JP2007211146A - Phosphate residue-containing (meth)acrylamide composition, polymer using the same, their applications and methods of preparing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphate residue-containing (meth)acrylamide composition that (a) has a high emulsification capacity and can be used as an emulsifier that copolymerizes with an unsaturated monomer subjected to emulsion polymerization, (b) can be used as a solubilizing agent for easily dissolving or dispersing a rubber in an organic solvent and (c) becomes a resin having a high conductivity when polymerized, a polymer using the same, their applications, and methods of preparing the same. <P>SOLUTION: The phosphate residue-containing (meth)acrylamide composition is obtained by introducing a phosphate residue to an optionally N-substituted (meth)acrylamide monomer and reacting the obtained phosphate residue-containing (meth)acrylamide with an alcoholic hydroxyl group-containing compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is a phosphoric acid ester residue-containing (meth) acrylamide composition that is suitable as an emulsifier and solubilizer and is useful as a raw material for conductive resins, a polymer using the composition, uses thereof, and It relates to the manufacturing method.

  Acrylamide compounds having an electrolyte group such as a phosphoric acid residue such as (poly) phosphate group and (poly) phosphonic acid group; sulfonate group are conductive materials, emulsifiers, solubilizers, paper modifiers. It is useful in a wide range of applications such as sanitary materials and agricultural materials. Among them, acrylamide-based high polymers having phosphoric acid residues as electrolyte groups are particularly conductive resins because they are hydrophilic but hardly soluble in water and have excellent oxidation resistance and flame retardancy. It is useful in each application of antistatic agent, paper modifier and coating agent.

  For example, Japanese Patent Application Laid-Open No. 5-237355 (Patent Document 1) discloses a polymer emulsifier for obtaining an aqueous resin emulsion capable of forming a film having good water resistance. A macromonomer having a radical polymerizable group at one end of the polymer molecule, (b) at least one selected from the group consisting of a radical polymerizable monomer having a carboxyl group, a sulfo group or a phosphate group, or a salt thereof; and (c) A polymer emulsifier comprising a water-soluble graft copolymer obtained by copolymerizing other radically polymerizable monomers is disclosed. Patent Document 1 mentions an acrylamide group as a radical polymerizable group of the macromonomer (a). However, since this polymer emulsifier itself is poor in unsaturated groups, it does not form a film by copolymerizing with an unsaturated monomer that forms the film. Therefore, the combination is limited by the compatibility between the polymer constituting the film and the polymer emulsifier.

  In the field of solubilizers, rubber is modified by grafting a functional group-containing unsaturated monomer (such as a phosphoric acid group-containing unsaturated monomer) onto a rubber (for example, a liquid organic oligomer) by a solution graft polymerization method. There is a need for a solubilizer that is used when a functional group of a rubber containing (for example, an epoxy group or the like) is modified with an acid (for example, phosphoric acid or the like). This is because a solvent is usually used in these treatments, but there are limited solvents that can dissolve or highly disperse both the raw rubber and the treated grafted rubber or acid-modified rubber. This is because even if it is dissolved in gel, it often gels if it is grafted or acid-modified.

  As a solubilizer comprising an acrylamide polymer having an electrolyte group, JP-A-9-20615 (Patent Document 2) discloses (meth) acrylamide alkylsulfonic acid and / or a salt thereof, N-substituted (meth) acrylamide, Discloses a solubilizer comprising a water-soluble amphiphilic polymer electrolyte obtained by copolymerization of However, Patent Document 2 only describes the use of this solubilizer to solubilize fragrances, drugs, and the like in water, and the above water-solubility is used when rubber is grafted or acid-modified in an organic solvent. The use of amphiphilic polymer electrolytes is not described.

（ただしR^1'は水素基又はメチル基であり、R²¹及びR²²は水素基又は炭素数１〜３のアルキル基であり、R²³は炭素数１〜３のアルキレン基であり、M²は水素基、アルカリ金属又はアンモニウムイオンもしくはアミン残基である。）により表される構成単位からなるポリマーに、（ポリ）ホスホン酸基を導入したスルホン酸塩基含有アクリルアミド重合体を用いた導電材を提案した［特開2004-331810号（特許文献３）］。特許文献３では、上記ポリマーとリン酸源化合物とを反応させることによりリン酸誘導体基／スルホン酸塩基含有アクリルアミド重合体を調製する。しかし（ポリ）ホスホン酸基の導入量が十分とはいえなかった。 In the field of conductive resins, electrolyte group-containing acrylamide polymers that have not only high conductivity but also water resistance and oxidation resistance are desired. Therefore, the applicant has the following general formula (74):

(Wherein R ^{1 'is} a hydrogen group or a methyl group, R ²¹ and R ²² are a hydrogen group or an alkyl group having 1 to 3 carbon atoms, R ²³ is an alkylene group having 1 to 3 carbon atoms, M ² Is a hydrogen group, an alkali metal, an ammonium ion, or an amine residue.) A conductive material using a sulfonate group-containing acrylamide polymer in which a (poly) phosphonic acid group is introduced into a polymer composed of structural units Proposed [JP 2004-331810 (Patent Document 3)]. In Patent Document 3, a phosphoric acid derivative group / sulfonate group-containing acrylamide polymer is prepared by reacting the polymer with a phosphoric acid source compound. However, the amount of (poly) phosphonic acid groups introduced was not sufficient.

（ただしR^1'は水素基又はメチル基であり、R^2'は水素基又は置換もしくは無置換の炭化水素基である。）により表される（メタ）アクリルアミド系単量体にリン系酸残基が導入されたリン系酸残基含有（メタ）アクリルアミドを重合してなる導電性樹脂を提案した［WO2005／080454（特許文献４）］。しかし導電性の一層の向上が望まれている。 Therefore, the present applicant must at least satisfy the following formula (75)

Where R ^{1 ′} is a hydrogen group or a methyl group, and R ^{2 ′} is a hydrogen group or a substituted or unsubstituted hydrocarbon group. A conductive resin obtained by polymerizing a phosphoric acid residue-containing (meth) acrylamide having a group introduced therein has been proposed [WO2005 / 080454 (Patent Document 4)]. However, further improvement in conductivity is desired.

JP-A-5-237355 Japanese Patent Laid-Open No. 9-20615 JP 2004-331810 A International Publication No. 05/080454 Pamphlet

  Therefore, the object of the present invention is (a) it can be used as an emulsifier having a high emulsifying ability and copolymerized with an unsaturated monomer to be emulsion-polymerized, and (b) dissolves or disperses rubber well in an organic solvent. (C) Phosphoric acid ester residue-containing (meth) acrylamide composition that can be used as a solubilizer and becomes a highly conductive resin when polymerized, a polymer using the composition, its use, and production thereof Is to provide a method.

  As a result of diligent research in view of the above object, the present inventor introduced a phosphoric acid residue into a (meth) acrylamide monomer which may be N-substituted, and obtained phosphoric acid residue-containing ( When an alcoholic hydroxyl group-containing compound is reacted with meth) acrylamide, it can be used as an emulsifier that (a) has high emulsifying ability and copolymerizes with an unsaturated monomer that is emulsion-polymerized, and (b) rubber is used as an organic solvent. It can be used as a solubilizer that dissolves or disperses well, and (c) a phosphoric acid ester residue-containing (meth) acrylamide composition that becomes a highly conductive resin when polymerized can be obtained. I came up with it.

（ただしR^1aは水素基又はメチル基であり、R^2aは水素基又は置換もしくは無置換の炭化水素基であり、-X^a-O-R^3aはリン系酸エステル残基である。）により表される化合物、下記式(2)：

（ただしR^1bは水素基又はメチル基であり、-X^bOHはリン系酸残基であり、-X^c-O-R^3bはリン系酸エステル残基であり、各々リン原子、酸素原子及び水素原子からなる原子団であるX^bとX^cは同じであっても異なっていてもよい。）により表される化合物、並びに下記式(3)：

（ただしR^1cは水素基又はメチル基であり、-X^d-O-R^3c及び-X^e-O-R^3dは各々リン系酸エステル残基であり、各々アルコール性水酸基含有化合物の残基であるR^3cとR^3dは同じであっても異なっていてもよく、各々リン原子、酸素原子及び水素原子からなる原子団であるX^dとX^eは同じであっても異なっていてもよい。）により表される化合物からなる群から選ばれた少なくとも一種であることを特徴とする。 That is, the phosphoric acid ester residue-containing (meth) acrylamide composition of the present invention is a phosphoric acid residue in which a phosphoric acid residue esterified with an alcoholic hydroxyl group-containing compound is directly bonded to the nitrogen atom of the amide group. A composition containing an acid ester residue-containing (meth) acrylamide, wherein the phosphoric acid ester residue-containing (meth) acrylamide is represented by the following formula (1):

Wherein R ^1a is a hydrogen group or a methyl group, R ^2a is a hydrogen group or a substituted or unsubstituted hydrocarbon group, and —X ^a —OR ^3a is a phosphorus acid ester residue. The following compound (2):

(However, R ^1b is a hydrogen group or a methyl group, -X ^b OH is a phosphorus acid residue, and -X ^c -OR ^3b is a phosphorus acid ester residue, and each contains a phosphorus atom, an oxygen atom, and a hydrogen atom. X ^b and X ^c which are atomic groups composed of atoms may be the same or different.) And a compound represented by the following formula (3):

(Wherein R ^1c is a hydrogen group or a methyl group, -X ^d -OR ^3c and -X ^e -OR ^3d are each a phosphorus acid ester residue, and each R ^3c is a residue of an alcoholic hydroxyl group-containing compound. And R ^3d may be the same or different, and X ^d and X ^e which are atomic groups each consisting of a phosphorus atom, an oxygen atom and a hydrogen atom may be the same or different. It is at least one selected from the group consisting of the above compounds.

（ただしR¹は水素基又はメチル基であり、R³はアルコール性水酸基含有化合物の残基である。）により表される化合物、下記式(5)：

（ただしR¹は水素基又はメチル基であり、R³はアルコール性水酸基含有化合物の残基である。）により表される化合物、及び下記式(6)：

（ただしR¹は水素基又はメチル基であり、R³はアルコール性水酸基含有化合物の残基である。）により表される化合物からなる群から選ばれた少なくとも一種であるのが好ましい。 The phosphorus acid ester residue-containing (meth) acrylamide has the following formula (4):

(Wherein R ¹ is a hydrogen group or a methyl group, and R ³ is a residue of an alcoholic hydroxyl group-containing compound), a compound represented by the following formula (5):

(Wherein R ¹ is a hydrogen group or a methyl group, and R ³ is a residue of an alcoholic hydroxyl group-containing compound), and the following formula (6):

(Wherein R ¹ is a hydrogen group or a methyl group, and R ³ is a residue of an alcoholic hydroxyl group-containing compound).

（ただしR^1dは水素基又はメチル基であり、R^2bは水素基又は置換もしくは無置換の炭化水素基であり、-X^fOHはリン系酸残基である。）、及び／又は下記式(8)：

（ただしR^1eは水素基又はメチル基であり、-X^gOH及び-X^hOHは各々リン系酸残基であり、各々リン原子、酸素原子及び水素原子からなる原子団であるX^gとX^hは同じであっても異なっていてもよい。）により表されるリン系酸残基含有（メタ）アクリルアミドを含んでもよい。 The phosphoric acid ester residue-containing (meth) acrylamide composition further comprises the following formula (7):

(Where R ^1d is a hydrogen group or a methyl group, R ^2b is a hydrogen group or a substituted or unsubstituted hydrocarbon group, and —X ^f OH is a phosphorus acid residue), and / or (8):

(However, R ^1e is a hydrogen group or a methyl group, -X ^g OH and -X ^h OH are each a phosphorus acid residue, and X ^g is an atomic group consisting of a phosphorus atom, an oxygen atom and a hydrogen atom, respectively. X ^h may be the same or different. The phosphoric acid residue-containing (meth) acrylamide represented by

（ただしR¹は水素基又はメチル基である。）により表されるホスホン酸（メタ）アクリルアミド、及び／又は下記式(10)：

（ただしR¹は水素基又はメチル基である。）により表されるN, N-ジホスホン酸（メタ）アクリルアミドであるのが好ましい。 The phosphorus acid residue-containing (meth) acrylamide has the following formula (9):

(Wherein R ¹ is a hydrogen group or a methyl group) and / or phosphonic acid (meth) acrylamide represented by the following formula (10):

N 1, N-diphosphonic acid (meth) acrylamide represented by (wherein R ¹ is a hydrogen group or a methyl group) is preferred.

  The ratio of the phosphoric acid ester residue-containing (meth) acrylamide and the phosphoric acid residue-containing (meth) acrylamide is such that the phosphorus acid ester residue-containing (meth) acrylamide and the phosphorus acid residue-containing (meta) ) The total of acrylamide is preferably 100 mol%, and the phosphorus acid ester residue-containing (meth) acrylamide is preferably 20 mol% or more.

  The alcoholic hydroxyl group-containing compound may be monohydric alcoholic or polyhydric alcoholic. The alcoholic hydroxyl group-containing compound includes aliphatic alcohol, alicyclic alcohol, aromatic alcohol, phenol and derivatives thereof, glycerin and derivatives thereof, fluorine-containing alcohol, polyoxyalkylene glycol, polyoxyalkylene monoalkyl ether, polyoxyalkylene. It is preferably at least one selected from the group consisting of esters, unsaturated alcohol copolymers, partially acetalized unsaturated alcohol polymers, and alcohol-modified or phenol-modified silicone oils.

（ただしa〜cは各々重合度である。）により表されるポリオキシプロピレングリセリルエーテル、下記式(12)：

（ただしa〜dは各々重合度である。）により表されるポリオキシエチレンメチルグルコシド、並びに下記式(13):

（ただしR⁵¹は置換もしくは無置換のアルキル基又はアリール基であり、R⁵²は置換もしくは無置換のアルキレン基であり、R⁵³OHはオキシアルキル基であり、nは重合度である。）により表される変性シリコーンオイルからなる群から選ばれた少なくとも一種であるのがより好ましい。 The alcoholic hydroxyl group-containing compound is nonylphenol ethoxyethanol, lauryl alcohol, octafluoropentanol, the following formula (11):

(Wherein a to c are degrees of polymerization, respectively), polyoxypropylene glyceryl ether represented by the following formula (12):

(Wherein a to d are each the degree of polymerization), and the following formula (13):

Where R ⁵¹ is a substituted or unsubstituted alkyl group or aryl group, R ⁵² is a substituted or unsubstituted alkylene group, R ⁵³ OH is an oxyalkyl group, and n is the degree of polymerization. More preferably, it is at least one selected from the group consisting of modified silicone oils.

  The phosphoric acid ester residue-containing (meth) acrylamide composition of the present invention is suitable for emulsifiers and rubber solubilizers.

  The phosphorus acid ester residue-containing (meth) acrylamide polymer of the present invention is characterized in that it is formed by polymerizing at least the phosphorus acid ester residue-containing (meth) acrylamide composition.

  The phosphoric acid ester residue-containing (meth) acrylamide polymer may contain another unsaturated compound as a copolymerization component. The other unsaturated compound includes (a) an unsaturated compound having one or more ethylenically unsaturated bonds and acidic groups in the molecule, and / or (b) one or more ethylenically unsaturated compounds in the molecule. An unsaturated compound having a bond but no acidic group, wherein the unsaturated compound having an acidic group is at least one selected from the group consisting of a phosphoric acid group, a sulfonic acid group, a carboxylic acid group, and an alcoholic hydroxyl group. The unsaturated compound having an acidic group and not having the acidic group is (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid ester, an alkylamino group-containing unsaturated monomer, a conjugated diene liquid oligomer or the like It is at least one selected from the group consisting of a derivative, a substituted or unsubstituted styrene, a halogen vinyl, a fatty acid vinyl ester, and a fluorine group-containing unsaturated monomer. Masui.

（ただしR⁴は水素基又はメチル基であり、R⁵及びR⁶はそれぞれ独立にアルキル基である。）により表されるN, N-ジアルキル（メタ）アクリルアミド、下記式(15)：

（但しR⁷及びR⁸はそれぞれ独立に水素基又はメチル基であり、かつR⁷及びR⁸の少なくとも一方は水素基であり、m及びnは各々重合度である。）により表されるエポキシ化共役ジエン系液状オリゴマーのリン酸変性物、並びにアクリロニトリルからなる群から選ばれた少なくとも一種であるのが好ましい。 The other unsaturated compound is represented by the following formula (14):

(However, R ⁴ is a hydrogen group or a methyl group, and R ⁵ and R ⁶ are each independently an alkyl group.) N, N-dialkyl (meth) acrylamide represented by the following formula (15):

Wherein R ⁷ and R ⁸ are each independently a hydrogen group or a methyl group, and at least one of R ⁷ and R ⁸ is a hydrogen group, and m and n are each a degree of polymerization. It is preferably at least one selected from the group consisting of a phosphoric acid modified product of a conjugated diene-based liquid oligomer and acrylonitrile.

  The conductive resin of the present invention is characterized by containing the phosphorus acid ester residue-containing (meth) acrylamide polymer as an essential component. The conductive resin may further contain other resins. Other resins include unsaturated alcohol copolymers containing unsaturated alcohol units and halogen vinyl units and / or fatty acid vinyl units, partially acetalized unsaturated alcohol polymers, melamine resins, poly (meth) acrylonitrile, poly At least one selected from the group consisting of (meth) acrylic acid ester, polyacrylamide, poly (meth) acrylic acid, polyacetal, urethane resin, cellulose or a modified product thereof, polystyrene, polyvinyl chloride, and polyvinyl acetate is preferable. The conductive resin of the present invention is suitable as a binder for conductive metal paste.

（ただしR¹は水素基又はメチル基であり、R²は水素基又は置換もしくは無置換の炭化水素基である。）により表される（メタ）アクリルアミド系単量体に、リン酸源化合物を反応させ、得られた反応生成物にアルコール性水酸基含有化合物を反応させることを特徴とする。前記リン酸源化合物として無水リン酸を用いるのが好ましい。 The method for producing a phosphoric acid ester residue-containing (meth) acrylamide composition of the present invention comprises the following formula (16) in a solvent not containing active hydrogen and / or an acidic solvent:

(Wherein R ¹ is a hydrogen group or a methyl group, and R ² is a hydrogen group or a substituted or unsubstituted hydrocarbon group.) The reaction product is reacted, and an alcoholic hydroxyl group-containing compound is reacted with the obtained reaction product. It is preferable to use phosphoric anhydride as the phosphoric acid source compound.

  The method for producing a phosphoric acid ester residue-containing (meth) acrylamide polymer of the present invention comprises a phosphoric acid source in the above (meth) acrylamide monomer in a solvent not containing active hydrogen and / or an acidic solvent. A phosphoric acid ester residue-containing (meth) acrylamide composition is prepared by reacting a compound and reacting the resulting reaction product with an alcoholic hydroxyl group-containing compound, and at least the obtained phosphoric acid ester residue It is characterized by polymerizing a containing (meth) acrylamide composition.

（ただしR⁴は水素基又はメチル基であり、R⁵及びR⁶はそれぞれ独立にアルキル基である。）により表されるN, N-ジアルキル（メタ）アクリルアミドを用いるのが好ましい。 As the solvent not containing active hydrogen, the following formula (14):

It is preferable to use N, N-dialkyl (meth) acrylamide represented by (wherein R ⁴ is a hydrogen group or a methyl group, and R ⁵ and R ⁶ are each independently an alkyl group).

  The phosphoric acid ester residue-containing (meth) acrylamide composition of the present invention is a phosphoric acid ester in which a phosphoric acid residue esterified with an alcoholic hydroxyl group-containing compound is directly bonded to the nitrogen atom of the amide group. Contains residue-containing (meth) acrylamide. This composition has hydrophilicity due to phosphoric acid residues and phosphoric acid ester residues and hydrophobicity due to (meth) acrylamide groups, and further selects the composition of residues of alcoholic hydroxyl group-containing compounds as appropriate. By doing so, either hydrophilicity or hydrophobicity can be imparted to this residue. Therefore, the phosphoric acid ester residue-containing (meth) acrylamide composition has a surface active action, and as an emulsifier added to form an aqueous resin emulsion, and a solubilizer that dissolves or disperses rubber well in an organic solvent. Is preferred.

  Resins containing the polymer of the present composition as an essential component include various kinds such as conductive resins, solid polymer electrolytes, conductive metal pastes, antistatic agents, antifogging materials, paper / pulp modifiers, and coating agents. Useful for applications. In particular, a conductive resin containing this polymer is excellent in conductivity derived from a high-density phosphorus acid residue. Therefore, the membrane using the conductive resin of the present invention is a solid electrolyte membrane for fuel cells, an electrolyte membrane for primary batteries, an electrolyte membrane for secondary batteries, a display element, various sensors, a signal transmission medium, a solid capacitor, an ion exchange membrane, etc. Can be suitably used.

  According to the method for producing a phosphoric acid ester residue-containing (meth) acrylamide composition of the present invention, a phosphoric acid source compound is reacted with an N-substituted (meth) acrylamide monomer. Since the resulting reaction product is reacted with the alcoholic hydroxyl group-containing compound, the phosphorus acid ester residue can be easily introduced into the (meth) acrylamide monomer.

（ただしR¹は水素基又はメチル基であり、R²は水素基又は置換もしくは無置換の炭化水素基である。）により表される（メタ）アクリルアミド系単量体に、リン酸源化合物を反応させ、得られた反応生成物にアルコール性水酸基含有化合物を反応させてなる。 [1] Phosphoric acid ester residue-containing (meth) acrylamide composition The phosphoric acid ester residue-containing (meth) acrylamide composition has the following formula (16):

(Wherein R ¹ is a hydrogen group or a methyl group, and R ² is a hydrogen group or a substituted or unsubstituted hydrocarbon group.) A phosphoric acid source compound is added to a (meth) acrylamide monomer represented by The reaction product is reacted with an alcoholic hydroxyl group-containing compound.

(1) (Meth) acrylamide monomer R ¹ in formula (16) is preferably a hydrogen group in order to improve the polymerizability of the composition. R ² is preferably a hydrogen group in order to improve the electrolyte group density when a phosphorus acid ester residue is introduced to prepare a polymer. When R ² is a hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-methylbutyl group, 3- Examples thereof include alkyl groups such as methylbutyl group, n-octyl group and 2-ethylhexyl group; cycloalkyl groups such as cyclopropyl group and cyclohexyl group; aryl groups such as phenyl group and the like. These hydrocarbon groups may be substituted, and examples of the substituent include a sulfonic acid group that may form a complex salt; a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, and an isopropoxymethyl group. And alkoxymethyl groups such as tert-butoxymethyl group; amino groups such as N, N-dimethylamino group and N, N-diethylamino group. Among them, the substituted hydrocarbon group preferably has a sulfonic acid group that may form a complex salt in order to improve the electrolyte group density when a polymer is prepared.

（ただしR¹は水素基又はメチル基であり、R²⁰及びR^20'は水素基又は炭素数１〜３のアルキル基であり、R^20''は炭素数１〜３のアルキレン基であり、M¹は水素基、金属又は３級アミン残基である。）により表されるアクリルアミドアルカンスルホン酸塩からなる群から選ばれた少なくとも一種が好ましい。 Examples of (meth) acrylamide monomers include acrylamide, methacrylamide and the following formula (17):

(However, R ¹ is a hydrogen group or a methyl group, R ²⁰ and R ^{20 ′} are a hydrogen group or an alkyl group having 1 to 3 carbon atoms, R ^{20 ″} is an alkylene group having 1 to 3 carbon atoms, M ¹ is preferably a hydrogen group, a metal, or a tertiary amine residue.) At least one selected from the group consisting of acrylamide alkane sulfonates represented by:

により表されるターシャリーブチルアクリルアミドスルホン酸が好ましい。 As the acrylamide alkane sulfonate, the following formula (18):

The tertiary butyl acrylamide sulfonic acid represented by is preferable.

(2) Phosphate source compound The phosphorus acid residue introduced into the (meth) acrylamide monomer is derived from the phosphate source compound. Examples of the phosphoric acid source compound include phosphoric anhydride (phosphorus pentoxide: P ₂ O ₅ ), phosphorous trichloride, phosphorous oxychloride, etc., but phosphoric anhydride is preferred. Phosphoric anhydride is highly reactive, and by using this, the introduction of phosphoric acid residues into the (meth) acrylamide monomer proceeds smoothly.

(3) Alcoholic hydroxyl group-containing compound The alcoholic hydroxyl group-containing compound may be monohydric alcoholic or polyhydric alcoholic, and may be either a monomer or a polymer. Examples of alcoholic hydroxyl group-containing compounds include aliphatic alcohols, alicyclic alcohols, aromatic alcohols, phenols and derivatives thereof, glycerin and derivatives thereof, fluorine-containing alcohols, polyoxyalkylene glycols, polyoxyalkylene monoalkyl ethers, and polyoxyalkylenes. Examples include esters, unsaturated alcohol copolymers, partially acetalized unsaturated alcohol polymers, alcohol-modified or phenol-modified silicone oils, and the like. The alcoholic hydroxyl group-containing compound may be used alone or in combination of two or more.

(a) Aliphatic alcohol The aliphatic alcohol may be either saturated or unsaturated. Examples of the aliphatic saturated alcohol include linear or branched saturated alcohols having 1 to 24 carbon atoms. Specifically, methanol, ethanol, n- and iso-propanol, butanol, pentanol, hexanol, heptanol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol (dodecyl alcohol), tridecyl alcohol, tetradecyl Alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, eicosyl alcohol, heneicosyl alcohol, docosyl alcohol, tricosyl alcohol, tetracosyl alcohol and the like can be mentioned.

  Examples of the aliphatic unsaturated alcohol include cis- or trans- unsaturated aliphatic alcohols having 2 to 24 carbon atoms. Specifically, ethenyl alcohol, 1-propenyl alcohol, allyl alcohol, methallyl alcohol, butenyl alcohol, pentynyl alcohol, hexenyl alcohol, heptenyl alcohol, nonenyl alcohol, decenyl alcohol, undecenyl alcohol, Dodecenyl alcohol, tridecenyl alcohol, tetradecenyl alcohol, pentadecenyl alcohol, hexadecenyl alcohol, heptadecenyl alcohol, octadecenyl alcohol, nonadecenyl alcohol, eicosenyl Alcohol, henecosenyl alcohol, dococenyl alcohol, tricocenyl alcohol and tetracocenyl alcohol, oxo method alcohol ("Dovanol" manufactured by Shell Chemicals Japan Co., Ltd., "Dai" manufactured by Mitsubishi Chemical Corporation Doll ", etc.) and the like.

(b) Alicyclic alcohol, aromatic alcohol and phenol derivative Examples of the alicyclic alcohol include cyclopentanol and cyclohexanol. Examples of the aromatic alcohol include benzyl alcohol. Examples of the phenol derivative include phenol having a hydrocarbon group having 1 to 24 carbon atoms. Examples include octylphenol, nonylphenol, dodecylphenol, polystyrylphenol, polystyrylcumylphenol, and polystyrylcresol.

（ただし-R³⁰COは脂肪酸残基であり、a及びbは各々重合度である。）により表されるポリオキシエチレン脂肪酸グリセリル（例えば日本油脂株式会社製「ユニグリMC」、「同ML」、「同MO」、「同MT」、「同MK」等。）、下記式(20)：

（ただし-R³¹COはイソステアリン酸残基であり、a〜cは各々重合度である。）により表されるイソステアリン酸ポリオキシエチレングリセリル（日本油脂株式会社製「ユニオックスGM」等。）、下記式(21)：

（ただし-R³²COはイソステアリン酸残基であり、a〜cは各々重合度である。）により表されるトリイソステアリン酸ポリオキシエチレングリセリル（日本油脂株式会社製「ユニオックスGT」等。）等が挙げられる。 (c) Glycerin derivative As the glycerin derivative, the following formula (19):

(However, -R ³⁰ CO is a fatty acid residue, and a and b are the degrees of polymerization.) "Same MO", "Same MT", "Same MK", etc.), following formula (20):

(However, -R ³¹ CO is an isostearic acid residue, and a to c are degrees of polymerization.) Following formula (21):

(However, -R ³² CO is an isostearic acid residue, and a to c are degrees of polymerization.) Etc.

(d) Fluorine-containing alcohol Examples of the fluorine-containing alcohol include hydrofluoroalcohol and perfluoroalcohol. Examples of the hydrofluoroalcohol include alcohols having 1 to 24 carbon atoms in which a part of hydrogen atoms are substituted with fluorine atoms. Examples of the perfluoroalcohol include alcohols having 1 to 24 carbon atoms in which all hydrogen atoms bonded to the alkyl group are substituted with fluorine atoms. Examples of hydrofluoroalcohol include F ₂ CH (CF ₂ ) ₃ CH ₂ OH, CF ₃ CH ₂ OH, CF ₃ CF ₂ CH ₂ OH, CF ₃ CF ₂ (CH ₂ ) ₆ OH, F (CF ₂ ) ₃ CH ₂ OH, F (CF ₂ ) ₄ CH ₂ CH ₂ CH ₂ OH, F (CF ₂ ) ₄ (CH ₂ ) ₆ OH, F (CF ₂ ) ₃ OCF (CF ₂ ) CHOH, F (CF ₂ ) ₆ CH ₂ CH ₂ OH, F (CF ₂ ) ₆ (CH ₂ ) ₃ OH, F (CF ₂ ) ₆ (CH ₂ ) ₆ OH, F (CF ₂ ) ₆ CH ₂ CH ₂ OH, F (CF ₂ ) ₈ ( CH ₂ ) ₆ OH, F (CF ₂ ) ₁₀ CH ₂ CH ₂ OH, C ₃ F ₇ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OH, (CF ₃ ) ₂ CF (CH ₂ ) ₆ OH , (CF ₃ ) ₂ CF (CH ₂ ) ₂ CH ₂ CH ₂ OH, (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ OH, (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ OH, CHF ₂ CF ₂ CH ₂ OH, H (CF ₂ ) ₆ CH ₂ OH, H (CF ₂ ) ₈ CH ₂ OH, (CF ₃ ) ₂ CHOH, CF ₃ CHFCF ₂ CH ₂ OH, HOCH ₂ (CF ₂ ) ₄ CH ₂ OH, HOCH ₂ (CF ₂ ) ₆ CH ₂ OH, (CF ₃ ) ₂ C (CH ₃ ) CH ₂ OH, and the like. These hydrofluoroalcohols are available from, for example, Daikin Industries, Ltd.

（ただしnは重合度である。）により表されるポリエチレングリコール（例えば日本油脂株式会社「マクロゴール」等。）、下記式(23)：

（ただしnは重合度である。）により表されるポリプロピレングリコール（例えば日本油脂株式会社「ユニオール」等。）、下記式(24)：

（ただしa〜cは各々重合度である。）により表されるポリオキシエチレンポリオキシプロピレングリコール（例えば日本油脂株式会社「ユニルーブ」、日進化成株式会社「プロノン」等。）、下記式(25)：

（ただしnは重合度である。）により表されるポリグリセリン（日本油脂株式会社製「ユニグリG-2」等。）、下記式(26)：

（ただしa〜cは各々重合度である。）により表されるポリオキシエチレングリセリン（日本油脂株式会社製「ユニオックスG-1200」等。）、下記式(11)：

（ただしa〜cは各々重合度である。）により表されるポリオキシプロピレングリセリルエーテル（日本油脂株式会社製「ユニオール」等。）、下記式(27)：

（ただしa〜c及びx〜zは各々重合度である。）により表されるポリオキシエチレンポリオキシプロピレングリセリルエーテル（日本油脂株式会社製「ユニルーブ」等。）、下記式(28)：

（ただしa〜c及びx〜zは各々重合度である。）により表されるポリオキシエチレンポリオキシプロピレントリメチロールプロパン（日本油脂株式会社製「ユニルーブ」等。）、下記式(29)：

（ただしa〜dは各々重合度である。）により表されるポリオキシプロピレンジグリセリルエーテル（日本油脂株式会社製「ユニルーブ」等。）、下記式(30)：

（ただしa〜d及びw〜zは各々重合度である。）により表されるポリオキシエチレンポリオキシプロピレンペンタエリスリトールエーテル（日本油脂株式会社製「ユニルーブ」等。）、下記式(31)：

（ただしa〜fは各々重合度である。）により表されるポリオキシプロピレンソルビット（日本油脂株式会社製「ユニルーブ」等。）等が挙げられる。 (e) Polyoxyalkylene glycol As polyoxyalkylene glycol, for example, the following formula (22):

(Where n is the degree of polymerization) represented by polyethylene glycol (for example, “Nippon Yushi Co., Ltd.“ Macrogol ””), the following formula (23):

(Where n is the degree of polymerization) (e.g., Nippon Oil & Fats Co., Ltd. “Uniol”), the following formula (24):

(Where a to c are degrees of polymerization, respectively) represented by polyoxyethylene polyoxypropylene glycol (for example, Nippon Oil & Fats Co., Ltd. “Unilube”, Nihon Kasei Co., Ltd. “Pronon”, etc.), ):

(Where n is the degree of polymerization) represented by polyglycerin (“Unigly G-2” manufactured by NOF Corporation), the following formula (26):

(Where a to c are degrees of polymerization, respectively) represented by polyoxyethylene glycerin (such as “Uniox G-1200” manufactured by NOF Corporation), the following formula (11):

(Where a to c are degrees of polymerization, respectively) represented by polyoxypropylene glyceryl ether (“Uniol” manufactured by NOF Corporation), the following formula (27):

(Where a to c and x to z are the degrees of polymerization, respectively) represented by polyoxyethylene polyoxypropylene glyceryl ether (“Unilube” manufactured by NOF Corporation), the following formula (28):

(However, a to c and x to z are the degrees of polymerization.) Polyoxyethylene polyoxypropylene trimethylol propane (“Unilube” manufactured by Nippon Oil & Fats Co., Ltd.) represented by the following formula (29):

(However, a to d are each the degree of polymerization.) Polyoxypropylene diglyceryl ether represented by (“Unilube” manufactured by NOF Corporation), the following formula (30):

(However, a to d and w to z are respectively degrees of polymerization.) Polyoxyethylene polyoxypropylene pentaerythritol ether (“Unilube” manufactured by NOF Corporation), represented by the following formula (31):

(However, af is each a polymerization degree.) The polyoxypropylene sorbitol represented by (Nippon Yushi Co., Ltd. "unilube" etc.) etc. are mentioned.

（ただしnは重合度である。）により表されるポリオキシエチレンモノアルキルエーテル（例えばポリオキシエチレンラウリルエーテル等、市販品として日本油脂株式会社製「ノニオンK」、「同P」、「同E」、「同S」、「同NC」、「同NG」、「同T」、「同M」、「同IC」、「同IS」、「同B」、「同OD」、「同LA」、「ユニオックスB」等がある。）、下記式(33)：

（ただしnは重合度である。）により表されるポリオキシエチレンコレステリルエーテル（日本油脂株式会社製「ユニオックスCS」等。）、下記式(34)：

（ただしR³³はアルキル基であり、nは重合度である。）により表されるポリオキシエチレンアルキルフェニルエーテル（例えばポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等、市販品として日本油脂株式会社製「ノニオンHS」、「同NS」等がある。）、下記式(35)：

（ただしnは重合度である。）により表されるポリオキシエチレンジノニルフェニルエーテル（日本油脂株式会社製「ユニオックスDN」等。）、下記式(36)：

（ただしnは重合度である。）により表されるポリオキシプロピレンアルキルエーテル（例えばポリオキシプロピレンブチルエーテル等、市販品として日本油脂株式会社製「ユニルーブMB」、「同MM」、「同MP」、「同MS」、「同MLA」等がある。）、下記式(37)：

（ただしm及びnは各々重合度である。）により表されるポリオキシエチレンポリオキシプロピレンアルキルエーテル（例えばポリオキシエチレンポリオキシプロピレンブチルエーテル、市販品として日本油脂株式会社製「ユニセーフ10P」、「同20P」、「同5P」、「同34S」、「ユニルーブ50MB」、「同10MS」、「ノニオンA」等がある。）、下記式(12)：

（ただしa〜dは各々重合度である。）により表されるポリオキシエチレンメチルグルコシド（例えば日本油脂株式会社製「マクビオブライドMG」等。）、下記式(38)：

（ただしa〜dは各々重合度である。）により表されるポリオキシプロピレンメチルグルコシド（例えば日本油脂株式会社製「マクビオブライドMG」、「グルコポリオールPP」等。）等が挙げられる。 (f) Polyoxyalkylene monoalkyl ether As polyoxyalkylene monoalkyl ether, for example, the following formula (32):

(Where n is the degree of polymerization.) Polyoxyethylene monoalkyl ethers represented by (for example, polyoxyethylene lauryl ether, etc., “Nonion K”, “Same P”, “E” ”,“ S ”,“ NC ”,“ NG ”,“ T ”,“ M ”,“ IC ”,“ IS ”,“ B ”,“ OD ”,“ LA ” ”,“ Uniox B ”, etc.), the following formula (33):

(Where n is the degree of polymerization) represented by polyoxyethylene cholesteryl ether (“Uniox CS” manufactured by NOF Corporation), the following formula (34):

(However, R ³³ is an alkyl group, and n is the degree of polymerization.) Polyoxyethylene alkylphenyl ether represented by (for example, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc.) There are “Nonion HS”, “Same NS”, etc. manufactured by Co., Ltd.), the following formula (35):

(Where n is the degree of polymerization) polyoxyethylene dinonyl phenyl ether (“Uniox DN” manufactured by NOF Corporation), represented by the following formula (36):

(Where n is the degree of polymerization) represented by polyoxypropylene alkyl ether (for example, polyoxypropylene butyl ether, etc., commercially available from Nippon Oil & Fat Co., Ltd. “Uniluve MB”, “Same MM”, “Same MP”, "Same MS", "Same MLA", etc.), following formula (37):

(However, m and n are the degree of polymerization.) Polyoxyethylene polyoxypropylene alkyl ether represented by (for example, polyoxyethylene polyoxypropylene butyl ether, commercially available as “Unisafe 10P”, “Same 20P ”,“ 5P ”,“ 34S ”,“ UniLube 50MB ”,“ 10MS ”,“ Nonion A ”, etc.), the following formula (12):

(Wherein a to d are degrees of polymerization, respectively) represented by polyoxyethylene methyl glucoside (for example, “Macbiobride MG” manufactured by NOF Corporation), the following formula (38):

(However, a to d are degrees of polymerization.) Polyoxypropylene methyl glucoside (for example, “Macbiobride MG”, “Glucopolyol PP” manufactured by Nippon Oil & Fats Co., Ltd.), etc.

（ただし-R³⁴COは脂肪酸残基であり、nは重合度である。）により表されるポリオキシエチレンモノエステル（例えばモノラウリン酸ポリエチレングリコール等、市販品として日本油脂株式会社製「ノニオンL」、「同O」、「同S」、「同MM」、「同IS」等がある。）、下記式(40)：

（ただし-R³⁵COは脂肪酸残基であり、nは重合度である。）により表されるポリプロピレングリコールモノエステル（例えばラウリン酸プロピレングリコール等、市販品として日本油脂株式会社製「ユニセーフPGML」、「ユニルーブO」、「同CF」等がある。）、下記式(41)：

（ただし-R³⁶COは脂肪酸残基であり、nは重合度である。）により表されるポリオキシエチレンジエステル（例えばジラウリン酸ポリエチレングリコール等、市販品として日本油脂株式会社製「ノニオンDL」、「同DP」、「同DO」、「同DS」、「同DIS」等がある。）、下記式(42)：

（ただしR³⁷はアルキル基であり、-R³⁸COは脂肪酸残基であり、nは重合度である。）により表されるポリオキシエチレンアルキルエーテルエステル（例えばミリスチン酸ポリオキシエチレン等、市販品として日本油脂株式会社製「ユニセーフUMM」、「ユニオックスUSP」、「同USS」等がある。）、下記式(43)：

（ただし-R³⁹COはステアリン酸残基であり、a〜cは各々重合度である。）により表されるジステアリン酸ポリオキシエチレントリメチロールプロパン（日本油脂株式会社製「ユニオックスTD」等。）、下記式(44)：

（ただし-R⁴⁰COは脂肪酸残基であり、a〜cは各々重合度である。）により表されるポリオキシエチレンソルビタンモノ脂肪酸エステル（例えば「オレイン酸ポリオキシエチレンソルビタン」等、市販品として日本油脂株式会社製「ポリソルベート」、「ノニオンLT」、「同PT」、「同OT」、「同ST」、「同IST」等がある。）、下記式(45)：

（ただし-R⁴¹COは脂肪酸残基であり、nは重合度である。）により表されるポリオキシエチレンソルビタン脂肪酸エステル（例えば「トリオレイン酸ポリオキシエチレンソルビタン」等、市販品として日本油脂株式会社製「ノニオンOT」、「同ST」等がある。）、下記式(46)：

（ただしa〜c及びx〜zは各々重合度である。）により表されるポリオキシエチレン硬化ヒマシ油（日本油脂株式会社製「ユニオックスHC」等。）、下記式(47)：

（ただし-R⁴²COは脂肪酸残基であり、a〜c及びx〜zは各々重合度である。）により表されるモノ脂肪酸ポリオキシエチレン硬化ヒマシ油（例えば「ラウリン酸ポリオキシエチレン」等、市販品として日本油脂株式会社製「ユニオックスHC」等がある。）、下記式(48)：

（ただしa〜c及びx〜zは各々重合度である。）により表されるポリオキシエチレン硬化ヒマシ油コハク酸（例えば日本油脂株式会社製「ユニオックスHC」等がある。）、下記式(49)：

（ただしa〜c及びx〜zは各々重合度である。）により表されるモノオキシエチレンヒマシ油（例えば日本油脂株式会社製「ノニオンC」等がある。）、下記式(50)：

（ただし-COR⁴³はオレイン酸残基であり、a〜fは各々重合度である。）により表されるテトラオレイン酸ポリオキシエチレンソルビット（例えば日本油脂株式会社製「ユニオックスSTO」、「同ST」等がある。）、下記式(51)：

（ただし-COR⁴⁴はオレイン酸残基であり、a〜fは各々重合度である。）により表されるペンタオレイン酸ポリオキシエチレンソルビット（例えば日本油脂株式会社製「ユニオックスSP」等がある。）、下記式(52)：

（ただし-COR⁴⁵はイソステアリン酸残基であり、a〜cは各々重合度である。）により表されるイソステアリン酸ポリオキシエチレンソルビット（例えば日本油脂株式会社製「ユニオックスST」等がある。）等が挙げられる。 (g) Polyoxyalkylene ester As the polyoxyalkylene ester, for example, the following formula (39):

(However, -R ³⁴ CO is a fatty acid residue, and n is the degree of polymerization.) Polyoxyethylene monoester (eg, polyethylene glycol monolaurate, etc., “Nonion L” manufactured by NOF Corporation as a commercial product) , “Same O”, “same S”, “same MM”, “same IS”, etc.), following formula (40):

(However, -R ³⁵ CO is a fatty acid residue, and n is the degree of polymerization.) Polypropylene glycol monoester (for example, propylene glycol laurate, such as “Unisafe PGML” manufactured by NOF Corporation, "Unilube O", "Same CF", etc.), following formula (41):

(However, -R ³⁶ CO is a fatty acid residue, and n is the degree of polymerization.) Polyoxyethylene diester (for example, polyethylene glycol dilaurate and the like, “Nonion DL” manufactured by NOF Corporation, "There is the same DP", "DO", "DS", "DIS", etc.), the following formula (42):

(Wherein R ³⁷ is an alkyl group, -R ³⁸ CO is a fatty acid residue, n represents the degree of polymerization.) Polyoxyethylene alkyl ether ester represented by (e.g. myristic acid, polyoxyethylene etc., commercially available products As “Unisafe UMM”, “Uniox USP”, “Same USS”, etc. manufactured by Nippon Oil & Fats Co., Ltd.), the following formula (43):

(However, -R ³⁹ CO is a stearic acid residue, and a to c are degrees of polymerization.) Disoxy stearate polyoxyethylene trimethylolpropane ("Uniox TD" manufactured by NOF Corporation). ), Following formula (44):

(However, -R ⁴⁰ CO is a fatty acid residue, and a to c are degrees of polymerization.) As a commercial product such as polyoxyethylene sorbitan monofatty acid ester (for example, “polyoxyethylene sorbitan oleate”) There are “Polysorbate”, “Nonion LT”, “Same PT”, “Same OT”, “Same ST”, “Same IST”, etc. manufactured by Nippon Oil & Fats Co., Ltd.), the following formula (45):

(However, -R ⁴¹ CO is a fatty acid residue, and n is the degree of polymerization.) Polyoxyethylene sorbitan fatty acid esters represented by the formula (for example, “polyoxyethylene sorbitan trioleate”) are commercially available as Nippon Oil & Fats. There are “Nonion OT”, “Same ST”, etc., manufactured by the company), the following formula (46):

(However, a to c and x to z are the degrees of polymerization.) Polyoxyethylene hydrogenated castor oil (“Uniox HC” manufactured by Nippon Oil & Fats Co., Ltd.), represented by the following formula (47):

(However, -R ⁴² CO is a fatty acid residue, and a to c and x to z are respectively degrees of polymerization.) Mono fatty acid polyoxyethylene hydrogenated castor oil (for example, “polyoxyethylene laurate”) As a commercially available product, there is “Uniox HC” manufactured by Nippon Oil & Fats Co., Ltd.), the following formula (48):

(However, a to c and x to z are respectively polymerization degrees.) Polyoxyethylene hydrogenated castor oil succinic acid represented by (for example, “Uniox HC” manufactured by Nippon Oil & Fats Co., Ltd.), the following formula ( 49):

(However, a to c and x to z are respectively polymerization degrees.) Monooxyethylene castor oil represented by (for example, “Nonion C” manufactured by Nippon Oil & Fats Co., Ltd.), the following formula (50):

(However, -COR ⁴³ is an oleic acid residue, and a to f are polymerization degrees.) Tetraoleic acid polyoxyethylene sorbitol (for example, “Uniox STO”, “ ST ”etc.), the following formula (51):

(However, -COR ⁴⁴ is an oleic acid residue, and a to f are the degree of polymerization, respectively.) There are pentaoleic acid polyoxyethylene sorbites (for example, “Uniox SP” manufactured by NOF Corporation). ), The following formula (52):

(However, -COR ⁴⁵ is an isostearic acid residue and a to c are degrees of polymerization.) There is an isostearic acid polyoxyethylene sorbite (for example, “Uniox ST” manufactured by NOF Corporation). ) And the like.

（ただしR⁴⁶はアルキル基であり、a及びbは各々重合度である。）により表されるポリオキシエチレンアルキルアミン（例えばポリオキシエチレンヤシ油アルキルアミン等、市販品として日本油脂株式会社製「ナイミーンF」、「同T2」、「同S」等がある。）、下記式(54)：

（ただしR⁴⁷COは脂肪酸残基であり、a及びbは各々重合度である。）、又は下記式(55)：

（ただしR⁴⁸COは脂肪酸残基であり、nは重合度である。）により表されるポリオキシエチレンアルキルアミド（例えばポリオキシエチレンヤシ油脂肪酸モノエタノールアミド等、市販品として日本油脂株式会社製「ナイミッドMF」、「同F」、「同DF」、「同ML」等がある。）、下記式(56)：

（ただしa及びbは各々重合度である。）により表されるエチレンジアミンテトラポリオキシアルキレン（例えば日本油脂株式会社製「ユニルーブ30TY-55B」等。）、下記式(57)：

により表されるジヒドロキシエチルラウリルアミンオキシド（例えば日本油脂株式会社製「ユニセーフA-LE」等。）等が挙げられる。 (h) Alcoholic hydroxyl group-containing nitrogen-containing compound The alcoholic hydroxyl group-containing compound may be a nitrogen-containing compound, for example, the following formula (53):

(However, R ⁴⁶ is an alkyl group, and a and b are polymerization degrees.) Polyoxyethylene alkylamines represented by (for example, polyoxyethylene coconut oil alkylamine, etc., manufactured by NOF Corporation “ Nymin F ”,“ T2 ”,“ S ”, etc.), the following formula (54):

(However, R ⁴⁷ CO is a fatty acid residue, and a and b are degrees of polymerization.) Or the following formula (55):

(However, R ⁴⁸ CO is a fatty acid residue, and n is the degree of polymerization.) Polyoxyethylene alkylamides (for example, polyoxyethylene coconut oil fatty acid monoethanolamide, etc., manufactured by NOF Corporation "Nymid MF", "Same F", "Same DF", "Same ML", etc.), following formula (56):

(Wherein a and b are degrees of polymerization, respectively) represented by ethylenediaminetetrapolyoxyalkylene (for example, “Unilube 30TY-55B” manufactured by NOF Corporation), the following formula (57):

And dihydroxyethyl lauryl amine oxide (for example, “Unisafe A-LE” manufactured by NOF Corporation) and the like.

（但しY¹は繰り返し単位毎に異なってもよいハロゲン原子又は−OCOR⁴⁹基であり、R⁴⁹はアルキル基であり、n及びmは各々重合度である。）により表すことができる。不飽和アルコール単位としては、ビニルアルコール単位、アリルアルコール単位等が挙げられるが、製造コストの観点からビニルアルコール単位が好ましい。なおビニルアルコールは、単量体としては存在しないが、水酸基含有ビニル系（共）重合体の構成単位としては存在する。ビニルアルコール単位を得るには、酢酸ビニル単位を含む水酸基含有ビニル系（共）重合体を調製し、鹸化すればよい。 (i) Unsaturated alcohol copolymer The unsaturated alcohol copolymer is represented by the following general formula (58):

Wherein Y ¹ is a halogen atom or —OCOR ⁴⁹ group which may be different for each repeating unit, R ⁴⁹ is an alkyl group, and n and m are each the degree of polymerization. Examples of the unsaturated alcohol unit include a vinyl alcohol unit and an allyl alcohol unit, and a vinyl alcohol unit is preferable from the viewpoint of production cost. Vinyl alcohol does not exist as a monomer, but exists as a constituent unit of a hydroxyl group-containing vinyl (co) polymer. In order to obtain vinyl alcohol units, a hydroxyl group-containing vinyl (co) polymer containing vinyl acetate units may be prepared and saponified.

  Examples of the fatty acid vinyl unit include a vinyl acetate unit, a vinyl propinate unit, and a vinyl butyrate unit, and a vinyl acetate unit is preferable. Examples of the halogen vinyl unit include a vinyl chloride unit, a vinyl fluoride unit, and a vinyl bromide unit, and a vinyl chloride unit is preferable. Each of the unsaturated alcohol unit, the fatty acid vinyl unit and the halogen vinyl unit may contain two or more kinds. Commercially available products may be used as the unsaturated alcohol copolymer. Examples of polyvinyl alcohol having vinyl acetate units include Kuraray LM Polymer and Poval (registered trademark, manufactured by Kuraray Co., Ltd.), Gohsenol (registered trademark, Nippon Synthetic Chemical). Kogyo Co., Ltd.). Further, as unsaturated alcohol copolymers having vinyl acetate units, vinyl chloride units and vinyl alcohol units, for example, SOLBIN A, AL, TA5R, TAO (registered trademark, manufactured by Nissin Chemical Industry Co., Ltd.), etc. Can be mentioned.

(j) Partially acetalized unsaturated alcohol polymer Partially acetalized unsaturated alcohol polymer is obtained by reacting an unsaturated alcohol polymer mainly composed of unsaturated alcohol units with an aldehyde at a predetermined ratio, Is acetalized. Therefore, the partially acetalized unsaturated alcohol polymer has a hydroxyl group. As the unsaturated alcohol polymer to be partially acetalized, polyvinyl alcohol is preferable.

(但しR⁵⁰はアルキル基であり、n及びmは各々重合度である。)により表すことができる。部分アセタール化不飽和アルコール系重合体としては、市販品を使用してもよく、例えばエスレックＢ及び同Ｋ（登録商標、積水化学工業株式会社製）が挙げられる。 An unsaturated alcohol polymer obtained by partially acetalizing polyvinyl alcohol (partially butyralized polyvinyl alcohol) is represented by the following general formula (59):

(Where R ⁵⁰ is an alkyl group, and n and m are each the degree of polymerization). Commercially available products may be used as the partially acetalized unsaturated alcohol polymer, and examples thereof include ESREC B and K (registered trademark, manufactured by Sekisui Chemical Co., Ltd.).

（ただしR⁵¹は置換もしくは無置換のアルキル基又はアリール基であり、R⁵²は置換もしくは無置換のアルキレン基であり、R⁵³OHはオキシアルキル基であり、nは重合度である。）により表される化合物、下記式(60)：

（ただしR⁵¹は置換もしくは無置換のアルキル基又はアリール基であり、R⁵⁴は置換もしくは無置換のアルキレン基であり、R⁵⁵は置換もしくは無置換のアルキル基又はアリール基であり、R⁵⁶OHはオキシアルキル基であり、nは重合度である。）により表される化合物、下記式(61)：

（ただしR⁵¹は置換もしくは無置換のアルキル基又はアリール基であり、R⁵⁷OHはオキシアルキル基であり、nは重合度である。）により表される化合物、下記式(62)：

（ただしR⁵¹及びR⁵⁸は置換もしくは無置換のアルキル基又はアリール基であり、R⁵⁹OHはオキシアルキル基であり、nは重合度である。）により表される化合物、下記式(63)：

（ただしR⁵¹及びR⁶⁰は置換もしくは無置換のアルキル基又はアリール基であり、R⁶¹(OH)₂はジオキシアルキル基であり、nは重合度である。）により表される化合物等が挙げられる。 (k) Alcohol-modified silicone oil As the alcohol-modified silicone oil, the following formula (13):

Where R ⁵¹ is a substituted or unsubstituted alkyl group or aryl group, R ⁵² is a substituted or unsubstituted alkylene group, R ⁵³ OH is an oxyalkyl group, and n is the degree of polymerization. A compound represented by the following formula (60):

(Where R ⁵¹ is a substituted or unsubstituted alkyl group or aryl group, R ⁵⁴ is a substituted or unsubstituted alkylene group, R ⁵⁵ is a substituted or unsubstituted alkyl group or aryl group, and R ⁵⁶ OH Is an oxyalkyl group and n is the degree of polymerization.), A compound represented by the following formula (61):

Wherein R ⁵¹ is a substituted or unsubstituted alkyl group or aryl group, R ⁵⁷ OH is an oxyalkyl group, and n is the degree of polymerization, and a compound represented by the following formula (62):

Wherein R ⁵¹ and R ⁵⁸ are a substituted or unsubstituted alkyl group or aryl group, R ⁵⁹ OH is an oxyalkyl group, and n is the degree of polymerization. :

Where R ⁵¹ and R ⁶⁰ are a substituted or unsubstituted alkyl group or aryl group, R ⁶¹ (OH) ₂ is a dioxyalkyl group, and n is the degree of polymerization. Can be mentioned.

The alkyl groups R ⁵¹ , R ⁵⁵ , R ⁵⁸ and R ⁶⁰ in the above formulas (13) and (60) to (63) are preferably methyl groups. The formula (13) and (60) the number of carbon atoms in each alkylene group R ⁵² and R ⁵⁴ in 1 to 3 are preferred. The oxyalkyl groups R ⁵³ OH, R ⁵⁶ OH, R ⁵⁷ OH and R ⁵⁹ OH in the above formulas (13) and (60) to (62) preferably have 1 to 3 carbon atoms.

(4) Production Method A method for producing a phosphoric acid ester residue-containing (meth) acrylamide composition using phosphoric anhydride as the phosphoric acid source compound will be described in detail below.

  The mixing molar ratio of phosphoric anhydride to the (meth) acrylamide monomer is preferably in the range of 0.8 to 1.2, more preferably in the range of 0.85 to 1.15, and particularly preferably in the range of 0.9 to 1.15. preferable. The compounding molar ratio of the alcoholic hydroxyl group-containing compound to the (meth) acrylamide monomer depends on the hydroxyl value of the alcoholic hydroxyl group-containing compound, but is generally preferably in the range of 0.1 to 1.2, preferably in the range of 0.2 to 1.1. Is more preferable.

  A solution consisting of [(meth) acrylamide monomer + solvent] is put into a reactor equipped with a stirrer and a reflux condenser, and the temperature is raised to 30 to 75 ° C. At this time, it is preferable to add a known polymerization inhibitor such as hydroquinone monomethyl ether and paramethoxyhydroquinone together. After reaching the predetermined temperature, phosphoric anhydride is added. Phosphoric anhydride is preferably added in 2 to 10 portions over a period of 0.5 to 7 hours. This promotes the formation reaction of the (poly) phosphonic acid group-containing acrylamide monomer and improves the yield. However, the purpose is not limited to the addition in divided portions. The addition of phosphoric anhydride generates heat, and the reaction temperature usually rises to about 40-60 ° C. Thereafter, the reaction is kept at 70 to 85 ° C. and the reaction is continued for 1 to 3 hours.

  An alcoholic hydroxyl group-containing compound is added to the obtained reaction solution and kept at 70 to 85 ° C. for alcoholysis. The alcoholic hydroxyl group-containing compound is preferably added in portions 2 to 10 times within 0.5 to 7 hours, whereby the formation reaction of the (poly) phosphonic acid group-containing acrylamide ester composition is promoted and the yield is improved. . However, the purpose is not limited to the addition in divided portions. Although it is not limited, it is preferable to hydrolyze excess (meth) acrylamide (di) pyrophosphate in the obtained reaction solution. The amount of water added is preferably in the range of 0.2 to 0.8 in molar ratio to the added phosphoric anhydride. The hydrolysis conditions are preferably a temperature of 70 to 80 ° C. and a time of 15 minutes to 1 hour. The resulting reaction solution is cooled to room temperature. When unreacted phosphoric anhydride, by-product inorganic polyphosphoric acid, etc. are deposited by cooling, the solid deposited by suction filtration is separated by filtration.

（ただしR⁴は水素基又はメチル基であり、R⁵及びR⁶はそれぞれ独立にアルキル基である。）により表されるN, N-ジアルキル（メタ）アクリルアミド、ジメチルホルムアミド（DMF）、N, N-ジメチルアセトアミド（DMAc）等のアミド系溶媒；ジメチルスルホキシド（DMSO）等のスルホキシド系溶媒が挙げられる。酸性溶媒としては、アルキルカルボン酸、アルキルリン酸等の有機酸系溶媒が挙げられる。これらの溶媒は単独で用いてもよいし、複数種を併用してもよい。 As the solvent, a solvent containing no active hydrogen and / or an acidic solvent is preferable. As a solvent not containing active hydrogen, the following formula (14):

(Wherein R ⁴ is a hydrogen group or a methyl group, and R ⁵ and R ⁶ are each independently an alkyl group.) N, N-dialkyl (meth) acrylamide, dimethylformamide (DMF), N, Examples include amide solvents such as N-dimethylacetamide (DMAc); and sulfoxide solvents such as dimethyl sulfoxide (DMSO). Examples of the acidic solvent include organic acid solvents such as alkyl carboxylic acids and alkyl phosphoric acids. These solvents may be used alone or in combination of two or more.

  Among them, the solvent is preferably at least one selected from the group consisting of N, N-dialkyl (meth) acrylamide, DMF, DMAc and DMSO. Among N, N-dialkyl (meth) acrylamides, N, N-dimethylacrylamide (DMAA) is soluble in (meth) acrylamide monomers, phosphoric acid anhydrides and (meth) acrylamide compositions containing phosphoric acid ester residues. Since the boiling point is 171 to 172 ° C., the reaction temperature can be selected from a wide range, and when a polymerization inhibitor is used in combination, the formation of a polymer can be sufficiently prevented.

  In order to promote the reaction and suppress the formation of a polymer, the reaction solution preferably has an initial concentration [(meth) acrylamide monomer concentration] of 20 to 35% by mass before addition of anhydrous phosphoric acid, More preferably, it is 20-30 mass%.

  After the reaction, in the case of isolating the (poly) phosphonic acid group-containing (meth) acrylamide ester composition, the reaction solution is deposited in small amounts in a poor solvent, and separated by filtration. As the poor solvent, a nonpolar solvent is preferable, and examples thereof include acetone, tetrahydrofuran (THF), dioxane, benzene, toluene, xylene, ether and the like. The nonpolar solvent preferably has a low specific gravity and a relatively low boiling point. The poor solvent is used in a large excess amount of 5 to 15 times the volume of the reaction product. What is necessary is just to repeat washing | cleaning operation of the viscous liquid by a poor solvent as needed. The isolated (poly) phosphonic acid group-containing (meth) acrylamide ester composition is dried. The drying method is preferably a method of vacuum treatment at room temperature to 100 ° C., a method of heat treatment at 60 to 100 ° C. for 1 to 4 hours using a hot air oven or the like.

（ただしR¹及びR²は式(16)と同じであり、R³OHはアルコール性水酸基含有化合物である。）に示すように、中間生成物としてジアクリルアミド系ピロホスホン酸が生成し、これが加アルコール分解され、ホスホン酸エステル基が導入された単量体が生成するとともに、ホスホン酸基が導入された単量体が副生するものと推定される。 (5) Reaction When a (meth) acrylamide monomer represented by the formula (16) is reacted with phosphoric anhydride, for example, the following formula (64):

(However, R ¹ and R ² are the same as those in the formula (16), and R ³ OH is an alcoholic hydroxyl group-containing compound.) As shown in FIG. It is presumed that alcohol is decomposed to produce a monomer having a phosphonic acid ester group introduced, and a monomer having a phosphonic acid group introduced is by-produced.

（ただしR¹は水素基又はメチル基であり、R³OHはアルコール性水酸基含有化合物である。）に示すように、中間生成物としてピロリン酸が（メタ）アクリルアミドにN, N-結合した化合物を介して、N, N-ジホスホン酸（メタ）アクリルアミドモノエステルが生成する反応が起こったり、下記式(66)：

（ただしR¹は水素基又はメチル基であり、R³OHはアルコール性水酸基含有化合物である。）に示すように、上記式(65)に示す反応とともに、中間生成物としてジピロリン酸が２つの（メタ）アクリルアミドに結合した化合物を介して、N, N-ジホスホン酸（メタ）アクリルアミドジエステル、N, N-ジホスホン酸（メタ）アクリルアミドモノエステル及びN, N-ジホスホン酸（メタ）アクリルアミドが生成する反応が起こったりするものと推定される。ただしR³が多価アルコール残基である場合、生成したモノエステルが他のモノエステルやリン系酸残基含有（メタ）アクリルアミドとさらに反応することもあると推定される。 However, when acrylamide and / or methacrylamide is used as a (meth) acrylamide monomer and phosphoric anhydride is reacted, not only a reaction in which a monomer having only one phosphonic acid group is introduced, Formula (65):

(However, R ¹ is a hydrogen group or a methyl group, and R ³ OH is an alcoholic hydroxyl group-containing compound.) As shown in FIG. , A reaction that produces N, N-diphosphonic acid (meth) acrylamide monoester occurs, or the following formula (66):

(However, R ¹ is a hydrogen group or a methyl group, and R ³ OH is an alcoholic hydroxyl group-containing compound.) As shown in the above formula (65), there are two dipyrophosphates as intermediate products. N, N-diphosphonic acid (meth) acrylamide diester, N, N-diphosphonic acid (meth) acrylamide monoester and N, N-diphosphonic acid (meth) acrylamide are produced via a compound bonded to (meth) acrylamide. It is estimated that a reaction will occur. However, when R ³ is a polyhydric alcohol residue, it is presumed that the produced monoester may further react with other monoesters or phosphorus acid residue-containing (meth) acrylamide.

（ただしR¹及びR²は式(16)と同じであり、xは１又は２である。）により表される化合物も生成すると推定される。式(67)により表される化合物を加アルコール分解すると、下記式(68)：

（ただしR¹及びR²は式(16)と同じであり、yは１又は２である。）により表されるポリホスホン酸基を有するモノエステル、及び下記式(69)：

（ただしR¹及びR²は式(1)と同じであり、xは式(67)と同じであり、yは式(68)と同じである。）により表される（ポリ）ホスホン酸基を有する単量体が生成する。従って、リン系酸エステル残基含有（メタ）アクリルアミド組成物は式(68)及び式(69)により表される単量体を含んでもよい。 Further, when the molar ratio of phosphoric anhydride to the (meth) acrylamide monomer is more than 1, an intermediate product represented by the following formula (67):

(However, R ¹ and R ² are the same as those in the formula (16), and x is 1 or 2). When the compound represented by the formula (67) is subjected to alcoholysis, the following formula (68):

(Wherein R ¹ and R ² are the same as those in the formula (16) and y is 1 or 2), and a monoester having a polyphosphonic acid group represented by the following formula (69):

(Wherein R ¹ and R ² are the same as in formula (1), x is the same as in formula (67), and y is the same as in formula (68)). A monomer having Accordingly, the phosphoric acid ester residue-containing (meth) acrylamide composition may contain monomers represented by the formulas (68) and (69).

（ただしR^1aは水素基又はメチル基であり、R^2aは水素基又は置換もしくは無置換の炭化水素基であり、-X^a-O-R^3aはリン系酸エステル残基である。）により表される化合物、下記式(2)：

（ただしR^1bは水素基又はメチル基であり、-X^bOHはリン系酸残基であり、-X^c-O-R^3bはリン系酸エステル残基であり、各々リン原子、酸素原子及び水素原子からなる原子団であるX^bとX^cは同じであっても異なっていてもよい。）により表される化合物、並びに下記式(3)：

（ただしR^1cは水素基又はメチル基であり、-X^d-O-R^3c及び-X^e-O-R^3dは各々リン系酸エステル残基であり、各々アルコール性水酸基含有化合物の残基であるR^3cとR^3dは同じであっても異なっていてもよく、各々リン原子、酸素原子及び水素原子からなる原子団であるX^dとX^eは同じであっても異なっていてもよい。）により表される化合物からなる群から選ばれた少なくとも一種である。 (6) Product A phosphorus acid ester residue-containing (meth) acrylamide obtained by directly bonding a phosphorus acid residue esterified with an alcoholic hydroxyl group-containing compound to a nitrogen atom of an amide group by the above production method. A composition comprising is obtained. The phosphoric acid ester residue-containing (meth) acrylamide according to a preferred embodiment of the present invention has the following formula (1):

Wherein R ^1a is a hydrogen group or a methyl group, R ^2a is a hydrogen group or a substituted or unsubstituted hydrocarbon group, and —X ^a —OR ^3a is a phosphorus acid ester residue. The following compound (2):

(However, R ^1b is a hydrogen group or a methyl group, -X ^b OH is a phosphorus acid residue, and -X ^c -OR ^3b is a phosphorus acid ester residue, and each contains a phosphorus atom, an oxygen atom, and a hydrogen atom. X ^b and X ^c which are atomic groups composed of atoms may be the same or different.) And a compound represented by the following formula (3):

(However, R ^1c is a hydrogen group or a methyl group, -X ^d -OR ^3c and -X ^e -OR ^3d are each a phosphorus acid ester residue, and each R ^3c is a residue of an alcoholic hydroxyl group-containing compound. And R ^3d may be the same or different, and X ^d and X ^e which are atomic groups each consisting of a phosphorus atom, an oxygen atom and a hydrogen atom may be the same or different. And at least one selected from the group consisting of the above compounds.

Phosphoric acid residues represented by -X ^a OH to -X ^e OH are phosphonic acid groups [—PO (OH) ₂ ], phosphinic acid groups [—PO (H) ( OH)], a polyphosphoric acid group, a polyphosphonic acid group, a pyrophosphonic acid group, a pyrophosphoric acid group, and the like, and a phosphonic acid group is preferred.

（ただしR¹は水素基又はメチル基であり、R³はアルコール性水酸基含有化合物の残基である。）により表される化合物、下記式(5)：

（ただしR¹は水素基又はメチル基であり、R³はアルコール性水酸基含有化合物の残基である。）により表される化合物、下記式(6)：

（ただしR¹は水素基又はメチル基であり、R³はアルコール性水酸基含有化合物の残基である。）により表される化合物からなる群から選ばれた少なくとも一種を主成分とするものとなる。中でも、式(5)により表されるモノエステルが多く生成する。これは式(65)により表される反応が主に起こることによると考えられる。 In particular, when (meth) acrylamide is used as the (meth) acrylamide monomer and phosphoric anhydride is used as the phosphoric acid source compound, the resulting composition has the following formula (4):

(Wherein R ¹ is a hydrogen group or a methyl group, and R ³ is a residue of an alcoholic hydroxyl group-containing compound), a compound represented by the following formula (5):

(Wherein R ¹ is a hydrogen group or a methyl group, and R ³ is a residue of an alcoholic hydroxyl group-containing compound), a compound represented by the following formula (6):

(However, R ¹ is a hydrogen group or a methyl group, and R ³ is a residue of an alcoholic hydroxyl group-containing compound.) . Among them, a large amount of monoester represented by the formula (5) is produced. This is considered to be mainly due to the reaction represented by the formula (65).

Type and number of carbon atoms of residues R ³ alcoholic hydroxyl group-containing compound may be appropriately selected depending on the use of phosphorous-based acid ester residue containing (meth) acrylamide composition. When the number of carbon atoms in R ³ is 4 or less, the ratio of phosphorus acid residues and phosphorus acid ester residues is high, so that the resulting composition generally has flame retardancy, antistatic properties, and proton conductivity. Is excellent. Therefore, a polymer of a phosphoric acid ester residue-containing (meth) acrylamide composition having a carbon number of R ³ of 4 or less is used in applications such as conductive resins, proton conductive solid polymer electrolytes, flame retardants, and pigment dispersants. Is preferred. When the carbon number of R ³ is 5 or more, the balance between the hydrophilicity due to the phosphorus acid residue and the phosphorus acid ester residue and the lipophilicity due to R ³ is good, so the resulting composition is a surfactant, Suitable as emulsifier, solubilizer and the like. When the phosphoric acid ester residue-containing (meth) acrylamide composition is used for these applications, the carbon number of R ³ may be appropriately selected according to the desired HLB.

  The phosphoric acid residue and phosphoric acid ester residue of the phosphoric acid ester residue-containing (meth) acrylamide may form a complex salt, thereby further improving, for example, hydrolysis resistance and heat resistance. . The complex salt is preferably an ammonium salt, an amine salt or a metal salt. In the case of forming an ammonium salt or amine salt, for example, ammonium ions or mono-containing compounds containing a primary, secondary, tertiary or quaternary alkyl group, allyl group, aralkyl group, etc. are used to neutralize the acid. It is preferable to form a complex salt with a di- or trialkanolamine residue. As metal salts, alkali metal salts such as potassium salts, cuprous oxide (reddish brown), cupric oxide (blue), equimolar mixture of cuprous oxide (1) and cupric salt (gray), oxidation Heavy metal salts such as ferric salt (brown) are preferred. These complex salts may be used alone or in combination.

（ただしR^1dは水素基又はメチル基であり、R^2bは水素基又は置換もしくは無置換の炭化水素基であり、-X^fOHはリン系酸残基である。）、及び下記式(8)：

（ただしR^1eは水素基又はメチル基であり、-X^gOH及び-X^hOHは各々リン系酸残基であり、各々リン原子、酸素原子及び水素原子からなる原子団であるX^gとX^hは同じであっても異なっていてもよい。）により表される。 As described above, the phosphoric acid ester residue-containing (meth) acrylamide composition contains, as a by-product, a phosphoric acid residue-containing (meth) acrylamide monomer that is not usually esterified. Such monomers are generally represented by the following formula (7):

(Where R ^1d is a hydrogen group or a methyl group, R ^2b is a hydrogen group or a substituted or unsubstituted hydrocarbon group, and —X ^f OH is a phosphorus acid residue), and the following formula (8 ):

(However, R ^1e is a hydrogen group or a methyl group, -X ^g OH and -X ^h OH are each a phosphorus acid residue, and X ^g is an atomic group consisting of a phosphorus atom, an oxygen atom and a hydrogen atom, respectively. X ^h may be the same or different.

（ただしR¹は水素基又はメチル基である。）により表されるホスホン酸（メタ）アクリルアミド、下記式(10)：

（ただしR¹は水素基又はメチル基である。）により表されるN, N-ジホスホン酸（メタ）アクリルアミド、下記式(70)：

（ただしR¹は水素基又はメチル基であり、R³はアルコール性水酸基含有化合物の残基であり、yは１又は２である。）により表される（メタ）アクリルアミド（ポリ）ホスホン酸エステル、及び下記式(71)：

（ただしR¹は水素基又はメチル基であり、xは１又は２であり、yは１又は２である。）により表される（ポリ）ホスホン酸基含有（メタ）アクリルアミドからなる群から選ばれた少なくとも一種を含んでもよい。 When (meth) acrylamide is used as a raw material, a phosphoric acid ester residue-containing (meth) acrylamide composition has the following formula (9) as a by-product:

(Wherein R ¹ is a hydrogen group or a methyl group), phosphonic acid (meth) acrylamide represented by the following formula (10):

(Wherein R ¹ is a hydrogen group or a methyl group) N, N-diphosphonic acid (meth) acrylamide represented by the following formula (70):

(Wherein R ¹ is a hydrogen group or a methyl group, R ³ is a residue of an alcoholic hydroxyl group-containing compound, and y is 1 or 2). (Meth) acrylamide (poly) phosphonic acid ester And the following formula (71):

(Wherein R ¹ is a hydrogen group or a methyl group, x is 1 or 2, and y is 1 or 2) selected from the group consisting of (poly) phosphonic acid group-containing (meth) acrylamides It may contain at least one kind.

  An esterified product (compound represented by the above formulas (1) to (3)) in a phosphoric acid ester residue-containing (meth) acrylamide composition and a non-esterified product (expressed by the above formulas (7) and (8)). The ratio of the compound to be produced is not particularly limited. This ratio depends on the hydroxyl value of the alcoholic hydroxyl group-containing compound. In general, the total of the esterified product and the non-esterified product is 100 mol%, and the esterified product is preferably 20 mol% or more, more preferably 50 mol% or more. More preferably. Specifically, for this ratio, when the alcoholic hydroxyl group-containing compound is polyhydric alcohol, 20 mol% is sufficient, but when the alcoholic hydroxyl group-containing compound is monohydric alcohol, 50 mol% The above is preferable.

[2] Use of phosphorus acid ester residue-containing (meth) acrylamide composition The phosphorus acid ester residue-containing (meth) acrylamide composition is suitable as an emulsifier and a solubilizer. These uses will be described in detail below.

(1) Emulsifier The phosphoric acid ester residue-containing (meth) acrylamide has a hydrophilicity due to a phosphoric acid residue and a phosphoric acid ester residue, and a hydrophobic property due to a (meth) acrylamide group, and further an alcohol. By appropriately selecting the composition of the residue of the functional hydroxyl group-containing compound, either hydrophilicity or hydrophobicity can be imparted to this residue. Therefore, the phosphoric acid ester residue-containing (meth) acrylamide composition has a surface active action and is suitable as an emulsifier added to form an aqueous resin emulsion.

  The residue of the alcoholic hydroxyl group-containing compound may be appropriately selected according to the unsaturated monomer used in the aqueous resin emulsion. For example, if the residue of the alcoholic hydroxyl group-containing compound has a polyalkylene glycol unit, it can be generally adapted to various unsaturated monomers. If the residue of the alcoholic hydroxyl group-containing compound is an organosilicon group, it can be adapted to the silicon-containing unsaturated monomer. If the residue of the alcoholic hydroxyl group-containing compound is a fluorine-containing hydrocarbon group, it can be adapted to the fluorine-containing unsaturated monomer.

  Furthermore, since the phosphoric acid ester residue-containing (meth) acrylamide composition can be copolymerized with the unsaturated monomer used in the aqueous resin emulsion, it can be used as a reactive emulsifier. Therefore, regardless of the type of unsaturated monomer, the emulsion (aqueous emulsion dispersion) in which the unsaturated monomer is dispersed by the emulsifier of the present invention is excellent in polymerizability.

  Examples of unsaturated monomers that form an aqueous resin emulsion include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) Tert-butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. And vinyl monomers such as alkyl (meth) acrylate, styrene, vinyl acetate and (meth) acrylonitrile.

  The emulsifier of the present invention is used by adding it to the water of the polymerization medium in the same manner as the conventional emulsifier during the production of the aqueous resin emulsion. The preferred amount of use is 1% by mass or more, preferably 5 to 30% by mass, based on the total amount of unsaturated monomers subjected to polymerization in the production of the aqueous resin emulsion. The emulsifier of the present invention can also be used in combination with a known emulsifier.

Examples of the emulsion polymerization method include known emulsion polymerization methods such as continuous emulsion polymerization, batch emulsion polymerization, two-stage emulsion polymerization, and divided addition polymerization. The polymerization temperature and the polymerization time are not particularly limited, and may be appropriately set according to the molecular weight, gel content, etc. of the target emulsion. In the emulsion polymerization, various additives and auxiliaries generally used in the conventional emulsion polymerization operation, such as a chain transfer agent, a polymerization initiator, and a chelating agent, can be used. Furthermore, you may add an organic solvent as needed. As polymerization initiators, organic peroxide initiators such as ammonium persulfate (APS), potassium persulfate (KPS), acetyl peroxide, isopropyl hydroperoxide, 2, 2′-azobisisobutyronitrile, twenty two '-Azobis (2,4-dimethylvaleronitrile), dimethyl 2, 2 '-Azobis (2-methylpropionate), dimethyl 2, 2 Examples thereof include azo initiators such as' -azobisisobutyrate, or peroxide initiators such as lauryl peroxide, benzoyl peroxide, tert-butylperoxy pivalate, and hydrogen peroxide.

  Applications of the aqueous resin emulsion using the emulsifier of the present invention include paints, adhesives, pressure-sensitive adhesives, coating agents, impregnating reinforcing agents, etc., and base materials include metals, wood, paper, cloth, concrete Etc. In the aqueous resin emulsion, various conventionally known additives such as tackifiers, plasticizers such as process oil, fillers such as calcium carbonate and clay, dispersants, antifoaming agents, antiseptics may be used as necessary. An agent, an antioxidant, a thickener, and the like may be appropriately added within a range that does not hinder the effects of the present invention.

  A film obtained by polymerizing an aqueous resin emulsion using the emulsifier of the present invention is excellent in strength and adhesiveness because an unsaturated monomer and an emulsifier are copolymerized. Furthermore, since it has a phosphorus acid residue and a phosphorus acid ester residue, it is excellent in oxidation resistance, flame retardancy, antistatic property and the like.

(2) Solubilizer The phosphoric acid ester residue-containing (meth) acrylamide composition can be used as a solubilizer for dissolving or dispersing rubber in an organic solvent. The rubber to be solubilized is not particularly limited. For example, at least one conjugated diene-based liquid oligomer selected from the group consisting of a butadiene oligomer, an isoprene oligomer, and derivatives thereof each having at least one ethylenically unsaturated bond in the molecule. Is mentioned.

（但しR⁹及びR¹⁰はそれぞれ独立にエチレン性不飽和結合を１個以上有し、かつ他の原子団を有してもよい炭化水素基であり、R¹¹及びR¹²はそれぞれ独立に水素基又はメチル基であり、かつR¹¹及びR¹²の少なくとも一方は水素基であり、mは重合度である。）により表されるものが挙げられる。ただし共役ジエン系液状オリゴマーとして、式(72)に示すような重合体鎖中の共役ジエン単位が1, 2-結合であるものに限定する趣旨ではなく、共役ジエン単位が1, 4-結合であるものであってもよい。 As the conjugated diene liquid oligomer, the following general formula (72):

(However, R ⁹ and R ¹⁰ are each independently a hydrocarbon group having one or more ethylenically unsaturated bonds and may have other atomic groups, and R ¹¹ and R ¹² are each independently hydrogen. Or a methyl group, and at least one of R ¹¹ and R ¹² is a hydrogen group, and m is the degree of polymerization.). However, the conjugated diene-based liquid oligomer is not limited to those in which the conjugated diene unit in the polymer chain is a 1,2-bond as shown in the formula (72), but the conjugated diene unit is a 1,4-bond. There may be something.

R ⁹ and R ¹⁰ are not particularly limited as long as they are hydrocarbon groups that have one or more ethylenically unsaturated bonds and may have other atomic groups. Examples of other atomic groups that R ⁹ and R ¹⁰ may have include at least one selected from the group consisting of urethane bonds, ester bonds, ether bonds, isocyanate groups, hydroxyl groups, carboxyl groups, and alkoxy groups. Specific examples of R ⁹ and R ¹⁰ include a (meth) acryl group.

（ただしR^9’はH又はCH₃である。）により表される基であるものの市販品として、例えば「NISSO-PB TEA-1000」、「NISSO-PB TE-2000」（以上日本曹達（株）製）等がある。共役ジエン系液状オリゴマーは上記式(72)により表される化合物を水素化したものであってもよく、その市販品として、例えば「NISSO-PB TEAI-1000」（日本曹達株式会社製）等がある。 Although there is no restriction | limiting in particular in the molecular weight of a conjugated diene type liquid oligomer, A thing with a number average molecular weight of 500-50,000 is preferable. Of the conjugated diene-based liquid oligomer represented by the formula (72), R ¹¹ and R ¹² are both hydrogen groups, and R ⁹ and R ¹⁰ are both represented by the following formula (73):

(However, R ^{9 ′} is H or CH _3. ) Commercially available products such as “NISSO-PB TEA-1000” and “NISSO-PB TE-2000” (Nippon Soda Co., Ltd.) ))). The conjugated diene-based liquid oligomer may be a compound obtained by hydrogenating the compound represented by the above formula (72). Examples of commercially available products thereof include “NISSO-PB TEAI-1000” (manufactured by Nippon Soda Co., Ltd.). is there.

（但しR⁷及びR⁸はそれぞれ独立に水素基又はメチル基であり、かつR⁷及びR⁸の少なくとも一方は水素基であり、m及びnは各々重合度である。）により表されるエポキシ化共役ジエン系液状オリゴマーも挙げられる。式(15)により表されるエポキシ化共役ジエン系液状オリゴマーの市販品として、例えば「アデカスタブBF-1000」（旭電化工業（株）製）がある。 As the conjugated diene liquid oligomer, the following general formula (15):

Wherein R ⁷ and R ⁸ are each independently a hydrogen group or a methyl group, and at least one of R ⁷ and R ⁸ is a hydrogen group, and m and n are each a degree of polymerization. Also included are conjugated diene-based liquid oligomers. As a commercial product of the epoxidized conjugated diene liquid oligomer represented by the formula (15), for example, “ADK STAB BF-1000” (manufactured by Asahi Denka Kogyo Co., Ltd.) is available.

  Examples of the conjugated diene-based liquid oligomer include those composed of a copolymer having at least a vinyl aromatic unit and a conjugated diene unit and having at least one ethylenically unsaturated bond in the molecule. Styrene is preferred as the vinyl aromatic component. As the conjugated diene component, isoprene and 1,3-butadiene are preferable. The ratio of the vinyl aromatic component and the conjugated diene component in the vinyl aromatic-conjugated diene-based liquid oligomer is not particularly limited, and may be appropriately set according to required physical properties such as toughness, flexibility, and mechanical strength. . Examples of commercially available vinyl aromatic-conjugated diene liquid oligomers include “Claprene LIR-310” (manufactured by Kuraray Co., Ltd.).

  The conjugated diene-based liquid oligomer may contain another conjugated diene as a polymerization component, if necessary. When the conjugated diene-based liquid oligomer is a butadiene oligomer or a derivative thereof, isoprene may be included as a copolymerization component. When the conjugated diene liquid oligomer is an isoprene oligomer or a derivative thereof, butadiene may be included as a copolymerization component. Other conjugated dienes include 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and 4,5-diethyl-1. , 3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like.

  The organic solvent may be appropriately selected according to the rubber and is not particularly limited. When the conjugated diene liquid oligomer is dissolved or dispersed as rubber, for example, a solvent containing no active hydrogen is preferable. Solvents that do not contain active hydrogen include amide solvents such as N, N-dialkyl (meth) acrylamide, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), and sulfoxides such as dimethyl sulfoxide (DMSO). Solvent; acrylonitrile and the like.

  The solubilizer of the present invention may be obtained by grafting a functional group-containing unsaturated monomer (for example, a phosphoric acid group-containing unsaturated monomer) to the conjugated diene liquid oligomer by a solution graft polymerization method, or by the above formula (15). It is suitable as a solubilizer used when the epoxy group of the rubber represented is modified with an acid (for example, phosphoric acid). Specifically, the conjugated diene-based liquid oligomer can be dissolved in an organic solvent, and the grafted product and phosphoric acid-modified product of the conjugated diene-based liquid oligomer with a phosphate group-containing unsaturated monomer can also be dissolved in the organic solvent. Can do. This is because the solubilizer has lipophilicity due to (meth) acrylamide groups, and has affinity for phosphoric acid group-containing unsaturated monomers, phosphoric acid and epoxy groups due to phosphoric acid residues and phosphoric acid ester residues. Furthermore, this is because, by appropriately selecting the composition of the residue of the alcoholic hydroxyl group-containing compound, lipophilicity or functional group affinity can be imparted to this residue. What is necessary is just to select suitably the alcoholic hydroxyl-containing compound residue of a solubilizer according to rubber | gum.

  Furthermore, since the phosphoric acid ester residue-containing (meth) acrylamide composition can be copolymerized with the conjugated diene liquid oligomer having an unsaturated bond as described above, it can be used as a reactive solubilizer. Therefore, the conjugated diene liquid oligomer can be modified by the solubilizer of the present invention.

  A preferable amount of the solubilizer of the present invention is 1% by mass or more, preferably 10 to 100% by mass with 100% by mass of rubber. The temperature and time of the graft polymerization are not particularly limited, and may be appropriately set according to the target grafting rate and the like. The method for modifying the epoxy group with phosphoric acid may be a known method. For example, the methods described in JP-A-2001-151854, JP-A-2002-327040 and the like can be employed.

[3] Phosphoric acid ester residue-containing (meth) acrylamide polymer The phosphoric acid ester residue-containing (meth) acrylamide polymer of the present invention contains at least the phosphoric acid ester residue-containing (meth) acrylamide composition. The product is polymerized.
(1) Other unsaturated compounds that can be copolymerized The polymer may contain other unsaturated compounds that can be copolymerized with the phosphoric acid ester residue-containing (meth) acrylamide composition. Examples of such other unsaturated compounds include unsaturated compounds that can contain a phosphorus acid residue-containing (meth) acrylamide polymer described in WO2005 / 080454 as a copolymerization component. This unsaturated compound comprises (a) an unsaturated compound having one or more ethylenically unsaturated bonds and acidic groups in the molecule, and / or (b) one or more ethylenically unsaturated bonds in the molecule. It can be broadly classified into unsaturated compounds having, but not having an acidic group. The unsaturated compound having an acidic group preferably has at least one acidic group selected from the group consisting of a phosphoric acid group, a sulfonic acid group, a carboxylic acid group, and an alcoholic hydroxyl group. The unsaturated compound having no acidic group is (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic ester, alkylamino group-containing unsaturated monomer, conjugated diene liquid oligomer or derivative thereof, substituted or unsubstituted It is preferably at least one selected from the group consisting of styrene, halogen vinyl, fatty acid vinyl ester, and fluorine group-containing unsaturated monomer. Among these, when the conjugated diene liquid oligomer is used as another unsaturated compound, the solvent resistance and water resistance of the polymer are further improved.

  The mass ratio (A) / (B) between the phosphoric acid ester residue-containing (meth) acrylamide composition (A) and the other unsaturated compound (B) is not particularly limited, and is appropriately determined according to the desired physical properties. Just choose. Usually, the mass ratio (A) / (B) is preferably in the range of 100/0 to 5/95. The lower limit of this ratio is more preferably 10/90 or more, and further preferably 20/80 or more. Further, among the other unsaturated compounds (B), the mass ratio (a) / (b) of the unsaturated compound containing an acidic group and the unsaturated compound containing no acidic group (a) / (b) is not particularly limited. However, it is usually preferable to set the range of (a) / (b) = 100/0 to 5/95, and more preferable to set the range of (a) / (b) = 95/5 to 20/80.

(2) Method for Producing Phosphoric Acid Ester Residue-Containing (Meth) acrylamide Polymer Phosphoric acid ester residue-containing (meth) acrylamide polymer is: (i) Phosphoric acid ester residue-containing (meth) An acrylamide composition or (ii) a mixture of a phosphoric acid ester residue-containing (meth) acrylamide composition and another unsaturated compound can be produced by radiation polymerization or thermal polymerization (unless otherwise noted) , “Phosphorus acid ester residue-containing (meth) acrylamide composition” and “Phosphorus acid ester residue-containing (meth) acrylamide composition and other unsaturated compounds” are collectively referred to as “unsaturated raw material” Call it.)

(a) Production Method by Radiation Polymerization Examples of radiation include light rays, X-rays, and electron beams, and light rays are preferred. Examples of light rays include visible light rays and ultraviolet rays, but ultraviolet rays are preferred. Hereinafter, the method for producing the polymer of the present invention will be described by taking as an example the case of producing a film comprising a phosphoric acid ester residue-containing (meth) acrylamide polymer by ultraviolet polymerization. The method for producing a polymer film by ultraviolet polymerization is based on a composition (unsaturated composition) containing an unsaturated raw material and a photopolymerization initiator (photosensitizer) by using a material (fluorine polymer or the like) to which this does not adhere. After casting on a coated plate and covering with a UV transparent plate, polymerization is performed by irradiating with UV rays.

As a photopolymerization initiator (photosensitizer) to be added to the unsaturated raw material,
(i) an adjacent polyketone compound represented by R— (CO) _x —R ′ (R, R ′ = hydrogen group or hydrocarbon group, x = 2 to 3) (for example, diacetyl, dibenzyl, etc.),
(ii) α-carbonyl alcohol (for example, benzoin) represented by R—CO—CHOH—R ′ (R, R ′ = hydrogen group or hydrocarbon group),
(iii) acyloin ether represented by R—CH (OR ″) — CO—R ′ (R, R ′, R ″ = hydrocarbon group) (for example, benzoin methyl ether),
(iv) α-substituted acyloin (eg, α-alkylbenzoin) represented by Ar—CR (OH) —CO—Ar (Ar = aryl group, R = hydrocarbon group), and
(v) There are polynuclear quinones (for example, 9, 10-anthraquinone, etc.).
These photopolymerization initiators can be used alone or in combination.

  The use amount of the photopolymerization initiator is preferably in the range of 1 to 10% by mass with respect to the total mass of the unsaturated raw materials. When the amount used is less than 1% by mass, polymerization is not completed within a predetermined ultraviolet irradiation time, and unreacted monomers remain, which is not preferable. On the other hand, if it exceeds 10% by mass, the polymer is colored, which is not preferable.

  The ultraviolet transmissive plate and the support substrate used for the ultraviolet irradiation polymerization of the unsaturated composition not only have a high ultraviolet transmittance, but also have heat resistance to withstand the temperature rise during polymerization due to ultraviolet irradiation, and the unsaturated composition. It is necessary to have good releasability without adhering to the product and a polymer obtained by polymerizing the product.

  The glass plate usually used as a support substrate is very good for UV transmittance and heat resistance, but because it adheres to the polymer, either a silicone-based or fluorine-based release agent is applied to the surface of the glass plate in advance, It is preferable to use after attaching a fluororesin thin transparent film.

  In addition to glass flat plates, the supporting substrate has good UV transmittance such as polyperfluorovinyl ether resin (PFA) and polyvinylidene fluoride resin (PVDF), as well as poly-3-methylpentene resin and polypropylene resin. A resin flat plate having heat resistance of 100 ° C. or higher can be used.

  In order to impart releasability to the polymer, a release agent may be added to the unsaturated composition in advance. As the release agent, those having good compatibility with the unsaturated composition are preferable. The release agent is preferably a fluorine-based surfactant, and more preferably a fluorine-based alcohol. Specific examples of the release agent include perfluorooctylethanol, perfluorooctylsulfoamidoethanol, and ethylene oxide adducts thereof; hydrocarbon surfactants; polymer polyoxyethylene glycol (eg, carbowax). The addition amount of the release agent is in the range of 0.5 to 5% by mass, preferably in the range of 0.5 to 1.5% by mass, based on the total mass of the unsaturated composition. If this addition amount is less than 0.5% by mass, the peelability is insufficient. On the other hand, even if this addition amount exceeds 5 mass%, the peeling effect is saturated.

After casting the unsaturated composition, it is covered with an ultraviolet transmissive plate, and when performing ultraviolet irradiation, air and excess unsaturated composition must be squeezed out of the system. For example, as shown in FIGS. 1 and 2, the composition 1 is sandwiched between two supporting substrates 2, 2, UV is applied while being kept horizontal with a pressure applied evenly and stopped with a clip or clamp 3. Irradiation is preferred. Irradiation is performed for at least one side for 1 to 15 minutes. Even when irradiation is performed alternately on the front and back sides, it is performed for 0.5 to 15 minutes on one side. The intensity of ultraviolet irradiation during polymerization is 5 to 150 mW / cm ² , preferably 10 to 120 mW / cm ² . The ultraviolet irradiation distance is appropriately set so as to be sufficiently cured within the above irradiation time range. The film obtained by the ultraviolet polymerization method may be subjected to heat treatment at 100 to 130 ° C. for about 1 to 15 minutes for the purpose of improving mechanical strength and solvent resistance. The thickness of the ultraviolet polymerization film is usually 20 to 200 μm, preferably about 20 to 100 μm.

  In the present invention, a low-boiling solvent such as methanol or the above N, N-dialkyl (meth) acrylamide can be added as a diluent for the purpose of supporting dissolution of the photopolymerization initiator in the unsaturated raw material. In particular, N, N-dialkyl (meth) acrylamide is preferable because it is polymerized together with the unsaturated raw material by ultraviolet polymerization. When N, N-dialkyl (meth) acrylamide is used, it is preferable to use N, N-dimethylacrylamide (DMAA) and N, N-dimethylmethacrylamide. When N, N-dialkyl (meth) acrylamide is used, the reaction obtained using N, N-dialkyl (meth) acrylamide as a solvent when preparing a phosphoric acid ester residue-containing (meth) acrylamide composition What is necessary is just to superpose | polymerize using a solution. Thereby, a polymer can be manufactured efficiently. Although the method for producing a polymer film by ultraviolet polymerization has been described above, the procedure for using other radiation such as X-rays and electron beams is basically the same. However, when X-rays or electron beams are used, it is not necessary to use a photopolymerization initiator.

(b) Production Method by Thermal Polymerization A method for producing a phosphoric acid ester residue-containing (meth) acrylamide polymer by thermal polymerization will be described. The polymerization reaction is performed by radical polymerization of an unsaturated raw material using a polymerization initiator. The polymerization initiator may be the same as that of the emulsifier. The amount of the polymerization initiator used is preferably 0.1 to 5 and more preferably 0.1 to 2 in terms of mass ratio when the unsaturated raw material is 100.

  The polymerization procedure is described. An unsaturated raw material is put into a reactor equipped with a stirrer, and after the inside of the reactor is brought to a nitrogen gas atmosphere, a polymerization initiator is added and stirred at room temperature so that a uniform solution is obtained. The obtained solution is placed in a mold, heated in an oven to a decomposition temperature of the polymerization initiator of 40 ° C to 70 ° C, and allowed to stand for several hours to 24 hours for polymerization. A preferable polymerization temperature is 50 ° C to 70 ° C.

  If necessary, the polymerization reaction may be performed in a common solvent in which both the unsaturated raw material and the produced polymer are dissolved. As a solvent, alcohol and / or a polar solvent are preferable. As the alcohol, an aliphatic lower alcohol is preferable. The aliphatic lower alcohol is preferably at least one selected from the group consisting of methanol, ethanol and isopropyl alcohol. Two or more of these may be used in combination. In addition, an ester, dioxane, ether or the like may be allowed to coexist within a range that does not impair the solubility. The polar solvent is more preferably at least one selected from the group consisting of dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and water. When water is used, it is preferable to use an aliphatic lower alcohol in combination.

  The polymerization procedure when a solvent is used will be described. First, a solution composed of (unsaturated raw material + solvent) is put into a reactor equipped with a stirrer and a reflux condenser, and after the inside of the reactor is made a nitrogen gas atmosphere, the temperature is raised to 40 ° C to 70 ° C. A polymerization initiator is added immediately after reaching the predetermined temperature. At this time, there is slight heat generation, and the start of polymerization can be confirmed. After reaching a predetermined temperature, a polymerization initiator is added 2 to 3 times at intervals of about 1 hour, and then the polymerization reaction is continued for about 1 hour. The reaction temperature does not need to be constant from the beginning to the end, and a method of increasing the temperature at the end of the polymerization to minimize the unreacted monomer may be used. In the polymerization solution, the initial solid content concentration of the unsaturated raw material is preferably 10 to 40% by mass, and more preferably 10 to 30% by mass. The total amount of polymerization initiator used may be the same as described above.

  When isolating a phosphoric acid ester residue-containing (meth) acrylamide polymer from the obtained polymerization solution, the polymer solution is concentrated until the solid content concentration is 10 to 80% by mass, and the resulting concentrated solution is A viscous solid is precipitated by pouring into a poor solvent and filtered. The solution after the reaction contains not only the desired phosphoric acid ester residue-containing (meth) acrylamide polymer but also impurities such as free phosphoric acid, unreacted monomers, and components with insufficient polymerization degree. Therefore, it is preferable to carry out purification. However, it is not intended to limit the purification. In the purification, the polymer solution is concentrated until the solid content concentration becomes 40 to 80% by mass, the obtained concentrated solution is poured into a poor solvent to precipitate a viscous solid, and the poor solvent is removed by a decantation method. To do. As the poor solvent, acetone, THF, ether, 1,1,1-trichloroethane and the like are preferable. The poor solvent is used in a large excess amount of 2 to 15 times the volume of the reaction product. The washing operation of the viscous solid with the poor solvent may be repeated as necessary. By performing such purification, the impurities can be removed.

  When forming a film of a phosphoric acid ester residue-containing (meth) acrylamide polymer prepared by thermal polymerization, it is preferable to use a casting method. In the casting method, a solution of a phosphoric acid ester residue-containing (meth) acrylamide polymer is cast on a horizontal glass plate or tray to evaporate the solvent. It is preferable to further heat the formed film (film) at normal pressure or reduced pressure at 100 to 140 ° C. for about 1 to 30 minutes, thereby further improving mechanical strength and solvent resistance. The mechanical strength can be increased by further stretching the cast film. Stretching preferably involves heating. The thickness of the cast film is usually 20 to 500 μm, preferably about 20 to 200 μm.

(3) Physical properties of phosphorus acid ester residue-containing (meth) acrylamide polymer The phosphorus acid ester residue-containing (meth) acrylamide polymer obtained by each of the above production methods is a polymer having a relatively low molecular weight. is there. Although it is not limited, a phosphorus acid ester residue-containing (meth) acrylamide polymer usually has a viscosity of 3 to 200 mPa · s (cP) when made into a methanol solution with a solid content concentration of 5 to 20% by mass. The degree of polymerization is preferably. The phosphoric acid ester residue-containing (meth) acrylamide polymer usually exhibits excellent conductivity of 1 × 10 ¹⁶ Ω or less under conditions where the surface resistivity is room temperature / RH = 40 to 75%. This is presumably because the phosphonic acid group density in the polymer is high.

[4] Conductive Resin The conductive resin of the present invention contains the phosphorus acid ester residue-containing (meth) acrylamide polymer as an essential component.
(1) Other resins that can be added The conductive resin may contain other resins. The phosphoric acid ester residue-containing (meth) acrylamide polymer is excellent in compatibility with other resins. Therefore, the conductive resin mixed with other resins has excellent physical properties such as film-forming properties, chemical resistance, flexibility, transparency, and adhesion to various substrates inherent in other resins, Combined with the excellent conductivity of acid ester residue-containing (meth) acrylamide polymers.

  Examples of other resins that can be added include resins that can contain the conductive resin described in WO2005 / 080454. Specifically, the unsaturated alcohol copolymer, the partially acetalized unsaturated alcohol polymer, a melamine resin (for example, trimethoxymethylmelamine resin), polyamide, poly (meth) acrylonitrile, poly (meth). It is at least one selected from the group consisting of acrylic ester, polyacrylamide, poly (meth) acrylic acid, polyacetal, urethane resin, cellulose or a modified product thereof, polystyrene, polyvinyl chloride, and polyvinyl acetate. Among these, as other resins, unsaturated alcohol copolymers, partially acetalized unsaturated alcohol polymers, and melamine resins are preferable.

(2) Mixing ratio of other resin Ratio of phosphoric acid ester residue-containing (meth) acrylamide polymer to other resin [(phosphoric acid ester residue-containing (meth) acrylamide polymer) / (other Resin)] is preferably 0.05 or more, and more preferably 0.1 or more on a solids mass basis. If this ratio is less than 0.05, the conductivity will be insufficient. The upper limit of this ratio is not particularly limited, and may be set as appropriate according to desired physical properties.

(3) Adding other resins
(a) Mixed polymerization method The conductive resin containing another resin is obtained by using the above unsaturated raw material [phosphorus acid ester residue-containing (meth) acrylamide composition (+ the above other unsaturated compound)] as the other resin. It can be obtained by radiation polymerization or thermal polymerization in the presence of coexistence. Since the methods of radiation polymerization and thermal polymerization are the same as in the case of the phosphoric acid ester residue-containing (meth) acrylamide polymer, description thereof is omitted.

(b) Solution mixing method Conductive resin containing other resin is also prepared by preparing a polymer solution in which other resin is added to the above-mentioned (meth) acrylamide polymer containing phosphoric acid ester residue. Obtained by heat treatment. The polymer solid concentration of the polymer solution is preferably 5 to 30% by mass. The solvent is evaporated and removed by heating the polymer solution, and then heated to 100 to 140 ° C. to obtain a conductive resin which is a solid homogeneous composition. The conductive resin thus obtained is a uniform composition having flexibility and transparency.

  In particular, when a melamine resin is added, when the resin composition after removal of the solvent is heated to 100 to 140 ° C., the (poly) phosphonic acid group incorporated in the polymer serves as a catalyst to promote the cross-linking reaction of the melamine resin. The mechanical strength and solvent resistance of the conductive resin are further improved. In the addition of the melamine resin, methylol melamine or methylated or butylated methylol melamine may be added and polymerized by heating together with the phosphoric acid ester residue-containing (meth) acrylamide polymer.

(4) Physical properties of conductive resin The conductive resin as described above is not only excellent in conductivity as described above, but also excellent in water resistance, chemical resistance and adhesion to various substrates. Conductive resins having such properties include conductive metal paste binders, coating agent raw materials, solid polymer electrolyte membrane raw materials, conductive resins for bioelectrodes interposed between skin and electrode elements when bioelectrodes are mounted, etc. Useful as. In addition, since conductive resin contains the phosphorus atom, it is excellent also in the flame retardance and the dispersibility of an inorganic filler. An example of a molded body made of a conductive resin is a cast film. The method for producing the cast film is as described above.

[5] Binder for conductive metal paste The conductive resin can be used as a binder for conductive metal paste. The conductive metal paste includes at least metal fine particles, a conductive resin functioning as an organic binder, and a solvent. When the conductive metal paste is heated and dried, the conductive resin has a function of filling the gap between the metal fine particles to fix the metal fine particles to each other and bonding the metal fine particles to the substrate. The conductive metal paste is used for applications such as a conductive coating agent, a conductive ink, a solder substitute conductive adhesive and the like used for circuit printing or the like.

  The metal constituting the metal fine particles is not particularly limited, and noble metals used in known conductive metal pastes (gold, silver, platinum, palladium, rhodium, osmium, ruthenium, iridium, etc.), copper, iron, tungsten, nickel, Examples include tantalum, bismuth, lead, indium, tin, zinc, and titanium. The average particle size of the metal fine particles is not particularly limited, and may be appropriately selected depending on the application. For example, in the case of circuit printing application, it is 1 to 100 nm.

  The content of the organic binder in the conductive metal paste is preferably in the range of 10 to 30% by mass with 100% by mass of the entire conductive metal paste. If the content is less than 10% by mass, the physical properties after molding as a structure are poor or the adhesion to the substrate is insufficient, and if it exceeds 30% by mass, the conductivity is low.

  The solvent is preferably the aliphatic lower alcohol described in [3] above. The conductive metal paste may contain other components as necessary. Other components are not particularly limited. For example, coating surface conditioners (for example, melamine crosslinking agent, methylol nylon, etc.), anti-sagging agents, surfactants, silane coupling agents, titanium coupling agents, glass resins, glass frits, etc. Paint additives; pigments such as colored pigments, extender pigments, metallic pigments, and the like.

  The conductive metal paste is kneaded to make a paste in which ultrafine metal particles are uniformly dispersed, and then, if necessary, in order to adjust its viscosity, an appropriate thixotropic agent is added, and the excess organic solvent is removed under reduced pressure. It can also be removed by transpiration, or an organic solvent can be added or added.

  The method for applying the conductive metal paste is not particularly limited, and a known method can be used. Specific examples include a printing method and a stamping method. The heating / drying process of the applied conductive metal paste is not particularly limited, and for example, it may be heated / dried under conditions of about 50 to 300 ° C. and about 1 second to 60 minutes. A conductive film obtained from a conductive metal paste is suitable for a substrate that is vulnerable to heat because it can obtain high conductivity even when heated and dried at a low temperature.

  The base material to which the conductive metal paste is applied is not particularly limited. For example, ceramic, glass, glass epoxy substrate, BT (Bismaleimide Triazine) substrate, 42 alloy (iron-nickel alloy) for bonding semiconductors, copper, etc. A lead frame can be mentioned. The structure using the conductive metal paste is not particularly limited, and examples thereof include a capacitor, a chip resistor, a conductor circuit, and a bonding portion between a lead frame and a semiconductor.

  Since the organic binder of the present invention has a phosphoric acid residue, a conductive film obtained by drying a conductive metal paste containing this has not only conductivity but also oxidation resistance, flame retardancy, and adhesion to a substrate. Also excellent. In particular, due to the excellent oxidation resistance, the oxidation of the substrate wiring is satisfactorily suppressed, and the oxidation when another wiring is connected to the conductive film is suppressed.

[6] Coating Agent The coating agent of the present invention contains the conductive resin. As the solvent, the solvents which can be used for the thermal polymerization described in [3] above can be used. When using the coating agent, it is preferable to dilute the coating agent to a concentration suitable for application using a good solvent. The good solvent is preferably the aliphatic lower alcohol described in [3] above.

  The coating agent includes the following additives used in ordinary coating agents, such as viscosity modifiers (eg thickeners), various coloring pigments for beautification purposes, fillers for the purpose of increasing hiding power, and smoothness of the coating surface. Leveling agent added for the purpose of improving, coupling agent added for the purpose of improving adhesion to the substrate, conventionally known antioxidants, lubricants, anti-blocking agents, anti-aging agents, flame retardants, conductive An agent, an antifoaming agent, and the like can be arbitrarily selected and used.

  An antistatic property, electrical conductivity, antifogging property, etc. can be provided by applying a coating agent to an object to be coated so as to have a thickness of 1 to 100 μm after drying and forming a coating film by heating. As a method for applying to the substrate surface, there is a method of coating or dipping the substrate surface by brush coating, bar coater coating, spraying, dipping, roll coating, blade coating, flow coating or electrostatic coating. The coating agent can be applied to any of a metal plate, a glass plate, a plastic molding, a sheet or film, a fiber, a woven fabric, or a non-woven fabric, and adheres to the surface. The coating film obtained by curing the coating agent is excellent in adhesion to the substrate, solvent resistance, water resistance, hardness, gloss, weather resistance, rust resistance, and the like.

[7] Solid polymer electrolyte membrane The solid polymer electrolyte membrane of the present invention is a membrane using the conductive resin as a solid polymer electrolyte. This membrane is excellent in proton conductivity derived from high density (poly) phosphonic acid groups.

  The solid polymer electrolyte membrane comprises a phosphoric acid ester residue-containing (meth) acrylamide composition, or a composition in which the above-mentioned other unsaturated compound and / or the above-mentioned other resin are added to the composition as required (a ) It can be obtained by forming into a film by radiation polymerization in a state of being sandwiched between ultraviolet transmissive supporting substrates, or (b) by forming into a film by a casting method after thermal polymerization. Since the radiation polymerization method, the thermal polymerization method, and the casting method are as described above, description thereof is omitted.

  The solid polymer electrolyte membrane preferably contains a cross-linked phosphorus acid ester residue-containing (meth) acrylamide polymer. The cross-linked solid polymer electrolyte membrane is excellent in solvent resistance, particularly methanol resistance. In order to produce a solid polymer electrolyte membrane containing a crosslinked (meth) acrylamide polymer containing a phosphoric acid ester residue, a crosslinking agent having a plurality of unsaturated groups is used as the unsaturated compound, and a radiation polymerization method is used. It is preferable to manufacture using.

  When using the radiation polymerization method, after impregnating or applying the unsaturated composition to the reinforcing material, the reinforcing material is sandwiched between ultraviolet transmissive support substrates, and irradiated with ultraviolet rays to photopolymerize the unsaturated composition, A composite film may be formed. Examples of the reinforcing material that can be used include a reinforcing material made of inorganic fibers, a reinforcing material made of organic fibers, and a resin film described in WO 2002/33709. For the purpose of reducing the viscosity of the unsaturated composition, facilitating the impregnation of the reinforcing material, reducing the amount of adhesion to the reinforcing material and thinning the composite membrane, a low-boiling solvent such as methanol as a diluent, or the above N, N-dialkyl (meth) acrylamide can also be added.

  The use ratio of the reinforcing material and the unsaturated composition varies greatly depending on the affinity of the reinforcing material to the unsaturated composition, in other words, the absorbability of the unsaturated composition, but generally the reinforcing material / unsaturated composition = It is in the range of 1/20 to 1/2 (mass ratio).

The polymer electrolyte membranes as described above are suitably used for electrolyte membranes for primary batteries, electrolyte membranes for secondary batteries, electrolyte membranes for fuel cells, display elements, various sensors, signal transmission media, solid capacitors, ion exchange membranes, etc. it can. In particular the solid polymer electrolyte membrane in the case of normal present _{^{invention, 10 - 4 ~10 - 2 S}} · cm - has ¹ excellent proton conductivity, so that temperature dependency is small, as the electrolyte membrane for a fuel cell Is preferred.

[8] Fuel Cell The structure of the fuel cell may be a known one. Usually, a fuel cell can be formed by laminating a plurality of unit fuel cells (membrane-electrode assemblies) via separators. The unit fuel cell is composed of a solid polymer electrolyte membrane and an anode electrode and a cathode electrode bonded to both sides thereof. The electrode is composed of a gas diffusion layer (such as a porous carbon-based material) and a catalyst layer (such as platinum particles). The catalyst layer is formed by applying catalyst particles on the gas diffusion layer.

  The separator separates fuel gas (hydrogen, methane, methanol, etc.) and oxidant gas (oxygen or air), secures a flow path for the fuel gas and oxidant gas, and further generates electricity generated by the fuel cell. It plays a role to communicate outside. Accordingly, the separator is made of a conductive material such as a carbon material, a carbon composite material (such as a composite material of carbon and a thermosetting resin or a thermoplastic resin), a metal material, or a metal composite material (such as a composite material of a metal and carbon). It is formed. Further, a groove (reactive gas flow path) that forms a flow path for the fuel gas and the oxidant gas is formed on the surface of the separator at the contact portion with the electrode.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1
(Synthesis of phosphoric acid ester residue-containing (meth) acrylamide composition)
71 g (1 mol) of acrylamide and 0.1 g of paramethoxyhydroquinone were placed in an automatic synthesis reactor (internal volume 1,000 mL, manufactured by Unichemical Co., Ltd.) connected to a reflux condenser, a powder inlet, and a thermometer. It was dissolved in g (1.9 mol) of N, N-dimethylacrylamide (DMAA) and heated to 30 ° C. After confirming that the internal temperature reached 30 ° C., 142 g (1 mol) of phosphoric anhydride was added in four portions at 15-minute intervals. While adding the phosphoric anhydride, the internal temperature was maintained in the range of 30 to 60 ° C. while stirring the solution. After adding phosphoric anhydride, 0.1 g of paramethoxyhydroquinone was further added, the temperature was raised to 80 to 82 ° C., and the aging reaction was carried out for 2 hours.

  To the reaction solution containing the obtained intermediate product (acrylamide pyrophosphonic acid), 280 g (0.91 mol) of nonylphenol ethoxyethanol [trade name “Nonion NS-202”, manufactured by NOF Corporation, hydroxyl value (1N KOH Measured value using an aqueous solution (the same shall apply hereinafter)): 180 mg / g, hydroxyl equivalent (analytical value; the same shall apply hereinafter): 311 g / eq.] Was added over 1 hour, and the reaction was carried out at 80 to 82 ° C. for 8 hours. I let you. In order to hydrolyze the remaining acrylamide pyrophosphonic acid, 4 g (0.22 mol) of water was added and held at a temperature of 80 ° C. for 30 minutes.

  The obtained composition (hereinafter referred to as “composition Nφ”) was analyzed by liquid chromatography. As a result, acrylamide diphosphonic acid nonylphenol ethoxyethyl monoester was the main component, in addition to solvent DMAA and a small amount of by-product acrylamide. It was confirmed that diphosphonic acid was contained [analytical conditions for liquid chromatography are as follows. Measuring instrument: SPD-10A manufactured by Shimadzu Corporation (using UV detector), column temperature: room temperature, solvent: methanol / water = 7/3 (mass ratio), concentration: 0.01% by mass (injection amount: 2.5 μl), Column: PRP-1 manufactured by HAMILTON, solvent flow rate: 0.3 ml / min. ].

Example 2
(Synthesis of phosphoric acid ester residue-containing (meth) acrylamide composition)
In the same manner as in Example 1 except that the amount of acrylamide used was 100 g (1.4 mol), the amount of DMAA used was 220 g (2.2 mol), and the amount of phosphoric anhydride used was 200 g (1.4 mol). A reaction solution containing acrylamide pyrophosphonic acid was prepared. 240 g (1 mol) of octafluoropentanol (trade name “OFPO”, manufactured by Asahi Glass Co., Ltd., hydroxyl value: 241 mg / g, hydroxyl equivalent: 232 g / eq.) Was added to the resulting reaction solution, The esterification reaction was carried out in the same manner as in Example 1. Residual acrylamide pyrophosphonic acid was hydrolyzed in the same manner as in Example 1 except that 10 g (0.56 mol) of water was added to the obtained solution. The obtained composition (hereinafter referred to as “composition FN”) was analyzed by liquid chromatography in the same manner as in Example 1. As a result, acrylamide diphosphonic acid octafluoropentyl monoester was the main component, and other solvents were used. It was confirmed to contain DMAA and a small amount of by-product acrylamide diphosphonic acid.

Example 3
(Synthesis of phosphoric acid ester residue-containing (meth) acrylamide composition)
In the same manner as in Example 1, except that the amount of acrylamide used was 71.5 g (1 mol), the amount of DMAA used was 191 g (1.9 mol), and the amount of phosphoric anhydride used was 143.5 g (1 mol). A reaction solution containing acrylamide pyrophosphonic acid was prepared. 150 g (0.8 mol) of a higher alcohol composition (composition: 95% by weight of lauryl alcohol + 3% by weight of tetradecyl alcohol + 2% by weight of decyl alcohol, trade name “NAA-42”, Japanese fats and oils) (Product number, hydroxyl value: 300 mg / g, hydroxyl equivalent: 187 g / eq.) Was added, and an esterification reaction was carried out in the same manner as in Example 1. Residual acrylamide pyrophosphonic acid was hydrolyzed in the same manner as in Example 1 except that 7 g (0.39 mol) of water was added to the resulting solution. The obtained composition (hereinafter referred to as “Composition C12”) was analyzed by liquid chromatography in the same manner as in Example 1. As a result, acrylamide diphosphonic acid lauryl monoester was the main component, and in addition to the solvents DMAA and It was confirmed to contain a small amount of by-product acrylamide diphosphonic acid.

Example 4
(Synthesis of phosphoric acid ester residue-containing (meth) acrylamide composition)
In the same manner as in Example 1, except that the amount of acrylamide used was 72 g (1 mol), the amount of DMAA used was 191 g (1.9 mol), and the amount of phosphoric anhydride used was 144 g (1 mol), A reaction solution containing acrylamide pyrophosphonic acid was prepared. Modified silicone oil with propoxyethanol groups bonded to both ends (the composition of the skeleton: Si _5.7 O _4.7 (CH ₃ ) _11.4 , trade name “X-22-160SS”, Shin-Etsu Chemical Co., Ltd.) 274 g (0.44 mol) of hydroxyl value: 184 mg / g, hydroxyl equivalent: 304.35 g / eq. Residual acrylamide pyrophosphonic acid was hydrolyzed in the same manner as in Example 1 except that 4.2 g (0.23 mol) of water was added to the obtained solution. The obtained composition (hereinafter referred to as “composition SiN”) was analyzed by liquid chromatography in the same manner as in Example 1. As a result, a monoester in which acrylamide diphosphonic acid was bonded to one end of the modified silicone oil was obtained. It was confirmed that the main component was a diester component (a diester component in which acrylamide diphosphonic acid was bonded to both ends of the modified silicone oil), a solvent DMAA, and a small amount of by-product acrylamide diphosphonic acid.

Example 5
(Synthesis of phosphoric acid ester residue-containing (meth) acrylamide composition)
In the same manner as in Example 1, except that the amount of acrylamide used was 72 g (1 mol), the amount of DMAA used was 191 g (1.9 mol), and the amount of phosphoric anhydride used was 144 g (1 mol), A reaction solution containing acrylamide pyrophosphonic acid was prepared. To the obtained reaction solution, 315.5 g (0.3 mol) of polyoxypropylene glyceryl ether (trade name “Uniol TG-1000”, manufactured by NOF Corporation, hydroxyl value: 160 mg / g, hydroxyl equivalent: 350 g / eq .) Was added and an esterification reaction was carried out in the same manner as in Example 1. Residual acrylamide pyrophosphonic acid was hydrolyzed in the same manner as in Example 1 except that 4.1 g (0.23 mol) of water was added to the obtained solution. The obtained composition (hereinafter referred to as “composition G6N”) was analyzed by liquid chromatography in the same manner as in Example 1. As a result, a monoester in which one acrylamide diphosphonic acid was bonded to polyoxypropylene glyceryl ether was obtained. Main component, diester (compound in which two acrylamide diphosphonic acids are bonded to polyoxypropylene glyceryl ether), triester (compound in which three acrylamide diphosphonic acids are bonded to polyoxypropylene glyceryl ether), solvent Of DMAA and a small amount of by-product acrylamide diphosphonic acid.

Example 6
(Synthesis of phosphoric acid ester residue-containing (meth) acrylamide composition)
In the same manner as in Example 1, except that the amount of acrylamide used was 150 g (2.1 mol), the amount of DMAA used was 340 g (3.4 mol), and the amount of phosphoric anhydride used was 300 g (2.1 mol), A reaction solution containing acrylamide pyrophosphonic acid was prepared. To the obtained reaction solution, 230 g (0.7 mol) of polyoxypropylene glyceryl ether (trade name “Uniol TG-330”, manufactured by NOF Corporation, hydroxyl value: 519 mg / g, hydroxyl equivalent: 108 g / eq .) Was added and an esterification reaction was carried out in the same manner as in Example 1. Residual acrylamide pyrophosphonic acid was hydrolyzed in the same manner as in Example 1 except that 5 g (0.28 mol) of water was added to the resulting solution. The obtained composition (hereinafter referred to as “composition G2N”) was analyzed by liquid chromatography in the same manner as in Example 1. As a result, a monoester in which one acrylamide diphosphonic acid was bonded to polyoxypropylene glyceryl ether was obtained. In addition to the main component, in addition, a diester (a compound in which two acrylamide diphosphonic acids are bonded to polyoxypropylene glyceryl ether), a triester (a compound in which three acrylamide diphosphonic acids are bonded to polyoxypropylene glyceryl ether), It was confirmed to contain the solvent DMAA and a small amount of by-product acrylamide diphosphonic acid.

Example 7
(Synthesis of phosphoric acid ester residue-containing (meth) acrylamide composition)
In the same manner as in Example 1 except that the amount of acrylamide used was 72 g (1 mol), the amount of DMAA used was 192 g (1.9 mol), and the amount of phosphoric anhydride used was 144 g (1 mol). A reaction solution containing acrylamide pyrophosphonic acid was prepared. To the obtained reaction solution, 137 g (0.23 mol) of polyoxyethylene methyl glucoside (trade name “Macbiobride MG-10E”, manufactured by NOF Corporation, hydroxyl value: 367 mg / g, hydroxyl equivalent: 152 g / Eq.) Was added and an esterification reaction was carried out in the same manner as in Example 1. Residual acrylamide pyrophosphonic acid was hydrolyzed in the same manner as in Example 1 except that 5 g (0.28 mol) of water was added to the resulting solution. The obtained composition (hereinafter referred to as “Composition 3EO”) was analyzed by liquid chromatography in the same manner as in Example 1. As a result, a compound in which acrylamide diphosphonic acid was monoesterified with polyoxyethylene methyl glucoside was obtained. It was confirmed that it contains the main component and also contains DMAA as a solvent and a small amount of by-product acrylamide diphosphonic acid.

Example 8
(Evaluation as an emulsifier)
The compositions Nφ, C12 and G6N prepared in Examples 1, 3 and 5 were evaluated as emulsifiers. Each of compositions Nφ, C12, and G6N, vinyl acetate, and water were mixed at a mass ratio of 1: 4: 10 to prepare an aqueous emulsion dispersion. 90 parts of the obtained aqueous emulsion dispersion was put into a flask equipped with a stirrer, a condenser, a thermometer and a nitrogen introduction tube, heated to 65 ° C., and then 4 parts of 5 mass% ammonium persulfate water was added. While stirring at 65-70 ° C, 3 parts of 5 mass% ammonium persulfate water was added twice at an interval of 1 hour (10 parts in total). The polymerization was terminated by continuing. The polymerization was stable with no separation or blocking except that agglomerates slightly adhered to the wall of the flask during the polymerization. Even when the obtained aqueous resin dispersion was allowed to stand at room temperature for 1 month, almost no precipitate was observed.

Example 9
(Evaluation as a solubilizer)
Using 25 g of the composition Nφ prepared in Example 1 (composition based on acrylamide diphosphonic acid nonylphenol ethoxyethyl monoester) as solubilizer, 25 g of normal phosphoric acid and 50 g of acrylonitrile were used in the reactor. The acrylonitrile solution of 100 g of epoxidized liquid rubber (trade name “FB-1000”, manufactured by Asahi Denka Kogyo Co., Ltd., epoxy equivalent: 200 g / eq.) With stirring at a temperature of 20 to 40 ° C. (Concentration: 50% by mass) was gradually added. The resulting mixture was whitened by stirring while maintaining the temperature at 30 to 40 ° C. However, when 50 g of composition Nφ was further added and stirring was continued, a transparent and viscous solution was obtained. The phosphoric acid-modified epoxidized liquid rubber in the obtained solution had photopolymerizability. From this, it is considered that the epoxidized liquid rubber is not only phosphoric acid-modified but also polymerized with the composition Nφ.

Comparative Example 1
A phosphoric acid modification reaction of the epoxidized liquid rubber was performed in the same manner as in Example 9 except that the composition Nφ was not added. However, the compatibility of acrylonitrile and the epoxidized liquid rubber during stirring was poor, and the mixture was gelled. This is presumably because the epoxidized liquid rubber was phosphoric acid-crosslinked.

Examples 10-17
(Preparation of conductive resin film)
To each phosphoric acid ester residue-containing (meth) acrylamide composition synthesized in Examples 1, 2, 4 to 7, phosphoric acid-modified epoxidized liquid rubber synthesized in Example 9 / composition Nφ / acrylonitrile solution, and Acrylonitrile was mixed to prepare a composition having a blending ratio shown in Table 1. Further, the phosphoric acid-modified epoxidized liquid rubber synthesized in Example 9 / composition Nφ / acrylonitrile solution and acrylonitrile were mixed to prepare a composition having a blending ratio shown in Table 1. Each composition obtained was subjected to photopolymerization initiator [Irgacure 651 (2,2-dimethoxy-1,2-diphenylethane-1-one; manufactured by Ciba Specialty Chemicals) and Irgacure 500 (1-hydroxycyclohexylphenyl). Equi-mass ratio mixture of ketone, benzophenone; manufactured by Ciba Specialty Chemicals Co., Ltd.] was added at the blending ratio (composition) shown in Table 1. A polyethylene film is affixed on a square glass plate with a side of 20 cm, a spacer tape with a thickness of 100 μm is attached to the peripheral edge of the polyethylene film, and the above-mentioned polymerization initiator-containing composition is dropped at the diagonal center, and from above A glass plate with a polyethylene film attached was placed, and the composition was sandwiched between two glass flat plates (see FIGS. 1 and 2). In this state, photopolymerization was performed by irradiating the front and back with ultraviolet rays for 10 minutes each (irradiation distance: 20 cm) with a high-pressure mercury lamp (400 W). The obtained film was transparent and excellent in uniformity.

(Evaluation of physical properties of conductive resin film)
The physical properties of the conductive resin film were measured by the following method. The results are shown in Table 1.
(1) Water resistance: A strip sample having a length of 1 cm and a width of 4 cm was cut out, and the area of the length and width was measured and used as a reference. The cut out sample was immersed in water at room temperature, taken out after 30 minutes, the length and width were measured, the area of length and width was calculated, and the increase rate relative to the reference area was defined as the swelling rate.
(2) Methanol resistance: A strip sample having a length of 1 cm and a width of 4 cm was cut out, and the area of the length and width was measured and used as a reference. The cut out sample was immersed in methanol at room temperature, taken out after 30 minutes, the length and width were measured, the vertical and horizontal areas were calculated, and the rate of increase relative to the reference area was taken as the swelling rate. Moreover, the film after immersion was touched with a finger, and the strength was determined based on the tactile sensation. Symbols indicating the judgment criteria are ◎: “excellent in tensile strength”, ○: “practically sufficient tensile strength” and △: “slightly lacking tensile strength, but no problem in practical use” .
(3) Hot water resistance: A strip sample measuring 1 cm in length x 4 cm in width was cut out, and the area in the length and width was measured and used as a reference. The cut sample was immersed in hot water at 80 ° C., taken out after 2 hours, the length and width were measured, the vertical and horizontal areas were calculated, and the increase rate relative to the reference area was defined as the swelling rate.
(4) Surface resistivity: Measured with a surface resistivity meter (SME-8310, manufactured by Toa Denpa Kogyo Co., Ltd.) under the conditions of RH 45% / 15 ° C.

表１（続き）

表１（続き）

Table 1 (continued)

Table 1 (continued)

Notes: (1) A composition mainly composed of acrylamide diphosphonic acid nonylphenol ethoxyethyl monoester prepared in Example 1.
(2) A composition comprising acrylamide diphosphonic acid octafluoropentyl monoester prepared in Example 2 as a main component.
(3) A composition mainly composed of acrylamide diphosphonic acid / modified silicone oil monoester prepared in Example 4.
(4) A composition mainly composed of a monoester in which one acrylamide diphosphonic acid prepared in Example 5 is bonded to polyoxypropylene glyceryl ether.
(5) A composition mainly comprising a monoester in which one acrylamide diphosphonic acid prepared in Example 6 is bonded to polyoxypropylene glyceryl ether.
(6) A composition mainly composed of a monoester in which one acrylamide diphosphonic acid prepared in Example 7 is bonded to polyoxyethylene methyl glucoside.
(7) The composition synthesized in Example 9.
(8) Irgacure 651 / Irgacure 500 = 1/1 (mass ratio, manufactured by Ciba Specialty Chemicals Co., Ltd.).
(9) 15 ° C / RH 45%.
(10) Surface exposed to air during film formation.
(11) The surface that was in contact with the container during film formation.

As shown in Table 1, although the conductive resin films of Examples 10 to 16 are slightly swollen by immersion in water, methanol, and hot water, they are at a level that causes no problem in practice. The surface specific resistance values of the conductive resin films of Examples 10 to 16 are in the order of 10 ¹⁰ to 10 ¹⁵ Ω in the measurement of RH 45% / 15 ° C., and the conductivity based on the phosphoric acid residue as an electrolyte group. It was a good level as a resin.

Example 17
(Preparation of polymer)
36 g of the composition Nφ was placed in a reaction vessel (internal volume 100 mL), 4 g of 5% by mass of ammonium persulfate water was added, and the mixture was stirred to obtain a uniform solution. The resulting solution was placed in an oven and allowed to stand at a temperature of 40 to 65 ° C. for 18 hours for polymerization. This polymer (hereinafter referred to as polymer “NφP”) was a polymer that was soft and stretchable at a temperature of 40 to 50 ° C. A 10% by mass methanol solution of the obtained polymer NφP was prepared, and the viscosity measured at 18 ° C. was 13.4 mPa / s. The acid value of the obtained polymer NφP was 498.4 mg / g. The acid value was measured by dissolving 1 g of a polymer in 100 g of a 50% by mass aqueous methanol solution and using a 1N aqueous KOH solution (the same applies hereinafter). The obtained polymer was mixed with 300 g of a methanol / water mixture [methanol: water = 70: 30 (volume ratio). same as below. ]. Most of the resulting solution was a clear solution that passed through an 80 mesh wire mesh. This dissolution phenomenon is presumed to be due to the fact that the polymer NφP does not have a crosslinked structure but has a linear structure.

Example 18
(Preparation of polymer)
Example 17 except that the composition FN (composition mainly composed of acrylamide diphosphonic acid octafluoropentyl monoester) prepared in Example 2 was used as the phosphoric acid ester residue-containing (meth) acrylamide composition. Similarly, a polymer was prepared. A 10 mass% methanol solution of the obtained polymer (hereinafter referred to as polymer “FNP”) was prepared, and the viscosity measured at 18 ° C. was 9.9 mPa / s. The acid value of the obtained polymer FNP was 551.2 mg / g. The polymer FNP was also soluble in a methanol / water mixture.

Example 19
(Preparation of polymer)
As the phosphoric acid ester residue-containing (meth) acrylamide composition, in the same manner as in Example 17, except that the composition C12 prepared in Example 3 (composition mainly composed of lauryl diphosphonic acid lauryl monoester) was used. Thus, a polymer was prepared. A 10 mass% methanol solution of the obtained polymer (hereinafter referred to as polymer “C12P”) was prepared, and the viscosity measured at 18 ° C. was 18.1 mPa / s. The acid value of the obtained polymer C12P was 431.0 mg / g. The polymer C12P was also soluble in a methanol / water mixture.

Example 20
(Preparation of polymer)
Example 17 except that the composition SiN (composition mainly composed of acrylamide diphosphonic acid / modified silicone oil monoester) prepared in Example 4 was used as the phosphoric acid ester residue-containing (meth) acrylamide composition. In the same manner as described above, a polymer was prepared. A 10% by mass methanol solution of the obtained polymer (hereinafter referred to as polymer “SiNP”) was prepared, and the viscosity measured at 18 ° C. was 9.8 mPa / s. The acid value of the obtained polymer SiNP was 425.2 mg / g. The polymer SiNP was soluble in a methanol / water mixture, suggesting that it was not crosslinked. The reason for this is that the composition SiN contains a diester form in which acrylamide diphosphonic acid is bonded to both ends of the modified silicone oil. For example, it is speculated that this diester form becomes cyclic due to the association of phosphonic acid groups at both ends. . In addition, ortho diallyl phthalate is mentioned as a well-known example of the compound which does not show crosslinkability even if it has two or more double bonds in one molecule. Ortho-diallyl phthalate forms a linear polymer because of the adjacent double bonds (for example, “Chemical Products of 13599”, Chemical Industry Daily, January 1999, pp. 972-973).

Example 21
(Preparation of polymer)
As a phosphoric acid ester residue-containing (meth) acrylamide composition, the composition G6N prepared in Example 5 (composition mainly composed of a monoester in which one acrylamide diphosphonic acid is bonded to polyoxypropylene glyceryl ether) A polymer was prepared in the same manner as in Example 17 except that was used. A 10 mass% methanol solution of the obtained polymer (hereinafter referred to as polymer “G6NP”) was prepared, and the viscosity measured at 18 ° C. was 10.9 mPa / s. The acid value of the obtained polymer G6NP was 289.2 mg / g. The polymer G6NP was also soluble in a methanol / water mixture, suggesting that it was not crosslinked. The reason is presumed that the acrylamide groups of the diester or triester are not adjacent to each other so that the double bond can be cross-linked, and thus do not cross-link like the above orthodiallyl phthalate.

Example 22
(Preparation of polymer)
As a phosphoric acid ester residue-containing (meth) acrylamide composition, composition G2N prepared in Example 6 (composition mainly composed of a monoester in which one acrylamide diphosphonic acid is bonded to polyoxypropylene glyceryl ether) A polymer was prepared in the same manner as in Example 17 except that was used. A 10 mass% methanol solution of the obtained polymer (hereinafter referred to as polymer “G2NP”) was prepared, and the viscosity measured at 18 ° C. was 15.0 mPa / s. The acid value of the obtained polymer G2NP was 521.9 mg / g. The polymer G2NP was also soluble in the methanol / water mixture, suggesting that it was not crosslinked. The reason is assumed to be the same as above.

Example 23
(Preparation of polymer)
As a phosphoric acid ester residue-containing (meth) acrylamide composition, composition 3EO prepared in Example 7 (composition mainly composed of a monoester in which one acrylamide diphosphonic acid is bonded to polyoxyethylene methylglucoside) A polymer was prepared in the same manner as in Example 17 except that was used. A 10 mass% methanol solution of the obtained polymer (hereinafter referred to as polymer “3EOP”) was prepared, and the viscosity measured at 18 ° C. was 9.7 mPa / s. The acid value of the obtained polymer 3EOP was 431.2 mg / g. Polymer 3EOP was also soluble in a methanol / water mixture, suggesting that it was not crosslinked. The reason is assumed to be the same as above.

Example 24
(Preparation of conductive resin film made of phosphorus acid ester residue-containing (meth) acrylamide polymer and polyvinyl alcohol)
10% by mass methanol solution of the polymer FNP obtained in Example 18 and polyvinyl alcohol (trade name “Exeval RS-2113”, degree of saponification: 97.5-99.0, manufactured by Kuraray Co., Ltd., the same shall apply hereinafter) The solution was mixed according to the solid content ratio shown in Table 2 to prepare a polymer solution. The obtained polymer solution is cast into a container made of polypropylene film (bottom; 100 mm x 100 mm), placed in an air flow dryer, heated from room temperature to 50 ° C and dried for 12 hours. did. The produced film was peeled off with a spatula, and this was heat-treated at 130 ° C. for 3 minutes with a high-temperature air circulation dryer to produce a conductive resin film having a thickness of 100 μm.

(Preparation of conductive resin film comprising phosphorus acid ester residue-containing (meth) acrylamide polymer and polyamide)
A conductive resin film was prepared in the same manner as described above except that N-methoxymethylated nylon-6 (trade name “Toresin EF-30T”, manufactured by Nagase ChemteX Corporation, the same shall apply hereinafter) was used instead of polyvinyl alcohol. Produced.

(Preparation of conductive resin film comprising phosphorus acid ester residue-containing (meth) acrylamide polymer, polyamide and melamine resin)
Instead of polyvinyl alcohol, N-methoxymethylated nylon-6 and trimethoxymethylmelamine (trade name “Sumitex Resin M-3”, manufactured by Sumitomo Chemical Co., Ltd., the same shall apply hereinafter) are used, and the solids shown in Table 2 are used. The polymer solution was prepared by mixing according to the blending ratio of minutes. A conductive resin film was produced in the same manner as above except that the obtained polymer solution was used.

(Surface specific resistance measurement)
The surface specific resistance of each conductive resin film was measured under the condition of RH 45% / 15 ° C. using a resistance measuring instrument (SME-8310 manufactured by Toa Denpa Kogyo Co., Ltd., the same shall apply hereinafter). The results are shown in Table 2.

Example 25
(Preparation of conductive resin film made of phosphorus acid ester residue-containing (meth) acrylamide polymer and polyvinyl alcohol)
A 10% by mass methanol solution of the polymer C12P obtained in Example 19 and a 10% by mass methanol solution of polyvinyl alcohol were mixed according to the blending ratio of the solid content shown in Table 3 to prepare a polymer solution. A conductive resin film having a thickness of 100 μm was produced in the same manner as in Example 24 except that the obtained polymer solution was used.

(Preparation of conductive resin film comprising phosphorus acid ester residue-containing (meth) acrylamide polymer and polyamide)
A conductive resin film was produced in the same manner as described above except that N-methoxymethylated nylon-6 was used instead of polyvinyl alcohol.

(Preparation of conductive resin film comprising phosphorus acid ester residue-containing (meth) acrylamide polymer, polyamide and melamine resin)
Instead of polyvinyl alcohol, N-methoxymethylated nylon-6 and trimethoxymethylmelamine were used and mixed according to the solid content ratio shown in Table 3 to prepare a polymer solution. A conductive resin film was produced in the same manner as above except that the obtained polymer solution was used.

(Surface specific resistance measurement)
The surface specific resistance of each conductive resin film was measured with a resistance meter under the condition of RH 45% / 15 ° C. The results are shown in Table 3.

Example 26
(Preparation of conductive resin film made of phosphorus acid ester residue-containing (meth) acrylamide polymer and polyvinyl alcohol)
A 10% by mass methanol solution of the polymer G6NP obtained in Example 21 and a 10% by mass methanol solution of polyvinyl alcohol were mixed according to the blending ratio of the solid content shown in Table 4 to prepare a polymer solution. A conductive resin film having a thickness of 100 μm was produced in the same manner as in Example 24 except that the obtained polymer solution was used.

(Preparation of conductive resin film comprising phosphorus acid ester residue-containing (meth) acrylamide polymer and polyamide)
A conductive resin film was produced in the same manner as described above except that N-methoxymethylated nylon-6 was used instead of polyvinyl alcohol.

(Preparation of conductive resin film comprising phosphorus acid ester residue-containing (meth) acrylamide polymer, polyamide and melamine resin)
Instead of polyvinyl alcohol, N-methoxymethylated nylon-6 and trimethoxymethylmelamine were used and mixed according to the solid content ratio shown in Table 4 to prepare a polymer solution. A conductive resin film was produced in the same manner as above except that the obtained polymer solution was used.

(Surface specific resistance measurement)
The surface specific resistance of each conductive resin film was measured with a resistance meter under the condition of RH 45% / 15 ° C. The results are shown in Table 4.

Example 27
(Preparation of conductive resin film comprising phosphorus acid ester residue-containing (meth) acrylamide polymer, polyamide and melamine resin)
A methanol solution of the polymer G2NP obtained in Example 22, a methanol solution of N-methoxymethylated nylon-6, and a methanol solution of trimethoxymethylmelamine were mixed according to the solid content ratio shown in Table 5. A polymer solution was prepared. A conductive resin film having a thickness of 100 μm was produced in the same manner as in Example 24 except that the obtained polymer solution was used.

(Surface specific resistance measurement)
The surface specific resistance of each conductive resin film was measured with a resistance meter under the condition of RH 45% / 15 ° C. The results are shown in Table 5.

Example 28
(Preparation of conductive resin film made of phosphorus acid ester residue-containing (meth) acrylamide polymer and polyvinyl alcohol)
A 10% by mass methanol solution of the polymer 3EOP obtained in Example 23 and a 10% by mass methanol solution of polyvinyl alcohol were mixed according to the blending ratio of the solids shown in Table 6 to prepare a polymer solution. A conductive resin film having a thickness of 100 μm was produced in the same manner as in Example 24 except that the obtained polymer solution was used.

(Preparation of conductive resin film comprising phosphorus acid ester residue-containing (meth) acrylamide polymer and polyamide)
A conductive resin film was produced in the same manner as described above except that N-methoxymethylated nylon-6 was used instead of polyvinyl alcohol.

(Preparation of conductive resin film comprising phosphorus acid ester residue-containing (meth) acrylamide polymer, polyamide and melamine resin)
Instead of polyvinyl alcohol, N-methoxymethylated nylon-6 and trimethoxymethylmelamine were used and mixed according to the solid content ratio shown in Table 6 to prepare a polymer solution. A conductive resin film was produced in the same manner as above except that the obtained polymer solution was used.

(Surface specific resistance measurement)
The surface specific resistance of each conductive resin film was measured with a resistance meter under the condition of RH 45% / 15 ° C. The results are shown in Table 6.

As shown in Tables 2 to 6, the surface resistivity values of the films of Examples 24 to 28 are on the order of 10 ⁷ to 10 ¹⁵ Ω under the measurement conditions of RH 45% / 15 ° C. It was a good level as a conductive resin based on an electrolyte.

It is a partial section side view showing the state where an unsaturated composition was inserted between two glass plates. It is a top view which shows the state which sandwiched the unsaturated composition between two glass flat plates.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Unsaturated composition 2 ... Glass flat plate 3 ... Clip

Claims (28)

A phosphoric acid residue esterified with an alcoholic hydroxyl group-containing compound is a composition containing a phosphoric acid ester residue-containing (meth) acrylamide formed by directly bonding to a nitrogen atom of an amide group, The acid ester residue-containing (meth) acrylamide has the following formula (1):

Wherein R ^1a is a hydrogen group or a methyl group, R ^2a is a hydrogen group or a substituted or unsubstituted hydrocarbon group, and —X ^a —OR ^3a is a phosphorus acid ester residue. The following compound (2):

(However, R ^1b is a hydrogen group or a methyl group, -X ^b OH is a phosphorus acid residue, and -X ^c -OR ^3b is a phosphorus acid ester residue, and each contains a phosphorus atom, an oxygen atom, and a hydrogen atom. X ^b and X ^c which are atomic groups composed of atoms may be the same or different.) And a compound represented by the following formula (3):

(Wherein R ^1c is a hydrogen group or a methyl group, -X ^d -OR ^3c and -X ^e -OR ^3d are each a phosphorus acid ester residue, and each R ^3c is a residue of an alcoholic hydroxyl group-containing compound. And R ^3d may be the same or different, and X ^d and X ^e which are atomic groups each consisting of a phosphorus atom, an oxygen atom and a hydrogen atom may be the same or different. A phosphoric acid ester residue-containing (meth) acrylamide composition, wherein the phosphoric acid ester residue-containing (meth) acrylamide composition is at least one selected from the group consisting of: The phosphorus acid ester residue-containing (meth) acrylamide composition according to claim 1, wherein the phosphorus acid ester residue-containing (meth) acrylamide is represented by the following formula (4):

(Wherein R ¹ is a hydrogen group or a methyl group, and R ³ is a residue of an alcoholic hydroxyl group-containing compound), a compound represented by the following formula (5):

(Wherein R ¹ is a hydrogen group or a methyl group, and R ³ is a residue of an alcoholic hydroxyl group-containing compound), and the following formula (6):

(Wherein R ¹ is a hydrogen group or a methyl group, and R ³ is a residue of an alcoholic hydroxyl group-containing compound). (Meth) acrylamide composition containing an acid ester residue. In the phosphoric acid ester residue-containing (meth) acrylamide composition according to claim 1 or 2, the following formula (7):

(Where R ^1d is a hydrogen group or a methyl group, R ^2b is a hydrogen group or a substituted or unsubstituted hydrocarbon group, and —X ^f OH is a phosphorus acid residue), and / or (8):

(However, R ^1e is a hydrogen group or a methyl group, -X ^g OH and -X ^h OH are each a phosphorus acid residue, and X ^g is an atomic group consisting of a phosphorus atom, an oxygen atom and a hydrogen atom, respectively. A phosphoric acid ester residue-containing (meth) acrylamide composition characterized by comprising a phosphoric acid residue-containing (meth) acrylamide represented by X ^h may be the same or different. The phosphoric acid ester residue-containing (meth) acrylamide composition according to claim 3, wherein the phosphoric acid residue-containing (meth) acrylamide is represented by the following formula (9):

(Wherein R ¹ is a hydrogen group or a methyl group) and / or phosphonic acid (meth) acrylamide represented by the following formula (10):

A phosphoric acid ester residue-containing (meth) acrylamide composition characterized by being N, N-diphosphonic acid (meth) acrylamide represented by (wherein R ¹ is a hydrogen group or a methyl group). 5. The phosphoric acid ester residue-containing (meth) acrylamide composition according to claim 3, wherein a ratio of the phosphoric acid ester residue-containing (meth) acrylamide and the phosphoric acid residue-containing (meth) acrylamide is as follows: The total of the phosphorus acid residue-containing (meth) acrylamide and the phosphorus acid residue-containing (meth) acrylamide is 100 mol%, and the phosphorus acid ester residue-containing (meth) acrylamide is 20 mol% or more. A phosphoric acid ester residue-containing (meth) acrylamide composition, characterized in that 6. The phosphorus acid ester residue-containing (meth) acrylamide composition according to claim 1, wherein the alcoholic hydroxyl group-containing compound is monohydric alcoholic or polyhydric alcoholic. (Meth) acrylamide composition containing an acid ester residue. The phosphoric acid ester residue-containing (meth) acrylamide composition according to any one of claims 1 to 6, wherein the alcoholic hydroxyl group-containing compound is an aliphatic alcohol, an alicyclic alcohol, an aromatic alcohol, phenol, and the like. Derivatives, glycerin and derivatives thereof, fluorinated alcohols, polyoxyalkylene glycols, polyoxyalkylene monoalkyl ethers, polyoxyalkylene esters, unsaturated alcohol copolymers, partially acetalized unsaturated alcohol polymers, and alcohol-modified or A phosphoric acid ester residue-containing (meth) acrylamide composition, which is at least one selected from the group consisting of phenol-modified silicone oils. The phosphoric acid ester residue-containing (meth) acrylamide composition according to claim 1, wherein the alcoholic hydroxyl group-containing compound is nonylphenol ethoxyethanol, lauryl alcohol, octafluoropentanol, the following formula (11 ):

(Wherein a to c are degrees of polymerization, respectively), polyoxypropylene glyceryl ether represented by the following formula (12):

(Wherein a to d are each the degree of polymerization), and the following formula (13):

Where R ⁵¹ is a substituted or unsubstituted alkyl group or aryl group, R ⁵² is a substituted or unsubstituted alkylene group, R ⁵³ OH is an oxyalkyl group, and n is the degree of polymerization. A phosphoric acid ester residue-containing (meth) acrylamide composition, which is at least one selected from the group consisting of modified silicone oils. An emulsifier comprising the phosphoric acid ester residue-containing (meth) acrylamide composition according to any one of claims 1 to 8. A rubber solubilizer comprising the phosphoric acid ester residue-containing (meth) acrylamide composition according to any one of claims 1 to 8. A phosphoric acid ester residue-containing (meth) acrylamide polymer obtained by polymerizing at least the phosphoric acid ester residue-containing (meth) acrylamide composition according to claim 1. 12. The phosphoric acid ester residue-containing (meth) acrylamide polymer according to claim 11, further comprising another unsaturated compound as a copolymerization component. Polymer. 13. The phosphoric acid ester residue-containing (meth) acrylamide polymer according to claim 12, wherein the other unsaturated compound includes (a) one or more ethylenically unsaturated bonds and acidic groups in the molecule. And / or (b) an unsaturated compound having at least one ethylenically unsaturated bond but having no acidic group in the molecule, and the unsaturated compound having an acidic group is a phosphate group , An unsaturated compound having at least one acidic group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, and an alcoholic hydroxyl group, and having no acidic group is (meth) acrylonitrile, (meth) acrylamide, (meta ) Acrylic acid ester, alkylamino group-containing unsaturated monomer, conjugated diene liquid oligomer or derivative thereof, substituted or unsubstituted styrene, halogen vinyl, fatty acid vinyl ester And a phosphoric acid ester residue-containing (meth) acrylamide polymer, which is at least one selected from the group consisting of a fluorine group-containing unsaturated monomer. The phosphoric acid ester residue-containing (meth) acrylamide polymer according to claim 12 or 13, wherein the other unsaturated compound is represented by the following formula (14):

(However, R ⁴ is a hydrogen group or a methyl group, and R ⁵ and R ⁶ are each independently an alkyl group.) N, N-dialkyl (meth) acrylamide represented by the following formula (15):

Wherein R ⁷ and R ⁸ are each independently a hydrogen group or a methyl group, and at least one of R ⁷ and R ⁸ is a hydrogen group, and m and n are each a degree of polymerization. A phosphoric acid ester residue-containing (meth) acrylamide polymer, which is at least one selected from the group consisting of a phosphoric acid modified product of a conjugated diene-based liquid oligomer and acrylonitrile. 15. A conductive resin comprising the phosphorus acid ester residue-containing (meth) acrylamide polymer according to any one of claims 11 to 14 as an essential component. The conductive resin according to claim 15, wherein the unsaturated alcohol copolymer further includes an unsaturated alcohol unit and a halogen vinyl unit and / or a fatty acid vinyl unit, a partially acetalized unsaturated alcohol polymer, a melamine resin, Selected from the group consisting of poly (meth) acrylonitrile, poly (meth) acrylic acid ester, polyacrylamide, poly (meth) acrylic acid, polyacetal, urethane resin, cellulose or modified product thereof, polystyrene, polyvinyl chloride, and polyvinyl acetate. A conductive resin comprising at least one kind. 17. A conductive metal paste binder comprising the conductive resin according to claim 15 or 16. In a solvent not containing active hydrogen and / or an acidic solvent, the following formula (16):

(Wherein R ¹ is a hydrogen group or a methyl group, and R ² is a hydrogen group or a substituted or unsubstituted hydrocarbon group.) A phosphoric acid source compound is added to a (meth) acrylamide monomer represented by A method for producing a phosphoric acid ester residue-containing (meth) acrylamide composition, wherein the reaction product is reacted with an alcoholic hydroxyl group-containing compound. 19. The method for producing a phosphoric acid ester residue-containing (meth) acrylamide composition according to claim 18, wherein the solvent containing no active hydrogen is represented by the following formula (14):

(Wherein R ⁴ is a hydrogen group or a methyl group, and R ⁵ and R ⁶ are each independently an alkyl group.) A method using N, N-dialkyl (meth) acrylamide represented by: 20. The method for producing a phosphoric acid ester residue-containing (meth) acrylamide composition according to claim 18 or 19, wherein anhydrous phosphoric acid is used as the phosphoric acid source compound. 21. The method for producing a phosphoric acid ester residue-containing (meth) acrylamide composition according to claim 18, wherein the alcoholic hydroxyl group-containing compound is monohydric alcohol or polyhydric alcohol. And how to. The method for producing a phosphoric acid ester residue-containing (meth) acrylamide composition according to any one of claims 18 to 21, wherein the alcoholic hydroxyl group-containing compound is an aliphatic alcohol, an alicyclic alcohol, an aromatic alcohol, Phenol and derivatives thereof, glycerin and derivatives thereof, fluorine-containing alcohol, polyoxyalkylene glycol, polyoxyalkylene monoalkyl ether, polyoxyalkylene ester, unsaturated alcohol copolymer, partially acetalized unsaturated alcohol polymer, and A method comprising at least one selected from the group consisting of alcohol-modified or phenol-modified silicone oils. The method for producing a phosphoric acid ester residue-containing (meth) acrylamide composition according to any one of claims 18 to 22, wherein the alcoholic hydroxyl group-containing compound is nonylphenol ethoxyethanol, octafluoropentanol, lauryl alcohol, Formula (11):

(Wherein a to c are degrees of polymerization), polyoxypropylene glyceryl ether represented by the following formula (12):

(Wherein a to d are each the degree of polymerization), and the following formula (13):

Where R ⁵¹ is a substituted or unsubstituted alkyl group or aryl group, R ⁵² is a substituted or unsubstituted alkylene group, R ⁵³ OH is an oxyalkyl group, and n is the degree of polymerization. A method characterized by being at least one selected from the group consisting of modified silicone oils. In a solvent not containing active hydrogen and / or an acidic solvent, the following formula (16):

(Wherein R ¹ is a hydrogen group or a methyl group, and R ² is a hydrogen group or a substituted or unsubstituted hydrocarbon group.) A phosphoric acid source compound is added to a (meth) acrylamide monomer represented by By reacting and reacting the resulting reaction product with an alcoholic hydroxyl group-containing compound, a phosphoric acid ester residue-containing (meth) acrylamide composition is prepared, and at least the obtained phosphoric acid ester residue-containing ( A method for producing a phosphoric acid ester residue-containing (meth) acrylamide polymer, characterized by polymerizing a (meth) acrylamide composition. 25. The method for producing a phosphoric acid ester residue-containing (meth) acrylamide polymer according to claim 24, wherein the solvent containing no active hydrogen is represented by the following formula (14):

(Wherein R ⁴ is a hydrogen group or a methyl group, and R ⁵ and R ⁶ are each independently an alkyl group.) N, N-dialkyl (meth) acrylamide represented by A N-N-dialkyl (meth) acrylamide and a phosphoric acid ester residue-containing (meth) acrylamide composition are copolymerized using a reaction solution obtained by preparing a (meth) acrylamide And how to. The method for producing a phosphorus acid ester residue-containing (meth) acrylamide polymer according to claim 24 or 25, wherein the alcoholic hydroxyl group-containing compound is monohydric alcoholic or polyhydric alcoholic. Method. 27. The method for producing a phosphoric acid ester residue-containing (meth) acrylamide polymer according to claim 24, wherein the alcoholic hydroxyl group-containing compound is an aliphatic alcohol, an alicyclic alcohol, or an aromatic alcohol. Phenol and derivatives thereof, glycerin and derivatives thereof, fluorine-containing alcohol, polyoxyalkylene glycol, polyoxyalkylene monoalkyl ether, polyoxyalkylene ester, unsaturated alcohol copolymer, partially acetalized unsaturated alcohol polymer, And at least one selected from the group consisting of alcohol-modified or phenol-modified silicone oils. The method for producing a phosphorus acid ester residue-containing (meth) acrylamide polymer according to any one of claims 24 to 27, wherein the alcoholic hydroxyl group-containing compound is nonylphenol ethoxyethanol, octafluoropentanol, lauryl alcohol, Following formula (11):

(Wherein a to c are degrees of polymerization, respectively), polyoxypropylene glyceryl ether represented by the following formula (12):

(Wherein a to d are each the degree of polymerization), and the following formula (13):

Where R ⁵¹ is a substituted or unsubstituted alkyl group or aryl group, R ⁵² is a substituted or unsubstituted alkylene group, R ⁵³ OH is an oxyalkyl group, and n is the degree of polymerization. A method characterized by being at least one selected from the group consisting of modified silicone oils.

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