JPH06313029A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing trisphenols having a specific number of hydroxybenzyl groups added thereto and an epoxy resin, excellent in curing uniformity and heat and moisture resistances and useful as electrical and electronic materials, etc. CONSTITUTION:This resin composition contains (A) a mixture of hydroxybenzyl group adducts of trisphenols expressed by formula I [X is group expressed by formula II; one or more groups of R<i> [(i) is 1-15] on each aromatic ring are OH and at least one of groups R<i-1> and R<i+1> adjacent to the OH is (substituted)hydroxybenzyl expressed by formula III {at least one of groups Q<j> [(j) is 1-5] is OH and the rest are H, lower (cyclo)alkyl or aromatic group}; the remaining groups R<i> are H, lower (cyclo)alkyl or aromatic group] and (B) an epoxy resin. The number of hydroxybenzyl groups based one molecule of this mixture on the average is 3-6.

Description

Detailed Description of the Invention

[0001]

The present invention contains, as a curing agent, a composition comprising a mixture which is a novel addition product of hydroxybenzyl group to trisphenol together with an epoxy resin,
The present invention relates to a thermosetting resin composition which gives a cured product having excellent workability and physical properties.

[0002]

2. Description of the Related Art Conventionally, amines, acid anhydrides, phenol novolac resins, etc. have been used as curing agents for epoxy resins, but in recent years, they have also been used in laminated plates, sealing materials and powder coatings. In response to the demand for higher product performance, phenol novolac resins have been reviewed and are being used particularly favorably in electrical and electronic materials.

The phenol novolac resin is generally obtained by subjecting phenols and formaldehyde to an addition condensation reaction in the presence of an acid catalyst. Therefore, the phenol novolac resin is a resin having a broad molecular weight distribution, in which the phenol nuclei are mainly bonded by methylene bonds and the phenol nuclei are usually composed of a range of 2 to 20. Thus, the phenol novolac resin is
Due to its wide molecular weight distribution, it is difficult to obtain a cured product with a high cross-linking density when used as a curing agent for epoxy resins, and when repeated production is performed, there are slight differences in the raw material formulation and production conditions. Therefore, there is a problem in the reproducibility of the molecular weight and the molecular weight distribution, and therefore, there is a problem in the reliability of the quality of the cured product.

On the other hand, plastics usually contain various additives in order to prevent their deterioration.
In particular, in order to prevent oxidation, an antioxidant called a hindered phenol compound is usually used.
However, conventionally, as the hindered phenol antioxidant, a monophenol type or a bisphenol type is used, and when added to plastics, they volatilize because of their small molecular weight,
Since it evaporates or moves to the surface in the resin, there is a problem in the retention of the antioxidant ability for a long period of time.

Regarding the hydroxybenzyl group adduct to a phenol compound, bis-
The case of using phenol A and p, p'-bisphenol F is described in Japanese Patent Application No. 3-200776.
The use of trisphenols as the phenol compound has not been known so far.

[0006]

In view of the above-mentioned conventional techniques, the present invention comprises an epoxy resin containing as a curing agent a composition comprising a novel mixture of hydroxybenzyl group adducts with trisphenols, An object of the present invention is to provide a thermosetting resin composition which is excellent in uniform curing reactivity at the time of curing and which can provide a thermosetting product having excellent heat resistance and moisture resistance.

[0007]

The thermosetting resin composition according to the present invention comprises (a) the general formula (I)

[0008]

[Chemical 4]

[Wherein X is

[0010]

[Chemical 5]

A trivalent group selected from the group consisting of
R ⁱ on each aromatic ring (i = 1 to 5, 6 to 10 and 11 to 1)
At least one of 5) represents a hydroxyl group, and at least one of R ^i-1 and R ^{i + 1} adjacent to the hydroxyl group on each aromatic ring is represented by the general formula (II).

[0012]

[Chemical 6]

(In the formula, at least one of Q ^j (j = 1 to 5) represents a hydroxyl group, and the rest represents hydrogen, a lower alkyl group, a lower cycloalkyl group, or an aromatic group.) It represents a substituted or substituted hydroxybenzyl group, and the rest of R ⁱ represents hydrogen, a lower alkyl group, a lower cycloalkyl group or an aromatic group. ] A mixture of hydroxybenzyl group adducts to trisphenols represented by the above formula, wherein the average number of hydroxybenzyl groups per molecule of these hydroxybenzyl group adducts to trisphenols is in the range of 3 to 6. It is characterized by containing a composition comprising a mixture and (b) an epoxy resin.

That is, the thermosetting resin composition according to the present invention is an epoxy resin containing a composition comprising, as a curing agent, a mixture of hydroxybenzyl group adducts with trisphenols represented by the general formula (I). Consists of. First, a composition (hereinafter referred to as composition (a)) composed of a mixture of such a hydroxybenzyl group adduct to trisphenol will be described.

In the composition (a), the trisphenols represented by the general formula (I) are, for example, 1,1,
1-tris (4-hydroxyphenyl) methane, 1,1,1
-Tris (4-hydroxyphenyl) ethane, 1,1-di (3,5-dimethyl-4-hydroxyphenyl) -1-
(2-hydroxyphenyl) methane, 1,1,1-tris (3-methyl-4-hydroxyphenyl) ethane, 1,1
-Di (2-methyl-4-hydroxy-5-cyclohexylphenyl) methane, 1,1-di (4-hydroxyphenyl) -1- [4- [2- (4-hydroxyphenyl)-
2-propyl] phenyl] ethane etc. can be mentioned.

In the composition (a), the hydroxybenzyl group represented by the general formula (II) is, for example, 4-hydroxybenzyl group, 2-hydroxybenzyl group, 4-hydroxy-3-group. Methylbenzyl group, 2-hydroxy-3-methylbenzyl group, 2-hydroxy-5-methylbenzyl group, 4-hydroxy-3,5
-Dimethylbenzyl group, 4-hydroxy-3,5-di-t
-Butylbenzyl group, 4-hydroxy-2-methyl-5
-T-butylbenzyl group, 2-hydroxy-6-methyl-3-t-butylbenzyl group, 2-hydroxy-5methyl-3-sillohexylbenzyl group, 2-hydroxy-
Examples thereof include 6-methyl-3-cyclohexylbenzyl group.

In the present invention, a composition comprising a mixture of hydroxybenzyl group adducts with trisphenols used as a curing agent for epoxy resins is used as a first step in the presence of a basic catalyst. To obtain a methylolated trisphenol by a reaction between styrene and formaldehyde, and then, as a second step, reacting the methylolated trisphenol with an unsubstituted or substituted phenol compound in the presence of an acidic catalyst. You can

The above first step is usually carried out in the presence of a basic catalyst in a water solvent or a mixed solvent of water and an organic solvent,
It is carried out by excessively reacting formaldehyde with the hydroxyl groups of the starting material, trisphenol. As the formaldehyde used in this first step, a commercially available formalin aqueous solution can be used as it is, and paraformaldehyde or trioxane that acts similarly to formaldehyde in the presence of water can also be used.

Examples of the above-mentioned basic catalyst include divalent metals such as alkali metal hydroxides and acetates such as sodium hydroxide, potassium hydroxide and lithium hydroxide, calcium hydroxide, zinc hydroxide and magnesium hydroxide. Metals, preferably alkaline earth metal hydroxides and acetates, pyridine,
Examples thereof include tertiary amines such as trimethylamine and tributylamine. Of these, sodium hydroxide or potassium hydroxide is particularly preferably used.

The first step is usually carried out in the presence of water, but in order to increase the affinity of trisphenols for water, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n- An alcoholic solvent such as butanol, ethylene glycol, ethylene glycol monomethyl ether, diethylene glycol, carbitol, etc., or a water-soluble organic solvent such as tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. is also used in some cases. .

In the first step, the use ratio of formaldehyde to trisphenol is usually in the range of 2.0 to 10 times mol, preferably 2.5 to the number of hydroxyl groups of trisphenol. It is in the range of 5.0 times the mole. The amount of the basic catalyst used is usually in the range of 1.0 to 5 times by mole, and preferably in the range of 1.1 to 1.5 times by mole with respect to the number of hydroxyl groups contained in the trisphenol. . As for the solvent, the total weight of trisphenols and formalin which are raw materials is usually 10 to 50% by weight, and preferably 30.
It is used in the range of about 45% by weight.

The first step is usually 0 to 60.
C., preferably at a temperature in the range of 30 to 40.degree. C., usually for 1 to 72 hours, preferably for 4 to 12 hours, but the method of the present invention is particularly limited to these conditions. It is not something that will be done. When the first step is completed, after neutralizing the basic catalyst in the obtained reaction mixture with an acid, by adjusting the solvent mixing ratio of the organic solvent and water in the reaction mixture, Methylolated trisphenol can be obtained by precipitating crystals from a solvent and filtering the crystals from the reaction mixture.

Then, in the second step, the reaction of the unsubstituted or substituted phenol compound with the methylolated trisphenol obtained as described above is usually carried out in the presence of an acidic catalyst, without solvent or with an organic solvent. Below, it is carried out by reacting an excess amount of an unsubstituted or substituted phenol compound with respect to the number of hydroxyl groups of the methylolated trisphenol.

Examples of the unsubstituted or substituted phenol compound used in the second step include phenol, o-cresol, p-cresol, m-cresol, o-isopropylphenol, o-sec-butylphenol, m-sec-butylphenol, p-se
c-butylphenol, ot-butylphenol, m
-T-butylphenol, pt-butylphenol,
o-styrenated phenol, o-cyclohexylphenol, p-cyclohexylphenol, 2,4-dimethylphenol (2,4-xylenol), 2,5-dimethylphenol (2,5-xylenol), 2,6-dimethylphenol (2,6-xylenol), 2,4-di-sec-butylphenol, 2,6-di-sec-butylphenol, 2,4-di-t-butylphenol, 2,6-di-t-
Butylphenol, 2-methyl-6-t-butylphenol, 2-methyl-4-t-butylphenol, 3-methyl-6-t-butylphenol, 4-methyl-2-t
-Butylphenol, 2-methyl-4-cyclohexylphenol, 3-methyl-6cyclohexylphenol and the like can be mentioned.

Of these, phenol compounds having relatively small steric hindrance, such as phenol, o-cresol, p-cresol, 2,4 xylenol, and 2,6 xylenol, are preferable for the composition for use as a curing agent for epoxy resin. Used, and also o-t-butylphenol, o-styrenated phenol, o-cyclohexylphenol, 2,6-
Phenol compounds having a relatively large steric hindrance, such as di-t-butylphenol, 2-methyl-6-t-butylphenol, 3-methyl-6-t-butylphenol, and 3-methyl-6cyclohexylphenol, are used to prevent resin oxidation. It is suitable for use as an additive, but is not limited thereto.

These unsubstituted or substituted phenol compounds are used alone or as a mixture of two or more kinds. In the second step, examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid, and carboxylic acids such as oxalic acid and acetic acid. Of these, hydrochloric acid is particularly preferably used.

The second step can be carried out in the absence of a solvent, but in order to facilitate the adjustment of the reaction temperature during the reaction, the adjustment of the viscosity of the reaction system, etc., it should be carried out in the presence of an organic solvent. You can also Here, as the organic solvent, for example, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, tetrahydrofuran,
Examples thereof include ethers such as dioxane, and aliphatic amides such as dimethylformamide and dimethylacetamide, but are not limited thereto.

Further, in the second step, the ratio of the unsubstituted or substituted phenol compound to the methylolated trisphenol is usually 1 to 100 times mol based on the number of methylol groups of the methylolated trisphenol. The range is preferably 5 to 20 times the molar range.
The amount of the acidic catalyst used is usually in the range of 0.01 to 1 times mol, and preferably, to the methylolated trisphenol.
It is in the range of 0.1 to 0.5 times by mole. When a solvent is used, the total weight of the methylolated trisphenol and the unsubstituted or substituted phenol compound is usually 20 to 95% by weight, preferably 50 to 90% by weight.

In the second step, the reaction is usually carried out at a temperature in the range of 10 to 100 ° C., preferably 20 to 50 ° C. for usually 1 to 48 hours, preferably 5 to 2
It is carried out for about 0 hours, but the present invention is not particularly limited to these conditions. When the second step is completed, the acidic catalyst used is neutralized and removed, and the excess phenolic compound and, if a solvent is used, are distilled off to remove the solvent. It is possible to obtain a composition consisting of a mixture of hydroxybenzyl group adducts to trisphenols according to the invention.

That is, in the present invention, the composition (a) used as a curing agent for an epoxy resin is prepared by reacting trisphenol with formaldehyde in the presence of a basic catalyst as a first step. Hydroxybenzyl group addition to the above-mentioned trisphenols, which can be obtained by producing methylolated trisphenol and then reacting this methylolated trisphenol with a phenol compound in the presence of an acidic catalyst as a second step. The number of hydroxybenzyl groups on the aromatic nucleus of the above trisphenol is in the range of 1 to 2 per aromatic nucleus, and therefore, on average, of the hydroxybenzyl group adduct to trisphenols. The number of hydroxybenzyl groups per molecule is in the range of 4-6.

Such a composition (a) may be mainly composed of a highly purified product of a hexabenzyl adduct of hydroxybenzyl group on trisphenol. For example, the adduct of hydroxybenzyl group on a single trisphenol is 60% or more, and in some cases 80% or more, or 90%.
The above-mentioned high-purity product may be a main component. When the composition (a) is mainly composed of such a high-purity product, the structure at the position where the hydroxybenzyl group adjacent to the hydroxyl group on the aromatic nucleus of the hydroxybenzyl adduct to trisphenol is not added, The structure of trisphenols used as a raw material may be retained as it is, or may be a structure in which a methylol group is added.

In the present invention, the composition (a) has different main components depending on the trisphenol used as a raw material, but the above-mentioned trisphenol is first reacted with formaldehyde and then reacted with a phenol compound. By the method, the following composition comprising a mixture containing a hydroxybenzyl group adduct to trisphenol as a main component can be obtained.

That is, as a specific example of the hydroxybenzyl group adduct to 1,1,1-tris (4-hydroxyphenyl) methane, 4-hydroxyl-1,4-triphenyl (4-hydroxyphenyl) methane is added to 1,1,1-tris (4-hydroxyphenyl) methane. Hydroxybell group adduct and 2-hydroxybenzyl group adduct, 4-hydroxy-3-methylbenzyl group adduct to 1,1,1-tris (4-hydroxyphenyl) methane and 2-hydroxy-3-methylbenzyl Group addition product, 2-hydroxy-5-methylbenzyl group addition product to 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl)
4-Hydroxy-3,5-dimethylbenzyl group adduct to methane, 4-hydroxy-3,5-di-t-butylbenzyl group adduct to 1,1,1-tris (4-hydroxyphenyl) methane 4-Hydroxy-2-methyl-5-t-to 1,1,1-tris (4-hydroxyphenyl) methane
Butylbenzyl group adduct and 2-hydroxy-6-methyl-3-t-butylbenzyl group adduct, 2-hydroxy-5-methyl-3-to 1,1,1-tris (4-hydroxyphenyl) methane t-butylbenzyl group adduct, 1,1,
4-to 1-tris (4-hydroxyphenyl) methane
Examples thereof include a hydroxy-2-methyl-5-cyclohexylhenzyl group adduct and a 2-hydroxy-6-methyl-3-cyclohexylhenzyl group adduct.

Specific examples of the hydroxybell group adduct to 1,1,1-tris (4-hydroxyphenyl) ethane include 4-hydroxybell to 1,1,1-tris (4-hydroxyphenyl) ethane. Group adduct and 2-hydroxybenzyl group adduct, 4-hydroxy-3-methylbenzyl group adduct and 2-hydroxy-3-methylbenzyl group adduct to 1,1,1-tris (4-hydroxyphenyl) ethane Body, an addition product of 2-hydroxy-5-methylbenzyl group to 1,1,1-tris (4-hydroxyphenyl) ethane,
4-hydroxy-3,5-dimethylbenzyl group addition product to 1,1,1-tris (4-hydroxyphenyl) ethane, 1,
4 to 1,1-tris (4-hydroxyphenyl) ethane
-Hydroxy-3,5-di-t-butylbenzyl group adduct, 4-hydroxy-2-methyl-5-t-butylbenzyl group adduct to 1,1,1-tris (4-hydroxyphenyl) ethane And 2-hydroxy-6-methyl-3-t
-Butylbenzyl group adduct, 2-hydroxy-5-methyl-3-t-butylbenzyl group adduct to 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (4 4-hydroxy-2-methyl-5-cyclohexylbenzyl group addition product 2 to -hydroxyphenyl) ethane
-Hydroxy-6-methyl-3-cyclohexylbenzyl adduct and the like can be mentioned.

Further, 1,1-di (4-hydroxyphenyl) -1- [4- [2- (4-hydroxyphenyl)-
Specific examples of the hydroxybenzyl group addition product to 2-propyl] phenyl] ethane include 1,1-di (4-hydroxyphenyl) -1- [4- [2- (4-hydroxyphenyl) -2-propyl]. ] Phenyl] ethane 4-hydroxybenzyl group adduct and 2-hydroxybenzyl group adduct, 1,1-di (4-hydroxyphenyl) -1-
[4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethane adduct with 4-hydroxy-3-methylbenzyl group and 2-hydroxy-3-methylbenzyl group, 1,1- Di (4-hydroxyphenyl)-
2-Hydroxy-5-methylbenzyl group addition product to 1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethane, 1,1-di (4-hydroxyphenyl) -1- [4- [2- (4-hydroxyphenyl)
4-Hydroxy-3,5-dimethylbenzyl group adduct to 2-propyl] phenyl] ethane, 1,1-di (4-hydroxyphenyl) -1- [4- [2- (4-hydroxyphenyl)] 4-to 2-propyl] phenyl] ethane
-Hydroxy-3,5-di-t-butylbenzyl group adduct, 1,1-di (4-hydroxyphenyl) -1- [4-
4-Hydroxy-2-methyl-5-to [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethane
t-Butylbenzyl group adduct and 2-hydroxy-6-
Methyl-3-t-butylbenzyl group adduct, 1,1-di (4-hydroxyphenyl) -1- [4- [2- (4-
Hydroxyphenyl) -2-propyl] phenyl] ethane adduct with 2-hydroxy-5-methyl-3-t-butylbenzyl group, 1,1-di (4-hydroxyphenyl)
-1- [4- [2- (4-hydroxyphenyl) -2-
4-hydroxy-2-to propyl] phenyl] ethane
Methyl-5-cyclohexylbenzyl group adduct and 2-
Examples thereof include a hydroxy-6-methyl-3-cyclohexylbenzyl group adduct.

According to a preferred embodiment of the present invention, a single trisphenol is used as a raw material, and in the presence of a basic catalyst, excess formaldehyde is reacted with the hydroxyl group of trisphenol to form methylol. After obtaining trisphenol, the methylolated trisphenol is further reacted with an excess of a phenol compound with respect to the methylol group in the presence of an acidic catalyst to give a single trisphenol hydroxybenzyl as described above. 60% or more, preferably 80%, of the base adduct
As described above, particularly preferably, it can be obtained with a purity of 90% or more.

In the thermosetting resin composition according to the present invention, the epoxy resin is not particularly limited, but for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, phenol novolac. Type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin such as triglycidyl isocyanate and hydantoin epoxy, hydrogenated bisphenol A type epoxy resin, propylene glycol diglycidyl ether and pentaerythritol poly Aliphatic epoxy resin such as glycidyl ether, epoxy resin obtained by reaction of aromatic carboxylic acid and epichlorohydrin, spiro ring-containing epoxy resin, o-allylphenol novolac compound Glycidyl ether type epoxy resin which is a reaction product with epichlorohydrin, glycidyl ether type epoxy resin which is a reaction product of diallyl bisphenol compound having an allyl group at the o-position of each hydroxyl group of bisphenol A and epichlorohydrin Epoxy resin or the like can be used.

In the thermosetting resin composition according to the present invention, the ratio of the composition comprising the mixture of hydroxybenzyl group adducts to trisphenols as described above and the epoxy resin depends on the use of the resin and the heat resistance. Although it is appropriately selected according to the required properties, etc., a composition comprising a mixture of adducts of hydroxybenzyl group with trisphenol is usually a hydroxybenzyl group with trisphenol relative to 1 equivalent of the epoxy group in the epoxy resin. The hydroxyl group in the composition comprising the mixture of adducts is used in the range of 0.2 to 10 equivalents, preferably 0.5 to 5 equivalents.

The thermosetting resin composition according to the present invention has its physical properties changed depending on the compounding ratio of the epoxy resin and the composition comprising the mixture of hydroxybenzyl group adducts to trisphenol as described above. However, compared with the case of combining a phenol novolac resin, which has been generally used as an epoxy resin curing agent in the past, the molecular weight distribution during curing is very narrow via trisphenol hydroxybenzyl group adducts. As a result, a uniform curing reaction occurs, resulting in excellent reproducibility when repeatedly manufactured, and excellent mechanical properties such as heat resistance such as glass transition temperature, strength, elastic modulus, dimensional stability, etc. A cured product can be obtained.

In the present invention, as described above, a composition comprising a mixture of hydroxybenzyl group adducts with trisphenols as described above is used as a curing agent for an epoxy resin. ,
Other conventionally known phenolic curing agents may be used in combination. Examples of such a phenol curing agent include phenol novolac resin, o-cresol.
Examples thereof include novolac resin, poly-p-vinylphenol, and a condensate of phenol and aralkyl ether.

The thermosetting resin composition according to the present invention may contain a proper amount of a curing accelerator known in the field of epoxy resins. Examples of such a curing accelerator include imidazole-based, amine-based, phosphorus-based, and the like. Furthermore, the thermosetting resin composition according to the present invention may contain an inorganic or organic filler, if necessary. Such a filler is not particularly limited in its material and shape, but examples thereof include fused silica, silver powder, carbon, glass fiber, ceramics and polymer beads. In addition to these, various additives such as pigments, dyes, coupling agents, and defoaming agents can be added to the resin composition in appropriate amounts, if necessary.

[0042]

According to the present invention, together with the epoxy resin,
By using a composition consisting of a mixture of a novel hydroxybenzyl group adduct to trisphenol as the curing agent, the molecular weight distribution is extremely narrow compared with the case where the conventional phenol novolac resin is used as the curing agent. Since no low molecular weight compound is contained, it is possible to obtain an epoxy resin cured product having excellent uniform reactivity during curing, excellent reproducibility during repeated production, and excellent heat resistance and mechanical properties.

[0043]

[Examples] The present invention will be described below with reference to Examples, together with Reference Examples that describe the production of a composition comprising a mixture of hydroxybenzyl group adducts with trisphenols. It is not limited in any way. In addition, in the reference example, the analysis of the reaction product of trisferrules and formaldehyde was performed by Shimadzu Corporation SPD-10A High Performance Liquid Chromatograph.
Shimadzu column (Shim pack CLC-ODS (6
(φ × 150 mm), methyl alcohol as solvent and methyl alcohol / 0.2% acetic acid as mobile phase solvent in 60 minutes to make a linear gradient from 50% to 100% methyl alcohol, flow rate 1 ml / min, column temperature It was measured under the conditions of 50 ° C. and a wavelength of 280 nm.

In the Reference Example, the ratio of the constituents in the composition comprising a mixture of hydroxybenzyl group adducts to trisphenols was Shimadzu Corporation LC-6.
A type A gel permeation chromatograph was equipped with a column (one Shodex KF-80M, one KF-802, two KF-802) manufactured by Showa Denko KK and tetrahydrofuran was used as a solvent. , 0.8 m1 / min.

Identification of reaction intermediates and reaction products is carried out by IR
And NMR were performed according to a conventional method. In addition, in Examples, the curing performance of the thermosetting resin composition was evaluated as follows. That is, a composition consisting of a mixture of hydroxybenzyl group adducts with trisphenols was added to an epoxy resin in a predetermined amount and mixed, and about 10 mg of the composition was mixed with DS.
It was enclosed in an aluminum pan for C and weighed accurately. Next, a sample in the range of 10 mg ± 1 mg was measured at a temperature rising rate of 10 ° C./min using 8111-C type DSC manufactured by Rigaku Denki Co., Ltd., and the peak temperature of the exothermic curve due to the curing reaction was observed. . The number of parts in the reference examples and examples indicates the number of parts by weight.

Reference Example 1 79 parts of a 17% aqueous sodium hydroxide solution was added to 1,1-di (4-
Hydroxyphenyl) -1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethane 42
Part of the solution, and after uniformly dissolving under stirring, add 30% to this.
73 parts of formaldehyde aqueous solution was dropped over 1 hour,
Further, the mixture was stirred for 7 hours and reacted. During the reaction, the temperature is 40
Keep at ~ 45 ° C.

After completion of the reaction, 68 parts of methyl alcohol was added to the obtained reaction mixture and neutralized with acetic acid.
After stirring for 4 hours, the precipitated crystals were filtered. The obtained crystals were reslurried in 68 parts of a 40% aqueous methanol solution at room temperature for 1 hour. After this, the slurry was filtered to obtain crystals, which were dried at 50 ° C. to give crystals 41
I got a part.

As a result of NMR analysis and IR analysis, this crystal was found to be 1,1-di (4-hydroxy-3,5-di (hydroxymethyl) phenyl-1- [4- [2- (4-hydroxy-3 , 5-Di (hydroxymethyl) phenyl) -2-propyl] phenyl] ethane (hereinafter, 1,1-di (4-hydroxyphenyl) -1- [4- [2- (4-hydroxyphenyl) -2- It is confirmed to be a hexa-addition product of a methylol group to propyl] phenyl] ethane).

Then, 30 parts of a hexa-adduct of a methylol group to the above 1,1-di (4-hydroxyphenyl) -1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethane. Was dissolved in 160 parts of methyl alcohol and 376 parts of phenol to prepare a uniform solution. Next, while maintaining this solution under stirring at 30 ° C. or lower, 26 parts of 35% hydrochloric acid aqueous solution was added dropwise thereto, and after the addition was completed, the mixture was stirred at 30 ° C. for 4 hours to carry out addition condensation of phenol to a methylol group. The reaction proceeded.

After completion of the reaction, 16% was added to the obtained reaction mixture.
63 parts of sodium hydroxide aqueous solution was added for neutralization, and concentrated distillation was performed under reduced pressure to distill a total of 537 parts of methyl alcohol, unreacted phenol and water out of the reaction system. Then, the concentrated distillation residue 11 thus obtained
To 8 parts of toluene, 80 parts of water and 186 parts of water were added, and the mixture was stirred well to transfer sodium chloride produced by neutralization from the residue to the aqueous layer, and then allowed to stand still for liquid separation to obtain a reaction product. 194 parts of a toluene solution containing was obtained.

By concentrating and distilling this toluene solution under normal pressure and then under reduced pressure, 143 parts of toluene, unreacted phenol and water in total are distilled off to give 1,1-di (4-hydroxyphenyl). ) -1- [4- [2- (4-
51 parts of a reaction product of a phenol adduct of a methylol group on hydroxyphenyl) -2-propyl] phenyl] ethane and phenol was obtained.

As a result of gel permeation chromatography of this reaction product, the peak area ratio of the compound corresponding to the main component was 79%, and the N
As a result of measuring MR, the compound corresponding to the main component is
1,1-di [4-hydroxy-3,5-di [(hydroxyphenyl) methyl] phenyl] -1- [4- [2- [4-
Hydroxy-3,5-di [(hydroxyphenyl) methyl] phenyl] -2-propyl] phenyl] ethane, i.e. 1,1-di (4-hydroxyphenyl) -1- [4-
It was confirmed to be a hexa-adduct of hydroxybenzyl group to [2- [4-hydroxyphenyl) -2-propyl] phenyl] ethane (position of hydroxyl group of hydroxybenzyl group is 4-position or 2-position). It was

Reference Example 2 In Reference Example 1, 1,1-di (4-hydroxyphenyl) -1- [4- [2- [4-hydroxyphenyl)-
Methylolation was carried out in the same manner as in Example 1 except that 29 parts of 1,1,1-tris (4-hydroxyphenyl) methane was used instead of 2-propyl] phenyl] ethane. React, then
Post-treatment was carried out in the same manner as in Example 1 to obtain 31 parts of a reaction product.

The reaction product is 1,1,1-tris [4-
It is IR and NMR that it is hydroxy-3,5-di [(hydroxymethyl) phenyl] methane (hereinafter referred to as a hexa-adduct of methylol group to 1,1,1-tris (4-hydroxyphenyl) methane). Confirmed by analysis. Next, the hexa-adduct 23 of the methylol group to the above 1,1,1-tris (4-hydroxyphenyl) methane
Parts, 1,1-di (4-hydroxyphenyl) -1- [4
-[2- (4-hydroxyphenyl) -2-propyl]
Of the methyl adduct of 1,1,1-tris (4-hydroxyphenyl) methane in the same manner as in Example 1, except that the methyl adduct of phenyl] ethane was used instead of the adduct of methylol. The methylol group was reacted with phenol and then post-treated in the same manner as in Example 1 to obtain 44 parts of a reaction product.

As a result of measuring the gel permeation chromatography of this reaction product, the proportion of the peak area corresponding to the main component was 80%, and the main component was
1,1,1-tris [[4-hydroxy-3,5-di (hydroxyphenyl) methyl] phenyl] methane, ie 1,
It was confirmed by NMR analysis that it was a hexa-adduct of hydroxybenzyl group to 1,1-tris (4-hydroxyphenyl) methane (position of hydroxyl group of hydroxybenzyl group was 4-position or 2-position).

Reference Example 3 In Reference Example 1, 1,1-di (4-hydroxyphenyl) -1- [4- [2- [4-hydroxy) -2-propyl] phenyl] ethane was replaced with 1, 1,1-Tris (4
Except that 30 parts of -hydroxyphenyl) ethane was used.
A methylolation reaction was performed using a 37% aqueous formaldehyde solution in the same manner as in Example 1, and then Example 1
Post-treatment was carried out in the same manner as above to obtain 32 parts of a reaction product.

This reaction product is 1,1,1-tris [(4
-Hydroxy-3,5-dihydroxymethyl) phenyl]
Ethane (hereinafter referred to as a hexa-adduct of methylol group to 1,1,1-tris (4-hydroxyphenyl) ethane)
Was confirmed by IR and NMR analysis. Then, 24 parts of the hexaaddition product of the methylol group to 1,1,1-tris (4-hydroxyphenyl) ethane was added to 1,1-di (4-hydroxyphenyl) -1- [4-
1,1,1-Tris (4) was prepared in the same manner as in Example 1 except that it was used in place of the hexaaddition product of the methylol group to [2- [4-hydroxyphenyl) -2-propyl] phenyl] ethane. Reaction of the methylol group of the hexa-adduct of methylol group with -hydroxyphenyl) ethane and phenol was carried out, and then post-treatment was carried out in the same manner as in Example 1 to obtain 45 parts of a reaction product.

As a result of measuring gel permeation chromatography of this reaction product, the proportion of the peak area corresponding to the main component was 79%, and the main component was 1,
1,1-tris [4-hydroxy-3,5-di [(hydroxyphenyl) methyl] phenyl] ethane, i.e., 1,1,
It was confirmed by NMR analysis that it was a hexa-adduct of hydroxybenzyl group to 1-tris (4-hydroxyphenyl) ethane (position of hydroxyl group of hydroxybenzyl group was 4-position or 2-position).

Reference Example 4 1,1-prepared by the same method as described in Reference Example 1
Di (4-hydroxyphenyl) -1- [4- [2- (4
Methylol was used in the same manner as in Example 1 except that 30 parts of a hexa-adduct of a methylol group to -hydroxyphenyl) -2-propyl] phenyl] ethane was used and 432 parts of o-cresol was used instead of phenol. O for radicals
-A cresol addition condensation reaction was allowed to proceed, and then post-treatment was carried out in the same manner as in Example 1 to obtain 55 parts of a reaction product.

As a result of measuring the gel permeation chromatography of this reaction product, the proportion of the peak area corresponding to the main component was 70%, and as a result of measuring its NMR, the compound corresponding to the main component was found to be , 1,1-di (4-hydroxyphenyl) -1- [4- [2- [4-
4-Hydroxy-3-methylbenzyl group to hydroxyphenyl) -2-propyl] phenyl] ethane and 2-
It was confirmed to be a hexa-adduct of hydroxy-3-methylbenzyl group (sum of both benzyl groups).

Reference Example 5 1,1-prepared by the same method as described in Reference Example 1
Di (4-hydroxyphenyl) -1- [4- [2- (4
-Hydroxyphenyl) -2-propyl] phenyl] ethane was used in the same manner as in Example 1 except that 30 parts of the hexaaddition product of a methylol group to ethane was used and 488 parts of 2,6 xylenol was used instead of phenol. For methylol group
The addition condensation reaction of 2,6 xylenol proceeds, and then
Post-treatment was carried out in the same manner as in Example 1 to obtain 57 parts of a reaction product.

As a result of gel permeation chromatography measurement of this reaction product, the proportion of the peak area corresponding to the main component was 69%, and its NMR measurement showed that the compound corresponding to the main component was , 1,1-di (4-hydroxyphenyl) -1- [4- [2- (4-
It was confirmed to be a hexa-adduct of 4-hydroxy-3,5-dimethylbenzyl group to hydroxyphenyl) -2-propyl] phenyl] ethane.

Reference Example 6 1,1-prepared by the same method as described in Reference Example 1
Di (4-hydroxyphenyl) -1- [4- [2- (4
30 parts of the hexa-adduct of methylol group to -hydroxyphenyl) -2-propyl] phenyl] ethane was used and dissolved in 540 parts of phenol without using methyl alcohol.

The solution thus obtained is then kept under stirring at a temperature of 30 ° C.
26 parts of a hydrochloric acid aqueous solution was added dropwise, and after the addition was completed, the reaction system was stirred under a sealed condition at 40 ° C. for 4 hours to promote the addition condensation reaction of phenol with the methylol group. Then, after completion of the reaction, post-treatment is carried out in the same manner as in Example 1,
1-di (4-hydroxyphenyl) -1- [4- [2-
52 parts of a reaction product of a hexa-adduct of a methylol group to (4-hydroxyphenyl) -2-propyl] phenyl] ethane and phenol was obtained.

As a result of measuring gel permeation chromatography of this reaction product, the proportion of the peak area corresponding to the main component was 97%, and as a result of measuring its NMR, the compound corresponding to the main component was , 1,1-di [4-hydroxy-3,5-di [(hydroxyphenyl)
Methyl] phenyl] -1- [4- [2- [4-hydroxy-3,5-di [(hydroxyphenyl) methyl] phenyl] -2-propyl] phenyl] ethane, ie 1,1-
Di (4-hydroxyphenyl) -1- [4- [2- (4
Hexa-adduct of hydroxybenzyl group to -hydroxyphenyl) -2-propyl] phenyl] ethane (position of hydroxy group of hydroxybenzyl group is 4-position or 2-
It was confirmed that it was.

Example 1 1,1-di (4-hydroxyphenyl) -1- [4- [2- [4-hydroxyphenyl) -described in Reference Example 1
17.5 parts of a composition containing a hexabenzyl adduct of hydroxybenzyl group to 2-propyl] phenyl] ethane as a main component was added to 18 parts of a bisphenol A type liquid epoxy resin (BPOMIK R 140 manufactured by Mitsui Petrochemical Co., Ltd.). The mixture was added and mixed, and then kneaded uniformly at room temperature to prepare a thermosetting resin composition. As a result of measuring the DSC of this thermosetting resin composition, the peak temperature of the exothermic curve showing that it has been cured is 165.
It was ℃.

Example 2 15.5 parts of a composition containing as a main component the hexabenzyl adduct of hydroxybenzyl group to 1,1,1-tris (4-hydroxyphenyl) methane described in Reference Example 2 was used. 18 parts of the same bisphenol A type liquid epoxy resin as described in 1 above were added and mixed, and then uniformly kneaded at room temperature to prepare a thermosetting resin composition. D of this thermosetting resin composition
As a result of measuring SC, the peak temperature of the exothermic curve of the curing reaction was 162 ° C.

Example 3 16 parts of a composition containing as a main component the hexabenzyl adduct of hydroxybenzyl group to 1,1,1-tris (4-hydroxyphenyl) ethane described in Reference Example 3 is described in Example 1. 18 parts of the same bisphenol A type liquid epoxy resin as described above was added and mixed, and then uniformly kneaded at room temperature to prepare a thermosetting resin composition. DS of this thermosetting resin composition
As a result of measuring C, the peak temperature of the exothermic curve of the curing reaction was 164 ° C.

Example 4 1,1-di (4-hydroxyphenyl) -1- [4- [2- [4-hydroxyphenyl) -described in Reference Example 4
4-Hydroxy-to 2-propyl] phenyl] ethane
The same bisphenol A type liquid epoxy resin as described in Example 1 with 19 parts of a composition containing a hexa (adduct of both benzyl groups) adduct of 3-methylbenzyl group and 2-hydroxy-3-methylbenzyl group as a main component. 18 parts were added and mixed, and then uniformly kneaded at room temperature to prepare a thermosetting resin composition. As a result of measuring the DSC of this thermosetting resin composition, the peak temperature of the exothermic curve of the curing reaction was 169 ° C.
Met.

Example 5 1,1-di (4-hydroxyphenyl) -1- [4- [2- (4-hydroxyphenyl) -described in Reference Example 5
4-Hydroxy-to 2-propyl] phenyl] ethane
20.5 parts of a composition comprising a hexa-adduct of 3,5-dimethylbenzyl group as a main component was added to and mixed with 18 parts of the same bisphenol A type liquid epoxy resin as described in Example 1,
Then, the mixture was uniformly kneaded at room temperature to prepare a thermosetting resin composition. As a result of measuring the DSC of this thermosetting resin composition, the peak temperature of the exothermic curve of the curing reaction was 172 ° C.

Example 6 1,1-di (4-hydroxyphenyl) -1- [4- [2- (4-hydroxyphenyl) -described in Reference Example 6
17.5 parts of a composition comprising a hexabenzyl adduct of hydroxybenzyl group on 2-propyl] phenyl] ethane as a main component was added to 18 parts of the same bisphenol A type liquid epoxy resin as described in Example 1, and then mixed. Then, the mixture was homogeneously kneaded at room temperature to prepare a thermosetting resin composition. As a result of measuring DSC of this thermosetting resin composition, the peak temperature of the exothermic curve of the curing reaction was 163 ° C.

Claims (8)

[Claims] 1. (a) General formula (I): [In the formula, X is Represents a trivalent group selected from the group consisting of, at least one of R ⁱ (i = 1 to 5, 6 to 10 and 11 to 15) on each aromatic ring represents a hydroxyl group, At least one of R ^i-1 and R ^{i + 1} adjacent to the hydroxyl group has the general formula (I
I) [Chemical 3] (In the formula, at least one of Q ^j (j = 1 to 5) represents a hydroxyl group, and the rest represents hydrogen, a lower alkyl group, a lower cycloalkyl group, or an aromatic group), which is unsubstituted or substituted. And the rest of R ⁱ is hydrogen, a lower alkyl group, a lower cycloalkyl group or an aromatic group. ] A mixture of hydroxybenzyl group adducts to trisphenols represented by the following formula, wherein the average number of hydroxybenzyl groups per molecule of these hydroxybenzyl group adducts to trisphenols is 3 to
A thermosetting resin composition comprising a composition comprising a mixture within the range of 6 and (b) an epoxy resin. 2. The main component of the composition (a) is 1,1,1-tris (4).
The thermosetting resin composition according to claim 1, which is composed of a mixture which is a hydroxybenzyl group addition product to -hydroxyphenyl) methane. 3. The main component of the composition (a) is 1,1,1-tris (4).
2. A thermosetting resin composition according to claim 1, comprising a mixture which is a hydroxybenzyl group addition product to -hydroxyphenyl) ethane. 4. The main component of the composition (a) is 1,1-di (4-hydroxyphenyl) -1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethane. The thermosetting resin composition according to claim 1, which comprises a mixture which is a hydroxybenzyl group adduct. 5. The heat according to claim 1, wherein the main component of the composition (a) is a mixture of a 4-hydroxybenzyl group adduct and a 2-hydroxybenzyl group adduct to trisphenol. Curable resin composition 6. The composition (a) is mainly composed of a mixture of a 4-hydroxy-3-methylbenzyl group adduct and a 2-hydroxy-3-methylbenzyl group adduct to trisphenol. The thermosetting resin composition according to claim 1. 7. The thermosetting resin composition according to claim 1, wherein the main component of the composition (a) is a mixture which is an adduct of 2-hydroxy-5-methylbenzyl group to trisphenol. object 8. The thermosetting composition according to claim 1, wherein the main component of the composition (a) is a mixture which is an adduct of 4-hydroxy-3,5-methylbenzyl group to trisphenol. Resin composition