JP3458379B2 - Silane-modified epoxy resin composition and cured product thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silane-modified epoxy resin composition and a cured product thereof.

[0002]

2. Description of the Related Art Epoxy resins have hitherto been generally used as a composition in combination with a curing agent, and the composition has been favored in the field of electric / electronic materials. However, with the recent development of the electric / electronic material field, a cured product of an epoxy resin composition is required to have higher performance, and in particular, improvement in heat resistance is desired.

In order to improve the heat resistance of a cured product of an epoxy resin composition, for example, a method using a composition in which a filler such as glass fiber, glass particles and mica is mixed in addition to an epoxy resin and a curing agent is used. There is. However, even with this method, sufficient heat resistance cannot be obtained. In addition, the transparency of the cured product obtained by this method is lost, and the adhesiveness at the interface between the filler and the epoxy resin is poor, so that mechanical properties such as elongation are insufficient.

Further, as a method for improving the heat resistance of a cured product of an epoxy resin composition, a method using a composite of an epoxy resin and silica has been proposed (JP-A-8-10).
No. 0107). The complex is a solution of a partially cured epoxy resin, hydrolyzable alkoxysilane,
It can be obtained by further curing the cured product, hydrolyzing the alkoxysilane to form a sol, and further polycondensing to form a gel. However, the cured product obtained from such a composite has improved heat resistance to some extent as compared with the cured product of the epoxy resin alone, but due to water in the composite, water generated during curing, and alcohol, a cured product is obtained. Voids are generated inside. Further, when the amount of alkoxysilane is increased for the purpose of further improving heat resistance, transparency of the cured product obtained by aggregation of silica generated by the sol-gel curing reaction is lost and whitening occurs, and a large amount of alkoxysilane is added. A large amount of water is required to turn it into a sol, and as a result, warpage and cracks of the cured product are caused.

Further, a composition in which a silane-modified epoxy resin obtained by reacting an epoxy resin with a silicone compound and a phenol novolac resin as a curing agent are combined (Japanese Patent Laid-Open No. 3-201466), a bisphenol A type epoxy resin, A composition in which a silane-modified epoxy resin obtained by reacting tetrabisbromobisphenol A and a methoxy group-containing silicone intermediate is combined with a phenol novolac resin which is a curing agent (JP-A-61-27224).
No. 3, JP-A-61-272244, etc.) are also proposed. However, the cured products of these epoxy resin compositions have insufficient heat resistance because the main constituent units of the silicone compound and the methoxy group-containing silicone intermediate are diorganopolysiloxane units and cannot form silica. .

[0006]

The present invention provides a silane-modified epoxy resin composition having excellent heat resistance and capable of obtaining a cured product free from voids, cracks, etc., and a cured product obtained from the composition. The purpose is to do.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that an alkoxy group-containing silane-modified epoxy resin comprising a specific epoxy resin and a specific alkoxysilane partial condensate, and The inventors have found that an epoxy resin-silica hybrid cured product that meets the above purpose can be obtained with a composition comprising a curing agent for an epoxy resin, and have completed the present invention.

That is, the present invention has an epoxy equivalent of 400
Bisphenol type epoxy resin (1) having an epoxy equivalent of more than g / eq and less than 10,000 g / eq and an epoxy equivalent of 170 g / eq
Used weight ratio ((1) / (2)) with the bisphenol type epoxy resin (2) of more than 400 g / eq and less than 0.1
Alkoxy group-containing silane-modified epoxy resin (A) obtained by subjecting a bisphenol-type epoxy resin mixture of 1.0 to 1.0 to a dealcoholization condensation reaction with an alkoxysilane partial condensate (3), and a curing agent for an epoxy resin (B).
The present invention relates to a silane-modified epoxy resin composition containing: The present invention also relates to an epoxy resin-silica hybrid cured product obtained by curing the epoxy resin composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the bisphenol type epoxy resin mixture which is the raw material of the alkoxy group-containing silane-modified epoxy resin (A) in the present invention has a bisphenol content of more than 400 g / eq and less than 10,000 g / eq of epoxy equivalent. Type epoxy resin (1) (hereinafter, simply referred to as epoxy resin (1)) and bisphenol type epoxy resin (2) (hereinafter, simply referred to as epoxy resin (2)) having an epoxy equivalent of more than 170 g / eq and less than 400 g / eq. To be done. Epoxy resin (1) and epoxy resin (2)
Is bisphenol and epichlorohydrin or β-
It is obtained by reaction with a haloepoxide such as methylepichlorohydrin. The bisphenols include those obtained by reacting phenol or 2,6-dihalophenol with aldehydes or ketones such as formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone, benzophenone; obtained by oxidation of dihydroxyphenyl sulfide with peracid. Examples thereof include those obtained by an etherification reaction of hydroquinones and the like.

Each of the epoxy resin (1) and the epoxy resin (2) has a hydroxyl group capable of forming a silicate ester by a dealcoholization condensation reaction with the alkoxysilane partial condensate (3). The hydroxyl group does not have to be contained in all the molecules constituting the epoxy resin (1) and the epoxy resin (2), and it is sufficient that these resins have a hydroxyl group.

Among these bisphenol-type epoxy resins, the bisphenol A-type epoxy resin using bisphenol A as the bisphenol is most widely used and is preferable because it is inexpensive.

The bisphenol A type epoxy resin has the general formula (a):

[0013]

[Chemical 1]

It is a compound represented by:

The epoxy resin (1) used in the present invention has an epoxy equivalent of more than 400 g / eq and less than 10,000 g / eq, and has a number average molecular weight of 800 to 200.
It is about 00. When the epoxy resin (1) is a bisphenol A type epoxy resin, the average value of the number m of repeating units in the general formula (a) corresponds to 1.6 to 69. When the epoxy equivalent is 400 g / eq or less, the number of hydroxyl groups in the epoxy resin that reacts with the alkoxysilane partial condensate (3) decreases, and therefore the unreacted alkoxysilane in the obtained alkoxy group-containing silane-modified epoxy resin. Since the content of the partial condensate increases and it becomes difficult to obtain a flexible semi-cured product (sol-gel cured product),
Not preferable. On the other hand, the epoxy equivalent is 10,000 g / e
When it is q or more, the epoxy resin (1) and the alkoxysilane partial condensate (3) are not compatible with each other at the reaction temperature and the dealcoholization reaction is difficult to proceed. Incidentally, the epoxy resin (1) may contain one having a repeating unit number m of zero as long as the epoxy equivalent satisfies the above range.

The epoxy resin (2) as a raw material of the alkoxy group-containing silane-modified epoxy resin (A) in the present invention is
It is mandatory for the following reasons. That is, the resulting silane-modified epoxy resin composition is finally completely cured (ring opening / crosslinking of the epoxy group in the epoxy group in the alkoxy group-containing silane-modified epoxy resin (A) and the epoxy resin curing agent (B)). It is used for the intended purpose after being cured by the reaction, and in the state where the sol-gel curing by the hydrolysis and condensation in the alkoxy group-containing silane-modified epoxy resin (A) has progressed). However, in a specific application, it may be handled or commercialized in a semi-cured state at an intermediate stage before being completely cured. In such a case, a semi-cured state (alkoxy group in the alkoxy group-containing silane-modified epoxy resin (A) and the epoxy group curing agent (B) does not undergo ring-opening / cross-linking reaction of the epoxy group, Sufficient flexibility is required in the group-containing silane-modified epoxy resin (A), which means a state in which only sol-gel curing by hydrolysis and condensation has proceeded). Therefore, in the present invention, the alkoxy group-containing silane-modified epoxy resin (A)
The required performance is satisfied by using the epoxy resin (1) and the epoxy resin (2) in combination at a predetermined ratio as the constituent raw materials.

The epoxy resin (2) has an epoxy equivalent of 17
It is more than 0 g / eq and less than 400 g / eq and has a number average molecular weight of about 340 to 800. When the epoxy resin (2) is a bisphenol A type epoxy resin,
The average value of the repeating unit number m in the general formula (a) is 0 to 1.
Corresponding to 62. As long as the epoxy resin (2) satisfies the above epoxy equivalent range, the number of repeating units is m.
May include more than one. As will be described later, in order to use the resulting alkoxy group-containing silane-modified epoxy resin (A) in a solventless application, when the dealcoholization condensation reaction is attempted to proceed in the absence of a solvent, the epoxy resin (2) Significant to use. That is, when the epoxy resin (1) and the alkoxysilane partial condensate (3) are subjected to a dealcoholization condensation reaction in the absence of a solvent, the two may not be sufficiently compatible at the reaction temperature. In this case, the epoxy resin This is because (2) functions as a compatibilizer. However, when a bisphenol type epoxy resin having an epoxy equivalent of 400 g / eq or more is used, the compatibilizing effect is reduced and the reaction is difficult to proceed due to non-uniformity in the system during dealcoholization condensation reaction.

In the present invention, as described above, it is essential to use the bisphenol type epoxy resin mixture obtained by using the epoxy resin (1) and the epoxy resin (2) together in a predetermined ratio. This is because the combined use can achieve the object of the present invention that a semi-cured product (sol-gel cured product) that is flexible and has a high processability can be easily prepared. The weight ratio of the epoxy resin (1) and the epoxy resin (2) used is
Since the performance of the obtained epoxy resin composition or semi-cured product is greatly affected, (1) / (2) must be in the range of 0.1 to 1.0, preferably 0.2 to 0.8. It is said that The equivalent weight of the bisphenol type epoxy resin mixture in which the epoxy resin (1) and the epoxy resin (2) are combined is preferably 200 to 350 g / eq. If the weight ratio exceeds 1.0 or the equivalent weight of the bisphenol type epoxy resin mixture exceeds 350 g / eq, the tendency to gel during the reaction with the epoxy resin becomes high, and if the weight ratio is less than 0.1. Or the epoxy equivalent is 2
If the amount is less than 00 g / eq, the amount of the alkoxysilane partial condensate (3) remaining in the alkoxy group-containing silane-modified epoxy resin (A), which is a reaction product, increases, so that both are not preferable.

Further, the alkoxysilane partial condensate (3) constituting the alkoxy group-containing silane-modified epoxy resin (A) in the present invention, in the presence of an acid or base catalyst,
The following alkoxysilane compound and water may be added and partially hydrolyzed and condensed to be used.

Examples of the alkoxysilane compound include
For example, general formula (b): R¹ _pSi (OR²)_4-p (In the formula, p represents 0 or 1. R¹Is directly on the carbon atom
A lower alkyl group which may have a bonded functional group, ari
Group or unsaturated aliphatic residue. R²Is a methyl group
Or an ethyl group, R²Even though they are the same, they are different
It may be. The compound represented by these can be illustrated.

Specific examples of the above-mentioned alkoxysilane which is a constituent raw material of the alkoxysilane partial condensate (3) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyltri. Ethoxysilane, n-
Examples thereof include propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane.

As the above-mentioned alkoxysilane partial condensate (3), those obtained from methoxysilanes among the alkoxysilane compounds which are the constituent raw materials are reactive with the epoxy resin (1) and the epoxy resin (2). It is preferable because it is rich in epoxy resin and a cured epoxy resin-silica hybrid product can be prepared at a relatively low temperature. Further, in consideration of heat resistance and thickening of the hybrid cured product, a trifunctional alkoxysilane (p = 1 in the general formula (b)) is preferable among the alkoxysilane compounds which are the constituent raw materials, and particularly considering general versatility. Methyltrimethoxysilane is more preferred.

The alkoxysilane partial condensate (3) is represented by, for example, the following general formula (c) or (d). General formula (c):

[0024]

[Chemical 2]

(In the formula, R ¹ represents a lower alkyl group, an aryl group or an unsaturated aliphatic residue which may have a functional group directly bonded to a carbon atom. R ² represents a methyl group or an ethyl group. , R ² may be the same or different.)

General formula (d):

[0027]

[Chemical 3]

(In the general formula (d), R ¹ and R ² are the same as those in the general formula (c).)

The alkoxysilane partial condensate (3) has a number average molecular weight of about 230 to 2000, and in the general formulas (c) and (d), the average number of repeating units n is 2 to 11.
Is preferred. When the value of n exceeds 11, the solubility is deteriorated, the compatibility with the epoxy resin (1) and the epoxy resin (2) is significantly lowered at the reaction temperature, and the reactivity with the epoxy resin (1) is lowered. It is not preferable because it tends to occur. When n is 2 or less, alcohol is distilled out together with alcohol out of the reaction system during the reaction, which is not preferable.

The alkoxy group-containing silane-modified epoxy resin (A) according to the present invention is an epoxy resin (1), an epoxy resin (2) and an alkoxysilane partial condensate (3).
Is obtained by a dealcoholization condensation reaction in the presence of a solvent or in the absence of a solvent. The epoxy resin (1)
The weight ratio of (2) to the alkoxysilane partial condensate (3), that is, the weight of the alkoxysilane partial condensate (3) in terms of silica / the weight of the bisphenol epoxy resin mixture is not particularly limited, but is usually Is 0.
It is 1 to 0.5, and preferably 0.13 to 0.4. Here, the weight of the alkoxysilane partial condensate (3) in terms of silica means that the alkoxysilane partial condensate (3) undergoes a sol-gel curing reaction to give a compound represented by the general formula (e); R ¹ _p SiO 2.
_{(4-p) / 2} (the values in the formula are the same as those in the general formula (b)) are the weights when the silica is obtained, and excess water is added to the alkoxysilane partial condensate (3). It can be calculated by obtaining the weight ratio of silica produced by heating at 120 ° C. If the weight ratio is less than 0.1, the heat resistance is not improved so much, and if it exceeds 1.0, the hybrid cured product becomes brittle, which is not preferable.

When a high molecular weight epoxy resin (1) having an average epoxy equivalent of 800 or more is used in a weight ratio of the epoxy resin mixture (epoxy resin (1) / epoxy resin (2)) of 0.7 or more. When the average number of repeating units n> 7 of the general formula (c) is used as the starting material for the alkoxysilane partial condensate (3), the hydroxyl groups of the epoxy resin (1) and the epoxy resin (2) are completely If the dealcoholization condensation reaction is carried out until it disappears, it tends to cause high viscosity and gelation. In such a case, a method such as stopping the dealcoholization reaction during the reaction is used to prevent the increase in viscosity and gelation. For example, when the viscosity is increased, the alcohol flowing out may be refluxed to adjust the amount of alcohol distilled off from the reaction system, or the reaction system may be cooled to terminate the reaction.

The production of the alkoxy group-containing silane-modified epoxy resin (A) can be carried out in the presence or absence of a solvent, as described above. In the dealcoholization condensation reaction in the present invention, the reaction temperature is about 50 to 130 ° C, preferably 70 to 110 ° C, and the total reaction time is about 1 to 15 hours. This reaction is preferably carried out under substantially anhydrous conditions in order to prevent the polycondensation reaction of the alkoxysilane partial condensate (3) itself. The resin (A) can also be produced under reduced pressure of about 10 to 30 kPa. By the way, the alkoxy group-containing silane-modified epoxy resin (A) produced in the absence of solvent has an advantage that it can be used as it is as a solvent-free application, for example, as a material for adhesives, molded products, sealing agents and the like. . As an application to the solventless use, the organic solvent solution of the alkoxy group-containing silane-modified epoxy resin (A) produced in the presence of a solvent may be depressurized to remove the solvent. However, in the case of a normally used solvent, it is necessary to remove the solvent under heating conditions exceeding 130 ° C. In this case, the sol-gel reaction of the alkoxy group-containing silane-modified epoxy resin (A) becomes excessive. Since it proceeds, it is difficult to obtain the desired alkoxy group-containing silane-modified epoxy resin (A).

In the dealcoholization condensation reaction, a catalyst which does not open the epoxy ring can be used among the conventionally known catalysts in order to accelerate the reaction. Examples of the catalyst include lithium, sodium, potassium,
Metals such as rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese; oxides of these metals, organic acids Examples thereof include salts, halides and alkoxides. Among these, organic tin and organic acid tin are particularly preferable, and specifically dibutyltin dilaurate, tin octylate and the like are effective.

The alkoxy group-containing silane-modified epoxy resin (A) thus obtained contains the epoxy resin (1),
The epoxy resin (2) and the alkoxysilane partial condensate (3) may be contained in an unreacted state as long as they are in a slight amount. The unreacted alkoxysilane partial condensate (3) becomes silica by hydrolysis and polycondensation during curing with the epoxy resin cured product (B), and bonds with the alkoxy group-containing silane-modified epoxy resin (A). The alkoxy group-containing silane-modified epoxy resin (A) in the present invention is
The molecule has an alkoxy group derived from the alkoxysilane partial condensate (3). The content of the alkoxy group is not particularly limited, but the alkoxy group is subjected to a sol-gel reaction or dealcohol condensation by heat treatment or reaction with moisture (humidity) to form a hybrid cured product bonded to each other. Therefore, the alkoxy group-containing silane-modified epoxy resin (A) is usually 40 to 95 mol%, preferably 50 to 90 mol% of the alkoxy groups of the alkoxysilane partial condensate (3) used as a reaction raw material. It is better to keep the unreacted. Such a hybrid cured product has a gelled fine silica site (a higher-order network structure of siloxane bonds).

In the present invention, a silane-modified epoxy resin composition obtained by combining the alkoxy group-containing silane-modified epoxy resin (A) and the epoxy resin curing agent (B) is used. The silane-modified epoxy resin composition of the present invention,
When applied to various uses, various epoxy resins can be used together depending on the use. Examples of the epoxy resin which can be used in combination include novolak type epoxy resins such as the bisphenol type epoxy resin (1), orthocresol novolac type epoxy resin, and phenol novolac type epoxy resin described as constituent components of the present invention; phthalic acid and dimer acid. Glycidyl ester-type epoxy resin obtained by reacting polybasic acids such as and epichlorohydrin; Glycidylamine-type epoxy resin obtained by reacting polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin; Olefin bond Examples thereof include linear aliphatic epoxy resins and alicyclic epoxy resins obtained by oxidizing peroxyacetic acid with peracid such as peracetic acid.

As the epoxy resin curing agent (B), a phenol resin curing agent, a polyamine curing agent, a polycarboxylic acid curing agent, an imidazole curing agent, which is usually used as a curing agent for epoxy resins, is used. Agents and the like can be used without particular limitation. Specifically, examples of the phenol resin type include phenol novolac resin, bisphenol novolac resin, poly p-vinylphenol, and the like, and polyamine type curing agents include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, Polyamide amine (polyamide resin), ketimine compound, isophorone diamine, m-
Xylylenediamine, m-phenylenediamine, 1,3-
Bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 4,4'-diaminodiphenylmethane,
4,4'-diamino-3,3'-diethyldiphenylmethane, diaminodiphenylsulfone, dicyandiamide and the like can be mentioned. Examples of the polycarboxylic acid type curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and 3 , 6-endomethylenetetrahydrophthalic anhydride, hexachloroendmethylenetetrahydrophthalic anhydride, and methyl-3,6-endmethylenetetrahydrophthalic anhydride. Examples of the imidazole-based curing agent include 2-methylimidazole and 2-methylimidazole. Ethylhexyl imidazole, 2-undecyl imidazole, 2-phenyl imidazole, 1-cyanoethyl-2-
Examples thereof include phenylimidazolium trimellitate and 2-phenylimidazolium isocyanurate.
The curing agent (B) for epoxy resin not only reacts with the epoxy ring to ring-open and cure, but the alkoxysilyl moieties and alkoxy groups in the alkoxy group-containing silane-modified epoxy resin (A) undergo siloxane condensation with each other. It also serves as a catalyst for the reaction. Among the above curing agents for epoxy resin (B), the polyamine curing agent is most suitable as the curing catalyst for the alkoxysilyl moiety and the alkoxy group, and the curing agent (B) for the alkoxy group-containing silane-modified epoxy resin (A). As is the best.

The ratio of the curing agent (B) for epoxy resin to be used is usually 0.2 functional group having active hydrogen in the curing agent with respect to 1 equivalent of epoxy group in the alkoxy group-containing silane-modified epoxy resin composition. It is prepared by blending at a ratio of about 1.5 equivalents.

The epoxy resin composition may contain a curing accelerator for promoting the curing reaction between the epoxy resin and the curing agent. For example, tertiary amines such as 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2 -Imidazoles such as methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine; Tetraphenyl such as tetraphenylphosphonium / tetraphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate Such as boron salt can be mentioned. The curing accelerator is preferably used in a proportion of 0.1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.

If necessary, the epoxy resin composition may contain an organic solvent, a filler, a mold release agent, a surface treatment agent, a flame retardant, a viscosity modifier, a plasticizer, as long as the effect of the present invention is not impaired. Antibacterial agent, antifungal agent, leveling agent, defoaming agent, coloring agent,
You may mix | blend a stabilizer, a coupling agent, etc.

When the above-mentioned silane-modified epoxy resin composition is used as various coating agents, adhesives and sealing agents, a conventionally known pigment is added to 100 parts by weight of the solid residue of the silane-modified epoxy resin composition. It is used by blending 0 to 150 parts by weight. When the resin composition is used outdoors, it is preferable to blend a conventionally known sol-gel curing catalyst such as an acid or basic catalyst or a metal catalyst. The amount of the catalyst used can be appropriately determined depending on the activity of the catalyst used. Usually, the molar ratio to the alkoxy group of the alkoxy group-containing silane-modified epoxy resin (A) used is about 0.01 to 5 mol% of paratoluenesulfonic acid or tin octylate having a high catalytic capacity, and the catalytic capacity It is used in low formic acid, acetic acid, etc. at about 0.1 to 50 mol%. For the purpose of further softening and toughening the cured film, epoxy resin,
You may mix | blend an alkyd resin and a maleated oil.

Directly from the silane-modified epoxy resin composition,
In order to obtain a hybrid cured product, the above epoxy resin composition is cured at room temperature to 250 ° C. The curing temperature is appropriately determined by the curing agent (B) for epoxy resin. When a phenol resin-based curing agent or a polycarboxylic acid-based curing agent is used as the curing agent (B), a sol-gel curing catalyst is used in an amount of 0.1% or more in addition to the curing agent (B).
It is preferable to cure at 0 to 250 ° C. When a polyamine-based curing agent is used, low temperature curing at room temperature to 100 ° C. is possible, but it is preferable to use a highly active sol-gel curing catalyst such as tin octylate in an amount of 0.3% or more for curing. Because alcohol is generated in the sol-gel curing reaction of the alkoxysilyl moiety, ring opening / crosslinking of the epoxy group between the epoxy group in the alkoxy group-containing silane-modified epoxy resin (A) and the epoxy resin curing agent (B). If the alcohol is generated after curing by reaction, foaming or cracking occurs. Therefore, it is necessary to adjust the sol-gel curing reaction rate by appropriately selecting the catalyst.

In order to obtain a semi-cured film or a molding intermediate material from the silane-modified epoxy resin composition, as the epoxy curing agent (B) of the above epoxy resin composition, a phenol resin curing agent, a polycarboxylic acid curing agent, Using latent curing agents such as imidazoles and ketimines, tin-based sol-
It is preferable to incorporate a gel curing catalyst. In order to produce a semi-cured film or an intermediate material for molding using the epoxy resin composition, it is preferable to heat the epoxy resin composition at 40 to 150 ° C. or less so that 70% of siloxane bonds due to sol-gel curing are contained in the epoxy resin composition. The sol-gel curing reaction needs to proceed so as to generate the above, preferably 90% or more. Because alcohol is generated in the sol-gel curing reaction of the alkoxysilyl site, if the progress of sol-gel curing during the production of semi-cured product is small, curing shrinkage, cracks, and foaming may occur in the subsequent complete curing reaction. Because there is a nature.

Further, such a semi-cured product is subjected to thermoforming or thermocompression bonding, and is then completely cured at a temperature of usually 160 ° C. or higher and 250 ° C. or lower to be an epoxy resin-silica hybrid cured product.

[0044]

INDUSTRIAL APPLICABILITY The epoxy resin composition of the present invention can be used in a wide range of applications such as coating agents for paints, adhesives, sealing agents, etc., and particularly, insulating coating agents, printed wiring board materials, IC encapsulating materials, and insulating materials. It is useful as a sealant. The semi-cured product (sol-gel cured product) obtained from the epoxy resin composition of the present invention is flexible and has excellent moldability, and is therefore useful as an intermediate material such as a molding intermediate material, a prepreg, and a sealing agent. . The cured product (completely cured product) obtained from the epoxy resin composition of the present invention is transparent and has high hardness without cracks and the like. Further, it is excellent in adhesion, electric insulation, etc., and is also excellent in heat resistance (does not soften at high temperature, has a small expansion coefficient, and heat-resistant adhesion). Therefore, it is useful as a molding material for the above-mentioned wide range of applications, particularly electric / electronic parts, automobile parts, civil engineering building materials, sports equipment materials and the like.

[0045]

EXAMPLES The present invention will be specifically described below with reference to Production Examples, Comparative Production Examples, Examples and Comparative Examples. In each example,% is based on weight unless otherwise specified.

Production Example 1 (Production of Alkoxy Group-Containing Silane-Modified Epoxy Resin (A)) A bisphenol A type epoxy resin (Tohto Kasei Co., Ltd.) Made, brand name "Epototo YD-011", epoxy equivalent 475 g / eq, m = 2.2) 300 g and bisphenol A type epoxy resin (Toto Kasei Co., Ltd. make, brand name "Epototo YD-127", epoxy equivalent 190
1250 g (g / eq, m = 0.11) was added and dissolved at 80 ° C. Further poly (methyltrimethoxysilane)
(Tama Chemical Co., Ltd., trade name "MTMS-A", average number of repeating units 3.5) 581.2 g and dibutyltin laurate 2.0 g as a catalyst were added, and the mixture was placed under a nitrogen stream to give 10
The methanol was reacted at 0 ° C. for 8 hours. After further cooling to 60 ° C., the pressure was reduced to 13 kPa to completely remove the dissolved methanol to obtain an alkoxy group-containing silane-modified epoxy resin (hereinafter referred to as resin (A-1)). The weight of the epoxy resin (1) at the time of charging / the weight of the epoxy resin (2) = 0.24, the epoxy equivalent of the bisphenol type epoxy resin mixture ((1) + (2)) =
It is 245 g / eq. Further, the weight of the alkoxysilane partial condensate (3) in terms of silica / the weight of the bisphenol type epoxy resin mixture (weight ratio used) was 0.20. According to ¹ H-NMR (CDCl ₃ solution) measurement of the resin (A-1), 100% of the methine peak of the epoxy ring (around 3.3 ppm) was retained, and the peak of the hydroxyl group in the epoxy resin (3.85 ppm). It has been confirmed that (near) has disappeared. The epoxy equivalent of the resin (A-1) was 280 g / eq.

Production Example 2 A bisphenol A type epoxy resin (trade name "Epototo YD-011") 19 was placed in the same reactor as in Production Example 1.
3.34.8 g and bisphenol A type epoxy resin (trade name "Epototo YD-134") 1104.8 g were added and dissolved at 80 ° C. Further, 374.5 g of poly (methyltrimethoxysilane) (trade name “MTMS-A”) and 2.0 g of dibutyltin laurate as a catalyst were added, and the methanol removal reaction was carried out at 100 ° C. for 8 hours under a nitrogen stream. After further cooling to 60 ° C., the pressure was reduced to 13 kPa to completely remove the dissolved methanol, whereby an alkoxy group-containing silane-modified epoxy resin (hereinafter referred to as resin (A-
2)) was obtained. The weight of the epoxy resin (1) at the time of preparation / the weight of the epoxy resin (2) = 0.17,
Epoxy equivalent of bisphenol type epoxy resin mixture =
It is 283 g / eq. The weight of the alkoxysilane partial condensate (3) in terms of silica / weight of the bisphenol type epoxy resin mixture was 0.16. Resin (A-
According to ¹ H-NMR (CDCl ₃ solution) measurement of 2), 100% of the methine peak of the epoxy ring is retained.
It was confirmed that the peak of the hydroxyl group in the epoxy resin had disappeared. Epoxy equivalent of resin (A-2) is 34
It was 0 g / eq.

Production Example 3 A bisphenol A type epoxy resin (trade name "Epototo YD-011") 35 was placed in the same reactor as in Production Example 1.
Add 0.0 g and 1050 g of bisphenol A type epoxy resin (trade name "Epototo YD-127"), and add 8
Dissolved at 0 ° C. Further, 678 g of poly (methyltrimethoxysilane) (trade name "MTMS-A") and 2.0 g of dibutyltin laurate as a catalyst were added, and a methanol removal reaction was carried out at 100 ° C for 8 hours under a nitrogen stream. After further cooling to 60 ° C., the pressure was reduced to 13 kPa to completely remove the dissolved methanol to obtain an alkoxy group-containing silane-modified epoxy resin (hereinafter referred to as resin (A-3)). The weight of the epoxy resin (1) at the time of charging / the weight of the epoxy resin (2) = 0.33, and the epoxy equivalent of the epoxy resin mixture = 261 g / eq. The weight of the alkoxysilane partial condensate (3) in terms of silica / the weight of the bisphenol type epoxy resin mixture = 0.
It was 25. ¹ H-NMR of resin (A-3) (CDC
l ₃ solution) measurement showed that the methine peak of the epoxy ring was 1
It was confirmed that the content was held at 00% and the peak of the hydroxyl group in the epoxy resin had disappeared. Resin (A
The epoxy equivalent of -3) was 320 g / eq.

Comparative Production Example 1 A bisphenol A type epoxy resin (trade name "Epototo YD-127") was used as it was. Hereinafter, the resin is referred to as resin (a-1).

Comparative Production Example 2 Bisphenol A type epoxy resin (trade name "Epototo YD-011") 300 was placed in the same reactor as in Production Example 1.
g and 1250 g of bisphenol A type epoxy resin (trade name "Epototo YD-127") were added and dissolved at 80 ° C. After cooling to room temperature, poly (methyltrimethoxysilane) (trade name "MTMS-A") 581.2
An epoxy resin composition was obtained by mixing g.
Hereinafter, the resin composition will be referred to as resin (a-2). The weight of the epoxy resin (1) at the time of charging / the weight of the epoxy resin (2) = 0.24, and the epoxy equivalent of the bisphenol type epoxy resin mixture = 245 g / eq. The weight of the alkoxysilane partial condensate (3) in terms of silica / the weight of the bisphenol type epoxy resin mixture is 0.20.
The epoxy equivalent of the resin (a-2) was 280 g / eq.

Comparative Production Example 3 A bisphenol A type epoxy resin (trade name "Epototo YD-127") 155 was placed in the same reactor as in Production Example 1.
0 g was added and dissolved at 80 ° C. Furthermore, poly (methyltrimethoxysilane) (trade name "MTMS-A") 58
1.2 g and 2.0 g of dibutyltin laurate as a catalyst were added, and the methanol removal reaction was carried out at 100 ° C. for 8 hours under a nitrogen stream. After further cooling to 60 ° C., the pressure was reduced to 13 kPa to completely remove the dissolved methanol, whereby the alkoxy group-containing silane-modified epoxy resin (hereinafter,
Resin (a-3) was obtained. The weight of the epoxy resin (1) at the time of preparation / the weight of the epoxy resin (2) =
0, epoxy equivalent of epoxy resin mixture = 190 g / e
It was q. Further, partial condensate of alkoxysilane (3)
The weight in terms of silica / the weight of the bisphenol type epoxy resin mixture was 0.20. ¹ H- of resin (a-3)
By NMR (CDCl ₃ solution) measurement, it could be confirmed that 100% of the methine peak of the epoxy ring was retained and that the peak of the hydroxyl group in the epoxy resin had disappeared. The epoxy equivalent of the resin (a-3) is 260 g / eq.
Met.

Comparative Production Example 4 A bisphenol A type epoxy resin (trade name "Epototo YD-011") 125 was placed in the same reactor as in Production Example 1.
0 g and 300 g of bisphenol A type epoxy resin (trade name "Epototo YD-127") are added, and the temperature is 80 ° C.
It was dissolved in. Further poly (methyltrimethoxysilane)
(Brand name "MTMS-A") 581.2 g and dibutyltin laurate 2.0 g as a catalyst were added, and under a nitrogen stream, 1
Gelation occurred when the reaction was carried out at 00 ° C for 1 hour. The weight of the epoxy resin (1) at the time of charging / epoxy resin (2) = 4.2. The weight of the alkoxysilane partial condensate (3) in terms of silica / the weight of the bisphenol type epoxy resin mixture was 0.20.

Examples 1 to 3 and Comparative Examples 1 to 3 Triethylenetetramine (equivalent weight 24 g / eq) was added to each of the resins obtained in Production Examples 1 to 3 and Comparative Production Examples 1 to 3.
Add at a ratio of epoxy equivalent / amine equivalent of 1/1,
Each epoxy resin composition was prepared.

Each epoxy resin composition obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was coated with a fluororesin so as to have a film thickness of about 300 μm (length × width × depth = 10 cm ×). 10 cm x 1.5 cm) and pour 120
Curing was carried out at 0 ° C for 1 hour. The state (shrinkage, appearance) of the obtained cured film was evaluated according to the following criteria. The results are shown in Table 1.

(Shrinkage) ◯: There is no crack in the cured product. Δ: The cured product has cracks. X: The cured product has many cracks.

(Appearance) ○: Transparent. Δ: There is cloudiness. X: Whitened.

[0057]

[Table 1]

As is clear from Table 1, in each of Examples and Comparative Example 1, a transparent cured film was obtained. However, the cured film obtained in Comparative Example 2 was whitened due to phase separation between the epoxy resin and silica, and was extremely brittle.

(Heat Resistance) Examples 1 and 2 and Comparative Examples 1 and 3
The cured film obtained in step 1 was cut into 6 mm × 25 mm, and a viscoelasticity measuring device (Rheology, trade name “DVE-V” was used.
4 ”, measurement conditions: amplitude 1 μm, frequency 10 Hz, slope 3 ° C./min) to measure the dynamic storage elastic modulus to evaluate heat resistance. The measurement results are shown in FIG.

As is clear from FIG. 1, in Examples 1 and 2 and Comparative Example 3, the glass transition point of the cured film is higher than in Comparative Example 1, the elastic modulus at high temperature is high, and the heat resistance is high. Excellent in.

(Linear Expansion) Examples 1 and 2 and Comparative Example 1
Using the cured film obtained in step 1, a thermal stress strain measuring device (manufactured by Seiko Electronics Co., Ltd., trade name TMA120
In C), the coefficient of linear expansion of 40 to 100 ° C. was measured.

[0062]

[Table 2]

(Electrical Characteristics) Examples 1 and 2 and Comparative Example 1
The dielectric constant and dielectric loss were measured at a frequency of 1 MHz using the cured film obtained in 1. The results are shown in Table 3.

[0064]

[Table 3]

It was confirmed that Examples 1 and 2 were superior to Comparative Example 1 in the insulating property and there was no difference in the dielectric loss.

Examples 4 and 5 and Comparative Examples 4 and 5 Each of the resins obtained in Production Examples 1 and 2 and Comparative Production Examples 1 and 3 was prepared by adding an aminopolyamide resin (manufactured by Toto Kasei Co., Ltd. under the trade name “Goodmide G”). -725 ", equivalent weight 130g / eq)
Was added at a ratio of 1/1 epoxy equivalent / amine equivalent to prepare each epoxy resin composition. The adhesiveness and heat resistant adhesiveness of these compositions were measured under the following conditions, and the properties as an adhesive material were evaluated mainly.

(Adhesiveness) Each resin composition was applied to a glass plate, a mortar, and an aluminum plate so as to have a film thickness of 20 μm,
After curing at 130 ° C. for 30 minutes, JIS K-5400
The cellophane tape peeling test was performed according to the general test method, and the judgment was made according to the following criteria. The evaluation results are shown in Table 4. ◎ --- 100/100 ○ --- 99 to 95/100 △ --- 94 to 70/100 × --- 69 to 0/100

[0068]

[Table 4]

(Heat Resistance Adhesion) After the test plate used for the adhesion test was left at 180 ° C. for 8 hours, a cellophane tape peeling test was carried out and judged according to the same criteria as described above. The results are shown in Table 5.

[0070]

[Table 5]

Examples 6 to 8 and Comparative Examples 6 to 8 Each of the resins obtained in Production Examples 1 to 3 and Comparative Production Examples 1 to 3 was mixed with an aminopolyamide resin (trade name "Goodmide G-
725 ") at a ratio of epoxy equivalent / amine equivalent of 1/1 and diluted to 50% with methyl isobutyl ketone to prepare each epoxy resin composition.

(Scratch resistance) Each resin composition was applied to an aluminum plate so as to have a film thickness of 20 μm, and the resin composition was heated at 130 ° C. for 30 minutes.
After curing for a minute, a pencil scratch test was carried out according to the general paint coating test method of JIS K-5400. The results are shown in Table 6.

[0073]

[Table 6]

Example 9 The resin (A-1) obtained in Production Example 1 was mixed with a novolac type phenol resin (manufactured by Arakawa Chemical Industry Co., Ltd., trade name: Tamanol 7).
A solution of 59) diluted with methyl ethyl ketone to 50% was added at a ratio of epoxy equivalent / phenol equivalent of 1/1 and stirred at room temperature for 30 minutes, and then tin octylate was added at 1% based on the solid content to prepare an epoxy resin composition. It was a thing. This epoxy resin composition was poured into a container coated with a fluororesin (length × width × depth = 10 cm × 10 cm × 1.5 cm), and the mixture was left at 80 ° C. for 30 minutes and 130 ° C. for 30 minutes to obtain a sol-gel. It was cured to obtain a rubber-like semi-cured sheet having a film thickness of 300 μm. The obtained semi-cured sheet was flexible (maximum elongation was about 15%) and could be molded at 50 ° C. or higher. The semi-cured product obtained in the same manner as above is heated to 100 ° C., and the mold (10 mm × 60
mm × 2 mm). 200 ° C, 1 × 10 ⁷ Pa
Press molding was carried out to obtain an epoxy resin-silica hybrid molded product. This epoxy resin-silica hybrid showed the same heat resistance as the cured product of Example 1.

Example 10 The resin (A-1) obtained in Production Example 1 was treated with dicyandiamide
Dimethylformamide solution (concentration 10%) with epoxy
Equivalent / amine equivalent is added at a ratio of 1/1, and 3 at room temperature
After stirring for 0 minutes, tin octylate was added at 1% based on the solid content,
An epoxy resin composition was prepared. This epoxy resin composition
A container coated with fluororesin (length x width x depth
= 10 cm x 10 cm x 1.5 cm) at 80 ° C
The sol is left for 30 minutes and at 110 ° C for 30 minutes.
-Gel-hardened, 100 μm thick film with no surface tack
A cured sheet was obtained. The resulting semi-cured sheet has maximum elongation
The rate was about 8%. Add this semi-cured sheet to 120 ° C
It is sandwiched between two aluminum plates while heating, and 1 x 10 ⁷Pressure at Pa
I wore it. Then, completely cure this at 210 ° C,
A xy resin-silica hybrid was obtained.

Comparative Example 9 The resin (a-3) obtained in Comparative Production Example was mixed with a novolac type phenolic resin (trade name: Tamanol 75, melted at 130 ° C.).
9) was added at a ratio of epoxy equivalent / phenol equivalent of 1/1, stirred at 80 ° C. for 30 minutes, and then tin octylate was added at 1% based on the solid content to obtain an epoxy resin composition. This epoxy resin composition was coated with a fluororesin-coated container (length x width x depth = 10 cm x 10 cm x 1.5 c).
m) and cured at 100 ° C for 30 minutes to give a film thickness of 30
A semi-cured sheet of 0 μm was obtained. The obtained semi-cured sheet had surface tack and was brittle, so that the elongation could not be measured.

[Brief description of drawings]

FIG. 1 shows the evaluation results of heat resistance of the cured films obtained in Examples 1 and 2 and Comparative Examples 1 and 3.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C09J 161/06 C09J 161/06 163/02 163/02 183/10 183/10 (56) Reference JP-A-2002-12818 (JP , A) JP-A-7-53673 (JP, A) JP-A-61-278537 (JP, A) JP-A-61-283628 (JP, A) JP-A-3-207774 (JP, A) JP-A-2001 -59011 (JP, A) JP 2001-261776 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 59/00-59/72 C09D 161/06-161/14 C09D 163/00-163/10 C09D 183/10-183/12 C09J 161/06-161/14 C09J 163/00-163/10 C09J 183/10-183/12

Claims (12)

(57) [Claims] 1. An epoxy equivalent of more than 400 g / eq 10
Bisphenol type epoxy resin (1) of less than 000 g / eq and epoxy equivalent of 170 g / eq and 400 g / eq.
A bisphenol type epoxy resin mixture having a use weight ratio ((1) / (2)) of 0.1 to 1.0 with a bisphenol type epoxy resin (2) of less than eq is used as an alkoxysilane partial condensate (3). Alkoxy group-containing silane-modified epoxy resin (A) obtained by dealcoholization condensation reaction,
And a curing agent (B) for epoxy resin, which is a silane-modified epoxy resin composition. 2. The silane-modified epoxy resin composition according to claim 1, wherein the dealcoholization condensation reaction is carried out in the absence of a solvent. 3. The silane-modified epoxy resin according to claim 1, wherein the weight of the alkoxysilane partial condensate (3) in terms of silica / the weight of the bisphenol type epoxy resin mixture (weight ratio) is 0.1 to 0.5. Composition. 4. The alkoxysilane partial condensate (3) is a partial condensate of methyltrimethoxysilane.
The silane-modified epoxy resin composition according to any one of 3 above. 5. The curing agent (B) for epoxy resin is at least one selected from the group consisting of phenol novolac resin, cresol novolac resin, imidazoles, dicyandiamide and polyamide. Epoxy resin composition. 6. An epoxy resin-silica hybrid cured product obtained by curing the silane-modified epoxy resin composition according to any one of claims 1 to 5. 7. A silane-modified epoxy resin composition comprising
The epoxy resin-silica hybrid cured product according to claim 6, which is obtained by sol-gel curing at 150 ° C. 8. A silane-modified epoxy resin composition at room temperature to
The epoxy resin-silica hybrid cured product according to claim 6, which is completely cured at 250 ° C. 9. The silane-modified epoxy resin composition according to claim 1, and the epoxy resin according to claim 6-8.
An insulating material for an electric / electronic material, containing at least one selected from the group consisting of a silica hybrid cured product. 10. A coating agent comprising at least one selected from the group consisting of the silane-modified epoxy resin composition according to claim 1 and the cured epoxy resin-silica hybrid product according to claims 6-8. . 11. An adhesive containing at least one selected from the group consisting of the silane-modified epoxy resin composition according to claim 1 and the epoxy resin-silica hybrid cured product according to claims 6-8. . 12. The coating agent according to claim 10, which is a paint.