, methanol was distilled off under reduced pressure and washed with hexane. After filtration, the residue was dispersed in 3 L of water at pH = 2 and extracted by adding ethyl acetate. Then, it washed with water, the ethyl acetate layer was isolate | separated, it was made to dry with magnesium sulfate, ethyl acetate was distilled off under pressure reduction, and the deposit was obtained. This precipitate was dissolved in methanol, dropped into water, re-precipitated, and the precipitate was filtered. This reprecipitation operation was repeated twice, and the residue was dried at 80 ° C. for 48 hours to obtain 26.5 g (yield = 23.8%) of a styrene derivative represented by the following chemical formula (X1).

(Chemical Formula (X1): Preparation of Mol Ratio of Styrene = 5.0: 95.0)
4.68 g of styrene derivative (X1) and 60.09 g of styrene were dispersed in 39 mL of toluene and heated to 110 ° C. under a nitrogen stream (50 mL / min). To this solution, a mixed solution of 39 mL of toluene and 4.27 g of tert-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, trade name: Perbutyl I) was added dropwise over 25 minutes. The reaction was further carried out at 110 ° C. for 4 hours, and then cooled. Thereafter, the reaction solution was dissolved in 150 mL of tetrahydrofuran. This solution was added dropwise with methanol to precipitate the reaction product, filtered, and dried under reduced pressure at 90 ° C. for 20 hours to obtain 47.3 g of a copolymer (Y1).

About the obtained copolymer (Y1), the volume resistivity was measured on the conditions as described in Example 1-C. As a result of the measurement, the volume resistivity of the copolymer (Y1) was 3.7 × 10 ¹⁴ Ωcm.

  The obtained copolymer (Y1) is obtained from the styrene derivative (X1), and is composed of a unit G not corresponding to the unit A and a unit D below corresponding to the unit B.

(Comparative Example 2)
50.0 g of p-cresol was dissolved in 450 mL of acetone, 94.5 g of potassium carbonate was added, and the mixture was heated to 56 ° C. To this reaction solution, 72.7 g of 4- (chloromethyl) styrene was added dropwise over 30 minutes and reacted at 56 ° C. for 12 hours. The reaction solution was cooled and then filtered, acetone in the filtrate was distilled off under reduced pressure, and the resulting residue was washed with hexane. After filtration, the residue was recrystallized from toluene. After filtration, the residue was dried at 80 ° C. for 48 hours to obtain 43.2 g (yield = 42.5%) of a styrene derivative represented by the following chemical formula (X2).

(Chemical Formula (X2): Preparation of Mol Ratio of Styrene = 5.0: 95.0)
3.56 g of styrene derivative (X2) and 31.44 g of styrene were dispersed in 21 mL of toluene and heated to 110 ° C. under a nitrogen stream (50 mL / min). To this solution, a mixed solution of 21 mL of toluene and 2.31 g of tert-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, trade name: Perbutyl I) was added dropwise over 17 minutes. Furthermore, after reacting at 110 ° C. for 4 hours, the mixture was cooled and dissolved in 150 mL of tetrahydrofuran. This solution was added dropwise with methanol to precipitate the reaction product, filtered, and dried under reduced pressure at 90 ° C. for 20 hours to obtain 27.9 g of a copolymer (Y2).

  The obtained copolymer (Y2) is obtained from the styrene derivative (X2), and is composed of a unit H that does not correspond to the unit A, and the following unit D that corresponds to the unit B.

(Example A) Evaluation of charge control characteristics in chargeability test A of charge control agent 1 part by weight of aluminum-containing copolymer resin (C1) obtained in the above Example, styrene-acryl copolymer resin (Mitsui Chemicals, Inc.) , 100 parts by weight of product name: CPR-100) were premixed, and then melt-kneaded with a heating roll (trade name: S-1, KRC kneader, manufactured by Kurimoto Steel Corporation). After cooling, coarsely pulverized with an ultracentrifugal crusher (manufactured by Retsch Co., Ltd., trade name: ULTRA CENTRIFUGAL MILL, screen opening 1.5 mm), and an air jet mill with a classifier (manufactured by Seishin Corporation, trade name: CO-) JET) is used to measure the average particle size with a laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd., trade name: Partica LA-950), and finely pulverized to 9.5 to 10.5 μm. Went. 2.5 parts by weight of the resin particles and 50.0 parts by weight of an iron powder carrier (manufactured by Powdertech Co., Ltd., trade name: TEFV200 / 300) are placed in a 100 mL ointment bottle, and a ball mill rotary mount (Asahi Rika Seisakusho Co., Ltd.) Manufactured, trade name: small ball mill rotating stand AV-1) while rotating at 100 rpm, a mixture obtained every set time was collected and blow-off charge measuring device (manufactured by Toshiba Chemical Corporation, trade name: TB-) 200), the charge amount was measured under the following conditions. The results of the negative charge confirmation data obtained are shown in Table 14 and FIG.
Measurement conditions: Metal mesh opening 34 μm Pressure 10.0 kPa Suction force 10.0 kPa Suction time 10.0 seconds

  Furthermore, the aluminum-containing copolymer resin (C2), (C3), (C4), (C5) and the comparative copolymers (Y1), (Y2) obtained in the above-mentioned examples were compared with the aluminum-containing copolymer resin ( The chargeability test A was performed in the same manner as in C1). The results are shown in Table 14 and FIG.

(Example B) Environmental stability evaluation of charge control agent which is resin particle obtained in Example A Aluminum-containing copolymer resin (C1), (C2), (C3), (C4) obtained in the above Example ), (C5) and the comparative copolymers (Y1), (Y2), the following environmental stability evaluation was performed using the resin particles obtained in Example A. The results are shown in Table 15.
Iron powder carrier (manufactured by Powder Tech Co., Ltd., trade name: TEFV200 / 300) 50.0 parts by weight and each resin particle prepared under the conditions of the above-mentioned chargeability test A are put in a 100 mL ointment bottle, and a 1 cm hole is formed in the center. I put an empty lid. This is set in a ball mill machine (manufactured by Asahi Rika Seisakusho Co., Ltd., ball mill rotary mount) in a thermo-hygrostat (manufactured by Tokyo Rika Machinery Co., Ltd., trade name: ENVIROS KCL-2000W). It was left in the environment for 24 hours. After 24 hours, the mixture was collected after stirring for 15 minutes while rotating a 100 mL ointment bottle at 100 rpm, and using a blow-off charge measuring device (trade name: TB-200, manufactured by Toshiba Chemical Co., Ltd.) The charge amount was measured under the following conditions.
Measurement conditions: Metal mesh opening 34 μm Pressure 10.0 kPa Suction force 10.0 kPa Suction time 10.0 seconds

ここで、ＬＬは低温低湿、ＨＨは高温高湿を示すものとする。

Here, LL indicates low temperature and low humidity, and HH indicates high temperature and high humidity.

(Example C) Evaluation of charge control property in chargeability test B of charge control agent 1 part by weight of aluminum-containing copolymer resin (C1) obtained in the above example, polyester resin (trade name: ER, manufactured by Mitsubishi Rayon Co., Ltd.) -508) After premixing 100 parts by weight, the mixture was melt-kneaded with a heating roll (manufactured by Kurimoto Steel Works, trade name: S-1, KRC kneader). After cooling, coarsely pulverized with an ultracentrifugal crusher (manufactured by Retsch Co., Ltd., trade name: ULTRA CENTRIFUGAL MILL, screen opening 1.5 mm), and an air jet mill with a classifier (manufactured by Seishin Corporation, trade name: CO-) JET) is used to measure the average particle size with a laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd., trade name: Partica LA-950), and finely pulverized to 9.5 to 10.5 μm. Went. 2.5 parts by weight of the resin particles and 50.0 parts by weight of an iron powder carrier (manufactured by Powdertech Co., Ltd., trade name: TEFV200 / 300) are placed in a 100 mL ointment bottle, and a ball mill rotary mount (Asahi Rika Seisakusho Co., Ltd.) Manufactured, trade name: small ball mill rotating stand AV-1) while rotating at 100 rpm, a mixture obtained every set time was collected and blow-off charge measuring device (manufactured by Toshiba Chemical Corporation, trade name: TB-) 200), the charge amount was measured under the following conditions. The results of the negative charge confirmation data obtained are shown in Table 16 and FIG.
Measurement conditions: Metal mesh opening 34 μm Pressure 10.0 kPa Suction force 10.0 kPa Suction time 10.0 seconds

  Furthermore, the aluminum-containing copolymer resin (C2), (C3), (C4), (C5) and the comparative copolymers (Y1), (Y2) obtained in the above-mentioned examples were compared with the aluminum-containing copolymer resin ( The chargeability test B was performed as in C1). The results are shown in Table 16 and FIG.

(Example D) Environmental stability evaluation of charge control agent which is resin particle obtained in Example C Aluminum-containing copolymer resin (C1), (C2), (C3), (C4) obtained in the above Example ), (C5) and comparative copolymers (Y1), (Y2) were evaluated for environmental stability in the same manner as in Example B, using the resin particles obtained in Example C. The results are shown in Table 17.

ここで、ＬＬは低温低湿、ＨＨは高温高湿を示すものとする。

Here, LL indicates low temperature and low humidity, and HH indicates high temperature and high humidity.

  As is apparent from the figure, the charge control agent, which is the aluminum-containing copolymer resin of the present invention, has a fast charge rise and a high charge amount regardless of whether the rotation is high speed or low speed.

  The aluminum-containing copolymer resin of the present invention has a good charge control function, shows the function of a charge control resin, has uses as a charge imparting agent, a charge control agent, and an enhancer, heat resistance, charging characteristics, Excellent environmental stability, so it is used in industries that use various electric charges and charges, such as electrostatic powder coatings, electrophotographic toners, electrostatic inkjet recording applications, electronic paper, pressure-sensitive copying paper, and developers can do.

Claims (13)

The following chemical formula (1)

(In the formula, each R ¹ is independently the same or different and is a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or a linear or branched chain having 1 to 18 carbon atoms. R ² is a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or a linear or branched alkoxy group having 1 to 18 carbon atoms, h is 1 to 3, and M is any one selected from a hydrogen atom, an alkali metal, an ammonium atom group, and a mixture thereof), and includes at least one of the units A An aluminum-containing copolymer resin, wherein a part is metal complexed or metal chlorided with aluminum.   The aluminum-containing copolymer resin according to claim 1, wherein the aluminum content is 0.1 to 8.0% by weight. The copolymer includes a unit B obtained from a vinyl group-containing monomer,
At least one of the units B has the following chemical formula (2)

2. wherein R ³ , R ⁴ and R ⁵ are the same or different and are each selected from a hydrogen atom, an alkyl group, a halogen atom and an alkoxy group. Or the aluminum-containing copolymer resin of 2. The copolymer is obtained from a vinyl group-containing monomer and has the following chemical formula (10)

Wherein R ⁶ is a methyl group or a hydrogen atom, and R ⁷ is an optionally substituted alkoxy group or a hydroxyl group . The aluminum-containing copolymer resin according to any one of the above.   5. The aluminum-containing copolymer resin according to claim 1, wherein 0.1 to 15 mol% of the unit A is contained in the copolymer. The aluminum-containing copolymer resin according to any one of claims 1 to 5, wherein the glass transition temperature is from 60 ° C to 150 ° C. The aluminum-containing copolymer resin according to any one of claims 1 to 6, wherein weight loss is measured at 200 ° C to 450 ° C in differential thermogravimetric analysis. The aluminum-containing copolymer resin according to claim 1, wherein the volume resistivity is 0.5 × 10 ^{16 to} 7.0 × 10 ¹⁷ Ωcm.   The aluminum-containing copolymer resin according to any one of claims 1 to 8, wherein the crystallinity is 0.0 to 20.0%.   A charge control agent comprising the aluminum-containing copolymer resin according to any one of claims 1 to 9 as an active ingredient. The following chemical formula (1)

(In the formula, each R ¹ is independently the same or different and is a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or a linear or branched chain having 1 to 18 carbon atoms. R ² is a hydrogen atom, a hydroxyl group, a halogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or a linear or branched alkoxy group having 1 to 18 carbon atoms, h is 1 to 3, and M is any one selected from a hydrogen atom, an alkali metal, an ammonium atom group, and a mixture thereof) and a vinyl group-containing monomer different from that A polymerization reaction step of polymerizing a monomer containing the product and a metalation step of reacting with a metallizing agent containing aluminum to form a metal complex or metal chloride. Manufacturing method of an aluminum-containing copolymer resin to.   The said polymerization reaction process contains a polymerization initiator, The manufacturing method of the aluminum containing copolymer resin of Claim 11 characterized by the above-mentioned.   The metallization step of reacting the obtained polymer with the metallizing agent containing aluminum to form a metal complex or metal chloride after the polymerization reaction step is performed. The manufacturing method of aluminum-containing copolymer resin of description.