JP2000119489A - Epoxy resin composition and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide epoxy resin compositions excellent in mechanical properties, deflection temperature under load, adhesion at high temperatures and resistance to moisture without marring surface properties. SOLUTION: An epoxy resin compositions comprises an epoxy resin and a silane clay composite, and the silane clay composite is prepared by introducing a silane compound represented by the formula: YnSiX4-n (wherein n is an integer of 0-3; Y is a 1-25C hydrocarbon group or an organic functional group constituted by a 1-25C hydrocarbon group and a substituent; X is a hydrolyzable group and/or a hydroxyl group; and respective Y of n and respective X of n may be the same or different from one another) into a swelling silicate salt, and the average layer thickness of the silane clay composite in the resin composition is not more than 500 Å.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an epoxy resin composition containing an epoxy resin and a silane clay composite, and a method for producing the resin composition.

[0002]

2. Description of the Related Art A resin composition containing an epoxy resin as a main component has been conventionally cast and sealed because of its balance between mechanical properties and heat resistance, and excellent electrical properties, adhesive properties, corrosion resistance and moldability. , Laminate and other electrical and electronic fields, adhesives,
Widely used for composite materials, civil engineering, paints, etc.

[0003] In recent years, in the field of electronic components, further mechanical strength and heat resistance have been required as the size and thickness have been reduced. In the field of semiconductors, heat resistance at the solder temperature accompanying the development of surface mounting methods for printed wiring boards has been required. Is required, and TAB (Tape
An adhesive layer of a tape (so-called TAB tape) used in an automated bonding method is required to have an adhesive strength, an elastic modulus and a moisture resistance at a high temperature. In response to the above requirements, there are methods of increasing the toughness of the resin structure, increasing the strength and lowering the water absorption by increasing the amount of particulate inorganic matter such as silica,
Although the improvement effect is recognized, it is not sufficiently satisfactory.

[0004] The disadvantages of the compounding of the particulate inorganic material are that the particulate inorganic material is not sufficiently finely dispersed and that the adhesion between the matrix resin and the particulate inorganic material is poor. It is considered that this is due to a decrease in thin-wall moldability.

[0005] As techniques for finely dispersing inorganic substances, WO 95/06090, US Pat. No. 5,514,734,
WO 93-04118 and WO 9
And the method disclosed in JP-A-3-11190.
According to the publication, a resin composite containing a resin matrix and a layered particle or the like having an average layer thickness of about 50 ° or less and a maximum layer thickness of about 100 ° or less is bonded to an organometallic compound such as a silane-based compound. An invention relating to a material is disclosed, and a nylon 6-based composite material comprising montmorillonite treated with a silane-based compound and nylon 6 as a resin matrix is disclosed. According to the above technology, the tensile modulus of the nylon 6-based composite material comprising montmorillonite and nylon 6 bonded with isocyanatopropyltriethoxysilane and the like to which caprolactam has been copolymerized is improved as compared with nylon 6 alone. Is not enough.

[0006]

As described above, a nylon 6-based composite material is disclosed. However, by directly applying the nylon 6-based method to an epoxy resin system, an epoxy resin having finely dispersed layered particles is obtained. It was difficult to make a resin composite material.

On the other hand, in Japanese Patent Application Laid-Open No. Hei 9-118792, when a layered particle is separated into individual particles and dispersed in a molecular form in a polypropylene resin or a vinyl polymer, the layer itself has a originally high elastic modulus. It has been pointed out that when the layered particles are separated in a state close to the unit layer, the particles are distorted and the elastic modulus as originally expected cannot be obtained.

Further, the present inventors have obtained a composite material by incorporating layered particles into an epoxy resin in a very thin plate-like structure close to a unit layer (the layer thickness of the unit layer is about 10 °) to obtain a composite material. As a result, when compared with those in which the layered particles were contained in the epoxy resin in a laminated / agglomerated state,
Certainly, although the moisture resistance and the surface properties were improved, it was found that the balance between the initial strength before moisture absorption and the initial adhesiveness was never sufficient.

Therefore, the layered silicate has an average layer thickness of about 50.
Even when dispersed in a resin matrix in a state close to the unit layer such that the maximum layer thickness is about 100 mm or less,
Or even if it is contained in a state of being laminated and aggregated,
In any case, it is difficult to obtain an epoxy resin composition that is excellent in balance between mechanical properties and heat resistance, adhesion at high temperatures, moisture resistance, surface properties, and the like. In order to obtain an epoxy resin composition having a good physical property balance, it is essential to disperse layered particles having an appropriate layer thickness.

However, at present, such a technique has not been provided yet, and an object of the present invention is to solve such a conventional problem.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have reached the present invention. That is, the unit layers of the swellable silicate are separated and cleaved,
An epoxy resin obtained by containing a thin silane clay complex prepared by subdividing aggregated particles of two swellable silicates into a very large number of very small thin plate particles is contained in an epoxy resin. A resin composition and a method for producing the same.

According to the present invention, the epoxy resin composition of claim 1 is an epoxy resin composition containing an epoxy resin and a silane clay composite, wherein the silane clay composite is converted to a swellable silicate. following general formula _{(1) Y n SiX 4-} n (1) ( where, n is an integer of 0 to 3, Y is 1 to carbon atoms
X is a hydrolyzable group and / or a hydroxyl group, which is an organic functional group composed of 25 hydrocarbon groups and a hydrocarbon group having 1 to 25 carbon atoms and a substituent. n Y and 4-n X may be the same or different. Is prepared by introducing the silane compound represented by the formula (1), and the average layer thickness of the silane clay composite in the resin composition is 500 ° or less. According to a second aspect of the present invention, in the epoxy resin composition according to the first aspect, the maximum thickness of the silane clay composite is 2000 ° or less.

[0013] The epoxy resin composition according to claim 3 is an epoxy resin composition containing an epoxy resin and a silane clay composite, wherein the silane clay composite is converted into a swellable silicate by the following general formula (1): Y _n SiX _4-n (1) (where n is an integer of 0 to 3, and Y is 1 to 3 carbon atoms)
X is a hydrolyzable group and / or a hydroxyl group, which is an organic functional group composed of 25 hydrocarbon groups and a hydrocarbon group having 1 to 25 carbon atoms and a substituent. n Y and 4-n X may be the same or different. ) Is prepared by introducing a silane compound represented by the formula (1), and the resin composition has an average aspect ratio (ratio of layer length / layer thickness) of 10 to 300, and [ N] value is 30 or more, where the [N] value is defined as the number of particles per unit ratio of the silane clay complex present in an area of 100 μm ² of the resin composition.

[0014] The epoxy resin composition according to claim 4 is the epoxy resin composition according to claim 1 or 2,
The [N] value is 30 or more, where the [N] value is defined as the number of particles per unit ratio of the silane clay complex present in an area of 100 μm ² of the resin composition.

[0015] The epoxy resin composition according to claim 5 is the epoxy resin composition according to claim 1 or 2,
The average aspect ratio (layer length / layer thickness ratio) of the silane clay composite in the resin composition is 10 to 300.

The method for producing an epoxy resin composition according to claim 6 is the method for producing an epoxy resin composition according to claim 1, 2, 3, 4 or 5, wherein (A) the silane clay composite. And a step of preparing a clay dispersion containing the epoxy resin oligomer and (B) a step of curing the epoxy resin oligomer.

In the method for producing an epoxy resin composition according to the present invention, the distance between the bottom surfaces of the silane clay composite in the clay dispersion obtained in the step (A) may be as follows. It is at least three times the distance between the bottom surfaces of the swellable silicate.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The epoxy resin used in the present invention has two or more reactive epoxy groups (oxirane groups) in one molecule and has a molecular weight of about 100 to about 10,000.
It is intended to be a cured resin obtained by curing (bridging) the epoxy resin oligomer of the above with a curing agent.

Examples of the epoxy resin oligomer include a glycidyl ether type in which epichlorohydrin and phenols or alcohols form a main skeleton, a glycidyl ester type in which epichlorohydrin and carboxylic acids form a main skeleton, epichlorohydrin and amines, cyanuric acid or In addition to the glycidylamine type in which hindatoin forms the main skeleton, an alicyclic type and the like can be mentioned.

Specific examples of the epoxy resin include glycidyl ether type such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin and hydrogenated bisphenol A type epoxy resin. , Bisphenol S type epoxy resin, bisphenol AF type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin,
Fluorene-type epoxy resin, ethylene glycol-type epoxy resin, diethylene glycol-type epoxy resin, triethylene glycol-type epoxy resin, phenol novolak-type epoxy resin, orthocresone novolak-type epoxy resin, DPP novolak-type epoxy resin, Examples include a trifunctional epoxy resin, a trishydroxyphenylmethane type epoxy resin, and a tetraphenylolethane type epoxy resin.

The glycidyl ester type includes, for example, cyclohexyldicarboxylic acid type epoxy resin, orthophthalic acid type epoxy resin and the like.

In the brisidylamine type, a tetraglycidyldiaminodiphenylmethane type epoxy resin,
Triglycidyl isocyanurate type epoxy resin, hydantoin type epoxy resin, 1,3-bis (N, N-
(Diglycidylaminomethyl) cyclohexane type epoxy resin, aminophenol type epoxy resin, aniline type epoxy resin, toluidine type epoxy resin and the like.

As the epoxy resin other than the above, a straight-chain aliphatic epoxy resin, a heterocyclic epoxy resin and the like can also be mentioned.

Among these epoxy resins, glycidyl ether type epoxy resins such as pisphenol A type epoxy resin, pisphenol F type epoxy resin, biphenyl type epoxy resin and phenol novolak type are easily available and handled. It is preferable from the viewpoints of properties and a small amount of impurities.

As the curing agent, for example, diethylene triamine (DETA), triethylene tetramine (TET)
A) aliphatic polyamine compounds such as meta-xylylenediamine (MXDA); isophorone diamine (IPD);
1,3-bisaminomethylcyclohexane (1,3BA
C) and other alicyclic polyamine compounds; diaminodiphenylmethane (DDM), metaphenylenediamine (MPD)
A), aromatic polyamine compounds such as diaminodiphenyl sulfone (DDS), and dicyandiamide (DIC)
Y), polyamine-based curing agents such as organic acid dihydrazide, dimer acid-modified polyamine compound, ketimine, epoxy adduct, thiourea-modified polyamine compound, Mannich-modified polyamine compound; dodecenyl succinic anhydride (DDS)
A), aliphatic anhydrides such as polyazelain anhydride (PAPA); alicyclic anhydrides such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), and methylnadic anhydride (MNA) Products: trimellitic anhydride (TMA), pyromellitic anhydride (PMD)
A), aromatic acid anhydrides such as benzophenonetetracarboxylic acid (BTDA); tetrabromophthalic anhydride (TBP)
Halogen acid anhydrides such as A); polyphenol compounds such as novolak type phenol resins and phenol polymers;
Polymercaptan compounds such as polysulfides, thioesters, thioethers; isocyanate compounds such as isocyanate prepolymers; organic acids such as carboxylic acid-containing polyester resins; benzyldimethylamine (BDM
A) tertiary amine compounds such as 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole (2MZ), 2-ethyl-4-methylimidazole (EMI24), 2-heptadecyl Imidazole compounds such as imidazole (HDI2); Lewis acids such as BF3 monoethylamine and BF3 piperazine; Bronsted acid salts such as aromatic sulfonium salts and aromatic diazonium salts.

In addition to the above curing agents, a curing accelerator and a diluent may be used. The curing accelerator is not particularly limited as long as it does not have reactivity with the epoxy resin oligomer but has an action of lowering the activation energy of the curing reaction, and any commonly known compounds can be used. Imidazoles such as imidazole and benzimidazole; tertiary amines such as benzyldimethylamine; and tertiary phosphines.

The diluent has an effect of lowering the viscosity of the composition of the present invention to improve workability, and the diluent is not limited as long as it has an effect of diluting the epoxy resin oligomer. For example, methyl ethyl ketone, 2
-Methoxyethanol, 2- (2-methoxyethoxy)
Various organic solvents such as ethanol and acetone, n-butyl glycidyl ether, allyl glycidyl ether,
Reactive diluents such as 2-ethylhexyl glycidyl ether, styrene oxide and phenyl glycidyl ether are exemplified.

[0028] a silane clay complex used in the present invention is represented by the following general formula swellable silicate _{(1) Y n SiX 4-} n (1) ( where, n is an integer of 0 to 3, Y Has 1 to 1 carbon atoms
X is a hydrolyzable group and / or a hydroxyl group, which is an organic functional group composed of 25 hydrocarbon groups and a hydrocarbon group having 1 to 25 carbon atoms and a substituent. n Y and 4-n X may be the same or different. ) Is introduced.

The above-mentioned swellable silicate is mainly composed of a tetrahedral sheet of silicon oxide and an octahedral sheet of metal hydroxide, and examples thereof include smectite group clay and swellable mica. Can be When the smectite group clay and the swellable mica are used as the swellable silicate, the dispersibility of the swellable silicate in the epoxy resin composition of the present invention, the availability of the swellable silicate, and the improvement of the physical properties of the resin composition It is preferable from the point of view.

The above smectite group clay is represented by the following general formula (2): X _0.2 to _0.6 Y ₂ to ₃ Z ₄ O ₁₀ (OH) ₂ .nH ₂ O (2) (where X is K, Na, 1 / 2Ca , And 1 / 2Mg
At least one member selected from the group consisting of
e, Mn, Ni, Zn, Li, Al, and at least one member selected from the group consisting of Cr, and Z is at least one member selected from the group consisting of Si and Al. Note that H ₂ O represents a water molecule bonded to an interlayer ion, and n varies remarkably depending on the interlayer ion and the relative humidity. Specific examples of the smectite group clay include, for example, montmorillonite,
Examples include beidellite, nontronite, saponite, iron saponite, hectorite, sauconite, stevensite, bentonite, and the like, and substituted substances, derivatives, and mixtures thereof. The distance between the bottom surfaces of the smectite group clay in the initial aggregation state is about 10 to 1
7 °, and the average particle size of the smectite group clay in the agglomerated state is approximately 1000-1,000,000 °.

The swellable mica is represented by the following general formula (3): X _0.5 to _1.0 Y ₂ to ₃ (Z ₄ O ₁₀ ) (F, OH) ₂ (3) (where X is Li, Na, K , Rb, Ca, Ba, and Sr, at least one selected from the group consisting of
g, one or more selected from the group consisting of Fe, Ni, Mn, Al, and Li, and Z is Si, Ge, Al, F
at least one selected from the group consisting of e and B. )
And natural or synthetic. These are substances having the property of swelling in water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. For example, lithium-type teniolite, sodium-type teniolite, lithium-type Examples thereof include silicon mica, sodium tetrasilicic mica, and the like, and substituted substances, derivatives, and mixtures thereof. The distance between the bottom surfaces of the swellable mica in the initial aggregation state is approximately 10 to 17
Å, and the average particle size of the swellable mica in the aggregated state is about 10
It is 00 to 1,000,000 °.

Some of the above-mentioned swellable mica have a structure similar to that of vermiculite, and such a vermiculite equivalent can be used. The said vermiculite such equivalent has three octahedral type and dioctahedral the following general formula (4) (Mg, Fe, Al) 2 ~ 3 (Si 4-x Al x) O 10 (OH) 2 · (M ⁺ , M ²⁺ _1/2 ) _x · nH ₂ O (4) (where M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x = 0.6 to 0.9) , N =
3.5 to 5). The distance between the bottom surfaces of the vermiculite in the initial aggregation state is about 10 to 17 °, and the average particle size of the vermiculite in the aggregation state is about 1000 to 5,000,000 °.

The swellable silicate may be used alone.
It may be used in combination of more than one kind. Of these,
Montmorillonite, bentonite, hectorite, and swellable mica having sodium ions between layers are preferred from the viewpoint of dispersibility in the epoxy resin composition of the present invention, availability, and the effect of improving the physical properties of the resin composition.

The crystal structure of the swellable silicate is desirably high in purity, which is regularly stacked in the c-axis direction, but a so-called mixed layer mineral in which the crystal cycle is disordered and a plurality of types of crystal structures are mixed is also used. Can be done.

As the silane compound to be introduced into the swellable silicate, any commonly used silane compound can be used, and those represented by the following general formula (1) Y _n SiX _4-n (1) It is. N in the general formula (1) is an integer of 0 to 3, and Y is a group having 1 carbon atom which may have a substituent.
~ 25 hydrocarbon groups. When the hydrocarbon group having 1 to 25 carbon atoms has a substituent, examples of the substituent include a group bonded by an ester bond, a group bonded by an ether bond, an epoxy group, an amino group, and a carboxyl group. , A group having a carbonyl group at the terminal, an amide group, a mercapto group, a group bonded by a sulfonyl bond, a group bonded by a sulfinyl bond, a nitro group, a nitroso group, a nitrile group, a halogen atom and a hydroxyl group. . One of these may be substituted, or two or more may be substituted. X is a hydrolyzable group and / or
A hydroxyl group, and examples of the hydrolyzable group include at least one selected from the group consisting of an alkoxy group, an alkenyloxy group, a ketoxime group, an acyloxy group, an amino group, an aminoxy group, an amide group, and a halogen atom. . In the general formula (1), when n or 4-n is 2 or more, n Y or 4-n X may be the same or different.

As used herein, the term "hydrocarbon group" means a linear or branched (ie, having a side chain) saturated or unsaturated monovalent or polyvalent aliphatic hydrocarbon group, and an aromatic hydrocarbon group. An alicyclic hydrocarbon group means an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, a naphthyl group, a cycloalkyl group and the like. In the present specification, the term “alkyl group” is intended to include a polyvalent hydrocarbon group such as an “alkylene group” unless otherwise specified. Similarly, the alkenyl group, alkynyl group, phenyl group, naphthyl group, and cycloalkyl group include alkenylene group, alkynylene group, phenylene group, naphthylene group, cycloalkylene group, and the like, respectively.

In the above general formula (1), Y has 1 carbon atom.
Examples of the hydrocarbon group having from 25 to 25 include those having a linear long-chain alkyl group such as decyltrimethoxysilane, those having a lower alkyl group such as methyltrimethoxysilane, and 2-hexenyltrimethoxy. Those having an unsaturated hydrocarbon group such as silane, those having an alkyl group having a side chain such as 2-ethylhexyltrimethoxysilane, those having a phenyl group such as phenyltriethoxysilane, and 3-β-naphthyl Examples include those having a naphthyl group such as propyltrimethoxysilane, and those having an aralkyl group such as p-vinylbenzyltrimethoxysilane. Examples of the case where Y is a group having a vinyl group among hydrocarbon groups having 1 to 25 carbon atoms include vinyltrimethoxysilane, vinyltrichlorosilane, and vinyltriacetoxysilane. Y
Is a group having a group substituted with a group bonded by an ester group, and examples thereof include γ-methacryloxypropyltrimethoxysilane. Examples of the case where Y is a group having a group substituted with a group bonded by an ether group include γ-polyoxyethylenepropyltrimethoxysilane and 2-ethoxyethyltrimethoxysilane. Examples of a case where Y is a group substituted with an epoxy group include γ-glycidoxypropyltrimethoxysilane. Examples of the case where Y is a group substituted with an amino group include γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane. No. Examples of the case where Y is a group substituted with a group having a carbonyl group at the terminal include γ-ureidopropyltriethoxysilane. Examples of the case where Y is a group substituted with a mercapto group include γ-mercaptopropyltrimethoxysilane. Examples of a case where Y is a group substituted with a halogen atom include γ-chloropropyltriethoxysilane. Examples of the case where Y is a group having a group substituted with a group bonded by a sulfonyl group include γ-phenylsulfonylpropyltrimethoxysilane. Examples of the case where Y is a group having a group substituted with a group bonded by a sulfinyl group include γ-phenylsulfinylpropyltrimethoxysilane. Examples of a case where Y is a group substituted with a nitro group include γ-nitropropyltriethoxysilane. Examples of the case where Y is a group substituted by a nitroso group include γ-
Nitrosopropyltriethoxysilane may be mentioned. Y
Is a group substituted with a nitrile group, examples thereof include γ-cyanoethyltriethoxysilane and γ-cyanopropyltriethoxysilane. Examples of the case where Y is a group substituted with a carboxyl group include γ- (4-carboxyphenyl) propyltrimethoxysilane. In addition to the above, silane compounds in which Y is a group having a hydroxyl group can also be used. Such an example includes N, N-di (2-hydroxyethyl) amino-3-propyltriethoxysilane. Hydroxyl groups can also be in the form of silanol groups (SiOH).

Substitutes or derivatives of the above silane compounds can also be used. These silane compounds can be used alone or in combination of two or more.

The silane clay composite can be obtained, for example, by adding a silane-based compound after expanding the swellable silicate in a dispersion medium to increase the distance between the bottom surfaces.

The above-mentioned dispersion medium means water, a polar solvent compatible with water, and a mixed solvent of water and the polar solvent. Examples of the polar solvent include alcohols such as methanol, ethanol and isopropanol; glycols such as ethylene glycol, propylene glycol and 1,4-butanediol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran. And amide compounds such as N, N-dimethylformamide and N, N-dimethylacetamide, and other solvents such as pyridine, dimethylsulfoxide and N-methylpyrrolidone.

These polar solvents may be used alone.
It may be used in combination of more than one kind.

The spacing between the bottom surfaces of the swellable silicate can be increased in the dispersion medium by sufficiently stirring and dispersing the swellable silicate in the dispersion medium. The spacing between the bottom surfaces after the enlargement is preferably at least 3 times, more preferably at least 4 times, particularly preferably at least 5 times, as compared to the initial spacing of the swellable silicate. There is no particular upper limit. However, when the distance between the bottom surfaces is increased by about 10 times or more, the measurement of the distance between the bottom surfaces becomes difficult. In this case, the swellable silicate is substantially present in a unit layer.

Here, in the present specification, the initial spacing between the bottom surfaces of the swellable silicate means a particulate swellable silicate in which unit layers are stacked and aggregated before addition to the dispersion medium. It is intended to be the bottom spacing.

The distance between the bottom surfaces can be determined by small angle X-ray diffraction (SAXS) or the like. That is, the X-ray diffraction peak angle value of the dispersion containing the dispersion medium and the swellable silicate is determined by SA
XS is measured, and the peak angle value is applied to Bragg's formula to calculate the bottom surface interval.

In order to efficiently increase the distance between the bottom surfaces of the swellable silicate, stirring at several thousand rpm or more, or a method of applying a physical external force described below can be mentioned. Physical external forces can be applied by using commonly performed wet milling of fillers. As a general wet-milling method of a filler, for example, a method using hard particles can be mentioned. In this method, the hard particles, the swellable silicate, and an optional solvent are mixed and stirred, and the swellable silicate is separated by physical collision between the hard particles and the swellable silicate. Hard particles generally used are filler grinding beads, for example, glass beads or zirconia beads. These grinding beads are selected in consideration of the hardness of the swellable silicate or the material of the stirrer, and are not limited to the above-mentioned glass or zirconia. The particle size is also not specifically limited by a numerical value because it is determined in consideration of the size of the swellable silicate and the like, but a particle having a diameter of 0.1 to 6.0 mm is preferable. . Although the solvent used here is not particularly limited, for example, the above-described dispersion medium is preferable.

As described above, the interval between the bottom surfaces of the swellable silicate is enlarged, and the layers that have been in the aggregated state are cleaved and separated. After the layers are independently present, the silane compound is added and stirred. . In this way, a silane clay composite is obtained by introducing the silane compound to the surface of the cleaved swellable silicate layer.

In the case of using a dispersion medium, the silane-based compound is introduced by adding the silane-based compound to a dispersion containing the swellable silicate having an enlarged bottom surface space and the dispersion medium, followed by stirring. Can be done. When it is desired to introduce the silane compound more efficiently, the rotation speed of the stirring is set to 1000 rpm.
Or more, preferably 1500 rpm or more, more preferably 2000 rpm or more, or 500 (1 / s) or more, preferably 1000 (1) using a wet mill or the like.
/ S) or more, more preferably 1500 (1 / s) or more. The upper limit of the number of revolutions is about 25,000 rp
m, and the upper limit of the shear rate is about 500000 (1 /
s). Stir with a value larger than the upper limit,
It is not necessary to stir at a value greater than the upper limit because the effect does not tend to change any further when shearing is applied.

In the case of a method using a physical external force, a silane compound is added thereto while applying a physical external force to the swellable silicate (for example, while wet milling).
A silane compound may be introduced.

Alternatively, by adding a swellable silicate having an enlarged bottom space by a physical external force to a dispersion medium and adding a silane compound to the dispersion medium in the same manner as in the above-described method using a dispersion medium. Alternatively, a silane compound can be introduced into the swellable silicate.

The introduction of the silane compound into the swellable silicic acid is carried out by reacting a hydroxyl group present on the surface of the swellable silicate having an increased bottom distance with a hydrolyzable group and / or a hydroxyl group of the silane compound. By doing so, a silane compound can be introduced into the swellable silicate.

When the silane compound introduced into the swellable silicate further has a reactive group such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group, or a vinyl group, such a silane compound may be used. It is also possible to further add a compound capable of reacting with a reactive group and react the compound with the reactive group. Thus, the chain length of the functional group chain of the silane compound introduced into the swellable silicate and the polarity can be changed. In this case, as the compound to be added, the above-mentioned silane-based compound itself can be used, but the compound is not limited thereto, and any compound can be used according to the purpose. For example, an epoxy group-containing compound, an amino group Examples of the compound include a compound containing a carboxyl group, a compound containing an acid anhydride group, and a compound containing a hydroxyl group.

The reaction proceeds sufficiently at room temperature, but may be heated if necessary. The maximum temperature during heating can be arbitrarily set as long as it is lower than the decomposition temperature of the silane compound used and lower than the boiling point of the dispersion medium.

The amount of the silane compound used depends on the dispersibility of the silane clay composite in the clay dispersion, the affinity between the silane clay composite and the resin, and the dispersibility of the silane clay composite in the epoxy resin composition. It can be prepared to be sufficiently high. If necessary, a plurality of silane compounds having different functional groups may be used in combination. Therefore, the amount of the silane compound to be added is not limited to a numerical value, but is 0.1 to 200 parts by weight, preferably 0.2 to 180 parts by weight, based on 100 parts by weight of the swellable silicate. Parts by weight, more preferably from 0.3 to 160 parts by weight, even more preferably from 0.4 to 140 parts by weight, particularly preferably from 0.5 to 120 parts by weight. When the amount of the silane compound is less than 0.1 part by weight, the effect of finely dispersing the obtained silane clay composite tends to be insufficient. Also, 20
If the amount is more than 0 parts by weight, the effect does not change, so it is not necessary to add more than 200 parts by weight.

The distance between the bottom surfaces of the silane clay composite obtained as described above can be enlarged compared to the initial distance between the bottom surfaces of the swellable silicate due to the presence of the introduced silane compound. For example, a swellable silicate dispersed in a dispersion medium and having an increased bottom surface interval, when the silane-based compound is not introduced, when the dispersion medium is removed, the layers return to a state in which the layers are aggregated again. For example, by introducing the silane compound after expanding the bottom surface interval, even after removing the dispersion medium, the obtained silane clay composite can exist in a state where the bottom surface interval is expanded without the layers being aggregated. . The distance between the bottom surfaces of the silane clay complex is at least 1.3 times, preferably at least 1.5 times, more preferably at least 1.7 times, particularly preferably at least 2 times, the initial distance of the swellable silicate. It is expanding. As described above, the affinity between the silane clay composite and the resin can be increased by introducing the silane-based compound and by increasing the distance between the bottom surfaces. Here, the introduction of the silane compound into the swellable silicate can be confirmed by various methods. As a method for confirmation, for example, the following method can be mentioned.

First, by simply washing the silane clay complex with an organic solvent such as tetrahydrofuran or chloroform, the adsorbed silane compound is simply washed and removed. The washed silane clay composite is powdered in a mortar or the like and then dried sufficiently. Subsequently, the silane clay composite is sufficiently mixed with a window material such as powdered potassium bromide (KBr) at a predetermined ratio to form a tablet under pressure, and the Fourier transform (FT) -IR is used to perform a transmission method or the like. , The absorption band derived from the silane compound is measured. When more accurate measurement is desired, or when the amount of the introduced silane compound is small, it is possible to measure a sufficiently dried powdery silane clay complex by a diffuse reflection method (DRIFT) as it is. desirable.

It can be confirmed by various methods that the distance between the bottom surfaces of the silane clay composite is larger than that of the swellable silicate. As a method for confirmation, for example, the following method can be mentioned.

That is, in the same manner as described above, the adsorbed silane-based compound is removed from the silane-clay composite by washing with an organic solvent, dried, and then subjected to small-angle X-ray diffraction (SAX).
S) or the like. In this method, the X-ray diffraction peak angle value derived from the (001) plane of the powdery silane clay composite is measured by SAXS, and the angle is applied to Bragg's formula to calculate the bottom surface interval. Similarly, the base spacing of the initial swellable silicate is measured, and by comparing the two, the expansion of the base spacing can be confirmed.

After washing with an organic solvent as described above,
The absorption band derived from the added silane compound is FT-IR
By measuring with SAXS or the like that the bottom surface interval is larger than that of the raw material swellable silicate, it can be seen that a silane clay complex has been formed.

In the epoxy resin composition of the present invention,
The compounding amount of the silane clay composite with respect to 100 parts by weight of the epoxy resin is typically 0.1 to 50 parts by weight, preferably 0.2 to 45 parts by weight, more preferably 0.3 to 40 parts by weight, and The amount is preferably adjusted to 0.4 to 35 parts by weight, particularly preferably 0.5 to 30 parts by weight. If the compounding amount of the silane clay composite is less than 0.1 part by weight, the effect of improving mechanical properties, heat resistance, adhesiveness, and moisture resistance may be insufficient. , Mechanical properties, adhesion and the like tend to be impaired.

The ash content of the epoxy resin composition derived from the silane clay composite is typically 0.1 to 30% by weight, preferably 0.2 to 28% by weight, more preferably 0.3%. To 25% by weight, more preferably 0.4 to 23% by weight, particularly preferably 0.5 to 20% by weight. If the ash content is less than 0.1% by weight, the effect of improving mechanical properties, heat resistance, adhesion, and moisture resistance may be insufficient. If it exceeds 30% by weight, the surface properties, mechanical properties, Adhesion and the like tend to be impaired.

The structure of the silane clay composite dispersed in the epoxy resin composition of the present invention has a swellable silicate before compounding, and has a multi-layered layer of μm-size aggregated silicate. Completely different from the structure. That is, a silane compound having an affinity for the matrix resin is introduced, and the layers are cleaved by using a silane clay composite in which the distance between the bottom surfaces is enlarged compared to the initial swellable silicate,
Subdivide independently of each other. As a result, the silane clay composite is dispersed in the epoxy resin composition in a very fine and independent thin plate shape, and the number thereof is significantly increased as compared with the swellable silicate as a raw material. The dispersion state of such a thin silane clay composite can be expressed by the aspect ratio (ratio of layer length / layer thickness), the number of dispersed particles, the maximum layer thickness, and the average layer thickness described below.

First, when the average aspect ratio is defined as the number average value of the ratio of the layer length / layer thickness of the silane clay composite dispersed in the resin, the silane clay in the epoxy resin composition of the present invention is defined as follows. The average aspect ratio of the composite is 10 to 300, preferably 15 to 300. More preferably, it is 20 to 300. If the average aspect ratio of the silane clay composite is less than 10, the effect of improving the elastic modulus and dimensional stability of the epoxy resin composition of the present invention may not be sufficiently obtained. Further, even if it is larger than 300, the effect does not change any more, so that it is not necessary to make the average aspect ratio larger than 300.

When the [N] value is defined as the number of dispersed particles per unit weight ratio of the swellable silicate in the area of 100 μm ² of the epoxy resin composition, the epoxy resin composition of the present invention The [N] value of the silane clay composite in the above is 30 or more, preferably 45 or more, and more preferably 60 or more. There is no particular upper limit, but when the [N] value exceeds about 1000, the effect does not change any more. The [N] value can be obtained, for example, as follows. That is, the epoxy-based resin composition is about 50 μm to 1 μm.
On an image obtained by cutting out an ultrathin section having a thickness of 00 μm and photographing the section with a TEM or the like, the number of particles of the silane clay composite present in an arbitrary area having an area of 100 μm ² was determined by the weight of the swellable silicate used. It can be determined by dividing by a ratio. Alternatively, on a TEM image, an arbitrary region (area is measured) in which 100 or more particles are present is selected, and the number of particles present in the region is divided by the weight ratio of the swellable silicate used. Then, a value converted to an area of 100 μm 2 may be used as the [N] value. Therefore, the [N] value is the TE value of the epoxy resin composition.
It can be quantified by using an M photograph or the like.

When the average layer thickness is defined as the number average value of the layer thickness of the silane clay composite dispersed in a thin plate shape,
The upper limit of the average layer thickness of the silane clay composite in the epoxy resin composition of the present invention is 500 ° or less, preferably 4 ° C.
It is 50 ° or less, more preferably 400 ° or less. If the average layer thickness is larger than 500 °, the effect of improving the mechanical properties and adhesiveness of the epoxy resin composition of the present invention may not be sufficiently obtained. The lower limit of the average layer thickness is not particularly limited, but is preferably larger than 50 °, more preferably 60 ° or more, and further preferably 70 ° or more.

When the maximum layer thickness is defined as the maximum value of the layer thickness of the silane clay composite dispersed in the form of a thin plate in the epoxy resin composition of the present invention, the maximum layer thickness of the silane clay composite is determined. The upper limit is 2000 ° or less, preferably 1800 ° or less, and more preferably 1500 ° or less. If the maximum layer thickness is more than 2000 °, the balance of moisture resistance, adhesiveness, mechanical properties and surface properties of the epoxy resin composition of the present invention may be impaired. The lower limit of the maximum layer thickness of the silane clay composite is not particularly limited,
Preferably greater than 100 °, more preferably 150 °
Å or more, and more preferably 200 ° or more.

The thickness and length of the layer are determined by heating a thin molded article obtained by curing the epoxy resin composition of the present invention.
It can be determined from an image captured using a microscope or the like.

That is, the thickness of the film prepared by the above-described method on the XY plane is about 0.5 to 0.5.
It is assumed that a thin flat injection-molded test piece of about 2 mm is placed. Approximately 50 μm to 100 μm of the above film or test piece in a plane parallel to the XZ plane or the YZ plane
The thickness can be determined by cutting out an ultrathin section and observing the section with a transmission electron microscope or the like at a high magnification of about 4 to 100,000 or more. The measurement is performed by placing an arbitrary area containing 100 or more silane clay composites on an elephant of the transmission electron microscope obtained by the above method, forming an image with an image processing device or the like, and performing computer processing. And the like. Alternatively, it can also be obtained by measuring using a ruler or the like.

The method for producing the epoxy resin composition of the present invention is not particularly limited. For example, (A) a step of preparing a clay dispersion containing a silane clay composite and an epoxy resin oligomer; A method including a step of curing the resin oligomer is preferred. As described above, the epoxy resin oligomer refers to an oligomer having two or more reactive epoxy groups (oxirane groups) in one molecule and having a molecular weight of about 100 to about 10,000, for example, epichlorohydrin. And phenols or alcohols form a main skeleton, glycidyl ether type where epichlorohydrin and carboxylic acids form a main skeleton, glycidyl ester type where epichlorohydrin and carboxylic acids form a main skeleton, and glycidylamine type where epichlorohydrin and amines or cyanuric acid or hindatoin form a main skeleton. And alicyclic type.

Here, the above clay dispersion may contain a diluent for the epoxy resin oligomer as a component other than the epoxy resin oligomer. Such diluents are the same as those described above, for example, various organic solvents such as methyl ethyl ketone, 2-methoxyethanol, 2- (2-methoxyethoxy) ethanol and acetone, n-butyl glycidyl ether, allyl Reactive diluents such as glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, and phenyl glycidyl ether are exemplified.

The method of preparing the clay dispersion in the above step (A) is not particularly limited. For example, a method of sufficiently mixing a silane clay composite and an epoxy resin oligomer prepared in advance, or a method of mixing a silane clay composite and a dilution After mixing the agents sufficiently, a method of further adding and mixing an epoxy resin oligomer may be used.

For efficient mixing, a shearing speed of 500 rpm or more or a shear rate of 300 (1 / s) or more is applied. The upper limit of the number of revolutions is 25000 rp
m, and the upper limit of the shear rate is 500000 (1 / s).
It is. There is a tendency that the effect does not change even if the stirring is performed at a value larger than the upper limit, so that it is not necessary to perform the stirring at a value larger than the upper limit.

In the silane clay composite contained in the clay dispersion obtained in the step (A), the initial lamination / agglomeration structure such as that of the swellable silicate disappears almost completely and becomes a thin plate. Either it is subdivided or the interval between the layers is enlarged, so that a so-called swollen state is obtained. The bottom surface interval can be used as an index indicating the swelling state. The distance between the bottom surfaces of the silane clay composite in the clay dispersion is preferably at least three times, preferably at least four times, the initial distance between the bottom surfaces of the swellable silicate in order for the silane clay complex to be finely divided and formed into a thin plate. Is more preferable, and more preferably 5 times or more. Then, the step (B), that is, the step of curing the epoxy resin oligomer can be performed. The curing method is not particularly limited, and the curing can be performed by a method generally used, usually using a curing agent and curing at room temperature or under heating. As described above, a specific example of the curing agent is diethylenetriamine (D
ETA), triethylenetetramine (TETA), metaxylylenediamine (MXDA), diaminodiphenylmethane (DDM), metaphenylenediamine (MPD)
A), dimer acid-modified polyamine compound, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA),
Polyaddition type such as novolak type phenol resin and phenol polymer; benzyldimethylamine (BDMA), 2,
4,6-trisdimethylaminomethylphenol (DM
P-30) and the like; and condensed types such as resol-type phenol resins, methylol group-containing urea resins, and methylol group-containing melamine resins. In addition to the above-mentioned curing agents, a curing accelerator may be used in combination with a curing accelerator for the purpose of accelerating curing, and a diluent may be used in combination for the purpose of improving workability.

When another epoxy resin oligomer is introduced into the resin component, it is obtained by adding and mixing another desired epoxy resin oligomer and performing a curing reaction. The reason why the epoxy resin composition of the present invention has excellent mechanical properties, heat resistance, adhesiveness at high temperature, moisture resistance, excellent surface properties, and the like, is that the silane clay composite in the epoxy resin has a large number of fine particles. This is because the average thickness, the maximum thickness, the number of dispersed particles, and the average aspect ratio of the silane clay composite, which serve as indicators of the dispersion state, are in the above-mentioned ranges.

The dispersion state of the silane clay composite can be controlled by one or more steps selected from the step of preparing the silane clay composite and the step (A) in the above-mentioned method for producing an epoxy resin composition.

That is, for example, in the step of preparing the silane clay composite, if the stirring force and the shearing force at the time of dispersing the swellable silicate are constant, the type of the dispersion medium and a plurality of types of dispersion medium are used. When used, the state of swelling / cleavage of the swellable silicate changes according to the mixing ratio and the order of mixing. For example, when montmorillonite is used as the swellable silicate, if the dispersion medium is only water, the montmorillonite swells and cleaves to a state close to the unit layer.
When a silane compound having a highly polar group such as an amino group, a mercapto group or a nitrile group is reacted in that state, a dispersion in which a silane clay complex having a unit layer thickness of approximately approximately is dispersed is prepared. On the other hand, ethanol, tetrahydrofuran (THF), methyl ethyl ketone (MEK), pyridine, N, N-dimethylformamide (DMF), N, N
-When a mixed solvent of a polar solvent such as dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP) and water is used as a dispersion medium, or when montmorillonite is dispersed in the polar solvent and then water is added, about It is cleaved and subdivided into a state in which several to about hundreds of unit layers are stacked.

When the silane compound is reacted in this state, a dispersion in which the silane clay composite having a thickness of about several to about several hundreds is dispersed is prepared. The dispersion state of the silane clay composite can be controlled by performing steps (A) and (B) in the method for producing an epoxy resin composition so as to maintain those states.

In the step (A), the dispersion state of the silane clay composite changes depending on the type and molecular weight of the epoxy resin oligomer mixed with the clay dispersion, the type of diluent used as required, and the like. To keep those states,
The dispersion state of the silane clay composite can be controlled by performing the step (B) in the method for producing an epoxy resin composition.

The epoxy resin composition of the present invention may contain, if necessary, polybutadiene, butadiene-styrene copolymer, acrylic rubber, ionomer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, natural Rubber, chlorinated butyl rubber, homopolymer of α-olefin, copolymer of two or more α-olefins (including any copolymer such as random, block, and graft, or a mixture thereof) Alternatively, an impact modifier such as an olefin-based elastomer can be added. These may be modified with an acid compound such as maleic anhydride or an epoxy compound such as glycidyl methacrylate. Further, any other resin, for example, a thermoplastic resin such as a rubbery polymer reinforced styrene resin, or a thermosetting resin such as an unsaturated polyester resin alone or
More than one species may be used in combination. Further, the epoxy resin composition of the present invention, depending on the purpose, pigments and dyes, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants,
Additives such as plasticizers, flame retardants, and antistatic agents can be added. The epoxy resin composition of the present invention may be molded by cast molding, and other molding methods such as filament winding may be employed.

Such a molded article has mechanical properties, heat resistance,
Since it is excellent in adhesiveness at high temperature, moisture resistance, surface properties, and the like, it is suitably used, for example, for adhesives, sealants, paints, composite materials, and the like.

In the epoxy resin composition of the present invention, since the silane clay composite is very fine and thinly dispersed in a plate shape, the specific gravity is significantly increased without impairing the surface smoothness. The elastic modulus and dimensional stability can be improved without any problem.

[0081]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

The main raw materials used in the examples and comparative examples are shown below. Unless otherwise specified, the raw materials were not purified. Tetrahydrofuran: Tetrahydrofuran (hereinafter, THF) manufactured by Wako Pure Chemical Industries, Ltd. was used. -2-methoxyethanol: 2-methoxyethanol (hereinafter, referred to as 2ME) manufactured by Wako Pure Chemical Industries, Ltd. was used. -2- (2-methoxyethoxy) ethanol: 2- (2-methoxyethoxy) ethanol (hereinafter referred to as 22MEE) manufactured by Wako Pure Chemical Industries, Ltd. was used. Epoxy resin oligomer: Epicoat 828 (hereinafter referred to as EP828) manufactured by Yuka Shell Co., Ltd., which is a reaction product of bisphenol A and epichlorohydrin, was used. -4,4'-diaminodiphenylmethane: 4,4'-diaminodiphenylmethane (hereinafter referred to as DDM) manufactured by Wako Pure Chemical Industries, Ltd. was used. Montmorillonite: Natural montmorillonite from Yamagata Prefecture (bottom spacing = 13 °) was used. Swellable mica: A mixture obtained by mixing 25.4 g of talc and 4.7 g of finely pulverized sodium silicofluoride and heat-treating the mixture at 800 ° C. (bottom interval = 12 °) was used. -Γ-glycidoxypropyltrimethoxysilane: A-187 manufactured by Nippon Unicar Co., Ltd. (hereinafter referred to as A187) was used. Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane: A-186, manufactured by Nippon Unicar Co., Ltd.
(Hereinafter referred to as A186). The evaluation methods in Examples and Comparative Examples are summarized below. (FT-IR) 1.0 g of the silane clay complex was added to 50 ml of tetrahydrofuran (THF), and the mixture was stirred for 24 hours to wash and remove the adsorbed silane compound, followed by centrifugation to separate the supernatant. This washing operation was repeated three times. After washing, about 1 mg of the sufficiently dried silane clay complex and about 200 mg of KBr powder were sufficiently mixed using a mortar, and a KBr disk for measurement was prepared using a tabletop press. Next, an infrared spectrometer (Shimadzu Corporation)
, 8100M). The detector used was an MCT detector cooled with liquid nitrogen, and the resolution was 4c.
m ⁻¹ and the number of scans were 100. (Measurement of dispersion state) Regarding the silane clay composite, TE
The following procedure was performed using M.

An ultra-thin section having a thickness of 50 to 100 μm was used. Transmission electron microscope (JEOL JEM-1200E
Using X), the dispersion state of the silane clay composite was observed and photographed at an acceleration voltage of 80 kV and a magnification of 40,000 to 1,000,000 times. TEM
In the photograph, a region where 100 or more dispersed particles are present is selected, and the number of particles ([N] value), layer thickness and layer length are manually measured using a ruler with a scale, or interquest as required. The measurement was performed by processing using an image analysis device PIASIII of the company.

The average aspect ratio was a number average value of the ratio between the layer length and the layer thickness of each silane clay composite. [N] value was measured as follows. First, on the TEM image, the number of particles of the silane clay composite existing in the selected region is determined. Separately, the ash content of the resin composition derived from the silane clay composite is measured. Divide the number of particles by the ash content,
The value converted to the area of 100 μm ² was defined as the [N] value.

The average layer thickness was the number average value of the individual silane clay composite layer thicknesses, and the maximum layer thickness was the maximum value among the individual silane clay composite layer thicknesses.

When the dispersed particles are large and observation with a TEM is inappropriate, the [N] value can be determined using an optical microscope (optical microscope BH-2 manufactured by Olympus Optical Co., Ltd.) in the same manner as described above. I asked.

The aspect ratio of the dispersed particles that are not dispersed in a plate shape was a value of major axis / minor axis. Here, the long diameter is intended to be the long side of the rectangle assuming a rectangle having the smallest area among rectangles circumscribing the target particle in a microscope image or the like. Further, the minor axis is intended to mean the short side of the minimum rectangle. (Measurement of bottom spacing by small angle X-ray diffraction (SAXS))
Using an X-ray generator (RU-200B, manufactured by Rigaku Corporation), target CuKα ray, Ni filter, voltage 4
0 kV, current 200 mA, scanning angle 2θ = 0.2 to 16.0
°, the step angle = 0.02 ° under the measurement conditions, the bottom spacing was measured.

The distance between the bottom surfaces is represented by a small angle X-ray diffraction peak angle value of B
It was calculated by substituting into the formula of ragg. However, when it is difficult to confirm the small-angle X-ray peak angle value, it is confirmed that the layer has been sufficiently cleaved and the crystallinity has substantially disappeared, or the peak angle value is approximately 0.8 ° or less. Was considered difficult, and the evaluation result of the bottom surface spacing was set to> 100 °. (Bending characteristics) Approximately 10 × 100 × 6m by casting method
m test pieces were prepared. The bending strength and the flexural modulus of the test piece of the obtained test piece were measured according to ASTM D-790. (Adhesion strength) The surface to be adhered was made of aluminum, and the epoxy resin composition of the present invention was applied and adhered.
% RH, after 24 hours) and after immersion in water (40 ° C, 90% R
H, after 96 hours), a tensile shear was applied in a high temperature environment (100 ° C.), and the measurement was performed according to ASTM D1002. (Heat resistance) Test pieces were prepared in the same manner as in the bending property test. The deflection temperature under load was measured according to ASTM D-648. (Surface property) The surface property was evaluated by the center line average roughness of a test piece prepared by the same method as in the bending property test. The center line surface roughness is a surface roughness meter manufactured by Tokyo Seimitsu Co., Ltd .;
It measured using 500A. (Ash content) The ash content of the epoxy resin composition derived from the silane clay composite was measured according to JIS K7052.

(Example 1) Step (A) 125 g of montmorillonite was added to 3500 g of ion-exchanged water, and the resulting mixture was mixed with a wet mill manufactured by Nippon Seiki Co., Ltd. for 500 minutes.
The mixture was stirred at 0 rpm for 5 minutes and mixed. Thereafter, 28 g of A187 (previously hydrolyzed at pH 5.0) was added, and the mixture was further stirred under the conditions shown in Table 1 to prepare a silane clay composite. (Confirmation of the silane clay composite was carried out by separating, drying, and pulverizing the solid content, measuring the bottom distance by SAXS, and washing the solid with THF.
The measurement was performed by measuring the absorption band of the functional group derived from the silane compound by T-IR. The results are shown in Table 1.
Examples 2-6 are the same). Then 1400g of 22MEE
Was added and mixed well, and then water was removed. Then 1
Add 350 g of EP828 and mix thoroughly with stirring to obtain the silane clay complex, 22MEE and EP8.
A clay dispersion containing 28 was prepared. The bottom spacing of the silane clay composite in the clay dispersion was> 100 °. Step (B) To the above clay dispersion, 380 g of DDM was added as a curing agent, and a curing reaction was allowed to proceed under the conditions shown in Table 2 to obtain an epoxy resin composition containing a silane clay composite. evaluated. The ash content and properties are shown in Table 2 together with the following examples.

(Example 2) In step (A), A18
Example 7 was repeated except that the amount of 7 was changed to 18 g.
An epoxy resin composition containing a silane clay composite was obtained and evaluated.

(Example 3) In step (A), A18
Example 7 was repeated in the same manner as in Example 1 except that 35 g of A186 (preliminarily hydrolyzed with PH 5.0) was used instead of 7, to obtain and evaluate an epoxy resin composition containing a silane clay composite. .

Example 4 An epoxy resin containing a silane clay composite was prepared in the same manner as in Example 1 except that swelling mica was used in place of montmorillonite and that the amount of A187 was 45 g in step (A). A resin composition was obtained and evaluated. The bottom spacing of the silane clay complex in the clay dispersion is
It was 65Å.

Comparative Example 1 An epoxy resin was obtained and evaluated in the same manner as in Example 1 without using a clay dispersion.
The results are shown in Table 3 together with the following comparative examples. (Comparative Example 2) 125 g of montmorillonite, 1400 g
Of 22MEE and 1350 g of EP828 were thoroughly mixed with stirring. The bottom spacing of the montmorillonite in the mixture was 13 °. Next, 380 g of DDM was added, and a curing reaction was allowed to proceed under the conditions shown in Table 3 to obtain an epoxy resin composition containing montmorillonite.
evaluated.

Comparative Example 3 28 g of A187 was directly sprayed on 125 g of montmorillonite using a spray.
The montmorillonite was silane treated by mixing for hours. The bottom spacing of silane treated montmorillonite is 13Å
After washing with THF, absorption bands derived from oxirane groups, ether groups and ethylene groups were observed as a result of measurement by FT-IR.

An epoxy resin composition was obtained and evaluated in the same manner as in Comparative Example 2, except that the above-mentioned silane-treated montmorillonite was used instead of montmorillonite.

(Example 5) Step (A) 36 g of montmorillonite was added to 1000 g of ion-exchanged water, and the mixture was cooled to 5000 using a wet mill manufactured by Nippon Seiki Co., Ltd.
The mixture was stirred for 5 minutes at rpm. Then, 8 g of A1
After adding 87 (previously hydrolyzed at pH 5.0), the mixture was further stirred under the conditions shown in Table 1 to prepare a silane clay composite. Then, 400 g of 2ME was added and mixed well, after which the water was removed. Then, by adding 390 g of EP828 and stirring and mixing well,
A clay dispersion was prepared containing the silane clay complex, 22MEE and EP828. The bottom spacing of the silane clay composite in the clay dispersion was> 100 °. Step (B) To the above clay dispersion, 109 g of DDM was added as a curing agent, and the mixture was sufficiently stirred and mixed. Then, it was applied on an aluminum plate and semi-cured under the conditions shown in Table 4 to form an adhesive layer. Then, superimpose the polyimide film,
By allowing the curing reaction to proceed under the conditions shown in Table 4, the epoxy resin composition containing the silane clay composite was adhered and evaluated. The ash content and properties are shown in Table 4 together with Example 6 below.

(Example 6) In step (A), A18
Example 7 was repeated in the same manner as in Example 5 except that 10 g of A186 (preliminarily hydrolyzed at pH 5.0) was used instead of 7, and the epoxy resin composition containing the silane clay composite was adhered and evaluated. did.

Comparative Example 4 An epoxy resin was adhered to an aluminum plate in the same manner as in Example 5 without using a clay dispersion, and evaluated. Combining the results with the following comparative examples,
The results are shown in Table 5. (Comparative Example 5) 36 g of montmorillonite, 400 g of 2
2MEE and 390g of EP828 were thoroughly stirred and mixed. The bottom spacing of montmorillonite in the mixture is 13Å
Met. Next, 109 g of DDM was added, and adhered to an aluminum plate under the conditions shown in Table 5, and evaluated.

Comparative Example 6 Montmorillonite was silane-treated by directly spraying 8 g of A187 onto 36 g of montmorillonite using a spray and mixing for 1 hour. The bottom surface interval of the silane-treated montmorillonite was 13 °, and after washing with THF, as measured by FT-IR, absorption bands derived from oxirane groups, ether groups, and ethylene groups were observed.

The montmorillonite was bonded and evaluated in the same manner as in Comparative Example 5 except that the above-mentioned silane-treated montmorillonite was used instead of montmorillonite.

[0101]

As described in detail above, in the epoxy resin composition, the unit layers of the swellable silicate are separated and cleaved to form one aggregated particle of the swellable silicate. Subdivision into a number of ultra-fine lamellar layers, that is, an average layer thickness of 500 ° or less, or a maximum layer thickness of 2000 ° or less, or an average aspect ratio (layer length / layer thickness Ratio) is 10 to 300, and the number of particles per unit ratio of the silane clay composite existing in the area of 100 μm ² is 30 or more, so that the surface properties are not impaired, and the mechanical properties and the adhesion at high temperatures are maintained. Properties, moisture resistance and heat resistance can be improved. For the swellable silicate to be finely divided into thin plates as described above in the epoxy resin, it is essential to introduce a silane compound into the swellable silicate to form a silane clay composite.

The epoxy resin composition of the present invention can be produced, for example, by the production method of the present invention, that is, (A) a step of preparing a clay dispersion containing a silane clay composite and an epoxy resin oligomer, and (B) an epoxy resin. And a step of curing the oligomer.

[0103]

[Table 1]

[0104]

[Table 2]

[0105]

[Table 3]

[0106]

[Table 4]

[0107]

[Table 5]

Claims (7)

[Claims] 1. An epoxy resin composition containing an epoxy resin and a silane clay composite, wherein the silane clay composite is added to a swellable silicate by the following general formula (1): Y _n SiX _4-n (1) (Where n is an integer of 0 to 3 and Y is 1 to 3 carbon atoms)
X is a hydrolyzable group and / or a hydroxyl group, which is an organic functional group composed of 25 hydrocarbon groups and a hydrocarbon group having 1 to 25 carbon atoms and a substituent. n Y and 4-n X may be the same or different. An epoxy resin composition prepared by introducing a silane compound represented by the formula (1), wherein the average layer thickness of the silane clay composite in the resin composition is 500 ° or less. 2. The maximum thickness of the silane clay composite is 2000.
エ ポ キ シ The epoxy resin composition according to claim 1, wherein: 3. An epoxy resin composition containing an epoxy resin and a silane clay composite, wherein the silane clay composite is added to a swellable silicate by the following general formula (1): Y _n SiX _4-n (1) (Where n is an integer of 0 to 3 and Y is 1 to 3 carbon atoms)
X is a hydrolyzable group and / or a hydroxyl group, which is an organic functional group composed of 25 hydrocarbon groups and a hydrocarbon group having 1 to 25 carbon atoms and a substituent. n Y and 4-n X may be the same or different. ) Is prepared by introducing a silane compound represented by the formula (1), and the resin composition has an average aspect ratio (ratio of layer length / layer thickness) of 10 to 300, and [ N] value is 30 or more, wherein the [N] value is defined as the number of particles per unit ratio of the silane clay complex present in an area of 100 μm ² of the resin composition. Composition. 4. The [N] value is 30 or more, where the [N] value is defined as the number of particles per unit ratio of the silane clay complex present in an area of 100 μm ² of the resin composition. The epoxy resin composition according to claim 1, wherein the composition is prepared. 5. The epoxy resin composition according to claim 1, wherein an average aspect ratio (ratio of layer length / layer thickness) of the silane clay composite in the resin composition is from 10 to 300. 6. A step of preparing a clay dispersion containing a silane clay composite and an epoxy resin oligomer,
The method for producing an epoxy resin composition according to claim 1, 2, 3, 4, or 5, comprising a step of curing the epoxy resin oligomer (B). 7. The method according to claim 6, wherein the bottom spacing of the silane clay complex in the clay dispersion obtained in the step (A) is at least three times the bottom spacing of the swellable silicate. A process for producing the epoxy resin composition according to the above.