JP5139627B2 - Flame retardant epoxy resin composition and laminate using the same - Google Patents

Description

  The present invention relates to a flame retardant epoxy resin composition that is substantially free of halogen-based flame retardant, has a low environmental load, and has excellent heat resistance, and a laminate using the same.

  Epoxy resins are widely used in electronic and electrical equipment applications due to their excellent electrical properties, adhesiveness, and cured product strength. Many of these applications require high flame retardancy, so various flame retardants are used. A flame retardant epoxy resin composition to which is added is used.

  Conventionally, it has been common to use a halogen-based compound such as brominated bisphenol A type epoxy resin as a method for flame retarding an epoxy resin. However, in recent years, it has been strongly desired to use a flame retardant containing no halogen at all because of concerns about hydrogen halide gas generated during the combustion of products and dioxin-like compounds.

  As a method for flame-retarding an epoxy resin without using a halogen compound, a metal hydroxide, a phosphorus compound, a combined use of a phosphorus compound and a metal hydroxide, and the like are known. It is described in Patent Document 2. However, when any compound is used, it is necessary to add a large amount to obtain sufficient flame retardancy. As a result, workability is reduced due to deterioration of curability and storage stability, and heat resistance of the cured product. However, there has been a drawback that the mechanical properties and electrical properties are significantly reduced.

JP-A-10-204260 JP-A-10-95898

  An object of the present invention is to provide an epoxy resin composition that has high flame retardancy without adding a halogen compound and does not deteriorate the basic properties (particularly heat resistance) of a cured product. .

  As a result of intensive studies to achieve the above object, the present inventors have obtained an epoxy resin composition excellent in flame retardancy and heat resistance by using a specific organophosphorus compound as a non-halogen flame retardant. And reached the present invention.

（式中、Ｘ^１、Ｘ^２は同一もしくは異なり、下記一般式（２）で表される芳香族置換アルキル基である。）

（式中、ＡＬは炭素数１〜５の分岐状または直鎖状の脂肪族炭化水素基であり、Ａｒはその芳香環に置換基を有してもよいフェニル基、ナフチル基またはアントリル基であり、置換基としてはメチル、エチル、プロピル（異性体を含む）、ブチル（異性体を含む）もしくはその芳香環への結合が、酸素原子、イオウ原子または炭素数１〜４の脂肪族炭化水素基を介する炭素数６〜１４のアリール基である。ｎは１〜３の整数を示し、ＡｒはＡＬ中の任意の炭素原子に結合することができる。） That is, according to the present invention,
1. The resin component in the resin composition is an epoxy resin, and with respect to 100 parts by weight of the epoxy resin (component A), 1 to 200 parts by weight of a curing agent (component B) and an organic phosphorus system represented by the following formula (1) A flame retardant epoxy resin composition containing 1 to 100 parts by weight of a compound (component C).

(In formula, X < ¹ >, X < ² > is the same or different, and is an aromatic substituted alkyl group represented by following General formula (2).)

(In the formula, AL is a branched or straight-chain aliphatic hydrocarbon group having 1 to 5 carbon atoms, and Ar is a phenyl group, naphthyl group or anthryl group which may have a substituent on the aromatic ring. Yes, as a substituent, methyl, ethyl, propyl (including isomers), butyl (including isomers), or a bond to an aromatic ring is an oxygen atom, a sulfur atom, or an aliphatic hydrocarbon having 1 to 4 carbon atoms. An aryl group having 6 to 14 carbon atoms through the group , n represents an integer of 1 to 3, and Ar can be bonded to any carbon atom in AL.)

2. The flame retardant according to claim 1, wherein the organophosphorus compound (component C) is a compound represented by the following general formula (1-a), (1-b), (1-c) or (1-d). Epoxy resin composition.

  3. The flame retardant epoxy resin composition according to item 1, wherein the organic phosphorus compound (component C) has an acid value of 0.7 mgKOH / g or less.

4). 2. The flame retardant epoxy resin composition according to item 1, which contains 5 to 50 parts by weight of an organic phosphorus compound (C component) with respect to 100 parts by weight of the epoxy resin (A component).

5. A laminate obtained by impregnating a fiber base material with the epoxy resin composition according to any one of items 1 to 4 and laminating the fiber substrate.
Is provided.

<About the epoxy resin of component A>
The epoxy resin (component A) used in the present invention is not particularly limited, but a halogen atom-free epoxy resin is preferable because the present invention exhibits an excellent difficult effect even if the present invention is halogen-free. However, a chlorine content mixed in the production of the epoxy resin may be included to some extent, and specifically, the halogen atom amount is preferably 1000 ppm or less.

  As such an epoxy resin (component A), for example, bisphenol A {(2,2-bis (4-hydroxyphenyl) propane) type epoxy resin, bisphenol F {bis (4-hydroxyphenyl) methane} type epoxy resin Bisphenol AD {1,1-bis (4-hydroxyphenyl) ethane} type epoxy resin, bisphenol S (4,4'-dihydroxydiphenylsulfone) type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene Type epoxy resin, biphenol type epoxy resin and the like are mentioned, but it is not particularly limited thereto. These epoxy resins are not limited to one type in use, and two or more types of combined or various modified resins can be used.

<B component curing agent>
As the curing agent (component B) used in the present invention, any one known to those skilled in the art can be used, and in particular, C _{2 to} C ₂₀ such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine and the like. Linear aliphatic diamine, metaphenylenediamine, paraphenylenediamine, paraxylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl Sulfone, 4,4′-diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5-diaminonaphthalene, metaxylylenediamine, paraxylylenediamine, 1,1-bis (4-aminophenyl) cyclohexane Dicyanodiamide Amines, phenol novolac resins, cresol novolac resins, tert-butylphenol novolac resins, novolac type phenol resins such as nonylphenol novolac resins, resol type phenol resins, polyoxystyrenes such as polyparaoxystyrene, phenol aralkyl resins, naphthol type aralkyl resins Examples thereof include a phenol resin obtained by cocondensation of a carbonyl compound with a phenol compound in which a hydrogen atom bonded to a benzene ring, naphthalene ring or other aromatic ring is substituted with a hydroxyl group, and an acid anhydride. However, it is not particularly limited to these.

  In this invention, content of the hardening | curing agent (B component) with respect to an epoxy resin (A component) is mix | blended in consideration of the ratio of a functional group. The B component is in the range of 1 to 200 parts by weight and preferably in the range of 3 to 100 parts by weight with respect to 100 parts by weight of the A component. If the functional group of either the A component or the B component is excessively large, moisture resistance, moldability, and electrical properties of the cured product are deteriorated, which is not preferable.

（式中、Ｘ^１、Ｘ^２は同一もしくは異なり、下記一般式（２）で表される芳香族置換アルキル基である。）

（式中、ＡＬは炭素数１〜５の分岐状または直鎖状の脂肪族炭化水素基であり、Ａｒは置換基を有しても良いフェニル基、ナフチル基、またはアントリル基である。ｎは１〜３の整数を示し、ＡｒはＡＬ中の任意の炭素原子に結合することができる。） <About the organophosphorus compound of component C>
In the present invention, the organophosphorus compound used as the component C is represented by the following general formula (1).

(In formula, X < ¹ >, X < ² > is the same or different, and is an aromatic substituted alkyl group represented by following General formula (2).)

(In the formula, AL is a branched or linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and Ar is a phenyl group, a naphthyl group, or an anthryl group which may have a substituent. Represents an integer of 1 to 3, and Ar can be bonded to any carbon atom in AL.)

Among the general formula (1), an organic phosphorus compound represented by the following general formulas (3), (4), (5) and (6) is preferable.

In the general formula (3), in the formula, R ¹ and R ² are the same or different and are a phenyl group, a naphthyl group or an anthryl group which may have a substituent on the aromatic ring, of which a phenyl group is preferred. . The phenyl group, naphthyl group or anthryl group of R ¹ and R ² may have a hydrogen atom of the aromatic ring substituted, and as a substituent, methyl, ethyl, propyl, butyl or a bonding group of the aromatic ring is Examples thereof include an aryl group having 6 to 14 carbon atoms via an oxygen atom, a sulfur atom, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the general formula (4), R ¹ and R ⁴ may be the same or different and are a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Preferred are a hydrogen atom, a methyl group, and an ethyl group, and particularly preferred is a hydrogen atom. R ³ and R ⁶ may be the same or different and each represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group. R ² and R ⁵ may be the same or different and are a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent on the aromatic ring. Preferably, it represents a phenyl group and may have a substituent on the aromatic ring, and methyl, ethyl, propyl (including isomers), butyl (including isomers), or a bonding group to the aromatic ring , Oxygen, sulfur or an aryl group having 6 to 14 carbon atoms via an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the general formula (4), preferred specific examples of R ² and R ⁵ include phenyl group, cresyl group, xylyl group, trimethylphenyl group, 4-phenoxyphenyl group, cumyl group, naphthyl group, 4-benzylphenyl group. In particular, a phenyl group is preferable.

In the general formula (5), Ar ¹ and Ar ² may be the same or different, and are a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent on the aromatic ring. The aromatic ring may have a substituent, and methyl, ethyl, propyl (including isomers), butyl (including isomers), or a bonding group to the aromatic ring is oxygen, sulfur or carbon number It is a C6-C14 aryl group via a 1-4 aliphatic hydrocarbon group.

In the general formula (5), preferred specific examples of Ar ¹ and Ar ² include phenyl group, cresyl group, xylyl group, trimethylphenyl group, 4-phenoxyphenyl group, cumyl group, naphthyl group, 4-benzylphenyl group. In particular, a phenyl group is preferable.

In the general formula (5), R ¹ , R ² , R ³ and R ⁴ may be the same or different, and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a phenyl group, a naphthyl group or It is an anthryl group, and the aromatic ring may have a substituent. Preferably it is a hydrogen atom.

In the general formula (5), AL ¹ and AL ² may be the same or different and are branched or straight-chain aliphatic hydrocarbon groups having 1 to 4 carbon atoms. A branched or straight chain aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and a branched or straight chain aliphatic hydrocarbon group having 1 to 2 carbon atoms is particularly preferable.

In the general formula (5), preferred specific examples of AL ¹ and AL ² include a methylene group, an ethylene group, an ethylidene group, a trimethylene group, a propylidene group, an isopropylidene group, and the like. In particular, a methylene group, an ethylene group, And ethylidene groups are preferred.

In the general formula (5), Ar ³ and Ar ⁴ may be the same or different, and are a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent on the aromatic ring. Preferably, it represents a phenyl group and may have a substituent on the aromatic ring, and methyl, ethyl, propyl (including isomers), butyl (including isomers), or a bonding group to the aromatic ring , Oxygen, sulfur or an aryl group having 6 to 14 carbon atoms via an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the general formula (5), p and q is an integer of 0 to 3, Ar ³ and Ar ⁴ may be bonded to any carbon atoms of AL ¹ and AL ^2, respectively. p and q are preferably 0 or 1, particularly preferably 0.

In the general formula (6), R ¹ and R ⁴ may be the same or different, and are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a phenyl group, a naphthyl group, or an anthryl group, The aromatic ring may have a substituent. Preferably they are a hydrogen atom, a C1-C3 aliphatic hydrocarbon group, or a phenyl group which may have a substituent. When R ¹ and R ⁴ are phenyl groups, they may have a substituent on the aromatic ring, to methyl, ethyl, propyl (including isomers), butyl (including isomers) or the aromatic ring Is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the general formula (6), preferred specific examples of R ¹ and R ⁴ include a hydrogen atom, a methyl group, an ethyl group, a propyl group (including isomers), a phenyl group, a cresyl group, a xylyl group, and a trimethylphenyl group. , 4-phenoxyphenyl group, cumyl group, naphthyl group, 4-benzylphenyl group, etc., particularly preferably a hydrogen atom, a methyl group, or a phenyl group.

In the general formula (6), R ² , R ³ , R ⁵ and R ⁶ may be the same or different and are a phenyl group, a naphthyl group or an anthryl group, and have a substituent in the aromatic ring. May be. Preferably, it represents a phenyl group and may have a substituent on the aromatic ring, methyl, ethyl, propyl (including isomers), butyl (including isomers), or a bonding group to the aromatic ring Is an aryl group having 6 to 14 carbon atoms via oxygen, sulfur or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

In the general formula (6), preferred specific examples of R ² , R ³ , R ⁵ and R ⁶ include phenyl group, cresyl group, xylyl group, trimethylphenyl group, 4-phenoxyphenyl group, cumyl group and naphthyl group. , 4-benzylphenyl group, and the like, and a phenyl group is particularly preferable.

Of the general formula (1), the most preferred representative compounds are organophosphorus compounds represented by the following formulas (1-a), (1-b), (1-c) and (1-d). .

Next, a method for synthesizing the organophosphorus compound (component C) in the present invention will be described. In addition, C component may be manufactured by methods other than the method demonstrated below.
The component C is, for example, a method in which pentaerythritol is reacted with phosphorus trichloride, and then the oxidized reaction product is treated with an alkali metal compound such as sodium methoxide and then aralkyl halide is reacted. Pentaerythritol is reacted with aralkylphosphonic acid dichloride. Can be obtained by reacting aralkyl alcohol with a compound obtained by reacting pentaerythritol with phosphorus trichloride and then performing Arbuzov transition at high temperature.
Methods for carrying out the Arbuzov transition are disclosed, for example, in US Pat. No. 3,141,032, JP-A-54-157156, and JP-A-53-39698.

A specific synthesis method of the C component will be described below. This synthesis method is merely for the purpose of explanation, and the C component used in the present invention is not limited to these synthesis methods, but also modifications thereof and other synthesis methods. It may be synthesized by. A more specific synthesis method will be described in the preparation examples described later.
(I) the organophosphorus compound (1-a) in component C;
A reaction product obtained by reacting pentaerythritol with phosphorus trichloride and then oxidizing with tertiary butanol can be obtained by treating with sodium methoxide and reacting with benzyl bromide.
(II) the organophosphorus compound of (1-b) in component C;
A reaction product obtained by reacting pentaerythritol with phosphorus trichloride and then oxidizing with tertiary butanol can be obtained by treating with sodium methoxide and reacting with 1-phenylethyl bromide.
(III) The organophosphorus compound (1-c) in component C;
A reaction product obtained by reacting pentaerythritol with phosphorus trichloride and then oxidizing with tertiary butanol can be obtained by treating with sodium methoxide and reacting with 2-phenylethyl bromide.
(IV) The organophosphorus compound (1-d) in component C;
It can be obtained by reacting pentaerythritol with diphenylmethylphosphonic acid dichloride.

  Alternatively, it can be obtained by reacting pentaerythritol with phosphorus trichloride and heat-treating the resulting product and the reaction product of diphenylmethyl alcohol in the presence of a catalyst.

  As the C component, those having an acid value of preferably 0.7 mgKOH / g or less, more preferably 0.5 mgKOH / g or less are used. By using the component C having an acid value within this range, an epoxy resin composition excellent in various physical properties such as flame retardancy and heat resistance can be obtained. As for C component, that whose acid value is 0.4 mgKOH / g or less is the most preferable. Here, the acid value means the amount (mg) of KOH necessary to neutralize the acid component in 1 g of the sample (C component).

  Furthermore, as the component C, one whose HPLC purity is preferably at least 90%, more preferably at least 95% is used. Such a high-purity product is preferable because of its excellent physical properties such as flame retardancy and heat resistance of the epoxy resin composition. Here, the HPLC purity of the C component can be effectively measured by using the following method.

  As the column, Develosil ODS-7 300 mm × 4 mmφ manufactured by Nomura Chemical Co., Ltd. was used, and the column temperature was 40 ° C. As a solvent, a mixed solution of acetonitrile and water 6: 4 (volume ratio) was used, and 5 μl was injected. The detector used was UV-260 nm.

  The method for removing impurities in component C is not particularly limited, but a method of performing repulp washing (washing with a solvent, repeating filtration several times) with a solvent such as water or methanol is the most effective. It is also advantageous in terms of cost.

In the present invention, the content of the epoxy resin (A component) organophosphorus compound to the component (C) per 100 parts by weight of component A, C Ingredient 1-100 parts by weight, particularly preferably 5 to 50 parts by weight Range. The suitable range of the mixing ratio of component C is determined by the desired flame retardancy level, the type of epoxy resin, and the like. Furthermore, the blending amount of the C component can be changed by using other flame retardants and flame retardant aids. In many cases, the blending ratio of the C component is reduced by using these other flame retardants and flame retardant aids. be able to. If the amount is less than 1 part by weight, the flame retardant effect is insufficient. If the amount exceeds 100 parts by weight, the heat resistance and moldability may be adversely affected, and the cost is disadvantageous.

<About other additives>
The epoxy resin composition of the present invention can be used as a varnish for a laminate by using an organic solvent (component D). The solvent to be used needs to exhibit good solubility in part or all of the composition, but a poor solvent can be used as long as it does not adversely affect the composition.

  Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, methyl cellosolve, ethyl cellosolve, butyl cellosolve, isobutyl cellosolve, and diethylene glycol monomethyl ether. , Various glycol ethers such as triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether Solvent, Ester solvents such as lucerosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethyl acetate, dialkyl glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, N, N-dimethylacetamide, N, N-dimethyl There are amide solvents such as formamide and N-methyl-2-pyrrolidone, and alcohol solvents such as methanol and ethanol. These may be used in combination.

  The amount of the organic solvent (component D) used is not particularly limited, but it has a solid content concentration of 30 to 70% by weight from the viewpoint of excellent impregnation into the substrate and resin adhesion when preparing a prepreg. A range is preferable.

  The epoxy resin composition of the present invention can further contain a curing accelerator (E component) in addition to the above components. The curing accelerator (component E) that can be used is not particularly limited. For example, tertiary amines such as benzyldimethylamine, various imidazoles such as 2-ethyl-4-methylimidazole, and various metals. A compound etc. are mentioned, The compounding quantity has the preferable range of 0.01-1 weight part of E components with respect to 100 weight part of A components.

In addition to the C component, the epoxy resin composition of the present invention includes a phosphorus flame retardant other than the C component (such as phosphate ester and condensed phosphate ester), an inorganic flame retardant (such as aluminum hydroxide and magnesium hydroxide). Compounds that improve flame retardancy, such as silicon-containing flame retardants and flame retardant aids, can be blended for the purpose of reducing the proportion of component C used or improving the flame retardancy of the epoxy resin composition.
Various additives, fillers, etc. can be suitably mix | blended with the epoxy resin composition of this invention as needed further.

<About cured product of epoxy resin composition>
The epoxy resin composition of the present invention is a flame retardant epoxy resin composition whose cured product has flame retardancy equivalent to V-0 by a vertical combustion test defined in UL-94 of the US UL standard. .

  A varnish obtained by dissolving the resin composition of the present invention in the organic solvent is coated, impregnated on a fiber base material such as a glass woven fabric, a glass nonwoven fabric, paper, or a cloth containing components other than glass fibers, and dried. Thus, a prepreg can be obtained. This prepreg can be formed into a laminate by stacking a predetermined number of layers and heating and pressing. Such a laminate is suitably used as a printed board. This laminated board exhibits an excellent flame retardant effect without containing a halogen-based flame retardant, and can dramatically improve heat resistance.

  The epoxy resin composition of the present invention is used for laminated boards such as printed circuit boards, as well as various electrical and electronic parts such as semiconductor sealing materials and electrical insulating materials, fiber reinforced composite materials, coating materials, molding materials, and adhesive materials. It can also be applied.

  The present invention provides a flame retardant epoxy resin composition having excellent physical properties such as heat resistance without using a halogen compound, and the epoxy resin composition is used in applications such as laminates and electronic and electrical equipment. It is preferably used and its industrial effect is extremely large.

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
(1) Flame retardance The copper foil of the obtained laminated board was removed, and this was evaluated according to the vertical combustion test prescribed | regulated to UL-94 of US UL specification.
(2) Solder heat resistance The obtained laminate was subjected to a moisture absorption treatment for 2 hours after boiling in accordance with JIS C6481, and then floated in a solder bath at 260 ° C. for 180 seconds, and then examined for appearance abnormality.
(3) Acid value The prepared organophosphorus compound was measured according to JIS-K-3504.

Preparation Example 1
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dibenzyl-3,9-dioxide (FR-1) Thermometer, condenser, and dropping funnel The reaction vessel was charged with 816.9 g (6.0 mol) of pentaerythritol, 19.0 g (0.24 mol) of pyridine, and 2250.4 g (24.4 mol) of toluene and stirred. To the reaction vessel, 1651.8 g (12.0 mol) of phosphorus trichloride was added using the dropping funnel. After the reaction, the reaction mixture was cooled to room temperature, and 26.50 parts of methylene chloride was added to the resulting reaction product, and 889.4 g (12.0 moles) of tertiary butanol and 150.2 g (1.77 moles) of methylene chloride were cooled with ice. Mol) was added dropwise. The obtained crystals were washed with toluene and methylene chloride and filtered. The obtained filtered product was dried at 80 ° C. and 1.33 × 10 ² Pa for 12 hours to obtain 1341.1 g (5.88 mol) of a white solid. The obtained solid was found to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dihydro-3,9-dioxide according to ³¹ P, ¹ HNMR spectrum. confirmed.

2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dihydro-3,9-dioxide obtained in a reaction vessel equipped with a thermometer, condenser and dropping funnel 1341.0 g (5.88 mol) and DMF6534.2 g (89.39 mol) were charged and stirred. Sodium methoxide 648.7 g (12.01 mol) was added to the reaction vessel under ice cooling. After stirring for 2 hours under ice cooling, the mixture was stirred for 5 hours at room temperature. After further distilling off DMF, 2613.7 g (35.76 mol) of DMF was added, and 2037.79 g (11.91 mol) of benzyl bromide was added dropwise to the reaction mixture under ice cooling. After stirring for 3 hours under ice cooling, DMF was distilled off, 8 L of water was added, and the precipitated solid was collected by filtration and washed twice with 2 L of water. The obtained crude product and 4 L of methanol were put into a reaction vessel equipped with a condenser and a stirrer and refluxed for about 2 hours. After cooling to room temperature, the crystals were separated by filtration, washed with 2 L of methanol, and the obtained filtered product was dried at 120 ° C. and 1.33 × 10 ² Pa for 19 hours to obtain 1863.5 g of white scaly crystals ( 4.56 mol) was obtained. The crystals obtained are ³¹ P, ¹ HNMR spectrum and elemental analysis with 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dibenzyl-3,9-dioxide. I confirmed it. The yield was 76% and ³¹ PNMR purity was 99%. The HPLC purity measured by the method described in the text was 99%. The acid value was 0.06 mgKOH / g.

¹ H-NMR (DMSO-d ₆ , 300 MHz): δ 7.2-7.4 (m, 10H), 4.1-4.5 (m, 8H), 3.5 (d, 4H), ³¹ P _{-NMR (DMSO-d 6, 120MHz} ): δ23.1 (S), melting point: 255-256 ° C., elemental analysis: calculated: C, 55.89; H, 5.43 , measurement values: C, 56.24 H, 5.35

Preparation Example 2
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dibenzyl-3,9-dioxide (FR-2) Reaction with stirrer, thermometer, condenser In a container, 22,9-dibenzyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane 22.55 g (0.055 mol), benzyl bromide 19.01 g (0.11 mol) ) And 33.54 g (0.32 mol) of xylene, and dry nitrogen was allowed to flow while stirring at room temperature. Next, heating was started in an oil bath, and the mixture was heated and stirred at a reflux temperature (about 130 ° C.) for 4 hours. After heating, the mixture was allowed to cool to room temperature, 20 mL of xylene was added, and the mixture was further stirred for 30 minutes. The precipitated crystals were separated by filtration and washed twice with 20 mL of xylene. The obtained crude product and 40 mL of methanol were placed in a reaction vessel equipped with a condenser and a stirrer and refluxed for about 2 hours. After cooling to room temperature, the crystals were separated by filtration and washed with 20 mL of methanol, and the obtained filtered product was dried at 120 ° C. and 1.33 × 10 ² Pa for 19 hours to obtain white scaly crystals. The product was confirmed to be bisbenzylpentaerythritol diphosphonate by mass spectral analysis, ¹ H, ³¹ P nuclear magnetic resonance spectral analysis and elemental analysis. The yield was 20.60 g, the yield was 91%, and ³¹ PNMR purity was 99%. The HPLC purity measured by the method described in the text was 99%. The acid value was 0.05 mgKOH / g.

¹ H-NMR (DMSO-d ₆ , 300 MHz): δ 7.2-7.4 (m, 10H), 4.1-4.5 (m, 8H), 3.5 (d, 4H), ³¹ P _{-NMR (DMSO-d 6, 120MHz} ): δ23.1 (S), melting point: 257 ° C.

Preparation Example 3
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-diα-methylbenzyl-3,9-dioxide (FR-3) Thermometer, condenser, A reaction vessel equipped with a dropping funnel was charged with 816.9 g (6.0 mol) of pentaerythritol, 19.0 g (0.24 mol) of pyridine, and 2250.4 g (24.4 mol) of toluene and stirred. To the reaction vessel, 1651.8 g (12.0 mol) of phosphorus trichloride was added using the dropping funnel. After the reaction, the reaction mixture was cooled to room temperature, and 5180.7 g (61.0 mol) of methylene chloride was added to the obtained reaction product, and 889.4 g (12.0 mol) of tertiary butanol and 150. 2 g (1.77 mol) was added dropwise. The obtained crystals were washed with toluene and methylene chloride and filtered. The obtained filtered product was dried at 80 ° C. and 1.33 × 10 ² Pa for 12 hours to obtain 1341.1 g (5.88 mol) of a white solid. The obtained solid was found to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dihydro-3,9-dioxide according to ³¹ P, ¹ HNMR spectrum. confirmed.

2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dihydro-3,9-dioxide obtained in a reaction vessel equipped with a thermometer, condenser and dropping funnel 1341.0 g (5.88 mol) and DMF6534.2 g (89.39 mol) were charged and stirred. Sodium methoxide 648.7 g (12.01 mol) was added to the reaction vessel under ice cooling. After stirring for 2 hours under ice cooling, the mixture was stirred for 5 hours at room temperature. After further distilling off DMF, 2613.7 g (35.76 mol) of DMF was added, and 2204.06 g (11.91 mol) of 1-phenylethyl bromide was added dropwise to the reaction mixture under ice cooling. After stirring for 3 hours under ice cooling, DMF was distilled off, 8 L of water was added, and the precipitated solid was collected by filtration and washed twice with 2 L of water. The obtained crude product and 4 L of methanol were put into a reaction vessel equipped with a condenser and a stirrer and refluxed for about 2 hours. After cooling to room temperature, the crystals were separated by filtration, washed with 2 L of methanol, and the obtained filtered product was dried at 120 ° C. and 1.33 × 10 ² Pa for 19 hours to obtain 1845.9 g of white scaly crystals ( 4.23 mol) was obtained. The obtained solid was analyzed by ³¹ PNMR, ¹ HNMR spectrum and elemental analysis, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-diα-methylbenzyl-3,9. -Confirmed that it was a geoxide. ³¹ PNMR purity was 99%. The HPLC purity measured by the method described in the text was 99%. The acid value was 0.03 mgKOH / g.

¹ H-NMR (CDCl ₃ , 300 MHz): δ 7.2-7.4 (m, 10H), 4.0-4.2 (m, 4H), 3.4-3.8 (m, 4H), 3.3 (qd, 4H), 1.6 (ddd, 6H), ³¹ P-NMR (CDCl ₃ , 120 MHz): δ 28.7 (S), melting point: 190-210 ° C., elemental analysis calculated value: C, 57.80; H, 6.01, measured value: C, 57.83; H, 5.96

Preparation Example 4
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-di (2-phenylethyl) -3,9-dioxide (FR-4) Thermometer A reaction vessel equipped with a condenser and a dropping funnel was charged with 816.9 g (6.0 mol) of pentaerythritol, 19.0 g (0.24 mol) of pyridine, and 2250.4 g (24.4 mol) of toluene and stirred. To the reaction vessel, 1651.8 g (12.0 mol) of phosphorus trichloride was added using the dropping funnel. After the reaction, the reaction mixture was cooled to room temperature, and 5180.7 g (61.0 mol) of methylene chloride was added to the obtained reaction product, and 889.4 g (12.0 mol) of tertiary butanol and 150. 2 g (1.77 mol) was added dropwise. The obtained crystals were washed with toluene and methylene chloride and filtered. The obtained filtered product was dried at 80 ° C. and 1.33 × 10 ² Pa for 12 hours to obtain 1341.1 g (5.88 mol) of a white solid. The obtained solid was found to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dihydro-3,9-dioxide according to ³¹ P, ¹ HNMR spectrum. confirmed.

2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dihydro-3,9-dioxide obtained in a reaction vessel equipped with a thermometer, condenser and dropping funnel 1341.0 g (5.88 mol) and DMF6534.2 g (89.39 mol) were charged and stirred. Sodium methoxide 648.7 g (12.01 mol) was added to the reaction vessel under ice cooling. After stirring for 2 hours under ice cooling, the mixture was stirred for 5 hours at room temperature. After further distilling off DMF, 2613.7 g (35.76 mol) of DMF was added, and 2183.8 g (11.8 mol) of (2-bromoethyl) benzene was added dropwise to the reaction mixture under ice cooling. After stirring for 3 hours under ice cooling, DMF was distilled off, 8 L of water was added, and the precipitated solid was collected by filtration and washed twice with 2 L of water. The obtained crude product and 4 L of methanol were put into a reaction vessel equipped with a condenser and a stirrer and refluxed for about 2 hours. After cooling to room temperature, the crystals were separated by filtration and washed with 2 L of methanol, and the resulting filtered product was dried at 120 ° C. and 1.33 × 10 ² Pa for 19 hours to give 1924.4 g (4. 41 mol) was obtained. The obtained solid was found to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-di (2-phenylethyl) -3 by ³¹ PNMR, ¹ HNMR spectrum and elemental analysis. , 9-Dioxide was confirmed. ³¹ PNMR purity was 99%. The HPLC purity measured by the method described in the text was 99%. The acid value was 0.03 mgKOH / g.

¹ H-NMR (CDCl ₃ , 300 MHz): δ 7.1-7.4 (m, 10H), 3.85-4.65 (m, 8H), 2.90-3.05 (m, 4H), 2.1-2.3 (m, 4H), ³¹ P-NMR (CDCl ₃ , 120 MHz): δ 31.5 (S), melting point: 245-246 ° C., elemental analysis calculated: C, 57.80; H , 6.01, measured value: C, 58.00; H, 6.07

Preparation Example 5
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-di (2-phenylethyl) -3,9-dioxide (FR-5) Stirrer, temperature In a reaction vessel having a total condenser, 3,9-di (2-phenylethoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane 436.4 g (1.0 mol) Then, 370.1 g (2.0 mol) of 2-phenylethyl bromide was charged, and dry nitrogen was allowed to flow while stirring at room temperature. Next, heating was started in an oil bath, and the oil bath temperature was maintained at 180 ° C. for 10 hours. Thereafter, the oil bath was removed and the system was cooled to room temperature. To the obtained white solid reaction product, 2000 ml of methanol was added and washed with stirring, and then the white powder was filtered off using a glass filter. Next, the filtered white powder and 4000 ml of methanol were put into a reaction vessel equipped with a condenser and a stirrer and refluxed for about 2 hours. After cooling to room temperature, the crystals were separated by filtration and washed with 2000 mL of methanol. The obtained white powder was dried at 100 Pa and 120 ° C. for 8 hours to obtain 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-di (2-phenylethyl). 362.3 g of -3,9-dioxide was obtained. The product was bis 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-di (by mass spectral analysis, ¹ H, ³¹ P nuclear magnetic resonance spectral analysis and elemental analysis. 2-phenylethyl) -3,9-dioxide was confirmed. The yield was 83%, HPLC purity was 99.3%, and the acid value was 0.41 KOH mg / g.

¹ H-NMR (CDCl ₃ , 300 MHz): δ 7.1-7.4 (m, 10H), 3.85-4.65 (m, 8H), 2.90-3.05 (m, 4H), 2.1-2.3 (m, 4H), ³¹ P-NMR (CDCl ₃ , 120 MHz): δ 31.5 (S), melting point: 245-246 ° C.

Preparation Example 6
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (diphenylmethyl) -3,9-dioxide (FR-6) Stirrer, stirrer In a 10-liter three-necked flask equipped with a reflux condenser and a thermometer, 2058.5 g (7.22 mol) of diphenylmethylphosphonic dichloride, 468.3 g (3.44 mol) of pentaerythritol, 1169.4 g of pyridine ( 14.8 mol) and 8200 g of chloroform were charged, heated to 60 ° C. under a nitrogen stream, and stirred for 6 hours. After completion of the reaction, chloroform was replaced with methylene chloride, and 6 L of distilled water was added to the reaction mixture and stirred to precipitate a white powder. This was collected by suction filtration, and the obtained white product was washed with methanol and then dried at 100 ° C. and 1.33 × 10 ² Pa for 10 hours to obtain 1156.2 g of a white solid. The obtained solid was found to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (diphenylmethyl) by ³¹ P-NMR, ¹ H-NMR spectrum and elemental analysis. It was confirmed that it was −3,9-dioxide. ^{The 31} P-NMR purity was 99%. The HPLC purity measured by the method described in the text was 99%. The acid value was 0.3 mgKOH / g.

¹ H-NMR (DMSO-d6, 300 MHz): δ 7.20-7.60 (m, 20H), 5.25 (d, 2H), 4.15-4.55 (m, 8H), ³¹ P- NMR (DMSO-d6, 120 MHz): δ 20.9, melting point: 265 ° C., elemental analysis calculated: C, 66.43; H, 5.39, measured: C, 66.14; H, 5.41

Preparation Example 7
Preparation of 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (diphenylmethyl) -3,9-dioxide (FR-7) , A thermometer, and a condenser, and 40.4 g of 3,9-bis (diphenylmethoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane was added to the flask under a nitrogen stream. (0.072 mol), 35.5 g (0.14 mol) of diphenylmethyl bromide and 48.0 g (0.45 mol) of xylene were added, and the mixture was heated and stirred at a reflux temperature (about 130 ° C.) for 3 hours. After heating, the mixture was allowed to cool to room temperature, 30 mL of xylene was added, and the mixture was further stirred for 30 minutes. The precipitated crystals were separated by filtration and washed twice with 30 mL of xylene. The obtained crude product and 100 mL of methanol were placed in an eggplant type flask, a condenser was attached, and the mixture was refluxed for about 1 hour. After cooling to room temperature, the crystals were separated by filtration, washed twice with 50 mL of methanol, and dried under reduced pressure at 120 ° C. The obtained solid was found to be 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (diphenylmethyl) by ³¹ P-NMR, ¹ H-NMR spectrum and elemental analysis. It was confirmed that it was −3,9-dioxide. The obtained solid was a white powder, the yield was 36.8 g, and the yield was 91%. ³¹ PNMR purity was 99%. The HPLC purity measured by the method described in the text was 99%. The acid value was 0.07 mg KOH / g.

¹ H-NMR (DMSO-d ₆ , 300 MHz): δ 7.2-7.6 (m, 20H), 6.23 (d, J = 9 Hz, 2H), 3.89-4.36 (m, 6H) ), 3.38-3.46 (m, 2H), ³¹ P-NMR (CDCl ₃ , 120 MHz): δ 20.9 (S), melting point: 265 ° C., elemental analysis calculated: C, 66.43; H , 5.39, found: C, 66.14; H, 5.41

[Example 1]
Phenol novolac type epoxy resin EPICLON N-770 (manufactured by Dainippon Ink Industries, Ltd., epoxy equivalent 190 g / eq) 100 parts by weight, dicyandiamide 5.5 parts by weight, organophosphorus compound (FR-1) 30 parts by weight, 2 -Methyl ethyl ketone was added to 0.1 part of ethyl-4-methylimidazole, and the varnish was adjusted so as to have a nonvolatile content concentration of 50% by weight. Using this resin varnish, 100 parts of glass cloth (thickness 0.18 mm, manufactured by Nitto Boseki Co., Ltd.) is impregnated with 80 parts of varnish solids and dried in a dryer oven at 150 ° C. for 4 minutes to contain the resin. A prepreg having an amount of 44.4% was prepared. The resulting stacked eight prepregs, overlapping the electrolytic copper foil having a thickness of 35μm on the upper and lower, carried out a pressure 3.9 × ¹⁰ 6 Pa, a 120-minute hot pressing at a temperature 170 ° C., 1.6mm thick A double-sided copper-clad laminate was obtained. About the obtained laminated board, the flame retardance and solder heat resistance were measured. The evaluation results are shown in Table 1.

[Examples 2-42 and Comparative Examples 1-6]
With the compositions shown in Tables 1 to 5, double-sided copper-clad laminates were prepared in the same manner as in Example 1, and the flame resistance and solder heat resistance of the obtained laminates were measured. The evaluation results are shown in Tables 1-5.

Each component shown in the table is as follows.
(I) Epoxy resin (component A)
(I) Phenol novolac type epoxy resin (EPICLON N-770 manufactured by Dainippon Ink and Chemicals, Epoxy equivalent 190 g / eq)
(Ii) Cresol novolac type epoxy resin (Epiclon N-690 manufactured by Dainippon Ink and Chemicals, epoxy equivalent 210 g / eq)
(Iii) Bisphenol A type epoxy resin (Epicoat 1001 manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 460 g / eq)

(II) Curing agent (component B)
(I) Dicyandiamide (DICY)
(Ii) Phenol novolac resin (PR-53195 manufactured by Sumitomo Durez Co., Ltd., hydroxyl group equivalent 110 g / eq)

(III) Organophosphorus compounds (C component)
(I) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-dibenzyl-3,9-dioxide synthesized in Preparation Example 1 {the above general formula (1- a) phosphorus compound (FR-1)}
(Ii) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-dibenzyl-3,9-dioxide synthesized in Preparation Example 2 {the above general formula (1- a) Phosphorus compound (FR-2)}
(Iii) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-diα-methylbenzyl-3,9-dioxide synthesized in Preparation Example 3 Phosphorus compound of formula (1-b) (FR-3)}
(Iv) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-di (2-phenylethyl) -3,9-dioxide synthesized in Preparation Example 4 Phosphorus compound of general formula (1-c) (FR-4)}
(V) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-di (2-phenylethyl) -3,9-dioxide synthesized in Preparation Example 5 Phosphorus compound of general formula (1-c) (FR-5)}
(Vi) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (diphenylmethyl) -3,9-dioxide synthesized in Preparation Example 6 Phosphorus compound of formula (1-d) (FR-6)}
(Vii) 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-bis (diphenylmethyl) -3,9-dioxide synthesized in Preparation Example 7 Phosphorus compound of formula (1-d) (FR-7)}
<Organic phosphorus flame retardants other than component C>
(I) Triphenyl phosphate (TPP manufactured by Daihachi Chemical Industry Co., Ltd.)

(IV) Curing accelerator (E component)
2-Ethyl-4-methylimidazole (2E4MZ)

Claims (5)

The resin component in the resin composition is an epoxy resin, and with respect to 100 parts by weight of the epoxy resin (component A), 1 to 200 parts by weight of a curing agent (component B) and an organic phosphorus system represented by the following formula (1) A flame retardant epoxy resin composition containing 1 to 100 parts by weight of a compound (component C).

(In formula, X < ¹ >, X < ² > is the same or different, and is an aromatic substituted alkyl group represented by following General formula (2).)

(In the formula, AL is a branched or straight-chain aliphatic hydrocarbon group having 1 to 5 carbon atoms, and Ar is a phenyl group, naphthyl group or anthryl group which may have a substituent on the aromatic ring. Yes, as a substituent, methyl, ethyl, propyl (including isomers), butyl (including isomers), or a bond to an aromatic ring is an oxygen atom, a sulfur atom, or an aliphatic hydrocarbon having 1 to 4 carbon atoms. An aryl group having 6 to 14 carbon atoms through the group, n represents an integer of 1 to 3, and Ar can be bonded to any carbon atom in AL.) The flame retardant according to claim 1, wherein the organophosphorus compound (component C) is a compound represented by the following general formula (1-a), (1-b), (1-c) or (1-d). Epoxy resin composition.

  The flame retardant epoxy resin composition according to claim 1, wherein the organic phosphorus compound (component C) has an acid value of 0.7 mgKOH / g or less.   The flame-retardant epoxy resin composition according to claim 1, comprising 5 to 50 parts by weight of an organic phosphorus compound (C component) with respect to 100 parts by weight of the epoxy resin (A component). The laminated board formed by impregnating the epoxy resin composition of any one of Claims 1-4 in a fiber base material, and laminating | stacking this.