WO2012011519A1

WO2012011519A1 - Fire retarding agent containing cyclic amine salt, and fire-retardant resin composition

Info

Publication number: WO2012011519A1
Application number: PCT/JP2011/066534
Authority: WO
Inventors: 小林　淳一; 快三輪; 喜一平田; 石川　章
Original assignee: 丸菱油化工業株式会社
Priority date: 2010-07-22
Filing date: 2011-07-21
Publication date: 2012-01-26
Also published as: TW201209143A; JP2012025840A

Abstract

Disclosed is a fire retarding agent that is for a resin, does not contain a halogen, has excellent fire retarding properties, and suppresses problems with moisture resistance and blooming. Specifically disclosed are: a fire retarding agent containing a cyclic amine salt having a particular chemical structure; and a fire retarding resin composition that contains said fire retarding agent and a resin component and that contains 1-100 parts by weight of said cyclic amine salt for every 100 parts by weight of the resin component.

Description

Flame retardant containing cyclic amine salt and flame retardant resin composition

The present invention relates to a novel flame retardant and a flame retardant resin composition. In particular, the present invention relates to a flame retardant containing a cyclic amine salt, a flame retardant resin composition containing the flame retardant, and a molded product thereof. More specifically, it is useful for molding injection-molded articles and extrusion-molded articles. For example, it is suitable for home appliances, OA equipment, automobile parts, wire coating materials, etc. It relates to molded products.

Polyolefin resins, polystyrene resins, polyacrylic resins, polyamide resins, polyester resins, polyether resins, thermoplastic resins such as polycarbonate resins, thermosetting resins such as phenol resins and epoxy resins, or these Resin alloys by combination, for example, various materials in addition to building materials, electrical equipment materials, vehicle parts, automobile interior parts, household goods, etc., depending on the characteristics such as specific mechanical characteristics, thermal characteristics, moldability, etc. Widely used in industrial products.

However, since these synthetic resins generally have the disadvantage of being easily combusted, many various methods for making the synthetic resins flame-retardant have been proposed. As a general method for flame-retarding a synthetic resin, a method of blending a flame retardant with a resin is employed. Of the conventional methods for making flame retardant, the most used example is a method of adding antimony oxide and a halogen-based organic compound. Examples of halogen-based organic compounds include tetrabromobisphenol A, hexabromocyclododecane, bisdibromopropyl ether of tetrabromobisphenol A, bisdibromopropyl ether of tetrabromobisphenol S, tris 2,3-dibromopropyl isocyanurate, bistribromophenoxy Examples include ethane, hexabromobenzene, decabromobiphenyl ether, decabromobiphenyl ethane, and the like.

However, in view of recent efforts to deal with global environmental problems, halogen-based organic compounds that easily generate harmful gases (hydrogen bromide) during combustion are strongly required to be self-reliant. For this reason, several methods for imparting flame retardancy to a synthetic resin without using a halogen-based flame retardant have been proposed. One of them is a method of adding an inorganic hydroxide such as aluminum hydroxide or magnesium hydroxide. However, since the inorganic hydroxide exhibits flame retardancy due to water generated by thermal decomposition, the flame retardancy is not exhibited unless added in a considerably large amount. Due to such a large amount of addition, there is a problem that functions inherent to the resin such as processability and mechanical properties are remarkably lowered.

There is a method using an organic phosphorus compound such as triphenyl phosphate and tricresyl phosphate as another method not using a halogen-based flame retardant. However, these organophosphorus compounds belong to phosphate ester type flame retardants. When heat-kneaded with synthetic resins such as polyester at high temperatures, transesterification occurs and the molecular weight of the synthetic resin is significantly reduced. As a result, the original physical properties of the resin are impaired. Moreover, the phosphoric ester-type flame retardant itself may gradually hydrolyze with moisture in the air to produce phosphoric acid. When phosphoric acid is produced in a synthetic resin, the molecular weight of the synthetic resin is reduced. There is a danger of causing a short circuit when used for electrical or electronic parts.

On the other hand, the use of phosphates such as ammonium polyphosphate has been proposed as a non-halogen flame retardant. However, when a large amount of this type of phosphates is added, the phosphates are low in flame retardancy and inferior in moisture resistance, so the appearance and mechanical properties of the molded product are greatly reduced. . In addition, if a resin molded article made of this flame retardant composition is used under high humidity, phosphates bleed out on the surface, and there are also fatal defects that cause numerous blooming phenomena. .

Ammonium polyphosphate coated with a surface treatment agent of melamine cross-linking type, phenol cross-linking type, epoxy cross-linking type or silane coupling agent and end-capped polyethylene glycol cross-linking type with improved moisture resistance, in order to improve the above-mentioned drawbacks Has also been proposed. However, these have a problem that resin compatibility or dispersibility is poor and high mechanical strength cannot be obtained. Further, when a resin composition containing a large amount of coated ammonium polyphosphate is kneaded, the coating is broken by heat and stress, and problems similar to the above (problems such as bleeding out due to moisture absorption) often occur.

Generally, since a resin composition containing ammonium polyphosphate undergoes thermal decomposition from around 200 ° C. during kneading, the pyrolyzed product bleeds out even during kneading, causing strand wetness. This is a cause of extremely worsening the physical properties and productivity of the flame retardant resin composition. For example, in the prior art, polyphosphate piperazine salts have been proposed (Patent Documents 1 to 4). However, these conventional techniques have the same problems as described above, and there are many points that should be improved in practice. In other words, condensed ammonium phosphate salts such as ammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate are basically water-soluble or water-absorbing substances, and therefore their addition is heat resistance and moisture resistance of the resin composition. Is a direct cause of decline.

In order to improve this, organic salts such as aliphatic amine salts of aromatic phosphoric acid monoesters have been proposed (Patent Documents 5 to 7). However, the aliphatic amine salt of the aromatic phosphoric acid monoester is a water-soluble organic salt having a very strong water absorption property although having a predetermined flame retardancy. As an example, a monotolylpiperazine phosphate salt represented by the following chemical formula (1) corresponds to this.

This substance is an onium salt in which tolyl dihydrogen phosphate ion, which is an anionic component, and piperazine ion, which is a cation component, are alternately coordinated, and is highly water-soluble and insoluble in most organic solvents. The resin compatibility is also very poor. For this reason, monotolylpiperazine phosphate has low heat resistance, and particularly when it is kneaded as a resin composition, a large amount of highly toxic p-cresol gas is generated by thermal decomposition at a kneading temperature of 180 to 200 ° C. It has a fatal defect that it is not practically satisfactory.

JP 2000-169731 A JP 2003-026935 A WO2004-000973 WO2010-013400 JP 2001-064453 JP 2001-288309 A JP 2002-080633 A

Accordingly, the main object of the present invention is to solve the problems of the prior art and to provide a flame retardant capable of imparting more excellent flame retardancy, and further to a flame retardant resin composition containing the composition and molding the same. It is to provide a molded article.

As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by employing a cyclic amine salt of a specific aromatic phosphate as an active ingredient of a flame retardant, The present invention has been completed.

That is, the present invention particularly relates to a flame retardant and a flame retardant resin composition containing the following cyclic amine salt.
1. A flame retardant composition comprising a cyclic amine salt of an aromatic phosphate diester composed of 1) an aromatic phosphoric diester as an anionic component and 2) a cyclic amine as a cationic component, the cyclic amine salt being Formula (I)

[Wherein R ₁ to R ₁₀ are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. n represents an integer of 1 to 10. m represents an integer of 0 to 9. l represents an integer of 1 to 10. ]
The flame retardant composition containing cyclic amine salt represented by these.
2. In the cyclic amine salt of the aromatic phosphoric diester,
The following general formula (II)

[Wherein R ₁ to R ₁₀ are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A component represented by
The following general formula (III)

[Wherein, A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. m represents an integer of 0 to 9. ]
2. The flame retardant composition according to item 1, wherein the composition ratio of the component B to the component B is an ion equivalent ratio of A component / B component = 0.8 / 1.0 to 1.0 / 1.2 .
3. Item 2. The flame retardant composition according to Item 1, wherein the content of the aromatic phosphoric acid monoester is 1% by weight or less in the flame retardant composition.
4). Item 2. The flame retardant composition according to Item 1, further comprising at least one phosphate.
5. A flame retardant composition comprising the flame retardant composition according to item 1 and a resin component, the flame retardant comprising 1 to 100 parts by weight of a cyclic amine salt of the aromatic phosphoric diester with respect to 100 parts by weight of the resin component Resin composition.
6). 5. A resin composition comprising the flame retardant composition according to item 4 and a resin component, wherein 1 to 50 parts by weight of a cyclic amine salt of the aromatic phosphoric diester, 100 parts by weight of the resin component, and the phosphates A flame retardant resin composition comprising 1 to 50 parts by weight.
7. Item 7. The flame retardant resin composition according to Item 5 or 6, wherein the resin component is a polyolefin resin.
8). 8. A flame retardant resin molded product obtained by molding the flame retardant resin composition according to any one of items 5 to 7.
9. Item 9. The flame-retardant resin molded article according to Item 8, which is used for electrical / electronic parts, OA equipment parts, household electrical equipment parts, automotive parts or equipment mechanism parts.
10. The following general formula (I)

[Wherein R ₁ to R ₁₀ are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. n represents an integer of 1 to 10. m represents an integer of 0 to 9. l represents an integer of 1 to 10. ]
A process for producing a cyclic amine salt of an aromatic phosphoric diester represented by
(1) The following general formula (IV)

[Wherein R ₁ to R ₅ are the same or different from each other and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
Is reacted with phosphorus oxyhalide in the presence of an amine,
The following general formula (V)

[Wherein R ₁ to R ₁₀ are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A step of synthesizing a halogen-containing aromatic phosphate ester derivative represented by:
(2) By hydrolyzing the halogen-containing aromatic phosphate ester derivative,
The following general formula (II)

[Wherein R ₁ to R ₁₀ are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A step of synthesizing an aromatic phosphate diester represented by:
(3) For the aromatic phosphoric acid diester, the following general formula (VI)

[Wherein, A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. m represents an integer of 0 to 9. ]
A method for producing a cyclic amine salt of an aromatic phosphoric diester, comprising a step of synthesizing a compound represented by the general formula (I) by adding a compound represented by formula (I).

Since the flame retardant of the present invention contains a cyclic amine salt having a specific chemical structure, it can exhibit flame retardancy superior to conventional flame retardants. Therefore, the desired flame retardancy can be imparted even with a relatively small amount of addition. That is, it is possible to provide excellent flame retardancy while effectively maintaining the original characteristics of the material to be added (resin etc.).

Further, since the flame retardant of the present invention is excellent in moisture resistance, problems such as bleeding out and blooming due to moisture absorption, and deterioration of flame resistance due to bleeding out can be effectively suppressed or prevented.

Furthermore, since the cyclic amine salt, which is an active ingredient of the flame retardant of the present invention, does not contain a halogen element in the molecule, it can effectively suppress the generation of harmful gases even when the flame retardant resin and the molded product burn. it can.

In particular, in the present invention, when applied as a flame retardant such as a polyolefin resin, it is possible to exhibit excellent flame retardancy with a smaller amount of flame retardant by using phosphates together with the cyclic amine salt. it can. Conventionally, phosphates such as polyphosphates have high water solubility or high water absorption. For this reason, the flame-retardant resin composition and molded product containing phosphate as a flame retardant cannot effectively suppress mold deposits and bleed-out (or blooming) of the flame retardant. On the other hand, the flame-retardant resin composition and molded product containing the flame retardant of the present invention can highly compatibilize polyphosphates with the resin while maintaining good physical properties of various resins. In addition, it is possible to impart a high degree of flame retardancy equal to or higher than that of the prior art to the polyolefin resin and the like while effectively suppressing mold deposits and bleed out (or blooming) of polyphosphates.

Thus, the flame retardant of the present invention can be suitably used as a flame retardant for adding to a material containing an organic component, for example. In particular, it can be preferably used as a flame retardant for addition to a composition containing a resin component (for example, a composition containing 50% by weight or more of a resin component).

Hereinafter, a flame retardant composition containing the cyclic amine salt of the present invention as a main component, a flame retardant resin composition containing this as a resin component, and a molded product formed by molding this composition will be described in detail. .

1. Flame retardant composition containing cyclic amine salt (1) Cyclic amine salt and synthesis method thereof (1-1) Cyclic amine salt The flame retardant for resin of the present invention is 1) an aromatic phosphate diester as an anionic component and 2) A flame retardant comprising a cyclic amine salt of an aromatic phosphoric diester composed of a cyclic amine which is a cationic component,
The cyclic amine salt of the aromatic phosphoric diester is
The following general formula (I)

[Wherein R ₁ to R ₁₀ are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. n represents an integer of 1 to 10. m represents an integer of 0 to 9. l represents an integer of 1 to 10. And a cyclic amine salt of an aromatic phosphoric acid diester represented by the formula:

That is, the aromatic phosphoric diester cyclic amine salt represented by the following general formula (I) (hereinafter also referred to as “the present cyclic amine salt”) functions as an active ingredient of the present flame retardant. The flame retardant of the present invention contains one or more of the cyclic amine salts of the present invention.

The cyclic amine salt of the present invention contains an aromatic phosphate diester as an anion component (component A) and is composed of a cyclic amine as a cation component (component B). As such a cyclic amine salt, a known or commercially available one can also be used. Hereinafter, the cyclic amine salt of the present invention will be described separately for component A and component B.

A component The aromatic phosphoric acid diester which comprises A component among cyclic amine salt of this invention is shown by the following general formula (II).

[Wherein R ₁ to R ₁₀ are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]

R ₁ to R ₁₀ in the general formula (II) represent a hydrogen atom or a hydrocarbon group which may have a substituent. Further, each of R ₁ to R ₁₀ may be the same substituent as each other, or may be different from each other. In particular, in the present invention, R ₁ to R ₁₀ are more preferably a hydrogen atom than an optionally substituted hydrocarbon group from an economical viewpoint.

The hydrocarbon group is not particularly limited, and may be any of a chain (which may be either a straight chain or a branched chain) or a ring (which may be a monocyclic ring, a condensed polycyclic ring, a bridged ring or a spiro ring). Also good. For example, a cyclic hydrocarbon group having a side chain can also be used. Further, the hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.

Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an allyl group, an aryl group, an alkylaryl group, and an arylalkyl group. The total number of carbon atoms of these hydrocarbon groups (including the number of carbon atoms of the substituent group if it has a substituent group) is not limited, but is generally about 1 to 18, and preferably about 1 to 4. . More specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group and the like can be exemplified.

In addition, a substituent may be introduced into the hydrocarbon group. Examples of the substituent include an amino group, hydroxyl group, alkoxyl group, nitro group, cyano group, carbonyl group, aldehyde group, carboxyl group, sulfone group, and sulfhydryl group.

Among these, the most preferred specific examples are R ₁ , R ₃ , R ₅ , R ₆ , R ₈ and R ₁₀ are hydrogen atoms or methyl groups, and R ₂ , R ₄ , R ₇ and R _9. Is a hydrogen atom.

More specific examples of the aromatic phosphoric acid diester represented by the general formula (I) include compounds represented by the following formulas (1) to (5). As these compounds themselves, known or commercially available compounds can also be used.

B component Among the cyclic amine salts of the present invention, the cyclic amine constituting the B component is represented by the following general formula (III).

[A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. m represents an integer of 0 to 9. ]

A is a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Therefore, when m = 0, Z becomes an imino group. In the case of m = 0, for example, piperidine, pyrrolidine and the like are applicable.

Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group. In the present invention, an alkylene group having 2 to 6 carbon atoms is particularly preferable.

As such a cyclic amine, for example, a compound in which one or more imino groups (—NH—) are cyclically bonded through an oxygen atom, a sulfur atom or an imino group and an alkylene group can be used. More preferably, a cyclic amine in which two or more imino groups are bonded cyclically via an alkylene group is used.

Specific examples of the cyclic amine include aziridine, azetidine, pyrrolidine, piperidine, azepan, azocan, azonan, azecan, diazetidine, imidazolidine, pyrazolidine, piperazine, morpholine, thiomorpholine, 1,4,7-triazacyclononane. 1,4,7,10-tetraazacyclododecane, 1,4,7,10,13-pentaazacyclopentadecane, 1,4,7,10,13,16-hexaazacyclooctadecane and the like.

Among these, in the present invention, as the cyclic amine A, cyclic amines or cyclic polyamines can be appropriately selected and used. Examples of cyclic amines include pyrrolidine, imidazolidine, pyrazolidine, piperazine, morpholine, thiomorpholine, and the like. Examples of the cyclic polyamines include cyclic polyamines in which two or more combinations of imino group (—NH—) and ethylene group (—CH ₂ —CH ₂ —) are linked in a cyclic manner. Among these, piperazine is most preferable from the viewpoint of being inexpensive and easy to obtain.

Specific examples of the cyclic amine represented by the general formula (III) include compounds represented by the following formulas (6) to (10).

As the cyclic amine salt of the present invention, those having high heat resistance during kneading or molding with a resin component can be suitably used. For this reason, the cyclic amine A is preferably a secondary amine or a tertiary amine rather than a primary amine. Also, from the viewpoint of preventing flushing due to pyrolysis gas that may occur during molding, a cyclic amine can be used more suitably than an aliphatic amine having low heat resistance.

The component ratio of the A component and the B component in the cyclic amine salt of the present invention is not particularly limited, but in order to more effectively retain flame retardancy, moisture resistance, etc., the respective ion equivalents of the A component and the B component Are preferably equal. By making each ion equivalent equal, the content of excess ionic components can be lowered, so that the expression of water solubility or hygroscopicity can be effectively suppressed or prevented, resulting in poor appearance of molded products, etc. In addition, deterioration of physical properties can be avoided.

From this viewpoint, the component ratio (ion equivalent ratio) of the A component and the B component in the cyclic amine salt of the present invention is in the range of A component / B component = 0.8 / 1.0 to 1.0 / 1.2. If it exists, it can be used more suitably as a flame retardant without causing the above-mentioned problems. Furthermore, in the present invention, it is most preferable that the constituent ratio of the A component and the B component is completely equal.

Preferred embodiments of the cyclic amine salt of the present invention The role of the cyclic amine salt of the present invention in the flame retardant resin composition of the present invention and its molded article is not only to function as a flame retardant, but also to a moisture absorption inhibitor, blooming inhibitor, etc. Can exhibit various functions. In view of this point, specific examples of the more preferred cyclic amine salt of the present invention are shown by the following formulas (11) to (16) when piperazine is selected as a preferred example of the constituent B component. Compounds.

In addition, a well-known thing can be used for the aromatic phosphoric acid diester which is A component which comprises the cyclic amine salt of this invention, and the cyclic amine which is B component, respectively. Moreover, the cyclic amine salt of the aromatic phosphoric acid diester obtained by a well-known manufacturing method can also be used.

(1-2) Method for Synthesizing the Cyclic Amine Salt of the Present Invention The cyclic amine salt of the present invention can be produced by a known production method, but is particularly preferably produced by the production method of the present invention.

As a known method for synthesizing the aromatic phosphate ester derivative represented by the general formula (II) from the compound represented by the general formula (IV), conventionally, Phosphorus and its compounds Volume 2, 1961, Interscience
The method described in Pubublishers, Inc., New York, 1230-, ie, a method of production by partial hydrolysis using alkali from trialkyl phosphate, after producing a mixture of monoalkyl dihydroxy phosphate and dialkyl hydroxy phosphate, There are manufacturing methods for selective distribution according to the difference.

When the synthetic route disclosed in the above publication is applied, by reacting an excess of the compound represented by the general formula (IV) with phosphorus pentoxide or phosphorus oxychloride, aromatic monophosphate ester, aromatic diphosphate ester And a mixture of aromatic triphosphates can be synthesized. However, this method is not economically advantageous because of low yield and labor for purification. For example, in the case of phosphorylation of phenol with phosphorus oxychloride, it is possible to preferentially synthesize dichloromonophenyl phosphate (monoester) by adding a large excess of phosphorus oxychloride. By adding 3 equivalents to the reaction, triphenyl phosphate (triester form) can be preferentially synthesized with good yield. However, even if the synthesis route of the above publication is applied, it is difficult to selectively synthesize preferentially only monochlorodiphenyl phosphate (diester).

On the other hand, in the production method of the present invention, the compound represented by the chemical formula (IV) is reacted with phosphorus oxyhalide in the presence of an amine via the compound represented by the general formula (V). This is a synthetic route for producing a cyclic amine salt represented by the general formula (I). According to the production method of the present invention, the target compound can be obtained directly in one pot with higher yield. More specifically, in each process leading to the synthesis of the cyclic amine salt of the present invention which is the target compound, the intermediate product can be continuously transferred to the next process without performing the isolation and production process. In addition, since the yield reduction associated with the intermediate purification does not occur, a high yield can be obtained, and the production cost can be reduced by simplifying the process, so that it is an economically excellent method. From this viewpoint, it is preferable to use the production method of the present invention in the production of the cyclic amine salt of the present invention.

The production method of the present invention comprises:
(1) The following chemical formula (IV)

[Wherein R ₁ to R ₁₀ are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A step of synthesizing a halogen-containing aromatic phosphoric acid ester derivative represented by (A step),
(2) By hydrolyzing the halogen-containing aromatic phosphate ester derivative,
The following general formula (II)

[Wherein R ₁ to R ₁₀ are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A step of synthesizing an aromatic phosphoric diester represented by formula (step B),
(3) For the aromatic phosphoric acid diester,
The following general formula (VI)

[Wherein, A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. m represents an integer of 0 to 9. ]
A step of obtaining a compound represented by the general formula (I) by adding a compound represented by formula (I) in an organic solvent (step C)
It is a manufacturing method containing.

Step A In Step A, an amine is added to a reaction system containing phosphorus oxyhalide and the phenol derivative represented by the general formula (IV) to cause a dehydrohalogenation reaction. ) -Containing halogen-containing aromatic phosphate ester derivatives. The amine added at this time functions as a catalyst that efficiently promotes the selective ester reaction.

The compound represented by the general formula (IV) may be reacted using commercially available phenol and phosphorus oxyhalide as raw materials. As phosphorus oxyhalide, for example, phosphorus oxychloride, phosphorus oxybromide and the like can be used. If phosphorus oxychloride is used, the halogen atom of the compound represented by the general formula (V) becomes chlorine. If phosphorus oxybromide is used instead of phosphorus oxychloride, the halogen atom of the compound represented by the general formula (V) is bromine.

Also, an amine is allowed to coexist in the reaction system as a catalyst for efficiently promoting the selective esterification reaction. The type of amine is not particularly limited. For example, triethylamine, pyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] At least one of -5-nonene, 4-dimethylaminopyridine and the like. Among these, triethylamine is preferable from an economical viewpoint.

As a method of synthesizing the compound represented by the general formula (V), for example, an amine that serves as a dehydrohalogenation catalyst is added to both the phosphorus oxyhalide and the phenol derivative represented by the general formula (IV) at about room temperature (about 10 to 40 ° C.). When the reaction temperature is lower than 10 ° C., the reaction rate decreases, so the reaction time becomes longer. In addition, when the reaction temperature exceeds 40 ° C., the reaction runs away, and by-products such as triesters are generated in addition to the diesters represented by the general formula (V), resulting in a reduction in reaction yield. There is.

The mixing ratio of each raw material is about 0.4 to 0.6 mol, preferably about 0.45 to 0.55 mol of phosphorus oxyhalide with respect to 1 mol of the phenol derivative represented by the general formula (IV). Just do it. Further, the amount of amine is about 0.8 to 1.2 mol, preferably about 0.9 to 1.1 mol, per mol of the phenol derivative represented by the general formula (IV). When the charging ratio of the raw material is out of the above range, there is a risk that by-products such as monoesters and triesters other than the diesters represented by the general formula (V) may be generated.

In the above reaction, an amine hydrogen halide salt is always generated, and therefore the above reaction is preferably carried out in a solvent. Examples of the solvent include, but are not limited to, hydrocarbon solvents such as benzene, toluene, and n-hexane; ether solvents such as tetrahydrofuran and dioxane; aprotic organic solvents such as halogenated hydrocarbon solvents such as dichloromethane and chloroform. A solvent etc. can be used conveniently.

In order to separate and purify the diester compound represented by the general formula (V) (existing in the organic solvent layer) by liquid-liquid extraction with respect to the above solvent, the amine hydrohalide salt is made into an aqueous solution and separated. It is necessary to remove the aqueous hydrogen halide salt solution. Therefore, in order to perform a continuous reaction, it is more preferable to use a water-insoluble light solvent (a solvent having a specific gravity lighter than water) as the reaction solvent.

It is preferable to continuously synthesize the aromatic phosphate diester represented by the general formula (II) in the same reaction vessel. The amine hydrogen halide salt formed as a by-product in the previous reaction is made into an aqueous solution as described above and separated into layers, and the diester represented by the general formula (V) (present in the organic solvent layer) is obtained by liquid-liquid extraction. In order to perform separation and purification, it is preferable to introduce water into the reaction system. The mixture is thoroughly stirred at room temperature or lower (40 ° C or lower), and then left to separate into an organic solvent layer and an aqueous layer. Thereafter, the aqueous layer is removed, and the amine hydrogen halide salt is reacted with the reaction system. Remove from inside.

When the temperature at this time is equal to or higher than normal temperature (temperature exceeding 40 ° C.), the hydrolysis reaction proceeds slightly from the diester represented by the general formula (V), and is acidic in the general formula (II). Since it is considered that the phosphoric acid diester is generated and slightly moves from the organic solvent layer to the aqueous layer, the reaction yield may be lowered as a result.

In the production method of the present invention, in particular, in step A, the phenol derivative represented by the general formula (III) and the oxyhalogenation necessary for obtaining one equivalent of the aromatic phosphoric diester represented by the general formula (II) The charging ratio of phosphorus is about 1 equivalent for the phenol derivative and about 0.5 equivalent for phosphorus oxyhalide, which is very economically advantageous because it can be synthesized without loss of stoichiometry.

Step B In Step B, an aromatic phosphate diester is synthesized by hydrolyzing a halogen-containing aromatic phosphate ester derivative. That is, in order to obtain the aromatic phosphoric acid diester represented by the general formula (II) from the halogen-containing aromatic phosphoric acid ester derivative (aromatic halogenated phosphoric acid diester) represented by the general formula (V), Hydrolysis may be promoted by adding water to the halogen-containing aromatic phosphate ester derivative.

The amount of water required for the hydrolysis can be obtained by adding a stoichiometric amount of water equal to or greater than the halogen-containing aromatic phosphoric acid ester derivative (aromatic halogenated phosphoric acid diester) represented by the general formula (V). It ’s fine. The reaction temperature is not critical, but the stirring is preferably performed at a temperature not lower than room temperature (particularly a temperature exceeding 40 ° C.), more preferably 80 to 120 ° C. In the step B, it is preferable to reflux at the boiling point of the organic solvent present in the system at the same time or the azeotropic point of the organic solvent and water.

As the above-mentioned organic solvent, the organic solvent used in the previous reaction may be used continuously as it is, or another organic solvent may be used in addition, and after the organic solvent in the reaction system is removed under reflux. You may perform the solvent exchange which throws in another organic solvent in a reaction system. As the kind of solvent that can be used, the same solvents as those mentioned in the above step A can be used.

In step B, the removal of excess water after hydrolysis can also remove the aromatic phosphate monoester, which is slightly by-produced, out of the reaction system. Aromatic phosphoric acid monoesters are very water-soluble, so when liquid-liquid extraction is performed, the aromatic phosphoric acid monoester does not exist in the organic solvent layer and moves completely to the aqueous layer, contrary to the aromatic phosphoric acid diester. The cyclic amine salt of the aromatic phosphoric acid monoester and the cyclic amine salt of the aromatic phosphoric acid diester also exhibit the above-described properties.

Therefore, in the final reaction in Step B, non-uniform hydrolysis of the water-insoluble organic solvent layer and the water layer not only contributes to the one-pot continuous reaction, but also increases the selectivity of the monoester and diester forms. It can be said that this is an excellent synthesis method that contributes to this.

Of course, after the completion of Step B, the aromatic phosphate diester can be recovered in accordance with a known purification method, solid-liquid separation method, etc., so that it is prepared separately when the flame retardant is kneaded into the resin after the recovery. After the dry aromatic phosphate diester and the cyclic amine are dry blended, they may be added to the resin component. In this case, aromatic phosphoric diesters do not have very strong water absorption, but most cyclic amines and cyclic polyamines are water-absorbing or hydrated. It is necessary to do this, and it may take much time to obtain the flame retardant of the present invention later.

Therefore, as in the production method of the present invention, after the completion of the B step, by continuously performing the C step to obtain an aromatic phosphoric diester cyclic amine salt, even if it is necessary to dehydrate and dry, Since it can be used effectively without high drying, it can be said to be a more preferable and simple method.

In Step C, Step C, the aromatic amine represented by the general formula (I) is continuously added by adding a cyclic amine represented by the general formula (III) to the reaction system after the completion of the step B and stirring and mixing. A phosphoric diester cyclic amine salt can be synthesized.

The amount of cyclic amine represented by the general formula (III) is represented by the general formula (II) so that the ionic equivalents of both are equal to each other in order to maintain high flame retardancy and moisture resistance as described above. It is preferable to add an equal amount of an appropriately selected cyclic amine salt with respect to the stoichiometric amount contained in the aromatic phosphate diester. A known or commercially available cyclic amine may be used as the cyclic amine represented by the general formula (III).

Also in the C step, it can be carried out in a solvent as necessary. Examples of the solvent include hydrocarbon solvents such as benzene, toluene and n-hexane; alcohol solvents such as methanol and isopropyl alcohol; halogenated hydrocarbon solvents such as dichloromethane and chloroform.

After step C, the cyclic amine salt of the present invention can be recovered according to a known purification method, solid-liquid separation method, or the like. When synthesizing the cyclic amine salt of the present invention represented by the general formula (I) by the production method of the present invention, it can be produced with a very high yield and can be efficiently produced. The target product can be obtained in a very high yield of 80% or more (relative to the phenol derivative) in the total process yield.

Among the cyclic amine salts of the present invention, for example, when diphenyl hydrogen phosphate (DPHP) is selected as the aromatic phosphate diester represented by the general formula (II), and piperazine is selected as the cyclic amine represented by the general formula (III), When analyzed by ¹ H-NMR of the obtained compound, a ¹ H-NMR chemical shifts of piperazine (methylene) from δ2.84ppm to 3.23Ppm, Similarly, in ³¹ P-NMR, DPHP (phosphorus ) Shifts from δ-11.31 ppm to -10.54 ppm, both of which shift by a low magnetic field. This shows that an onium salt composed of a piperazine-1,4-diium cation and a diphenylhydrogen phosphate anion is formed by coordination bond between piperazine and DPHP.

(2) Flame retardant composition containing the cyclic amine salt of the present invention The flame retardant composition of the present invention (the flame retardant of the present invention) contains one or more of the cyclic amine salts of the present invention. That is, it contains at least one of the cyclic amine salts shown in (1) as an active ingredient.

In the present invention, in terms of moisture resistance and water resistance, which are essential and most important performances of the cyclic amine salt of the present invention, the presence of an aromatic phosphate monoester that can be mixed in the cyclic amine salt causes deterioration of the performance. Therefore, the smaller the amount of the aromatic phosphate monoester mixed in the flame retardant of the present invention, the better. That is, the content of the aromatic phosphoric acid monoester in the flame retardant of the present invention is preferably 1% by weight or less, more preferably 0.1% by weight or less, and further preferably 0% by weight. Is most preferred.

In addition, the abundance ratio of the aromatic phosphoric acid monoester and the aromatic phosphoric acid diester as the component A can be examined by measuring, for example, LC / MS or GC / MS. Further, by measuring ³¹ P-NMR, it can be easily confirmed that the chemical shift of the diester is about δ-12 to -10 ppm and the chemical shift of the monoester is about δ-3 to -4 ppm. it can.

In addition, the flame retardant of the present invention may contain additives blended with known flame retardants in addition to the cyclic amine salt of the present invention.

In particular, phosphates (C component) can be preferably used in the flame retardant of the present invention. Even if only phosphates are used as flame retardants, it is very difficult to simultaneously acquire flame retardancy, moisture resistance, and blooming resistance. However, the cyclic amine salt of the present invention and phosphates should be contained at the same time. Thus, in addition to highly enhancing the flame retardancy and moisture resistance, it is possible to obtain an effect of more effectively preventing the blooming phenomenon. As described above, in the conventional flame retardant, phosphates are basically difficult to mix with the synthetic resin and difficult to stabilize. If these flame retardant components are not well dispersed in the resin, various physical properties such as moldability and impact resistance of the flame retardant resin are deteriorated, and more often bleed out. In contrast, in the present invention, the cyclic amine salt of the present invention is superior to the prior art in that it functions as a dispersion stabilizer and / or a compatibilizer in the synthetic resin with respect to phosphates. is there.

Although it does not specifically limit as said phosphates, For example, 1) Inorganic condensed ammonium phosphate salts, such as ammonium polyphosphate, 2) Inorganic condensed ammonium phosphate salts, such as coated ammonium polyphosphate, 3) Phosphoric acid, pyrroline Examples thereof include at least one of organic salts composed of an acid or condensed phosphoric acid and a triazine derivative.

Examples of commercially available products of inorganic condensed ammonium phosphates such as C component 1) inorganic condensed ammonium phosphate such as ammonium polyphosphate include product names “Exorit AP422”, “Exorit AP700” (both manufactured by Clariant), and product names “Terrage S”. -10 "," Terrage S-20 "(all manufactured by Chisso Corporation), and the product name" Sumisafe P "(manufactured by Sumitomo Chemical Co., Ltd.).

2) The coated inorganic condensed ammonium phosphate salt such as ammonium polyphosphate coated with component C may be microencapsulated with a thermosetting resin to compensate for the disadvantages of the ammonium polyphosphate salt that is easily hydrolyzed by moisture absorption. Further, surface treatment such as coating is performed by melamine cross-linking, and surface treatment of granules is performed by a surfactant, a silicon compound, or the like. Examples of these commercially available products are product names “Exorit AP462” (manufactured by Clariant), product names “Terrage C-30”, “Terrage C-60”, “Terrage C-70”, “Terrage C-80” ( All of them are manufactured by Chisso Corporation).

Specific examples of organic salts composed of 3) phosphoric acid, pyrophosphoric acid or condensed phosphoric acid of the C component and an amine composed of a triazine derivative include melamine, guanamine, methylguanamine, ethylguanamine, benzoguanamine, benzylguanamine, Guanidine, guanidine, phosphates of triazine derivatives such as 2,4-diamino-6-morpholino-1,3,5-triazine, 2,4-diamino-6-thiomorpholino-1,3,5-triazine, pyrroline An acid salt, and a polyphosphate condensed with three or more molecules of phosphoric acid.

In the flame retardant of the present invention, in addition to the cyclic amine salt of the present invention, a flame retardant composition containing at least one phosphate among the C components is mixed with various resin components to make a synthetic resin composition and the like highly advanced. Can be flame retardant.

The flame retardant of the present invention is a char-forming phosphorus / nitrogen flame retardant, but typical char-forming flame retardants include red phosphorus, polyphosphate amine salts, most phosphate esters, and triazine derivatives. Susceptible to moisture. That is, characteristics of phosphorus compounds that are fatal defects as flame retardants, such as generation of phosphine (PH ₃ ) gas derived from red phosphorus, occurrence of blooming phenomenon derived from polyphosphate amine salt, hydrolysis of phosphate ester Defects such as coloring derived from decomposition, generation of amine (nitrogen) -based decomposition gas, resin coloring and molecular weight reduction are caused by moisture caused by moisture absorption and active radicals derived from moisture.

That is, the most important performance in practical use as a char-forming phosphorus-based flame retardant is to impart high flame resistance to the synthetic resin and at the same time have high moisture absorption resistance.

In addition, most of the char-forming phosphorus flame retardants generally have poor resin compatibility. For example, even when added to polyolefin resins with low polarity, they do not continue to disperse uniformly and stably in the resin. There is a problem that the flame retardant is transferred to the resin surface and the mechanical properties of the resin are extremely lowered.

Some flame retardants composed of phosphate esters have excellent resin compatibility, but most liquids have a low melting point and low thermal decomposition starting temperature, so the plasticity is too strong and the moldability is low. In many cases, the flame retardancy may be lowered, and high flame retardancy may not be imparted to the molded product.

The cyclic amine salt of the present invention alone is a non-hygroscopic flame retardant, but the cyclic amine salt of the present invention is also contained in the resin even when a C component having hygroscopicity is added at the same time in order to further enhance the flame retardancy. Since it acts as a kind of protective buffer that can stably disperse or compatibilize the components, it suppresses hygroscopicity and also maintains dispersion uniformity in the resin of the flame retardant composition. Transferability to the product surface, blooming phenomenon, or surface roughness of the molded product can be suppressed at the same time.

2. Flame retardant resin composition containing the flame retardant of the present invention (the composition of the present invention)
(1) Flame Retardant Resin Composition The present invention is a resin composition comprising the flame retardant of the present invention and a resin component, and comprises 1 to 100 parts by weight of the cyclic amine salt of the present invention per 100 parts by weight of the resin component. Includes flammable resin composition.

The resin component is not particularly limited, and can be selected from, for example, known synthetic resins. More specifically, polyolefin resins, polystyrene resins, polyvinyl resins, polyamide resins, poly-meaning clock resins, polyester resins, polyether resins, polycarbonate resins, polyacetal resins, polyether ether ketone resins. , Thermoplastic resins such as polyphenylene / sulfide resin, polyamide / imide resin, polyether / sulfone resin, polysulfone resin, polymethyl / pentene resin, urea resin, melamine resin, epoxy resin, polyurethane resin, phenol resin, etc. And resin alloys by homopolymers or copolymers alone or in combination thereof.

Suitable polyolefin resins in the composition of the present invention include homopolymers of α-olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and the above α- Resins such as random or block copolymers of olefins and mixtures thereof, and polyolefin resins such as resins obtained by copolymerizing these with vinyl acetate or maleic anhydride can be suitably used. More specifically, polypropylene resins such as propylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-ethylene-butene copolymer, low density ethylene homopolymer, Examples thereof include polyethylene resins such as high-density ethylene homopolymer, ethylene-α-olefin random copolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer. Further, in the present invention, in order to improve the physical properties of the flame retardant resin composition, a polyethylene-based synthetic rubber, a polyolefin-based synthetic rubber, or the like can be blended as necessary.

Examples of the polystyrene resin include polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and the like.

Examples of the polyvinyl resin include homopolymers of vinyl monomers such as alkyl acrylates, alkyl methacrylates, vinyl acetate, vinyl alcohol and the like, and copolymers of these vinyl monomers and the aforementioned α-olefins. Etc.

Examples of the polyamide-based resin include polyamide 6, polyamide 6 • 6, polyamide 11, polyamide 12, polyamide 6 • 3, polyamide 6 • 4, polyamide 4 • 6, polyamide 6 • 10, and the like.

Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly (1,4-cyclohexanedimethylene terephthalate), and the like.

Examples of polyether resins include polyphenylene ether and polyethylene ether.

Examples of the polycarbonate resin include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and the like. Generally, bisphenol such as 2,2-bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, etc. Polymers or copolymers consisting of the above are mentioned.

Further, as the resin component in the composition of the present invention, in addition to the above-mentioned resins, two or more types of resin components were kneaded in the presence or absence of an appropriate compatibilizer. Alloy resins are also included. Examples of alloy resins include polypropylene / polyamide, polypropylene / polybutylene terephthalate, acrylonitrile / butadiene / styrene copolymer / polybutylene terephthalate, acrylonitrile / butadiene / styrene copolymer / polyamide, and polycarbonate / acrylonitrile / butadiene / styrene copolymer. Polycarbonate / polymethyl methacrylate, polycarbonate / polyamide, polycarbonate / polyethylene terephthalate, polycarbonate / polybutylene terephthalate, and the like.

Further, as a resin component, a modified product of the above-described synthetic resin, for example, a synthetic resin is obtained by unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, etc.) A modified product obtained by grafting can also be used.

Among the above resin components, the combination of the polyolefin resin and the flame retardant of the present invention is particularly preferred from the viewpoint that a molded product having higher versatility, lower cost, and balance of various physical properties can be obtained. In particular, a flame retardant resin composition containing at least one of a polypropylene homopolymer, an ethylene-propylene random copolymer, and an ethylene-propylene block copolymer and the flame retardant of the present invention has moldability, heat resistance, and moisture absorption resistance. With regard to the properties and particularly high flame retardancy, it is more preferable because it can exhibit particularly excellent performance that has not been achieved in the past.

In the composition of the present invention, the blending ratio of the cyclic amine salt of the present invention is not particularly limited, and a blending amount sufficient to maintain various physical properties and flame retardancy may be added. Among these, the cyclic amine salts 1 to 100 of the present invention are added to 100 parts by weight of the resin component in order to keep the kneading stability and moldability, and to give the molded article moisture resistance and high flame retardancy. What is necessary is just to mix | blend a weight part, and what is necessary is just to mix | blend 10 to 50 weight part more preferably. If the blending ratio of the flame retardant of the present invention is less than 1 part by weight, the flame retardancy may be insufficient. On the other hand, if it exceeds 100 parts by weight, the inherent properties of the resin may not be obtained.

In addition to the cyclic amine salt of the present invention, by further adding the component C, the char forming ability characteristic of the composition of the present invention is enhanced by the effect of promoting carbonization by foaming (phosphorus such as amine, triazine and melamine). As a result of the synergistic occurrence of acid salts, etc., it becomes possible to obtain higher flame retardancy.

In the resin composition containing the flame retardant composition and the resin component in the present invention, the blending ratio is 1 to 50 parts by weight of the cyclic amine salt of the present invention and 1 to 50 parts by weight of the C component with respect to 100 parts by weight of the resin component. The cyclic amine salt of the present invention is preferably 10 to 30 parts by weight, and the C component is more preferably 10 to 30 parts by weight.

In addition to the above components, the composition of the present invention can be appropriately blended with known or commercially available additives as necessary within the range not impeding the effects of the present invention. Illustrative examples are antioxidants such as phenol compounds, phosphine compounds, thioether compounds, UV absorbers or light stabilizers such as benzophenone compounds, benzotriazole compounds, salicylate compounds, hindered amine compounds; cationic compounds, anions Compounds, nonionic compounds, amphoteric compounds, metal oxides, π-based conductive polymer compounds, carbon and other antistatic agents and conductive agents; fatty acids, fatty acid amides, fatty acid esters, fatty acid metal salts and other lubricants; benzylidene sorbitols Nucleating agents such as compounds; in addition to fillers such as talc, calcium carbonate, barium sulfate, mica, glass fiber, glass beads, low melting glass, metal deactivators, colorants, antiblooming agents, surface modifiers, Anti-blocking agent, anti-fogging agent, adhesive, gas adsorbent, freshness preservation Agents, enzymes, deodorants, fragrances, and the like.

Also, as the drip control agent of the composition of the present invention, polytetrafluoroethylene-containing mixed particle powder having fibril forming ability can be added. Addition of polytetrafluoroethylene-containing mixed particle powder having fibril-forming ability enables drip of test pieces during combustion in a flammability test of a flame retardant resin composition, particularly in a UL standard vertical combustion test (UL94V) The prevention performance can be further increased.

Examples of the polytetrafluoroethylene-containing mixed particle powder having a fibril-forming ability include polytetrafluoroethylene and a tetrafluoroethylene-based copolymer, and polytetrafluoroethylene (PTFE) is preferable.

In this case, the average particle size of the powder is not limited, but it is usually about 0.1 to 1000 μm. The addition amount can be appropriately set according to the desired drip prevention performance and the like, but is generally preferably about 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin component.

(2) Method for Producing Flame Retardant Resin Composition The composition of the present invention can be obtained by uniformly mixing the above components. Preferably, it can manufacture by melt-kneading said each component. The kneading order in that case is not particularly limited, either may be mixed at the same time, or several types may be mixed in advance and the rest may be mixed later.

The mixing method is not limited. For example, a high-speed stirrer such as a tumbler type V-type blender, a Henschel mixer, or a ribbon mixer, a single-screw or twin-screw continuous kneader, or a method that uses a roll mixer alone or in combination. Can be adopted.

In the present invention, a synthetic resin and a high-concentration composition can be prepared using several types of master batches in advance, and then further mixed and diluted with the resin to obtain a predetermined resin composition.

(3) Use of flame retardant resin composition The composition of the present invention achieves excellent flame retardancy and can effectively suppress bleed, and therefore can be suitably used as a molded product. That is, the flame retardant resin composition of the present invention can be suitably used as a resin composition for producing a molded product. Thereby, the molded article excellent in the flame retardance can be provided.

3. Molded Article The present invention includes a flame retardant resin molded article obtained by molding the flame retardant resin composition of the present invention.

The molding method is not particularly limited, and known molding methods such as injection molding and extrusion molding can be used. For example, a method using an extrusion molding machine, a sheet once prepared, a method using secondary processing such as vacuum molding and press molding, a method using an injection molding machine, and the like can be mentioned, but the present invention is highly versatile. In particular, injection molding is preferred.

Also in injection molding, a molded product can be manufactured not only by a normal cold runner injection molding method but also by a hot runner method that enables runnerless operation. Furthermore, for example, gas assist injection molding, injection compression molding, ultra-high speed injection molding, or the like can be employed.

The molded article made of the flame-retardant resin composition of the present invention can be applied to uses that require flame retardancy in home appliances, OA products, automobile fields, and the like. Specifically, insulation coating materials such as electric wires and cables or various electric parts, meter boxes, lamp housings, corrugated tubes, electric wire coating materials, various automobiles such as battery parts, ships, aircraft parts, wash basin parts, toilet parts, Various bathroom equipment parts, floor heating parts, lighting fixtures, various housing equipment parts such as air conditioners, roofing materials, ceiling materials, wall materials, flooring materials, TVs, radios, recording / recording equipment, washing machines, refrigerators, cleaning It is suitably used for home appliances such as a machine, rice cooker, and lighting equipment.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

In addition, various physical properties of each compound obtained in the following synthesis examples were measured as follows.

(1) Purity Gas chromatography with FID detector (GC-2010: manufactured by Shimadzu Corporation) and high performance liquid chromatography with photodiode array (PDA) three-dimensional UV detector (Alliance HPLC system:
Purity was confirmed with Waters).
(2) Melting point The melting point was measured with a fully automatic melting point measurement apparatus (FP-62: manufactured by METTLER TOLEDO).
(3) Elemental analysis High-frequency coupled plasma emission spectrometer (EA1110: manufactured by CE Instruments) after wet decomposition of carbon, hydrogen, and nitrogen with a microwave sample decomposition apparatus (ETHOS1: manufactured by Milestone General) ( ICP-OES, 720ES (manufactured by Varian, Inc.) was subjected to elemental analysis of phosphorus and each compound.
(4) Structural analysis Infrared absorption analyzer (FT-IR, FT-720, manufactured by Horiba, Ltd.), gas chromatography with mass spectrometer (GCMS-QP2010Plus: manufactured by Shimadzu Corporation), 300 MHz nuclear magnetic resonance The structure of each compound was identified from the hydrogen nuclear magnetic resonance ( ¹ H-NMR) spectrum and phosphorus nuclear magnetic resonance ( ³¹ P-NMR) spectrum obtained by an absorption analyzer (JNM-AL300: manufactured by JEOL Ltd.). .

<Synthesis Example 1>
1. Synthesis of diphenyl hydrogen phosphate piperazine salt (DPHPP) 1.1 Synthesis of diphenyl chlorophosphate (DPCP)

A 4-neck flask with a stirrer equipped with a condenser, a dropping funnel with a side tube and a thermometer was charged with 94.1 g (1.0 mol) of phenol, 76.67 g (0.5 mol) of phosphorus oxychloride and 700 g of toluene, The dropping funnel with a side tube was charged with 106.25 g (1.05 mol) of triethylamine. A calcium chloride tube was attached to the upper end of the condenser to prevent moisture in the air from entering the reaction system, and stirring was then started in a nitrogen atmosphere while maintaining the flask at 30 ° C. in a constant temperature water bath. After the start of stirring, triethylamine was dropped from the dropping funnel over 2 hours so that the temperature of the reaction product did not exceed 40 ° C. After the reaction ripening for 1 hour from the end of the dropwise addition, the reaction product was sampled and GC / MS was measured. As a result, the purity of the obtained reaction intermediate of the slightly yellow transparent liquid was 98% or more. From the molecular ion peak of the spectrum (M ⁺ : m / z 268), diphenylchlorophosphate (DPCP: Mw) represented by the above formula (17) as a reaction product was obtained.
268.63) was obtained.

1.2 Synthesis of diphenylhydrogen phosphate (DPHP)

From 1.1 above, after confirming by GC / MS that the raw material phenol contained in the reaction had completely disappeared, the flask was cooled to 20 ° C. in a constant temperature water bath, and 140 g of water was added to the flask. The mixture was stirred for 30 minutes after the addition. After completion of the stirring, the reaction solution was allowed to stand for 30 minutes to be separated into an organic layer and an aqueous layer, and the aqueous layer was extracted. While gradually heating the flask with a mantle heater, toluene in the reaction solution was distilled off until the temperature of the reaction solution in the flask reached 120 ° C. When the amount of toluene distilled out reached 560 g, heating was temporarily stopped and the reaction product was cooled to 80 ° C., then 140 g of water was added and reheated, and toluene was reacted by azeotropy of toluene and water. While removing from the system, diphenylhydrogen phosphate (DPHP) was simultaneously hydrolyzed over 2 hours by refluxing. After cooling this to room temperature, 300 g of ethyl acetate was added to the flask and stirred, and then the layers were separated and the aqueous layer was extracted. After the organic layer was washed with water, the reaction product in the organic layer was sampled to confirm the purity of the reaction intermediate. As a result, the purity was 99% or higher (HPLC). When this reaction product was completely dried under reduced pressure, it became a white solid having a melting point of 69 ° C. From the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, it was confirmed that the obtained reaction product was diphenyl hydrogen phosphate (DPHP) represented by the above formula (18).
¹ H-NMR (300 MHz, DMSO-d6): δ / ppm 7.11-7.23 (4H, m), 7.29-7.40 (6H, m)
³¹ P-NMR (109 MHz, DMSO-d6): δ / ppm -11.31

1.3 Synthesis of diphenylhydrogen phosphate piperazine salt (DPHPP)

Following 1.2, 1000 g of methanol was added to the organic layer containing the reaction product diphenyl hydrogen phosphate (DPHP) and dissolved, and anhydrous piperazine 21.20 dissolved in 200 g of methanol in a dropping funnel with a side tube. 5 g (0.25 mol) solution was added. When the piperazine solution was added dropwise over 2 hours while stirring the reaction solution, a white solid was precipitated. The white solid was recrystallized from methanol / water (2/1, wt) to obtain 117.1 g (0.20 mol, yield 80%) of white crystal powder. The melting point of this white crystal powder was 202.2 ° C. Further, from the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained reaction product was converted to a diphenyl hydrogen phosphate piperazine salt represented by the above formula (19) ( DHPPP).
¹ H-NMR (300 MHz, DMSO-d6): δ / ppm 3.23 (8H, s), 6.96-7.01 (4H, m), 7.11-7.14 (8H, m), 7.20-7.27 (8H, m)
³¹ P-NMR (109 MHz, DMSO-d6): δ / ppm -10.54
As elemental analysis C ₂₈ H ₃₂ N ₂ O ₈ P ₂ (Mw 586.51),
Calculated: C, 57.34; H, 5.50; N, 4.78; P, 10.56
Found: C, 57.13; H, 5.52; N, 4.77; P, 10.54

<Synthesis Example 2>
2. Synthesis of di-p-tolyl hydrogen phosphate piperazine salt (DTHPP) 2.1 Synthesis of di-p-tolyl chlorophosphate (DTCP)

Using 108.14 g (1.0 mol) of p-cresol in place of the phenol of 1.1, the reaction product was sampled and GC / MS was measured by performing the same operation as 1.1. However, the purity of the reaction product of the obtained pale yellow transparent liquid is 98% or more, and from the molecular ion peak of the GC / MS spectrum (M ⁺ : m / z 296), the reaction product is represented by the above formula (20). Diphenylchlorophosphate (DPCP: Mw)
296.69) was obtained.

2.2 Synthesis of di-p-tolyl hydrogen phosphate (DTHP)

Subsequent to the step shown in 2.1, the same operation as in 1.2 was performed, and the obtained reaction product was sampled to confirm the purity of the reaction product. As a result, the purity was 99% or higher (HPLC )Met. When this reaction product was completely dried under reduced pressure, it became a white solid having a melting point of 79 ° C. From the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, it was confirmed that the obtained reaction product was di-p-tolyl hydrogen phosphate (DPHP) represented by the above formula (21). It was.
¹ H-NMR (300 MHz, DMSO-d6): δ / ppm 2.25 (6H, s), 7.03-7.08 (4H, m), 7.12-7.17 (4H, m).
³¹ P-NMR (109 MHz, DMSO-d6): δ / ppm -10.91

2.3 Synthesis of di-p-tolyl hydrogen phosphate piperazine salt (DTHPP)

Subsequent to the step shown in 2.2, the same operation as in 1.3 was performed to obtain 112.5 g (0.18 mol, yield 70%) of white crystalline powder. The melting point of this white crystal powder was 206.2 ° C. Further, from the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained reaction product was converted into di-p-tolyl hydrogen represented by the above formula (22). It was confirmed to be phosphate piperazine salt (DTHPP).
¹ H-NMR (300 MHz, DMSO-d6): δ / ppm 2.21 (12H, s), 3.21 (8H, s), 6.98-7.05 (16H, m)
³¹ P-NMR (109 MHz, DMSO-d6): δ / ppm −9.97
As Elemental Analysis _{_{_{_{C 32 H 40 N 2 O 8}}}} P 2 (Mw 642.62),
Calculated: C, 59.81; H, 6.27; N, 4.36; P, 9.64
Found: C, 59.43; H, 6.08; N, 4.32; P, 9.63

<Synthesis Example 3>
3. Synthesis of di-2,6- xylenyl hydrogen phosphate piperazine salt (DTHPP) 3.1 Synthesis of di-2,6-xylenyl chlorophosphate (DXCP)

In place of the phenol of 1.1, 122.16 g (1.0 mol) of 2,6-xylenol was used and the same operation as in 1.1 was performed. As a result, the purity of the reaction product of the slightly yellow transparent liquid obtained was 99% or more. From the molecular ion peak of the GC / MS spectrum (M ⁺ : m / z 324), the reaction product represented by the above formula (23 Di-2,6-xylenylchlorophosphate (DXCP: Mw)
324.74) was obtained.

3.2 Synthesis of di-2,6-xylenyl hydrogen phosphate (DTHP)

Subsequent to the step shown in 3.1, the same operation as in 1.2 was performed, and the purity of the reaction product was confirmed by sampling the obtained reaction product. The purity was 98% or more ( HPLC). When this reaction product was completely dried under reduced pressure, it became a white solid with a melting point of 140.4 ° C. From the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, the obtained reaction product is di-2,6-xylenyl hydrogen phosphate (DXHP) represented by the above formula (24). I was able to confirm.
¹ H-NMR (300 MHz, DMSO-d6): δ / ppm 2.27 (12H, s), 6.95-7.06 (6H, m)
³¹ P-NMR (109 MHz, DMSO-d6): δ / ppm −9.97

3.3 Synthesis of di-2,6-xylenyl hydrogen phosphate piperazine salt (DXHPP)

Subsequent to the step shown in 3.2, the same operation as in 1.3 was performed to obtain 108.3 g (0.16 mol, yield 62%) of white crystalline powder. The melting point of this white crystal powder was 224.2 ° C. In addition, from the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained reaction product was converted to the di-2,6-xyx represented by the above formula (25). It was confirmed that it was a rhenyl hydrogen phosphate piperazine salt (DXHPP).
¹ H-NMR (300 MHz, DMSO-d6): δ / ppm 2.28 (24H, s), 2.97 (8H, s), 6.81-6.85 (4H, m), 6.93- 6.95 (12H, m)
³¹ P-NMR (109 MHz, DMSO-d6): δ / ppm −8.49
As Elemental Analysis _{_{_{_{C 36 H 48 N 2 O 8}}}} P 2 (Mw 698.72),
Calculated values: C, 61.88; H, 6.92; N, 4.01; P, 8.87
Found: C, 61.63; H, 6.85; N, 3.98; P, 8.81

<Synthesis Example 4>
4). Synthesis of di-4-t-butyl hydrogen phosphate piperazine salt (DBHPP) 4.1 Synthesis of di-4-t-butyl chlorophosphate (DBCP)

Using 150.22 g (1.0 mol) of 4-t-butylphenol in place of the phenol of 1.1, the reaction product was sampled by performing the same operation as in 1.1, and GC / MS was determined. As a result, the purity of the obtained yellow solid reaction product was 97% or more, and the melting point was 101.0 ° C. Further, from the molecular ion peak of the GC / MS spectrum (M ⁺ : m / z 380), di-4-t-butylchlorophosphate (DXCP: Mw 380.85) represented by the above formula (26) was obtained as a reaction product. It was confirmed that it was obtained.

4.2 Synthesis of di-4-tert-butyl hydrogen phosphate (DBHP)

Subsequent to the step shown in 4.1, the same operation as in 1.2 was performed, and the reaction product obtained was sampled to confirm the purity of the reaction product. As a result, the purity was 98% or more ( HPLC). When this reaction product was completely dried under reduced pressure, a light reddish brown solid with a melting point of 137.4 ° C. was obtained. From the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, it was found that the obtained reaction product was di-4-tert-butyl hydrogen phosphate (DBHP) represented by the above formula (27). It could be confirmed.
¹ H-NMR (300 MHz, DMSO-d6): δ / ppm 1.26 (18H, s), 7.08-7.11 (4H, m), 7.35-7.38 (4H, m)
³¹ P-NMR (109 MHz, DMSO-d6): δ / ppm -10.88

4.3 Synthesis of di-4-tert-butylhydrogen phosphate piperazine salt (DBHPP)

Subsequent to the step shown in 4.2, the same operation as in 1.3 was performed to obtain 162.2 g (0.20 mol, yield 80%) of pale yellowish white crystalline powder. . The melting point of this white crystal powder was 252.1 ° C. Further, from the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained reaction product was di-4-t-butyl represented by the above formula (28). It was confirmed that it was hydrogen phosphate piperazine salt (DXHPP).
¹ H-NMR (300 MHz, DMSO-d6): δ / ppm 1.23 (36H, s), 3.18 (8H, s), 7.02-7.05 (8H, m), 7.20- 7.24 (8H, m)
³¹ P-NMR (109 MHz, DMSO-d6): δ / ppm -10.04
As elemental analysis C ₄₄ H ₆₄ N ₂ O ₈ P ₂ (Mw 810.94),
Calculated values: C, 65.17; H, 7.95; N, 3.45; P, 7.64
Found: C, 65.30; H, 7.89; N, 3.47; P, 7.61

<Comparative Example 1>
5. Synthesis of phenyl dihydrogen phosphate piperazine salt (PDHPP) 5.1 Synthesis of phenyl dichlorophosphate (PDCP)

94.11 g (1.00 mol) of phenol, 459.99 g (3.00 mol) of phosphorus oxychloride and 2.73 g (0.02 mol) of zinc chloride are charged into a four-necked flask equipped with a stirrer and equipped with a condenser and a thermometer. did. A calcium chloride tube was attached to the upper end of the condenser to prevent moisture in the air from entering the reaction system, and then stirring was started in a nitrogen atmosphere and the temperature was gradually raised with a mantle heater. Since hydrogen chloride gas was generated during the reaction, it was heated to 80 ° C. over 5 hours so as not to bump. Thereafter, it was confirmed by GC and HPLC that the phenol peak had disappeared in the reaction product, and the reaction product was distilled and purified under reduced pressure. Distillation under reduced pressure was performed at a distillation temperature of 34 to 100 ° C. and a degree of vacuum of 50 Torr to distill off excess phosphorus oxychloride in the reaction product to obtain 291 g of phosphorus oxychloride (recovery rate 95%). It was. The reaction product was further distilled at a distillation temperature of 118 to 120 ° C. and a degree of vacuum of 6 Torr to obtain 159.92 g (0.76 mol: yield 75.8%) of a colorless transparent liquid. The purity of the obtained compound was 99% or more (GC), and the boiling point was 243 ° C./760 Torr. From the molecular ion peak of the GC / MS spectrum of this compound (M ⁺ : m / z 210), the obtained compound was converted to phenyldichlorophosphate (PDCP: Mw) represented by the above formula (29).
209.98).

5.2 Synthesis of phenyl dihydrogen phosphate (PDHP)

In a four-necked flask equipped with a stirrer and equipped with a condenser and a thermometer, 159.92 g (0.76 mol) of phenyldichlorophosphate and 341.1 g (18.95 mol) of water were charged. After stirring, the mixture was heated to reflux for 5 hours. After confirming that the peak of phenyldichlorophosphate had disappeared by GC, the reaction solution was concentrated to dryness with an evaporator to obtain a red viscous liquid. The viscose was triturated with dichloromethane to precipitate a solid. This solid was washed with dichloromethane and dried to obtain 110.85 g (0.64 mol: yield 84.0%) of a pale brown white solid. The purity of the obtained compound was 99% or higher (HPLC), and the melting point was 100.0 ° C. From the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, it was confirmed that the obtained compound was phenyl dihydrogen phosphate (PDHP) represented by the above formula (30).
¹ H-NMR (300 MHz, D ₂ O): δ / ppm 6.86-6.89 (3H, m), 7.03-7.08 (2H, m)
³¹ P-NMR (109 MHz, D ₂ O): δ / ppm -4.10

5.3 Synthesis of phenyl dihydrogen phosphate piperazine salt (PDHPP)

110.85 g (0.64 mol) of phenyl dihydrogen phosphate and 998 g of methanol were charged into a four-necked flask equipped with a stirrer equipped with a condenser, a dropping funnel with a side tube and a thermometer. To the dropping funnel with a side tube, 86.14 g (0.64 mol) of piperazine previously dissolved in 494 g of methanol was added. After the start of stirring, the piperazine solution was dropped from the dropping funnel over 1 hour at room temperature, and further stirring was continued for 1 hour after completion of the dropping, whereby a white cotton-like product was precipitated. This product was washed with methanol and dried to obtain 157.41 g (0.60 mol: yield 95.0%) of a white solid. The purity of the obtained compound was 99% or higher (HPLC), but did not show a clear melting point. Further, from the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained compound was converted to phenyl dihydrogen phosphate piperazine salt (PDHPP) represented by the above formula (31). It was confirmed that.
¹ H-NMR (300 MHz, D ₂ O): δ / ppm 3.19-3.20 (8H, m), 7.01-7.10 (3H, m), 7.23-7.29 (2H , M)
³¹ P-NMR (109 MHz, D ₂ O): δ / ppm −1.51
As Elemental Analysis _{_{_{_{C 10 H 17 N 2 O 4}}}} P (Fw 260.23),
Calculated: C, 46.15; H, 6.58; N, 10.77; P, 11.90
Found: C, 45.91; H, 6.33; N, 10.61; P, 11.85

<Comparative Example 2>
6). Synthesis of p-tolyl dihydrogen phosphate piperazine salt (TDHPP) 6.1 Synthesis of p-tolyl dichlorophosphate (TDCP)

By using 108.14 g (1.0 mol) of p-cresol in place of the phenol of 5.1, the same operation as in 5.1 was performed to obtain 174.16 g of a yellow transparent liquid (0.77 mol: yield). Rate 77.4%). When GC / MS of this compound was measured, the purity of the obtained compound was 98% or more, and it was represented by the above formula (32) from the molecular ion peak of the GC / MS spectrum (M ⁺ : m / z 224). Phenyldichlorophosphate (TDCP: Mw
223.96) was obtained.

6.2 Synthesis of p-tolyl dihydrogen phosphate (TDHP)

Subsequent to the step shown in 6.1, the same operation as in 5.2 was performed. As a result, 116.48 g (0.62 mol: yield 80.0%) of a white solid (melting point: 98.7 ° C. ) When the purity of the obtained compound was confirmed, the purity was 98% or higher (HPLC). From the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, it was confirmed that the obtained compound was p-tolyl dihydrogen phosphate (TDHP) represented by the above formula (33).
¹ H-NMR (300 MHz, D ₂ O): δ / ppm 2.05 (3H, s), 6.84-6.87 (2H, m), 6.95-6.98 (2H, m).
³¹ P-NMR (109 MHz, D ₂ O): δ / ppm −3.89

6.3 Synthesis of p-tolyldihydrogen phosphate piperazine salt (TDHPP)

Subsequent to the step shown in 6.2, the same operation as in 5.3 was performed to obtain 152.83 g (0.56 mol, yield 90.0%) of a white solid. The purity of the obtained compound was 99% or higher (HPLC), but did not show a clear melting point. Further, from the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained compound was converted into p-tolyl dihydrogen phosphate piperazine salt represented by the above formula (34) ( TDHPP) was confirmed.
¹ H-NMR (300 MHz, D ₂ O): δ / ppm 2.15 (3H, s), 3.19 (8H, s), 6.94-6.96 (2H, m), 7.03- 7.06 (2H, m)
³¹ P-NMR (109 MHz, D ₂ O): δ / ppm −0.87
As Elemental Analysis _{_{_{_{C 11 H 19 N 2 O 4}}}} P (Fw 274.25),
Calculated: C, 48.17; H, 6.98; N, 10.21; P, 11.29
Found: C, 48.00; H, 7.06; N, 10.21; P, 11.21

<Comparative Example 3>
7. Synthesis of 2,6- Xylenyl Dihydrogen Phosphate Piperazine Salt (XDHPP) 7.1 Synthesis of 2,6-Xylenyl Dichlorophosphate (XDCP)

By using 122.16 g (1.0 mol) of 2,6-xylenol in place of the phenol of 5.1, the same operation as in 5.1 was performed to obtain 239.04 g of a brown liquid (1.0 mol: Yield 100%). When GC / MS of this compound was measured, the purity of the obtained compound was 95% or more, and it was represented by the above formula (35) from the molecular ion peak of the GC / MS spectrum (M ⁺ : m / z 238). 2,6-Xylenyldichlorophosphate (XDCP: Mw
237.97) was obtained.

7.2 Synthesis of 2,6-xylenyl dihydrogen phosphate (XDHP)

Subsequent to the process shown in 7.1, the same operation as in 5.2 was performed. As a result, 87.93 g (0.44 mol: yield 43.5%) of a white solid (melting point: 139.0 ° C. ) When the purity of the obtained compound was confirmed, the purity was 98% or higher (HPLC). From the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, it was confirmed that the obtained compound was 2,6-xylenyl dihydrogen phosphate (XDHP) represented by the above formula (36). It was.
¹ H-NMR (300 MHz, D ₂ O): δ / ppm 2.16 (6H, s), 6.84-6.89 (1H, m), 6.94-6.96 (2H, m).
³¹ P-NMR (109 MHz, D ₂ O): δ / ppm −3.83

7.3 Synthesis of 2,6-xylenyl dihydrogen phosphate piperazine salt (XDHPP)

Subsequent to the step shown in 7.2, the same operation as in 5.3 was performed to obtain 111.23 g (0.39 mol, yield 88.7%) of a white solid. The purity of the obtained compound was 99% or higher (HPLC), but did not show a clear melting point. From the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained compound was 2,6-xylenyl dihydrogen phosphate piperazine represented by the above formula (37). It was confirmed to be a salt (XDHPP).
¹ H-NMR (300 MHz, D ₂ O): δ / ppm 2.17 (6H, s), 3.09 (8H, s), 6.80-6.84 (1H, m), 6.91- 6.94 (2H, m)
³¹ P-NMR (109 MHz, D ₂ O): δ / -1.75
As Elemental Analysis _{_{_{_{C 12 H 21 N 2 O 4}}}} P (Fw 288.28),
Calculated values: C, 50.00; H, 7.34; N, 9.72; P, 10.74
Found: C, 49.91; H, 7.29; N, 9.69; P, 10.61

<Comparative example 4>
8. Synthesis of 4-t -butyl dihydrogen phosphate piperazine salt (BDHPP) 8.1 Synthesis of 4-t-butyl dichlorophosphate (BDCP)

By using 150.22 g (1.0 mol) of 4-t-butylphenol instead of the phenol of 5.1, the same operation as in 5.1 was performed, whereby 267.09 g of a brown liquid (1.0 mol: Yield 100%). When GC / MS of this compound was measured, the purity of the obtained compound was 95% or more, and it was represented by the above formula (38) from the molecular ion peak of the GC / MS spectrum (M ⁺ : m / z 266). 4-t-butyldichlorophosphate (BDCP: Mw
266.00) was obtained.

8.2 Synthesis of 4-tert-butyl dihydrogen phosphate (BDHP)

Subsequent to the step shown in 8.1, the same operation as in 5.2 was performed. As a result, 115.56 g (0.5 mol: yield 50.2%) of a yellow solid (melting point: 96.2 ° C. ) When the purity of the obtained compound was confirmed, the purity was 97% or higher (HPLC). From the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, it was confirmed that the obtained compound was 4-t-butyldihydrogen phosphate (XDHP) represented by the above formula (39).
¹ H-NMR (300 MHz, D ₂ O): δ / ppm 1.14 (9H, s), 6.97-7.02 (2H, m), 7.29-7.34 (2H, m).
³¹ P-NMR (109 MHz, D ₂ O): δ / ppm −3.73

8.3 Synthesis of 4-t-butyl dihydrogen phosphate piperazine salt (BDHPP)

Subsequent to the step shown in 8.2, the same operation as in 5.3 was performed to obtain 135.14 g (0.43 mol, yield 85.1%) of a white solid. The purity of the obtained compound was 99% or higher (HPLC), but did not show a clear melting point. Further, from the results of ¹ H-NMR measurement and ³¹ P-NMR measurement of this compound, and further from the results of the following elemental analysis, the obtained compound was converted to 4-t-butyldihydrogen phosphate piperazine represented by the above formula (40). It was confirmed to be a salt (BDHPP).
¹ H-NMR (300 MHz, D ₂ O): δ / ppm 1.19 (9H, s), 3.15 (8H, s), 7.03-7.06 (2H, m), 7.33- 7.36 (2H, m)
³¹ P-NMR (109 MHz, D ₂ O): δ / ppm −1.48
As elemental analysis C ₁₄ H ₂₅ N ₂ O ₄ P (Fw 316.33),
Calculated: C, 53.16; H, 7.97; N, 8.86; P, 9.79.
Found: C, 52.81; H, 7.78; N, 8.93; P, 9.71

2. Preparation of flame retardant synthetic resin composition A flame retardant synthetic resin composition was prepared using the cyclic amine salt obtained in each of the above synthesis examples. The component which comprises a flame-retardant synthetic resin composition consists of a synthetic resin and a flame retardant, and shows each component below. The following components were dry blended according to the blending ratio (parts by weight) described in Tables 1 and 2, and then melt-mixed and extruded and kneaded in a twin-screw extruder, cut into strands, and pellets. A flame retardant resin composition was obtained. As the twin screw extruder, a twin screw extruder “KTX30 type” (screw diameter 30 mm, L / D = 37, with vent) manufactured by Kobe Steel, Ltd. was used.

(1) Synthetic resin Sumitomo Nobrene AY564 (manufactured by Sumitomo Chemical Co., Ltd., PP)
(2) Flame retardant DPHPP: Diphenyl hydrogen phosphate piperazine salt DTHPP: Di-p-tolyl hydrogen phosphate piperazine salt DXHPP: Di-2,5-xylenyl hydrogen phosphate piperazine salt BDHPP: Di-4-t-butyl Phenyl hydrogen phosphate piperazine salt PDHPP: Phenyl dihydrogen phosphate piperazine salt TDHPP: p-tolyl dihydrogen phosphate piperazine salt XDHPP: 2,5-xylenyl dihydrogen phosphate piperazine salt BDHPP: 4-t-butylphenyl dihydrogen phosphate piperazine Salt APP: Exolit AP422 (Ammonium polyphosphate manufactured by Clariant)
cAPP: Exorit AP462 (Melamine-coated ammonium polyphosphate manufactured by Clariant)

3. Evaluation of molded product of flame retardant resin composition A molded product was produced by an injection molding method using the flame retardant synthetic resin composition obtained above. For injection molding, an injection molding machine “FE80S type” manufactured by Nissei Plastic Industry Co., Ltd. (clamping pressure: 80 tons) was used. After obtaining various test pieces by injection molding, the test pieces were conditioned for 48 hours at 23 ° C. and 50% RH, and then subjected to initial flammability evaluation, moisture resistance evaluation and bleed evaluation, respectively. It was. Further, the flammability evaluation was performed again after the moisture resistance test. The results are shown in Tables 1 and 2.

In addition, these evaluation methods were specifically performed by the following methods.
(1) Flammability Evaluation of flammability is based on the UL94 vertical combustion test method, and 1.6 mm (1/16 inch) thickness and 0.8 mm (1/32 inch) thickness UL test pieces are prepared and a combustion test is performed. went. As a result of the UL94 vertical combustion test, a four-level evaluation of “V-0”, “V-1”, “V-2”, and “impossible” was performed.
(2) Bleed test A black flat plate test piece (with 1 phr of carbon black added) having a thickness of 2 mm / 3 mm was prepared and heated at 150 ° C. for 7 days, and then the test piece was aged for 48 hours at 23 ° C. and 50% Rh. Then, the presence or absence of a flame retardant or the like on the surface of the test piece was visually observed. The results of the moisture resistance test are “○ (no seepage)”, “△ (some exudation is seen)”, “× (significant seepage or blooming is observed). The evaluation was made in four stages: “XX” (remarkable exudation or blooming was observed, and cracks were observed in the test piece).
(3) Moisture resistance test After preparing a UL test piece of 1.6 mm (1/16 inch) thickness and 0.8 mm (1/32 inch) thickness, it was subjected to a high humidity state treatment for 30 days at 60 ° C. and 90% Rh, Thereafter, the test piece was subjected to an aging treatment for 48 hours under the conditions of 23 ° C. and 50% Rh, and then the presence or absence of a flame retardant or the like on the surface of the test piece was visually observed. The results of the moisture resistance test are “○ (no seepage)”, “△ (some exudation is seen)”, “× (significant seepage or blooming is observed). It was evaluated in three stages.

When ammonium polyphosphate and coated ammonium polyphosphate are used alone as a flame retardant, flame retardancy, moisture resistance, and bleed resistance are all insufficient for practical use, especially when ammonium polyphosphate is used alone. In the bleed test, many cracks were observed in the test pieces (Comparative Examples 5 and 6).

In addition, when aromatic phosphate monoester piperazine salt is used as a flame retardant, the bleed resistance is slightly increased, but the moisture resistance and flame resistance are almost the same as those of ammonium polyphosphate, and the hygroscopicity is high. Therefore, it was confirmed that it was not practically usable (Comparative Examples 1 to 4).

On the other hand, when an aromatic phosphate diester piperazine salt is used alone as a flame retardant, flame retardancy equivalent to that of ammonium polyphosphate can be imparted, and further high moisture resistance and bleed resistance are imparted. Was confirmed (Examples 1 to 4).

On the other hand, when flame retardant is used in combination with ammonium polyphosphate or coated polyphosphate and piperazine salt of aromatic phosphate ester (monoester, diester), high flame retardancy can be achieved even with relatively small amount of addition. (Examples 5 to 10, Comparative Examples 7 to 14).

However, among them, when ammonium polyphosphate or coated ammonium polyphosphate and an aromatic phosphate monoester piperazine salt are used in combination, in any case, high flame retardancy is imparted at the initial stage after molding, but high humidity Along with the deterioration with time, the appearance deteriorated and the flame retardancy decreased (Comparative Examples 7 to 12). In comparison, it was confirmed that when the aromatic phosphate diester piperazine salt is used in combination, in addition to high flame retardancy, it can exhibit high moisture resistance and high bleed resistance (Examples 5 to 10).

However, in the combined use of aromatic phosphate diester piperazine salt and coated ammonium polyphosphate, the dispersibility of the coated ammonium polyphosphate is slightly inferior, and a slight spot pattern may be seen after the bleed test, but after the moisture resistance test In the UL94V test, the flame retardancy performance of V-0 to V-2 was still maintained (Examples 6 and 8).

In addition, when the aromatic phosphate diester, aromatic phosphate monoester and ammonium polyphosphate are used in combination, the aromatic phosphate diester has high moisture absorption, so that the aromatic phosphate diester has moisture resistance and bleed resistance. Inhibited (Comparative Examples 13 to 14).

Claims

A flame retardant composition comprising a cyclic amine salt of an aromatic phosphate diester composed of 1) an aromatic phosphoric diester as an anionic component and 2) a cyclic amine as a cationic component, the cyclic amine salt being Formula (I)

[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. n represents an integer of 1 to 10. m represents an integer of 0 to 9. l represents an integer of 1 to 10. ]
The flame retardant composition containing cyclic amine salt represented by these.
In the cyclic amine salt of the aromatic phosphoric diester,
The following general formula (II)

[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A component represented by
The following general formula (III)

[Wherein, A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. m represents an integer of 0 to 9. ]
2. The flame retardant composition according to claim 1, wherein the composition ratio of the component B to the component B is an ion equivalent ratio of A component / B component = 0.8 / 1.0 to 1.0 / 1.2. .
The flame retardant composition according to claim 1, wherein the content of the aromatic phosphoric acid monoester is 1% by weight or less in the flame retardant composition.
The flame retardant composition according to claim 1, further comprising at least one phosphate.
A resin composition comprising the flame retardant composition according to claim 1 and a resin component, wherein the flame retardant composition comprises 1 to 100 parts by weight of a cyclic amine salt of the aromatic phosphoric diester with respect to 100 parts by weight of the resin component. Resin composition.
A resin composition comprising the flame retardant composition according to claim 4 and a resin component, wherein 1 to 50 parts by weight of a cyclic amine salt of the aromatic phosphoric diester, 100 parts by weight of the resin component, and the phosphates A flame retardant resin composition comprising 1 to 50 parts by weight.
The flame retardant resin composition according to claim 5 or 6, wherein the resin component is a polyolefin resin.
A flame retardant resin molded product obtained by molding the flame retardant resin composition according to any one of claims 5 to 7.
The flame-retardant resin molded product according to claim 8, which is used for electric / electronic parts, OA equipment parts, home appliance parts, automotive parts or equipment mechanism parts.
The following general formula (I)

[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. n represents an integer of 1 to 10. m represents an integer of 0 to 9. l represents an integer of 1 to 10. ]
A process for producing a cyclic amine salt of an aromatic phosphoric diester represented by
(1) The following general formula (IV)

[Wherein R 1 to R 5 are the same or different from each other and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
Is reacted with phosphorus oxyhalide in the presence of an amine,
The following general formula (V)

[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A step of synthesizing a halogen-containing aromatic phosphate ester derivative represented by:
(2) By hydrolyzing the halogen-containing aromatic phosphate ester derivative,
The following general formula (II)

[Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
A step of synthesizing an aromatic phosphate diester represented by:
(3) For the aromatic phosphoric acid diester, the following general formula (VI)

[Wherein, A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group. Y represents an imino group. Z represents an oxygen atom, a sulfur atom or an imino group. m represents an integer of 0 to 9. ]
A method for producing a cyclic amine salt of an aromatic phosphoric diester, comprising a step of synthesizing a compound represented by the general formula (I) by adding a compound represented by formula (I).