JP2011084697A - Polymerizable phosphorus-containing (poly)xylylene aryl ether compound, method for producing the same, flame-retardant thermocurable resin composition, cured product and laminated board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound which is low in environmental loads and free from the bleed out of a flame retardant, which imparts excellent flame retardancy, heat resistance and electric properties to a thermocurable resin composition even when the addition amount thereof is made smaller than before and which makes it possible to obtain a cured product excellent in heat resistance and electric properties. <P>SOLUTION: A polymerizable phosphorus-containing (poly)xylylene aryl ether compound shown by general formula (1) (wherein R<SP>1</SP>is a residual group of a diphenylphosphinic acid derivative; W is an aromatic hydrocarbon group; R<SP>2</SP>is an alkyl group or an aryl group; o is an integer of 0-4; n is a number of ≥1) is provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a compound that provides a cured product having excellent heat resistance, electrical properties, and water resistance, and flame retardancy, and a method for producing the same. More specifically, a polymerizable phosphorus-containing (poly) xylylene aryl ether compound obtained by reacting a phosphorus-containing compound having two phenolic hydroxyl groups with a xylylene dihalide compound and an ethenyl group-containing benzyl halide compound and the production thereof The present invention relates to a method, a flame retardant thermosetting resin composition using the polymerizable phosphorus-containing (poly) xylylene aryl ether compound, a cured product thereof, and a laminate.
The flame retardant thermosetting resin composition of the present invention is suitably used as a semiconductor encapsulant, a laminate, a coating material, a composite material, and the like.

  Many epoxy resins and phenol resins are used in the field of electrical and electronic materials. However, in recent years, the trend toward downsizing and higher density of mounted components is remarkable in the field of electronic equipment, and the materials used therewith have excellent heat resistance, flame retardancy, dimensional stability and electrical characteristics. When these resins are used as a base material, there is a problem that electric characteristics, particularly dielectric characteristics are poor in a high frequency region.

In these fields, high flame retardancy is required for mounting components, and until now, flame retardancy has been generally imparted by using halogen compounds. However, in recent years, the use of halogen compounds has become a problem from the viewpoint of reducing the burden on the environment.
Therefore, as an alternative to such a flame retardant formulation with a halogen compound, phosphate esters such as triphenyl phosphate and condensed phosphate esters such as 1,3-phenylenebis (di-2,6-xylenyl phosphate) Phosphorus compounds typified by the class have been used. However, when these phosphorus compounds are used as additive-type flame retardants for thermosetting resins, there is a problem that the heat resistance of the cured product, particularly the glass transition temperature (Tg), is significantly reduced.

  Therefore, instead of the additive type flame retardant, epoxy resins containing 20% by weight or more of novolak type epoxy resin, quinone compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and diphenyl Techniques have been proposed for improving flame retardancy, water resistance and the like by using a reactive phosphorus compound obtained by reacting a phosphorus compound such as phosphine oxide (for example, Patent Documents 1 to 3). reference). These are techniques in which an epoxy resin modified with a phosphorus compound is used to improve the heat resistance, flame retardancy, and the like of a molded product. However, the dielectric properties of molded products using these compounds are equivalent to those using conventional epoxy resins, and the properties in the high frequency region are insufficient.

  On the other hand, many proposals have been made to use a compound having a benzoxazine structure as a curing agent for a curable resin (for example, see Patent Documents 4 to 6). In these inventions, high flame retardancy is achieved by using a compound having a benzoxazine structure. However, in the dielectric properties of molded products using these compounds, the properties in the high frequency region are insufficient as described above.

  Further, as a material for improving dielectric characteristics in a high frequency region, for example, a polyvinyl benzyl ether compound has been proposed (see, for example, Patent Document 7). This polyvinyl benzyl ether compound has excellent electrical properties, heat resistance and reliability. By applying it to thermosetting resin compositions, prepregs, copper-clad laminates, etc., Improved characteristics are seen. However, it is necessary to use a flame retardant separately because only the polyvinyl benzyl ether compound cannot exhibit sufficient flame retardancy.

Furthermore, it has been proposed to use a polyvinyl benzyl ether compound, a benzoxazine compound, and an additive-type phosphorus compound (aromatic phosphate ester compound or phosphazene compound) (see, for example, Patent Document 8). By applying this to thermosetting resin compositions, prepregs, copper-clad laminates, etc., it is possible to improve electrical characteristics in the high-frequency region and achieve high flame retardancy without using halogen-containing compounds. is doing.
However, when an additive-type specific phosphorus compound is used as the phosphorus compound as described in Patent Document 8, an improvement in electrical characteristics and high flame retardancy in a high frequency region can be obtained, but a decrease in heat resistance or lamination There is a problem that bleed-out of the phosphorus compound occurs from the plate surface.

Japanese Patent Laid-Open No. 4-11662 JP-A-11-279258 JP 2000-309623 A JP 2001-220455 A JP 2003-147165 A JP 2004-352670 A JP-A-9-31006 JP 2007-2187 A

  The object of the present invention is that the environmental load is small, there is no bleed out of the flame retardant, excellent flame retardancy, heat resistance and electrical properties are imparted with a smaller amount of addition than before, and excellent in heat resistance and electrical properties. It is providing the compound which can obtain hardened | cured material.

  In order to solve the above problems, the present inventors have conducted extensive studies and, as a result, contain a phosphorus atom that can impart flame retardancy, and include a polymerizable ethenyl group that can function as a curable resin. By using a phosphorus-containing (poly) xylylene aryl ether compound, the thermosetting resin composition can be imparted with excellent flame retardancy, heat resistance and electrical properties with a smaller amount of addition than before, and heat resistance and electrical properties. The present inventors have found that an excellent cured product can be obtained, and have completed the present invention.

That is, the present invention relates to the following [1] to [7].
[1] A polymerizable phosphorus-containing (poly) xylylene aryl ether compound represented by the following general formula (1).

(In the formula, R ¹ is a group represented by the following general formula (2), W is a group represented by the following general formula (3) or (4). R ² has 1 to 6 carbon atoms. An alkyl group or a substituted or unsubstituted aryl group having 6 to 10 ring carbon atoms, o represents an integer of 0 to 4, and n represents a number of 1 or more.)

(In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 ring carbon atoms. P and q are each independently selected. And represents an integer of 0 to 5.)

(Wherein R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 ring carbon atoms. R is an integer of 0 to 3) And s represents an integer of 0 to 5.)
[2] The polymerizable phosphorus-containing (poly) xylyl according to the above [1], wherein o, p, q, r and s in the general formulas (1), (2), (3) and (4) are all 0 Lenaryl ether compounds.
[3] The following general formula (5) or (6)

(Wherein R ^{3 to} R ⁶ , p, q, r and s are as defined above.)
A phosphorus-containing compound having two phenolic hydroxyl groups represented by the following general formulas (7) and (8):

(In the formula, R ² is as defined above. X ¹ and X ² each independently represents a chlorine atom or a bromine atom. O is as defined above.)
Or a benzyl halide compound containing an ethenyl group in a polar solvent in the presence of an alkali or in a mixture of an organic solvent and water in the presence of an alkali and a phase transfer catalyst. The manufacturing method of the said polymeric phosphorus containing (poly) xylylene aryl ether compound which has the process made to react.
[4] A flame-retardant thermosetting resin composition comprising the polymerizable phosphorus-containing (poly) xylylene aryl ether compound according to the above [1] or [2] and a thermosetting resin having radical polymerizability.
[5] A cured product obtained by heat-curing the flame retardant thermosetting resin composition according to [4].
[6] A laminate obtained by pressure-molding the flame retardant thermosetting resin composition according to [4] above and laminating metal foils.
[7] The laminate as described in [6] above, which has a metal foil on one side or both sides.

The flame retardant thermosetting resin composition containing the polymerizable phosphorus-containing (poly) xylylene aryl ether compound of the present invention does not contain a halogen atom, and therefore has a low environmental load, and additionally requires the addition of a flame retardant. Therefore, there is no problem that the added flame retardant bleeds out. Moreover, high flame retardancy can be imparted only by adding the polymerizable phosphorus-containing (poly) xylylene aryl ether compound to the resin composition in a small amount (for example, 50% by mass or less based on the total resin components). At the same time, it excels in heat resistance and electrical properties.
Thus, the polymerizable phosphorus-containing (poly) xylene aryl ether compound of the present invention and the flame-retardant thermosetting resin composition containing the compound are laminated boards for electronic boards (printed wiring boards), semiconductor sealing materials, and the like. Can be suitably used.

[Polymerizable phosphorus-containing (poly) xylylene aryl ether compound]
First, the polymerizable phosphorus-containing (poly) xylylene aryl ether compound represented by the following general formula (1) of the present invention will be described. The “(poly) xylylene aryl ether compound” refers to both a xylylene aryl ether compound (n = 1) and a polyxylylene aryl ether compound (n> 1).

In the general formula (1), R ² represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 ring carbon atoms. Moreover, o represents an integer of 0 to 4, and n represents a number of 1 or more. Since the compound represented by the general formula (1) has an ethenyl group at both ends, radical polymerizability is imparted.
Examples of the alkyl group having 1 to 6 carbon atoms represented by R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. Examples of the substituted or unsubstituted aryl group having 6 to 10 ring carbon atoms represented by R ² include a phenyl group, a tolyl group, and a naphthyl group.
o is preferably 0 or 1, more preferably 0. n is preferably 1 to 50, more preferably 1 to 10, and still more preferably 1 to 5.
R ¹ is a group represented by the following general formula (2).

In the general formula (2), R ³ and R ⁴ each independently represent an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 ring carbon atoms. p and q represent the integer of 0-5 each independently.
Examples of the alkyl group having 1 to 6 carbon atoms and the substituted or unsubstituted aryl group having 6 to 10 ring carbon atoms each independently represented by R ³ and R ⁴ are the same as those exemplified for R ² . .
Each of p and q is preferably 0 or 1, more preferably 0.
W is a group represented by the following general formula (3) or (4).

In the general formula (3) or (4), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 ring carbon atoms. . r represents an integer of 0 to 3, and s represents an integer of 0 to 5.
As the alkyl group having 1 to 6 carbon atoms and the substituted or unsubstituted aryl group having 6 to 10 ring carbon atoms each independently represented by R ⁵ and R ⁶ , the same examples as in R ² can be mentioned. .
r is preferably 0 or 1, more preferably 0. s is preferably 0 or 1, more preferably 0.
In any of the above general formulas (3) and (4), it is preferable that they are bonded to two oxygen atoms at the para position.

[Method for producing polymerizable phosphorus-containing (poly) xylylene aryl ether compound]
The phosphorus-containing (poly) xylylene aryl ether compound includes a phosphorus-containing compound having two phenolic hydroxyl groups represented by the following general formula (5) or (6) and a xylylene represented by the following general formula (7). It is obtained by reacting a range halide compound and an ethenyl group-containing benzyl halide compound represented by the following general formula (8).

In the general formulas (5) and (6), R ^{3 to} R ⁶ , p, q, r, and s are as defined above in the general formulas (2) to (4), and the same can be exemplified. The preferred ones are the same.
Moreover, in said general formula (7) and (8), R < ² > is as the said definition and can illustrate the same thing. X ¹ and X ² each independently represent a chlorine atom or a bromine atom, preferably a chlorine atom.
o is as defined above.

Specific examples of the phosphorus-containing compound represented by the general formula (5) include 2-diphenylphosphinyl-1,4-hydroquinone and the like, but are not particularly limited thereto. Specific examples of the phosphorus-containing compound represented by the general formula (6) include 2-diphenylphosphinyl-1,4-dihydroxynaphthalene, but are not particularly limited thereto.
Specific examples of the xylylene dihalide compound represented by the general formula (7) include, for example, α, α′-dichloro-o-xylene, α, α′-dichloro-m-xylene, α, α′- Examples include dichloro-p-xylene, but are not limited thereto.
Specific examples of the ethenyl group-containing benzyl halide compound represented by the general formula (8) include, for example, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, and the like. It is not limited to.

The production method for the compound of the present invention can utilize a known and usual etherification reaction as described in Patent Document 7 (Japanese Patent Laid-Open No. 9-31006).
Specifically, for example, the phosphorus-containing compound represented by the general formula (5) or (6) and the xylylene dihalide compound represented by the general formula (7) are reacted in a polar solvent in the presence of an alkali. Or, in the presence of an alkali and a phase transfer catalyst, the mixture is reacted in a mixed solution of an organic solvent and water, and then an ethenyl group-containing halide compound represented by the general formula (8) is preferably added together with a polymerization inhibitor. It can implement by the method of making it react.

Alkalis include alkoxides, hydrides or hydroxides of alkali metals or alkaline earth metals.
Examples of the alkali metal or alkaline earth metal alkoxide include sodium methoxide and sodium ethoxide. Examples of alkali metal or alkaline earth metal hydrides include sodium hydride and potassium hydride. Examples of the alkali metal or alkaline earth metal hydroxide include sodium hydroxide and potassium hydroxide.
The alkali species may be appropriately selected depending on whether the reaction system is non-aqueous or hydrous.
The use ratio of the alkali is preferably 1.1 to 3 equivalents relative to 1 equivalent of the halomethyl group of the xylylene dihalide compound represented by the general formula (7). If it is this range, reaction rate will not become remarkably slow, reaction will fully advance and a raw material will not remain, and it can prevent having a bad influence on the physical property of the hardened | cured material mentioned later. In addition, the amount of washing water or the like used for removing the remaining alkali is small.

As the phase transfer catalyst, various onium salts can be used, for example, quaternary ammonium compounds such as tetra-N-butylammonium bromide, tetra-N-butylammonium hydrogen sulfate, benzyltrimethylammonium chloride, tricaprylmethylammonium chloride; And quaternary phosphonium compounds such as tetra-N-butylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium chloride, and tetraphenylphosphonium bromide; and tertiary sulfonium compounds such as benzyltetramethylenesulfonium bromide. These may be used individually by 1 type and may use 2 or more types together.
The amount of the phase transfer catalyst may be appropriately selected depending on the type and reaction temperature, but is usually 0.01 to 0.5 with respect to 1 equivalent of the halomethyl group of the xylylene dihalide compound represented by the general formula (7). It is sufficient to use equivalent amounts.

  Examples of the organic solvent include dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, dioxane, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, 2-propanol, 1,3-dimethoxypropane, 1,2-dimethoxypropane, and tetramethylene. In addition to polar solvents such as sulfone, hexamethylphosphoamide, methyl ethyl ketone, methyl isobutyl ketone and acetone, cyclohexanone, methylcyclohexane, toluene, xylene and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

The reaction temperature and reaction time may be appropriately selected depending on the type of raw material to be used and the reaction conditions, but are usually within a range of 0.5 to 20 hours at 30 to 100 ° C. When the reaction temperature and reaction time are in this range, undesirable reactions such as side reactions do not occur at the same time, and the reaction time does not become unnecessarily long.
The use ratio of the xylylene dihalide compound represented by the general formula (7) is preferably 0.5 to 1.0 mol with respect to 1 mol of the phosphorus-containing compound represented by the general formula (5) or (6). More preferably, it is 0.6-0.8 mol. If it is this range, the residual amount of an unreacted raw material will decrease.
Moreover, the use ratio of the ethenyl group-containing benzyl halide compound represented by the general formula (8) is preferably 0.1 to 0.00 per mole of the phosphorus-containing compound represented by the general formula (5) or (6). 7 mol, more preferably 0.2 to 0.5 mol. If it is this range, the residual amount of an unreacted raw material will decrease.

The polymerizable phosphorus-containing (poly) xylylene aryl ether compound of the present invention thus obtained is mixed with a radically polymerizable thermosetting resin or the like to obtain a resin composition. Acts as a flame retardant.
That is, by heating the resin composition, radical polymerization of a phosphorus-containing (poly) xylylene aryl ether compound containing a polymerizable ethenyl group and a resin capable of radical polymerization occurs, so that the resin composition is cured. Is possible.
Thus, when the resin composition containing the polymerizable phosphorus-containing (poly) xylylene aryl ether compound of the present invention and a thermosetting resin capable of radical polymerization is heated, a polymerizable ethenyl group is formed in the resin skeleton. Since the phosphorus-containing (poly) xylylene aryl ether compound is incorporated by chemical bonding, the heat resistance is reduced like additive-type flame retardants, the glass transition temperature is lowered, and separately added flame retardants are bleed. The problem of being out is suppressed.

[Flame-retardant thermosetting resin composition]
The flame retardant thermosetting resin composition of the present invention comprises (a) the polymerizable phosphorus-containing (poly) xylylene aryl ether compound and (b) a radically polymerizable thermosetting resin, and if necessary (c ) A curing agent, (d) an additive, and (e) an organic solvent.

((A) component)
As the component (a), the polymerizable phosphorus-containing (poly) xylylene aryl ether compound represented by the above general formula (1) is used. The content ratio of the component (a) in the flame retardant thermosetting resin composition is preferably in the total of the components (a) and (b) from the viewpoint of sufficiently making the thermosetting resin composition flame retardant. Is adjusted so as to be 5 to 80% by mass, more preferably 20 to 50% by mass.

((B) component)
As the component (b), a thermosetting resin capable of radical polymerization is used.
As the thermosetting resin capable of radical curing, a commonly used one can be used, such as vinyl benzyl ether resin (for example, see JP-A-2001-181383), vinyl benzyl resin (for example, JP-A-2006). -63230), terminal unsaturated group-modified polyphenylene ether resins (for example, see JP-T-2006-516297) and the like, but are not limited thereto. Moreover, these may be used individually by 1 type and may use 2 or more types together.
The content ratio of the component (b) in the flame-retardant thermosetting resin composition is preferably in the total of the components (a) and (b) from the viewpoint of sufficiently curing the thermosetting resin resin composition. It adjusts so that it may exist 20-95 mass%, More preferably, 50-80 mass%.

(Component (c))
The flame retardant thermosetting resin composition of the present invention preferably contains a curing agent.
As a hardening | curing agent, what is generally used in radical polymerization can be used, For example, a peroxyester compound, a diacyl peroxide compound, a dialkyl peroxide compound, a hydroperoxide compound, a ketone peroxide compound, etc. are mentioned.
Examples of the peroxyester compound include t-butyl peroxy 2-ethylhesanoate, t-butyl peroxybenzoate, and the like.
Examples of the diacyl peroxide compound include benzoyl peroxide, m-toluyl and benzoyl peroxide.
Examples of the dialkyl peroxide compound include dicumyl peroxide and t-butyl peroxide.
Examples of the hydroperoxide compound include cumene hydroperoxide.
Examples of the ketone peroxide compound include methyl ethyl ketone peroxide.
These may be used individually by 1 type and may use 2 or more types together.
When the component (c) is contained in the flame-retardant thermosetting resin composition of the present invention, the content thereof is usually preferably 0.00 with respect to a total of 100 parts by mass of the components (a) and (b). It is 01-10 mass parts, More preferably, it is 0.1-5 mass parts.

(Component (d))
The flame retardant thermosetting resin composition of the present invention includes various flame retardants, fillers, coupling agents, lubricants, mold release agents, plasticizers, colorants, thickeners, and the like as necessary. Additives may be added.
Examples of other flame retardants include metal hydroxides such as aluminum hydroxide, and phosphorus-containing compounds such as phosphate esters and phosphazenes. The flame retardant thermosetting resin composition of the present invention includes component (d). When it is contained, the content is usually preferably 5 to 150 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass in total of the components (a) and (b).

((E) component)
The flame retardant thermosetting resin composition of the present invention may contain an organic solvent as necessary. Examples of the organic solvent include alcohols such as methoxypropanol; ketones such as methyl ethyl ketone; cyclic ethers such as dioxane and dioxolane; amides such as dimethylacetamide; aromatic hydrocarbons such as toluene.
When the flame retardant thermosetting resin composition of the present invention contains the component (e), the content thereof is usually preferably 10 to 10 parts by mass with respect to a total of 100 parts by mass of the components (a) and (b). 90 mass parts, More preferably, it is 40-80 mass parts, More preferably, it is 50-70 mass parts.

The flame retardant thermosetting resin composition of the present invention may be used by impregnating a reinforcing fiber base material when forming a laminate to be described later. Examples of the reinforcing fiber substrate include, but are not limited to, carbon fiber, glass fiber, aramid fiber, polyester fiber, nylon fiber, and silicon carbide fiber.
When impregnating the reinforcing fiber base material with the flame retardant thermosetting resin composition, the reinforcing fiber base material is preferably 5 to 500 parts by mass with respect to 100 parts by mass of the flame retardant thermosetting resin composition, More preferably, the amount is 10 to 300 parts by mass.

[Hardened product, laminate]
The flame retardant thermosetting resin composition of the present invention prepared as described above is cured by applying heat under the following conditions to obtain a cured product.
The curing temperature and the curing time are usually preferably 140 to 240 ° C. for 30 to 180 minutes, more preferably 160 to 220 ° C. for 60 to 120 minutes. If it is this range, hardening can fully be advanced and it can suppress that the physical property of hardened | cured material falls by heat deterioration.

A known method can be used as a molding method for obtaining a cured product by subjecting the flame-retardant thermosetting resin composition of the present invention to a heat reaction.
Examples of the molding method include a melt casting method, a compression molding method in which heat is applied by a compression molding machine, a transfer molding method in which a plasticized molding material is press-fitted into a heated mold cavity, and several prepregs are formed. Lamination molding method to obtain a laminate by superposing and curing by heating and pressing; Matched die molding method in which preform is impregnated with resin and compression molding; SMC method; BMC method; Die after impregnating resin in unidirectional fiber Examples thereof include a pultrusion method in which the resin is impregnated; a filament winding method in which a roving impregnated with a resin is wound around a core material; and a RIM method.

The flame retardant thermosetting resin composition of the present invention is excellent in flame retardancy and heat resistance as compared with a resin composition using a conventional flame retardant and flame retardant technology and a cured product obtained therefrom.
Due to this excellent characteristic, the flame retardant thermosetting resin composition of the present invention is suitably used for electronic materials such as laminates for electronic boards (printed wiring boards), semiconductor sealing materials and printed circuit boards. Can do.

The present invention also provides a laminate obtained by pressure-molding the flame retardant thermosetting resin composition of the present invention under heating. Since the flame retardant thermosetting resin composition of the present invention is excellent in adhesiveness with a metal foil, the laminated plate can be provided with a metal foil or the like on one side or both sides. This laminated board is suitably used as a printed wiring board substrate or the like.
Although it will not specifically limit if it is a metal used normally as metal foil, For example, aluminum, copper, nickel, or these alloys are mentioned. Among these, from the viewpoint of physical and electrical performance, a copper foil and an alloy foil containing copper as a main component are preferable.
The method for providing the metal foil on one side or both sides of the laminate is not particularly limited. For example, the reinforcing fiber base material is impregnated with a flame retardant thermosetting resin composition, and the component (e) After drying the solvent, it is preheated at about 100 to 180 ° C., a metal foil or the like is attached to one or both sides, and further heat-molded at about 180 to 230 ° C. under a pressure of about 1 to 5 MPa. Preferably mentioned.

  Furthermore, the flame-retardant thermosetting resin composition of the present invention can be applied not only to electronic materials but also to automobile parts, OA equipment parts, and the like.

  EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Example 1 (Production of polymerizable phosphorus-containing polyparaxylylene aryl ether compound (a-1))
By reacting 158.2 g (1.0 mol) of 1,4-naphthoquinone and 202 g (1.0 mol) of diphenylphosphine oxide in toluene for 3 hours under reflux, the crystal was separated by filtration to give 2-diphenylphosphini. 295 g of ru-1,4-dihydroxynaphthalene (yield 82%) was obtained.
180 g (0.5 mol) of 2-diphenylphosphinyl-1,4-dihydroxynaphthalene obtained, 70 g (0.4 mol) of α, α′-dichloro-p-xylene and 33.9 g of tetrabutylphosphonium bromide ( 0.1 mol) was dissolved in 660 g of methyl ethyl ketone and warmed to 75 ° C. After heating to 75 ° C., 45 g (1.125 mol) of sodium hydroxide and 33 g of distilled water were added and reacted for 6 hours. Next, after cooling to 70 ° C., 53.4 g of CMS-P (Chloromethylstyrene m- / p-ratio 50/50, 0.35 mol, manufactured by Seimi Chemical Co., Ltd.) and 0.33 g (0.1 phr) of phenothiazine were added. . Reaction was performed at 70 degreeC for 4 hours.
After completion of the reaction, the reaction mixture was cooled to room temperature, and neutralized by adding 8.8 g (0.09 mol) of phosphoric acid and 165 g of distilled water. After standing, the lower layer was removed after separating into two layers. Furthermore, 330 g of distilled water was added and the action of removing the lower layer after stirring and standing was performed twice.
Finally, the solvent was distilled off under reduced pressure to obtain a phosphorus-containing polyparaxylylene aryl ether compound (a-1) having an ethenyl group having the following physical properties and having the following structure.

Elemental analysis: phosphorus element content 5.1% (theoretical value 5.7%)
Number average molecular weight: 1820, weight average molecular weight: 5640
¹ H-NMR (300 MHz, DMSO-d, TMS, ppm) δ: 4.7 (0.9H), 5.1 (3.0H), 5.3 (0.7H), 5.8 (0. 6H), 6.6 (0.7H), 7.0-8.3 (20.6H)
Infrared absorption spectrum (cm ⁻¹ ): 3055, 1620, 1587, 1512, 1483, 1448, 1437, 1385, 1385, 1352, 1329, 1264, 1233, 1180, 1160, 1095, 1080, 1026, 988, 918, 862, 825, 770, 750, 723

Example 2 (Production of polymerizable phosphorus-containing polymetaxylylene aryl ether compound (a-2))
By reacting 158.2 g (1.0 mol) of 1,4-naphthoquinone and 202 g (1.0 mol) of diphenylphosphine oxide in toluene for 3 hours under reflux, the crystals were separated by filtration to give 2-diphenylphosphine. 295 g (82% yield) of finyl-1,4-dihydroxynaphthalene was obtained.
180 g (0.5 mol) of 2-diphenylphosphinyl-1,4-dihydroxynaphthalene obtained, 70 g (0.4 mol) of α, α′-dichloro-m-xylene and 33.9 g of tetrabutylphosphonium bromide ( 0.1 mol) was dissolved in 660 g of methyl ethyl ketone and warmed to 75 ° C. After heating to 75 ° C., 45 g (1.125 mol) of sodium hydroxide and 33 g of distilled water were added and reacted for 6 hours. Next, after cooling to 70 ° C., 53.4 g of “CMS-P” (chloromethylstyrene m- / p-ratio 50/50, 0.35 mol, manufactured by Seimi Chemical Co., Ltd.), 0.33 g (0.1 phr) of phenothiazine was added. Added. Reaction was performed at 70 degreeC for 4 hours.
After completion of the reaction, the reaction mixture was cooled to room temperature, and neutralized by adding 8.8 g (0.09 mol) of phosphoric acid and 165 g of distilled water. After standing, the lower layer was removed after separating into two layers. Furthermore, 330 g of distilled water was added, and the operation of removing the lower layer after stirring and standing was performed twice.
Finally, the solvent was distilled off under reduced pressure to obtain a phosphorus-containing polymetaxylylene aryl ether compound (a-2) containing an ethenyl group having the following physical properties and having the following structure.

Elemental analysis: phosphorus element content 5.2% (theoretical value 5.7%)
Number average molecular weight: 1910, weight average molecular weight: 5820
¹ H-NMR (300 MHz, DMSO-d, TMS, ppm) δ: 4.6 (0.8H), 5.0 (2.7H), 5.3 (0.6H), 5.8 (0. 6H), 6.6 (0.6H), 7.0-8.2 (20.6H)
Infrared absorption spectrum (cm ⁻¹ ): 3054, 1587, 1484, 1434, 1385, 1351, 1329, 1264, 1232, 1189, 1161, 1080, 1027, 990, 910, 863, 828, 771, 749, 723

Example 3 (Production of polymerizable phosphorus-containing polyparaxylylene aryl ether compound (a-3))
By reacting 108.1 g (1.0 mol) of 1,4-benzoquinone and 202 g (1.0 mol) of diphenylphosphine oxide in toluene for 3 hours under reflux, the crystals were separated by filtration to give 2-diphenylphosphini. 223 g of ru-1,4-hydroquinone (yield 72%) was obtained.
155 g (0.5 mol) of 2-diphenylphosphinyl-1,4-hydroquinone obtained, 70 g (0.4 mol) of α, α′-dichloro-p-xylene and 33.9 g of tetrabutylphosphonium bromide (0 0.1 mol) was dissolved in 600 g of methyl ethyl ketone and warmed to 75 ° C. After heating to 75 ° C., 45 g (1.125 mol) of sodium hydroxide and 33 g of distilled water were added and reacted for 6 hours. Next, after cooling to 70 ° C., 53.4 g of “CMS-P” (chloromethylstyrene m- / p-ratio 50/50, 0.35 mol, manufactured by Seimi Chemical Co., Ltd.), 0.33 g (0.1 phr) of phenothiazine was added. Added. Reaction was performed at 70 degreeC for 4 hours.
After completion of the reaction, the reaction mixture was cooled to room temperature, and neutralized by adding 8.8 g (0.09 mol) of phosphoric acid and 150 g of distilled water. After standing, the lower layer was removed after separating into two layers. Further, 300 g of distilled water was added, and the action of removing the lower layer after stirring and standing was performed twice.
Finally, the solvent was distilled off under reduced pressure to obtain a polymerizable phosphorus-containing polyparaxylylene aryl ether compound (a-3) having the following properties and having the following structure.

Elemental analysis: phosphorus element content 6.0% (theoretical value 6.3%)
Number average molecular weight: 1620, weight average molecular weight: 5370
¹ H-NMR (300 MHz, DMSO-d, TMS, ppm) δ: 4.9 (1.7 H), 5.1 (1.7 H), 5.3 (0.7 H), 5.8 (0. 6H), 6.6 (0.7H), 6.8 to 7.6 (18.6H)
Infrared absorption spectrum (cm ⁻¹ ): 3056, 1638, 1576, 1482, 1463, 1436, 1399, 1375, 1272, 1206, 1180, 1118, 1103, 1064, 997, 907, 811, 749, 728

Reference Example 1 (Production of phosphorus-containing epoxy compound (f-1))
2-Diphenylphosphinyl-1 was obtained by reacting 108 g (1.0 mol) of 1,4-benzoquinone and 202 g (1.0 mol) of diphenylphosphine oxide in toluene for 3 hours under reflux, and separating the crystals by filtration. , 4-hydroquinone 223 g (yield 72%) was obtained.
155 g (0.5 mol) of 2-diphenylphosphinyl-1,4-hydroquinone obtained, 340 g (2 equivalents) of bisphenol F type epoxy resin “YDF-170” (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 170) and 0.75 g of tetradecyldimethylbenzylammonium chloride was dissolved in 100 g of γ-butyrolactone, heated to 150 ° C., reacted for 3 hours, and then cooled to obtain a phosphorus-containing epoxy compound (f-1). The epoxy equivalent of the obtained compound (f-1) was 643.

Examples 4 to 6 and Comparative Examples 1 to 4 (thermosetting resin composition)
With the formulation shown in Table 1, each component was dissolved in a solvent by the following method to prepare a varnish. Furthermore, it hardened on the following conditions, and produced the double-sided copper clad laminated board and the shaping | molding board. Flame retardancy (UL) was measured using a laminate, and tests of Tg (DMA method, TMA method), linear expansion coefficient, and electrical property (dielectric property) were performed using a molded plate. The evaluation results are shown in Table 1.

Below, each component used in Examples 4-6 and Comparative Examples 1-4 is demonstrated easily.
<Phosphorus-containing compound>
(I) Component (a) Polymerizable phosphorus-containing polyxylylene aryl ether compounds (a-1) to (a-3) obtained in Examples 1 to 3 above.
(Ii) Component (f) Phosphorus-containing epoxy compound (f-1) obtained in Reference Example 1 above
(Iii) (d) component cyclophosphazene oligomer “SPE-100” (Otsuka Chemical Co., Ltd., phosphorus atom content 13.0% by mass)
Phosphate ester: 1,3-phenylenebisdixylenyl phosphate (“PX-200” (manufactured by Daihachi Chemical Co., Ltd., phosphorus atom content: 9.0% by mass))
<Vinyl benzyl resin>
(B) Component fluorene type vinyl benzyl resin “V-5000X” (manufactured by Showa Polymer Co., Ltd.)
<Epoxy resin>
(G) Component Cresol novolac type epoxy resin “EPICLON N-680” (manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent = 208 g / equivalent)
<Phenolic resin>
(H) Component Cresol novolak type phenol resin “Shonol CRG-951” (manufactured by Showa Polymer Co., Ltd., hydroxyl group equivalent = 118 g / equivalent)
<Curing agent>
(C) Component 2,5-dimethyl-2,5-di (t-butylperoxy) hexane “Perhexa 25B” (peroxide manufactured by NOF Corporation)
<Curing accelerator>
(I) Component 2-ethyl-4-methylimidazole “Curazole 2E4MZ” (manufactured by Shikoku Kasei Co., Ltd.)
<Solvent>
(E) Component Toluene, methoxypropanol

[Preparation of varnish]
The mixing ratio shown in Table 1 for each component ((a) component, (b) component, (d) component, and (f) component to (h) component) shown in Table 1 other than the curing accelerator and the solvent in advance. In a mixed solvent of toluene and methoxypropanol (component (e)), the curing agent (component (c)) and curing accelerator (component (i)) shown in Table 1 were added, and the non-volatile content (N V.) varnishes (flame retardant thermosetting resin compositions A to G) having a mass of 60% by mass were prepared.

[Production of laminates]
After impregnating the varnishes prepared in Examples 4 to 6 or Comparative Examples 1 to 4 with a glass cloth “WE18K105” (manufactured by Nitto Boseki Co., Ltd.) having a thickness of about 180 μm, the solvent was dried.
Next, preheating was performed at 120 ° C. for 3 minutes and then at 160 ° C. for 3 minutes to prepare a prepreg. Four prepregs were bonded together, and further laminated by heating under a pressure of 3.92 MPa at 200 ° C. for 60 minutes. The obtained laminated board had a thickness of about 0.8 mm and a resin content of about 40% by mass.

[Production of molded plate]
The resin varnish was obtained by drying the varnish prepared in Examples 4-6 or Comparative Examples 1-4 under reduced pressure (1.33 × 10 ⁻³ MPa) at 90 ° C. for 30 minutes. The obtained resin solid was heat-molded under pressure (1.0 MPa) at 200 ° C. for 60 minutes to produce a molded plate.

[Physical property test items and measurement conditions]
Among the measurement items below, (1) to (5) are the compounds obtained in Examples 1 to 3 or Reference Example 1, and (6) is the above laminate and (7) to (9 ) Was measured using the molded plate.

(1) Elemental analysis: After the sample was decomposed with sulfuric acid and nitric acid, the phosphorus content was measured using the ICP emission method. The phosphorus atom content (%) was determined by dividing the phosphorus content by the mass of the flame retardant thermosetting resin composition.
(2) Molecular weight: Measured using gel permeation chromatography. For measurement, "Shodex GPC System-21" (columns KF-802, KF-803, KF-805) manufactured by Showa Denko Co., Ltd. was used, and the measurement conditions were column temperature 40 ° C, eluent tetrahydrofuran, elution rate. 1 ml / min. It was expressed in terms of standard polystyrene equivalent molecular weight (Mw).
(3) ¹ H-nuclear magnetic resonance spectrum ( ¹ H-NMR): Measured using “JNM-LA300” manufactured by JEOL Ltd. with tetramethylsilane as an internal standard substance.
(4) IR spectrum: Measured using a Fourier transform infrared spectrophotometer “Spectrum One” manufactured by PerkinElmer.
(5) Epoxy equivalent: Measured according to JIS-K7236.

(6) Flame retardancy: measured in accordance with UL-94 vertical combustion test.

(7) Glass transition temperature (Tg): Measured by DMA method (temperature rising speed 3 ° C./min) and TMA method (temperature rising speed 10 ° C./min) and used as an index of heat resistance. In the DMA method, measurement was performed using “RTM-1T” manufactured by Orientec Co., Ltd., and in the TMA method, “TAS200” manufactured by Rigaku Corporation.
(8) Linear expansion coefficient: Measured by the TMA method (temperature increase speed 10 ° C./min) and used as an index of heat resistance. For measurement, “TAS200” manufactured by Rigaku Corporation was used.
(9) Dielectric constant and dielectric loss tangent: Measured by using cavity resonance perturbation method using 1.5 mm × 1.5 mm × 75 mm prismatic test piece using “Network Analyzer 8753ES” manufactured by Agilent Technologies (application) The frequency is 1 GHz).

From the evaluation results in Table 1, the laminate obtained by heat curing from the flame retardant thermosetting resin composition containing the polymerizable phosphorus-containing polyxylylene aryl ether compound of the present invention exhibits high flame retardancy. At the same time, it is clear that both heat resistance and electrical characteristics (dielectric constant, dielectric loss tangent) are excellent.
In addition, in the system which does not contain phosphorus element in the composition as in Comparative Example 1, it is natural that flame retardancy cannot be obtained. As in Comparative Example 2, in a system using a compound in which a phosphorus atom is incorporated in an epoxy compound without using the component (a) as a flame retardant, the electrical characteristics (dielectric constant, dielectric loss tangent) are inferior. . As in Comparative Examples 3 and 4, in the system using the additive-type phosphorus-containing compound as a flame retardant without using the component (a), the flame resistance is imparted, but the heat resistance is reduced, There is a concern about bleed-out during long-term storage and use.

  The flame retardant thermosetting resin composition containing the polymerizable phosphorus-containing (poly) xylylene aryl ether compound of the present invention is suitably used in the field of electronic materials as a semiconductor sealant, a laminate, a coating material, a composite material, and the like. used. Moreover, it is used suitably also as a motor vehicle part, OA equipment part, etc.

Claims (7)

A polymerizable phosphorus-containing (poly) xylylene aryl ether compound represented by the following general formula (1).

(In the formula, R ¹ is a group represented by the following general formula (2), W is a group represented by the following general formula (3) or (4). R ² has 1 to 6 carbon atoms. An alkyl group or a substituted or unsubstituted aryl group having 6 to 10 ring carbon atoms, o represents an integer of 0 to 4, and n represents a number of 1 or more.)

(In the formula, R ³ and R ⁴ each independently represent an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 ring carbon atoms. P and q are each independently selected. And represents an integer of 0 to 5.)

(Wherein R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 10 ring carbon atoms. R is an integer of 0 to 3) And s represents an integer of 0 to 5.)   The polymerizable phosphorus-containing (poly) xylylene aryl ether according to claim 1, wherein o, p, q, r and s in the general formulas (1), (2), (3) and (4) are all 0. Compound. The following general formula (5) or (6)

(Wherein R ^{3 to} R ⁶ , p, q, r and s are as defined above.)
A phosphorus-containing compound having two phenolic hydroxyl groups represented by the following general formulas (7) and (8):

(In the formula, R ² is as defined above. X ¹ and X ² each independently represents a chlorine atom or a bromine atom. O is as defined above.)
Or a benzyl halide compound containing an ethenyl group in a polar solvent in the presence of an alkali or in a mixture of an organic solvent and water in the presence of an alkali and a phase transfer catalyst. The manufacturing method of the said polymeric phosphorus containing (poly) xylylene aryl ether compound which has the process made to react.   A flame retardant thermosetting resin composition comprising the polymerizable phosphorus-containing (poly) xylylene aryl ether compound according to claim 1 or 2 and a thermosetting resin having radical polymerizability.   Hardened | cured material formed by heat-hardening the flame-retardant thermosetting resin composition of Claim 4.   The laminated board formed by pressure-molding the flame-retardant thermosetting resin composition of Claim 4 under heating, and laminating | stacking metal foil.   The laminated board according to claim 6 which has metal foil on one side or both sides.