JP3468291B2 - Alkoxy group-containing silane-modified phenolic resin, resin composition, epoxy resin curing agent, and organic / inorganic hybrid. - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an alkoxy group-containing silane-modified phenol resin, a resin composition containing the resin and a curing agent for an epoxy resin, and an organic / inorganic hybrid body 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, or alumina in a resin has been widely used for the purpose of improving heat resistance and mechanical strength of a phenol resin. However, this method does not provide sufficient heat resistance. Further, in this method, the transparency of the phenol resin is lost and the adhesive property at the interface between the filler and the resin is poor, so that the mechanical properties such as elongation are insufficient.

Further, by using a composite of a phenol resin and silica particles obtained by hydrolyzing and polycondensing 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 Laid-Open No. 11-92623). However, in such a composite, the mechanical strength cannot be sufficiently improved because the bond between the silica particles and the phenol resin is not sufficient. In addition, voids (air bubbles) are likely to occur in the cured product due to water in the curing agent, water generated during curing, and alcohol such as methanol. Further, in order to improve the heat resistance, it is conceivable to increase the introduction amount of the alkoxysilane, which is a component of the composite, but in this case, the transparency of the cured product obtained by aggregating the generated silica is likely to be lost. Therefore, as a result of limiting the amount of alkoxysilane introduced, the heat resistance of the obtained composite cannot be sufficiently improved.

Conventionally, phenolic resins have been used as curing agents for epoxy resins. Especially in the fields of electrical and electronic materials, they are excellent in heat resistance, chemical resistance, electrical characteristics, etc. Was said to be suitable. However, with the recent development of the electric and electronic materials field,
Epoxy resin compositions are also required to have high performance, and heat resistance is particularly insufficient when a general curing agent composed of a phenol resin is used.

As a curing agent for epoxy resin, hydrolysis of alkoxysilane in the presence of phenol resin,
A method for improving the heat resistance of an epoxy resin cured product by using a complex of a phenol resin and silica obtained by polycondensation has been proposed (JP-A-9-21).
6938). In the epoxy resin cured product using such a composite as a curing agent, although the heat resistance is improved to some extent, voids (air bubbles) are generated in the cured product due to water in the curing agent or water or alcohol such as methanol generated during curing. ) Occurs. Further, when the amount of alkoxysilane is increased for the purpose of further improving heat resistance, the transparency of the cured product obtained by aggregation of the generated silica is lost and whitening occurs, and a large amount of alkoxysilane is sol-ized. Water is required, and as a result, warpage of the cured product, cracks and the like are caused.

[0006]

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

[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 a specific phenol resin and a specific alkoxysilane partial condensate (2) is contained. When a silane-modified phenol resin was used, it was found that a resin composition containing the resin and a curing agent for an epoxy resin can achieve the above-mentioned object, and the present invention has been completed.

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. Furthermore, the present invention relates to a cured product obtained by curing the resin composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As the phenol resin (1) constituting the alkoxy group-containing silane-modified phenol resin of the present invention, a novolac type phenol resin obtained by reacting phenols and aldehydes in the presence of an acid catalyst, Further, any of the resol type phenol resins obtained by reacting phenols and aldehydes in the presence of an alkali catalyst can be used. Of these, the resol-type phenol resin usually contains condensation water, and the alkoxysilyl moiety of the glycidyl ether group-containing alkoxysilane partial condensate (2) may be hydrolyzed. Preference is given to using phenolic resins. Further, as the phenol resin (1), it is usually preferable to use one having an average number of phenol nuclei of about 3 to 8.

Examples of the above-mentioned phenols include phenol, cresol, xylenol, ethylphenol, isopropylphenol, tertiary butylphenol, amylphenol, octylphenol, nonylphenol, dodecylphenol, chlorophenol and bromophenol. The position of the substituent in these phenols is not limited. As the formaldehydes, in addition to formalin, formaldehyde generating source substances such as paraformaldehyde, trioxane and tetraoxane can also be used. Further, as the acidic catalyst or the alkaline catalyst, any conventionally known one can be used.

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

Such alkoxysilane partial condensate (B)
Is, for example, general formula (1): R¹ _mSi (OR²)
_(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. R²Is charcoal
Indicates a lower alkyl group with a prime number of 4 or less, even if each is the same
It may be different. ) Hydrolyzable Alkoxy
Hydrolyze the silane monomer in the presence of acid or alkali.
What is obtained and 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,
Examples thereof include trialkoxysilanes such as methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane and isopropyltriethoxysilane. Usually, among these, since the alkoxysilane partial condensate (B) is particularly highly reactive with glycidol, a compound synthesized by using 70 mol% or more of tetramethoxysilane or methyltrimethoxysilane is preferable.
More preferably, it is synthesized using tetramethoxysilane in an amount of 70 mol% or more.

As the alkoxysilane partial condensate (B), those exemplified above can be used without any particular limitation. When two or more of these exemplified compounds are mixed and used, the alkoxysilane partial condensate is used. It is preferable to use tetramethoxysilane partial condensate or methyltrimethoxysilane in an amount of 60% by weight or more in the total amount of the substance (B). More preferably, 60 wt% or more of tetramethoxysilane partial condensate is used.

The average number of Si in the alkoxysilane partial condensate (B) is preferably 2 to 100. S
When the average number of i is less than 2, the amount of alkoxysilanes that flow out of the system together with alcohol without reaction during the demethanol reaction with glycidol (A) is not preferable. On the other hand, when it is 100 or more, the reactivity with glycidol (A) deteriorates, and the desired glycidyl ether group-containing alkoxysilane partial condensate (2) is difficult to obtain.

The glycidyl ether group-containing alkoxysilane partial condensate (2) can be obtained by subjecting the glycidol (A) and the alkoxysilane partial condensate (B) to dealcoholation (ester exchange). 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 resulting glycidyl ether group-containing alkoxysilane partial condensate ( The ratio of the glycidyl ether group in 2) is usually the equivalent of the epoxy group of the glycidol (A) / the 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 dealcoholized at a charging ratio. Since the proportion of the alkoxysilane partial condensate (B) not modified with epoxy increases as the charging ratio decreases, the charging ratio is more preferably 0.03 or more / 1. Further, when the charging ratio is increased, the glycidyl ether group of the glycidyl ether group-containing alkoxysilane partial condensate (2) is polyfunctionalized, and gelation easily occurs during the synthesis of the silane-modified phenol resin, so the charging ratio is 0.5. It is preferable that the ratio is equal to or less than 1.

The reaction between the alkoxysilane partial condensate (B) and the glycidol (A) is carried out by, for example, charging the above-mentioned components and carrying out a dealcoholization reaction while distilling off the alcohol produced by heating. The reaction temperature is about 50 to 150 ° C,
It is preferably 70 to 110 ° C., and the total reaction time is 1 to 1
It takes about 5 hours. The dealcoholization reaction is conducted at 110 ° C.
If it is carried out at a temperature higher than 1, a new siloxane bond is generated in the reaction system due to the alkoxysilane partial condensate (B), and the reaction product is liable to have high viscosity and gelation, which is not preferable.

In the dealcoholization reaction of the above-mentioned alkoxysilane partial condensate (B) and glycidol (A), a conventionally known catalyst that does not open the epoxy ring should be used to accelerate the reaction. You can 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, tin octylate and the like 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 phenolic resin which is the object of the present invention is the above-mentioned phenolic resin (1).
It is obtained by subjecting the glycidyl ether group-containing alkoxysilane partial condensate (2) to an oxirane ring-opening reaction.
By this reaction, an alkoxy group-containing silane-modified phenol resin in which a part of the hydroxyl groups of the phenol resin (1) is modified with the glycidyl ether group-containing alkoxysilane partial condensate (2) is produced. The proportion of the phenol resin (1) and the glycidyl ether group-containing alkoxysilane partial condensate (2) used in this reaction is not particularly limited,
It is preferable that the ratio of the glycidyl ether group equivalent of the glycidyl ether group-containing alkoxysilane partial condensate (2) / the hydroxyl group equivalent of the phenol resin (1) is in the range of 0.1 to 1. However, when a phenolic resin having an average number of nuclides of 3 or more is used, gelation is likely to occur due to the reaction between the oxirane ring and the phenolic hydroxyl group, so the ratio of the equivalent of the oxirane ring / the equivalent of the hydroxyl group is 0. 5
It is preferable to adjust it to less than.

In the production of the alkoxy group-containing silane-modified phenol 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 undergo an oxirane ring-opening reaction. It is done by This reaction is preferably carried out in a substantially anhydrous state in order to prevent the polycondensation reaction of the glycidyl ether group-containing alkoxysilane partial condensate (2) itself. This reaction mainly aims at the reaction between the hydroxyl group of the phenol resin (1) and the oxirane group of the glycidyl ether group-containing alkoxysilane partial condensate (2),
During this reaction, it is necessary to suppress the production of silica by the sol-gel reaction of the alkoxysilyl moiety of the glycidyl ether group-containing alkoxysilane partial condensate (2) and the dealcoholation reaction of the alkoxysilyl moiety with 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 oxirane ring-opening reaction, a known catalyst can be used to accelerate the reaction. 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; Tetraphenylphosphonium / tetraphenylborate, 2
Examples thereof include tetraphenylborate salts such as -ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate. The reaction catalyst is preferably used in a proportion of 0.01 to 5 parts by weight with respect to 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 a solvent,
There is no particular limitation as long as it is a solvent capable of dissolving 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 an alkoxy group derived from the alkoxysilane partial condensate (B) and a phenolic hydroxyl group derived from the phenol resin (1) in its molecule. , Does not have an oxirane group derived from glycidol (A). The content of the alkoxy group is not particularly limited, but the alkoxy group is bound to each other by sol-gel reaction or dealcohol condensation by evaporation of solvent or heat treatment or by reaction with water (humidity). Since it is necessary for forming a cured product, the alkoxy group-containing silane-modified phenol resin usually contains 50 to 95 mol%, preferably 60 to 90 mol%, of unreacted alkoxy groups of the alkoxysilane partial condensate (B). It is good 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 thermally cured by combining amines and epoxy resins according to the same reaction mechanism as that of conventional novolac type phenol resins. When the alkoxy group-containing silane-modified phenol resin is cured with amines, or when the alkoxy group-containing silane-modified phenol resin and the epoxy resin are used in combination, in order to allow the reaction to proceed sufficiently, The alkoxy group-containing silane-modified phenol resin must have a phenolic hydroxyl group. That is, the alkoxy group-containing silane-modified phenol resin is usually 30 to 95 mol% of the hydroxyl groups of the phenol resin (1), preferably 60.
It is preferable to keep ˜90 mol% unreacted.
A cured product obtained from the alkoxy group-containing silane-modified phenol resin is an alkoxysilane partial condensate (B).
It has a gelled fine silica site (higher-order network structure of siloxane bond) formed from the above. Further, the alkoxy group-containing silane-modified phenol resin of the present invention contains a phenol resin (1) in which a part of the hydroxyl groups is silane-modified, as a main component. Is an unreacted phenol resin (1), an alkoxysilane partial condensate (B) (this means an unreacted substance contained in the glycidyl group-containing alkoxysilane partial condensate (2)), a glycidyl group-containing alkoxysilane partial condensation The substance (2), the solvent and the catalyst used in the reaction may be contained. The unreacted alkoxysilane partial condensate (B) and the unreacted alkoxysilane partial condensate (B) are hydrolyzed or polycondensed to form silica during curing, and are integrated with the alkoxy group-containing silane-modified phenolic resin. Turn into.

Alkoxy group-containing silane-modified phenolic tree
In the resin composition containing fat, the resin composition
The content of Si in the curing residue is 2 in terms of silica weight.
It is preferably about 50% by weight. Curing residue here
Si content in terms of silica content in the content means the content of alkoxy groups.
The alkoxysilyl moiety of the silane-modified phenolic resin
Higher-order siloxane bonds are formed through the sol-gel curing reaction.
Done, General 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 are shown,
It may be the same or different. ) Is represented approximately by
The weight of silica part in the curing residue when cured to the silica part
The amount is percent. If less than 2% by weight, heat resistance and strength
It is difficult to obtain the effects of the present invention such as
If it exceeds, the cured product will become too brittle and strength will decrease.
Tend to The resin composition may be dissolved depending on the purpose of use.
The concentration can be adjusted appropriately depending on the agent. As a solvent,
Capable of dissolving silane-modified phenolic resin containing coroxy groups
If so, it can be used without particular limitation. Also, cured products
Hardened silica for the purpose of adjusting mechanical strength and heat resistance
If it is necessary to adjust the amount,
The orchid-modified phenolic resin composition contains an alkoxysilane part.
Even if the condensate (B) or the phenol resin (1) is blended,
I don't know. Further, the alkoxy group silane modified resin composition,
Various cures used to cure conventionally known phenolic resins
You may use an agent. Specifically, hexamethylene
Suitable amines such as tetramine and melamine resin
It Furthermore, the silane-modified phenol resin composition,
Previously known for the purpose of promoting the silica curing reaction even at low temperatures
Sol-gel curing of acid or basic catalysts, metal catalysts, etc.
You may contain a catalyst and water. However add water
If the alkoxy group silane-modified resin composition is
Alkoxy group-containing silane-modified phenol
0.6 mol or less per 1 mol of the alkoxy group of the resin
Is preferred. In addition, the alkoxy group-containing
The orchid-modified phenolic resin composition impairs the effects of the present invention.
Filler, mold release agent, surface, if necessary, within the range not touched
Treatment agents, flame retardants, viscosity modifiers, plasticizers, antibacterial agents, antifungal agents
Agents, leveling agents, defoamers, colorants, stabilizers, coupling agents
You may mix | blend a stinging agent etc.

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

As the epoxy resin to which the curing agent for epoxy resin of the present invention is applied, various known ones can be exemplified. For example, orthocresol novolac type epoxy resins, novolac type epoxy resins such as novolac phenol type epoxy resins; diglycidyl ethers derived from bisphenol A, bisphenol F, polybasic acids such as phthalic acid and dimer acid, and epichlorohydride. Glycidyl ester type epoxy resin obtained by reacting phosphorus; glycidyl amine type epoxy resin obtained by reacting polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin; Olefin bond is oxidized by peracid such as peracetic acid The linear aliphatic epoxy resin and alicyclic epoxy resin obtained by the above can be mentioned, and these 1 type can be used individually or in combination of 2 or more types.

In addition, in the epoxy resin composition of the present invention, when the alkoxysilyl moiety of the alkoxy group-containing silane-modified phenol resin is cured, hydrolysis and polycondensation are promoted. , Catalytic amount of formic acid, acetic acid, propionic acid, p-toluenesulfonic acid, methanesulfonic acid and other organic acid catalysts, boric acid, phosphoric acid and other inorganic acid catalysts and alkaline catalysts, organic tin, organic acid tin catalysts It can also be included. Furthermore, the epoxy resin composition of the present invention may contain a curing accelerator for promoting the curing reaction between the epoxy resin and the curing agent. As the effect accelerator, the same compounds as those used in the production of the alkoxy group-containing silane-modified phenol resin can be used. 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.

The concentration of the epoxy resin composition can be adjusted appropriately with a solvent. As the solvent, the same ones as those used for producing the alkoxy group-containing silane-modified phenol resin can be used. In addition, as 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 in the preparation of the alkoxy group-containing silane-modified phenol resin composition You may mix | blend.

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 the alkoxy group-containing silane-modified phenol resin composition is 100 parts by weight. Then, 0 to 150 parts by weight of a conventionally known pigment is blended and used. The coating material is coated on a substrate using a conventionally known coating device such as a sprayer or a coater,
Preferably, it is baked at 60 ° C. or higher to form a coating film. When the coating material is for outdoor use, it is preferable to add 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 silane-modified phenol resin used is 0.01 to 5 mol% for paratoluenesulfonic acid or tin octylate, which have a high catalytic ability, and 0 for formic acid and acetic acid, which have a low catalytic ability. It is used at about 1 to 50 mol%. Further, for the purpose of softening and strengthening the cured film, an epoxy resin, an alkyd resin, a maleated oil or the like may be added.

When an alkoxy group-containing silane-modified phenol resin composition or an epoxy resin composition is used as a molded article, an alkoxy group-containing silane-modified phenol resin is synthesized without using a solvent, and the above amine-based curing agent or A resin composition is prepared by combining an epoxy resin, a curing catalyst, various fillers, various fibers, and water as the case may be. The molding method is not particularly limited, and conventionally known thermosetting resin molding methods can be applied, and examples thereof include compression molding, transfer molding, and injection molding. Considering the dimensional stability of the molded product, 70% or more, preferably 90% or more before press-fitting the mold, in order to suppress shrinkage due to methanol generated during silica curing.
% Or more silica curing reaction must be completed,
For that, preheat at 100-150 ℃ before mold injection,
It is only necessary to advance the sol-gel curing reaction that forms the silica site. In order to allow the sol-gel curing reaction to proceed while maintaining the fluidity of the resin, it is preferable to use an alkoxy group-containing silane-modified phenol resin formed by using alkylphenol such as o-cresol or nonylphenol.

[0032]

When the resin composition using the alkoxy group-containing silane-modified phenol resin of the present invention or the resin composition using the alkoxy group-containing silane-modified phenol resin as a curing agent for epoxy resin is used, heat resistance and mechanical strength are improved. A cured product that is excellent and does not generate voids (air bubbles) can be obtained. These resin compositions and cured products can be suitably used for various applications such as IC encapsulants, epoxy resin-based laminates, coating agents for electric / electronic materials, paints and inks.

[0033]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. In the examples, 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 placed in a reactor equipped with a stirrer, water divider, thermometer and nitrogen gas inlet tube. , Trade name “Epiol OH”) and tetramethoxysilane partial condensate (manufactured by Tama Chemical Co., Ltd., trade name “methyl silicate 56”, average number of Si in one molecule: 12) 1
Charge 997.6 g and stir under nitrogen stream while stirring 90
After the temperature was raised to 0 ° C., 2 g of dibutyltin dilaurate as a catalyst was added 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 mixture was cooled. The time required for cooling after temperature rising was 6 hours. Then, after cooling to 50 ° C., the nitrogen blowing stopper and the water separator were removed, the decompression line was connected, and the system was kept at 13 kPa for about 20 minutes to give about 29% residual methanol.
g was distilled off. Then, cool the system to room temperature,
0.2 g of a glycidyl ether group-containing alkoxysilane partial condensate (hereinafter, referred to as condensate (2A)) was obtained. The equivalent of methoxy group of hydrolyzable methoxysilane / equivalent of hydroxyl group of glycidol at the time of charging was 14, product 1
Average Si number per molecule / product Average number of oxirane rings per molecule is 6.8, epoxy equivalent is 782 g / e
q.

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

Example 1 700 g of orthocresol novolac resin (trade name "KP7516" manufactured by Arakawa Chemical Industry Co., 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. , Melted at 85 ° C. Furthermore, 683.9 g of the glycidyl ether group-containing alkoxysilane partial condensate (2A) and 2.0 g of 2-methylimidazole as a catalyst were added, and the mixture was reacted at 85 ° C. for 4 hours. After cooling to 80 ° C., an alkoxy group-containing silane-modified phenol resin solution having a curing residue of 55% (hereinafter referred to as a resin solution (1A), a phenolic hydroxyl group equivalent of 40 of the solution)
0 g / eq) was obtained. The equivalent ratio at the time of charging (glycidyl ether group-containing alkoxysilane partial condensate (2)
Of glycidyl group / equivalent of phenolic hydroxyl group of phenol resin (1)) = 0.15. The Si content in the curing residue is 33% in terms of silica weight.

Example 2 In Example 1, orthocresol novolac resin 7
800 g of t-butylphenol novolac resin (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "Tamanor 100S") 800
g and change the amount of methyl ethyl ketone charged to 50
The reaction was performed in the same manner as in Example 1 except that the amount of the glycidyl ether group-containing alkoxysilane partial condensate (2A) charged to 0 g was changed to 771.3 g, and an alkoxy group-containing silane-modified phenol resin having a curing residue of 60% was used. A solution (hereinafter, referred to as a resin solution (1B), a phenolic hydroxyl group equivalent of the solution was 522 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)) was 0.2.
The Si content in the curing residue is 33% in terms of silica weight.

Example 3 In Example 1, orthocresol novolak resin 7
600 g of t-butylphenol novolac resin (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "Tamanor 100S")
g and change the amount of methyl ethyl ketone charged to 50
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) charged to 0 g was changed to 867.7 g, and an alkoxy group-containing silane-modified phenol resin having a curing residue of 56% was obtained. A solution (hereinafter, referred to as a resin solution (1C), a phenolic hydroxyl group equivalent of the solution was 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)) was 0.3.
The Si content in the curing residue is 42% in terms of silica weight.

Example 4 In Example 1, orthocresol novolac resin 7
800 g of t-octylphenol novolac resin (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "KP7515")
Changed to 500 and the charged amount of methyl ethyl ketone was changed to 500.
g, the reaction was performed 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 curing residue was 60% and the alkoxy group-containing silane-modified phenol resin was used. Solution (hereinafter,
A resin solution (1D), which was a phenolic hydroxyl group equivalent of 732 g / eq of the solution, 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)
Of the phenolic hydroxyl group of) = 0.25. The Si content in the curing residue is 31% in terms of silica weight.

Comparative Example 1 Orthocresol novolac resin (Arakawa Chemical Industry Co., Ltd.)
(Trade name: “KP7516” manufactured by K.K.) 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 t-Butylphenol novolac resin (trade name "Tamanor 100S" manufactured by Arakawa Chemical Industry Co., Ltd.) was dissolved in methyl ethyl ketone to prepare a resin solution having a nonvolatile content of 50% (hereinafter,
Comparative resin solution (b)).

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

Examples 5-9 and Comparative Examples 4-7 (Preparation of Epoxy Resin Composition) The alkoxy-containing silane-modified phenol resin, epoxy resin, catalyst and solvent were mixed at the compounding ratios shown in Table 1 and Table 2. , 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 Tohto 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 is a value of (equivalent of oxirane ring of epoxy resin / equivalent of phenolic hydroxyl group of alkoxy group-containing phenol resin) in the epoxy resin composition.

[0045]

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

The epoxy resin compositions obtained in Examples 5 to 9 and Comparative Examples 4 to 7 were placed in aluminum foil containers (length x width x).
Depth = 5 cm x 5 cm x 1.5 cm) at 90 ° C
The solvent was removed and the resin was cured at 210 ° C. for 1 hour. For Examples 5 to 9 and Comparative Examples 4 to 7, transparent cured films (film thickness of about 0.3 mm) could be prepared.

Cured films obtained from the epoxy resin compositions of Examples 5-9 and Comparative Examples 4-7 were measured with a viscoelasticity measuring instrument (Rheology Co., trade name DVE-V4, measurement conditions: amplitude 1 μm, frequency 10 Hz). , Slope 3 ° C./min) was used to measure the dynamic storage elastic modulus to 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 glass transition point (Tg) that tends to disappear, and that they have excellent heat resistance.

Example 10 An orthocresol novolac resin (manufactured by Arakawa Chemical Industry Co., Ltd., trade name “KP751” was added to a reactor similar to that used 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, and the mixture was mixed at 90 ° C. for 1 hour.
The reaction was carried out for a time to obtain an alkoxy group-containing silane-modified phenol resin solution (hereinafter referred to as resin solution (1E), which is equivalent to 194 g / eq of phenolic hydroxyl group in the solution). 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
It is 0. The Si content in the curing residue is 14% in terms of silica weight. 10 g of tin octylate was added to the obtained alkoxy group-containing silane-modified phenol resin with stirring at the same temperature, and stirring was continued for 5 minutes at the same temperature. The obtained silane-modified phenol resin composition was transferred to an aluminum container and cured at 150 ° C. for 30 minutes and 210 ° C. for 1 hour to synthesize a phenol resin-silica hybrid (preliminary cured product).

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

Comparative Example 8 A molded article was prepared in the same manner as in Example 11, except that a novolac phenol resin (manufactured by Arakawa Chemical Industry Co., Ltd., trade name “Tamanor 759”) was used in place of the phenol resin-silica hybrid. Got

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

[0052]

[Table 3]

[Brief description of drawings]

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

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

FIG. 3 shows the evaluation results of 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.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 62-50324 (JP, A) JP 57-142992 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 8/04-8/36 C08G 59/00-59/72 C08L 61/04-61/14 CA (STN) REGISTRY (STN)

Claims (9)

(57) [Claims] 1. An oxirane ring-opening reaction is carried out by phenolic resin (1) and glycidyl ether group-containing alkoxysilane partial condensate (2) obtained by dealcoholization reaction of glycidol (A) and alkoxysilane partial condensate (B). An alkoxy group-containing silane-modified phenol resin characterized by being reacted. 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) / phenol resin 0.1 as the equivalent (equivalent ratio) of phenolic hydroxyl groups
The alkoxy group-containing silane-modified phenolic resin according to claim 1, which is in the range from 1 to 1. 3. The alkoxy group-containing silane-modified phenol 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 novolac type phenol resin. 5. The alkoxy group-containing silane-modified phenol resin according to claim 4, wherein the novolac type phenol resin is a novolac type alkylphenol 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, which comprises 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 any one of claims 1 to 5. 9. A cured product obtained by curing the resin composition according to claim 6.