JPWO2006051731A1 - Epoxy resin composition - Google Patents

Abstract

Provided is a novel epoxy resin composition capable of exhibiting an extremely high flame retardant effect without containing a flame retardant having atoms such as halogen and phosphorus. Epoxy resin (A), curing agent (B), curing accelerator (C), inorganic filler (D), metal hydrate (E), and average composition formula (1) R1mR2nSiO (4-mn) / 2 ( 1) (wherein the carbon directly bonded to the R1 silicon atom represents a group selected from the group consisting of aliphatic carbon, hydroxyl group and alkoxy group, R2 represents an aromatic hydrocarbon group having 6 to 24 carbon atoms; R1; , R2 may be present in two or more, and m and n represent numbers satisfying 1.1 ≦ m + n ≦ 1.7 and 0.4 ≦ n / m ≦ 2.5. It is obtained by the composition containing the silicone compound (F) represented.

Description

  The present invention relates to a highly flame-retardant epoxy resin composition which does not contain atoms such as halogen and phosphorus.

  Epoxy resin molding materials have a good balance of physical properties such as adhesive strength, dimensional stability, chemical resistance, and moisture resistance in addition to thermal and electrical properties such as excellent heat resistance and insulation. Widely used in electronic parts materials such as materials and printed wiring board materials.

  Semiconductor encapsulated molding materials and printed wiring board materials must be used for applications that require a high degree of flame resistance for fire safety and that meet V-0 of the UL Standard (U.S. Underwriters Laboratory Standard). Therefore, various flame retardants are blended so as to be able to perform (see, for example, Non-Patent Document 1).

  Conventionally used as flame retardants for epoxy resin molding materials are halogen flame retardants typified by brominated epoxy resins, and halogen flame retardants and antimony flame retardants such as antimony trioxide. Has been widely practiced since. However, in recent years, flame retardants that replace halogenated compounds and antimony compounds have been demanded from the viewpoint of environmental impact.

  As an alternative to the halogen-based flame retardant, there is a method using a phosphorus compound. However, the phosphorus compound has a high hygroscopicity, and there is a problem that electrical characteristics are lowered by hydrolysis.

  As a method of making flame retardant without using halogen-based or phosphorus-based flame retardants, the use of metal hydrates is generally considered, but in order to satisfy high flame retardancy, it is necessary to add a large amount, There existed a subject that workability | operativity, a moldability, and the workability of hardened | cured material were inferior.

As another method for flame-retarding an epoxy resin molding material without using a halogen-based or phosphorus-based flame retardant, a method using a silicone compound has been reported. For example, a polycarbonate resin and a specific structure of an epoxy resin composition are reported. Although a method of adding an organopolysiloxane is disclosed (for example, refer to Patent Document 1), in this case, since a thermoplastic resin is blended with an epoxy resin that is a thermosetting resin, blending and molding conditions are complicated. There is a problem. Furthermore, a technique has been reported in which a silicone compound is added to a resin composition obtained by adding a specially modified phenolic resin and a benzoxazine compound to an epoxy resin composition to improve flame retardancy (see, for example, Patent Document 2). The compounded resin composition is special and further general-purpose technology is required.
Epoxy resin technical association published review epoxy resin JP2003-165897 JP2004-27000

  In view of the above situation, the present invention is to provide a highly flame-retardant epoxy resin composition that does not contain halogen or phosphorus atoms.

  The present inventor has paid attention to the flame retardant effect of metal hydrate, and as a result of earnestly examining a method for achieving flame retardant with a small amount of a compounding system that does not deteriorate moldability and workability, it is combined with a silicone compound having a specific structure. As a result, it was found that excellent flame retardancy was obtained, and the present invention was completed.

That is, the present invention includes an epoxy resin (A), a curing agent (B), a curing accelerator (C), an inorganic filler (D), a metal hydrate (E), and an average composition formula (1).
R ¹ _m R ² _n SiO _{(4-mn) / 2} (1)
(In the formula, R ¹ represents a group selected from a group in which carbon directly bonded to a silicon atom is an aliphatic carbon, a hydroxyl group, and an alkoxy group, and R ² represents an aromatic hydrocarbon group having 6 to 24 carbon atoms. Two or more types of R ¹ and R ² may exist, and m and n represent numbers satisfying 1.1 ≦ m + n ≦ 1.7 and 0.4 ≦ n / m ≦ 2.5. It is related with the epoxy resin composition characterized by containing the silicone compound (F) represented by this.

A preferred embodiment is a hydrocarbon group in which R ¹ of the silicone compound of component (F) has one or more reactive groups selected from an epoxy group, a hydroxyl group, an alkoxy group, an amino group, a carboxy group, and a carboxylic anhydride group. It is related with the said epoxy resin composition characterized by the above-mentioned.

A preferred embodiment relates to the epoxy resin composition according to any one of the above, wherein the SiO ₂ unit is contained in an amount of 10 mol% or more of all siloxane units constituting the silicone compound of the component (F).

  A preferred embodiment relates to the epoxy resin composition according to any one of the above, wherein the metal hydrate (E) is surface-treated with a surface treatment agent selected from an aluminum compound and a silicon compound.

  The epoxy resin composition of the present invention exhibits extremely excellent flame retardancy without using generally used flame retardants such as chlorine, bromine, phosphorus, and the like, and the characteristics inherent to the resin are rarely impaired. Such an epoxy resin composition is very useful industrially.

  The present invention is described in detail below.

The epoxy resin (A) used in the present invention is one generally used which has at least two epoxy groups in one molecule and reacts with a curing agent to form a crosslinked network structure. No. For example, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, phenol resin including epoxy resin having triphenylmethane skeleton, phenols such as cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F and / or α -Epoxy novolak resin obtained by condensation or cocondensation of naphthols such as naphthol, β-naphthol, dihydroxynaphthalene and the like and compounds having aldehyde groups such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc. in the presence of an acidic catalyst. The one that became.
Also, diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, bisphenol A / D, biphenyl type epoxy resins that are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols, phenols and / or naphthols and dimethoxyparaxylene or Epoxidized phenol / aralkyl resin synthesized from bis (methoxymethyl) biphenyl, stilbene type epoxy resin, hydroquinone type epoxy resin, glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid with epichlorohydrin Glycidylamine type epoxy resin obtained by reaction of polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin.
Also, dicyclopentadiene type epoxy resin, epoxide of co-condensation resin of dicyclopentadiene and phenols, epoxy resin having naphthalene ring, triphenolmethane type epoxy resin, trimethylolpropane type epoxy resin, terpene modified epoxy resin , Linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid, alicyclic epoxy resins, and these epoxy resins with silicone, acrylonitrile, butadiene, isoprene rubber, polyamide resin, etc. Examples thereof include modified epoxy resins.

  These epoxy resins may be used alone or in combination of two or more.

  As the curing agent (B) used in the present invention, those generally used as a curing agent for epoxy resins, such as phenol compounds, amine compounds, acid anhydrides, etc., are generally applied and are not particularly limited. A phenol resin having two or more hydroxyl groups can be preferably used. Specific examples of phenolic resins include novolak-type phenolic resins such as phenol novolac resins and cresol novolak resins, resol-type phenolic resins, phenolaralkyl resins, triphenolmethane-type resins, and triphenolpropane-type resins. Examples thereof include bisphenol type phenol resins such as resins and polymers thereof, naphthalene ring-containing phenol resins, dicyclopentadiene-modified phenol resins, bisphenol F type resins, bisphenol A type resins, and the like. Or 2 or more types can be mixed and used.

  There is no restriction | limiting in particular as a hardening accelerator (C) used for this invention, It is using the hardening accelerator generally used for epoxy resin molding materials, such as a phosphorus compound type hardening accelerator and a nitrogen compound type hardening accelerator. it can. Examples of the phosphorus compound curing accelerator include trialkylphosphine such as trimethylphosphine, triethylphosphine, tripropylphosphine, and tributylphosphine, dialkylarylphosphine such as dimethylphenylphosphine, alkyldiarylphosphine such as diphenylphosphine and methyldiphenylphosphine, Tris (alkylphenyl) phosphine such as triphenylphosphine, tris (4-methylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) Phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tri Organic phosphines such as (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, diphenylphosphine, diphenyl (p-tolyl) phosphine, tetrabutylphosphonium tetraphenylborate, butyltriphenylphosphonium tetraphenylborate, tetraphenylphosphoniumtetrabutyl Examples thereof include phosphonium borates such as borate, tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate, and complexes of organic phosphines and organic borons.

  Of these, tributylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tetrabutyltetrabutylphosphonium tetraphenylborate, and tetraphenylphosphonium tetraphenylborate are preferable.

  Examples of the nitrogen compound-based curing accelerator include 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5, 5,6-dibutylamino- Cycloamidine compounds such as 1,8-diazabicyclo [5.4.0] undecene-7 and their derivatives, tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol And derivatives thereof, triethylammonium tetraphenylborate, 1,8-diazabicyclo [5.4.0] -7-undecenium tetraphenylborate and the like, among which 1,8-diazabicyclo [5.4. 0] undecene-7 and 1,5-diazabicyclo [4.3.0] nonene-5 Masui.

  The inorganic filler (D) used in the present invention is blended for hygroscopicity, linear expansion coefficient reduction, thermal conductivity improvement and strength improvement, and is generally used for epoxy resin molding materials and is particularly limited. For example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, Examples thereof include powders such as spinel, mullite, and titania, beads formed by spheroidizing these, and glass fibers. The inorganic filler is preferably surface-treated with a silane coupling agent, a titanate coupling agent or the like in order to enhance the adhesion with the resin component, or such a coupling agent is preferably added at the time of blending the epoxy resin composition. Specific examples of such a coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Of aminosilanes such as epoxy silane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptotrimethoxysilane And silane coupling agents such as mercaptosilane.

  Examples of the metal hydrate (E) used in the present invention include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide. These metal hydrates may be blended as a mixture of two or more. Further, magnesium hydroxide is particularly preferable from the decomposition temperature for the recent lead-free soldering. Moreover, the surface-treated thing is preferable for the affinity improvement with resin, prevention of the fall of the mechanical characteristic of a resin composition, improvement of water resistance, acid resistance, etc. That is, the metal hydrate (E) is preferably surface-treated with a surface treatment agent selected from an aluminum compound and a silicon compound. Examples of the aluminum compound include inorganic materials such as alumina, aluminum coupling agents, and the like. Examples of the silicon compound include inorganic substances such as silica and silane coupling agents such as epoxy silane. As other surface treatment agents, titanium compounds such as titanium oxide and titanate coupling agents, higher fatty acids such as stearic acid, oxalate anions and the like may be selected, and two or more of these may be used in combination.

The silicone compound (F) used in the present invention comprises an aromatic group-containing organosiloxane compound, and is composed of Q unit (SiO ₂ ), T unit (RSiO _1.5 ), D unit (R ₂ SiO), and M unit (R ₃ SiO _0.5). ) R ¹ _m R ² _n SiO _{(4-mn) / 2} (1) produced using a compound composed of any combination of the four types of structural units
(In the formula, R ¹ represents a group selected from a group in which carbon directly bonded to a silicon atom is an aliphatic carbon, a hydroxyl group, and an alkoxy group, and R ² represents an aromatic hydrocarbon group having 6 to 24 carbon atoms. Two or more types of R ¹ and R ² may exist, and m and n represent numbers satisfying 1.1 ≦ m + n ≦ 1.7 and 0.4 ≦ n / m ≦ 2.5. .) Is a silicone compound represented by an average composition formula.

The aromatic group-containing organosiloxane compound represented by the average composition formula (1) has a group R ¹ and a carbon number selected from a group in which carbon directly bonded to a silicon atom is an aliphatic carbon, a hydroxyl group, and an alkoxy group in the molecule. Having both 6 to 24 aromatic hydrocarbon groups R ² , that the number of moles m + n of all substituents on these silicon atoms is in the range 1.1 ≦ m + n ≦ 1.7, and directly connected to the silicon atom The molar ratio n / m of R ¹ selected from a group in which the carbon to be aliphatic is an aliphatic carbon, a hydroxyl group, and an alkoxy group and an aromatic hydrocarbon group R ² having 6 to 24 carbon atoms is 0.4 ≦ n / m ≦ It is in the range of 2.5. In addition, each element and the ratio of m and n can be calculated using NMR of hydrogen, carbon, and silicon.

The group R ¹ in which the carbon directly bonded to the silicon atom is an aliphatic carbon is a saturated aliphatic hydrocarbon group, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group. , T-butyl group, and the like. Among these, a methyl group and an ethyl group are preferable because of their excellent flame retarding effect, and a methyl group is more preferable. When the number of carbon atoms of the saturated aliphatic hydrocarbon group is 5 or more, the flame retardancy of the aromatic group-containing organosiloxane compound itself is lowered, so the flame retarding effect is lowered.

Furthermore, examples of the alkoxy group selected as R ¹ include a methoxy group, an ethoxy group, and an isopropoxy group. Among these, a methoxy group is preferable from the viewpoint of availability of raw materials.

Further, by introducing a reactive group capable of bonding with an epoxy resin or a curing agent into the silicone compound, the silicone compound is more uniformly dispersed in the cured epoxy resin, and the flame retardancy is excellent. That is, R ¹ of the silicone compound of component (F) is a hydrocarbon group having one or more reactive groups selected from an epoxy group, a hydroxyl group, an alkoxy group, an amino group, a carboxy group, and a carboxylic anhydride group. Is preferred. In order to introduce these reactive groups into the silicone compound, a polymerizable monomer having the reactive group-substituted hydrocarbon group as a substituent on the silicon atom is used, or a SiH group is introduced into the silicone compound. After the introduction, it can be achieved by a method such as reacting a carbon-carbon unsaturated compound by a hydrosilylation reaction. These methods are not particularly limited.

The aromatic hydrocarbon group R ² having 6 to 24 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a naphthyl group, and an anthracenyl group. Among these, an aromatic group having no substituent on the aromatic ring is preferable because of its excellent flame retardant effect, and a phenyl group is more preferable. The plurality of R ² may be all the same or different groups may be mixed.

The number of moles m + n of all substituents on the silicon atom is in the range 1.1 ≦ m + n ≦ 1.7. The value of m + n is preferably in the range of 1.15 ≦ m + n ≦ 1.65, more preferably 1.18 ≦ m + n ≦ 1.6, and even more preferably 1.20 ≦ m + n ≦ 1.55. Even if the value of m + n is less than 1.1 or above 1.7, the flame retardant effect of the aromatic group-containing organosiloxane compound is lowered, which is not preferable. Construction of the structure in the above range can be achieved by introducing T units and / or Q units into the skeleton of the organosiloxane compound. In general, the above range is easily achieved as the amount of introduction of these units increases. it can. In particular, when the introduction amount of the Q unit is large, the compatibility with the inorganic filler which is the component (D) of the present invention is improved and the flame retardancy is improved. That is, it is preferable to contain 10 mol% or more of SiO ₂ units among all siloxane units constituting the silicone compound of component (F). The content of SiO ₂ units is more preferably 20 mol% or more, and most preferably 30 mol% or more.

The molar ratio n / m of the group R ¹ selected from a group in which carbon directly bonded to a silicon atom is an aliphatic carbon, a hydroxyl group, and an alkoxy group and an aromatic hydrocarbon group R ² having 6 to 24 carbon atoms is 0.00. It is within the range of 4 ≦ n / m ≦ 2.5. When n / m is less than 0.4, the aromatic group is reduced in the molecule, so the heat resistance of the aromatic group-containing organosiloxane compound is lowered and the flame retardancy effect of the aromatic group-containing organosiloxane compound is lowered. Cause. On the other hand, even if n / m is 2.5 or more, the flame retardant effect of the aromatic group-containing organosiloxane compound is reduced. The value of n / m is preferably 0.43 ≦ n / m ≦ 2.3, more preferably 0.45 ≦ n / m ≦ 2.1, and further preferably 0.47 ≦ n / m ≦ 2.0. It is.

Such an aromatic group-containing organosiloxane compound can be easily synthesized by a known silicone synthesis method. That is, a monofunctional silicon compound represented by R ₃ SiX, a bifunctional silicon compound represented by R ₂ SiX ₂ , a trifunctional silicon compound represented by RSiX ₃ , silicon tetrahalide, tetraalkoxysilane, And a condensation reaction of at least one, preferably at least two silicon compounds selected as necessary from organic silicon compounds which are condensates thereof and inorganic silicon compounds such as water glass and metal silicates. Can be synthesized. In the formula, R represents an aromatic hydrocarbon group or a group in which the carbon directly bonded to the silicon atom is an aliphatic carbon. X represents a group that can be condensed to form a siloxane bond, such as a halogen, a hydroxyl group, or an alkoxy group.

  The reaction conditions vary depending on the substrate used and the composition and molecular weight of the target compound. In general, the reaction can be carried out by mixing a silicon compound with heating, if necessary, in the presence of water, acid and / or alkali, and an organic solvent as necessary. The proportion of each silicon compound used should be appropriately set in consideration of the content of each unit and the ratio of aromatic hydrocarbon groups to aliphatic hydrocarbon groups so that the resulting aromatic group-containing organosiloxane compound satisfies the above conditions. That's fine.

  Furthermore, the epoxy resin composition of the present invention includes, as other additives, carnauba wax, montanic acid, stearic acid, higher fatty acids, higher fatty acid metal salts, montanic acid esters, etc., in order to ensure mold releasability. Conventional wax release agents such as ester waxes, oxidized or non-oxidized polyolefin waxes such as polyethylene and polyethylene oxide, stress relieving agents such as silicone oil and silicone rubber powder, carbon black, organic dyes, organic pigments, Coloring agents such as titanium oxide, red lead, and bengara can be blended as necessary.

  The epoxy resin composition of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. However, as a general method, a predetermined amount of raw materials are sufficiently mixed by a mixer or the like. Used for molding. In the case where the epoxy resin composition is solid, a method of further melting and kneading with a mixing roll, kneader, extruder, etc., followed by cooling and pulverization can be exemplified. Further, the epoxy resin composition of the present invention can be used as a liquid epoxy resin composition by using a liquid resin or dissolved in various organic solvents, and the liquid epoxy resin composition is thinly applied on a plate or a film. Further, it can also be used as a sheet or film-like epoxy resin composition obtained by scattering an organic solvent under conditions such that the resin curing reaction does not proceed so much.

The resin composition of the present invention comprises an epoxy resin (A), a curing agent (B), a curing accelerator (C), an inorganic filler (D), a metal hydrate (E), and a silicone compound (F) in total 100 weights. Per part,
2-50 parts by weight of epoxy resin (A), 1-50 parts by weight of curing agent (B), 0.01-5 parts by weight of curing accelerator (C), 30-95 parts by weight of inorganic filler (D), metal Examples thereof include 1 to 30 parts by weight of hydrate (E) and 0.1 to 20 parts by weight of silicone compound (F). The component (F) is preferably 0.2 to 15 parts by weight, more preferably 0.5 to 12 parts by weight.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. In the following description, “part” means part by weight and “%” means weight% unless otherwise specified.

(Production Example 1): Production of Silicone Compound (F1) Dichlorodiphenylsilane (468 g), dichlorodimethylsilane (80 g), M silicate 51 (291 g) manufactured by Tama Chemical Industry Co., Ltd. was weighed into a 5 L flask, and MIBK (1200 g) was measured. After the addition, water (336 g) was added dropwise at 10 ° C. or lower. Thereafter, the reaction mixture was heated to 80 ° C. and reacted for 3 hours. Thereafter, after returning to room temperature, chlorotrimethylsilane (268 g) and then water (44 g) were added dropwise, followed by reaction at 60 ° C. for 3 hours. The obtained reaction mixture was washed with water until neutrality, and the solvent was distilled off under reduced pressure to obtain the desired silicone compound (F1). From the NMR analysis, the composition ratio represented by the average composition formula (1) was m = 0.82, n = 0.60, and therefore m + n = 1.42 and n / m = 1.37 could be calculated. .

(Production Example 2): Production of silicone compound (F2) Trichlorophenylsilane (241 g) and dichlorodimethylsilane (49 g) were weighed into a 2 L flask, MIBK (400 g) was added, and water (112 g) was added at 10 ° C. or lower. It was dripped. Thereafter, the reaction mixture was heated to 80 ° C. and reacted for 3 hours. Thereafter, after returning to room temperature, chlorotrimethylsilane (124 g) and then water (15 g) were added dropwise, followed by reaction at 60 ° C. for 3 hours. The obtained reaction mixture was washed with water until neutral, and the separated organic phase was evaporated under reduced pressure to obtain the desired silicone compound (F2). From the NMR analysis, the constitutional ratio represented by the average composition formula (1) was m = 0.70 and n = 0.69, and therefore m + n = 1.39 and n / m = 0.98 could be calculated. .

(Production Example 3): Production of silicone compound intermediate dichlorodiphenylsilane (468 g), dichlorodimethylsilane (80 g), M silicate 51 (291 g) manufactured by Tama Chemical Industry Co., Ltd. was weighed into a 5 L flask, and MIBK (1200 g) was added. After that, water (336 g) was added dropwise at 10 ° C. or lower. Thereafter, the reaction mixture was heated to 80 ° C. and reacted for 3 hours. Thereafter, chlorodimethylsilane (233 g) and then water (44 g) were added dropwise at 10 ° C. or lower and reacted for 3 hours. The obtained reaction mixture was washed with water until neutral, and the organic phase separated was distilled off under reduced pressure to obtain the desired silicone compound.

(Production Example 4): Measurement of 200 g of the silicone compound intermediate obtained in Production of Silicone Compound (F3) (Production Example 3), 1 L of toluene was added, and 3% platinum-divinylsiloxane complex xylene solution (N, Y 18.4 μL of PTVTSC 3.0 xylene manufactured by Chemcat) was added, and then allyl glycidyl ether (28 g) was added dropwise and reacted at 100 ° C. for 5 hours. The obtained reaction mixture was distilled off the solvent under reduced pressure to obtain the desired silicone compound (F3). From the NMR analysis, the composition ratio represented by the average composition formula (1) was m = 0.82, n = 0.58, and therefore m + n = 1.40 and n / m = 1.41 could be calculated. .

(Production Example 5): 200 g of the silicone compound intermediate obtained in Production of Silicone Compound (F4) (Production Example 4) was weighed, 1 L of toluene was added, and 3% platinum-divinylsiloxane complex xylene solution (N, Y 18.4 μL of PTVTSC 3.0 xylene manufactured by Chemcat) was added, and o-allylphenol (33 g) was added dropwise, followed by reaction at 100 ° C. for 5 hours. The obtained reaction mixture was distilled off the solvent under reduced pressure to obtain the desired silicone compound (F4). From the NMR analysis, the composition ratio represented by the average composition formula (1) was m = 0.84, n = 0.56, and therefore m + n = 1.40 and n / m = 1.50 could be calculated. .

The raw materials used in Examples and Comparative Examples are summarized below.
Epoxy resin: Cresol novolac type epoxy resin (Epiclon N-637 manufactured by Dainippon Ink and Chemicals, Inc.)
Curing agent: Novolac type phenolic resin (Showon High Polymer Shounol BRG-556)
Curing accelerator: Triphenylphosphine (manufactured by Wako Pure Chemical Industries)
Inorganic filler: fused silica (FB-74, manufactured by Denki Kagaku Kogyo)
Metal hydrate E1: Aluminum hydroxide (Showa Denko Hygielite H-21)
Metal hydrate E2: Higher fatty acid surface-treated magnesium hydroxide (Magsees W-H25, manufactured by Kamishima Chemical)
Metal hydrate E3: inorganic substance + epoxysilane surface-treated magnesium hydroxide (Magseeds EP1-E manufactured by Kamishima Chemical)
Metal hydrate E4: inorganic surface-treated magnesium hydroxide (Magsees EP1-A manufactured by Kamishima Chemical)
Silane coupling agent: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (Nihon Unicar A-186)
Mold release agent: Fine powder Carnauba S (manufactured by Toa Kasei)
(Example 1)
Adjustment <br/> epoxy resin 5 parts of an epoxy resin composition, curing agent, 5 parts, 70 parts of silica, 10 parts of aluminum hydroxide, silicone compound prepared in Preparation Example 4 (F3), 5 parts of triphenyl phosphine 0.1 Part, 0.5 part of silane coupling agent and 0.1 part of fine powder carnauba S were mixed, and then kneaded with a superheated roll at 100 ° C. for 5 minutes.

Preparation of molded body After the obtained resin composition was pulverized with a pulverizer, it was heated with a compression molding machine at 165C for 3 minutes to obtain a test piece having a width of 10 mm, a length of 100 mm, and a thickness of 1.6 mm. The molded body thus prepared was further heated in an oven at 175 ° C. for 6 hours and post-cured.

Evaluation method The obtained molded product was evaluated for flame retardancy in a V test according to the UL-94 standard.
(Examples 2-12 and Comparative Examples 1-5)
Resin compositions were obtained and evaluated in the same manner as in Example 1 except that the types and addition amounts of the metal hydrate and the silicone compound were changed.

  As shown in Table 1, in the examples, very good flame retardancy was obtained.

  In the comparative example, the silicone compound of the present invention was not added, and the flame retardancy was insufficient.

  The epoxy resin composition of the present invention exhibits extremely excellent flame retardancy without using generally used flame retardants such as chlorine, bromine, phosphorus, and the like, and the characteristics inherent to the resin are rarely impaired. Such an epoxy resin composition is very useful industrially.

Claims (4)

Epoxy resin (A), curing agent (B), curing accelerator (C), inorganic filler (D), metal hydrate (E), and average composition formula (1)
R ¹ _m R ² _n SiO _{(4-mn) / 2} (1)
(In the formula, R ¹ represents a group selected from a group in which carbon directly bonded to a silicon atom is an aliphatic carbon, a hydroxyl group, and an alkoxy group, and R ² represents an aromatic hydrocarbon group having 6 to 24 carbon atoms. Two or more types of R ¹ and R ² may exist, and m and n represent numbers satisfying 1.1 ≦ m + n ≦ 1.7 and 0.4 ≦ n / m ≦ 2.5. The epoxy resin composition characterized by containing the silicone compound (F) represented by this. R ¹ of the silicone compound of component (F) is a hydrocarbon group having one or more reactive groups selected from an epoxy group, a hydroxyl group, an alkoxy group, an amino group, a carboxy group, and a carboxylic anhydride group. The epoxy resin composition according to claim 1. 3. The epoxy resin composition according to claim 1, comprising 10 mol% or more of SiO ₂ units among all siloxane units constituting the silicone compound of component (F).   The epoxy resin composition according to any one of claims 1 to 3, wherein the metal hydrate (E) is surface-treated with a surface treatment agent selected from an aluminum compound and a silicon compound.