JP4763836B2 - Phosphoric acid residue-containing (meth) acrylamide-containing composition, phosphorus acid residue-containing vinyl polymer-containing composition, production method and use thereof - Google Patents

Description

  The present invention relates to a phosphoric acid residue-containing vinyl polymer-containing composition excellent in flame retardancy, insulation and transparency, a phosphoric acid residue-containing (meth) acrylamide-containing composition as a raw material thereof, and such a composition. The present invention relates to a production method and use of a polymer-containing composition.

  A polymer (vinyl polymer) of an ethylenically unsaturated bond-containing compound such as an acrylic resin is excellent in moldability, insulation, transparency, and the like, and thus is used in various fields. However, since a vinyl polymer burns easily, a flame retardant is generally added. As the flame retardant, a phosphorus-based compound not containing halogen is preferable so that not only excellent flame retardancy is imparted to the vinyl polymer, but also a toxic gas is not generated at the time of fire or recycling treatment. However, if the phosphorus compound is kneaded or applied to the vinyl polymer, the phosphorus compound may bleed out or fall off, and permanent flame retardancy can be imparted to the vinyl polymer. There wasn't.

Therefore, JP 2007-106803 (Patent Document 1) discloses the following formula (I) as a vinyl polymer having permanent flame retardancy:

(Wherein R is a hydrogen group or a methyl group) and an amine-modified product of N-monophosphonic acid (meth) acrylamide represented by the following formula (II):

(However, R is a hydrogen group or a methyl group) N, N-diphosphonic acid (meth) acrylamide modified with amines and other unsaturated compounds ((meth) acrylonitrile, (meth) acrylic acid, etc.) Has been proposed as a copolymer.

  However, it is not easy to mix N-monophosphonic acid (meth) acrylamide and amine-modified N, N-diphosphonic acid (meth) acrylamide with other unsaturated compounds, and a transparent copolymer is not always necessary. In some cases, the vinyl polymer of Patent Document 1 was not good in appearance. In addition, N-monophosphonic acid (meth) acrylamide and N, N-diphosphonic acid (meth) acrylamide have conductivity, and even if they are amine-modified, good insulation cannot be obtained. It was not suitable for applications that required insulation.

JP 2007-106803 JP

  Accordingly, an object of the present invention is to provide a phosphorus acid residue-containing vinyl polymer-containing composition that is excellent in flame retardancy, insulation, and transparency, and a phosphorus acid residue-containing (meth) acrylamide-containing composition that is a raw material thereof. And a method for producing such a polymer-containing composition and use thereof.

  As a result of intensive studies in view of the above object, the present inventor has found that (1) a composition containing (meth) acrylamide having a phosphorus acid residue and a nitrogen-containing surfactant is composed of other ethylenically unsaturated bond-containing compounds. When a transparent mixture is obtained with good compatibility and (2) the phosphoric acid residue-containing (meth) acrylamide and other ethylenically unsaturated bond-containing compound in the mixture are reacted, flame retardancy The present inventors have found that a vinyl polymer-containing composition having excellent properties, insulating properties and transparency can be obtained, and arrived at the present invention.

That is, the phosphoric acid residue-containing (meth) acrylamide-containing composition of the present invention has a (meth) acrylamide (A) having a phosphoric acid residue composed of a (poly) phosphonic acid group and / or a (poly) phosphoric acid group. ) And a nitrogen-containing surfactant (B),
The phosphorus acid residue-containing (meth) acrylamide (A) has the formula (1):

(Wherein R ¹ is a hydrogen group or a methyl group, and X ¹ and X ² are each independently a (poly) phosphonic acid group or a (poly) phosphoric acid group) N, N-substituted (meth) Acrylamide and formula (2):

(Wherein R ¹ is a hydrogen group or a methyl group, and X ³ is a (poly) phosphonic acid group or a (poly) phosphoric acid group), or any of N-substituted (meth) acrylamides represented by these or a mixture thereof And
The nitrogen-containing surfactant (B) is any one of an amine-based surfactant containing a (poly) ether group and a cationic surfactant containing a quaternary ammonium base, or a mixture thereof. And

The (poly) ether group-containing amine surfactant has the formula (3):

[However, R ² is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ³ is 2 to 2 carbon atoms. 4 linear or branched alkylene groups, R ⁴ is a — (R ^4a O) _k H group (R ^4a is a linear or branched alkylene group having 2 to 4 carbon atoms), carbon A linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a hydrogen group, and f and k are each independently 1 to 30 A first (poly) ether group-containing amine surfactant represented by formula (4):

[Wherein R ⁵ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ⁶ is — (R ^6a O) _s H group (R ^6a is a linear or branched alkylene group having 2 to 4 carbon atoms), a linear or branched alkyl group having 1 to 30 carbon atoms, 6 to 30 carbon atoms An aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a hydrogen group, R ⁷ is a linear or branched alkylene group having 1 to 6 carbon atoms, and R ⁸ is a straight chain having 2 to 4 carbon atoms. A chain or branched alkylene group, R ⁹ is a — (R ^9a O) _t H group (R ^9a is a linear or branched alkylene group having 2 to 4 carbon atoms); 30 linear or branched alkyl group, aryl group having 6 to 30 carbon atoms, arylalkyl group having 7 to 30 carbon atoms, or hydrogen group, and r, s and t are each independently 1 to 1 It is preferably any one of the second (poly) ether group-containing amine surfactants represented by the following formula: or a mixture thereof.

The cationic surfactant has the formula (5):

(However, R ¹⁰ and R ¹³ are each independently a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms; ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, and each of R ^{10 to} R ¹³ is at least selected from the group consisting of a hydroxyl group, an ester bond and an amino group. A first cationic surfactant represented by formula (6), wherein one species may be bound, Y ^- is a counter ion:


(However, R ¹⁴ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and Y ⁻ is a counter ion. ) A second cationic surfactant represented by formula (7):

(However, R ¹⁵ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ¹⁶ and R ¹⁷ are respectively Independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R ¹⁸ is a linear or branched alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, or a carbon number 7 to 30 arylene alkyl group, and each of R ^{15 to} R ¹⁸ may be bonded to at least one selected from the group consisting of a hydroxyl group, an ester bond and an amino group. Cationic surfactant and formula (8):

Wherein R ¹⁹ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. It is preferably at least one selected from the group consisting of cationic surfactants.

The N, N-substituted (meth) acrylamide has the formula (1a):

(Wherein R ¹ is a hydrogen group or a methyl group, and n and n ′ are each independently an integer of 0 to 2), N, N-di (poly) phosphonic acid (meth) acrylamide Is preferred. The N-substituted (meth) acrylamide has the formula (2a):

(Wherein R ¹ is a hydrogen group or a methyl group, and m is an integer of 0 to 2), and is preferably N-mono (poly) phosphonic acid (meth) acrylamide.

The first (poly) ether group-containing amine surfactant is represented by the formula (3a):

(Wherein R ^2a is a linear or branched alkyl group having 1 to 30 carbon atoms, and f and k are the same as those in the formula (3)). The second (poly) ether group-containing amine surfactant is represented by the formula (4a):


It is preferable that R ^5a is a linear or branched alkyl group having 1 to 30 carbon atoms, and r, s, and t are the same as those in the formula (4).

The first cationic surfactant has the formula (5a):

(Wherein R ¹⁰ and Y ⁻ are the same as in formula (5)), a trimethyl-type cationic surfactant represented by formula (5b):

(However, R ¹⁰ and Y ⁻ are the same as those in formula (5), and R ^13a is a linear or branched alkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 8 to 8 carbon atoms. A dialkyl-type cationic surfactant represented by formula (5c):

(Wherein R ¹⁰ and Y ⁻ are the same as in formula (5)), and a benzylic cationic surfactant represented by formula (5d):

(Wherein R ^10a and R ^13b are each independently a linear or branched alkyl group having 1 to 20 carbon atoms, and Y ⁻ is the same as in formula (5)). Preferably any one of the surfactants or a combination thereof.

The third cationic surfactant has the formula (7a):

(However, R ¹⁵ is the same as in formula (7)).

  The nitrogen-containing surfactant (B) is preferably blended in a molar ratio of 0.5 to 4 with respect to one phosphorus acid residue of the phosphorus acid residue-containing (meth) acrylamide (A).

The phosphorus acid residue-containing vinyl polymer-containing composition of the present invention comprises the above phosphorus acid residue-containing (meth) acrylamide-containing composition (A + B) and other ethylenically unsaturated bond-containing compounds (C )
The other ethylenically unsaturated bond-containing compound (C) includes an unsaturated compound (C-1) having at least one ethylenically unsaturated bond but no acidic group in the molecule, and an ethylenically unsaturated compound in the molecule. It is any one of unsaturated compounds (C-2) each having at least one saturated bond and an acidic group, or a mixture thereof.

The acidic group-free unsaturated compound (c-1) includes (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, dialkylaminoalkyl (meth) acrylate, N, N-dialkyl (meth) acrylamide, Styrene, styrene having at least some hydrogen groups substituted with methyl groups, divinylbenzene, fatty acid vinyl ester, vinyl halide, (meth) acrylic acid ester having at least some hydrogen groups substituted with fluorine groups, at least one And at least one selected from the group consisting of (meth) acrylic acid in which part of the hydrogen groups are substituted with fluorine groups, and vinyl containing an alkyl group in which at least some of the hydrogen groups are substituted with fluorine groups. preferable. The acidic group-containing unsaturated compound (C-2) includes tertiary butyl acrylamide sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, p-styrene sulfonic acid, butyl-4-sulfone (meth) acrylate. Acid, (meth) acrylooxybenzenesulfonic acid, (meth) acrylic acid, crotonic acid, maleic acid and its anhydride, fumaric acid, itaconic acid, hydroxyalkyl (meth) acrylate, and formula (9):

(However, R ²⁰ is a hydrogen group or a methyl group, R ²¹ is an alkylene group having 2 to 4 carbon atoms, linear or branched, and at least a part of the hydrogen groups may be substituted with chlorine groups. And x is an integer of 1 to 6), and is preferably at least one selected from the group consisting of compounds represented by:

  The mass ratio (A + B) / (C) of the phosphoric acid residue-containing (meth) acrylamide-containing composition (A + B) and the other ethylenically unsaturated bond-containing compound (C) is: 15/85) to (60/40).

  The flame retardant resin of the present invention is characterized by comprising the above-mentioned phosphorus acid residue-containing vinyl polymer-containing composition.

  The insulating resin of the present invention is characterized by comprising the above-mentioned phosphoric acid residue-containing vinyl polymer-containing composition.

  The method for producing the phosphoric acid residue-containing vinyl polymer-containing composition of the present invention comprises (meth) acrylamide, N-hydroxy (meth) acrylamide or a mixture thereof, phosphoric acid, pyrophosphoric acid, polyphosphoric acid and oxychlorination. A phosphoric acid residue-containing (meth) acrylamide (A) which is a reaction product or a hydrolyzate thereof with at least one selected from the group consisting of phosphorus is prepared, and the nitrogen-containing surfactant (B) is added to this. It is characterized by mixing and reacting the resulting composition (A + B) with the other ethylenically unsaturated bond-containing compound (C).

  As a method of reacting the composition (A + B) and the (C), it is preferable to use emulsion polymerization using an emulsifier and a polymerization initiator in an aqueous medium.

  Since the phosphoric acid residue-containing (meth) acrylamide-containing composition of the present invention contains (meth) acrylamide having a phosphoric acid residue and a nitrogen-containing surfactant, other ethylenically unsaturated bond-containing compounds and A well-miscible and transparent mixture is obtained. The phosphoric acid residue-containing vinyl polymer-containing composition of the present invention obtained by reacting a phosphoric acid residue-containing (meth) acrylamide in the mixture with another ethylenically unsaturated bond-containing compound is a flame retardant. Excellent in properties, insulation and transparency. Phosphoric acid residue-containing vinyl polymer-containing compositions having such properties are useful as flame retardant resins and insulating resins, and phosphoric acid residue-containing (meth) acrylamide-containing compositions are flame retardant. This is useful for designing a resin having excellent properties and insulation properties.

It is an infrared measurement chart of acrylamide. 2 is an infrared measurement chart of the phosphonic acid group-containing hydrolyzate of Example 1. FIG. It is an infrared measurement chart of polyoxyethylene-stearylamine. It is an infrared measurement chart of the composition of the phosphonic acid group containing hydrolyzate of Example 1, and polyoxyethylene-stearylamine. 3 is an infrared measurement chart of the phosphonic acid group-containing hydrolyzate of Example 2. It is an infrared measurement chart of the composition of the phosphonic acid group containing hydrolyzate of Example 2, and polyoxyethylene-stearylamine. 2 is an infrared measurement chart of tetradecyldimethylbenzyl-ammonium chloride. It is an infrared measurement chart of the composition of the phosphonic acid group containing hydrolyzate of Example 7, and tetradecyl dimethyl benzyl-ammonium chloride. It is an infrared measurement chart of the composition of the phosphonic acid group containing hydrolyzate of Example 8, and a tetradecyl dimethyl benzyl- ammonium chloride.

[1] Phosphorus acid residue-containing (meth) acrylamide-containing composition
(1) Phosphoric acid residue-containing (meth) acrylamide Phosphoric acid residue-containing (meth) acrylamide has the formula (1):

(Wherein R ¹ is a hydrogen group or a methyl group, and X ¹ and X ² are each independently a (poly) phosphonic acid group or a (poly) phosphoric acid group) N, N-substituted (meth) Acrylamide and formula (2):

(Wherein R ¹ is a hydrogen group or a methyl group, and X ³ is a (poly) phosphonic acid group or a (poly) phosphoric acid group) It is. In the case of a mixture, the molar ratio of N, N-substituted (meth) acrylamide to N-substituted (meth) acrylamide is preferably (50/50) or more, more preferably (60/40) or more, (70/30) The above is most preferable.

As N, N-substituted (meth) acrylamide, the formula (1a):

N, N-di (poly) phosphonic acid (meth) acrylamide represented by (wherein R ¹ is a hydrogen group or a methyl group, and n and n ′ are each independently an integer of 0 to 2) is preferable, N, N-diphosphonic acid (meth) acrylamide in which n and n ′ are 0 is more preferable.

As N-substituted (meth) acrylamide, the formula (2a):

N-mono (poly) phosphonic acid (meth) acrylamide represented by (wherein R ¹ is a hydrogen group or a methyl group, and m is an integer of 0 to 2), and m is 0. Acid (meth) acrylamide is more preferred.

The phosphorus acid residue-containing (meth) acrylamide is at least selected from the group consisting of (meth) acrylamide, N-hydroxy (meth) acrylamide or a mixture thereof, and phosphoric acid, pyrophosphoric acid, polyphosphoric acid, and phosphorus oxychloride It is obtained by reacting with one species and hydrolyzing as necessary. (Meth) acrylamide may be acrylamide, methacrylamide or a mixture thereof. The N-hydroxy (meth) acrylamide may be N-hydroxyacrylamide, N-hydroxymethacrylamide or a mixture thereof. As phosphoric acid, orthophosphoric acid, phosphoric anhydride (phosphorus pentoxide = P ₂ O ₅ ) or a mixture thereof may be used, but phosphoric anhydride is preferred. Hereinafter, the case where (meth) acrylamide and phosphoric anhydride are used as raw materials will be described.

The reaction and hydrolysis procedures and conditions are described in, for example, WO2005-080454, and thus detailed description thereof is omitted. However, when (meth) acrylamide is reacted with phosphoric anhydride and hydrolyzed, (meth) When acrylamide and phosphoric anhydride are reacted at a molar ratio of 1: 1, (meth) acrylamide is, for example, the formula (10):


(Wherein R ¹ is a hydrogen group or a methyl group), a compound in which pyrophosphate is N, N-bonded to (meth) acrylamide as an intermediate product and / or two (meta) via dipyrophosphate. ) N, N-diphosphonic acid (meth) acrylamide is obtained through a process in which an acrylamide-bound compound is formed and an intermediate product is hydrolyzed.

When (meth) acrylamide and phosphoric anhydride are reacted at a molar ratio of 2: 1, (meth) acrylamide is represented by, for example, formula (11):

As shown in (wherein R ¹ is a hydrogen group or a methyl group), N-monophosphonic acid (meth) acrylamide is obtained.

Other examples include formula (12):


(Wherein R ¹ is a hydrogen group or a methyl group, and x, x ′, x ″, y, y ′ and y ″ are each independently an integer of 0 to 2), N, N -Di (poly) phosphonic acid (meth) acrylamide and N-mono (poly) phosphonic acid (meth) acrylamide may be produced.

  When N, N-diphosphonic acid (meth) acrylamide is mainly produced, the molar ratio of phosphoric anhydride to (meth) acrylamide is preferably in the range of 0.9 to 1.2. When N-monophosphonic acid (meth) acrylamide is mainly produced, the molar ratio of phosphoric anhydride to (meth) acrylamide is preferably in the range of 0.5 to 0.8.

  Both N, N-diphosphonic acid (meth) acrylamide and N-monophosphonic acid (meth) acrylamide can be copolymerized with acrylates etc. without gelation (Journal of Chemical Society of Japan, July 2009 issue) And September issue ad column).

(2) Nitrogen-containing surfactants Nitrogen-containing surfactants are roughly classified into the following (poly) ether group-containing amine surfactants and cationic surfactants.

(i) (Poly) ether group-containing amine surfactant The following first and second (poly) ether group-containing amine surfactants are preferred as the (poly) ether group-containing amine surfactant. The first (poly) ether group-containing amine surfactant is represented by the formula (3):

[However, R ² is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ³ is 2 to 2 carbon atoms. 4 linear or branched alkylene groups, R ⁴ is a — (R ^4a O) _k H group (R ^4a is a linear or branched alkylene group having 2 to 4 carbon atoms), carbon A linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a hydrogen group, and f and k are each independently 1 to 30 It is an integer of].

R ² is preferably a linear or branched alkyl group having 10 to 25 carbon atoms. R ³ is preferably an ethylene group or a propylene group, more preferably an ethylene group. R ⁴ is preferably the above-mentioned — (R ^4a O) _k H group or hydrogen group. The above - The _{^{(R 4a O) k H R}} 4a group, ethylene group and propylene group are preferred, and more preferably an ethylene group. f and k are preferably each independently an integer of 1 to 25.

The first (poly) ether group-containing amine surfactant is represented by the formula (3a):

A compound represented by the formula (wherein R ^2a is a linear or branched alkyl group having 1 to 30 carbon atoms, and f and k are the same as those in formula (3)) is most preferable.

  The commercial products of the first (poly) ether group-containing amine surfactants are: Naimine L-201, L-202, L-207, F-215, S-202, S-204, S-210, S-215, S-220, O-205, T2-202, T2-210, T2-230 (manufactured by NOF Corporation).

The second (poly) ether group-containing amine surfactant is represented by the formula (4):

[Wherein R ⁵ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ⁶ is — (R ^6a O) _s H group (R ^6a is a linear or branched alkylene group having 2 to 4 carbon atoms), a linear or branched alkyl group having 1 to 30 carbon atoms, 6 to 30 carbon atoms An aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a hydrogen group, R ⁷ is a linear or branched alkylene group having 1 to 6 carbon atoms, and R ⁸ is a straight chain having 2 to 4 carbon atoms. A chain or branched alkylene group, R ⁹ is a — (R ^9a O) _t H group (R ^9a is a linear or branched alkylene group having 2 to 4 carbon atoms); 30 linear or branched alkyl group, aryl group having 6 to 30 carbon atoms, arylalkyl group having 7 to 30 carbon atoms, or hydrogen group, and r, s and t are each independently 1 to 1 It is an integer of 30].

R ⁵ is preferably an alkyl group having 10 to 25 carbon atoms. R ⁶ is preferably the above-mentioned — (R ^6a O) _s H group or hydrogen group. The above - The (R ^6a O) _s of H radicals R ^6a, ethylene group and propylene group are preferred, and more preferably an ethylene group. R ⁷ is preferably a propylene group. R ⁸ is preferably an ethylene group or a propylene group, more preferably an ethylene group. R ⁹ is preferably the aforementioned — (R ^9a O) _t H group or hydrogen group. The above - The (R ^9a O) _t H group R ^9a, ethylene group and propylene group are preferred, and more preferably an ethylene group. It is preferable that r, s and t are each independently an integer of 1 to 25.

The second (poly) ether group-containing amine surfactant is represented by the formula (4a):


A compound represented by the formula (wherein R ^5a is a linear or branched alkyl group having 1 to 30 carbon atoms, and r, s, and t are the same as those in formula (4)) is most preferable.

  As commercially available products of the second (poly) ether group-containing amine-based surfactant, there are Nimin DT-203, L-208 (manufactured by NOF Corporation) and the like.

(ii) Cationic surfactant The cationic surfactant contains a quaternary ammonium base. As the cationic surfactant, the following first to fourth cationic surfactants are preferable. The first cationic surfactant is of formula (5):

(However, R ¹⁰ and R ¹³ are each independently a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms; ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, and each of R ^{10 to} R ¹³ is at least selected from the group consisting of a hydroxyl group, an ester bond and an amino group. One type may be bonded, and Y ⁻ is a counter ion).

As the first cationic surfactant, the formula (5a):

(Wherein R ¹⁰ and Y ⁻ are the same as in formula (5)), a trimethyl-type cationic surfactant represented by formula (5b):

(However, R ¹⁰ and Y ⁻ are the same as those in formula (5), and R ^13a is a linear or branched alkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 8 to 8 carbon atoms. A dialkyl-type cationic surfactant represented by formula (5c):

(Wherein R ¹⁰ and Y ⁻ are the same as in formula (5)), and a benzylic cationic surfactant represented by formula (5d):

(Wherein R ^10a and R ^13b are each independently a linear or branched alkyl group having 1 to 20 carbon atoms, and Y ⁻ is the same as in formula (5)). A surfactant is preferred.

Examples of the counter ion Y ⁻ include halogen ions (such as chlorine ions), alkyl sulfate ions (such as CH ₃ SO ₄ ^— ), alkyl or aryl sulfonate ions, alkyl sulfite ions, and alkyl phosphate ions.

Commercially available trimethyl-type cationic surfactants include Nissan Cation BB, FB, FB-500, PB-40R, PB-300, ABT2-500, AB, AB-600, VB- M2 flakes, VB-F (manufactured by NOF Corporation), etc. Examples of commercially available dialkyl type cationic surfactants include Nissan Cations 2-DB-500E, 2-DB-800E, 2ABT, 2-OLR (above NOF Corporation). Examples of commercially available benzyl type cationic surfactants include Nissan Cation F ₂ -40R, F ₂ -50R, M ₂ -100R (manufactured by NOF Corporation) and the like. Examples of commercially available hydroxy ester type cationic surfactants include Nissan Cation EQ-01D (manufactured by NOF Corporation).

The second cationic surfactant is of formula (6):


(However, R ¹⁴ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and Y ⁻ is a counter ion. ). Y ^- is be the same as described above. As a commercial product of the second cationic surfactant, Nissan Cation AR-4 (manufactured by NOF Corporation) and the like can be mentioned.

The third cationic surfactant has the formula (7):

(However, R ¹⁵ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ¹⁶ and R ¹⁷ are respectively Independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R ¹⁸ is a linear or branched alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, or a carbon number 7 to 30 arylene alkyl groups, and each of R ^{15 to} R ¹⁸ may be bound to at least one selected from the group consisting of a hydroxyl group, an ester bond and an amino group.

As the third cationic surfactant, the formula (7a):

A compound represented by the formula (wherein R ¹⁵ is the same as in formula (7)) is most preferred.

  Nissan Anon BF, BL, BL-SF, BDL-SF, BDC-SF, BDF-SF, BDF-R (Nippon Oil Co., Ltd.) Manufactured) and the like.

The fourth cationic surfactant has the formula (8):

(Wherein R ¹⁹ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms). As commercial products of the fourth cationic surfactant, Nissan Anon GLM-R, GLM-R-LV (manufactured by NOF CORPORATION) and the like can be mentioned.

(3) Mixing ratio Regarding the mixing ratio of phosphorus acid residue-containing (meth) acrylamide and nitrogen-containing surfactant, one phosphorus acid residue of phosphorus acid residue-containing (meth) acrylamide (phosphorus acid residue) It is preferable that the nitrogen-containing surfactant is blended in a molar ratio of 0.5 to 4 with respect to the formulas (1a) and (2a)). Specifically, N, N-substituted (meth) acrylamide has two phosphoric acid residues per molecule (the total number of acidic hydroxyl groups is 4 or more). As a mol%, the ratio of the nitrogen-containing surfactant is preferably 100 to 800 mol%. Since N-substituted (meth) acrylamide has one phosphoric acid residue per molecule, N-substituted (meth) acrylamide is 100 mol%, and the ratio of nitrogen-containing surfactant is 50 to 400 mol%. Is preferred. When the blending ratio of the nitrogen-containing surfactant to one phosphorus acid residue is less than 0.5 molar ratio, the compatibility with other ethylenically unsaturated bond-containing compounds is deteriorated, and the transparency of the vinyl polymer is deteriorated. . On the other hand, even if this ratio exceeds 4 molar ratio, the effect of improving compatibility is saturated. The mixing ratio is more preferably 1 to 3 molar ratio, and most preferably 1 to 2 molar ratio.

(4) Preparation Method A method for preparing a phosphoric acid residue-containing (meth) acrylamide-containing composition will be described. Phosphorus acid residue-containing (meth) acrylamide is liquid at room temperature, so if the nitrogen-containing surfactant is liquid at room temperature, mix phosphorous acid residue-containing (meth) acrylamide with nitrogen-containing surfactant Can be prepared. If necessary, it may be heated or mixed in a solvent. The heating temperature is preferably about 50 ° C to about 70 ° C.

  Phosphoric acid residue-containing vinyl polymer by copolymerization with other ethylenically unsaturated bond-containing compounds described later, that is, phosphoric acid residue-containing (meth) acrylamide or its nitrogen-containing surfactant-modified product (described later) When the ethylenically unsaturated bond-containing compound used for preparing the containing composition is liquid, a phosphoric acid residue-containing (meth) acrylamide-containing composition may be prepared using this as a solvent.

(5) Structure of Phosphoric Acid Residue-Containing (Meth) acrylamide-Containing Composition The phosphoric acid residue-containing (meth) acrylamide-containing composition is very uniform and excellent in transparency. The phosphoric acid residue-containing (meth) acrylamide-containing composition may be (i) a simple mixture of a phosphoric acid residue-containing (meth) acrylamide and a nitrogen-containing surfactant, or (ii) a phosphoric acid. A modified product in which the amino group of the nitrogen-containing surfactant reacts with at least a part of the hydroxyl group in the phosphorus acid residue of the residue-containing (meth) acrylamide may be (iii) these (i ) And (ii). The modified product (ii) is a product in which a phosphorus acid residue-containing (meth) acrylamide and a nitrogen-containing surfactant are subjected to an acid / base reaction to form a quaternary ammonium salt. The degree of modification by the nitrogen-containing surfactant (the degree to which the hydrogen atom of the hydroxyl group in the phosphoric acid residue is replaced by the nitrogen-containing surfactant) depends on the (meth) acrylamide containing the phosphorus acid residue and the nitrogen-containing surfactant. It can be changed depending on the blending ratio and the like.

Hereinafter, the structure of the modified product (ii) will be described. When N, N-di (poly) phosphonic acid (meth) acrylamide represented by the formula (1a) is used, the resulting (poly) phosphonic acid group-containing (meth) acrylamide modified product is represented by the formula (1b):

[Wherein R ¹ , n and n ′ are the same as those in the formula (1), Z is independently an —OH group or —O ^{− +} NR ₄ unit ( ⁺ NR ₄ is a cationized nitrogen-containing surfactant) And at least one of Z is —O ^{− +} NR ₄ units]. When N-mono (poly) phosphonic acid (meth) acrylamide represented by the formula (2a) is used, the resulting (poly) phosphonic acid group-containing (meth) acrylamide modified product is represented by the formula (2b):

Wherein R ¹ and m are the same as in formula (2), Z is the same as in formula (1b), and at least one of Z is —O ^{− +} NR ₄ units. Have

When the first (poly) ether group-containing amine surfactant represented by the formula (3) is used, the cationized nitrogen-containing surfactant ⁺ NR ₄ is represented by the formula (3b):

(Wherein R ^{2 to} R ⁴ and f are the same as those in the formula (3)), when the second (poly) ether group-containing amine surfactant shown in the formula (4) is used, the formula ( 4b):

(Wherein R ^{5 to} R ⁹ and r are the same as in formula (4)) or formula (4c):


(Wherein R ^{5 to} R ⁹ and r are the same as those in formula (4)), when the first cationic surfactant shown in formula (5) is used, formula (5e):

(Wherein R ^{10 to} R ¹³ are the same as in formula (5)), and when the second cationic surfactant shown in formula (6) is used, formula (6a):


(Where R ¹⁴ is the same as formula (6)), and when the third cationic surfactant shown in formula (7) is used, formula (7b):


(Wherein R ^{15 to} R ¹⁸ are the same as those in formula (7)), and when the fourth cationic surfactant shown in formula (8) is used, formula (8a):

(Wherein R ¹⁹ is the same as in formula (8)).

[2] Phosphoric acid residue-containing vinyl polymer-containing composition Phosphoric acid residue-containing vinyl polymer-containing composition includes the above-mentioned phosphoric acid residue-containing (meth) acrylamide-containing composition and other ethylene And a copolymer of a phosphoric acid residue-containing (meth) acrylamide and another ethylenically unsaturated bond-containing compound, and a nitrogen-containing surfactant. The phosphorus acid residue-containing vinyl polymer-containing composition comprises (i) a copolymer of phosphorus acid residue-containing (meth) acrylamide and other ethylenically unsaturated bond-containing compounds, a nitrogen-containing surfactant, Or (ii) a copolymer of the above-mentioned phosphorus acid residue-containing (meth) acrylamide modified with a nitrogen-containing surfactant and another ethylenically unsaturated bond-containing compound. Or (iii) a mixture of these (i) and (ii). When the phosphoric acid residue-containing (meth) acrylamide-containing composition is a modified product with a nitrogen-containing surfactant, the phosphoric acid residue-containing (meth) acrylamide and the nitrogen-containing surfactant are electrically coupled to each other. Since a quaternary ammonium salt is formed, the nitrogen-containing surfactant does not desorb even when the phosphoric acid residue-containing (meth) acrylamide-containing composition reacts with other ethylenically unsaturated bond-containing compounds. The copolymer of ii) is formed.

  Other ethylenically unsaturated bond-containing compounds are appropriately selected depending on the application, but the following two groups (1) unsaturated compounds having at least one ethylenically unsaturated bond in the molecule but no acidic group, And (2) It can be roughly classified into unsaturated compounds each having at least one ethylenically unsaturated bond and acidic group in the molecule.

(1) Unsaturated compounds that do not contain acidic groups As unsaturated compounds that do not contain acidic groups, all unsaturated compounds that are not gaseous at room temperature and have at least one ethylenically unsaturated bond in the molecule are targeted. (Meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide, dialkylaminoalkyl (meth) acrylate, N, N-dialkyl (meth) acrylamide, substituted or unsubstituted styrene, divinylbenzene, fatty acid vinyl ester (acetic acid Vinyl), vinyl halides, (meth) acrylic acid esters in which at least some hydrogen groups are substituted with fluorine groups, (meth) acrylic acids in which at least some hydrogen groups are substituted with fluorine groups, at least some And vinyl containing an alkyl group in which the hydrogen group is substituted with a fluorine group. These may be used alone or in combination of two or more.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meta ) Alkyl (meth) acrylates such as acrylate; ethylene glycol di (meth) acrylate; trimethylolpropane tri (meth) acrylate and the like.

  As N, N-dialkyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide is preferable. Examples of the dialkylaminoalkyl (meth) acrylate include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.

  Examples of the substituted styrene include styrene in which at least a part of hydrogen groups are substituted with methyl groups, and specific examples include α-methylstyrene and vinyltoluene. Examples of the vinyl halide include vinyl chloride, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene and the like.

  As (meth) acrylic acid esters in which at least some of the hydrogen groups are substituted with fluorine groups, fluoro such as 2,2,2-trifluoroethyl (meth) acrylate and tertiary butyl-α- (trifluoromethyl) acrylate (Meth) acrylic acid ester which has hydrofluoroalkyl groups, such as (meth) acrylic acid ester, or a perfluoroalkyl group is mentioned. Examples of (meth) acrylic acid in which at least a part of hydrogen groups are substituted with fluorine groups include hydrofluoroalkyl group-containing (meth) acrylic acid such as α- (trifluoromethyl) acrylic acid. Examples of the vinyl containing an alkyl group in which at least a part of the hydrogen groups are substituted with a fluorine group include perfluoroalkyl group-containing vinyls such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene. It is done.

(2) Unsaturated compound containing acidic group The acidic group is not particularly limited, and examples thereof include a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, and an alcoholic hydroxyl group. Examples of the skeleton having an ethylenically unsaturated bond include a (meth) acrylate skeleton, a (meth) allyl ester skeleton, a substituted or unsubstituted unsaturated aliphatic hydrocarbon skeleton, and an aromatic hydrocarbon skeleton substituted with an unsaturated group. Can be mentioned.

(i) Unsaturated monomer containing sulfonic acid group Examples of the unsaturated monomer containing a sulfonic acid group include those described in JP-A-2004-179154. Specifically, tertiary butyl acrylamide sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, p-styrene sulfonic acid, (meth) acrylic acid butyl-4-sulfonic acid, (meth) acrylooxybenzene Sulfonic acid and the like are preferable.

(ii) Unsaturated monomer containing a carboxylic acid group Examples of unsaturated monomers containing a carboxylic acid group include (meth) acrylic acid, crotonic acid, maleic acid and anhydrides thereof, fumaric acid, Itaconic acid and the like can be mentioned.

(iii) Unsaturated monomer having phosphoric acid group As the phosphoric acid group-containing unsaturated monomer, the formula (9):

(However, R ²⁰ is a hydrogen group or a methyl group, R ²¹ is an alkylene group having 2 to 4 carbon atoms, linear or branched, and at least a part of the hydrogen groups may be substituted with chlorine groups. And x is an integer of 1 to 6). As a commercial product of the phosphate group-containing unsaturated monomer represented by the general formula (9), there is a trade name “Phosmer (registered trademark)” manufactured by Unichemical Co., Ltd.

(iv) Unsaturated monomer containing alcoholic hydroxyl group Unsaturated monomer containing alcoholic hydroxyl group includes hexamethylenediol di (meth) acrylate; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meta ) Acrylate, 3-hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, and the like.

(3) Use ratio of each unsaturated compound Mass ratio (A + B) of phosphoric acid residue-containing (meth) acrylamide-containing composition (A + B) to other ethylenically unsaturated bond-containing compound (C) ) / (C) is not particularly limited, and may be appropriately selected according to desired physical properties. This mass ratio is preferably (15/85) to (60/40), more preferably (20/80) to (60/40).

(4) Preparation method The phosphoric acid residue-containing vinyl polymer-containing composition is obtained by reacting the phosphoric acid residue-containing (meth) acrylamide-containing composition with another ethylenically unsaturated bond-containing compound. Prepare by. This reaction is a copolymerization reaction between a phosphorus acid residue-containing (meth) acrylamide or its nitrogen-containing surfactant-modified product and another ethylenically unsaturated bond-containing compound. The copolymerization method may be any of known emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and radiation polymerization, but emulsion polymerization is preferred. The degree of polymerization can be appropriately changed according to the application. As described above, since the phosphoric acid residue-containing (meth) acrylamide-containing composition is very uniform, the phosphoric acid residue-containing vinyl polymer-containing composition obtained using this is very Uniform and excellent in transparency. As described above, when other ethylenically unsaturated bond-containing compound is used as a solvent when preparing a phosphoric acid residue-containing (meth) acrylamide-containing composition, a phosphoric acid residue-containing (meth) acrylamide-containing composition Subsequent to the preparation, it is preferred to carry out copolymerization by adding a polymerization initiator.

(i) Emulsion polymerization Emulsion polymerization is carried out by radical polymerization in an aqueous medium using an emulsifier and a polymerization initiator. Known emulsifiers can be used. Examples of the emulsifier include alkylene oxide adducts of compounds having a phenolic hydroxyl group such as phenol, cresol, butylphenol, nonylphenol, and dodecylphenol, and alkylbenzene sulfonates such as dodecylbenzene sulfonate. Polyoxyethylene nonyl phenol ether and dodecylbenzene sulfonate are preferable. The amount of the emulsifier used is 3% by mass or more, preferably 5-30% by mass, based on the total amount of unsaturated monomers used for polymerization in the production of the aqueous resin emulsion.

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 and tert-butylperoxy pivalate, and hydrogen peroxide.

  The polymerization procedure is described. Polymerization to be added after degassing the above-mentioned phosphoric acid residue-containing (meth) acrylamide-containing composition, other ethylenically unsaturated bond-containing compound, emulsifier and water in a reactor equipped with a stirrer and reflux condenser The temperature is raised to 40 ° C to 70 ° C, which is the decomposition temperature of the initiator. A preferable polymerization temperature is 50 ° C to 70 ° C. A polymerization initiator is added immediately after reaching the predetermined temperature. 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 10 to 24 hours. 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 emulsion polymerization, various additives and auxiliaries generally used in the conventional emulsion polymerization operations, such as chain transfer agents and chelating agents, can be used.

  The polymerization solution preferably has an initial solid content concentration of 10 to 40% by mass of unsaturated raw materials (phosphorus acid residue-containing (meth) acrylamide-containing composition and other ethylenically unsaturated bond-containing compounds). The total amount of the polymerization initiator used is preferably 0.1 to 5 by mass ratio when the unsaturated raw material is 100.

  After cooling the obtained polymer emulsion, it is mixed in a large amount of a poor solvent to separate the vinyl polymer and filtered using a wire mesh or the like to recover the vinyl polymer. The vinyl polymer is preferably washed using a poor solvent. Methanol etc. are mentioned as a poor solvent.

(ii) Suspension polymerization Suspension polymerization may be the same as emulsion polymerization except that radical polymerization using the above polymerization initiator is performed in an aqueous medium without using an emulsifier. However, it is preferable to use a suspending agent made of a water-soluble polymer such as polyvinyl alcohol for suspension polymerization.

(iii) Solution polymerization Solution polymerization is carried out without using an emulsifier in a common solvent in which both the phosphoric acid residue-containing (meth) acrylamide-containing composition and other ethylenically unsaturated bond-containing compounds are dissolved. It may be the same as emulsion polymerization except that radical polymerization using a polymerization initiator is performed.

(iv) Bulk Polymerization Bulk polymerization may be the same as emulsion polymerization except that radical polymerization using the polymerization initiator is performed without using a solvent and an emulsifier.

(v) Radiation polymerization The radiation is preferably ultraviolet rays. A method for producing a resin film by ultraviolet polymerization is a composition containing the above-mentioned phosphoric acid residue-containing (meth) acrylamide-containing composition, another ethylenically unsaturated bond-containing compound and a photopolymerization initiator (photosensitizer). Is cast on a plate coated with a material (fluorine polymer or the like) to which it does not adhere, covered with an ultraviolet transmissive plate, and then polymerized by irradiation with ultraviolet rays. Examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, and benzophenone. The amount of the photopolymerization initiator used is preferably in the range of 0.005 to 10% by mass with respect to the total mass of the phosphoric acid residue-containing (meth) acrylamide-containing composition and other ethylenically unsaturated bond-containing compounds. The ultraviolet irradiation intensity is preferably 5 to 150 mW / cm ² and the irradiation time is preferably 1 to 15 minutes.

(5) Properties and uses The phosphorus acid residue-containing vinyl polymer-containing composition has excellent flame retardancy, insulation, transparency, adhesiveness and solvent resistance. Specifically, the phosphoric acid residue-containing vinyl-based polymer-containing composition is placed at the tip of a gas burner and is carbonized even when exposed to a flame for 2 seconds or more, or has self-digestibility even when ignited. Its surface resistivity is 1 × 10 ¹⁴ Ω or more under conditions of relative humidity of 50 to 75% / room temperature. Moreover, transparency is high and there is no unevenness in refractive index. Therefore, the phosphorus acid residue-containing vinyl polymer-containing composition is useful as a flame retardant resin and an insulating resin. The phosphorus acid residue-containing vinyl polymer-containing composition can be molded into an arbitrary shape using injection molding, extrusion molding, press molding, or the like.

  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
(1) Preparation of phosphonic acid group-containing acrylamide
In the same manner as in Example 4 of WO2005-080454, a hydrolyzate having a phosphonic acid group was prepared using acrylamide and phosphoric anhydride. A poor solvent was added to the reaction solution containing the hydrolyzate, and the hydrolyzate separated by filtration was dried by heating at 100 ° C. for 1 hour.

(2) Measurement of Acid Value The acid value of the phosphonic acid group-containing hydrolyzate was measured using 1N KOH, and was 892 mg / g (theoretical acid value of N, N-diphosphonic acid acrylamide: 969.7 mg / g, theoretical acid value of N-monophosphonic acid acrylamide: 741.7 mg / g).

(3) Elemental analysis The nitrogen content of the hydrolyzate containing phosphonic acid groups was measured by the CHN coder method, the phosphorus content was measured by ICP emission spectroscopy, and the mass ratio of nitrogen and phosphorus was determined. 4.4, which is the same as the theoretical ratio in N, N-diphosphonic acid acrylamide.

(4) Infrared spectrum measurement About the acrylamide and the phosphonic acid group containing hydrolyzate, the infrared spectrum measurement was performed using the Fourier-transform infrared spectroscopy apparatus (form: IRPrestige-21, Shimadzu Corporation make). The results are shown in FIGS. In acrylamide, sharp peaks due to NH bonds were detected in the vicinity of 3,160 cm ⁻¹ and 3,340 cm ⁻¹ (FIG. 1). On the other hand, in the phosphonic acid group-containing hydrolyzate, peaks due to NH bonds were only slightly detected in the vicinity of 3,210 cm ⁻¹ and 3,360 cm ⁻¹ (FIG. 2). In the phosphonic acid group-containing hydrolyzate, a broad peak due to the phosphonic acid group was detected in the range of 700 to 1,300 cm ^-1 with 1,010 cm ^-1 as the apex (FIG. 2). From these facts, it was confirmed that two phosphonic acid groups were introduced into most acrylamide nitrogen atoms.

  From the results of acid value measurement, elemental analysis and infrared spectrum measurement, the phosphonic acid group-containing hydrolyzate contains N, N-diphosphonic acid acrylamide and N-monophosphonic acid acrylamide, and N, N-diphosphonic acid acrylamide is the main. It was confirmed that the composition was a component.

(5) Preparation of composition Phosphonic acid group-containing hydrolyzate and polyoxyethylene-stearylamine (trade name “Nymene S-210”, purity 100%, manufactured by NOF Corporation, f and k in the above formula (3a) 10 and molecular weight 709) are mixed so that the molar ratio is 1: 3. The phosphonic acid group-containing hydrolyzate is composed of 100 mol% of N, N-diphosphonic acid acrylamide (molecular weight 231). The number of moles was calculated] and stirred at 60 ° C. for 30 minutes to obtain a transparent composition.

(6) Infrared spectrum measurement The infrared spectrum measurement was performed about polyoxyethylene-stearylamine and the said composition. The results are shown in FIGS. In polyoxyethylene-stearylamine, a peak due to the ether chain was detected in the vicinity of 1,123 cm ^-1 and a peak due to the stearyl group was detected in the vicinity of 2,855 cm ^-1 and 2,924 cm ^-1 (Fig. 3). In addition to these peaks, a peak due to a carbon-oxygen double bond and / or a carbon-carbon double bond of N, N-diphosphonic acid acrylamide was detected in the vicinity of 1,678 cm ⁻¹ . However, in the composition, a peak near 1,010 cm ^{−1 of the} phosphonic acid group (see FIG. 2) was not detected, and this peak is considered to shift and overlap with the peak of the ether chain (near 1,123 cm ⁻¹ ). . From this peak shift, the composition is considered to be a modified product in which the phosphonic acid group of the phosphonic acid group-containing hydrolyzate and the amino group of polyoxyethylene-stearylamine are subjected to an acid / base reaction.

Example 2
(1) Preparation of phosphonic acid group-containing acrylamide
A hydrolyzate having a phosphonic acid group was prepared using acrylamide and phosphoric anhydride in the same manner as in Example 1 of WO2005-080454. A poor solvent was added to the reaction solution containing the hydrolyzate, and the hydrolyzate separated by a separatory funnel was dried by heating at 100 ° C. for 1 hour.

(2) Measurement of acid value The acid value of the phosphonic acid group-containing hydrolyzate was measured using 1N KOH. As a result, it was 674 mg / g. The acid value was confirmed to be 741.7 mg / g).

(3) Infrared spectrum measurement About the phosphonic acid group containing hydrolyzate, the infrared spectrum measurement was performed using the Fourier-transform infrared spectrometer. The results are shown in FIG. A peak due to NH bonding was detected in the vicinity of 3,210 cm ^-1 and 3,350 cm ^-1 , and a wide range of peaks due to phosphonic acid groups were detected in the range of 700 to 1,300 cm ^-1 with the peak at 984 cm ^-1 . From these facts, it was confirmed that the main component of the hydrolyzate was N-monophosphonic acid acrylamide.

(4) Preparation of composition Phosphonic acid group-containing hydrolyzate and polyoxyethylene-stearylamine (Nymine S-210, purity 100%) were mixed at a molar ratio of 1: 1.5 [phosphonic acid group-containing The number of moles was calculated on the assumption that the hydrolyzate was composed of 100 mol% of N-monophosphonic acid acrylamide.] When the mixture was stirred at 60 ° C. for 30 minutes, a transparent composition was obtained.

(5) Infrared spectrum measurement The above composition was subjected to infrared spectrum measurement. The results are shown in FIG. In the composition, carbon-oxygen of N-monophosphonic acid acrylamide is located near 1,680 cm ^{-1 in} addition to the peak due to ether chain (near 1,123 cm ^-1 ) and the peak due to stearyl group (near 2,855 cm ^-1 and 2,924 cm ^-1 ). Peaks due to double bonds and / or carbon-carbon double bonds were detected. However, even in this composition, a peak near 984 cm ^{−1 of the} phosphonic acid group (see FIG. 5) was not detected, and this peak is considered to shift and overlap with the peak of the ether chain (near 1,123 cm ⁻¹ ). It is done. From this peak shift, the composition is considered to be a modified product in which the phosphonic acid group of the phosphonic acid group-containing hydrolyzate and the amino group of polyoxyethylene-stearylamine are subjected to an acid / base reaction.

Performs infrared spectrum measured five times, and the peak intensity I ₁₁₂₃ of 1,123 cm ^-1 attributed to an ether chain, a carbon - oxygen double bonds and / or carbon - peak of 1,680Cm ^-1 attributable to carbon double bond The ratio I ₁₁₂₃ / I ₁₆₈₀ to the strength I ₁₆₈₀ was determined for each of the compositions of Examples 1 and 2, and averaged to be 4.9 for the composition of Example 1 and 2.5 for the composition of Example 2. there were. Further, the ratio I ₂₉₂₄ / I ₁₆₈₀ of the peak intensity I ₂₉₂₄ attributed to the stearyl group to 2,924 cm ⁻¹ and the peak intensity I ₁₆₈₀ was determined for each of the compositions of Examples 1 and 2, and averaged. The composition of Example 1 was 6.4, and the composition of Example 2 was 3.2. From these facts, it was found that the composition of Example 1 contained about twice as much polyoxyethylene-stearylamine as the composition of Example 2, which was consistent with the charging ratio.

Example 3
A composition was prepared in the same manner as in Example 1 except that Naimine S-204 (manufactured by NOF Corporation, total of f and k in the above formula (3a): 4, molecular weight 445) was used as polyoxyethylene-stearylamine. did.

Example 4
A composition was prepared in the same manner as in Example 1 except that Naimine S-202 (manufactured by NOF Corporation, total of f and k in formula (3a): 2, molecular weight 357) was used as polyoxyethylene-stearylamine. did.

Example 5
A composition was prepared in the same manner as in Example 2, except that Naimine S-204 (manufactured by NOF Corporation) was used as polyoxyethylene-stearylamine.

Example 6
A composition was prepared in the same manner as in Example 2 except that Naimine S-202 (manufactured by NOF Corporation) was used as polyoxyethylene-stearylamine.

Example 7
In the same manner as in Example 1, a phosphonic acid group-containing hydrolyzate containing N, N-diphosphonic acid acrylamide as a main component was prepared. Tetradecyldimethylbenzyl-ammonium chloride (trade name “Nissan Cation M ₂ -100R”, manufactured by NOF Corporation) is added to the hydrolyzate containing phosphonic acid groups so that the molar ratio is 1: 3 (phosphonic acid). The group-containing hydrolyzate was calculated as the number of moles of N, N-diphosphonic acid acrylamide as 100 mol%), placed in 2-propyl alcohol (solid content concentration 10% by mass), and stirred at room temperature for 30 minutes. The obtained reaction solution was heat-dried at 100 ° C. for 1 hour to obtain a transparent composition.

Infrared spectra were measured for tetradecyldimethylbenzyl-ammonium chloride and the above composition. The results are shown in FIGS. Tetradecyldimethylbenzylammonium - In Ann monitor skeleton ride, 720 cm ^-1 and near peaks attributable to the benzene ring in the vicinity of 1,610 cm ^-1 is detected, the tetradecyl group and a methyl group in the vicinity of 2,853 cm ^-1 and around 2,922 cm ^-1 An attributed peak was detected, and peaks due to NH bonds were detected in the vicinity of 3,380 cm ⁻¹ and 3,450 cm ⁻¹ (FIG. 7). In the above composition, in addition to these peaks, a peak due to a carbon-oxygen double bond and / or carbon-carbon double bond of N, N-diphosphonic acid acrylamide was detected in the vicinity of 1,676 cm ⁻¹ , and 995 cm ⁻¹ was detected. A broad peak due to the phosphonic acid group was detected in the range of 800 to 1,300 cm ^{-1 with} the peak at (Fig. 8). Peaks due to NH bonds shift from around 3,380 cm ^{-1 and} around 3,450 cm ^-1 (see Fig. 7) to around 3,340 cm ^{-1 and} around 3,430 cm ^-1 , and the peak of the phosphonic acid group is 1,010 cm ^-1 (Fig. 2 since the reference) is shifted to 995 cm ^-1, composition, phosphonic acid group and tetradecyl dimethyl benzyl phosphonic acid group-containing hydrolyzate - and amino groups Ann monitor skeleton ride is acid-base reaction denaturation It is considered a thing.

Example 8
In the same manner as in Example 2, a phosphonic acid group-containing hydrolyzate containing N-monophosphonic acid acrylamide as a main component was prepared. The phosphonic acid group-containing hydrolyzate and tetradecyldimethylbenzyl-ammonium chloride (Nissan cation M ₂ -100R, molecular weight 366) are mixed so that the molar ratio is 1: 1.5 (phosphonic acid group-containing hydrolyzate is N- The number of moles was calculated as consisting of 100 mol% monophosphonic acid acrylamide), placed in 2-propyl alcohol (solid content concentration 10 mass%), and stirred at room temperature for 30 minutes. The obtained reaction solution was heat-dried at 60 ° C. for 15 hours to obtain a transparent composition.

The infrared spectrum measurement was performed about the said composition. The results are shown in FIG. In addition to the peaks attributed to the benzene ring (near 720 cm ^-1 ) and the peaks attributed to the tetradecyl group and methyl group (near 2,853 cm ^-1 and 2,922 cm ^-1 ), N-monophosphonic acid acrylamide near 1,678 cm ^-1 The peak due to the carbon-oxygen double bond and / or the carbon-carbon double bond was detected. Also the 997 cm ^-1 as a vertex, within the range of 800~1,300 cm ^-1, broad peak due to the phosphonic acid group is detected. Since the peak of the phosphonic acid group is shifted from 984 cm ⁻¹ (FIG. 5) to 997 cm ⁻¹ , the composition contains the phosphonic acid group and tetradecyldimethylbenzyl-ammonium of the phosphonic acid group-containing hydrolyzate. It is considered to be a modified product obtained by an acid / base reaction with the amino group of chloride.

Infrared spectrum measurement was performed 5 times, and the peak intensity I ₂₉₂₄ of 2,924 cm ⁻¹ attributed to the tetradecyl group and the peak intensity I ₁₆₈₀ attributed to the carbon-oxygen double bond and / or carbon-carbon double bond The ratio I ₂₉₂₄ / I ₁₆₈₀ was determined for each of the compositions of Examples 7 and 8, and averaged to be 12.1 for the composition of Example 7 and 7.6 for the composition of Example 8. From these facts, it was found that the composition of Example 7 contained 1.6 times as much polyoxyethylene-stearylamine as the composition of Example 8, and almost coincided with the charging ratio.

Comparative Example 1
A composition was prepared in the same manner as in Example 1 except that stearylamine was used instead of polyoxyethylene-stearylamine.

Comparative Example 2
A composition was prepared in the same manner as in Example 1 except that oleylamine was used instead of polyoxyethylene-stearylamine.

Comparative Example 3
A composition was prepared in the same manner as in Example 2 except that stearylamine was used instead of polyoxyethylene-stearylamine.

Comparative Example 4
A composition was prepared in the same manner as in Example 2 except that oleylamine was used instead of polyoxyethylene-stearylamine.

Compatibility Evaluation The compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 4, and each of styrene monomer, methyl methacrylate, butyl acrylate and 2-ethylhexyl acrylate were mixed in equal mass, stirred, and then visually observed. Thus, the compatibility was evaluated. Compatibility was determined according to the following criteria. The results are shown in Table 1.
A: A transparent mixture was obtained at room temperature.
○: When heated at 60 ° C., a transparent mixture was obtained.
X: Only a cloudy mixture was obtained.

Table 1 (continued)

Table 1 (continued)

Notes: (1) A composition based on N, N-diphosphonic acid acrylamide.
(2) Polyoxyethylene-stearylamine (trade name “Naymin S-210”, manufactured by NOF Corporation).
(3) A composition mainly composed of N-monophosphonic acid acrylamide.
(4) Polyoxyethylene-stearylamine (trade name “Naimine S-204”, manufactured by NOF Corporation).
(5) Polyoxyethylene-stearylamine (trade name “Naimine S-202”, manufactured by NOF Corporation).
(6) Tetradecyldimethylbenzyl-ammonium chloride (trade name “Nissan Cation M ₂ -100R”, manufactured by NOF Corporation).
(7) Stearylamine
(8) Oleylamine

  From Table 1, it was found that all the compositions of Examples 1 to 8 had excellent compatibility with the styrene monomer and the alkyl acrylate. On the other hand, in Comparative Examples 1-4, since the surfactant which does not have an oxyalkylene group or a cationic group was used, compared with Examples 1-8, it became compatible with a styrene monomer and an alkyl acrylate. It was inferior.

Example 9
In an automatic synthesis reactor having a reflux condenser, a catalyst inlet, etc., 20 parts by mass of a phosphonic acid group-containing acrylamide-containing composition (modified product) prepared in Example 1, 20 parts by mass of methyl methacrylate, and 60 parts by mass of ion-exchanged water. The mixture was stirred while introducing nitrogen gas, heated to 60 ° C., and 10% by mass of polyoxyethylene nonylphenol ether and 100% by mass of the total of the phosphonic acid group-containing acrylamide-containing composition and methyl methacrylate and 4% by weight of ammonium persulfate was added. Thereafter, emulsion polymerization was carried out while maintaining at 60 to 65 ° C. for 22 hours to obtain an emulsion containing a vinyl polymer formed by copolymerizing a phosphonic acid group-containing acrylamide-containing composition (modified product) and methyl methacrylate. Cool the emulsion, add 5 parts by weight of methanol to the emulsion, stir, filter using a wire mesh, collect the solids, wash with ion-exchanged water, and dry at 60 ° C for 15 hours. By doing so, a vinyl polymer was prepared.

Example 10
A vinyl polymer was prepared in the same manner as in Example 9, except that the blending ratios of the phosphonic acid group-containing acrylamide-containing composition and methyl methacrylate were 13.3 parts by mass and 26.7 parts by mass, respectively.

Example 11
In the automatic synthesis reaction apparatus, 15 parts by mass of the phosphonic acid group-containing acrylamide-containing composition prepared in Example 2, 15 parts by mass of methyl methacrylate, and 70 parts by mass of ion-exchanged water were added, and the addition amount of ammonium persulfate was 5 masses. %, A vinyl polymer was prepared in the same manner as in Example 9, except that The phosphorus content (measured in accordance with JIS K0102) of this vinyl polymer was 0.97% by mass (theoretical value: 1.3% by mass).

Example 12
A vinyl polymer was prepared in the same manner as in Example 11 except that the blending ratios of the phosphonic acid group-containing acrylamide-containing composition and methyl methacrylate were 10 parts by mass and 20 parts by mass, respectively. The phosphorus content of this vinyl polymer was 0.75% by mass (theoretical value: 0.86% by mass).

Example 13
A vinyl polymer was prepared in the same manner as in Example 11 except that the blending ratios of the phosphonic acid group-containing acrylamide-containing composition and methyl methacrylate were 6 parts by mass and 24 parts by mass, respectively. The phosphorus content of this vinyl polymer was 0.59% by mass (theoretical value: 0.52% by mass).

Comparative Example 6
A vinyl polymer was prepared in the same manner as in Example 9 except that the blending ratios of the phosphonic acid group-containing acrylamide-containing composition and methyl methacrylate were 5.7 parts by mass and 34.3 parts by mass, respectively.

Comparative Example 7
A vinyl polymer was prepared in the same manner as in Example 11 except that the blending ratios of the phosphonic acid group-containing acrylamide-containing composition and methyl methacrylate were 4.3 parts by mass and 25.7 parts by mass, respectively. The phosphorus content of this vinyl polymer was 0.43% by mass (theoretical value: 0.37% by mass).

  For the vinyl polymers obtained in Examples 9 to 13 and Comparative Examples 6 and 7, flame retardancy and transparency were evaluated by the following methods. The results are shown in Table 2.

(1) Flame retardancy A vinyl polymer was placed at the tip of a gas burner, exposed to flame for 2 seconds, and self-extinguishing was examined to evaluate flame retardancy (number of specimens: 3). Self-extinguishing properties were determined according to the following criteria.
○: Self-extinguishing
X: There was no self-extinguishing property.

(2) Transparency Judged visually. Transparency was determined according to the following criteria.
○: Transparent.
X: It is cloudy.

Table 2 (continued)

Notes: (1) A composition based on N, N-diphosphonic acid acrylamide.
(2) Polyoxyethylene-stearylamine (trade name “Naymin S-210”, manufactured by NOF Corporation).
(3) Methyl methacrylate.
(4) A composition mainly composed of N-monophosphonic acid acrylamide.

  As is clear from Table 2, the vinyl polymers of Examples 9 to 13 were excellent in flame retardancy and transparency. On the other hand, in Comparative Examples 6 and 7, the molar ratio between the phosphonic acid group-containing acrylamide-containing composition and the other ethylenically unsaturated bond-containing compound was set to 1/6. Therefore, compared with Examples 9-13 It was inferior in flame retardancy.

Example 14
In an automatic synthesis reactor having a reflux condenser, a catalyst inlet, and the like, 25 parts by mass of the phosphonic acid group-containing acrylamide-containing composition prepared in Example 1, 25 parts by mass of 2-ethylhexyl acrylate, and 50 parts by mass of ion-exchanged water were added. The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 60 ° C. Then, the total of the phosphonic acid group-containing acrylamide-containing composition and 2-ethylhexyl acrylate was 100% by mass, 12.6% by mass dodecylbenzenesulfonate and 2% by mass Of ammonium persulfate was added. Thereafter, emulsion polymerization was carried out while maintaining at 60 to 65 ° C. for 22 hours to obtain an emulsion containing a vinyl polymer formed by copolymerizing a phosphonic acid group-containing acrylamide-containing composition (modified product) and methyl methacrylate. Cool the emulsion, add 5 parts by weight of methanol to the emulsion, stir, filter using a wire mesh, collect the solids, wash with ion-exchanged water, and dry at 60 ° C for 15 hours. As a result, a vinyl polymer was prepared (yield 49%).

Example 15
A vinyl polymer was prepared in the same manner as in Example 14 except that the composition prepared in Example 2 was used instead of the phosphonic acid group-containing acrylamide-containing composition prepared in Example 1 (yield: 34% ).

Example 16
A vinyl polymer was prepared in the same manner as in Example 14 except that butyl acrylate was used in place of 2-ethylhexyl acrylate (yield 68%).

Example 17
A vinyl polymer was prepared in the same manner as in Example 15 except that butyl acrylate was used instead of 2-ethylhexyl acrylate (yield 70%).

Comparative Example 8
A vinyl polymer was prepared in the same manner as in Example 14 using only 50 parts by mass of 2-ethylhexyl acrylate as a solute (yield 91%).

Comparative Example 9
A vinyl polymer was prepared in the same manner as Example 14 using only 50 parts by mass of butyl acrylate as a solute (yield 64%).

  The vinyl polymers obtained in Examples 14 to 17 and Comparative Examples 8 and 9 were evaluated for insulation, transparency and solvent resistance by the following methods (the evaluation criteria for transparency were the same as above). The results are shown in Table 3.

(1) Insulation The insulation was evaluated by measuring the surface resistivity with a surface resistivity meter (SME-8310, manufactured by Toa Denpa Kogyo Co., Ltd.) under the condition of relative humidity 60% / room temperature.

(2) Solvent resistance
10 parts by weight of the vinyl polymer was placed in 90 parts by weight of tetrahydrofuran and stirred for 60 minutes, then the state of the vinyl polymer was observed, and the solvent resistance was determined according to the following criteria.
○: Swelled but not dissolved at all.
Δ: Swelled and partly dissolved.
X: Completely dissolved.

Table 3 (continued)

Notes: (1) A composition based on N, N-diphosphonic acid acrylamide.
(2) Polyoxyethylene-stearylamine (trade name “Naymin S-210”, manufactured by NOF Corporation).
(3) 2-ethylhexyl acrylate.
(4) A composition mainly composed of N-monophosphonic acid acrylamide.
(5) Butyl acrylate.

As is apparent from Table 3, the vinyl polymers of Examples 14 and 16 have a surface resistivity of 1 × 10 ¹⁴ Ω or more, and the vinyl polymer of the present invention is excellent in insulation. I understand. Further, from Examples 15 and 17, the vinyl polymer using the composition mainly composed of N-monophosphonic acid acrylamide was excellent in solvent resistance. On the other hand, in Comparative Examples 8 and 9, only the other ethylenically unsaturated bond-containing compound was polymerized without using the phosphonic acid group-containing acrylamide-containing composition. In addition, the solvent resistance was poor.

Claims (19)

Phosphoric acid residue containing (meth) acrylamide (A) having a phosphorus acid residue consisting of (poly) phosphonic acid group and / or (poly) phosphoric acid group and nitrogen-containing surfactant (B) A (meth) acrylamide-containing composition comprising:
The phosphorus acid residue-containing (meth) acrylamide (A) has the formula (1):

(Wherein R ¹ is a hydrogen group or a methyl group, and X ¹ and X ² are each independently a (poly) phosphonic acid group or a (poly) phosphoric acid group) N, N-substituted (meth) Acrylamide and formula (2):

(Wherein R ¹ is a hydrogen group or a methyl group, and X ³ is a (poly) phosphonic acid group or a (poly) phosphoric acid group), or any of N-substituted (meth) acrylamides represented by these or a mixture thereof And
The nitrogen-containing surfactant (B) is any one of an amine-based surfactant containing a (poly) ether group and a cationic surfactant containing a quaternary ammonium base, or a mixture thereof. A phosphoric acid residue-containing (meth) acrylamide-containing composition. In the phosphoric acid residue-containing (meth) acrylamide-containing composition according to claim 1,
The (poly) ether group-containing amine surfactant is represented by the formula (3):

[However, R ² is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ³ is 2 to 2 carbon atoms. 4 linear or branched alkylene groups, R ⁴ is a — (R ^4a O) _k H group (R ^4a is a linear or branched alkylene group having 2 to 4 carbon atoms), carbon A linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a hydrogen group, and f and k are each independently 1 to 30 A first (poly) ether group-containing amine surfactant represented by formula (4):

[Wherein R ⁵ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ⁶ is — (R ^6a O) _s H group (R ^6a is a linear or branched alkylene group having 2 to 4 carbon atoms), a linear or branched alkyl group having 1 to 30 carbon atoms, 6 to 30 carbon atoms An aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a hydrogen group, R ⁷ is a linear or branched alkylene group having 1 to 6 carbon atoms, and R ⁸ is a straight chain having 2 to 4 carbon atoms. A chain or branched alkylene group, R ⁹ is a — (R ^9a O) _t H group (R ^9a is a linear or branched alkylene group having 2 to 4 carbon atoms); 30 linear or branched alkyl group, aryl group having 6 to 30 carbon atoms, arylalkyl group having 7 to 30 carbon atoms, or hydrogen group, and r, s and t are each independently 1 to 1 Any one of the second (poly) ether group-containing amine surfactants represented by the formula:
The cationic surfactant has the formula (5):

(However, R ¹⁰ and R ¹³ are each independently a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms; ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, and each of R ^{10 to} R ¹³ is at least selected from the group consisting of a hydroxyl group, an ester bond and an amino group. A first cationic surfactant represented by formula (6), wherein one species may be bound, Y ^- is a counter ion:


(However, R ¹⁴ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and Y ⁻ is a counter ion. ) A second cationic surfactant represented by formula (7):

(However, R ¹⁵ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ¹⁶ and R ¹⁷ are respectively Independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R ¹⁸ is a linear or branched alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, or a carbon number 7 to 30 arylene alkyl group, and each of R ^{15 to} R ¹⁸ may be bonded to at least one selected from the group consisting of a hydroxyl group, an ester bond and an amino group. Cationic surfactant and formula (8):

Wherein R ¹⁹ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. A phosphoric acid residue-containing (meth) acrylamide-containing composition, which is at least one selected from the group consisting of cationic surfactants. 3. The phosphoric acid residue-containing (meth) acrylamide-containing composition according to claim 1 or 2, wherein the N, N-substituted (meth) acrylamide is represented by the formula (1a):

(Wherein R ¹ is a hydrogen group or a methyl group, and n and n ′ are each independently an integer of 0 to 2), N, N-di (poly) phosphonic acid (meth) acrylamide, The N-substituted (meth) acrylamide has the formula (2a):

(Wherein R ¹ is a hydrogen group or a methyl group, and m is an integer of 0 to 2) N-mono (poly) phosphonic acid (meth) acrylamide represented by Group-containing (meth) acrylamide-containing composition. The phosphoric acid residue-containing (meth) acrylamide-containing composition according to claim 2 or 3, wherein the first (poly) ether group-containing amine surfactant is represented by the formula (3a):

Wherein R ^2a is a linear or branched alkyl group having 1 to 30 carbon atoms, and f and k are the same as those in the formula (3), and the second (poly ) The ether group-containing amine surfactant is represented by the formula (4a):

(Wherein R ^5a is a linear or branched alkyl group having 1 to 30 carbon atoms, and r, s, and t are the same as those in the formula (4)). The cationic surfactant is represented by the formula (5a):

(Wherein R ¹⁰ and Y ⁻ are the same as in formula (5)), a trimethyl-type cationic surfactant represented by formula (5b):

(However, R ¹⁰ and Y ⁻ are the same as those in formula (5), and R ^13a is a linear or branched alkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 8 to 8 carbon atoms. A dialkyl-type cationic surfactant represented by formula (5c):

(Wherein R ¹⁰ and Y ⁻ are the same as in formula (5)), and a benzylic cationic surfactant represented by formula (5d):

(Wherein R ^10a and R ^13b are each independently a linear or branched alkyl group having 1 to 20 carbon atoms, and Y ⁻ is the same as in formula (5)). Any of the surfactants or a combination thereof, and the third cationic surfactant is represented by the formula (7a):

A phosphoric acid residue-containing (meth) acrylamide-containing composition, which is a compound represented by the formula (wherein R ¹⁵ is the same as in formula (7)). 5. The phosphoric acid residue-containing (meth) acrylamide-containing composition according to claim 1, wherein the phosphoric acid residue-containing (meth) acrylamide (A) has one phosphoric acid residue. A phosphoric acid residue-containing (meth) acrylamide-containing composition, wherein the nitrogen-containing surfactant (B) is blended in a molar ratio of 0.5 to 4. Phosphoric acid residue containing (meth) acrylamide (A) having a phosphorus acid residue consisting of (poly) phosphonic acid group and / or (poly) phosphoric acid group, and nitrogen-containing surfactant (B) ( A (meth) acrylamide-containing composition (A + B) and another ethylenically unsaturated bond-containing compound (C), and a copolymer of (A) and (C), and A phosphorus acid residue-containing vinyl polymer-containing composition containing (B),
The phosphorus acid residue-containing (meth) acrylamide (A) has the formula (1):

(Wherein R ¹ is a hydrogen group or a methyl group, and X ¹ and X ² are each independently a (poly) phosphonic acid group or a (poly) phosphoric acid group) N, N-substituted (meth) Acrylamide and formula (2):

(Wherein R ¹ is a hydrogen group or a methyl group, and X ³ is a (poly) phosphonic acid group or a (poly) phosphoric acid group), or any of N-substituted (meth) acrylamides represented by these or a mixture thereof And
The other ethylenically unsaturated bond-containing compound (C) includes an unsaturated compound (C-1) having at least one ethylenically unsaturated bond but no acidic group in the molecule, and an ethylenically unsaturated compound in the molecule. Any one of unsaturated compounds (C-2) each having at least one saturated bond and an acidic group, or a mixture thereof;
The nitrogen-containing surfactant (B) is any one of an amine-based surfactant containing a (poly) ether group and a cationic surfactant containing a quaternary ammonium base, or a mixture thereof. Phosphoric acid residue-containing vinyl polymer-containing composition. The phosphorus acid residue-containing vinyl polymer-containing composition according to claim 6, wherein the (poly) ether group-containing amine surfactant is represented by the formula (3):

[However, R ² is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ³ is 2 to 2 carbon atoms. 4 linear or branched alkylene groups, R ⁴ is a — (R ^4a O) _k H group (R ^4a is a linear or branched alkylene group having 2 to 4 carbon atoms), carbon A linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a hydrogen group, and f and k are each independently 1 to 30 A first (poly) ether group-containing amine surfactant represented by formula (4):

[Wherein R ⁵ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ⁶ is — (R ^6a O) _s H group (R ^6a is a linear or branched alkylene group having 2 to 4 carbon atoms), a linear or branched alkyl group having 1 to 30 carbon atoms, 6 to 30 carbon atoms An aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a hydrogen group, R ⁷ is a linear or branched alkylene group having 1 to 6 carbon atoms, and R ⁸ is a straight chain having 2 to 4 carbon atoms. A chain or branched alkylene group, R ⁹ is a — (R ^9a O) _t H group (R ^9a is a linear or branched alkylene group having 2 to 4 carbon atoms); 30 linear or branched alkyl group, aryl group having 6 to 30 carbon atoms, arylalkyl group having 7 to 30 carbon atoms, or hydrogen group, and r, s and t are each independently 1 to 1 Any one of the second (poly) ether group-containing amine surfactants represented by the formula:
The cationic surfactant has the formula (5):

(However, R ¹⁰ and R ¹³ are each independently a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms; ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, and each of R ^{10 to} R ¹³ is at least selected from the group consisting of a hydroxyl group, an ester bond and an amino group. A first cationic surfactant represented by formula (6), wherein one species may be bound, Y ^- is a counter ion:


(However, R ¹⁴ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and Y ⁻ is a counter ion. ) A second cationic surfactant represented by formula (7):

(However, R ¹⁵ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ¹⁶ and R ¹⁷ are respectively Independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R ¹⁸ is a linear or branched alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, or a carbon number 7 to 30 arylene alkyl group, and each of R ^{15 to} R ¹⁸ may be bonded to at least one selected from the group consisting of a hydroxyl group, an ester bond and an amino group. Cationic surfactant and formula (8):

Wherein R ¹⁹ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. A phosphorus polymer-containing vinyl polymer-containing composition, which is at least one selected from the group consisting of cationic surfactants. The phosphoric acid residue-containing vinyl polymer-containing composition according to claim 6 or 7, wherein the acidic group-free unsaturated compound (c-1) is a (meth) acrylic acid ester, (meth) acrylonitrile, ( (Meth) acrylamide, dialkylaminoalkyl (meth) acrylate, N, N-dialkyl (meth) acrylamide, styrene, styrene having at least a part of hydrogen groups substituted with methyl groups, divinylbenzene, fatty acid vinyl ester, vinyl halide, (Meth) acrylic acid ester in which at least a part of hydrogen groups are substituted with fluorine groups, (meth) acrylic acid in which at least a part of hydrogen groups are substituted with fluorine groups, and at least part of the hydrogen groups are fluorine groups. Is at least one selected from the group consisting of vinyls containing substituted alkyl groups,
The acidic group-containing unsaturated compound (C-2) is tertiary butyl acrylamide sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, p-styrene sulfonic acid, (meth) acrylic acid butyl-4-sulfone. Acid, (meth) acrylooxybenzenesulfonic acid, (meth) acrylic acid, crotonic acid, maleic acid and its anhydride, fumaric acid, itaconic acid, hydroxyalkyl (meth) acrylate, and formula (9):

(However, R ²⁰ is a hydrogen group or a methyl group, R ²¹ is an alkylene group having 2 to 4 carbon atoms, linear or branched, and at least a part of the hydrogen groups may be substituted with chlorine groups. And x is an integer of 1 to 6). A phosphorus acid residue-containing vinyl polymer-containing composition, which is at least one selected from the group consisting of compounds represented by: The phosphorus acid residue-containing vinyl polymer-containing composition according to any one of claims 6 to 8, wherein the phosphorus acid residue-containing (meth) acrylamide-containing composition (A + B) and the other Phosphoric acid residue-containing vinyl, wherein the mass ratio (A + B) / (C) to the ethylenically unsaturated bond-containing compound (C) is (15/85) to (60/40) -Based polymer-containing composition. The phosphoric acid residue-containing vinyl polymer-containing composition according to any one of claims 6 to 9, wherein the N, N-substituted (meth) acrylamide is represented by the formula (1a):

(Wherein R ¹ is a hydrogen group or a methyl group, and n and n ′ are each independently an integer of 0 to 2), N, N-di (poly) phosphonic acid (meth) acrylamide, The N-substituted (meth) acrylamide is represented by the formula (2a):

(Wherein R ¹ is a hydrogen group or a methyl group, and m is an integer of 0 to 2) N-mono (poly) phosphonic acid (meth) acrylamide represented by A group-containing vinyl polymer-containing composition. The phosphorus acid residue-containing vinyl polymer-containing composition according to any one of claims 7 to 10, wherein the first (poly) ether group-containing amine surfactant is represented by the formula (3a):

Wherein R ^2a is a linear or branched alkyl group having 1 to 30 carbon atoms, and f and k are the same as those in the formula (3), and the second (poly ) The ether group-containing amine surfactant is represented by the formula (4a):

(Wherein R ^5a is a linear or branched alkyl group having 1 to 30 carbon atoms, and r, s, and t are the same as those in the formula (4)). The cationic surfactant is represented by the formula (5a):

(Wherein R ¹⁰ and Y ⁻ are the same as in formula (5)), a trimethyl-type cationic surfactant represented by formula (5b):

(However, R ¹⁰ and Y ⁻ are the same as those in formula (5), and R ^13a is a linear or branched alkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 8 to 8 carbon atoms. A dialkyl-type cationic surfactant represented by formula (5c):

(Wherein R ¹⁰ and Y ⁻ are the same as in formula (5)), and a benzylic cationic surfactant represented by formula (5d):

(Wherein R ^10a and R ^13b are each independently a linear or branched alkyl group having 1 to 20 carbon atoms, and Y ⁻ is the same as in formula (5)). Any of the surfactants or a combination thereof, and the third cationic surfactant is represented by the formula (7a):

A phosphorus polymer-containing vinyl polymer-containing composition, wherein the compound is represented by the formula (wherein R ¹⁵ is the same as that in formula (7)). 12. The phosphoric acid residue-containing vinyl polymer-containing composition according to any one of claims 6 to 11, wherein the phosphoric acid residue-containing (meth) acrylamide-containing composition (A + B) is the phosphoric acid residue. A phosphoric acid characterized in that the nitrogen-containing surfactant (B) is blended in a molar ratio of 0.5 to 4 with respect to one phosphoric acid residue of acid residue-containing (meth) acrylamide (A). Residue-containing vinyl polymer-containing composition. A flame retardant resin comprising the phosphoric acid residue-containing vinyl polymer-containing composition according to any one of claims 6 to 12. An insulating resin comprising the phosphoric acid residue-containing vinyl polymer-containing composition according to any one of claims 6 to 12. It is a reaction product of (meth) acrylamide, N-hydroxy (meth) acrylamide or a mixture thereof and at least one selected from the group consisting of phosphoric acid, pyrophosphoric acid, polyphosphoric acid and phosphorus oxychloride, or a hydrolyzate thereof. Prepare phosphoric acid residue-containing (meth) acrylamide (A) and mix it with nitrogen-containing surfactant (B). The resulting composition (A + B) and other ethylenically unsaturated bonds A method of producing a phosphorus acid residue-containing vinyl polymer-containing composition by reacting with a compound (C),
The nitrogen-containing surfactant (B) is either an amine-based surfactant containing a (poly) ether group, and a cationic surfactant containing a quaternary ammonium base, or a mixture thereof.
The other ethylenically unsaturated bond-containing compound (C) includes an unsaturated compound (C-1) having at least one ethylenically unsaturated bond but no acidic group in the molecule, and an ethylenically unsaturated compound in the molecule. A method comprising any one of unsaturated compounds (C-2) having at least one saturated bond and at least one acidic group, or a mixture thereof. 16. The method for producing a phosphorus acid residue-containing vinyl polymer-containing composition according to claim 15, wherein the phosphorus acid residue-containing (meth) acrylamide (A) is represented by the formula (1):

(Wherein R ¹ is a hydrogen group or a methyl group, and X ¹ and X ² are each independently a (poly) phosphonic acid group or a (poly) phosphoric acid group) N, N-substituted (meth) Acrylamide and formula (2):

(Wherein R ¹ is a hydrogen group or a methyl group, and X ³ is a (poly) phosphonic acid group or a (poly) phosphoric acid group) A method characterized in that 17. The method for producing a phosphorus acid residue-containing vinyl polymer-containing composition according to claim 15 or 16, wherein the (poly) ether group-containing amine surfactant is represented by the formula (3):

[However, R ² is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ³ is 2 to 2 carbon atoms. 4 linear or branched alkylene groups, R ⁴ is a — (R ^4a O) _k H group (R ^4a is a linear or branched alkylene group having 2 to 4 carbon atoms), carbon A linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a hydrogen group, and f and k are each independently 1 to 30 A first (poly) ether group-containing amine surfactant represented by formula (4):

[Wherein R ⁵ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ⁶ is — (R ^6a O) _s H group (R ^6a is a linear or branched alkylene group having 2 to 4 carbon atoms), a linear or branched alkyl group having 1 to 30 carbon atoms, 6 to 30 carbon atoms An aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a hydrogen group, R ⁷ is a linear or branched alkylene group having 1 to 6 carbon atoms, and R ⁸ is a straight chain having 2 to 4 carbon atoms. A chain or branched alkylene group, R ⁹ is a — (R ^9a O) _t H group (R ^9a is a linear or branched alkylene group having 2 to 4 carbon atoms); 30 linear or branched alkyl group, aryl group having 6 to 30 carbon atoms, arylalkyl group having 7 to 30 carbon atoms, or hydrogen group, and r, s and t are each independently 1 to 1 Any one of the second (poly) ether group-containing amine surfactants represented by the formula:
The cationic surfactant has the formula (5):

(However, R ¹⁰ and R ¹³ are each independently a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms; ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, and each of R ^{10 to} R ¹³ is at least selected from the group consisting of a hydroxyl group, an ester bond and an amino group. A first cationic surfactant represented by formula (6), wherein one species may be bound, Y ^- is a counter ion:


(However, R ¹⁴ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and Y ⁻ is a counter ion. ) A second cationic surfactant represented by formula (7):

(However, R ¹⁵ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ¹⁶ and R ¹⁷ are respectively Independently a linear or branched alkyl group having 1 to 6 carbon atoms, and R ¹⁸ is a linear or branched alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, or a carbon number 7 to 30 arylene alkyl group, and each of R ^{15 to} R ¹⁸ may be bonded to at least one selected from the group consisting of a hydroxyl group, an ester bond and an amino group. Cationic surfactant and formula (8):

Wherein R ¹⁹ is a linear or branched alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. A method comprising at least one selected from the group consisting of cationic surfactants. The method for producing a phosphorus acid residue-containing vinyl polymer-containing composition according to any one of claims 15 to 17, wherein the acidic group-free unsaturated compound (c-1) is a (meth) acrylic acid ester, (Meth) acrylonitrile, (meth) acrylamide, dialkylaminoalkyl (meth) acrylate, N, N-dialkyl (meth) acrylamide, styrene, styrene, divinylbenzene, fatty acid vinyl with at least some hydrogen groups substituted with methyl groups Esters, vinyl halides, (meth) acrylic acid esters in which at least some hydrogen groups are substituted with fluorine groups, (meth) acrylic acids in which at least some hydrogen groups are substituted with fluorine groups, and at least some The hydrogen group is at least one selected from the group consisting of vinyl containing an alkyl group substituted with a fluorine group,
The acidic group-containing unsaturated compound (C-2) is tertiary butyl acrylamide sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, p-styrene sulfonic acid, (meth) acrylic acid butyl-4-sulfone. Acid, (meth) acrylooxybenzenesulfonic acid, (meth) acrylic acid, crotonic acid, maleic acid and its anhydride, fumaric acid, itaconic acid, hydroxyalkyl (meth) acrylate, and formula (9):

(However, R ²⁰ is a hydrogen group or a methyl group, R ²¹ is an alkylene group having 2 to 4 carbon atoms, linear or branched, and at least a part of the hydrogen groups may be substituted with chlorine groups. And x is an integer of 1 to 6), and is at least one selected from the group consisting of compounds represented by: The method for producing a phosphoric acid residue-containing vinyl polymer-containing composition according to any one of claims 15 to 18, wherein the composition (A + B) and the (C) are reacted as water. A method using emulsion polymerization using an emulsifier and a polymerization initiator in a medium.