JP2016003216A - Phosphorus-containing epoxy compound, diastereomer mixture, and method for producing phosphorus-containing epoxy compound - Google Patents

Abstract

The present invention provides a novel compound suitable as a non-halogen flame retardant having sufficient flame retardancy and a method for producing the same. A phosphorus-containing epoxy compound represented by formula (1). (R1 and R2 are each independently a hydrogen atom, an allyl group or a glycidyl group, provided that at least one of R1 and R2 is a glycidyl group; X is H, a C1-12 linear or branched alkyl group, etc .; Y Is H, an allyl group or a glycidyl group; Z is H, a hydroxyl group, a C1-12 linear or branched alkyl group, or a C2-12 linear or branched alkenyl group). [Selection figure] None

Description

  The present invention relates to a phosphorus-containing epoxy compound, a diastereomeric mixture of the phosphorus-containing epoxy compound, a method for producing the phosphorus-containing epoxy compound, and a phosphorus-containing epoxy compound that is an equivalent of the phosphorus-containing epoxy compound.

  Epoxy resins, phenolic resins, polyester resins, polyimide resins, etc. are known as thermosetting resins. Among them, epoxy resins have electrical and electronic insulating materials, paints, adhesive materials, and composites due to their excellent characteristics. Widely used in materials. However, since these thermosetting resins are flammable, high halogen content flame retardants such as brominated bisphenol A have been conventionally used in large amounts to impart flame retardancy to these resins.

  However, halogen-based flame retardants have problems such as the release of toxic gases such as dioxins that are toxic during combustion. Therefore, in view of recent environmental problems, a flame retardant having a low halogen content is required. It is becoming.

  Furthermore, in the industry, electronic devices and the like have been increased in speed and integration, and electronic components that form them have been required to be reduced in size, weight, and thickness. Along with this, in addition to flame retardancy, flame retardants are also required to have higher quality such as non-halogen containing no halogen. For example, a semiconductor encapsulant or the like has a problem that a trace amount of halogen compound remaining therein corrodes a copper wire, and the trace amount of halogen compound has a significant adverse effect on the reliability of the substrate. Therefore, a non-halogen (non-halogen flame retardant) is eagerly desired as a flame retardant.

On the other hand, various phosphorus-containing flame retardants have been proposed as non-halogen flame retardants. For example, phosphorus flame retardants such as phosphate esters are disclosed (see Patent Documents 1 and 2).
Moreover, 9,10-dihydro-10- (2 ′, 5′-dihydroxyphenyl) -9-oxa-10-phosphaphenanthrene, which is a cyclic organophosphorus compound, is used as a reactive flame retardant that reacts with the resin to be used together. 10-oxide (“HCA-HQ” manufactured by Sanko Co., Ltd., hereinafter abbreviated as “HCA-HQ”), 9,10-dihydro-10- [2 ′-(1 ′, 4′-dihydroxynaphthyl) ] -9-Oxa-10-phosphaphenanthrene-10-oxide ("HCA-NQ" manufactured by Sanko Co., Ltd., hereinafter abbreviated as "HCA-NQ"), 9,10-dihydro-10- (2 ', 5'-dihydroxy-4'-tert-butylphenyl) -9-oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ t-Bu), 3 in the naphthalene ring skeleton of HCA-NQ Compounds in which a hydroxyl group is bonded to (HCA-NQ _{(OH) 3)} has been proposed (see Patent Documents 3 to 5).

Furthermore, in order to further enhance the flame retardancy, as the phosphorus-containing epoxy compound having an epoxy group in the phosphorus-containing molecular skeleton, diphenylphosphinyl-hydroquinone-diglycidyl ether (hereinafter referred to as “PH ₂ -HQ-G ₂ ”). Abbreviation), 9,10-dihydro-10- (2 ′, 5′-diglycidyloxyphenyl) -9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter “HCA-HQ-G ₂ ”) (Abbreviated) and these oligomers have been proposed (see Patent Documents 6 to 8).

JP 2002-20394 A JP 2002-80633 A JP-A-61-2236787 JP-A-5-331179 JP 2001-302686 A Japanese Patent Application Laid-Open No. 5-214068 JP-A-8-188638 JP 2007-119544 A

  However, the phosphorus-based flame retardants disclosed in Patent Documents 1 and 2 have insufficient thermal stability during resin molding processing, and the flame retardant bleeds out from the resin during molding processing. Since the flammability becomes insufficient, it is necessary to blend the resin with a high concentration.

  Moreover, the reactive flame retardant of the cyclic organophosphorus compound disclosed in Patent Documents 3 to 5 requires a large amount of solvent at the time of use because of its low solubility, and may still remain undissolved in the solution. There was a problem. In addition, these reactive flame retardants have low compatibility with epoxy resins, etc., so they cannot be kneaded uniformly with the resin, or are not dissolved in the resin and exist non-uniformly in the solid state. There is a problem in that the flame retardancy of the molded product becomes insufficient by bleeding out from the resin sometimes.

Also, _{PH 2 -HQ-G} 2 and _{HCA-HQ-G 2} disclosed in Patent Document 6-8, although compatibility with the solubility and resin in a solvent is improved, still in solution In other words, there were problems such as undissolved residue and inability to knead uniformly with resin. Moreover, since the oligomers of PH ₂ -HQ-G ₂ and HCA-HQ-G ₂ are difficult to purify and further difficult to separate from the halide, it is inevitable that a trace amount of halide is mixed. There was a problem.

  This invention is made | formed in view of the said situation, and makes it a subject to provide a novel compound suitable as a non-halogen flame retardant which has sufficient flame retardance, and its manufacturing method.

  In order to solve the above problems, the present invention provides a phosphorus-containing epoxy compound represented by the following general formula (1).

（式中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子、アリル基又はグリシジル基であり、ただし、Ｒ^１及びＲ^２の少なくとも一方はグリシジル基であり；Ｘは水素原子、炭素数１〜１２の直鎖状若しくは分岐鎖状のアルキル基、炭素数２〜１２の直鎖状若しくは分岐鎖状のアルケニル基、アリール基又はアラルキル基であり；Ｙは水素原子、アリル基又はグリシジル基であり；Ｚは水素原子、水酸基、炭素数１〜１２の直鎖状若しくは分岐鎖状のアルキル基、又は炭素数２〜１２の直鎖状若しくは分岐鎖状のアルケニル基である。）

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an allyl group or a glycidyl group, provided that at least one of R ¹ and R ² is a glycidyl group; X is a hydrogen atom, having 1 to 12 carbon atoms. A linear or branched alkyl group, a linear or branched alkenyl group having 2 to 12 carbon atoms, an aryl group or an aralkyl group; Y is a hydrogen atom, an allyl group or a glycidyl group; Z is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched alkenyl group having 2 to 12 carbon atoms.)

  The phosphorus-containing epoxy compound of the present invention is preferably represented by the following general formula (1) -1.

（式中、Ｘは前記と同じである。）

(In the formula, X is the same as described above.)

  The present invention also provides a diastereomeric mixture comprising diastereomers of the phosphorus-containing epoxy compound.

  Moreover, this invention provides the phosphorus containing epoxy compound represented by following General formula (2).

（式中、Ｒはアリル基又はグリシジル基であり；Ｘは水素原子、炭素数１〜１２の直鎖状若しくは分岐鎖状のアルキル基、炭素数２〜１２の直鎖状若しくは分岐鎖状のアルケニル基、アリール基又はアラルキル基であり；Ｙは水素原子、アリル基又はグリシジル基であり；Ｚは水素原子、水酸基、炭素数１〜１２の直鎖状若しくは分岐鎖状のアルキル基、又は炭素数２〜１２の直鎖状若しくは分岐鎖状のアルケニル基である。）

(In the formula, R is an allyl group or a glycidyl group; X is a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched chain group having 2 to 12 carbon atoms. An alkenyl group, an aryl group or an aralkyl group; Y is a hydrogen atom, an allyl group or a glycidyl group; Z is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or carbon (It is a linear or branched alkenyl group having a number of 2 to 12.)

  The present invention also includes a step of reacting a compound represented by the following general formula (3) with epihalohydrin in the presence of a catalyst to obtain a reaction product, and an alkali metal alkoxide or an alkali metal hydride to the reaction product. A step of producing a phosphorus-containing epoxy compound equivalent, a step of separating a crystal of the phosphorus-containing epoxy compound equivalent, and heating and melting the crystal, or preparing a solution of the crystal, And a step of obtaining a phosphorus-containing epoxy compound represented by the following general formula (1).

（式中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子、アリル基又はグリシジル基であり、ただし、Ｒ^１及びＲ^２の少なくとも一方はグリシジル基であり；Ｒ^３及びＲ^４はそれぞれ独立に水素原子、アリル基又はグリシジル基であり、ただし、Ｒ^３及びＲ^４の少なくとも一方は水素原子であり；Ｘは水素原子、炭素数１〜１２の直鎖状若しくは分岐鎖状のアルキル基、炭素数２〜１２の直鎖状若しくは分岐鎖状のアルケニル基、アリール基又はアラルキル基であり；Ｙは水素原子、アリル基又はグリシジル基であり；Ｚは水素原子、水酸基、炭素数１〜１２の直鎖状若しくは分岐鎖状のアルキル基、又は炭素数２〜１２の直鎖状若しくは分岐鎖状のアルケニル基である。）

Wherein R ¹ and R ² are each independently a hydrogen atom, an allyl group or a glycidyl group, provided that at least one of R ¹ and R ² is a glycidyl group; R ³ and R ⁴ are each independently hydrogen An atom, an allyl group or a glycidyl group, wherein at least one of R ³ and R ⁴ is a hydrogen atom; X is a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a carbon number A straight chain or branched chain alkenyl group, aryl group or aralkyl group having 2 to 12; Y is a hydrogen atom, allyl group or glycidyl group; Z is a hydrogen atom, hydroxyl group, straight chain having 1 to 12 carbon atoms; A chain or branched alkyl group, or a linear or branched alkenyl group having 2 to 12 carbon atoms.)

  ADVANTAGE OF THE INVENTION According to this invention, the novel compound suitable as a non-halogen flame retardant which has sufficient flame retardance, and its manufacturing method are provided.

2 is IR spectrum data of the compound (1) -101 obtained in Example 1. 3 is IR spectrum data of the compound (1) -201 obtained in Example 3. 3 is IR spectrum data of the compound (1) -301 obtained in Example 4. 3 is IR spectrum data of the compound (1) -102 obtained in Example 5. It is IR spectrum data of the wet crystal (i) obtained in Example 6. It is IR spectrum data of the glassy solidified product obtained in Example 6. It is IR spectrum data of the wet crystal (i) chloroform solution obtained in Example 6. It is IR spectrum data of the wet white crystal (ii) obtained in Example 6. It is IR spectrum data of the wet crystal (iii) obtained in Example 6.

<Phosphorus-containing epoxy compound, diastereomer mixture>
The phosphorus-containing epoxy compound according to the present invention is represented by the following general formula (1) (hereinafter sometimes abbreviated as “compound (1)”).
Moreover, the diastereomeric mixture according to the present invention comprises a diastereomer of the phosphorus-containing epoxy compound (compound (1)).
Since the compound (1) is a non-halogen compound containing no halogen in its structure, it has a low environmental load, has sufficient flame retardancy, and is soluble in a solvent and compatible with a resin. It is excellent as a flame retardant used in combination with various resins.

（式中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子、アリル基又はグリシジル基であり、ただし、Ｒ^１及びＲ^２の少なくとも一方はグリシジル基であり；Ｘは水素原子、炭素数１〜１２の直鎖状若しくは分岐鎖状のアルキル基、炭素数２〜１２の直鎖状若しくは分岐鎖状のアルケニル基、アリール基又はアラルキル基であり；Ｙは水素原子、アリル基又はグリシジル基であり；Ｚは水素原子、水酸基、炭素数１〜１２の直鎖状若しくは分岐鎖状のアルキル基、又は炭素数２〜１２の直鎖状若しくは分岐鎖状のアルケニル基である。）

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an allyl group or a glycidyl group, provided that at least one of R ¹ and R ² is a glycidyl group; X is a hydrogen atom, having 1 to 12 carbon atoms. A linear or branched alkyl group, a linear or branched alkenyl group having 2 to 12 carbon atoms, an aryl group or an aralkyl group; Y is a hydrogen atom, an allyl group or a glycidyl group; Z is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched alkenyl group having 2 to 12 carbon atoms.)

Compound (I) is represented by the general formula (1), and a 9-oxa-10-phosphaphenanthrene group contributing to flame retardancy and an epoxy group contributing to reaction curability exist in the same molecular structure. Therefore, it has both excellent flame retardancy and curability.
Further, the compound (I) is extremely useful for use as a diastereomeric mixture described later.

In the formula, R ¹ and R ² are each independently a hydrogen atom, an allyl group (2-propenyl group) or a glycidyl group. Provided that at least one of R ¹ and R ² are glycidyl groups, both R ¹ and R ² may be a glycidyl group.

In the formula, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, an aryl group, or an aralkyl group.
Examples of the alkyl group in X include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, and neopentyl group. Tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2 -Methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2 , 2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group Dodecyl group and the like.
The alkyl group in X preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and particularly preferably 1 to 5 carbon atoms.

As the alkenyl group in X, in the alkyl group having 2 or more carbon atoms in X, such as vinyl group (ethenyl group), allyl group (2-propenyl group), methallyl group (2-methyl-2-propenyl group), etc. Examples thereof include a group in which one single bond (C—C) between carbon atoms is substituted with a double bond (C═C).
The alkenyl group in X preferably has 2 to 10 carbon atoms, more preferably 2 to 7 carbon atoms, and particularly preferably 2 to 5 carbon atoms.

  The aryl group in X preferably has 6 to 12 carbon atoms, and includes a phenyl group, 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group ( Dimethylphenyl group) and the like, and one or more hydrogen atoms of these aryl groups are substituted with a linear or branched alkyl group or an aryl group. Here, examples of the linear or branched alkyl group for substituting a hydrogen atom include those exemplified as the alkyl group in X, and examples of the aryl group include those exemplified above.

Examples of the aralkyl group in X include a monovalent group in which one hydrogen atom of the alkyl group in X is substituted with the aryl group in X.
The aralkyl group preferably has 7 to 20 carbon atoms, and more specifically, a benzyl group (phenylmethyl group), an о-methylbenzyl group (о-methylphenylmethyl group), or an m-methylbenzyl group. Examples include (m-methylphenylmethyl group), p-methylbenzyl group (p-methylphenylmethyl group), phenylethyl group, naphthylmethyl group, naphthylethyl group and the like.

  In the formula, Y is a hydrogen atom, an allyl group (2-propenyl group) or a glycidyl group.

In the formula, Z is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched alkenyl group having 2 to 12 carbon atoms.
Examples of the alkyl group and alkenyl group in Z are the same as the alkyl group and alkenyl group in X.
Z is bonded to the benzene ring skeleton to which Y is not bonded among the naphthalene ring skeleton in the general formula (1), and the bonding position is not particularly limited as long as it is in this benzene ring skeleton.

  The compound (I) is preferably represented by the following general formula (1) -1, (1) -2, (1) -3 or (1) -4.

（式中、Ｘは前記と同じである。）

(In the formula, X is the same as described above.)

  In the formula, X is the same as X in the general formula (1).

Preferred examples of compound (I) include, but are not limited to, those shown below.
9,10-dihydro-10- [2 ′-(1 ′, 4′-diglycidyloxy) naphthyl] -9-oxa-10-phosphaphenanthrene-10-oxide (represented by the following formula (1) -101) Compound),
8-Benzyl-9,10-dihydro-10- [2 ′-(1 ′, 4′-diglycidyloxy) naphthyl] -9-oxa-10-phosphaphenanthrene-10-oxide (the following formula (1) — Compound represented by 102),
9,10-dihydro-10- [2 ′-(1′-glycidyloxy-4′-allyloxy) naphthyl] -9-oxa-10-phosphaphenanthrene-10-oxide (represented by the following formula (1) -201) Compound),
9,10-dihydro-10- [2 ′-(1′-allyloxy-4′-glycidyloxy) naphthyl] -9-oxa-10-phosphaphenanthrene-10-oxide (represented by the following formula (1) -301) Compound),
8-Methyl-9,10-dihydro-10- [2 ′-(1 ′, 4′-diglycidyloxy) naphthyl] -9-oxa-10-phosphaphenanthrene-10-oxide (the following formula (1) — 103)
8-Isopropyl-9,10-dihydro-10- [2 ′-(1 ′, 4′-diglycidyloxy) naphthyl] -9-oxa-10-phosphaphenanthrene-10-oxide (the following formula (1) — 104)
8-Phenyl-9,10-dihydro-10- [2 ′-(1 ′, 4′-diglycidyloxy) naphthyl] -9-oxa-10-phosphaphenanthrene-10-oxide (the following formula (1) — 105)
9,10-dihydro-10- [2 ′-(1′-hydroxy-3′-allyl-4′-glycidyloxy) naphthyl] -9-oxa-10-phosphaphenanthrene-10-oxide (the following formula (1 ) -401 compound),
8-ethyl-9,10-dihydro-10- [2 ′-(1′-hydroxy-3′-allyl-4′-glycidyloxy) naphthyl] -9-oxa-10-phosphaphenanthrene-10-oxide ( A compound represented by the following formula (1) -402),
8-Benzyl-9,10-dihydro-10- [2 ′-(1′-hydroxy-3′-allyl-4′-glycidyloxy) naphthyl] -9-oxa-10-phosphaphenanthrene-10-oxide ( Compound represented by the following formula (1) -403).
In the present specification, hereinafter, for the compound (1), for example, the compound represented by the formula (1) -101 is abbreviated as “compound (1) -101”. Abbreviations may be described.

  The compound (1) is more preferably represented by the general formula (1) -1.

Since the compound (1) has an asymmetric point at least in the carbon atom and phosphorus atom of the methine group in the epoxy group in the structure, the compound (1) may exist as a diastereomeric mixture unless purification is performed after the production. There is. The diastereomers of the compound (1) have the same molecular weight and the same chemical structure, but have different steric structures, and have different physicochemical properties such as optical characteristics, melting point, solubility, and chromatograph.
And compound (1) is a novel compound, and the existence of the diastereomeric mixture has not been known so far.

Since the compound (1) is excellent in solubility in a solvent and compatibility with a resin as described above, for example, a large amount of solvent is not required at the time of use, and the compound (1) may remain unevenly in a solid state in the resin. In addition, it can be kneaded with the resin with high uniformity and does not bleed out from the resin during molding. Thus, compound (1) is excellent in handleability and imparts excellent flame retardancy to the resin.
In addition, since the diastereomeric mixture according to the present invention is a diastereomeric mixture, the solubility in a solvent and the compatibility with a resin are improved as compared with the case of the compound (1) which is not a diastereomeric mixture. It is easy to handle, and it is more excellent in handleability. Further, the diastereomeric mixture according to the present invention can be easily reduced in melting point.

  Conventionally, it is known that a mixture of different types of epoxy compounds is mixed into a low-melting-point mixture (see, for example, “DIC Technical Review No. 7/2001”). Therefore, it is known that any compound including an epoxy compound has a lower melting point than that of only one compound in a mixture of diastereomers and an improvement in solubility in a solvent and compatibility with a resin. Not. Thus, by using a diastereomer mixture, it is not necessary to use a plurality of industrialized compounds to achieve a low melting point and to improve solubility in a solvent and compatibility with a resin. Very practical.

  Among the compounds (1), 9,10-dihydro-10- [2 ′-(1 ′, 4′-diglycidyloxy) naphthyl] -9-oxa is particularly preferable for forming a diastereomeric mixture. -10-phosphaphenanthrene-10-oxide (compound (1) -101) and 8-benzyl-9,10-dihydro-10- [2 '-(1', 4'-diglycidyloxy) naphthyl]- An example is 9-oxa-10-phosphaphenanthrene-10-oxide (compound (1) -102).

<Method for Producing Compound (1)>
Compound (1) is obtained by reacting, for example, a compound represented by the following general formula (3) (hereinafter sometimes abbreviated as “compound (3)”) with an epihalohydrin in the presence of a catalyst. Obtaining a phosphorus-containing epoxy compound equivalent by allowing an alkali metal alkoxide or alkali metal hydride to act on the reaction product, separating the crystals of the phosphorus-containing epoxy compound equivalent, and The compound can be produced by a production method having a step of obtaining the compound (1) by heating and melting the crystal or preparing a solution of the crystal.

（式中、Ｒ^３及びＲ^４はそれぞれ独立に水素原子、アリル基又はグリシジル基であり、ただし、Ｒ^３及びＲ^４の少なくとも一方は水素原子であり；Ｒ^１、Ｒ^２、Ｘ、Ｙ及びＺは、前記と同じである。）

(Wherein R ³ and R ⁴ are each independently a hydrogen atom, an allyl group or a glycidyl group, provided that at least one of R ³ and R ⁴ is a hydrogen atom; R ¹ , R ² , X, Y and Z is the same as above.)

[Step of obtaining the reaction product]
In the production method, first, compound (3) is reacted with epihalohydrin to obtain a reaction product.
The compound (3) is a raw material compound represented by the general formula (3) and used in this step.
In the formula, R ³ and R ⁴ are each independently a hydrogen atom, an allyl group or a glycidyl group. Provided that at least one of R ³ and R ⁴ are hydrogen atom, both R ³ and R ⁴ may be hydrogen atoms.
In the formula, X, Y and Z are the same as X, Y and Z in the general formula (1).

  Examples of the epihalohydrin to be reacted with the compound (3) include epichlorohydrin, epibromohydrin and epiiodohydrin, but epichlorohydrin is preferable. For example, the epihalohydrin may be preliminarily mixed with the compound (3) and then reacted by raising the temperature, or after the temperature of the liquid containing the compound (3) reaches the reaction temperature, the epihalohydrin is added to the liquid. May be reacted.

  The amount of epihalohydrin used is preferably 1 to 40 equivalents, more preferably 2 to 30 equivalents, and 4 to 25 equivalents per 1 equivalent of the phenolic hydroxyl group of compound (3) as a substrate. Is particularly preferred.

Catalysts used in the reaction of compound (3) with epihalohydrin include inorganic alkali, alkali metal alkoxide, alkali metal hydride, quaternary ammonium salt, imidazole, N, N-dimethylformamide (DMF), organic amine, triphenylphosphine And sulfonium salts.
A catalyst may be used individually by 1 type and may use 2 or more types together.

  The amount of the catalyst used is preferably 0.1 to 20% by mass and more preferably 0.5 to 5% by mass with respect to the amount of the compound (3) used as the substrate.

The reaction between compound (3) and epihalohydrin may be performed using, for example, epihalohydrin as a solvent, or may be performed separately using a solvent.
Examples of the solvent used separately include aromatic hydrocarbons such as toluene, xylene and mesitylene (1,3,5-trimethylbenzene); halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane and chlorobenzene; tetrahydrofuran (THF), dioxane, Ethers such as dimethoxyethane and diethylene glycol dimethyl ether; esters such as ethyl acetate, butyl acetate and benzyl acetate; methanol, ethanol, 2-propanol, 2-methyl-2-propanol (tert-butyl alcohol), 1-butanol, 2-methoxy Examples include aliphatic alcohols such as ethanol (methyl cellosolve) and 2-ethoxyethanol (ethyl cellosolve); ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; and acetonitrile. It can be.
A solvent may be used individually by 1 type and may use 2 or more types together.

  The reaction temperature when the compound (3) is reacted with epihalohydrin is preferably 50 ° C. to the boiling point of epihalohydrin, and 60 ° C. to the boiling point of epihalohydrin (for example, when epichlorohydrin is used, 60 to 118 ° C) is more preferable.

  The reaction time when the compound (3) is reacted with epihalohydrin is preferably 1 to 12 hours, and more preferably 1 to 8 hours.

[Step of producing phosphorus-containing epoxy compound equivalent]
After the compound (3) and epihalohydrin are reacted to obtain a reaction product, an alkali metal alkoxide or an alkali metal hydride is allowed to act on the reaction product to produce a phosphorus-containing epoxy compound equivalent. In this step, an epoxidation reaction composition containing the phosphorus-containing epoxy compound equivalent is obtained.
At this time, after obtaining the reaction product, the reaction product may be allowed to continue to react with an alkali metal alkoxide or an alkali metal hydride, or after performing a known post-treatment, Alkali metal alkoxide or alkali metal hydride may be allowed to act on. An example of the post-treatment here is removal (evaporation) of unreacted epihalohydrin.

  The phosphorus-containing epoxy compound equivalent obtained in this step has a biphenol structure formed by cleavage of the “PO” bond of the substrate-derived phosphalene ring, and can be easily separated as a crystal. Specifically, the equivalent is represented by the following general formula (2) (hereinafter sometimes abbreviated as “compound (2)”).

（式中、Ｒはアリル基又はグリシジル基であり；Ｘは水素原子、炭素数１〜１２の直鎖状若しくは分岐鎖状のアルキル基、炭素数２〜１２の直鎖状若しくは分岐鎖状のアルケニル基、アリール基又はアラルキル基であり；Ｙは水素原子、アリル基又はグリシジル基であり；Ｚは水素原子、水酸基、炭素数１〜１２の直鎖状若しくは分岐鎖状のアルキル基、又は炭素数２〜１２の直鎖状若しくは分岐鎖状のアルケニル基である。）

(In the formula, R is an allyl group or a glycidyl group; X is a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched chain group having 2 to 12 carbon atoms. An alkenyl group, an aryl group or an aralkyl group; Y is a hydrogen atom, an allyl group or a glycidyl group; Z is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or carbon (It is a linear or branched alkenyl group having a number of 2 to 12.)

In the formula, R is an allyl group or a glycidyl group. X, Y and Z are the same as X, Y and Z in the general formula (1).
The two oxygen atoms whose bonding positions are not specified are all the benzene ring skeleton to which Y is bonded out of the naphthalene ring skeleton in the general formula (2) (that is, the 1′-position or 4′-position). Carbon atom).

  The compound (2) includes a compound represented by the following general formula (2a) and a compound represented by the following general formula (2b).

（式中、Ｒ、Ｘ、Ｙ及びＺは、前記と同じである。）

(In the formula, R, X, Y and Z are the same as described above.)

  The temperature (reaction temperature) when the alkali metal alkoxide or alkali metal hydride is allowed to act on the reaction product is preferably -10 to 80 ° C, more preferably -5 to 40 ° C, A temperature of 20 ° C. is particularly preferable.

The reaction product is preferably an alkali metal alkoxide, such as sodium methoxide (CH ₃ ONa), sodium ethoxide (CH ₃ CH ₂ ONa), potassium tert-butoxide ((CH ₃ ) ₃ COK. ) Is more preferable.
Any of the alkali metal alkoxides and alkali metal hydrides may be used alone or in combination of two or more.

  The amount of the alkali metal alkoxide or alkali metal hydride used is preferably 0.5 to 2.5 equivalents, and 0.9 to 2.2 equivalents per 1 equivalent of the phenolic hydroxyl group of the compound (3). More preferably.

The alkali metal alkoxide is usually in the form of a solution of alcohol (for example, methanol in the case of sodium methoxide, ethanol in the case of sodium ethoxide). When the alkali metal alkoxide is allowed to act on the reaction product, This alcohol can be used as a solvent as it is.
Also, when an alkali metal hydride is used, alcohol can be used as a solvent.
And when making an alkali metal alkoxide or an alkali metal hydride act, in any case, you may use solvents other than the said alcohol.

Examples of the solvent used when the alkali metal alkoxide or alkali metal hydride is allowed to act include the same solvents as those used in the reaction of the compound (3) with epihalohydrin, such as toluene, xylene, mesitylene (1,3 , 5-trimethylbenzene) and the like; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane and chlorobenzene; ethers such as tetrahydrofuran (THF), dioxane, dimethoxyethane and diethylene glycol dimethyl ether are preferred.
The said solvent when making an alkali metal alkoxide or an alkali metal hydride act may be used individually by 1 type, and may use 2 or more types together.

[Step of separating crystals of the phosphorus-containing epoxy compound equivalent]
After an alkali metal alkoxide or an alkali metal hydride is allowed to act on the reaction product to produce a phosphorus-containing epoxy compound equivalent, the crystals of the phosphorus-containing epoxy compound equivalent are separated.
At this time, after the phosphorus-containing epoxy compound equivalent is produced, the crystals may be separated as they are, or the crystals may be separated after performing known post-treatment. Examples of the post-treatment here include removal or concentration of salt produced as a by-product when alkali metal alkoxide or alkali metal hydride is allowed to act on the reaction product.

  Since the phosphorus-containing epoxy compound equivalent is stable as a crystal, it can be easily separated. And the said compound (1) (phosphorus containing epoxy compound) which is a target object is obtained with high purity and a high yield by isolate | separating the said phosphorus containing epoxy compound equivalent and performing isolation and purification.

If the crystals of the phosphorus-containing epoxy compound equivalent are precipitated in the epoxidation reaction composition in the previous step, they can be separated, and the epoxidation reaction composition can be separated into a solvent (poor solvent). May be separated after precipitation. In order to improve the yield of the crystal, it is preferable to separate after adding a poor solvent.
The crystal may be separated by a known method such as filtration.

Examples of the poor solvent include alcohols such as methanol, ethanol, and 2-propanol; phenols such as phenol and methylphenol (cresol) (compounds having a phenolic hydroxyl group); ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone; Esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, ethyl benzoate; aromatic hydrocarbons such as benzene, toluene, xylene; tetrahydrofuran (THF), dioxane, diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether And ethers such as anisole (methoxybenzene).
Among these, the poor solvent is preferably toluene, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethanol, or 2-propanol, and particularly preferably ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, or ethanol.
The said poor solvent may be used individually by 1 type, and may use 2 or more types together.

  The separated crystals of the phosphorus-containing epoxy compound equivalent may be further purified by crystallization, decolorization treatment, etc. in order to obtain high purity such as a good hue.

Solvents used for crystallization include alcohols such as methanol, ethanol and methoxypropanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate and propyl acetate; diethyl ether, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. And ethers such as tetrahydrofuran (THF) and dioxane; halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane; aromatic hydrocarbons such as benzene, toluene and xylene; and acetonitrile.
The said crystallization solvent may be used individually by 1 type, and may use 2 or more types together.

The crystal decoloring treatment may be performed by a known method such as activated carbon treatment.
In the case of the activated carbon treatment, for example, the crystal is dissolved in a solvent, and the amount of the obtained solution is preferably 0.1 to 10% by mass, more preferably 0.2 to 5.0% by mass. After decolorizing by adding activated carbon and stirring, the activated carbon is filtered off and the obtained filtrate is cooled, or a poor solvent is added to the obtained filtrate to extract the precipitated crystals. . Examples of the solvent used for dissolving the crystals include the same ones as the crystallization solvent described above, and examples of the poor solvent include the same ones as described above.

[Step of obtaining compound (1)]
After the crystals of the phosphorus-containing epoxy compound equivalent are separated, the crystals (1) are obtained by heating and melting the crystals or preparing a solution of the crystals (making the crystals into solution).
In this step, a high-purity compound (1) can be obtained in a high yield by using separated crystals of the equivalent having a high purity.

The equivalent has a different chemical structure from the target compound (1), but the crystals of the biphenol ring are recombined with each other by melting the solution by heating or melting it as described above. Thus, the phosphalene ring is regenerated to produce the compound (1).
Further, when the compound (1) is dissolved and crystallized using a solvent, the equivalent crystal is obtained. That is, the compound (1) and the equivalent are quite unexpectedly in a reversible relationship between the above-mentioned crystal heating and melting step or solution step and the crystallization step (compound (1)). Changes to its equivalent, and the equivalent of compound (1) changes to compound (1)).
In this way, the equivalent crystal is obtained by melting or crystallizing the equivalent crystal to form the compound (1), or by dissolving and crystallizing the compound (1). This has been found for the first time by the present inventors.

When the equivalent crystal is heated and melted, for example, the obtained melt is cooled and solidified to obtain the compound (1).
On the other hand, when the crystal solution is prepared (the crystal is made into a solution), the compound (1) is obtained by removing the solvent from the obtained solution by heat concentration or the like.

Compound (1) may be further purified by crystallization, decolorization treatment or the like. The purification at this time can be performed by the same method as the purification of the crystals of the equivalents described above.
For example, when performing a decoloring process, activated carbon may be removed from the solution after decoloring by filtration, and the solvent may be removed by heat concentration or the like.
On the other hand, when performing crystallization, since it is a crystal (namely, the said equivalent) taken out, it is necessary to use this crystal again for the above-mentioned heating-melting process or solution process.

  The manufacturing method of compound (1) is not limited to the above-mentioned method, For example, the method by which one part process (operation) was added, abbreviate | omitted or changed in the above-mentioned method may be sufficient.

  Compound (1) and the equivalent are, for example, nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), infrared spectroscopy (IR), ultraviolet / visible spectroscopy (UV-VIS absorption spectrum), etc. The structure can be confirmed by a known method. And in order to distinguish a compound (1) and the said equivalent body, it is preferable to analyze combining several types of methods.

Since the production method can obtain the compound (1), which is a phosphorus-containing epoxy compound, with high purity and high yield, and does not require complicated steps, it is highly practical on an industrial level.
On the other hand, for example, in the method for producing a phosphorus-containing epoxy compound described in the above-mentioned “Japanese Patent Laid-Open No. 5-214068 (Patent Document 6)”, it is necessary to separately produce an allyl-substituted product, and the number of steps There are many and practicality is low. In the reaction between the phosphorus compound and the epihalohydrin, an alkali metal hydroxide is used as an alkali. When applied to the production of the compound (1), the compound (1) is remarkably colored, and the phosphalene ring Various by-products such as by-products generated by hydrolysis and by-products generated by side reaction of the epoxy ring of compound (1) are produced in large quantities. In the method for producing a phosphorus-containing epoxy compound described in "JP-A-8-188638 (Patent Document 7)" and "JP-A 2007-119544 (Patent Document 8)" described above, the phosphorus compound and epihalohydrin There are similar problems in this reaction. Furthermore, in the methods described in these three documents, as described above, the oligomer of the obtained phosphorus-containing epoxy compound is difficult to purify and further difficult to separate from the halide. Inevitable contamination.
In addition, as a method for producing a phosphorus-containing epoxy compound, the method described in “China Patent Publication No. 393496” can also be mentioned. In this method, a phosphorous compound and an alkali metal alkoxide are used in advance. Although it is necessary to form a salt, this alkali metal salt is insoluble and has extremely low operability (see Comparative Examples described later). Further, since a large amount of methanol is used as a solvent, methanolysis occurs during the reaction, and a large amount of by-products are generated.
Thus, the conventional method for producing a phosphorus-containing epoxy compound is remarkably colored and a large amount of various by-products are produced, so that the target product cannot be obtained in high purity and high yield, and is complicated. A process was required and its practicality was low.

<Flame-retardant epoxy resin composition>
Compound (1) is suitable for the production of a flame retardant epoxy resin composition.
That is, the flame retardant epoxy resin composition in the present invention contains the compound (1) and the epoxy resin, preferably further contains a curing agent and a curing accelerator, and is used, for example, as a compound or varnish. .
The said flame-retardant epoxy resin composition has sufficient flame retardance with a non-halogen by using the compound (1).

In the flame retardant epoxy resin composition, compound (1) may be used alone or in combination of two or more.
In the flame-retardant epoxy resin composition, a part of the compound (1) may be replaced with an oligomer of the compound (1).

  In the flame-retardant epoxy resin composition, the ratio of the content of compound (1) to the total content of compound (1), epoxy resin, curing agent and curing accelerator is preferably 10 to 50% by mass. More preferably, it is 15-40 mass%. When the ratio of the content of compound (I) is not less than the lower limit, a cured product having more excellent flame retardancy is obtained, and the ratio of the content of compound (I) is not more than the upper limit. Excessive use of compound (I) is suppressed.

The said epoxy resin is not specifically limited, A well-known thing can be used.
As the epoxy resin, specifically, if it is a phosphorus-free epoxy resin, glycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, phenol novolak, cresol novolak, resorcinol novolak; butanediol, polyethylene glycol, polypropylene glycol, etc. Glycidyl ether of diol: glycidyl type in which the active hydrogen of the compound having active hydrogen bonded to nitrogen atom such as glycidyl ester of dicarboxylic acid such as phthalic acid, isophthalic acid, tetrahydrophthalic acid, aniline, isocyanuric acid, etc. Epoxy resin (including methyl glycidyl type); Vinylcyclohexene epoxide obtained by epoxidizing olefin bonds in the molecule; 3,4-epoxycyclohexylmethyl- , 4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane, and the like; bis (4-hydroxy) Epoxy product of thioether; glycidyl ether of paraxylylene-modified phenol resin; glycidyl ether of metaxylylene / paraxylylene-modified phenol resin; glycidyl ether of terpene-modified phenol resin; glycidyl ether of dicyclopentadiene-modified phenol resin; glycidyl of polycyclic aromatic ring-modified phenol resin Examples include ether; glycidyl ether of naphthalene ring-containing phenol resin; stilbene type epoxy resin; biphenyl type epoxy resin.
In the flame-retardant epoxy resin composition, the epoxy resin may be used alone or in combination of two or more.

  In the flame-retardant epoxy resin composition, the ratio of the content of the epoxy resin to the total content of the compound (1), the epoxy resin, the curing agent and the curing accelerator is preferably 30 to 80% by mass. More preferably, it is -70 mass%. When the proportion of the content of the epoxy resin is within such a range, a cured product having desired characteristics can be obtained more stably.

Examples of the curing agent include phenolic curing agents, acid anhydride curing agents, melamine curing agents, amine curing agents, and polymercaptan curing agents.
In the flame retardant epoxy resin composition, one type of curing agent may be used alone, or two or more types may be used in combination.

  Examples of the phenol-based curing agent include compounds having two phenolic hydroxyl groups such as bisphenol A, bisphenol F, bisphenol C, and 4,4′-dihydroxybiphenyl (4,4′-biphenol); phenol novolac, cresol novolac, phenol A novolak type phenol resin such as a condensation compound of a derivative and an aldehyde or a ketone can be exemplified. Here, the “phenol derivative” is a compound in which one or more hydrogen atoms of phenol are substituted with a group other than a hydrogen atom, and means a compound other than cresol.

  Examples of the acid anhydride curing agent include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and the like.

  Examples of the amine curing agent include diaminodiphenylmethane, diaminodiphenylsulfone, triethylenetetramine, isophoronediamine, polyamide resin which is a condensate of dimer acid and polyamine, and modified amine.

  Examples of the polymercaptan curing agent include polymercaptan and polysulfide resin.

  In the flame-retardant epoxy resin composition, the ratio of the content of the curing agent to the content of the epoxy resin is preferably 15 to 55% by mass, and more preferably 25 to 45% by mass. When the ratio of the content of the curing agent is not less than the lower limit, a cured product having high flame retardancy can be obtained more quickly, and the ratio of the content of the compound (I) is not more than the upper limit. , Excessive use of the curing agent is suppressed.

The said hardening accelerator is not specifically limited, A well-known thing can be used.
Specific examples of the curing accelerator include dicyandiamide and derivatives thereof, acetic anhydride, benzyldimethylamine, tetramethylammonium salts and derivatives thereof, triphenylphosphine, ethyltriphenylphosphonium salts and derivatives thereof, and 2-ethyl-4. -Methylimidazole and its derivatives can be exemplified. Here, “derivative” means a compound in which one or more hydrogen atoms of the compound are substituted with a group other than a hydrogen atom.
In the flame retardant epoxy resin composition, one type of curing accelerator may be used alone, or two or more types may be used in combination.

  In the flame-retardant epoxy resin composition, the ratio of the content of the curing accelerator to the total content of the compound (1), the epoxy resin, the curing agent, and the curing accelerator is 0.1 to 20% by mass. Preferably, it is 0.5-8 mass%. When the ratio of the content of the curing accelerator is equal to or higher than the lower limit value, a cured product can be obtained more quickly, and when the ratio of the content of the curing accelerator is equal to or lower than the upper limit value, the curing accelerator is excessive. Use is suppressed.

  The flame retardant epoxy resin composition may contain other components other than the compound (1), the epoxy resin, the curing agent, and the curing accelerator within a range not impairing the effects of the present invention.

Preferred examples of the other components include flame retardants other than the compound (1), fillers, additives, solvents, and the like.
The said other component may be used individually by 1 type, and may use 2 or more types together.

  The flame retardant other than the compound (1) in the other components includes metal hydrates such as aluminum hydroxide and magnesium hydroxide; phosphate esters such as triphenyl phosphate and tricresyl phosphate; 9,10-dihydro -10- (2 ', 5'-dihydroxyphenyl) -9-oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ), 9,10-dihydro-10- (2', 5'-dihydroxy- 4'-methylphenyl) -9-oxa-10-phosphaphenanthrene-10-oxide (HCA-Me-HQ), 9,10-dihydro-10- (2 ', 5'-dihydroxy-4'-tert- Butylphenyl) -9-oxa-10-phosphaphenanthrene-10-oxide (HCA-t-Bu-HQ), 9,10-dihy B-10- [2 ′-(1 ′, 4′-dihydroxynaphthyl)]-9-oxa-10-phosphaphenanthrene-10-oxide (HCA-NQ), 9,10-dihydro-10- [2 ′ -(1 ', 3', 4'-trihydroxynaphthyl)]-9-oxa-10-phosphaphenanthrene-10-oxide (HCA-HO-NQ), diphenylphosphinyl hydroquinone, bisphenol A bis (diphenyl) Examples thereof include condensed phosphate esters such as phosphate and resorcinol bis (diphenyl) phosphate; silicone flame retardants and the like.

  The filler in the other components is preferably an inorganic filler, and examples of the inorganic filler include silica powder; powder of clay minerals such as talc and clay.

  In the flame-retardant epoxy resin composition, the ratio of the filler content to the total content of components other than the filler is preferably 0 to 800 mass%.

Examples of additives in the other components include reaction aids, flame retardant aids, leveling agents, and colorants.
What is necessary is just to adjust suitably content of the said additive of the said phosphorus containing flame-retardant epoxy resin composition according to the kind of additive, and it is not specifically limited.

The solvent in the other components is used, for example, to adjust the viscosity of the flame retardant epoxy resin composition or to use the flame retardant epoxy resin composition as a varnish.
The solvent is preferably an organic solvent, and aromatic hydrocarbons such as benzene, toluene and xylene; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; acetone, methyl ethyl ketone and methyl isobutyl ketone Examples include ketones; alcohols such as methoxypropanol; ethers such as ethylene glycol monomethyl ether, methoxyethyl acetate, and tetrahydrofuran (THF).
What is necessary is just to adjust suitably content of the said solvent of a flame-retardant epoxy resin composition according to the objective, and it is not specifically limited.

  The phosphorus content of the flame retardant epoxy resin composition is preferably 0.1 to 8% by mass, and more preferably 0.3 to 3% by mass. The flame retardancy of the flame retardant epoxy resin composition is further improved when the phosphorus content is not less than the lower limit. In addition, the flame-retardant epoxy resin composition has a phosphorus content of not more than the above upper limit, so that excessive use of the compound (I) is suppressed without impairing the flame retardancy, and the economic efficiency is further improved. . In the present specification, the “phosphorus content of the flame retardant epoxy resin composition” means the mass of phosphorus (P) in the flame retardant epoxy resin composition with respect to the total mass of the flame retardant epoxy resin composition. It means a ratio and can be measured, for example, by a method based on JIS K 0102 46.3.1 and JIS K 0102 46.1.1.

The flame retardant epoxy resin composition is obtained by blending the compound (1) and components other than the compound (1) (necessary components such as an epoxy resin, a curing agent, a curing accelerator, and other components described above). After blending each component, the obtained product may be used as it is as a flame retardant epoxy resin composition, or a product obtained by performing known post-treatments as necessary as a flame retardant epoxy resin composition. Also good.
At the time of blending each component, all the components may be added and then mixed, or some components may be mixed while being added sequentially, or all components may be mixed while being added sequentially. Good. Further, for example, a blending component other than the solvent may be mixed and preferably dissolved using a solvent, and then the solvent may be removed from the resulting product to obtain a flame retardant epoxy resin composition.

  The mixing method of a compounding component is not specifically limited, What is necessary is just to select suitably from well-known methods, such as the method of using a ball mill, bead mill, a mixer, or a blender. During mixing, it is preferable to uniformly dissolve or disperse each component.

  The temperature and time during compounding are not particularly limited as long as each compounding component does not deteriorate, but the temperature is preferably 15 to 80 ° C., and the time is preferably 0.5 to 24 hours.

<Hardened product>
The flame retardant epoxy resin composition can be cured and used as a flame retardant cured product, and the cured product is useful as a member of, for example, an electric device and an electronic device, and particularly a sealing material. Etc. are suitable.
The said hardened | cured material is obtained by heating a flame-retardant epoxy resin composition. More specifically, for example, a liquid flame-retardant epoxy resin composition may be injected into a cup, cavity, package recess, or the like by a method using a dispenser or other methods, and cured by heating, or a solid A liquid or highly viscous liquid flame retardant epoxy resin composition may be flowed by heating or the like, and injected into a cup, cavity, package recess or the like in the same manner as described above, and further heated and cured.

<Film>
The flame retardant epoxy resin composition can be molded and used as a flame retardant film.
The film can be obtained, for example, by applying the above varnish-like flame retardant epoxy resin composition on a support and drying it.
The flame-retardant epoxy resin composition can be applied by a known method such as a printing method, a coating method, or an immersion method.
The flame-retardant epoxy resin composition can be dried, for example, by removing the solvent by heating, and may be blown during heating or may be dried by blowing hot air or the like.

The material of the support is not particularly limited, and examples thereof include polyolefins such as polystyrene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate and polyethylene naphthalate; polycarbonates; polyimides; paper; and metals such as copper and aluminum.
The coated surface of the support may be subjected to a surface treatment such as a mud treatment, a corona treatment, or a mold release treatment.
Although the thickness of the said support body is not specifically limited, It is preferable that it is 10-150 micrometers, and it is preferable that the said support body is a film form. As such a support, for example, a metal foil such as a copper foil and an aluminum foil may be used as long as it is made of metal.

<Prepreg>
The flame retardant epoxy resin composition is suitable for producing a flame retardant prepreg.
The prepreg is obtained, for example, by impregnating a fibrous base material with the above-mentioned varnish flame-retardant epoxy resin composition and heating.

The fibrous base material is not particularly limited, and examples thereof include woven and non-woven fabrics of inorganic fibers such as glass, aramid cloth, polyester cloth, carbon fiber, and paper.
Although the thickness of the said fibrous base material is not specifically limited, It is preferable that it is 20-200 micrometers, and it is preferable that the said fibrous base material is a sheet form.

The impregnation with the flame retardant epoxy resin composition can be performed by a known method such as an immersion method or a coating method.
The impregnation of the flame retardant epoxy resin composition may be performed only once, or may be performed twice or more, and when performed twice or more, the flame retardant epoxy resin composition used may be the same type every time. However, they may all be of different types, or only partially different types. Here, that the kind of flame retardant epoxy resin composition is different means that at least one of the kind and concentration of components contained in the flame retardant epoxy resin composition is different from each other. For example, the resin composition and amount of the prepreg obtained can be adjusted by performing impregnation a plurality of times using different types of flame-retardant epoxy resin compositions.

  In the heating after impregnation with the flame retardant epoxy resin composition, the solvent is removed and dried, and the resin component is semi-cured (B-staged). The heating at this time is preferably performed at 100 to 180 ° C. for 3 to 15 minutes, for example.

  The prepreg preferably has a resin content of 20 to 90% by mass. Here, “resin” means all resin components including the above-described epoxy resin and cured products thereof.

<Metal-clad laminate>
The prepreg is suitable for producing a metal-clad laminate.
The metal-clad laminate can be obtained by the following method using, for example, a single prepreg or a laminate in which a plurality of prepregs are laminated with their main surfaces overlapped. That is, a metal foil such as a copper foil is superposed on one or both of a single prepreg or the upper and lower surfaces of the laminate, and the superposed one is molded by heating and pressurizing. Thus, a single-sided metal foil-clad laminate having a metal foil on one surface (upper surface or lower surface) of one prepreg or the laminate, or both surfaces (upper surface and lower surface) of one prepreg or the laminate. ), A double-sided metal foil-clad laminate with a metal foil is obtained.

  The molding conditions are not particularly limited, and may be appropriately set according to the thickness of the target metal-clad laminate or the type of resin in the prepreg, but the temperature during heating is preferably 50 to 190 ° C. The pressure during pressurization is preferably 1 to 5000 kPa, and the heating and pressurization time is preferably 5 to 180 minutes.

<Printed wiring board>
The metal-clad laminate is suitable for manufacturing a printed wiring board.
The printed wiring board can be obtained, for example, by etching the metal foil on the surface of the metal-clad laminate to form a circuit pattern. The printed wiring board can also be obtained by directly forming a circuit pattern with a conductor by plating or the like on the surface of the metal-clad laminate from which the metal foil has been removed.

  The cured product, film, prepreg, metal-clad laminate and printed wiring board (hereinafter sometimes abbreviated as “cured product etc.”) are all non-flammable epoxy resin compositions. -Although it is a halogen, it has high flame retardancy and can constitute an electric device component or an electronic device component of good quality.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

[Example 1]
<Production of Compound (1)>
After the inside of the four-necked flask equipped with a stirrer and a thermometer was sufficiently substituted with nitrogen gas, HCA-NQ (9.35 g) and epichlorohydrin (46.8 g) were charged. Next, the internal temperature was maintained at 80 ° C. in a nitrogen gas atmosphere, and benzyltriethylammonium chloride (0.16 g) was added. Next, the reaction was carried out by stirring for 4 hours at an internal temperature of 90 ° C.
The progress of the reaction was confirmed by thin layer chromatography (plate: “60F254 silica gel plate” manufactured by Merck & Co., Ltd., developing solution: toluene / ethyl acetate = 5/10 (volume ratio), detection: 254 nm UV lamp). At the reaction time of 4 hours, the raw material HCA-NQ disappeared and a new product was formed.

  After completion of the reaction, the reaction solution was cooled to 60 ° C., and unreacted epichlorohydrin was distilled off under reduced pressure to obtain a concentrate. Dichloromethane (20 g) was added to the resulting concentrate and cooled until the internal temperature reached 20 ° C., and then a 20% sodium ethoxide ethanol solution (17 g) was added over 1 hour while maintaining the internal temperature at 20 ° C. or lower. The reaction was carried out by adding dropwise and stirring for another 4 hours. Next, dichloromethane was added to the reaction solution to wash the organic layer with water, and then the organic layer was concentrated to obtain an epoxidation reaction composition.

Subsequently, the concentrate obtained was subjected to silica gel column chromatography, thin layer chromatography (plate: “60F254 silica gel plate” manufactured by Merck & Co., Ltd.), developing solution: toluene / ethyl acetate = 5/10 (volume ratio), detection: 254 nm UV The fraction of Rf 0.39 component in the lamp) was fractionated. When this fraction was concentrated and ethyl acetate was added, crystals of phosphorus-containing epoxy compound equivalents were precipitated.
The equivalent crystal was separated by filtration and analyzed by infrared spectroscopy (IR). As a result, the equivalent crystal was found to be a biphenol produced by cleavage of the “PO” bond of the phosphalene ring derived from the substrate. Corresponding to having a phenolic hydroxyl group in the structure, an IR spectrum having absorption at 3543 cm ⁻¹ was given.

Next, the equivalent crystal was placed under reduced pressure at 90 ° C. to heat and melt it, and the solvent was removed, followed by cooling to obtain the target compound (1) -101 as a glassy solid. It was confirmed by analysis by IR, GC-MS, and ¹ H-NMR that the vitreous solidified product was Compound (1) -101. The results of these analyzes are shown below. IR spectrum data is shown in FIG.

(Analysis conditions)
IR: 1585 cm, 1332, 1234, 1199 906 (cm ⁻¹ ), no absorption of the phenolic hydroxyl group.
GC-MS: m / z = 486
¹ H-NMR (CDCl ₃ ): 2.25-2.41 (1H), 2.57-2.61 (1H), 2.76-3.08 (3H), 3.46-3.53 (1H), 3.60-3.89 (1H), 4.09-4.18 (2H) , 4.42-4.57 (1H), 7.25-8.35 (13H)

Thin layer chromatography (plate: “60F254 silica gel plate” manufactured by Merck & Co., Ltd., developing solution: toluene / ethyl acetate = 5/10 (volume ratio), detection: 254 nm UV lamp) was repeated three more times for the above Rf0.39 component. As a result, Rf0.39 component was separated into Rf0.67 component and Rf0.61 component (separated into two spots). Further, by HPLC photoarray analysis, the Rf 0.39 component corresponded to two peaks showing the same UV spectrum, and the ratio was 53 area% and 43 area% at a detection wavelength of 254 nm. HPLC analysis was performed under the following conditions.
From the above analysis results, the Rf0.67 component and the Rf0.61 component generated from the Rf0.39 component are diastereomers of the compound (1) -101, and the crystallized crystals from the Rf0.39 component are compound ( 1) It was confirmed to be a diastereomeric mixture of equivalents of -101.

(HPLC analysis conditions)
Analytical instrument: “HPLC20AD” manufactured by Shimadzu Corporation
Column: “Inertsil ODS-3 (5 μm, 4.6 × 250 mm)” manufactured by GL Sciences Inc.
Mobile phase: methanol / 1 mass% (pH 3.3) aqueous ammonium acetate solution = 60/40 (volume ratio)
Flow rate: 0.8 mL / min Detection: UV254 nm

<Confirmation of solubility of compound (1)>
About the compound (1) -101 obtained above and HCA-NQ, solubility in the solvent and resin calculated by the following formula (wherein the solute is Compound (1) -101 or HCA-NQ) It was confirmed. The results are shown in Table 1.
Solubility (%) = [Amount of dissolved solute (g)] / [Amount of solvent or resin required to dissolve solute (g)] × 100

  As is clear from the above results, compound (1) -101 is 50% soluble in ethanol at 80 ° C. and 50% or more soluble in bisphenol A-diglycidyl ether at 80 ° C. The solubility in the resin was remarkably excellent.

<Production of Compound (1)>
[Example 2]
HCA-NQ and epichlorohydrin were reacted in the same manner as in Example 1.
After completion of the reaction, the reaction solution was cooled to 60 ° C., and unreacted epichlorohydrin was distilled off under reduced pressure to obtain a concentrate. Dichloromethane (20 g) was added to the resulting concentrate and cooled until the internal temperature reached 20 ° C., and then 28% sodium methoxide methanol solution (7.71 g) was added for 1 hour while maintaining the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, methanol was concentrated, and the reaction was carried out by adding dropwise and stirring a 28% sodium methoxide methanol solution (1.94 g) at an internal temperature of 8 ° C. Next, dichloromethane was added to the reaction solution to wash the organic layer with water, and then the organic layer was concentrated to obtain an epoxidation reaction composition.
Next, after heating the obtained concentrate to 60 ° C., methyl isobutyl ketone (20 g) is added to precipitate crystals of the phosphorus-containing epoxy compound equivalent, cooled to 15 ° C., and the equivalent crystals are filtered off. did.
Subsequently, this equivalent crystal was heated and melted at 90 ° C. and dried under reduced pressure to obtain the target compound (1) -101 as an amorphous glassy solid (yield 43 g). When the glassy solid was subjected to HPLC analysis under the same conditions as described above, it was 99 area% pure.

[Example 3]
Instead of HCA-NQ (9.35 g), 9,10-dihydro-10- [2 ′-(1′-hydroxy-4′-allyloxy) naphthyl] -9-oxa-10-phosphaphenanthrene-10— An epoxidation reaction composition was obtained in the same manner as in Example 1 except that oxide (HCA-NQ-4-O-all) (10.35 g) was used.
Next, ethyl acetate (25 g) was added to the obtained concentrate at 60 ° C. to precipitate crystals of phosphorus-containing epoxy compound equivalent, which were filtered off.
Subsequently, this equivalent crystal is heated and melted at 90 ° C. and dried under reduced pressure, whereby the target compound (1) -201 (HCA-NQ-4-O-all-1-G) is solidified into a glassy state. (Yield 10.1 g). IR spectrum data of the compound (1) -201 is shown in FIG. The glassy solid was subjected to thin-layer chromatography (plate: “60F254 silica gel plate” manufactured by Merck & Co., Ltd., developing solution: toluene / ethyl acetate = 10/10 (volume ratio), detection: 254 nm UV lamp). 0.61 (Rf 0.61 component was detected).

[Example 4]
Instead of HCA-NQ (9.35 g), 9,10-dihydro-10- [2 ′-(1′-allyloxy-4′-hydroxy) naphthyl] -9-oxa-10-phosphaphenanthrene-10— An epoxidation reaction composition was obtained in the same manner as in Example 1 except that oxide (HCA-NQ-1-O-all) (10.35 g) was used.
Next, ethyl acetate (25 g) was added to the obtained concentrate at 60 ° C. to precipitate crystals of phosphorus-containing epoxy compound equivalent, which were filtered off.
Subsequently, this equivalent crystal is heated and melted at 90 ° C. and dried under reduced pressure, whereby the target compound (1) -301 (HCA-NQ-1-O-all-4-G) is solidified into a glassy state. (Yield 10.3 g). FIG. 3 shows the IR spectrum data of the compound (1) -301. The glassy solid was subjected to thin-layer chromatography (plate: “60F254 silica gel plate” manufactured by Merck & Co., Ltd., developing solution: toluene / ethyl acetate = 10/10 (volume ratio), detection: 254 nm UV lamp). 0.43 (Rf 0.43 component was detected).

[Example 5]
Instead of HCA-NQ (9.35 g), 8-benzyl-9,10-dihydro-10- [2 ′-(1 ′, 4′-dihydroxynaphthyl)]-9-oxa-10-phosphaphenanthrene- An epoxidation reaction composition was obtained in the same manner as in Example 1 except that 10-oxide (BzHCA-NQ) (11.6 g) was used.
Next, ethyl acetate (25 g) was added to the obtained concentrate at 60 ° C. to precipitate crystals of phosphorus-containing epoxy compound equivalent, which were filtered off.
Subsequently, this equivalent crystal was heated and melted at 160 ° C. and dried under reduced pressure to obtain the target compound of the formula (1) -102 (Bz-HCA-NQ-G2) as a glassy solid (yield) 12.1 g). FIG. 4 shows the IR spectrum data of the compound (1) -102.

[Comparative Example 1]
HCA-NQ and epichlorohydrin were reacted in the same manner as in Example 1.
After completion of the reaction, the reaction solution was cooled to 60 ° C., and unreacted epichlorohydrin was distilled off under reduced pressure to obtain a concentrate. Tetrahydrofuran (20 g) was added to and dissolved in the resulting concentrate (17.1 g), cooled to an internal temperature of 15 ° C., and then maintained at an internal temperature of 15 ° C. or lower with a 48% aqueous sodium hydroxide solution ( 4.17 g) was added dropwise, and the mixture was further stirred at 15 ° C. for 3 hours to carry out the reaction.
Hereinafter, production of the compound (1) was attempted in the same manner as in Example 1, but the compound (1) was not produced, and a large amount of by-products were generated in which the phosphalene ring was decomposed.

[Comparative Example 2]
HCA-NQ and epichlorohydrin were reacted in the same manner as in Example 1.
After completion of the reaction, the reaction solution was cooled to 60 ° C., and unreacted epichlorohydrin was distilled off under reduced pressure to obtain a concentrate. Tetrahydrofuran (20 g) was added and dissolved in the resulting concentrate (17.1 g), and the mixture was cooled until the internal temperature became 15 ° C., and then sodium hydroxide (2. A methanol solution (35 mL) in which 0 g) was dissolved in methanol was dropped, and the mixture was further stirred at 15 ° C. for 3 hours to carry out a reaction.
Hereinafter, compound (1) was obtained by the same method as in Example 1, but the production rate of compound (1) was 32% from the results of HPLC analysis, and a large amount of other by-products were produced.

[Comparative Example 3]
An attempt was made to produce compound (1) by the method described in “Republic of China Patent Publication No. 393496”.
That is, HCA-NQ (3.7 g) was dissolved in tetrahydrofuran (40 g), and 28% sodium methoxide methanol solution (4.2 g) was added. As a result, a large amount of white crystals precipitated. After heating the slurry in this state to 65 ° C., epichlorohydrin (4 g) was added to carry out the reaction. As a result, the reaction hardly proceeded and the compound (1) was not produced.

<Confirmation of reversibility between compound (1) and its equivalent>
[Example 6]
In the same manner as in Example 1, an epoxidation reaction composition was obtained.
Subsequently, after heating this concentrate to 60 degreeC, acetone (15g) was added, and the crystal | crystallization of the phosphorus containing epoxy compound equivalent precipitated. After cooling the slurry in this state to 15 ° C., the precipitated crystals were separated by filtration to obtain wet crystals (i) of the phosphorus-containing epoxy compound equivalent. And the IR spectrum of the wet crystal (i) was measured. The obtained IR spectrum data is shown in FIG.

Next, the wet crystal (i) after IR spectrum measurement was divided into two, and one wet crystal (i) was melt-dried in a 120 ° C. hot water bath under reduced pressure for 1 hour to give the compound (1) in a glassy state. Obtained as a solidified product. And the IR spectrum of the obtained glassy solidified material was measured. The obtained IR spectrum data is shown in FIG.
The other wet crystal (i) was dissolved in chloroform, and the IR spectrum of the resulting chloroform solution was measured. The obtained spectrum data of IR is shown in FIG.
As a result, the 3532 cm ⁻¹ OH absorption (absorption derived from the hydroxyl group bonded to the carbon atom at the 2-position of the biphenyl skeleton) observed in the IR spectrum of the wet crystal (i) is the IR of the glassy solidified product. Both the spectrum and the IR spectrum of the chloroform solution disappeared.

Subsequently, when acetone was added to the glassy solidified product, white crystals were formed. The white crystals were separated by filtration, and the IR spectrum of the resulting wet white crystals (ii) was measured. The obtained IR spectrum data is shown in FIG. Further, when chloroform in the chloroform solution was distilled off under reduced pressure and acetone was added, crystals were precipitated. The crystals were separated by filtration, and the IR spectrum of the obtained wet crystals (iii) was measured. The obtained IR spectrum data is shown in FIG.
As a result, the IR spectrum of the wet white crystal (ii) and the IR spectrum of the wet crystal (iii) agree with the IR spectrum of the wet crystal (i) described above, and the IR spectrum of the wet white crystal (ii) is 3526 cm ^−1. Absorption of 3536 cm ⁻¹ was observed in the IR spectrum of the wet crystal (iii), and a signal corresponding to OH absorption of 3532 cm ⁻¹ in the IR spectrum of the wet crystal (i) was regenerated.

  When the obtained wet crystal (i), glassy solid, the chloroform solution, the wet white crystal (ii) and the wet crystal (iii) were subjected to thin layer chromatography and HPLC photoarray analysis, the results were as follows: All these compounds were shown to be the same compound. That is, thin layer chromatography and HPLC photoarray analysis could not distinguish wet crystals (i), glassy solids, the chloroform solution, wet white crystals (ii), and wet crystals (iii).

  From the above results, compound (1) and its equivalent are in a reversible relationship (compound (1) changes to its equivalent and compound (1) equivalent changes to compound (1)). Was confirmed.

<Production and evaluation of cured product of flame retardant epoxy resin composition>
[Example 7]
(Manufacture of flame retardant epoxy resin composition)
Compound (1) -101 (4.86 g) obtained in Example 2 was added to bisphenol A-diglycidyl ether (Adeka “EP4001”) (9.07 g) and stirred at 70 ° C. Dissolved. Compound (1) -101 was completely dissolved into a uniform and transparent viscous solution. Bisphenol A (3.26 g) and dicyandiamide (0.6 g) were added to the viscous solution and mixed to obtain a composition. The phosphorus content of the obtained composition was 2% by mass.
Furthermore, the obtained composition, an inorganic filler, and a solvent were mixed, and the varnish-like flame-retardant epoxy resin composition was obtained.

(Manufacture of cured product (laminate))
A glass cloth was impregnated with the varnish-like flame-retardant epoxy resin composition obtained above, and then air-dried and dried at 160 ° C. to remove the solvent to obtain a prepreg. Furthermore, this prepreg was laminated | stacked, and the laminated board containing the hardened | cured material of a flame-retardant epoxy resin composition was obtained by heat-pressing for 30 minutes at 170 degreeC / 20kgf / cm < ² >.

(Evaluation of cured product (laminate))
The obtained laminate was subjected to a combustion test using five test pieces in accordance with a combustion test method of “Test for Flammability of Plastic Materials UL94” by Underwriters Laboratories, and flame retardancy was evaluated. As a result, the average value of the burning time was 82 seconds, the flame retardancy was V-1, and the flame retardancy was sufficient.
As described above, compound (1) provides a flame-retardant epoxy resin composition having excellent operability, such as high solubility in solvents and resins, homogeneous, high flame retardancy, and cured product thereof. It was possible.

<Production and evaluation of cured product of flame retardant epoxy resin composition>
[Comparative Example 4]
HCA-NQ (3.74 g) was added to bisphenol A-diglycidyl ether (Adeka “EP4001”) (7.06 g) and stirred with heating, but HCA-NQ did not dissolve and was a non-uniform slurry. A mixture was obtained. Hereinafter, the flame retardant epoxy resin composition and its cured product (laminated plate) were obtained in the same manner as in Example 6 except that this slurry mixture was used instead of the viscous solution of the compound (1) -101. ) And the cured product was evaluated.
As a result, blisters and cracks derived from unreacted HCA-NQ were observed on the surface of the cured product (laminate). In the combustion test of the cured product (laminate), the total combustion time was 124 seconds, and the flame retardancy was V-1.

[Comparative Example 5]
Bisphenol A (2.3 g) was added to bisphenol A-diglycidyl ether (Adeka “EP4001”) (7.6 g) and stirred with heating, but bisphenol A was not completely dissolved and was not uniform. A slurry mixture was obtained. Hereinafter, the flame retardant epoxy resin composition and its cured product (laminated plate) were obtained in the same manner as in Example 6 except that this slurry mixture was used instead of the viscous solution of the compound (1) -101. ) And the cured product was evaluated.
As a result, in the UL94 combustion test of the cured product (laminate), the flame retardancy was incompatible.

  The present invention can be used for manufacturing electrical equipment parts or electronic equipment parts.

Claims (5)

A phosphorus-containing epoxy compound represented by the following general formula (1).

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an allyl group or a glycidyl group, provided that at least one of R ¹ and R ² is a glycidyl group; X is a hydrogen atom, having 1 to 12 carbon atoms. A linear or branched alkyl group, a linear or branched alkenyl group having 2 to 12 carbon atoms, an aryl group or an aralkyl group; Y is a hydrogen atom, an allyl group or a glycidyl group; Z is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched alkenyl group having 2 to 12 carbon atoms.) The phosphorus-containing epoxy compound according to claim 1 represented by the following general formula (1) -1.

(In the formula, X is the same as described above.)   A diastereomeric mixture comprising diastereomers of the phosphorus-containing epoxy compound according to claim 1. A phosphorus-containing epoxy compound represented by the following general formula (2).

(In the formula, R is an allyl group or a glycidyl group; X is a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched chain group having 2 to 12 carbon atoms. An alkenyl group, an aryl group or an aralkyl group; Y is a hydrogen atom, an allyl group or a glycidyl group; Z is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or carbon (It is a linear or branched alkenyl group having a number of 2 to 12.) In the presence of a catalyst, a compound represented by the following general formula (3) is reacted with epihalohydrin to obtain a reaction product, and an alkali metal alkoxide or alkali metal hydride is allowed to act on the reaction product to contain phosphorus. The step of generating an epoxy compound equivalent, the step of separating the crystal of the phosphorus-containing epoxy compound equivalent, the heat-melting of the crystal, or preparing a solution of the crystal, the following general formula (1) A process for obtaining a phosphorus-containing epoxy compound represented by the formula:

Wherein R ¹ and R ² are each independently a hydrogen atom, an allyl group or a glycidyl group, provided that at least one of R ¹ and R ² is a glycidyl group; R ³ and R ⁴ are each independently hydrogen An atom, an allyl group or a glycidyl group, wherein at least one of R ³ and R ⁴ is a hydrogen atom; X is a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a carbon number A straight chain or branched chain alkenyl group, aryl group or aralkyl group having 2 to 12; Y is a hydrogen atom, allyl group or glycidyl group; Z is a hydrogen atom, hydroxyl group, straight chain having 1 to 12 carbon atoms; A chain or branched alkyl group, or a linear or branched alkenyl group having 2 to 12 carbon atoms.)

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