JP2003183525A - Flame retardant resin composition, sealing material and laminated plate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having flame retardation, a sealing material and a laminated plate using the same. <P>SOLUTION: The flame retardant resin composition contains a phosphorus- containing hydroquinone derivative represented by general formula (1): (wherein R<SP>1</SP>and R<SP>2</SP>are each a straight chained or branched alkyl group or a cycloalkyl group which may be substituted, one or more methylene groups in the alkyl group may be substituted with -CH=CH-, R<SP>1</SP>and R<SP>2</SP>may be a same group to or different groups, and R<SP>1</SP>and R<SP>2</SP>may form a cyclic one containing or not containing P; X is an oxygen atom or a sulfur atom; Y and Z are each a hydrogen atom, a hydroxyl group, a straight chained or branched alkyl group, an aralkyl group, an alkoxy group, an allyl group, an aryl group or a cyano group, Y and Z may be a same group or different groups, and Y and Z together may form a cyclic one). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has excellent moisture resistance,
The present invention also relates to a flame-retardant resin composition containing an addition-type non-halogen flame retardant capable of imparting excellent flame retardancy, a sealant using the same, and a laminate.

[0002]

2. Description of the Related Art Conventionally, halogen compounds such as chlorine and bromine, phosphorus compounds, nitrogen compounds, antimony and boron inorganic compounds have been used as flame retardants for resins. However, in recent years, bromine and chlorine compounds, which generate toxic dioxin for humans upon combustion, have been shunned, and there is an increasing demand for non-halogen flame retardants.

As a non-halogen flame retardant, for example, a resin composition in which red phosphorus is mixed with a curable resin (Japanese Patent Publication No. 59-49942), and hydrated alumina as a flame retardant for epoxy resin (Japanese Patent Laid-Open No. HEI 5 (1999) -58242). No. 25369), modified red phosphorus (JP-A-63-156860), phenol resin with calcium borate and aluminum hydroxide or magnesium hydroxide (JP-A-5-43774), phenol resin. On the other hand, boric acid and antimony trioxide (JP-A-60-81244), compounds having three triazine structures in the molecule with respect to polyurethane resin (JP-A-53-21241) and the like have been proposed. .

On the other hand, with respect to thermoplastic resins, magnesium hydroxide for polyamide resins (Japanese Patent Laid-Open No. 54-83)
952 and JP-A-54-131645),
And melamine cyanurate (JP-A-53-31759 and JP-A-54-91558), organic sulfonates for polycarbonate (JP-A-50-9853).
No. 9, JP-A No. 50-98540), sulfide salts (Japanese Patent Publication No. 1-23043), phosphonate compounds for polyphenylene oxide and ammonium polyphosphate (JP-A No. 52-86449), and phosphate compounds. And antimony trioxide (JP-A-49-329)
No. 747) and polyphosphonates (US Pat. No. 3,719,727) for polyesters have been proposed.

However, among the above flame retardants, since red phosphorus is reddish brown, the resin is colored by red phosphorus, making coloring impossible. In addition, when the resin is thermally processed or incinerated, phosphine gas is generated, which deteriorates the working environment, and there are some cases in which red phosphorus is coated with a coating agent to suppress this, but the generation of phosphine gas is completely eliminated. Cannot be suppressed. Organic phosphorus flame retardants are
It has received particular attention as a non-halogen flame retardant. At present, various types of phosphoric acid ester and phosphite-based flame retardants have been proposed.

[0006]

[Patent Document 1] Japanese Patent Publication No. 1-50
In Japanese Patent No. 712, the following general formula (4)

[Chemical 4] Represented by 10- (2,5-dihydroxyphenyl)-
10H-9-oxa-10-phosphaphenanthrene-
It is described that 10-oxide is useful as a flame retardant for polymer compounds.

However, the compound of the general formula (4) and the phosphoric acid ester-based compound have a problem of moisture resistance because they have a hydrolyzable P—O bond in the molecule, and are particularly used for resins for electric parts. However, there is a problem in that the phosphoric acid is eluted due to the decomposition of the organic phosphorus compound and the electrical characteristics are deteriorated.
Therefore, it is an object of the present invention to provide a flame-retardant resin composition having excellent moisture resistance, a sealing material using the same, and a laminate.

[0008]

[Means for Solving the Problems] This problem is solved by the following general formula (1):

[Chemical 5] (In the formula, R ¹ and R ² represent an optionally substituted linear or branched alkyl group or cycloalkyl group,
One or more methylene groups in the alkyl group may be replaced by -CH = CH-, R
¹ and R ² may be the same group or different groups,
In addition, R ¹ and R ² may form a cyclic compound containing P or not containing P. X represents an oxygen atom or a sulfur atom. Y and Z are a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, an aralkyl group, an alkoxy group, an allyl group,
It represents an aryl group or a cyano group, and Y and Z may be the same group or different groups, and Y and Z may form a ring. And a phosphorus-containing hydroquinone derivative represented by the formula (1).

The ring formed by R ¹ and R ² is preferably represented by the following general formula (2) or general formula (3).

[Chemical 6] (In the formula, R ³ represents an optionally substituted alkylene group.)

[0010]

[Chemical 7] (In the formula, R ⁴ represents an optionally substituted cycloalkylene group or arylene group.)

The phosphorus-containing hydroquinone derivative preferably has an average particle size of 100 μm or less.
The flame-retardant resin is preferably an epoxy resin.

Further, a second invention of the present invention is a sealing material comprising the above flame-retardant epoxy resin composition. A third invention of the present invention is a laminated board characterized by using the above flame-retardant epoxy resin composition.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The flame-retardant resin composition of the present invention has the following general formula (1).

[Chemical 8] It is characterized by containing the phosphorus-containing hydroquinone derivative represented by

<Phosphorus-containing hydroquinone derivative> In the general formula (1), R ¹ and R ² represent an optionally substituted linear or branched alkyl group, and the alkyl group has 1 carbon atom. To 18, preferably an alkyl group having 1 to 8 carbon atoms, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a tertiary butyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. Can be illustrated. R ¹ and R ² in the formula are
Each may be the same group or different groups. Further, one or two or more methylene groups in the alkyl group may be replaced by -CH = CH-, and specific examples thereof include a vinyl group, an allyl group and an isopropenyl group.

R ¹ and R ² may be substituted, and examples of the substituent include a phenyl group, an alkoxy group, a cyano group and a hydroxyl group. Specific examples of the substituted R ¹ and R ² include an aralkyl group such as a benzyl group, a cyanoalkyl group, a cyanoalkenyl group, a hydroxyalkyl group and a hydroxyalkenyl group.

R ¹ and R ² may form a ring containing P or not containing P. R ¹ and R ²
When P includes P to form a cyclic compound, a cyclic compound formed by a bond represented by the following general formula (2) can be mentioned.

[0017]

[Chemical 9]

In the general formula (2), R ³ represents an optionally substituted alkylene group. The alkylene group is an alkylene group having 3 to 9 carbon atoms, preferably 4 to 6 carbon atoms, and specifically, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group. , Nonamethylene group and the like. R ³ may be substituted, and examples of the substituent include a phenyl group, an alkoxy group, a cyano group and a hydroxyl group.

When R ¹ and R ² do not contain P to form a cyclic compound, a cyclic compound formed by a bond represented by the following general formula (3) can be mentioned.

[0020]

[Chemical 10] In formula (3), R ⁴ represents an optionally substituted cycloalkylene group or arylene group.

The cycloalkylene group has 4 to 4 carbon atoms.
9, preferably a cycloalkylene group having 5 to 7 carbon atoms, and specific examples thereof include a cyclobutylene group, a cyclopentamethylene group, a cyclohexamethylene group, a cycloheptamethylene group, a cyclooctylene group, and a cyclononylene group. be able to. Examples of the arylene group include a phenylene group, a biphenylene group and a naphthylene group.

R ⁴ may be substituted, and examples of the substituent include a phenyl group, an alkoxy group, a cyano group and a hydroxyl group. Further, a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom may be contained in the substituents of R ³ and R ⁴ .

X in the formula represents an oxygen atom or a sulfur atom, preferably an oxygen atom. In the formula, Y and Z are hydrogen atoms,
Hydroxyl group, linear or branched alkyl group, aralkyl group such as benzyl group, aryl group such as allyl group and phenyl group, alkoxy group such as methoxy group, ethoxy group, propoxy group and phenyloxy group, or cyano group . The alkyl group has 1 to 18 carbon atoms, preferably 1 carbon atom
To 6 and specific examples thereof include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a tertiary butyl group, and a cyclohexyl group. One or more methylene groups in the alkyl group are -CH = C.
It may be replaced by H-. Further, Y and Z may be the same group or different groups.

Further, Y and Z may be a group forming a ring, and examples of the group in which Y and Z form a ring include the ring groups represented by the following formulas and names.

[0025]

[Chemical 11] However, the name in parentheses represents the name of the ring containing hydroquinone. In addition, a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom may be contained in these substituents.

Specific examples of the phosphorus-containing hydroquinone derivative represented by the general formula (1) include dimethylphosphonyl-1,4-hydroquinone, diethylphosphonyl-1,4-hydroquinone and di-n-. Propylphosphonyl-1,4-hydroquinone, di-iso-propylphosphonyl-1,4-hydroquinone, di-n-butylphosphonyl-1,4-hydroquinone, di-sec
-Butylphosphonyl-1,4-hydroquinone, di-t
ert-butylphosphonyl-1,4-hydroquinone,
Dibenzylphosphonyl-1,4-hydroquinone,

Methylethylphosphonyl-1,4-hydroquinone, methyl-n-propylphosphonyl-1,4-
Hydroquinone, methyl-n-butylphosphonyl-1,
4-hydroquinone, methyl-iso-butylphosphonyl-1,4-hydroquinone, methyl-sec-butylphosphonyl-1,4-hydroquinone, methyl-ter
t-Butylphosphonyl-1,4-hydroquinone, ethyl-n-propylphosphonyl-1,4-hydroquinone, ethyl-iso-propylphosphonyl-1,4-hydroquinone, ethyl-tert-butylphosphonyl-
1,4-hydroquinone, n-propyl-iso-propylphosphonyl-1,4-hydroquinone, n-propyl-n-butylphosphonyl-1,4-hydroquinone,
n-propyl-sec-butylphosphonyl-1,4-hydroquinone, n-butyl-sec-butylphosphonyl-1,4-hydroquinone, n-butyl-tert-butylphosphonyl-1,4-hydroquinone,

Propylenephosphonyl-1,4-hydroquinone, butylenephosphonyl-1,4-hydroquinone, pentamethylenephosphonyl-1,4-hydroquinone, hexamethylenephosphonyl-1,4-hydroquinone, 1,4-cyclo. Pentylenephosphonyl-1,4-hydroquinone, 1,4-cyclooctylenephosphonyl-
1,4-hydroquinone, 1,5-cyclooctylenephosphonyl-1,4-hydroquinone,

2- (diethylphosphonyl) -1,4-naphthalenediol, 2- (dimethylphosphonyl) -1,
4-naphthalenediol, 2- (diethylphosphonyl)
-1,4-naphthalenediol, 2- (di-n-propylphosphonyl) -1,4-naphthalenediol, 2-
(Di-iso-propylphosphonyl) -1,4-naphthalenediol, 2- (di-n-butylphosphonyl)-
1,4-naphthalenediol, 2- (di-sec-butylphosphonyl) -1,4-naphthalenediol, 2-
(Di-tert-butylphosphonyl) -1,4-naphthalenediol, 2- (dibenzylphosphonyl) -1,4
-Naphthalene diol,

2- (methylethylphosphonyl) -1,4
-Naphthalenediol, 2- (methyl-n-propylphosphonyl) -1,4-naphthalenediol, 2- (methyl-n-butylphosphonyl) -1,4-naphthalenediol, 2- (methyl-iso-butylphosphonyl)-
1,4-naphthalenediol, 2- (methyl-sec-
Butylphosphonyl) -1,4-naphthalenediol, 2
-(Methyl-tert-butylphosphonyl) -1,4-
Naphthalenediol, 2- (ethyl-n-propylphosphonyl) -1,4-naphthalenediol, 2- (ethyl-iso-propylphosphonyl) -1,4-naphthalenediol, 2- (ethyl-tert-butylphosphonyl) -1,4-naphthalenediol, 2- (n-propyl-iso-propylphosphonyl) -1,4-naphthalenediol, 2- (n-propyl-n-butylphosphonyl) -1,4-naphthalenediol, 2- (N-Propyl-sec-butylphosphonyl) -1,4-naphthalenediol, 2- (n-butyl-sec-butylphosphonyl) -1,4-naphthalenediol, 2- (n-butyl-tert-butylphosphonyl) -1, 4-naphthalenediol,

2- (propylenephosphonyl) -1,4-
Naphthalenediol, 2- (butylenephosphonyl)-
1,4-naphthalene diol, 2- (pentamethylene phosphonyl) -1,4-naphthalene diol, 2- (hexamethylene phosphonyl) -1,4-naphthalene diol, 2- (1,4-cyclopentylene phospho) Nil)-
1,4-naphthalenediol, 2- (1,4-cyclooctylenephosphonyl) -1,4-naphthalenediol,
2- (1,5-cyclooctylenephosphonyl) -1,4
Examples thereof include naphthalene diol.

In the present invention, the phosphorus-containing hydroquinone derivative may be a mixture of the phosphorus-containing hydroquinone derivatives derived from the reaction raw material.

Next, a method for producing the phosphorus-containing hydroquinone derivative will be described. The phosphorus-containing hydroquinone derivative represented by the general formula (1) of the present invention is represented by at least one selected from the secondary phosphine derivative represented by the following general formula (5) and the following general formula (6). It can be produced by reacting with a benzoquinone derivative.

The following general formula (5)

[Chemical 12] In the formula of the secondary phosphine derivative represented by R ¹ and R
² is a group corresponding to R ¹ and R ² in the formula of the phosphorus-containing hydroquinone derivative represented by the general formula (1). That is, R ¹ and R ² represent a linear or branched alkyl group which may be substituted, and as the alkyl group,
An alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tertiary butyl group, a cyclobutyl group,
Examples thereof include alkyl groups such as cyclopentyl group and cyclohexyl group. Further, R ¹ and R ² in the formula may be the same group or different groups. Further, one or two or more methylene groups in the alkyl group may be replaced by -CH = CH-.

Further, R ¹ and R ² may be substituted. R ¹ and R ² may form a ring containing P or not containing P. When R ¹ and R ² include P to form a cyclic compound, the cyclic compound formed by the bond represented by the general formula (2) can be mentioned. When R ¹ and R ² do not contain P to form a cyclic compound, the cyclic compound formed by the bond represented by the general formula (3) may be mentioned. Further, X in the formula corresponds to X in the formula of the phosphorus-containing hydroquinone derivative represented by the general formula (1), represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom.

The secondary phosphine derivative represented by the general formula (5) can be produced by a known method. For example, if one example of cycloalkylenephosphine oxide in which R ¹ and R ² form a P-free ring is shown, the following reaction formula (1)

[Chemical 13] By the reaction represented by, phosphine (compound (7)) and 1,5-cyclooctadiene (compound (8)) are reacted in the presence of a radical generating catalyst to give 1,4-cyclooctylenephosphine (compound After obtaining a mixture of (9)) and 1,5-cyclooctylenephosphine (compound (10)) (see JP-A-55-122790), this is oxidized to obtain the desired 1,4 It is possible to obtain a mixture of cyclooctylenephosphine oxide and 1,5-cyclooctylenephosphine oxide.

In the method for producing the phosphorus-containing hydroquinone derivative represented by the general formula (1) of the present invention, the secondary phosphine derivative represented by the general formula (5) is
Since it forms a tautomer, the following general formula (5a) is used instead of the secondary phosphine derivative represented by the general formula (5) as a reaction raw material.

[Chemical 14] (In the formula, R ¹ and R ² and X have the same meanings as described above.) A secondary phosphine derivative represented by the formula may be used.

Further, the general formula (5) and the general formula (5
The tautomer of the secondary phosphine derivative represented by a) becomes one derivative depending on the temperature, but as the reaction raw material, the secondary phosphine derivative represented by the general formula (5) or the general formula (5a) is used. Either one of them may be used, or a mixture of both may be used. The secondary phosphine derivative represented by the general formula (5a) can be produced by a known method. One example is "KOZOLAPOF.
F ", Vol 4, page 475.

Another reaction raw material represented by the following general formula (6)

[Chemical 15] In the formula of the benzoquinone derivative represented by, Y and Z are groups corresponding to Y and Z in the formula of the phosphorus-containing hydroquinone derivative represented by the general formula (1).

That is, Y and Z are hydrogen atom, hydroxyl group, linear or branched alkyl group, aralkyl group such as benzyl group, aryl group such as allyl group and phenyl group, methoxy group, ethoxy group, propoxy group, An alkoxy group such as a phenyloxy group or a cyano group is shown. The alkyl group has 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms,
Specific examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a tertiary butyl group, and a cyclohexyl group. Further, Y and Z may be the same group or different groups.

Further, Y and Z may be a group forming a cyclic substance, and examples of the group in which Y and Z form a cyclic substance include the same groups as the above-mentioned cyclic group. In addition, a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom may be contained in these substituents.

At least one selected from the secondary phosphine derivatives represented by the general formulas (5) and (5a) and the benzoquinone derivative represented by the general formula (6) in the presence of an inert solvent. The desired phosphorus-containing hydroquinone derivative represented by the general formula (1) can be obtained by reacting with.

The molar ratio of the secondary phosphine derivative represented by the general formula (5) or (5a) to the benzoquinone derivative represented by the general formula (6) is 1 mole of the secondary phosphine derivative. Is usually 1.0 to 1.5, preferably 1.0 to 1.2. The reaction temperature depends on the kind of the reaction raw material, but at 300 ° C. or higher, the phosphorus-containing hydroquinone derivative represented by the general formula (1), which is the target product, is decomposed. The temperature is preferably 25 to 100 ° C. The reaction time is
It is usually 1 to 8 hours, preferably 2 to 5 hours.

The inert solvent is not particularly limited as long as it is a solvent in which the above-mentioned reaction raw materials and the target product are inert, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, and petroleum ether. Examples include aliphatic hydrocarbons, ethers such as dialkyl ethers, nitriles such as acetonitrile and propionitrile, halogenated aromatic hydrocarbons such as chlorobenzene, and haloalkanes such as methylene chloride and chloroform. These are one kind. Alternatively, two or more kinds can be used in combination.

In the production method of the present invention, if desired, an acid catalyst or a basic catalyst may be used to accelerate the reaction. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, oxalic acid, phosphoric acid, perchloric acid, periodic acid, hydrogen fluoride, methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, glacial acetic acid, and the like. Alternatively, two or more kinds can be used in combination.

As the basic catalyst, for example, sodium,
Use of one or more of alkali metals such as potassium or lithium, alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, alkyl metal compounds such as t-butyllithium and lithium diisopropylamide, etc. or a combination of two or more thereof. Can be done. In this case, the addition amount of the catalyst is usually 1 to 10 mol%, preferably 1 to 10 mol% with respect to the compound represented by the general formula (6).
It is 5 mol%.

After the completion of the reaction, the product can be filtered, dried, pulverized, and classified if desired to obtain a product. If necessary, the product may be further purified by a conventional purification means. By doing so, the phosphorus-containing hydroquinone derivative represented by the general formula (1) can be produced.

<Flame-retardant resin composition> Next, the flame-retardant resin composition according to the present invention will be described. The flame-retardant resin composition of the present invention is characterized by containing the above-mentioned phosphorus-containing hydroquinone derivative. The phosphorus-containing hydroquinone derivative is disclosed in Japanese Patent Application No. 2001-191 by the present applicants.
818 and Japanese Patent Application No. 2001-191819, for example, by reacting with epichlorohydrin,
The phosphorus-containing epoxy resin can be used as a reactive flame retardant, but in the present invention, it is used in the form of a resin composition by being blended as it is with various resins as an addition type flame retardant.

The phosphorus-containing hydroquinone derivative is pulverized by a jet mill or the like and has an average particle size of 100 μm or less, preferably 50 to 0.1, as determined by a laser method.
It is particularly preferable to use the resin having a thickness of μm, particularly 20 to 1 μm, in order to obtain dispersibility in various resins and an excellent flame retardant effect.

The proportion of the phosphorus-containing hydroquinone derivative is 0.1 to 1 as phosphorus based on 100 parts by weight of the resin.
It is 0 part by weight, preferably 2 to 8 parts by weight. The reason for this is that if the compounding ratio is less than 0.1 parts by weight, it is difficult to obtain a sufficient flame retardant effect, while if it is more than 10 parts by weight, the flame retardant effect increases but the mechanical properties of the molded product tend to deteriorate. This is because it is not preferable.

The flame retardant of the present invention can further enhance the flame retardant effect by being used in combination with other flame retardants.
Other flame retardants that can be used in combination include hydrated metal compounds, phosphorus flame retardants, nitrogen-containing flame retardants, and the like.

The hydrated metal compound depends on the endothermic reaction.
M with combustion suppressing effect_m O_n ・ XH ₂ O (M is metal,
m and n are integers of 1 or more determined by the valence of the metal, x
Represents the water of crystallization contained) or the compound
Is a double salt containing, specifically, aluminum hydroxide,
Calcium hydroxide, magnesium hydroxide, basic carbonate
Gnesium, barium hydroxide, zirconium hydroxide,
-Sonite, zinc stannate, zinc borate, aluminum borate
Um, basic zinc carbonate, borax, zinc molybdate, lithium
Zinc phosphate, magnesium phosphate, hydrotalcite,
Hydrocalumite, kaolin, talc, sericite,
Pyrophyllite, bentonite, kaolinite, sulfuric acid
Examples include calcium and zinc sulfate.

As the nitrogen-containing flame retardant, melamine, melamine cyanurate, methylolated melamine, (iso) cyanuric acid, melam, melem, melon, succinoguanine, acetoguanamine sulfate, melam sulfate, guanylmelamine sulfate, melamine resin, BT. Resin, cyanuric acid,
Examples thereof include isocyanic acid, isocyanuric acid, isocyanuric acid derivatives, melamine isocyanurate, melamine derivatives such as benzoguanamine and acetoguanamine, and guanidine compounds.

Examples of phosphorus flame retardants include red phosphorus, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diethylene phosphate ethyl ester, butyl dihydroxypropylene phosphate. Ester, disodium ethylene phosphate, methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methyl-propylphosphonic acid, t-butylphosphonic acid,
2,3-dimethylbutylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid,
Diethylphenylphosphinic acid, diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid, ammonium phosphate, ammonium polyphosphate, melamine phosphate, guanylurea phosphate, melamine polyphosphate, guanidine phosphate, ethylenediamine phosphate, phosphazene , Methylphosphonic acid melamine salt and the like.

These other flame retardants are used alone or in combination of two or more.
The amount is preferably 0.1 to 150 parts by weight, more preferably 0.5 to 100 parts by weight, based on 00 parts by weight.

The resin that can be used is not particularly limited, and examples thereof include epoxy resin, phenol resin, polyurethane resin, melamine resin, urea resin, aniline resin, furan resin, alkyd resin, xylene resin, unsaturated polyester resin, Curable resin such as diaryl phthalate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polycarbonate, polyphenylene oxide, polyphenylene ether, nylon 6, nylon 66, nylon 12, polyacetal, polyethylene, polypropylene, polybutadiene, polyacrylonitrile, polystyrene, polymethyl Methacrylate, polyethylene oxide, polytetramethylene oxide, thermoplastic polyurethane, phenoxy resin, polyamide, ethylene / prepolymer Pyrene copolymer, ethylene / 1
Butene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / propylene-g-maleic anhydride copolymer, polyester polyether Examples thereof include elastomers, polytetrafluoroethylene and modified products thereof. These resins are
It may be a homopolymer or a copolymer, 2
It may be a mixture of two or more species.

Here, the curable resin is a resin that undergoes a chemical change under the action of heat, a catalyst, ultraviolet rays, or the like to develop a cross-linking structure, increase in molecular weight, have a three-dimensional network structure, and harden. A synthetic resin that is semi-permanently insoluble and infusible. The thermoplastic resin refers to a resin that exhibits fluidity when heated and can be shaped by this.

Other components to be added to the resin include phosphorus-based, ionic-based, hindered phenol-based antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, release agents, dyes, and colorants including pigments. , A cross-linking agent, a softening agent, a dispersant, and other usual additives.

If necessary, a fibrous and / or granular filler can be added to significantly improve the rigidity of the resin. As such a filler, for example,
Glass fiber, carbon fiber, metal fiber, aramid resin, asbestos, potassium titanate whisker, wollastonite,
Glass flakes, glass beads, talc, mica, clay, calcium carbonate, calcium silicate, barium sulfate,
Titanium oxide, fused silica, crystalline silica, magnesia,
Aluminum oxide etc. are mentioned.

The phosphorus-containing hydroquinone derivative can be kneaded and molded into various resins by a usual method. For example, in the case of a curable resin, a method of simultaneously mixing the phosphorus-containing hydroquinone derivative with a curable resin and other compounds, and mixing one of the resin components with the phosphorus-containing hydroquinone derivative and an additive which is optionally added in advance. And then mix it with a curable resin,
In the case of a thermoplastic resin, a method of melt-mixing the phosphorus-containing hydroquinone derivative in an extruder, a method of uniformly mechanically mixing particles and then simultaneously molding with an injection molding machine, and the like can be mentioned.

The flame-retardant resin composition of the present invention is used as a safe plastic material, for example, electrical parts such as connectors, switches, case members, transformer members, coil bobbins, etc.
Building materials, transportation equipment such as automobiles, packaging materials, household products, flat cables, printed wiring boards, electric circuit boards, copper clad laminates, encapsulating materials, molding materials, casting materials, adhesives, electrically insulating paint materials, etc. Can be used for. Among the flame-retardant resin compositions of the present invention, those obtained by using an epoxy resin as a resin component to obtain a flame-retardant epoxy resin composition can be particularly suitably used as a sealing material or a laminated board.

<Sealing Material> Next, a sealing material using the flame-retardant epoxy resin according to the present invention will be described. Epoxy resins used as encapsulants include all monomers, oligomers and polymers having at least two epoxy groups in one molecule, such as bisphenol A type epoxy,
Bisphenol F type epoxy, bisphenol S type epoxy, phenol novolac type epoxy, cresol novolac type epoxy, naphthalene type epoxy, biphenyl type epoxy, N-glycidyl compound from aromatic amine and heterocyclic nitrogen base, for example, N, N-di Glycidyl aniline, triglycidyl isocyanurate, N,
Examples thereof include N, N ′, N′-tetraglycidyl-bis (p-aminophenyl) -methane, but are not particularly limited thereto. These may be used in combination of several kinds.

As the curing agent, all those known to those skilled in the art can be used, but in particular, C2-C20 linear aliphatic diamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, and meta. Phenylenediamine, paraphenylenediamine, paraxylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenylsulfone, 4,4'-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5-diaminonaphthalene, metaxylylenediamine, paraxylylenediamine, 1,1-bis (4 -Aminophenyl) cyclohexane, amines such as dicyanodiamide, phenol novolac resins, cresol novolac resins, tert-butylphenol novolac resins, nonylphenol novolac resins and other novolac type phenolic resins, resole type phenolic resins, polyparastyrenes such as polyparaoxystyrene , Phenol aralkyl resins, naphthol-based aralkyl resins, etc., phenol compounds in which hydrogen atoms bonded to benzene rings, naphthalene rings and other aromatic rings are substituted with hydroxyl groups, and And phenolic resins obtained by co-condensation with Le compound, an acid anhydride is exemplified, but the invention is not particularly limited thereto.

Examples of the filler include fused silica powder, crystalline silica powder, alumina, silicon nitride, etc. The blending ratio of these fillers is 60 to 90% by weight in the resin composition.
Is. In addition, natural waxes, synthetic waxes, metal salts of linear fatty acids, release agents such as acid amides, esters and paraffins, colorants such as carbon black and red iron oxide, and various curing accelerators, if necessary. Additives known to those skilled in the art such as agents can be used in combination.

When the flame-retardant epoxy resin composition of the present invention is used as a sealing resin for a sealing material, it is mixed uniformly,
It is preferably kneaded. As a kneading method, for example, heating is performed using a roll, a kneader, a mixer, or the like, and then the encapsulating resin is manufactured by a method such as cooling, crushing and tableting. Then, transfer molding or the like is performed using the sealing resin obtained above to seal the semiconductor element, the lead frame, or the like, so that a semiconductor device having excellent flame retardancy and humidity-resistant electrical reliability can be obtained. The molding method is not particularly limited except that the above sealing resin is used, and a general method can be used.

<Laminate> Next, a laminate made of the flame-retardant epoxy resin composition according to the present invention will be described. The epoxy resin used for the laminated plate includes all monomers, oligomers and polymers having at least two epoxy groups in one molecule, for example, bisphenol A type epoxy, bisphenol F type epoxy, bisphenol S type epoxy, phenol novolac type epoxy, Cresol novolac type epoxy, naphthalene type epoxy,
N-glycidyl compounds from biphenyl type epoxies, aromatic amines and heterocyclic nitrogen bases, such as N, N-diglycidylaniline, triglycidyl isocyanurate, N, N, N ', N'-tetraglycidyl-bis (p −
Aminophenyl) -methane and the like, but not limited thereto. These may be used in combination of several kinds.

A resin varnish can be obtained by dissolving the flame-retardant epoxy resin composition of the present invention in a solvent.
The solvent that can be used is preferably an aprotic one, and examples thereof include N-methylpyrrolidone, dimethylformamide, ether, diethyl ether, tetrahydrofuran, dioxane, and optionally branched alkyl groups having 1 to 6 carbon atoms. Having monoalcohol ethyl glycol ether, propylene glycol ether, butyl glycol ether, ketone, acetone,
Methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, ester, ethyl acetate, butyl acetate, ethylene glycol acetate and methoxypropyl acetate, methoxypropanol, other halogenated hydrocarbons and alicyclic and / or aromatic hydrocarbons, Of these, solvents such as hexane, heptane, cyclohexane, toluene and dixylene are preferable. These solvents can be used alone or as a mixture thereof.

In the present invention, the above-mentioned solvent may be used as a solvent for the above-mentioned polymerization reaction and used as it is as a resin varnish. The prepared varnish is applied to and impregnated into a base material such as paper, woven glass cloth, non-woven glass cloth, or cloth having a component other than glass, and then dried in a drying oven at 80 to 2
A prepreg can be prepared by drying within a range of 00 ° C., and a predetermined number of the prepregs can be stacked and heated and pressed to produce a laminate or a metal-clad laminate for a printed wiring board. it can.

[0069]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto.

Production Example 1 1,43-cyclooctadiene (manufactured by Tokyo Kasei) 1843 g (16.69 mol) and toluene 375 were placed in a reaction vessel.
0 ml was charged and the atmosphere was sufficiently replaced with nitrogen. Subsequently, 731 g (21.50 mol) of phosphine (manufactured by Nippon Kagaku Kogyo Co., Ltd.)
Was charged and the temperature was raised to 60 ° C. As a radical initiator,
2,2-Azobis- (2,4-dimethylvaleronitrile) (manufactured by Nippon Hydrazine Co.) 58.8 g (0.237 m)
ol) is pressed in for 3 hours and aged at 60 ° C. overnight,
A toluene solution of a mixture of 1,4-cyclooctylenephosphine and 1,5-cyclooctylenephosphine was obtained. (Purity of the mixture is 31.9 wt%, 1,4-cyclooctylenephosphine: 1,5-cyclooctylenephosphine = 38.4: 61.6 (GC relative area ratio))

A 2000 ml four-necked flask equipped with a stirrer, a condenser and a dropping funnel was sufficiently replaced with nitrogen, and then 434.6 g (0.975 m) of a part of the above reaction solution was used.
ol) was charged at room temperature. Methanol 440
g, and after cooling to about 5 ° C in an ice bath, hydrogen peroxide 1
06.5 g (1.05 mol) was added dropwise from the dropping funnel over about 3 hours. The end point of the reaction was judged by gas chromatography. After the completion of the oxidation reaction, the mixture was concentrated with a rotary evaporator to give 152.8 g (0.966) of a mixture of colorless crystals of 1,4-cyclooctylenephosphine oxide and 1,5-cyclooctylenephosphine oxide.
mol, 1,4-cyclooctylenephosphine oxide: 1,5-cyclooctylenephosphine oxide = 3
9.4: 60.6 (NMR relative area ratio)) was obtained.

Production Example 2 In a reaction vessel equipped with a stirrer and a thermometer, at room temperature, 900 ml of toluene and 183.5 g of a mixture of 1,4-cyclooctylenephosphine oxide and 1,5-cyclooctylenephosphine oxide were added. Purity 87.0%, 1.
(00 mol) was charged and dissolved by stirring. After the temperature of this reaction solution was raised to 70 ° C., 108.7 g (1.00 mol) of finely powdered 1,4-benzoquinone was added little by little over about 3 hours. After completion of the addition, the mixture was aged at 70 ° C for about 1 hour, cooled to room temperature, and the resulting precipitate was filtered, washed with cold methanol three times, and then dried under reduced pressure at 80 ° C to give 1,4-cyclooctylene. 192.7 g of a mixture of phosphonyl-1,4-hydroquinone and 1,5-cyclooctylenephosphonyl-1,4-hydroquinone (0.
724 mol) was obtained as a pale yellow crystalline powder. Yield 7
2.4%. Then, the powder was pulverized with a mixer to obtain a powder having an average particle size of 11.6 μm as determined by a laser scattering particle size measuring method (Microtrac).

¹ H NMR (300 MHz, CD ₃ OD) δ 1.4
3 to 2.83 (m, 14H), 6.77 to 6.91
(M, 3H) ³¹ P NMR (121.5 MHz, CD ₃ OD) δ 4
2.5 (s), 66.8 (s) FAB-MS (Pos., M / z) 267 [M + H] ⁺ IR (KBr, cm ⁻¹ ) 3157 (υOH), 3080
(Arom υC-H), 1225 (υP = O)

Production Example 3 A reaction vessel equipped with a stirrer and a thermometer was placed at room temperature in 500 ml of toluene and 200 parts of diethylphosphine oxide.
After charging g (1.89 mol) and heating to 70 ° C.,
Fine powder of 1,4-naphthoquinone 299 g (1.89 mo)
1) was added in small portions over about 3 hours. After the addition is complete
After reacting at 70 ° C for about 1 hour, the mixture was cooled to room temperature and the resulting precipitate was filtered and washed with cold methanol three times, and then at 80 ° C.
By drying under reduced pressure at 362 g of 2- (diethylphosphonyl) -1,4-naphthalenediol (1.37
mol) was obtained as a pale yellow crystalline powder. Yield 72.3
%. Then, it was pulverized with a mixer to obtain a powder having an average particle size of 11.7 μm as determined by a laser scattering particle size measuring method (Microtrac).

¹ H NMR (300 MHz, CD ₃ OD)
δ 0.90 to 1.12 (m, 6H), 2.11
2.58 (m, 4H), 6.60 (s, 1H), 7.3
8 (m, 1H), 7.80 (m, 1H), 8.07
(M, 2H) ³¹ P NMR (121.5 MHz, CD ₃ OD) δ 5
4.0 (s), 78.5 (S) IR (KBr, cm ^-1 ) 3179 (υOH), 3090
(Arom υC-H), 1205 (υP = O)

Production Example 4 In Production Example 3, 253 g of ethyl diethylphosphinite was dissolved in 500 ml of toluene in place of diethylphosphine oxide, and 3 mol / L hydrochloric acid was added to 500 ml and 2 ml.
The reaction was carried out at 5 ° C. After completion of the reaction, the reaction solution is separated, and the organic phase is added to 500 ml of a 5 mol% sodium hydrogen carbonate aqueous solution.
And washed twice with 500 ml of water. Then, after raising the temperature to 70 ° C. in the same manner as in Example 2, 299 g (1.89 mol) of fine powder 1,4-naphthoquinone was added little by little over about 3 hours. After the addition was completed, after reacting at 70 ° C. for about 1 hour,
The precipitate formed by cooling to room temperature was filtered, washed with cold methanol three times, and then dried under reduced pressure at 80 ° C.
320 g (1.21 mol) of-(diethylphosphonyl) -1,4-naphthalenediol was obtained as a pale yellow crystalline powder. Yield 64.0%. Then, it was pulverized with a mixer to obtain a powder having an average particle size of 11.7 μm as determined by a laser scattering particle size measuring method (Microtrac).

Production Example 5 750 ml of toluene was added to the same apparatus as in Production Example 2 at room temperature.
In addition, 263.6 g of a mixture of 1,4-cyclooctylenephosphine oxide and 1,5-cyclooctylenephosphine oxide (total purity 90.0%, 1.50 mol).
Was charged and stirred to dissolve. After heating this solution to 100 ° C., 23,4 g of 1,4-naphthoquinone (1.
(50 mol) and 1100 ml of toluene were added dropwise little by little over about 6 hours. After the dropping is completed,
Aged at 100 ° C for 2 hours, then cooled to room temperature, and the resulting precipitate was filtered, washed with cold methanol three times, and then at 80 ° C.
And dried under reduced pressure to give 2- (1,4-cyclooctylenephosphonyl) -1,4-naphthalenediol and 2- (1,5-cyclooctylenephosphonyl) -1,4.
A mixture of naphthalene diols 302.22 g (0.9
55 mol) was obtained as a pale yellow crystalline powder. Yield 6
3.6%. Then, it was pulverized with a mixer to obtain a powder having an average particle size of 9.8 μm determined by a laser scattering particle size measuring method (Microtrac).

¹ H NMR (300 MHz, CD ₃ OD)
δ 1.67 to 2.70 (m, 14H), 6.63
(S, 1H), 7.40 (m, 1H), 7.81 (m,
1H), 8.10 (m, 2H) ³¹ P NMR (121.5 MHz, CD ₃ OD) δ 5
5.3 (s), 79.8 (s) DI-EI (m / z) 316 IR (KBr, cm ^-1 ) 3179 (υOH), 3090
(Arom υC-H), 1205 (υP = O)

Production Example 6 2- (dibenzylphosphonyl) was prepared in the same manner as in Production Example 3 except that 200 g of dibenzylphosphine oxide was used instead of 200 g of diethylphosphine oxide.
135.9 g of -1,4-naphthalenediol was obtained. Yield 70.0%. Then by crushing with a mixer,
A powder having an average particle size of 7.9 μm obtained by a laser scattering particle size measuring method (Microtrac) was obtained.

Production Example 7 2- (Tetramethylenephosphonyl) -1,4- was carried out in the same manner as in Production Example 3 except that 44.0 g of tetramethylenephosphine oxide was used instead of 200 g of diethylphosphine oxide. Naphthalenediol 88.6
g was obtained. Yield 72.1%. Then, by pulverizing with a mixer, a powder having an average particle size of 11.8 μm obtained by a laser scattering particle size measuring method (Microtrac) was obtained. The compounds obtained in Production Examples 1 to 7 are shown in Table 1.

[0081]

[Table 1]

Examples 1 to 5 and Comparative Example 1 Ethylene ethyl acrylate (hereinafter abbreviated as EEA) resin and various additives were blended at the blending ratios shown in Table 2 and heated to a hot roll set at 120 to 130 ° C. 5-1
Kneaded for 0 minutes. Molding pressure 14.7 using a heating press
MPa (150 kg / cm ² ), pressurizing time 5 minutes, mold temperature 1
Create a sheet with a thickness of 3 mm at 15 ° C and add a length of 125
mm, width 13 mm, vertical burning test (94V-0, 94V-1 and 94V-) for materials classified as UL94.
The resin was tested for flame retardancy according to 2). As the magnesium hydroxide, Kisuma 5A manufactured by Kyowa Chemical Co., Ltd. was used.

[0083]

[Table 2]

Examples 6 to 19 and Comparative Examples 2 to 8 Various resins and additives were blended in the blending ratios shown in Tables 3 and 4, and test pieces were prepared in the same manner as in Examples 1 to 5 and carried out. The flame retardancy of the resin was tested in the same manner as in Examples 1-5. In addition,
The melt extrusion, pellet drying, and injection molding conditions for each resin are shown below.

Polycarbonate (hereinafter abbreviated as PC) Extrusion: 260 to 320 ° C./75 rpm Drying: 120 ° C./12 hours Molding: 260 to 320 ° C./die 110 ° C. Polybutylene terephthalate (hereinafter abbreviated as PBT) Extrusion: 250 ~ 290 ° C / 150 rpm Drying: 110 ° C / 12 hours Molding: 250-290 ° C / mold 80 ° C Nylon 6 Extrusion: 250-300 ° C / 150 rpm Drying: 100 ° C / 24 hours Molding: 250-300 ° C / mold 80 C. Mixture of polyphenylene oxide and polystyrene (mixing weight ratio: 60:40, hereinafter abbreviated as PPO) Extrusion: 240 to 310 ° C./70 rpm Drying: 110 ° C./4 hours Molding: 240 to 320 ° C./mold 90 ° C. Polyethylene ( Hereinafter abbreviated as PE) Extrusion: 180 to 210 ° C / 700 rpm Drying: 100 ° C / 1 Time molding: 180~210 ℃ / mold 100 ℃

Novolac resin Kneading: 80-90 ° C / 70rpm Molding: 240-320 ° C / mold 150 ° C Unsaturated polyester Sheet preparation: Aged at 40 ° C for 3 days Molding: Mold 140 ℃

[0087]

[Table 3]

[0088]

[Table 4]

Examples 20 to 21 and Comparative Examples 9 to 10 Resins and various additives were blended in the proportions (parts by weight) shown in Table 5, and the mixture was kneaded with a biaxial hot roll at 85 ° C. for 7 minutes. Peeling, cooling and pulverization gave a sealing material. Using a transfer molding machine, molding temperature of this sealing material is 170 ° C., molding pressure is 6.8 MPa (70 kg / cm ² ), molding time is 120 seconds,
Post-curing treatment 180 ° C x 2 hours, thickness 3mm, length 12.5
A test piece having a width of 65 mm and a width of 65 mm was prepared and subjected to a flame retardant test and an extraction test. The spherical silica is A3 manufactured by Nippon Kagaku Kogyo Co., Ltd.
0, crushed silica VLM30 manufactured by Tatsumori Co., phenol resin PSM4261 manufactured by Gunei Chemical Co., Ltd. triphenylphosphine manufactured by Hokuko Chemical Co., synthetic wax P manufactured by Hoechst Co.
O, carbon black is Mitsubishi Chemical Co., HCA-HQ is Sanko Chemical Co., aluminum hydroxide is Sumitomo Chemical CL30
3 was used.

[0090]

[Table 5]

<Flame Retardancy Test> In the flame retardancy test, a test piece was prepared in the same manner as in Examples 1 to 5 for the sealing resin prepared above, and a vertical combustion test (94) for materials classified as UL94 was conducted.
V-0, 94V-1 and 94V-2). The results are shown in Table 5.

<Extraction Test> The test pieces obtained in Examples 20 to 21 and Comparative Examples 9 to 10 were subjected to PCT extraction test (121 ° C. × 121 ° C.).
24 hours). For the extraction test, put 8 g of sample and 80 g of water in a pressure-resistant container with a capacity of 100 ml, and perform 2 at 121 ° C.
The mixture was extracted for 4 hours, cooled with water and filtered, and the concentrations of eluted PO ₄ ions, PHO ₃ ions and PH ₂ O ₂ ions in the filtrate were measured by ion chromatography. Furthermore, the temperature of this filtrate is 25 ° C.
The electrical conductivity of the sample was measured, and the results are shown in Table 6.

[0093]

[Table 6]

Example 22 100 parts of the epoxy resin synthesized in Example 6, 61.50 parts of a phenol resin (PSM4261 manufactured by Gunei Chemical Co., Ltd.),
2.26 parts of triphenylphosphine (manufactured by Hokuko Kagaku),
1.13 parts of OP wax (Hoechst), 1.13 parts of carbon black (manufactured by Mitsubishi Chemical Co., Ltd.), 820.0 parts of fused silica (Nippon Kagaku Kogyo, Sylstar M2430), novolac type phenol resin (hardening agent, Sumitomo Bakelite Co., Ltd .: PR53195) 31.5 parts of the mixture is mixed at room temperature with a mixer and kneaded with a biaxial hot roll at 80 to 85 ° C. for 7 minutes, then peeled, cooled and pulverized to prepare an epoxy resin encapsulant. did.

Example 23 To 100 parts of the epoxy resin synthesized in Example 6 was added 17 parts of metaxylylenediamine as a curing agent, 0.3 g of 2-ethyl-4-methylimidazole as a curing accelerator, and addition to methyl ethyl ketone. Then, the mixture was uniformly stirred to obtain a resin varnish. A prepreg was obtained by applying this resin varnish to a glass cloth and drying it at a temperature of 150 ° C. in an impregnation drying furnace. Four of these prepregs are piled up, and the pressure of 3.0 MPa (30 kg / cm ² ) is applied to 1
A laminate was obtained by heating at 60 ° C.

[0096]

As described above, since the flame-retardant resin composition of the present invention has excellent flame retardancy and moisture resistance, it can be used in connectors, switches, case members, transformer members, coil bobbins, etc. Electrical parts, building materials, transportation equipment such as automobiles, packaging materials, household products, flat cables, printed wiring boards, electric circuit boards, copper clad laminates,
It is useful for applications such as sealing materials, molding materials, casting materials, adhesives, and electrically insulating paint materials. In addition, among the flame-retardant resin compositions of the present invention, those obtained by using an epoxy resin as a resin component to obtain a flame-retardant epoxy resin composition are particularly useful for making a sealing material and a laminated board flame-retardant.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 BB021 BB051 BB071 BB111                       BB151 BC021 BD151 BF051                       BG061 BG101 BL001 CC031                       CC121 CC161 CC181 CC211                       CD001 CD041 CD051 CD061                       CD071 CF011 CF061 CF071                       CF101 CG001 CH021 CH071                       CH081 CK021 CL001 CL011                       CL031 EW146 EW166 FD010                       FD136 FD140 GF00 GQ00                       GQ01 GQ05                 4M109 AA01 BA01 CA21 EA03 EB07                       EC01 GA10

Claims (6)

[Claims] 1. The following general formula (1): (In the formula, R ¹ and R ² represent an optionally substituted linear or branched alkyl group or cycloalkyl group,
One or more methylene groups in the alkyl group may be replaced by -CH = CH-, R
¹ and R ² may be the same group or different groups,
In addition, R ¹ and R ² may form a cyclic compound containing P or not containing P. X represents an oxygen atom or a sulfur atom. Y and Z are a hydrogen atom, a hydroxyl group, a linear or branched alkyl group, an aralkyl group, an alkoxy group, an allyl group,
It represents an aryl group or a cyano group, and Y and Z may be the same group or different groups, and Y and Z may form a ring. ) A flame-retardant resin composition containing a phosphorus-containing hydroquinone derivative represented by 2. The flame-retardant resin composition according to claim ¹ , wherein the cyclic substance formed by R ¹ and R ² is represented by the following general formula (2) or general formula (3). . [Chemical 2] (In the formula, R ³ represents an optionally substituted alkylene group.) (In the formula, R ⁴ represents an optionally substituted cycloalkylene group or arylene group.) 3. The flame-retardant resin composition according to claim 1, wherein the phosphorus-containing hydroquinone derivative has an average particle size of 100 μm or less. 4. The flame-retardant resin composition according to claim 1, wherein the flame-retardant resin is an epoxy resin. 5. A sealing material comprising the flame-retardant resin composition according to claim 4. 6. A laminate comprising the flame-retardant resin composition according to claim 4.