WO2006051731A1

WO2006051731A1 - Epoxy resin composition

Info

Publication number: WO2006051731A1
Application number: PCT/JP2005/020192
Authority: WO
Inventors: Hiroshi Tsuneishi
Original assignee: Kaneka Corporation
Priority date: 2004-11-11
Filing date: 2005-11-02
Publication date: 2006-05-18
Also published as: JPWO2006051731A1; JP5153141B2

Abstract

A novel epoxy resin composition which can produce an extremely high flame-retardant effect without containing any flame retardant having atoms of a halogen, phosphorus, or the like. The composition comprises an epoxy resin (A), a hardener (B), a hardening accelerator (C), an inorganic filler (D), a metal hydrate (E), and a silicone compound (F) represented by the empirical formula (1): R1mR2nSiO(4-m-n)/2 (1) (wherein R1 represents a group selected among a group in which the carbon atom directly bonded to the silicon atom is an aliphatic carbon atom, hydroxy, and alkoxy and R2 represents a C6-24 aromatic hydrocarbon group, provided that R1 and R2 each may be of two or more kinds; and m and n are numbers satisfying 1.1≤m+n≤1.7 and 0.4≤n/m≤2.5).

Description

Specification

Epoxy resin composition

Technical field

The present invention relates to an epoxy resin composition that does not contain atoms such as halogen and phosphorus and is highly flame retardant.

Background art

[0002] Epoxy resin molding materials have excellent heat resistance and insulation properties, as well as good thermal and electrical properties, as well as good physical properties such as adhesion, dimensional stability, chemical resistance, and moisture resistance. Therefore, it is widely used in electronic component materials such as semiconductor sealing molding materials and printed wiring board materials.

[0003] Semiconductor encapsulated molding materials and printed wiring board materials require a high level of flame resistance for safety against fires, and are required to satisfy UL (US Underwriters Laboratory Standards) V-0. Various flame retardants are blended so that they can be used for applications (see Non-Patent Document 1, for example).

[0004] Flame retardants used in epoxy resin molding materials are used in combination with halogen-based flame retardants typified by brominated epoxy resins, and halogen-based flame retardants and antimony-based flame retardants such as antimony trioxide. It has been widely used. In recent years, however, flame retardants that replace halogenated compounds and antimony compounds have been demanded from the viewpoint of environmental impact.

[0005] As an alternative to the halogen flame retardant, there is a method using a phosphorus compound, but the phosphorus compound has a high hygroscopic property, and there is a problem when the electrical properties are lowered due to hydrolysis.

[0006] As a method of making flame retardant without using a halogen-based or phosphorus-based flame retardant, use of a metal hydrate is generally considered, but it is necessary to add a large amount in order to satisfy a high level of flame retardancy. However, there existed a subject that workability | operativity, a moldability, and the workability of hardened | cured material were inferior.

[0007] 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 an epoxy resin composition can be combined with a polycarbonate resin. Add onoreganopolysiloxane with specific structure Although a method is disclosed (for example, see Patent Document 1), in this case, since a thermoplastic resin is blended with an epoxy resin that is a thermosetting resin, the blending and molding conditions are complicated. There is. Furthermore, a technique for improving flame retardancy by adding a silicone compound to a resin composition obtained by adding a specially modified phenolic resin and a benzoxazine compound to an epoxy resin composition has been reported (for example, Patent Document 2). See), the compounded resin composition is special, and further general-purpose technology is required.

Non-Patent Document 1: Epoxy Resin Technology Association published review epoxy resin

Patent Document 1: JP 2003-165897

Patent Document 2: JP 2004-27000

Disclosure of the invention

Problems to be solved by the invention

[0008] In view of the above situation, the present invention is to provide a highly flame-retardant epoxy resin composition containing no halogen or phosphorus atom.

Means for solving the problem

[0009] The present inventor has paid attention to the flame retardant effect of metal hydrate, and as a result of earnestly studying a method for achieving flame retardant with a small amount of compounding system that does not reduce moldability and workability, a silicone having a specific structure The present invention was completed by finding that excellent flame retardancy can be obtained by combining with a compound.

That is, the present invention relates to 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 R ² SiO (1)

m n (4-m-n) / 2

(In the formula, R ¹ represents a group selected from a group in which carbon directly bonded to a carbon 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. R ¹ and R ² may be present in two or more types, m and n are 1. l≤m + n≤l .7 and 0.4≤n / m≤2.5 The epoxy resin composition characterized by containing the silicone compound (F) represented by this.

In a preferred embodiment, R ¹ of the silicone compound of component (F) is one or more selected from an epoxy group, a hydroxyl group, an alkoxy group, an amino group, a carboxy group, and a carboxylic acid anhydride group. The epoxy resin composition is characterized by being a hydrocarbon group having a reactive group.

[0012] In a preferred embodiment, the epoxy resin according to any one of the above, wherein the SiO unit is contained in an amount of 10 mol% or more of all siloxane units constituting the silicone compound of component (F).

2

The present invention relates to a xy resin composition.

[0013] Preferably, the embodiment is characterized in that the metal hydrate (E) is surface-treated with a surface treatment agent selected from an aluminum compound and a silicon compound. The present invention relates to a resin composition.

The invention's effect

[0014] The epoxy resin composition of the present invention exhibits very excellent flame retardancy without using generally used flame retardants such as chlorine, bromine and phosphorus, and impairs the inherent characteristics of the resin. There are few. Such an epoxy resin composition is very useful industrially.

BEST MODE FOR CARRYING OUT THE INVENTION

[0015] The present invention is described in detail below.

[0016] 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. There are no particular restrictions. For example, phenols such as phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, epoxy resin having triphenylmethane skeleton, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, etc. And / or naphthols such as α-naphthol, β naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetoaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, or the like by condensation or cocondensation under an acidic catalyst. Epoxidized novolak resin obtained. Also, diglycidyl ethers such as bisphenol Α, bisphenol F, bisphenol S, and bisphenol A / D, biphenyl epoxy resins that are diglycidyl ethers of alkyl-substituted or unsubstituted biphenol, phenols and / or Epoxidized phenolic aralkyl resin synthesized from naphthols and dimethoxyparaxylene or bis (methoxymethyl) bifuel, stilbene type epoxy resin, hydroquinone type epoxy resin Obtained by reaction of polyamines such as alicyclic acid such as fat, phthalic acid, and dimer acid with epicyclohydrin, and polyamines such as daricidyl ester type epoxy resin, diaminodiphenylmethane, and isocyanuric acid, and epichlorohydrin. Glycidinoleamine type epoxy resin.

In addition, dicyclopentagen type epoxy resin, epoxidized product of co-condensation resin of dicyclopentagen and phenols, epoxy resin having naphthalene ring, triphenol methane type epoxy resin, trimethylolpropane type epoxy resin, terpene modified epoxy resin, Linear aliphatic epoxy resins, alicyclic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid, and these epoxy resins with silicone, acrylonitrile, butadiene, isoprene rubber, polyamide resin, etc. Examples include modified epoxy resins.

[0017] These epoxy resins may be used alone or in combination of two or more.

[0018] 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 applied, and are not particularly limited. A phenol resin having two or more phenolic hydroxyl groups in the molecule can be suitably used. Specific examples of phenol resins include novolak-type phenol resins such as phenol novolak resins and cresol novolak resins, resol-type phenol resins, phenol aralkyl resins, triphenol methane-type resins, and triphenol propane-type resins. Examples include phenolalkane-type phenolic resins and polymers thereof, naphthalene ring-containing phenolic resins, dicyclopentagen-modified phenolic resins, bisphenol F-type resins, bisphenol A-type resins and other bisphenol type phenolic resins. These curing agents can be used alone or in combination of two or more.

[0019] The curing accelerator (C) used in the present invention is not particularly limited. A curing accelerator generally used in epoxy resin molding materials such as a phosphorus compound-based curing accelerator and a nitrogen compound-based curing accelerator. Can be used. Examples of the phosphorus compound-based curing accelerator include trialkylphosphine such as trimethylphosphine, triethylphosphine, tripropylphosphine, and tributylphosphine, and dialkylarylphosphine such as dimethylphenylphosphine, diphenylphosphine, and methyldiphenylphosphine. Tris (alkoxy) such as alkyldiarylphosphine such as phosphine, triphenylphosphine, tris (4-methylphenyl) phosphine Norephinorephosphine, tris (alkoxyphenenole) phosphine, tris (alkynole'alkoxyphenenole) phosphine, tris (dialkylphenenole) phosphine, tris (trialkylphenenole) phosphine, tris (tetraalkylphenol) Organic phosphines such as phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, diphenylphosphine, diphenyl (p-tolyl) phosphine, tetra Butylphosphonium tetraphenylborate, Butyltriphenylphosphine tetraphenylborate, Tetraphenylphosphonium tetrabutylborate, Tetraphenylphosphonium tetraphenylborate , Triphenyl phosphine tetra-phenylalanine borate etc. phosphonyl © Mubo rate, such complexes with organic phosphines and organic boron compound can be mentioned up.

Of these, tributylphosphine, triphenylphosphine, tris (4 methylphenyl) phosphine, tetrabutyltetrabutylphosphoniumtetraphenylborate, and tetraphenylphosphoniumtetraphenylborate are preferable.

[0021] Nitrogen-based curing accelerators include, for example, 1,8 diazabicyclo [5. 4. 0] undecene 1, 1, 5—diazabicyclo [4 · 3.0] nonene 1, 5, 5, 6 —Cycloamidine compounds such as dibutylamino-1,8-diazabicyclo [5.4.0] undecene 7 and their derivatives, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, etc. Tertiary amine compounds and their derivatives, triammonium tetraphenylborate, 1,8-diazabicyclo [5.4.0] -7-unde senemtetraphenylborate, and the like. However, 1,8-diazabicyclo [5.4.0] undecene 7 and 1,5-diazabicyclo [4.3.0] nonen-5 are preferred.

[0022] 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. For example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, ano-remi, boron nitride, beryllia, zirconia, dinolecon, fosterite , Powders of steatite, spinel, mullite, titania, or the like, or beads or glass fibers formed by spheroidizing these. Inorganic fillers are silane coupling agents to improve adhesion to resin components It is desirable that the surface treatment is performed with a titanate coupling agent or the like, or that such a coupling agent is added when the epoxy resin composition is blended. Examples of such coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl methyljetoxysilane, _ (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Silane power such as epoxy silane such as N-β (aminoethyl) 1 γ-aminopropyltrimethoxysilane, _Ί- aminopropyltriethoxysilane, Ν- _phenol γ-aminopropyltrimethoxy A pulling agent.

[0023] Examples of the metal hydrate (soot) used in the present invention include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide and the like. These metal hydrates may be blended as a mixture of two or more. Also, magnesium hydroxide is particularly preferred for the recent lead-free soldering because of its decomposition temperature. In addition, a surface-treated product is preferable in order to improve the affinity with the resin, to prevent the mechanical properties of the resin composition from being lowered, and to improve water resistance and acid resistance. That is, the metal hydrate (金属) is preferably surface-treated with a surface treatment agent selected from an aluminum compound and a key compound. Examples of the aluminum compound include inorganic substances such as alumina and aluminum coupling agents. Examples of the key compound include inorganic substances such as silica and silane coupling agents such as epoxy silane. Examples of other surface treatment agents include titanium compounds such as titanium oxide and titanate coupling agents, higher fatty acids such as stearic acid, and oxalate anion. Two or more of these may be used in combination.

[0024] The silicone compound (F) used in the present invention comprises an aromatic group-containing organosiloxane compound, and is composed of Q unit (SiO 2), Τ unit (RSiO), D unit (R SiO) and M unit. (R Si〇

2 1.5 2 3 0.5

) Is produced using a compound composed of any combination of the four types of structural units

R ¹ R ² SiO (1)

m n (4-m-n) / 2

(In the formula, R ¹ represents a group selected from a group in which carbon directly bonded to a carbon 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. R ¹ and R ² may be present in two or more types, m and n are 1. l≤m + n≤l .7 and 0 4≤n / m≤2. ) In the average composition formula.

[0025] The aromatic group-containing organosiloxane compound represented by the average composition formula (1) is a group R ¹ selected from a group in which carbon directly bonded to a carbon atom in the molecule is an aliphatic carbon, a hydroxyl group, and an alkoxy group. And an aromatic hydrocarbon group R ² having 6 to 24 carbon atoms, and the number of moles m + n of all substituents on these silicon atoms is 1.l≤m + n≤l .7 A molar ratio of 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 to an aromatic hydrocarbon group R ² having 6 to 24 carbon atoms n Satisfies that / m is in the range 0.4 ≤ n / m ≤ 2.5. Each element and the ratio of m and n can be calculated using NMR of hydrogen, carbon and silicon.

[0026] The group R ¹ in which the carbon directly bonded to the carbon atom is an aliphatic carbon is a saturated aliphatic hydrocarbon group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, Examples thereof include s-butyl group and t-butyl group. Among these, preferred are a methyl group and an ethyl group, and a methyl group is more preferred because of its excellent flame retardancy. When the saturated aliphatic hydrocarbon group has 5 or more carbon atoms, the flame retardancy of the aromatic group-containing organosiloxane compound itself is lowered, and the flame retarding effect is lowered.

[0027] Further, examples of the alkoxy group selected as R ¹ include a methoxy group, an ethoxy group, and an isopropoxy group. Among these, the availability of raw materials, etc. The methoxy group is preferred.

[0028] Further, by introducing a reactive group capable of bonding to 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. It is preferable that In order to introduce these reactive groups into the silicone compound, a polymerizable monomer having the above-mentioned reactive group-substituted hydrocarbon group as a substituent on the silicon atom is used, or SiH groups are introduced into the silicone compound. After introduction, it can be achieved by a method of reacting a carbon-carbon unsaturated compound by a hydrosilylation reaction. These methods are not particularly limited.

[0029] is not particularly restricted but includes aromatic hydrocarbon group R ² having a carbon number of 6-24, for example, Fuweni Examples include nore group, methylphenyl group, dimethylphenyl group, ethylphenyl group, naphthyl group, anthracenyl group, and the like. 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 the same or different groups may be mixed.

[0030] The number of moles m + n of all substituents on the key atom is in the range of 1. l≤m + n≤l. m + n is preferably 1.15≤m + n≤l.65, more preferably 1.18≤m + n≤l.6, more preferably 1.20≤m + n≤l.55 Range. Even if the value of m + n is less than 1.1 or above 1.7, the flame retarding effect of the aromatic group-containing organosiloxane compound is reduced, which is preferable. The 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 introduction amount 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 units among all the siloxane units constituting the silicone compound of component (F). The SiO unit content is more preferably 20 mol% or more, most preferably 30 mol% or more.

[0031] The molar ratio of a 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 to an aromatic hydrocarbon group R ² having 6 to 24 carbon atoms, n / m Is in the range of 0.4 ≤ n / m ≤ 2.5. When n / m is less than 0.4, the aromatic group-containing onoreganosiloxane compound decreases due to the decrease in aromatic groups in the molecule, and the aromatic group-containing onoreganosiloxane compound is reduced. This will cause the flame retardancy effect of the object to decrease. On the other hand, even if n / m is 2.5 or more, the flame retardant effect of the aromatic group-containing onoreganosiloxane compound is reduced. n / m is preferably 0.43≤n / m≤2.3, more preferably 0.45≤n / m≤2.1, and even more preferably 0.47≤n / m≤2. 0.

[0032] Such an aromatic group-containing organosiloxane compound can be easily synthesized by a known silicone synthesis method. That is, a monofunctional key compound represented by R SiX,

Bifunctional key compound represented by R SiX, Trifunctional key compound represented by RSiX

, Tetrahalogenated silicon, tetraalkoxysilane, and organic condensates thereof It can be synthesized by condensation reaction of at least one, preferably at least two, selected from among inorganic compounds such as silicon compounds, water glass and metal silicates. 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 capable of condensing to form a siloxane bond, such as a halogen, a hydroxyl group or an alkoxy group.

[0033] 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 the silicon compound with heating, if necessary, in the presence of water, an acid and / or an alkali, and an organic solvent as necessary. The usage ratio of each silicon compound takes into account the content of each unit and the ratio of aromatic hydrocarbon groups to aliphatic hydrocarbon groups so that the resulting aromatic group-containing onoreganosiloxane compound satisfies the above conditions. Therefore, it can be set as appropriate.

[0034] Further, 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, montan to ensure mold releasability. Conventionally known release agents such as ester waxes such as acid esters, oxidized or non-oxidized polyolefin waxes such as polyethylene and polyethylene oxide, stress relaxation agents such as silicone oil and silicone rubber powder, carbon black, organic It is possible to mix dyes, organic pigments, colorants such as titanium oxide, red lead, and bengara as necessary.

[0035] The epoxy resin composition of the present invention can be prepared using any of the above methods as long as various raw materials can be uniformly dispersed and mixed. Are mixed well with a mixer or the like and 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 by dissolving in various organic solvents, and the liquid epoxy resin composition can be used on a plate or a film. It can also be used as a sheet or a film-like epoxy resin composition obtained by spreading the organic solvent thinly and spraying the organic solvent under conditions such that the resin curing reaction does not proceed so much.

[0036] The resin composition of the present invention comprises an epoxy resin (A), a curing agent (B), a curing accelerator (C), 2 to 50 parts by weight of epoxy resin (A) and 100 to 50 parts by weight of curing agent (B) per 100 parts by weight of machine filler (D), metal hydrate (E) and silicone compound (F) Curing accelerator (C) 0.0:! To 5 parts by weight, inorganic filler (D) 30 to 95 parts by weight, metal hydrate (E):! To 30 parts by weight, silicone compound (F) 0. :! ~ 20 parts by weight can be exemplified. The component (F) is preferably 0.2 to 15 parts by weight, more preferably 0.5 to 12 parts by weight.

Example

[0037] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In the following, “part” means part by weight and “%” means weight% unless otherwise specified.

[0038] (Production Example 1): Production of silicone compound (F1)

Dichlorodiphenylsilane (468 g), dichlorodimethylsilane (80 g) and M silicate 51 (291 g) manufactured by Tama Chemical Industry Co., Ltd. are weighed into a 5 L flask, and MIBK (1200 g) is added. ) Was added dropwise. Thereafter, the reaction mixture was heated to 80 ° C. and reacted for 3 hours. 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 neutral, and the organic phase separated was evaporated under reduced pressure to obtain the desired silicone compound (F1). From N MR analysis, the composition ratio represented by the average composition formula (1) is m = 0.82, n = 0.60, and therefore, m + n = l .42, n / m = l.37 I was able to calculate.

[0039] (Production Example 2): Production of silicone compound (F2)

Trichloric phenylsilane (241 g) and dichlorodimethylsilane (49 g) were weighed into a 2 L flask, MIBK (400 g) was added, and water (112 g) was added dropwise at 10 ° C or lower. Thereafter, the reaction mixture was heated to 80 ° C. and reacted for 3 hours. 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 NMR analysis, the composition ratio represented by the average composition formula (1) is Sm = 0.70, n = 0.69, and therefore calculated as m + n = 1.39, n / m = 0.98. did it

[0040] (Production Example 3): Production of silicone compound intermediate Dichlorodiphenylsilane (468 g), dichlorodimethylsilane (80 g), M silicate 51 (291 g) manufactured by Tama Chemical Industries, Ltd. are weighed into a 5 L flask, MIBK (1200 g) is added, and water (336 g at 10 ° C or less is added. ) Was added dropwise. 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.

[0041] (Production Example 4): Production of silicone compound (F3)

Weigh 200 g of the silicone compound intermediate obtained in (Production Example 3), cover 1 L of toluene, and prepare a 3% platinum-dibutylsiloxane complex xylene solution (PTV TSC3.0 xylene manufactured by Yen, Yi, Chemcat) 18. After 4 z L was added, 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 represented by the average composition formula (1)]; power ratio Sm = 0.82, n = 0.58, therefore, m + n = l.40, n / m = l. I was able to calculate 41.

[0042] (Production Example 5): Production of silicone compound (F4)

Weigh 200 g of the silicone compound intermediate obtained in (Production Example 4), add 1 L of toluene, and add 3% platinum-divinylsiloxane complex xylene solution (PTV TSC3.0 xylene manufactured by Yen, Yi, Chemcat) 18 After removing 4 / i L of calo, o-aryno-enoenole (33g) 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 (F4). From the NMR analysis, the composition represented by the average composition formula (1) i power Sm = 0.84, n = 0.56, and therefore calculated as m + n = l.40, n / m = l.50. did it.

[0043] The raw materials used in Examples and Comparative Examples are summarized below.

Epoxy resin: Cresol monovolak type epoxy resin (EPI CLON N— 637, manufactured by Dainippon Ink and Chemicals, Inc.)

Curing agent: Novolac-type phenolic resin (Showa High Polymer Shounol BRG-556) Curing accelerator: Triphenylphosphine (Wako Pure Chemical Industries, Ltd.)

Inorganic filler: fused silica (FB-74, manufactured by Denki Kagaku Kogyo) Metal Hydrate El: Aluminum hydroxide (NO, Ijirite H-21 made by Showa Denko)

Metal Hydrate E2: Higher Fatty Acid Surface Treated Magnesium Hydroxide (Madashiz W-H25 from Kamishima Chemical)

Metal Hydrate E3: Inorganic + Epoxysilane Surface-treated Magnesium Hydroxide (Madashiz EP1-E)

Metal Hydrate E4: Mineral Surface-treated Magnesium Hydroxide (Madashies E P1-A manufactured by Kamishima Chemical)

Silane coupling agent: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (N-UNIKAR A-186)

Mold release agent: Fine powder carnauba S (manufactured by Toa Kasei)

(Example 1)

Words of epoxy formation

5 parts of epoxy resin, 5 parts of curing agent, 70 parts of silica, 10 parts of aluminum hydroxide, 5 parts of silicone compound (F3) produced in Production Example 4, 0.1 part of triphenylphosphine, 0.5 part of silane coupling agent After mixing 1 part of the fine powder carnauba SO., Knead with a superheated roll at 100 ° C for 5 minutes. 7

[0044] Creation of compact

The obtained resin composition was pulverized with a pulverizer and then heated with a compression molding machine at 165 ° C for 3 minutes to prepare a test piece having a width of 10 mm, a length of 100 mm, and a thickness of 1.6 mm. The body was further cured by heating in an oven at 175 ° C for 6 hours.

[0045] Evaluation method

The obtained molded product was evaluated for flame retardancy by V test according to UL-94 standard.

(Examples 2 to 12 and Comparative Examples 1 to 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.

[0046] [Table 1]

[0047] As shown in Table 1, in the Examples, very good flame retardancy was obtained.

[0048] In the comparative example, the silicone compound of the present invention was not added, and the flame retardancy was insufficient.

Industrial applicability

[0049] The epoxy resin composition of the present invention exhibits very excellent flame retardancy without using commonly used flame retardants such as chlorine, bromine and phosphorus, and impairs the inherent characteristics of the resin. Also Few. Such an epoxy resin composition is very useful industrially.

Claims

The scope of the claims

[1] Epoxy resin (A), curing agent (B), curing accelerator (C), inorganic filler (D), metal hydrate (E), and average composition formula (1)

R ¹ R ² SiO (1)

m n (4-m-n) / 2

(In the formula, R ¹ represents a group selected from a group in which carbon directly bonded to a carbon 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. There may be two or more types of R ¹ and R ² m and n satisfy 1. l≤m + n≤l .7 and 0.4≤n / m≤2.5 The epoxy resin composition characterized by containing the silicone compound (F) represented by this.

[2] 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, wherein:

[3] Of all the siloxane units composed of the silicone compound of component (F), 10 units of SiO units

2

The epoxy resin composition according to claim 1, wherein the epoxy resin composition is contained in an amount of at least 1%.

[4] The epoxy resin according to any one of [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. Composition.