JP2001294639A - Alkoxy-containing silane-modified phenolic resin, resin composition, epoxy resin hardener and organic-inorganic hybrid material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an alkoxy-containing silane-modified phenolic resin giving a cured material having excellent heat-resistance. SOLUTION: The objective alkoxy-containing silane-modified phenolic resin is produced by the oxirane ring-opening reaction of (1) a phenolic resin with (2) a partial condensation product of an alkoxysilane containing glycidyl ether group and obtained by the dealcoholation reaction of (A) glycidol with (B) a partial condensation product of an alkoxysilane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an alkoxy-containing silane-modified phenolic resin, a resin composition containing the resin, a curing agent for an epoxy resin, and an organic-inorganic hybrid obtained by curing the resin composition. .

[0002]

2. Description of the Related Art Conventionally, a method of dispersing and mixing a filler such as silica, titania and alumina in a phenol resin has been widely used for the purpose of improving heat resistance and mechanical strength of the phenol resin. However, this method does not provide sufficient heat resistance. Further, in this method, the transparency of the phenolic resin is lost, and the adhesiveness at the interface between the filler and the resin is poor, so that the mechanical properties such as the elongation are insufficient.

[0003] Further, by using a complex of a phenol resin and silica particles obtained by hydrolysis and polycondensation of an alkoxysilane in the presence of a phenol resin,
A method for improving the mechanical strength of a phenol resin has been proposed (Japanese Patent Application Laid-Open No. H11-92623). However, in such a composite, the bonding between the silica particles and the phenol resin is not sufficient, so that the mechanical strength cannot be sufficiently improved. In addition, voids (bubbles) are easily generated in the cured product due to water in the curing agent, water generated during curing, or alcohol such as methanol. In order to improve the heat resistance, it is conceivable to increase the amount of the alkoxysilane that is a component of the composite, but in this case, the transparency of the cured product obtained by agglomeration of the generated silica is likely to be lost. Therefore, the amount of the alkoxysilane to be introduced is limited, so that the heat resistance of the obtained composite cannot be sufficiently improved.

Further, phenol resins have been used as curing agents for epoxy resins in the past, and especially in the field of electric and electronic materials, they have excellent heat resistance, chemical resistance, electric properties and the like. As suitable. However, with the recent development of electric and electronic materials,
Epoxy resin compositions are also required to have a high degree of performance, and when a curing agent composed of a general phenol resin is used, heat resistance is particularly insufficient.

Further, as a curing agent for an epoxy resin, hydrolysis of alkoxysilane in the presence of a phenol resin,
There has been proposed a method for improving the heat resistance of a cured epoxy resin by using a composite of phenol resin and silica obtained by performing polycondensation (Japanese Patent Application Laid-Open No. 9-21).
No. 6938). Although the epoxy resin cured product using such a composite as a curing agent has improved heat resistance to some extent, voids (bubbles) are generated in the cured product due to water in the curing agent, water generated during curing, or alcohol such as methanol. ) Occurs. In addition, when the amount of alkoxysilane is increased for the purpose of further improving heat resistance, the resulting silica is aggregated to lose the transparency of the obtained cured product, causing whitening. Of water is required, and as a result, warpage, cracks and the like of the cured product are caused.

[0006]

SUMMARY OF THE INVENTION The present invention provides a cured product which uses a specific alkoxy group-containing silane-modified phenol resin, has excellent mechanical strength and heat resistance, and does not generate voids (bubbles) and cracks. It is intended to provide a specific resin composition and an epoxy resin curing agent that can be used.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that an alkoxy group-containing compound composed of a specific phenol resin and a specific alkoxysilane partial condensate (2). When a silane-modified phenol resin is used, it has been found that a resin composition containing the resin and a curing agent for an epoxy resin can achieve the above object, and have completed the present invention.

That is, the present invention relates to an alkoxy group-containing silane-modified phenol resin obtained by an oxirane ring-opening reaction between a phenol resin (1) and a glycidyl ether group-containing alkoxysilane partial condensate (2).
The present invention also relates to a curing agent for an epoxy resin containing the alkoxy group-containing silane-modified phenol resin. The present invention also relates to a resin composition containing the alkoxy group-containing silane-modified phenol resin or the epoxy resin curing agent. Further, the present invention relates to an organic-inorganic hybrid obtained by curing the resin composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The phenolic resin (1) constituting the alkoxy group-containing silane-modified phenolic resin of the present invention is a novolak type phenolic resin obtained by reacting a phenol and an aldehyde in the presence of an acid catalyst. Further, any resol type phenol resin obtained by reacting a phenol and an aldehyde in the presence of an alkali catalyst can be used. Among these, the resol type phenol resin usually contains condensation water, and the alkoxysilyl site of the glycidyl ether group-containing alkoxysilane partial condensate (2) may be hydrolyzed. Preferably, a phenolic resin is used. In addition, it is generally preferable to use a phenol resin (1) having an average number of phenol nuclei of about 3 to 8.

Examples of the phenols include various phenols such as phenol, cresol, xylenol, ethylphenol, isopropylphenol, tert-butylphenol, amylphenol, octylphenol, nonylphenol, dodecylphenol, chlorophenol, and bromophenol. The position of the substituent in these phenols is not limited. As formaldehyde, besides formalin, a formaldehyde-generating substance such as paraformaldehyde, trioxane and tetraoxane can also be used. Further, as the acidic catalyst or the alkaline catalyst, any of those conventionally known can be used.

The glycidyl ether group-containing alkoxysilane partial condensate (2) used in the present invention is obtained by a dealcoholation reaction between glycidol (A) and an alkoxysilane partial condensate (B).

The alkoxysilane partial condensate (B)
Is, for example, a compound represented by the general formula (1): R¹ _mSi (OR^Two)
_(4-m) (In the formula, m represents an integer of 0 or 1. R
¹Represents an alkyl group or an aryl group having 8 or less carbon atoms.
However, they may be the same or different. R^TwoIs charcoal
Represents a lower alkyl group having a prime number of 4 or less,
It may be different. ) Hydrolyzable alcohol
The silane monomer is hydrolyzed in the presence of an acid or alkali.
What is obtained by partially condensing is used.

Specific examples of such a hydrolyzable alkoxysilane monomer include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane and tetrabutoxysilane; methyltrimethoxysilane, Methyltriethoxysilane, methyltripropoxysilane,
Trialkoxysilanes such as methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, and isopropyltriethoxysilane are exemplified. In general, among these, in particular, because of high reactivity with glycidol, the alkoxysilane partial condensate (B) is preferably synthesized using 70% by mole or more of tetramethoxysilane or methyltrimethoxysilane.
More preferably, those synthesized using 70% by mole or more of tetramethoxysilane are good.

As the alkoxysilane partial condensate (B), those exemplified above can be used without any particular limitation. When two or more of these examples are used in combination, the alkoxysilane partial condensate may be used. It is preferable to use such that the partial condensate of tetramethoxysilane or methyltrimethoxysilane accounts for 60% by weight or more in the total amount of the product (B). More preferably, a partial condensate of tetramethoxysilane is used in an amount of 60% by weight or more.

The average number of Si in the alkoxysilane partial condensate (B) is preferably 2 to 100. S
If the average number of i is less than 2, the amount of alkoxysilanes that flow out of the system together with the alcohol without reacting during the demethanol reaction with glycidol (A) is not preferred. If it exceeds 100, the reactivity with glycidol (A) decreases, and it is difficult to obtain the desired glycidyl ether group-containing alkoxysilane partial condensate (2).

The glycidyl ether group-containing alkoxysilane partial condensate (2) can be obtained by subjecting the glycidol (A) and the alkoxysilane partial condensate (B) to a dealcoholization (ester exchange) reaction. The ratio of the glycidol (A) and the alkoxysilane partial condensate (B) to be used is not particularly limited as long as the alkoxy group substantially remains, but the obtained glycidyl ether group-containing alkoxysilane partial condensate ( The ratio of the glycidyl ether group in 2) is usually 0.01 equivalent of the epoxy group of glycidol (A) / equivalent of the alkoxyl group of the alkoxysilane condensate (B) = 0.01 / 1 to 0.7 / 1. It is preferable that the alkoxysilane condensate (B) and the glycidol (A) are subjected to a dealcoholization reaction at a charge ratio. When the charge ratio decreases, the ratio of the alkoxysilane partial condensate (B) that has not been epoxy-modified increases, so the charge ratio is more preferably 0.03 or more / 1. In addition, when the charging ratio increases, the glycidyl ether group of the glycidyl ether group-containing alkoxysilane partial condensate (2) becomes polyfunctional and easily gels during the synthesis of the silane-modified phenol resin. The ratio is preferably set to the following value / 1.

In the reaction between the alkoxysilane partial condensate (B) and glycidol (A), for example, the above-mentioned components are charged, and a dealcoholization reaction is performed while distilling off alcohol produced by heating. The reaction temperature is about 50 to 150 ° C,
Preferably it is 70-110 ° C, and the total reaction time is 1-1.
It is about 5 hours. In addition, the dealcoholization reaction was performed at 110 ° C.
If the reaction is carried out at a temperature higher than the above, a new siloxane bond is generated in the reaction system due to the alkoxysilane partial condensate (B), and the reaction product is liable to be increased in viscosity and gelled, which is not preferable.

In the dealcoholation reaction between the alkoxysilane partial condensate (B) and glycidol (A), a catalyst which does not open the epoxy ring among conventionally known catalysts may be used to promote the reaction. Can be. For example, metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese; Examples thereof include oxides, organic acid salts, halides, and alkoxides of these metals. Among these, organic tin and organic acid tin are particularly preferable, and specifically, dibutyltin dilaurate and tin octylate are effective.

The above reaction can be carried out with or without a solvent. The solvent is not particularly limited as long as it dissolves the alkoxysilane partial condensate (B) and glycidol (A) and is inert to the epoxy group of glycidol (A). Examples of such a solvent include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, xylene and the like.

The alkoxy group-containing silane-modified phenol resin which is the object of the present invention is the phenol resin (1)
And the glycidyl ether group-containing alkoxysilane partial condensate (2) by an oxirane ring-opening reaction.
By this reaction, an alkoxy group-containing silane-modified phenol resin in which a part of hydroxyl groups of the phenol resin (1) is modified with a glycidyl ether group-containing alkoxysilane partial condensate (2) is produced. Although the use ratio of the phenol resin (1) and the glycidyl ether group-containing alkoxysilane partial condensate (2) in this reaction is not particularly limited,
The ratio of the equivalent of the glycidyl ether group of the glycidyl ether group-containing alkoxysilane partial condensate (2) / the equivalent of the hydroxyl group of the phenol resin (1) is preferably in the range of 0.1 to 1. However, when a phenol resin having an average number of nuclei of 3 or more is used, gelation is likely to occur due to the reaction between the oxirane ring and the phenolic hydroxyl group. Therefore, the ratio of the equivalent of the oxirane ring to the equivalent of the hydroxyl group is set to 0.1. 5
It is preferred to adjust to less than.

In the production of the alkoxy group-containing silane-modified phenolic resin composition of the present invention, for example, a phenol resin (1) and a glycidyl ether group-containing alkoxysilane partial condensate (2) are charged and heated to cause an oxirane ring-opening reaction. It is done by doing. This reaction is preferably carried out in a substantially anhydrous state in order to prevent a polycondensation reaction of the glycidyl ether group-containing alkoxysilane partial condensate (2) itself. The main purpose of this reaction is to react the hydroxyl group of the phenol resin (1) with the oxirane group of the glycidyl ether group-containing alkoxysilane partial condensate (2).
During this reaction, it is necessary to suppress the formation of silica by a sol-gel reaction of the alkoxysilyl moiety of the glycidyl ether group-containing alkoxysilane partial condensate (2) and the dealcoholization reaction between the alkoxysilyl moiety and the phenol resin. Therefore, the reaction temperature is about 50 to 120 ° C, preferably 60 to 100 ° C, and the total reaction time is preferably about 1 to 10 hours.

In the above-mentioned oxirane ring-opening reaction, a known catalyst can be used to promote the reaction. For example, tertiary amines such as 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; Imidazoles such as -methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine; Tetraphenylphosphonium / tetraphenylborate, 2
And tetraphenylborate such as -ethyl-4-methylimidazole / tetraphenylborate and N-methylmorpholine / tetraphenylborate. The reaction catalyst is preferably used in a ratio of 0.01 to 5 parts by weight based on 100 parts by weight of the epoxy resin.

The above reaction can be carried out with or without a solvent depending on the purpose of use. As the solvent,
There is no particular limitation as long as the solvent dissolves the phenol resin (1) and the glycidyl ether group-containing alkoxysilane partial condensate (2). Examples of such a solvent include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, xylene and the like.

The alkoxy group-containing silane-modified phenol resin thus obtained has, in its molecule, an alkoxy group derived from the alkoxysilane partial condensate (B) and a phenolic hydroxyl group derived from the phenol resin (1). Has no oxirane group derived from glycidol (A). The content of the alkoxy group is not particularly limited, but the alkoxy group is mutually bound by a sol-gel reaction or a dealcohol condensation by evaporation or heat treatment of a solvent or by a reaction with water (humidity). Since it is necessary to form a cured product, the alkoxy group-containing silane-modified phenol resin usually contains 50 to 95 mol%, preferably 60 to 90 mol% of the alkoxy group of the alkoxysilane partial condensate (B) in an unreacted state. It is better to keep it as it is. The content of the phenolic hydroxyl group is not particularly limited. The alkoxy group-containing silane-modified phenol resin can also be thermoset by combining amines and epoxy resins according to the same reaction mechanism as a conventional novolak phenol resin. When the alkoxy group-containing silane-modified phenol resin is cured using an amine, or when the alkoxy group-containing silane-modified phenol resin and the epoxy resin are used in combination, the above-described reaction is allowed to proceed sufficiently. The alkoxy group-containing silane-modified phenolic resin must have a phenolic hydroxyl group. That is, the alkoxy group-containing silane-modified phenol resin usually has a hydroxyl group content of 30 to 95 mol%, preferably 60 mol%, of the phenol resin (1).
９０90 mol% is preferably kept unreacted.
A cured product obtained from such an alkoxy group-containing silane-modified phenol resin is an alkoxysilane partial condensate (B)
And has a gelled fine silica site (higher-order network structure of siloxane bonds). The alkoxy group-containing silane-modified phenol resin of the present invention is mainly composed of a phenol resin in which some of the hydroxyl groups in the phenol resin (1) are silane-modified. Are unreacted phenolic resin (1) and partially condensed product of alkoxysilane (B) (this means unreacted product contained in partially condensed product of glycidyl group-containing alkoxysilane (2)), and partially condensed glycidyl group-containing alkoxysilane It may contain the product (2), the solvent and the catalyst used in the reaction. The unreacted alkoxysilane partial condensate (B) and unreacted alkoxysilane partial condensate (B) are hydrolyzed or polycondensed during curing to form silica, and are integrated with the alkoxy group-containing silane-modified phenolic resin. Become

An alkoxy group-containing silane-modified phenol tree
In a resin composition containing fat, the resin composition
Content in the cured residue is 2 in terms of silica weight.
It is preferable that the content is about 50% by weight. Hardening residue here
The silica content in terms of silica weight in the
The alkoxysilyl moiety of the silane-modified phenol resin is
Higher order siloxane bonds are formed through sol-gel curing reaction
Formula (2): R¹ _mSi (O)_{(4-m) / 2}  (In the formula, m represents an integer of 0 or 1. R¹Is the carbon number
8 or less alkyl groups or aryl groups,
They may be the same or different. )
The weight of the silica part in the cured residue when cured to the silica part
Volume percent. Less than 2% by weight is heat resistant and strong
It is difficult to obtain the effects of the present invention such as the degree, and 50% by weight
If it exceeds, the cured product becomes too brittle, and the strength drops on the contrary.
Tend to. The resin composition is dissolved depending on the purpose of use.
The concentration can be appropriately adjusted depending on the agent. As the solvent, Al
Can dissolve silane-modified phenolic resin containing koxy group
Can be used without particular limitation. In addition, the cured product
For the purpose of adjusting mechanical strength and heat resistance, the cured silica
If it is necessary to adjust the amount,
An alkoxysilane moiety is added to the orchid-modified phenol resin composition.
The polycondensate (B) or the phenol resin (1) may be blended.
I don't know. In addition, the alkoxy group silane modified resin composition,
Various types of curing used to cure conventionally known phenolic resins
An agent may be used. Specifically, hexamethylene
Amines such as tetramine and melamine resins are preferred.
You. Further, in the silane-modified phenolic resin composition,
Conventionally known for the purpose of accelerating the silica curing reaction even at low temperatures
Sol-gel curing of acid or basic catalysts, metal catalysts, etc.
A catalyst or water may be contained. However add water
The viscosity of the alkoxy group silane-modified resin composition
In consideration of qualitative properties, alkoxy group-containing silane-modified phenol
0.6 mol or less per 1 mol of alkoxy group
It is preferred that In addition, the alkoxy group-containing silicone
The effect of the present invention is impaired in the orchid-modified phenolic resin composition.
Filler, release agent, surface if necessary
Processing agents, flame retardants, viscosity modifiers, plasticizers, antibacterial agents, fungicides
Agents, leveling agents, defoamers, coloring agents, stabilizers, couplings
, Etc., may be added.

The alkoxy group-containing silane-modified phenolic resin of the present invention can be used as a curing agent for epoxy resins.
In this case, the epoxy resin is prepared by blending the epoxy resin in a proportion such that the hydroxyl group in the curing agent is about 0.5 to 1.5 equivalents to 1 equivalent of the epoxy group of the conventionally known epoxy resin.

As the epoxy resin to which the curing agent for epoxy resin of the present invention is applied, various known epoxy resins can be exemplified. For example, novolak type epoxy resins such as orthocresol novolak type epoxy resin and novolak phenol type epoxy resin; diglycidyl ethers derived from bisphenol A and bisphenol F; polybasic acids such as phthalic acid and dimer acid; and epichlorohydrid Glycidyl ester type epoxy resin obtained by reacting phosphorus; Glycidylamine type epoxy resin obtained by reacting polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin; Oxidation of olefin bond with peracid such as peracetic acid Examples thereof include linear aliphatic epoxy resins and alicyclic epoxy resins obtained by the above method, and one of these can be used alone or two or more can be used in an appropriate combination.

The epoxy resin composition of the present invention promotes hydrolysis and polycondensation when curing the alkoxysilyl moiety of the alkoxy group-containing silane-modified phenolic resin. , A catalytic amount of organic acid catalysts such as formic acid, acetic acid, propionic acid, paratoluenesulfonic acid and methanesulfonic acid, inorganic acid catalysts such as boric acid and phosphoric acid, alkaline catalysts, organic tin and organic acid tin catalysts. It can also be contained. Further, the epoxy resin composition of the present invention can contain a curing accelerator for accelerating the curing reaction between the epoxy resin and the curing agent. As the effect promoter, the same compounds as used in the production of the alkoxy group-containing silane-modified phenol resin can be used. The curing accelerator is preferably used in a ratio of 0.1 to 5 parts by weight based on 100 parts by weight of the epoxy resin.

The concentration of the epoxy resin composition can be appropriately adjusted by a solvent. As the solvent, those similar to those used for producing the alkoxy group-containing silane-modified phenol resin can be used. In addition, the epoxy resin composition, if necessary, a filler, a release agent, a surface treatment agent, a flame retardant, etc., which are the same as those used during the preparation of the above-mentioned alkoxy group-containing silane-modified phenol resin fat composition May be blended.

When the above-mentioned alkoxy group-containing silane-modified phenol resin composition or epoxy resin composition is used as a paint or various coating agents, the curing residue of 100 parts by weight of the alkoxy group-containing silane-modified phenol resin composition is used. Conventionally known pigments are blended and used in an amount of 0 to 150 parts by weight. The coating is coated on a substrate using a conventionally known coating device such as a spray or a coater,
Preferably, it is baked at 60 ° C. or more to form a coating film. When the paint is for outdoor use, it is preferable to incorporate a conventionally known sol-gel curing catalyst such as an acid or basic catalyst and a metal catalyst. The amount of the catalyst used can be appropriately determined depending on the activity of the catalyst used. Usually, in terms of molar ratio to the alkoxy group of the silane-modified phenol resin used, paratoluenesulfonic acid or tin octylate having a high catalytic ability is about 0.01 to 5 mol%, and formic acid or acetic acid having a low catalytic ability is 0 to 5 mol%. It is used at about 1 to 50 mol%. Further, an epoxy resin, an alkyd resin, a maleated oil, or the like may be blended for the purpose of softening and toughening the cured film.

When an alkoxy group-containing silane-modified phenol resin composition or an epoxy resin composition is used as a molded product, an alkoxy group-containing silane-modified phenol resin is synthesized without using a solvent, and the above amine-based curing agent and A resin composition is formed by combining with an epoxy resin, a curing catalyst in some cases, various fillers, various fibers, and water. The molding method is not particularly limited, and a conventionally known molding method of a thermosetting resin can be applied, and examples thereof include compression molding, transfer molding, and injection molding. In consideration of the dimensional stability of the molded product, 70% or more, and preferably 90% or more, before press-fitting the metal mold, in order to suppress shrinkage caused by methanol generated during curing of silica.
% Of the silica curing reaction must be completed,
To do so, preheat at 100-150 ° C before injecting the mold,
The sol-gel curing reaction for forming the silica site may be allowed to proceed. In order to promote the sol-gel curing reaction while maintaining the fluidity of the resin, it is preferable to use an alkoxy group-containing silane-modified phenol resin using an alkylphenol such as o-cresol or nonylphenol.

[0032]

According to the present invention, when a resin composition using the alkoxy group-containing silane-modified phenol resin of the present invention or a resin composition using the alkoxy group-containing silane-modified phenol resin as a curing agent for an epoxy resin is used, heat resistance and mechanical strength are improved. An organic / inorganic hybrid which is excellent and has a cured product free from voids (bubbles) can be obtained. These resin compositions and organic / inorganic hybrids can be suitably used for various applications such as IC sealants, epoxy resin-based laminates, coating agents for electric and electronic materials, and other paints and inks.

[0033]

The present invention will be described below in detail with reference to examples and comparative examples. In addition, in each example, parts and% are based on weight unless otherwise specified.

Production Example 1 (Production of Glycidyl Ether Group-Containing Alkoxysilane Partial Condensate (2)) Glycidol (manufactured by NOF Corporation) was equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas inlet tube. , 200 g of a trade name “Epiol OH”) and a partial condensate of tetramethoxysilane (trade name “methyl silicate 56”, manufactured by Tama Chemical Co., Ltd., average number of Si in one molecule: 12) 1
997.6 g, and stirred under a stream of nitrogen for 90 hours.
After the temperature was raised to 0 ° C, 2 g of dibutyltin dilaurate was added as a catalyst and reacted. During the reaction, methanol was distilled off from the reaction system using a water separator, and when the amount reached about 60 g, the system was cooled. The time required for cooling after the temperature was raised was 6 hours. Then, after cooling to 50 ° C., the nitrogen blow stopper and the water separator were removed, and a vacuum line was connected, and the system was maintained at 13 kPa for about 20 minutes to obtain about 29 minutes of residual methanol.
g was distilled off. Then, the inside of the system was cooled to room temperature, and 211
0.2 g of a glycidyl ether group-containing alkoxysilane partial condensate (hereinafter, referred to as condensate (2A)) was obtained. The equivalent of the methoxy group of the hydrolyzable methoxysilane at the time of preparation / the equivalent of the hydroxyl group of glycidol was 14, the product 1
Average Si number per molecule / average number of oxirane rings per product molecule is 6.8, epoxy equivalent is 782 g / e
q.

Production Example 2 (Production of Partial Condensate (2) of Glycidyl Ether Group-Containing Alkoxysilane) In the same reactor as in Production Example 1, 400 g of glycidol (trade name “Epiol OH”, manufactured by NOF Corporation) and Tetramethoxysilane partial condensate (manufactured by Tama Chemical Co., Ltd.
Trade name: “Methyl silicate 51”, average number of Si in one molecule: 4) 1791.6 g was charged, heated to 90 ° C. while stirring under a nitrogen stream, 2 g of dibutyltin dilaurate was added as a catalyst and reacted. Was. During the reaction, methanol was distilled off from the reaction system using a water separator, and the amount was reduced to about 15%.
When it reached 0 g, it was cooled. The time required for cooling after the temperature was raised was 6 hours. Then, after cooling to 50 ° C, remove the nitrogen blow stopper and the water separator, connect the decompression line,
By keeping the inside of the system at 13 kPa for about 20 minutes, about 25 g of residual methanol was distilled off. Thereafter, the inside of the system was cooled to room temperature, and 20188.2 g of a glycidyl ether group-containing alkoxysilane partial condensate (hereinafter, condensate (2)
B)). The equivalent of the methoxy group of the hydrolyzable methoxysilane / the equivalent of the hydroxyl group of glycidol at the time of preparation was 7, the average number of Si per molecule of the product / the average number of oxirane rings per molecule of the product was 2.8, The epoxy equivalent is 374 g / eq.

EXAMPLE 1 700 g of ortho-cresol novolak resin (trade name "KP7516" manufactured by Arakawa Chemical Industries, Ltd.) and 600 g of methyl ethyl ketone were added to a reactor equipped with a stirrer, a cooling pipe, a thermometer and a nitrogen gas introducing pipe. At 85 ° C. Further, 683.9 g of a glycidyl ether group-containing alkoxysilane partial condensate (2A) and 2.0 g of 2-methylimidazole as a catalyst were added and reacted at 85 ° C. for 4 hours. After cooling to 80 ° C., a phenol-modified phenol resin solution containing 55% by weight of an alkoxy group (hereinafter referred to as “resin solution (1A)”) has a phenolic hydroxyl equivalent of 40%.
0 g / eq). In addition, the equivalent ratio at the time of charging (glycidyl ether group-containing alkoxysilane partial condensate (2)
Glycidyl group equivalent / phenol resin (1) phenolic hydroxyl group equivalent) = 0.15. The Si content in the cured residue is 33% in terms of silica weight.

Example 2 In Example 1, ortho-cresol novolak resin 7
800 g of t-butylphenol novolak resin (trade name “Tamanol 100S” manufactured by Arakawa Chemical Industry Co., Ltd.) 800
g, and the charged amount of methyl ethyl ketone
The reaction was carried out in the same manner as in Example 1 except that the charged amount of the glycidyl ether group-containing alkoxysilane partial condensate (2A) was changed to 771.3 g in 0 g, and the alkoxy group-containing silane-modified phenol resin having a curing residue of 60% was used. A solution (hereinafter referred to as resin solution (1B), a phenolic hydroxyl equivalent of the solution 522 g / eq) was obtained. The equivalent ratio at the time of preparation (equivalent of glycidyl group of glycidyl ether group-containing alkoxysilane partial condensate (2) / equivalent of phenolic hydroxyl group of phenol resin (1)) = 0.2.
The Si content in the cured residue is 33% in terms of silica weight.

Example 3 In Example 1, ortho-cresol novolak resin 7
600 g of t-butylphenol novolak resin (trade name “Tamanol 100S” manufactured by Arakawa Chemical Industries, Ltd.) 600
g, and the charged amount of methyl ethyl ketone
The reaction was carried out in the same manner as in Example 1 except that the amount of the glycidyl ether group-containing alkoxysilane partial condensate (2A) was changed to 867.7 g in 0 g, and the alkoxy group-containing silane-modified phenol resin having a curing residue of 56% was used. A solution (hereinafter, referred to as a resin solution (1C), a phenolic hydroxyl equivalent of the solution of 758 g / eq) was obtained. The equivalent ratio at the time of charging (equivalent of glycidyl group of glycidyl ether group-containing alkoxysilane partial condensate (2) / equivalent of phenolic hydroxyl group of phenol resin (1)) = 0.3.
The Si content in the cured residue is 42% in terms of silica weight.

Example 4 In Example 1, ortho-cresol novolak resin 7
800 g of t-octylphenol novolak resin (trade name "KP7515" manufactured by Arakawa Chemical Industries, Ltd.)
And then charge the methyl ethyl ketone
g, the reaction was carried out in the same manner as in Example 1 except that the charged amount of the glycidyl ether group-containing alkoxysilane partial condensate (2A) was changed to 716.5 g, and the alkoxy group-containing silane-modified phenol resin having a curing residue of 60% was used. Solution (hereinafter,
A phenolic hydroxyl equivalent (732 g / eq) of a resin solution (1D) was obtained. The equivalent ratio at the time of charging (equivalent of glycidyl group of glycidyl ether group-containing alkoxysilane partial condensate (2) / phenol resin (1))
Phenolic hydroxyl group equivalent) = 0.25. The Si content in the cured residue is 31% in terms of silica weight.

Comparative Example 1 Orthocresol novolak resin (Arakawa Chemical Industries, Ltd.)
(Trade name, KP7516) was dissolved in methyl ethyl ketone to obtain a resin solution having a nonvolatile content of 50% (hereinafter referred to as comparative resin solution (a)).

Comparative Example 2 A t-butylphenol novolak resin (trade name "Tamanol 100S", manufactured by Arakawa Chemical Industries, Ltd.) was dissolved in methyl ethyl ketone, and a resin solution having a nonvolatile content of 50% (hereinafter, referred to as "tamanol 100S") was used.
Comparative resin solution (b)).

Comparative Example 3 t-octylphenol novolak resin (trade name "KP7515" manufactured by Arakawa Chemical Industries, Ltd.) was dissolved in methyl ethyl ketone, and a resin solution having a nonvolatile content of 50% (hereinafter referred to as comparative resin solution (c)) was prepared. did.

Examples 5 to 9 and Comparative Examples 4 to 7 (Preparation of Epoxy Resin Composition) The above-mentioned alkoxy-containing silane-modified phenolic resin, epoxy resin, catalyst and solvent were mixed at the mixing ratios shown in Tables 1 and 2. And various epoxy resin compositions were prepared.

[0044]

[Table 1] In Table 1, product names, abbreviations, etc. indicate the following. EP1: bisphenol A type epoxy resin, manufactured by Toto Kasei Co., Ltd., trade name “Epototo YD-011” EP2: bisphenol A type epoxy resin, manufactured by Toto Kasei Co., Ltd., trade name “Epototo YD-127” SnL: dibutyltin dilaurate DMF: dimethylformamide In Table 1, the equivalent ratio indicates a value of (equivalent of oxirane ring of epoxy resin / equivalent of phenolic hydroxyl group of phenol resin containing alkoxy group) in the epoxy resin composition.

[0045]

[Table 2] In Table 2, the product names, abbreviations, etc. are the same as described above.

The epoxy resin compositions obtained in Examples 5 to 9 and Comparative Examples 4 to 7 were placed in aluminum foil containers (length × width × length).
Pour at depth = 5cm × 5cm × 1.5cm) at 90 ℃
The solvent was removed and cured for 1 hour at 210 ° C. for 2 hours. In Examples 5 to 9 and Comparative Examples 4 to 7, transparent cured films (thickness: about 0.3 mm) could be formed.

The cured films obtained from the epoxy resin compositions of Examples 5 to 9 and Comparative Examples 4 to 7 were applied to a viscoelasticity meter (DVE-V, manufactured by Rheology Co., Ltd., trade name: amplitude 1 μm, frequency 10 Hz). , Slope 3 ° C./min) to measure the dynamic storage modulus and evaluate the heat resistance. The measurement results are shown in FIGS. As is clear from FIGS. 1 to 4, it is recognized that the cured films of Examples have a tendency to lose the glass transition point (Tg) and are excellent in heat resistance.

Example 10 Orthocresol novolak resin (trade name “KP751” manufactured by Arakawa Chemical Industry Co., Ltd.) was added to the same reactor as in Example 1.
6 ") 700 g was added and melted at 90 ° C. Further, a glycidyl ether group-containing alkoxysilane partial condensate (2
B) 218.1 g, 100 g of methyl ethyl ketone and 1 g of 2-methylimidazole as a catalyst were added.
The reaction was carried out for an hour to obtain an alkoxy group-containing silane-modified phenol resin solution (hereinafter, referred to as a resin solution (1E), a phenolic hydroxyl group equivalent of the solution: 194 g / eq). The equivalent ratio at the time of charging (equivalent of glycidyl group of glycidyl ether group-containing alkoxysilane partial condensate (2) / equivalent of phenolic hydroxyl group of phenol resin (1)) = 0.1
0. The Si content in the cured residue is 14% in terms of silica weight. At the same temperature, 10 g of tin octylate was added to the obtained alkoxy group-containing silane-modified phenol resin while stirring, and stirring was continued at the same temperature for 5 minutes. The obtained silane-modified phenolic resin composition was transferred to an aluminum container and cured at 150 ° C. for 30 minutes and at 210 ° C. for 1 hour to synthesize a phenolic resin-silica hybrid (precured product).

Example 11 The phenolic resin-silica hybrid obtained in Example 10 was crushed by a pulverizer and pulverized. Then, 200 g of the powdered phenolic resin-silica hybrid and 15 g of hexamethylenetetramine powder were mixed, and then a mold (10 mm × 60mm
× 2 mm). Press molding was performed at 180 ° C. and 40 kg / cm ² to obtain a cured molded product of a phenol resin-silica hybrid.

Comparative Example 8 A molded product was obtained in the same manner as in Example 11 except that a novolak phenol resin (trade name “TAMANOL 759”, manufactured by Arakawa Chemical Industries, Ltd.) was used instead of the phenol resin-silica hybrid. I got

The molded products obtained in Example 11 and Comparative Example 8 were subjected to a three-point bending test to measure the mechanical properties of the molded products. Table 3 shows the results.

[0052]

[Table 3]

[Brief description of the drawings]

FIG. 1 shows the evaluation results of the heat resistance of the cured films obtained in Example 5 and Comparative Example 4.

FIG. 2 shows evaluation results of heat resistance of the cured films obtained in Example 6 and Comparative Example 5.

FIG. 3 shows the evaluation results of the heat resistance of the cured films obtained in Examples 7 and 8 and Comparative Example 6.

FIG. 4 shows the evaluation results of heat resistance of the cured films obtained in Example 9 and Comparative Example 7.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 4J033 CA01 CA02 CA03 CA11 CA12 CA26 CA33 CA44 CB18 HA12 HA13 HA28 HB03 HB06 HB08 4J036 AD08 AF08 AG07 AH07 AK06 FB08 JA01 JA07 JA08

Claims (9)

[Claims] 1. Oxirane ring-opening of a phenol resin (1) and a glycidyl ether group-containing alkoxysilane partial condensate (2) obtained by a dealcoholation reaction of glycidol (A) and an alkoxysilane partial condensate (B). An alkoxy group-containing silane-modified phenol resin obtained by reacting. 2. The use ratio of the phenol resin (1) and the glycidyl ether group-containing alkoxysilane partial condensate (2) is such that the glycidyl ether group equivalent of the glycidyl ether group-containing alkoxysilane partial condensate (2) / (equivalent of phenol resin) 0.1 equivalent of phenolic hydroxyl group (equivalent ratio)
The alkoxy group-containing silane-modified phenolic resin according to claim 1, wherein 3. The alkoxy group-containing silane-modified phenolic resin according to claim 1, wherein the alkoxysilane partial condensate (B) is a tetramethoxysilane partial condensate or a methyltrimethoxysilane partial condensate. 4. The alkoxy group-containing silane-modified phenol resin according to claim 1, wherein the phenol resin (1) is a novolak type phenol resin. 5. The alkoxy group-containing silane-modified phenolic resin according to claim 4, wherein the novolak-type phenolic resin is a novolak-type alkylphenolic resin. 6. A resin composition containing the alkoxy group-containing silane-modified phenol resin according to claim 1. 7. The resin composition according to claim 6, comprising an alkoxy group-containing silane-modified phenol resin and an epoxy resin. 8. A curing agent for an epoxy resin, comprising the alkoxy group-containing silane-modified phenol resin according to claim 1. 9. An organic-inorganic hybrid obtained by curing the resin composition according to claim 6 or 7.