JP5146644B2 - Method for modifying ammonium polyphosphate - Google Patents

Description

  The present invention relates to a method for modifying ammonium polyphosphate that does not generate a halogen-based gas and exhibits high flame retardancy, and relates to a method for modifying ammonium polyphosphate that does not cause slimming even when hot water is attached. is there.

  Conventionally, various flame retardant additives have been used for the purpose of imparting flame retardancy to resins, elastomers and coating agents. However, in recent years, a flame retardant composition in which a halogen-containing compound, which has been the mainstream of flame retardant technology, alone or in combination with an antimony compound such as antimony oxide is used as a flame retardant and blended with a resin or an emulsion, Generation of gas and carbon monoxide is a problem. In addition, a metal hydroxide with a small amount of harmful gas generated at the time of a fire needs to be blended in a large amount in order to exhibit flame retardancy, so that there is a problem that workability and mechanical strength are impaired.

  On the other hand, phosphorus compounds are expected as a powerful option and are actually widely used. Among various phosphorous compounds, there are concerns that phosphoric acid esters may bleed out to the surface of the added resin, and that there is a concern that there may be physiological activity on living organisms. Although red phosphorus has a very high flame retardancy, it has been pointed out that the resin turns red and phosphoric acid is eluted. Ammonium polyphosphate has the advantages that it is highly flame retardant and is highly safe to living organisms because it is an inorganic compound, and has less elution of phosphoric acid than red phosphorus.

  The use application of ammonium polyphosphate includes a flame retardant (backing agent) for fabric of automobile seats.

  However, when the sheet fabric is placed under conditions of high temperature and humidity, or when water or hot water is spilled on the sheet fabric, the surface of the ammonium polyphosphate is slimmed. Also, when processing into fabrics, after emulsifying ammonium polyphosphate with acrylic resin, coating the fabric fiber lining and pasting it to the urethane sheet base, but when the fabric is slipped and stuck from the sheet due to slime There is.

  As a solution for slimming, the present inventors have developed a compound (ammonium polyphosphate) containing both a phosphorus atom and a nitrogen atom as component (A) and an organosilicon compound and an amino group-containing alkoxysilane as component (B). Or, a flame retardant additive made by co-hydrolysis condensation of a partially hydrolyzed product thereof in the presence of an organic acid or an inorganic acid has been found to have excellent water resistance and dispersibility, and no sliminess (patent) Document 4: Japanese Patent Laid-Open No. 2006-111844).

  Ammonium polyphosphate produced by the above method does not have sliminess when immersed in water and exhibits high flame retardancy. However, when warm water (40 ° C or higher) is used, slimming may not be suppressed. For example, slimming may occur when a warm drink is spilled on the sheet. For this reason, ammonium polyphosphate which does not cause slimming even with warm water is necessary.

In addition, as a well-known document relevant to this invention, there exist the following.
Japanese Patent Publication No.53-15478 JP-A 61-103962 JP-A-8-134455 JP 2006-111844 A

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for modifying ammonium polyphosphate that does not cause slimming even when hot water is attached.

  As a result of intensive studies to achieve the above object, the present inventors have found that it is possible to eliminate the slime caused by water or warm water by acid treatment of the ammonium polyphosphate surface. It came to.

Accordingly, the present invention provides the following method for modifying ammonium polyphosphate.
(1) Ammonium polyphosphate characterized by eliminating the slimy feeling caused by moisture by treating ammonia on the surface of ammonium polyphosphate with 100 to 50 parts by weight of acid using 0.1 to 50 parts by weight of acid. Reforming method.
(2) The method for modifying ammonium polyphosphate according to (1), wherein the ammonium polyphosphate is treated with an acid in a solvent, and then the solvent is removed.
(3) The method for reforming ammonium polyphosphate according to (1) or (2), wherein the acid is hydrochloric acid or chlorosilane that decomposes with protons to generate hydrochloric acid.
(4) A method for modifying ammonium polyphosphate, comprising surface-treating ammonium polyphosphate treated with the acid according to any one of (1) to (3) with a hydrophobic compound.
(5) One or more hydrophobic compounds selected from silane coupling agents, titanate coupling agents, silicone oil, silicone resin, silicone rubber, hydrophobic silica , fatty acid, fatty acid metal salt, fatty acid ester, fatty acid alcohol (4) The method for modifying ammonium polyphosphate as described in (4) above.
(6)
Hydrophobic compounds
(I) The following general formula (1)
(R ¹ ) _a (OR ² ) _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, a is 0.75 to 1.5, and b is 0.2 to 3) And a positive number satisfying 0.9 <a + b ≦ 4.)
100 parts by mass of an organosilicon compound represented by:
(Ii) The following general formula (2)
R ³ R ⁴ NR ⁵ —SiR ⁶ _n (OR ² ) _3-n (2)
(However, in the formula, R ² is the same as above, R ³ and R ⁴ are the same or different hydrogen atoms, alkyl groups or aminoalkyl groups having 1 to 15 carbon atoms, and R ⁵ is 1 carbon atom.) -18 divalent hydrocarbon group, R ⁶ is an alkyl group having 1 to 4 carbon atoms, and n is 0 or 1.)
0.5 to 49 parts by mass of an amino group-containing alkoxysilane or a partial hydrolyzate thereof represented by
A co-hydrolysis condensate obtained by co-hydrolysis condensation in the presence of an organic acid or an inorganic acid,
Or
(I) 100 parts by mass of component, (ii) 0.5 to 49 parts by mass of component,
(Iii) 0.1 to 10 parts by mass of inorganic oxide fine particles and / or
(Iv) The following general formula (3)
(R ¹ ) _k (OR ² ) _3-k Si-Y-Si (R ¹ ) _k (OR ² ) _3-k (3)
(Wherein, R ¹ and R ² are the same as above, Y is a divalent organic group, — (OSi (R ⁷ ) ₂ ) _m O— group or —R— (SiR ⁷ ₂ O) _m — A SiR ⁷ ₂ —R— group, wherein R ⁷ is an alkyl group having 1 to 6 carbon atoms, R is a divalent hydrocarbon group having 1 to 6 carbon atoms, and m is an integer of 1 to 30. K is 1, 2 or 3.)
0.1 to 20 parts by mass of a bis (alkoxysilyl) group-containing compound represented by the formula:
Cohydrolyzed condensate obtained by cohydrolyzing and condensing in the presence of organic acid or inorganic acid
(4) The method for modifying ammonium polyphosphate according to (4), which is a silicone-based water repellent treatment agent.
Moreover, this invention provides the surface-treated ammonium polyphosphate obtained by said (4) , (5) or (6) .

  The modified ammonium polyphosphate of the present invention is not slimy even when warm water is attached.

  The method for modifying ammonium polyphosphate of the present invention involves treating ammonium polyphosphate with an acid. Here, the acid in the present invention means an acid in the definition of Arrhenius. The definition of Arrhenius is a definition proposed by Arrhenius in 1884, and is a substance that dissolves in water and generates hydrogen ions (protons).

  The acid in the present invention is a strong acid that reacts with ammonia on the surface of ammonium polyphosphate, and specific examples thereof include hydrochloric acid, sulfuric acid, acetic acid, formic acid, etc. Among them, a strong acid such as hydrochloric acid is preferred. Also preferred are chlorosilanes that decompose with protons to produce hydrochloric acid. As chlorosilanes, any of monochlorosilane, dichlorosilane, trichlorosilane, and silicon tetrachloride may be used.

  When hydrochloric acid is used, a method of treating ammonium polyphosphate with dry hydrochloric acid gas may be used, but it is more preferable to disperse ammonium polyphosphate in a solvent and treat with hydrochloric acid. In this case, a method of treating ammonium polyphosphate by adding chlorosilane containing no water instead of hydrochloric acid and generating hydrochloric acid with a small amount of water vapor or alcohol is also preferred.

  The acid in the definition of Arrhenius in this invention uses 0.1-50 mass parts with respect to 100 mass parts of ammonium polyphosphate, More preferably, it is 1-30 mass parts.

  In the present invention, the solvent is a liquid used for dispersing ammonium polyphosphate, and an organic solvent is preferable. As the organic solvent, those not reactive with ammonium polyphosphate are preferable, and examples thereof include methanol, ethanol, isopropyl alcohol, hexane, toluene, acetone, tetrahydrofuran, butanol, ethyl acetate, 1 propanol, and 2 propanol.

It is preferable that a solvent is 10-500 mass parts with respect to 100 mass parts of ammonium polyphosphate.
As a method for removing the solvent, the solvent is dried by heating at a melting point of 200 ° C. or lower or under reduced pressure.

  In addition, although the process conditions by an acid are selected suitably, process temperature is preferable 0-60 degreeC and it is preferable that process time is 10 to 180 minutes.

In the present invention, the ammonium polyphosphate having a small particle size is more excellent in dispersibility, and the average particle size is preferably 50 μm or less, more preferably 30 μm or less, as measured by a laser scattering particle size distribution analyzer. However, since the price of ammonium polyphosphate becomes higher as the particle diameter becomes smaller, the average particle diameter suitable for use considering the price is 10 to 30 μm. The bulk density is desirably 0.3 to 1.0 g / cm ³ .

  Commercially available products may be used as the ammonium polyphosphate in the present invention. Examples of the commercially available products include Exolit-422 (trade name, manufactured by Hoechst), Exolit-700 (trade name, Hoechst). ), Phos-check (Phos-chek) -P / 30 (trade name, manufactured by Monsanto), Phos-check (Phos-chek) -P / 40 (trade name, manufactured by Monsanto), Sumisafe-P (trade name, And Sumitomo Chemical Co., Ltd.), TERRAJU (registered trademark, manufactured by Budenheim Co.)-S10, and TERRAJU (registered trademark, manufactured by Budenheim Co., Ltd.)-S20.

  In the present invention, the acid-treated ammonium polyphosphate surface can be further improved in water repellency by surface treatment with a hydrophobic compound.

  In the treatment method, after the filtration, the hydrophobic compound is subjected to either a wet treatment or a dry treatment on the ammonium polyphosphate from which the solvent has been removed by drying or reduced pressure.

Specific examples of the hydrophobic compound include one selected from a silane coupling agent, a titanate coupling agent, silicone oil, silicone resin, silicone rubber, hydrophobic silica , fatty acid, fatty acid metal salt, fatty acid ester, and fatty acid alcohol. The above compounds can be mentioned.

  As the hydrophobic compound imparting water repellency, the following silicone compounds are particularly excellent in covering property and water repellency.

(I) The following general formula (1)
(R ¹ ) _a (OR ² ) _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, a is 0.75 to 1.5, and b is 0.2 to 3) And a positive number satisfying 0.9 <a + b ≦ 4.)
100 parts by mass of an organosilicon compound represented by:
(Ii) The following general formula (2)
R ³ R ⁴ NR ⁵ —SiR ⁶ _n (OR ² ) _3-n (2)
(However, in the formula, R ² is the same as above, R ³ and R ⁴ are the same or different hydrogen atoms, alkyl groups or aminoalkyl groups having 1 to 15 carbon atoms, and R ⁵ is 1 carbon atom.) -18 divalent hydrocarbon group, R ⁶ is an alkyl group having 1 to 4 carbon atoms, and n is 0 or 1.)
A cohydrolyzed condensate obtained by cohydrolyzing and condensing 0.5 to 49 parts by mass of an amino group-containing alkoxysilane or a partial hydrolyzate thereof represented by
Or
(I) 100 parts by mass of component, (ii) 0.5 to 49 parts by mass of component,
(Iii) 0.1 to 10 parts by mass of inorganic oxide fine particles and / or (iv) the following general formula (3)
(R ¹ ) _k (OR ² ) _3-k Si-Y-Si (R ¹ ) _k (OR ² ) _3-k (3)
(Wherein, R ¹ and R ² are the same as above, Y is a divalent organic group, — (OSi (R ⁷ ) ₂ ) _m O— group or —R— (SiR ⁷ ₂ O) _m — A SiR ⁷ ₂ —R— group, wherein R ⁷ is an alkyl group having 1 to 6 carbon atoms, R is a divalent hydrocarbon group having 1 to 6 carbon atoms, and m is an integer of 1 to 30. K is 1, 2 or 3.)
A silicone system comprising a cohydrolyzed condensate obtained by cohydrolyzing and condensing 0.1 to 20 parts by mass of a bis (alkoxysilyl) group-containing compound represented by the formula (1) or a partial hydrolyzate thereof in the presence of an organic acid or an inorganic acid. A water repellent treatment agent is preferred.

Hereinafter, each component (i)-(iv) is demonstrated.
The component (i) is an organosilicon compound represented by the following general formula (1).
(R ¹ ) _a (OR ² ) _b SiO _{(4-ab) / 2} (1)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, a is 0.75 to 1.5, and b is 0.2 to 3) And a positive number satisfying 0.9 <a + b ≦ 4.)

R ^{1 in the} above formula (1) is an alkyl group having 1 to 6, preferably 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, and an n-hexyl group, and a methyl group is particularly preferable. R ² is an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group, and a methyl group and an ethyl group are preferable.

Specific examples of such an organosilicon compound of formula (1) include the following compounds.
CH ₃ Si (OCH ₃ ) ₃ , CH ₃ Si (OC ₂ H ₅ ) ₃ , CH ₃ Si (OCH (CH ₃ ) ₂ ) ₃ , CH ₃ CH ₂ Si (OCH ₃ ) ₃ , CH ₃ CH ₂ Si ( _{OC 2 H 5) 3, CH} 3 CH 2 Si (OCH (CH 3) 2) 3, C 3 H 7 Si (OCH 3) 3, C 3 H 7 Si (OC 2 H 5) 3, C 3 H 7 Si (OCH (CH ₃ ) ₂ ) ₃ , C ₄ H ₉ Si (OCH ₃ ) ₃ , C ₄ H ₉ Si (OC ₂ H ₅ ) ₃ , C ₄ H ₉ Si (OCH (CH ₃ ) ₂ ) ₃ , _{C 5 H 11 Si (OCH 3} ) 3, C 5 H 11 Si (OC 2 H 5) 3, C 5 H 11 Si (OCH (CH 3) 2) 3, C 6 H 13 Si (OCH 3) 3, C ₆ H ₁₃ Si (OC ₂ H ₅ ) ₃ , C ₆ H ₁₃ Si (OCH (CH ₃ ) ₂ ) ₃

  In the present invention, the above various silanes may be used alone, or two or more kinds of mixtures may be used, or a partial hydrolyzate of mixed silanes may be used.

In this case, as the component (i), an alkoxy group-containing siloxane obtained by partially hydrolyzing and condensing the silane is preferably used. The number of silicon atoms of this partially hydrolyzed product (siloxane oligomer) is preferably 2 to 10, particularly 2 to 4. Furthermore, the component (i) may be obtained by a reaction of an alkyltrichlorosilane having 1 to 6 carbon atoms with methanol or ethanol in water. Also in this case, the number of silicon atoms in the siloxane oligomer is preferably 2 to 6, particularly 2 to 4. As the siloxane oligomer, a siloxane dimer represented by [CH ₃ (OR ² ) ₂ Si] ₂ O (where R ² is the same as described above) is particularly preferable. In this case, siloxane trimer or siloxane tetramer may be included. Moreover, what has a viscosity of 300 mm < ² > / s or less at 25 degreeC in the viscosity measuring method by a capillary-type viscometer is preferable, and especially the thing which has a viscosity of 1-100 mm < ² > / s is suitable.

Next, component (ii) is an amino group-containing alkoxysilane represented by the following general formula (2) or a partial hydrolyzate thereof.
R ³ R ⁴ NR ⁵ —SiR ⁶ _n (OR ² ) _3-n (2)
(However, in the formula, R ² is the same as above, and R ³ and R ⁴ are each the same or different hydrogen atoms, alkyl having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 alkyl atoms. A group or an aminoalkyl group, R ⁵ is a divalent hydrocarbon group having 1 to 18, preferably 1 to 8, more preferably 3 carbon atoms, and R ⁶ is an alkyl group having 1 to 4 carbon atoms, n is 0 or 1)

Examples of R ³ and R ⁴ in the above formula (2) include a methyl group, an ethyl group, a propyl group, a butyl group, an aminomethyl group, an aminoethyl group, an aminopropyl group, and an aminobutyl group. Examples of R ⁵ include alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of R ⁶ include a methyl group, an ethyl group, a propyl group, and a butyl group.

Specific examples of such an amino group-containing alkoxysilane of the above formula (2) include H ₂ N (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ Si (OCH ₂ CH ₃ ). ₃ , H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₅ Si (OCH ₃ ) ₃ , CH ₃ NH (CH ₂ ) ₅ Si (OCH ₂ CH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ NH (CH ₂ ) _{2 NH (CH 2) 3 Si (} OCH 3) 3, CH 3 NH (CH 2) 2 NH (CH 2) 3 Si (OCH 2 CH 3) 3, C 4 H 9 NH (C _{2) 2 NH (CH 2)} 3 Si (OCH 3) 3, C 4 H 9 NH (CH 2) 2 NH (CH 2) 3 Si (OCH 2 CH 3) 3, H 2 N (CH 2) 2 SiCH ₃ (OCH ₃ ) ₂ , H ₂ N (CH ₂ ) ₂ SiCH ₃ (OCH ₂ CH ₃ ) ₂ , H ₂ N (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ , H ₂ N (CH ₂ ) ₃ SiCH ₃ (OCH ₂ CH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₂ CH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₅ SiCH ₃ (OCH ₃ ) ₂ , CH ₃ NH (CH ₂ ) ₅ SiCH ₃ (OCH ₂ CH ₃ ) ₂ , H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₃ ) ₂ , H _{2 N (CH 2) 2 NH} (CH 2) 3 SiCH 3 (OCH 2 CH 3) 2, CH 3 NH (CH 2) 2 NH (CH 2) 3 _{iCH 3 (OCH 3) 2,} CH 3 NH (CH 2) 2 NH (CH 2) 3 SiCH 3 (OCH 2 CH 3) 2, C 4 H 9 NH (CH 2) 2 NH (CH 2) 3 SiCH 3 (OCH ₃ ) ₂ , C ₄ H ₉ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ SiCH ₃ (OCH ₂ CH ₃ ) _{2 and the} like, and these partial hydrolysates can also be used.

  Among these, in particular, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane or the like or a partial hydrolyzate thereof is preferably used.

  The component (iii) is inorganic oxide fine particles, and examples thereof include silicon oxide, titanium oxide, zinc oxide, aluminum oxide, and cerium oxide. Those having an average particle diameter of 1 to 200 nm are preferred. Particularly preferred is 5 to 100 nm. If this exceeds 200 nm, the substrate may become white or the water-repellent performance may deteriorate, which is not preferable. On the other hand, if it is less than 1 nm, the stability of the treatment agent may deteriorate, which is not preferable. The particle shape is not particularly limited, but is preferably spherical. When these inorganic oxide fine particles are used, it is preferable to use those dispersed in water or a solvent.

  Colloidal silica is particularly preferable from the viewpoint of cost and ease of use. Colloidal silica is obtained by dispersing silica fine particles in water or alcohol such as methanol, ethanol, isobutanol, or diacetone alcohol. Colloidal silica is a colloidal dispersion of fine silica particles in water or an alcohol solvent. For example, Snowtex O, Snowtex O-40, Snowtex OXS, Snowtex OS, Snowtex OL, Examples include Snowtex OUP, methanol silica sol, IPA-ST (manufactured by Nissan Chemical Industries, Ltd.).

The component (iv) is represented by the following general formula (3)
(R ¹ ) _k (OR ² ) _3-k Si-Y-Si (R ¹ ) _k (OR ² ) _3-k (3)
(Wherein, R ¹ and R ² are the same as above, Y is a divalent organic group, — (OSi (R ⁷ ) ₂ ) _m O— group or —R— (SiR ⁷ ₂ O) _m — A SiR ⁷ ₂ —R— group, wherein R ⁷ is an alkyl group having 1 to 6 carbon atoms, R is a divalent hydrocarbon group having 1 to 6 carbon atoms, and m is an integer of 1 to 30. K is 1, 2 or 3.)
Or a partially hydrolyzed product thereof.

R ^1, R ² in the formula (3) is the same as R ^1, R ² in the formula (1).
Y represents an organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms (preferably an alkylene group or — (CH ₂ ) _a (CF ₂ ) _b (CH ₂ ) _c — (a 1 to 6, b is 1 to 10, fluorine atom-containing alkylene group c is represented by 1~6)), - (OSi ( R 7) 2) m O- group or -R- (SiR ⁷ ₂ O) _m —SiR ⁷ ₂ —R— group (wherein R ⁷ is an alkyl group having 1 to 6, preferably 1 to 3 carbon atoms. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group) , N-butyl group, isobutyl group, n-pentyl group, n-hexyl group, etc., particularly methyl group, where R is a divalent hydrocarbon group having 1 to 6 carbon atoms, particularly 2 to 3 carbon atoms. In particular, an alkylene group is preferable, and m is an integer of 1 to 30, particularly 5 to 20.
k is 1, 2 or 3, preferably 2 or 3. In particular, k = 3 is preferable for improving water repellency.

Specific examples of the bis (alkoxysilyl) group-containing compound satisfying these include the following.
(CH ₃ O) ₃ SiCH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (OCH ₃ ) ₃ ,
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₄ F ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₆ F ₁₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₈ F ₁₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₁₀ F ₂₀ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C 4 F 8 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C 6 F 12 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C 8 F 16 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C 10 F 20 CH 2 CH 2 Si (CH 3) (OCH 3) 2,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₂ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₄ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₆ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₈ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₁₀ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₃ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₅ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₇ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₉ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

Among these, preferably _{(CH 3 O) 3 SiCH 2} CH 2 CH 2 CH 2 CH 2 CH 2 Si (OCH 3) 3,
(CH ₃ O) ₂ (CH ₃ ) SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₄ F ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₆ F ₁₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₆ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₈ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si (OSi (CH ₃ ) ₂ ) ₁₀ OSi (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₅ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₇ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ (Si (CH ₃ ) ₂ O) ₉ Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
Etc. Moreover, these partial hydrolysates are also used suitably.

  When the silicone-based water-repellent treatment agent is composed of only the components (i) and (ii), the amount used is (ii) 0.5 to 49 parts by mass, preferably 5 to 100 parts by mass of the component (i). -30 mass parts. When the component (ii) is less than 0.5 part by mass, the stability of the silicone-based water repellent agent itself is deteriorated. On the other hand, when the component (ii) exceeds 49 parts by mass, the water repellency is deteriorated or yellowing becomes severe when the component (A) is processed.

  In terms of molar conversion, it is preferable that the Si atom of the component (ii) is 0.01 to 0.3 mol, particularly 0.05 to 0.2 mol with respect to 1 mol of the Si atom of the component (i). .

  The proportion of use in the case of the silicone water-repellent treatment agent in the components (i), (ii) and (iii) and / or (iv) is (ii) component 0 with respect to 100 parts by mass of component (i). 5 to 49 parts by mass, preferably 5 to 30 parts by mass. When the component (ii) is less than 0.5 part by mass, the stability of the silicone-based water repellent agent itself is deteriorated. On the other hand, when the component (ii) exceeds 49 parts by mass, the water repellency is deteriorated or yellowing becomes severe when the component (A) is processed.

  (Iii) A component is 0.1-10 mass parts with respect to 100 mass parts of (i) component, Preferably it is 0.5-5 mass parts. (Iii) If the component is less than 0.1 part by mass, the water repellent effect is weakened. Moreover, when the component (iii) exceeds 10 parts by mass, the cost becomes disadvantageous, and the stability of the silicone-based water repellent agent is deteriorated.

  Moreover, (iv) component is 0.1-20 mass parts with respect to 100 mass parts of (i) component, Preferably it is 0.5-10 mass parts. If the component (iv) is less than 0.1 parts by mass, the water repellency effect is weakened. Further, when the component (iv) exceeds 20 parts by mass, it may be disadvantageous in terms of cost.

  In terms of mole, (i) + (iii) (added only when component (iii) is colloidal silica) + (iv) Si atom of component (ii) is 0.01 to 0 with respect to 1 mol of Si atom of component. It is preferable to use it so that it may become 0.3 mol, especially 0.05-0.2 mol.

  In order to produce a silicone-based water-repellent treatment agent using these components (i) and (ii), or (i), (ii), (iii) and / or (iv) components. Cohydrolysis and condensation may be performed in the presence of an organic acid or an inorganic acid.

  In this case, the component (i) is first hydrolyzed in the presence of an organic acid or an inorganic acid (if the component (iii) and / or (iv) is added, it is mixed with the component (i)). It is preferable that the decomposition product and the component (ii) are mixed and further hydrolyzed in the presence of an organic acid or an inorganic acid.

  First, as an organic acid and an inorganic acid used when hydrolyzing component (i) (when (iii) and / or (iv) component is added, it is mixed with component (i)), for example, hydrochloric acid is used. At least one acid selected from sulfuric acid, nitric acid, methanesulfonic acid, formic acid, acetic acid, propionic acid, citric acid, oxalic acid, maleic acid and the like is used, and particularly preferred are acetic acid and propionic acid. The amount of the acid used is preferably 2 to 40 parts by mass, particularly 3 to 15 parts by mass with respect to 100 parts by mass of component (i).

  The hydrolysis is preferably carried out in a state diluted with a solvent appropriately. As the solvent, alcohol solvents are preferable, and methanol, ethanol, isopropyl alcohol, and tertiary butyl alcohol are particularly preferable. The amount of the solvent used is 50 to 300 parts by mass with respect to 100 parts by mass of component (i) (when component (iii) and / or (iv) is added, the total amount mixed with component (i)), 70-200 mass parts is especially preferable. If the amount of the solvent used is less than 50 parts by mass, condensation may proceed, and if it exceeds 300 parts by mass, it takes time for hydrolysis.

  The amount of water added to hydrolyze component (i) (and (iii) and / or (iv)) is the sum of component (i) or (i), (iii) and / or (iv) An amount of 0.5 to 4 mol, particularly 1 to 3 mol, is preferable with respect to 1 mol. If the amount of water added is less than 0.5 mol, a large amount of alkoxy groups may remain, and if the amount exceeds 4 mol, condensation may proceed excessively. Moreover, when using the colloidal silica disperse | distributed in water as (iii) component, it is good also as the water used for a hydrolysis. The reaction conditions for hydrolyzing the component (i) or the components (i), (iii) and / or (iv) are preferably a reaction temperature of 10 to 40 ° C, particularly 20 to 30 ° C, and a reaction time of 1 to 3 It is better to carry out the hydrolysis reaction over time.

  The component (i) obtained above or the hydrolyzate of the components (i), (iii) and / or (iv) is reacted with the component (ii). The reaction conditions are preferably a reaction temperature of 60 to 100 ° C. and a reaction time of 1 to 3 hours. After completion of the reaction, the temperature is raised to the boiling point of the solvent or higher, and a solvent such as an alcohol solvent is distilled off. In this case, it is preferable to distill off the content of the solvent such as all alcohols in the system (alcohol as a reaction solvent and alcohol as a by-product) to 30% by mass or less, particularly 10% by mass or less.

  The silicone water repellent component in the present invention can be water-repellent simply by blending with ammonium polyphosphate, but it is more preferable to coat the surface of ammonium polyphosphate. The blending or surface coating method can be obtained by processing by a known method such as a phase separation method, a submerged drying method, a melt dispersion cooling method, a spray drying method, or a submerged curing method. Preferably, a method of removing the solvent after blending and coating a silicone-based water repellent agent dissolved in a volatile solvent with ammonium polyphosphate.

  The proportion of ammonium polyphosphate and silicone water repellent component used is 80 to 99.8 mass%, especially when the total amount of ammonium phosphate and silicone water repellent component is 100 mass%. 90 to 97% by mass, silicone water repellent component 0.2 to 20% by mass, particularly 3 to 10% by mass. If there are too few silicone water repellent components, water resistance and water repellency will become weak, and if there are too many silicone water repellent components, it will become disadvantageous in cost.

  When the ammonium polyphosphate is treated with an acid in a solution, it is used after removing the solvent by filtration or drying. Further, when the ammonium polyphosphate is treated with an acid in a solvent, a hydrophobic compound can be added together to carry out a surface treatment.

  In addition to fibers, the ammonium polyphosphate of the present invention can be added to and blended with resins (thermoplastic resins, thermosetting resins), elastomers, coating agents, sealants, etc. to impart flame retardancy, In this case, the addition / formulation form is an emulsion type coating agent containing 0.1 to 50% by mass, particularly 5 to 30% by mass of the ammonium polyphosphate, or 0.1 to 30% by mass of the ammonium polyphosphate. In particular, a flame retardant composition containing 5 to 20% by mass and having a resin or an elastomer as a base polymer can be obtained.

  In this case, the ammonium polyphosphate according to the present invention may be further added with a phosphorus-containing compound or a nitrogen-containing compound, or a polyhydric alcohol may be added thereto. Moreover, you may use together flame retardants generally known, such as a metal hydroxide.

  Polyhydric alcohols are acyclic and cyclic compounds in which a plurality of hydroxyl groups are bonded. For example, pentaerythritol, dipentaerythritol, tripentaerythritol, pentitols (such as adonitol and arabitol), There are xitols (such as dulcitol and inositol), saccharides (such as amylose and xylan), and derivatives thereof (such as N-methylglucamine).

  When the fiber is treated with the ammonium polyphosphate of the present invention to exhibit flame retardancy, the fiber is dipped in the above emulsion-type coating agent in which the additive of the present invention is dispersed and then dried, and the present invention is applied to the surface of the fiber. A method of obtaining flame retardancy by coating a flame retardant is preferred.

  In the ammonium polyphosphate of the present invention, additives can be blended depending on the purpose as long as the properties are not impaired. Additives include neutralizers, acid trapping agents, antioxidants, UV absorbers, stabilizers, light stabilizers, compatibilizers, other types of non-halogen flame retardants, lubricants, fillers, adhesion aids, rust prevention An agent etc. can be mentioned.

  Examples of the neutralizing agent and acid trapping agent that can be used in the present invention include calcium hydroxide, magnesium hydroxide, hydrotalcite, and ion exchange resin.

  Antioxidants usable in the present invention include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl). ) Propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4 , 4′-butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8 10-tetraoxaspiro [5,5] undecane, 4,4-thiobis- (2-tert-butyl-5-methylphenol), 2,2-methylenebis- (6-tert-butyl-methylphenol), 4, 4-methylenebis- (2,6-di-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris Nonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol phosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) Nyl) octyl phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-di-phosphonite, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′- Thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), 2,5,7,8-tetramethyl-2 (4,8,12-trimethyldecyl) chroman-2-ol, 5,7- Di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 , 6-Dipentylphenyl acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate , Tetrakis (methylene) -3- (dodecylthiopropionate) methane and the like.

  Stabilizers that can be used in the present invention include lithium stearate, magnesium stearate, calcium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc laurate, zinc ricinoleate, stearin Various metal soap stabilizers such as zinc acid, various organic tin stabilizers such as laurate, malate and mercapto, various lead stabilizers such as lead stearate and tribasic lead sulfate, and epoxy compounds such as epoxidized vegetable oil Phosphite compounds such as alkyl allyl phosphite and trialkyl phosphite, β-diketone compounds such as dibenzoylmethane and dehydroacetic acid, polyols such as sorbitol, mannitol and pentaerythritol, hydrotalcites and Mention may be made of a light class.

  Examples of light stabilizers that can be used in the present invention include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxalic anilide-based UV absorbers, hindered amine-based light stabilizers. Agents and the like.

  EXAMPLES Hereinafter, although a synthesis example and an Example and a comparative example demonstrate this invention concretely, this invention is not limited to a following example. In the following examples, the viscosity represents a value at 25 ° C. measured with a capillary viscometer, and the weight average molecular weight represents a polystyrene equivalent value measured with a GPC measuring device. Moreover, in the following Example, an average particle diameter shows the value measured with the laser scattering type particle size distribution measuring apparatus.

[Synthesis Example 1]
A 500 ml four-flask equipped with a condenser, thermometer and dropping funnel was charged with 85 g of methyltrimethoxysilane oligomer (0.37 mol in terms of dimer), 154 g of methanol and 5.1 g of acetic acid. 6.8 g (0.37 mol) of water was added and stirred at 25 ° C. for 2 hours. There, 17.7 g (0.08 mol) of 3-aminopropyltriethoxysilane was added dropwise. Then, after heating to the reflux temperature of methanol and reacting for 1 hour, the methanol was distilled off with an ester adapter until the internal temperature reached 110 ° C. to obtain 81 g of a pale yellow transparent solution having a viscosity of 71 mm ² / s (weight). Average molecular weight 1100). The amount of residual methanol in this system was 5% by mass (silicone-based water repellent agent 1).

[Example 1]
100 parts by mass of ammonium polyphosphate (P content 20% by mass, bulk density 0.7 g / cm ³ , average particle size 15 μm), 350 parts by mass of hexane, 5 parts by mass of trimethylchlorosilane (amount of generated hydrochloric acid 1.68 parts by mass) Part), and after stirring at room temperature for 30 minutes, 5 parts by mass of methanol is added and further stirred for 1 hour. After stirring, filter paper filtration is performed. Further, ammonium polyphosphate on the filter paper is washed with 1000 ml of methanol, spread thinly on a tray, and placed in a dryer at 90 ° C. for 3 hours. Obtained.
The bulk density of ammonium polyphosphate was measured in accordance with JIS Z8807.

[Example 2]
The silicone-based water repellent agent 1 produced in Synthesis Example 1 was stirred with 4.5 parts by mass and 100 parts by mass of ethanol for 30 minutes with respect to 95.5 parts by mass of the ammonium polyphosphate obtained in Example 1, and then under reduced pressure. The ethanol was distilled off to obtain a silicone-treated ammonium polyphosphate having an average particle size of 28 μm.

[Example 3]
100 parts by mass of ammonium polyphosphate (P content 20% by mass, bulk density 0.7 g / cm ³ , average particle size 15 μm), 350 parts by mass of hexane, 20 parts by mass of trimethylchlorosilane (the amount of hydrochloric acid generated is 6.72 masses) Part), and after stirring at room temperature for 30 minutes, 20 parts by mass of methanol is added and further stirred for 1 hour. After stirring, the filter paper was filtered, and the ammonium polyphosphate on the filter paper was washed with 1000 ml of methanol. . Using the obtained acid-treated ammonium polyphosphate, the silicone-based water repellent agent 1 produced in Synthesis Example 1 was treated under the same conditions as in Example 2 to obtain a silicone-treated ammonium polyphosphate having an average particle size of 29 μm. It was.

[Example 4]
With respect to 90 parts by mass of ammonium polyphosphate obtained in Example 1, 10 parts by mass of hydrophobic silica was put into a ribbon type mixer and subjected to stirring and mixing at a high speed for 1 minute. By the treatment operation, surface-treated ammonium polyphosphate 3 having an average particle diameter of 18 μm and coated with silica was obtained. When this hydrophobic silica-coated ammonium polyphosphate 3 was observed with an SEM, it was confirmed that the silica was closely adhered and coated on the surface of the ammonium polyphosphate particles.

[Example 5]
The treatment was performed in the same manner as in Example 3 except that 6N hydrochloric acid water (3.6 parts by mass of hydrochloric acid) was used as the trimethylchlorosilane of Example 3 to obtain a silicone-treated ammonium polyphosphate having an average particle size of 29 μm. .

[Example 6]
Ammonium polyphosphate (P content 20% by mass, bulk density 0.7 g / cm ³ , average particle size 15 μm) 95.5 parts by mass, methanol 350 parts by mass, trimethylchlorosilane 20 parts by mass (the amount of generated hydrochloric acid 6. 72 parts by mass) was stirred at room temperature for 1 hour, and then 4.5 parts by mass of the silicone-based water repellent agent 1 produced in Synthesis Example 1 was added, and the mixture was stirred at room temperature for 30 minutes, followed by filter paper filtration. The filtrate was thinly spread on a tray, placed in a dryer at 90 ° C. for 3 hours, and the solvent was removed to obtain a silicone-treated ammonium polyphosphate having an average particle size of 27 μm.

[Comparative Example 1]
Ammonium polyphosphate (P content 20% by mass, bulk density 0.7 g / cm ³ , average particle size 15 μm)

[Comparative Example 2]
4.5 parts by mass of the silicone-based water repellent agent 1 produced in Synthesis Example 1 was added to 95.5 parts by mass of ammonium polyphosphate (P content 20% by mass, bulk density 0.7 g / cm ³ , average particle size 15 μm). After stirring for 30 minutes with 100 parts by mass of ethanol, ethanol was distilled off under reduced pressure to obtain a silicone-treated ammonium polyphosphate having an average particle size of 29 μm.

[Comparative Example 3]
To 100 parts by mass of ammonium polyphosphate (P content 20% by mass, bulk density 0.7 g / cm ³ , average particle size 15 μm), 350 parts by mass of hexane, 0.05 part by mass of 6N hydrochloric acid water (amount of hydrochloric acid 0. 009 parts by mass), and after stirring at room temperature for 30 minutes, 5 parts by mass of methanol is added and further stirred for 1 hour. After stirring, filter paper filtration was performed, and ammonium polyphosphate on the filter paper was washed with 1000 ml of methanol, and then spread thinly on a tray and placed in a dryer at 90 ° C. for 3 hours to obtain acid-treated ammonium polyphosphate.
After stirring the silicone water-repellent agent 1 produced in Synthesis Example 1 with 4.5 parts by mass and 100 parts by mass of ethanol for 30 minutes with respect to 95.5 parts by mass of ammonium polyphosphate, the ethanol was distilled off under reduced pressure. A silicone-treated ammonium polyphosphate having an average particle size of 28 μm was obtained.

[Comparative Example 4]
The treatment was carried out in the same manner as in Comparative Example 2 except that 0.05 parts by mass of 6N hydrochloric acid in Comparative Example 2 was changed to 0.05 parts by mass of trimethylchlorosilane (the amount of generated hydrochloric acid was 0.0168 parts by mass). A silicone-treated ammonium polyphosphate having a particle size of 28 μm was obtained.

  The treated ammonium phosphate and untreated ammonium polyphosphate obtained in the above Examples and Comparative Examples were dispersed by 20% by mass in 25 ° C. water and 60 ° C. warm water, and the slimy feeling when applied to 10 fingers was evaluated. .

Claims (7)

  Modification of ammonium polyphosphate characterized by eliminating the slimy feeling caused by moisture by treating ammonia on the surface of ammonium polyphosphate with an acid of 0.1 to 50 parts by mass with respect to 100 parts by mass of ammonium polyphosphate Method.   2. The method for modifying ammonium polyphosphate according to claim 1, wherein the ammonium polyphosphate is treated with an acid in a solvent, and then the solvent is removed.   The method for modifying ammonium polyphosphate according to claim 1 or 2, wherein the acid is hydrochloric acid or chlorosilane which generates hydrochloric acid by being decomposed by protons.   A method for modifying ammonium polyphosphate, comprising surface-treating the ammonium polyphosphate treated with the acid according to any one of claims 1 to 3 with a hydrophobic compound. The hydrophobic compound is one or more compounds selected from silane coupling agents, titanate coupling agents, silicone oils, silicone resins, silicone rubber, hydrophobic silica , fatty acids, fatty acid metal salts, fatty acid esters, fatty acid alcohols. The method for modifying ammonium polyphosphate according to claim 4, wherein: Hydrophobic compounds
(I) The following general formula (1)
(R ¹ ) _a (OR ² ) _b SiO _{(4-a-b) / 2} (1)
(However, R in the formula ¹ Is an alkyl group having 1 to 6 carbon atoms, R ² Is an alkyl group having 1 to 4 carbon atoms, a is 0.75 to 1.5, b is 0.2 to 3, and is a positive number satisfying 0.9 <a + b ≦ 4. )
100 parts by mass of an organosilicon compound represented by:
(Ii) The following general formula (2)
R ^Three R ^Four NR ^Five -SiR ⁶ _n (OR ² ) _3-n (2)
(However, R in the formula ² Is the same as above, R ^Three , R ^Four Are the same or different hydrogen atoms, alkyl groups having 1 to 15 carbon atoms or aminoalkyl groups, R ^Five Is a divalent hydrocarbon group having 1 to 18 carbon atoms, R ⁶ Is an alkyl group having 1 to 4 carbon atoms. n is 0 or 1. )
0.5 to 49 parts by mass of an amino group-containing alkoxysilane or a partial hydrolyzate thereof represented by
A co-hydrolysis condensate obtained by co-hydrolysis condensation in the presence of an organic acid or an inorganic acid,
Or
(I) 100 parts by mass of component, (ii) 0.5 to 49 parts by mass of component,
(Iii) 0.1 to 10 parts by mass of inorganic oxide fine particles and / or
(Iv) The following general formula (3)
(R ¹ ) _k (OR ² ) _3-k Si-Y-Si (R ¹ ) _k (OR ² ) _3-k (3)
(However, R in the formula ¹ And R ² Is the same as above, Y is a divalent organic group,-(OSi (R ⁷ ) ₂ ) _m O-group or -R- (SiR ⁷ ₂ O) _m -SiR ⁷ ₂ -R- group, where R ⁷ Is an alkyl group having 1 to 6 carbon atoms, R is a divalent hydrocarbon group having 1 to 6 carbon atoms, and m is an integer of 1 to 30. K is 1, 2 or 3. )
0.1 to 20 parts by mass of a bis (alkoxysilyl) group-containing compound represented by the formula:
Cohydrolyzed condensate obtained by cohydrolyzing and condensing in the presence of organic acid or inorganic acid
The method for modifying ammonium polyphosphate according to claim 4, which is a silicone-based water repellent treatment agent. The surface-treated ammonium polyphosphate obtained in any one of Claims 4-6.