JPH01278520A - Epoxy resin and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject resin excellent in heat resistance, mechanical characteristics and processability and useful for casting, laminating, coating, semiconductor sealing, etc., by reacting a specified aromatic amine resin with an epihalohydrin in the presence of a hydrogen halide acceptor. CONSTITUTION:An aromatic amine resin (A) expressed by formula I (n is 0-50) is reacted with an epihalohydrin (B) (preferably epichlorohydrin) in the presence of a hydrogen halide acceptor (preferably potassium hydroxide or sodium hydroxide), preferably at 40-80 deg.C for several hr to provide the objective resin with such a structure that 50-100% hydrogen of amino groups in the formula I are substituted with glycidyl groups. The resin of the formula I is produced by adding aniline to 1mol bishalogenomethyl derivative of formula II (X is halogen) in a range of 1.1-10mol and reacting the resultant mixture at 170-240 deg.C for 10-40hr.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel epoxy resin and a method for producing the same. This resin has excellent heat resistance, mechanical properties, and workability, and can be used in a variety of applications, including casting, lamination, paint, and semiconductor applications.

[Prior Art] Conventionally, epoxy resins have been used in a wide variety of applications, such as matrix resins for one-sided thermal composite coatings, heat-resistant adhesives, and the like. These epoxy resins can typically be obtained by reacting phenols such as hisphenol A or aromatic diamines such as 4,4'-diaminodiphenylmethane with epihalohydrin.

The epoxy resins are generally used in the various applications described above by combining/combining with a suitable curing agent and reacting the epoxy groups with the functional groups of the curing agent. Further, as special products, epoxidized products of phenol novola resin and epoxidized products of phenol xylene bonded resin (Japanese Patent Publication No. 13782/1982) are known, and are used in the same manner.

Although the performance of the typical epoxy resin cured product is excellent in terms of electrical properties, dimensional stability, and chemical resistance, it is still insufficient in terms of heat resistance and mechanical properties. In addition, as a method to improve heat resistance, there is a method of introducing sulfone bonds into the epoxy resin skeleton using bisphenol sulfone or diaminodiphenyl sulfone, but this increases the hygroscopicity of the cured resin and reduces water resistance. Undesirable.

In recent years, these epoxy resins have been given more advanced performance (N
J addition is now required.

For example, materials for composite materials (7), adhesives, etc. are required to withstand external stress, especially instantaneous impacts such as stress concentration. For this reason, ideally, elastic deformation like rubber is attracting attention as an important element. As a criterion for determining such elastic deformation, elongation at break of Maru-'J Knox resin is particularly important. The greater the elongation of the matrix resin, the more it can compensate for the drawbacks of reinforcing materials such as glass fiber and carphone fiber required for composite materials. In other words, the strength of the composite material as a whole is 100%.

In addition, such composite materials and adhesives are generally formed by wet impregnation, and if the epoxy resin is liquid at room temperature or has a low melting point, unnecessary organic solvents and high-temperature heating may be used. It is not necessary to work in a molten state, and as a result, the amount of resin used is reduced and the workability is improved.

Furthermore, long-term storage stability is also important for these 7-trinox resins, and they are also required to be less susceptible to deterioration due to oxygen in the air. This oxidizing property is mainly derived from the structure of the resin, and methylene bonds due to formalin condensation are 4! A single resin structure cannot satisfy these requirements.

Therefore, conventional epoxy resins are no longer able to satisfy the advanced performance requirements of recent years.

[Problem to be solved by the invention]

The present invention was made in view of the above problems, and its purpose is to exhibit sufficient performance in heat resistance, water resistance, and oxidation resistance, excellent mechanical properties such as impact resistance, and furthermore, to provide workability. An object of the present invention is to provide an epoxy resin that is excellent in heat-resistant composite materials, useful for use in heat-resistant adhesives, etc., and a method for producing the same.

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the present inventors have completed the present invention.

That is, the present invention is based on the general formula (+)] (+) [where n represents an integer of O to 50]. ] y
) An object of the present invention is to provide an epoxy resin obtained by reacting an aromatic amine resin and Ebiha 1-J hydrin in the presence of a hydrogen halide acceptor.

Evo of aromatic amine resin obtained by the method of the present invention; 1-
Compounds give good cured products when combined with various general-purpose curing agents. For example, when liquefied) IPDA (meta-phenylenediamine) (trade name: Epicure Z, Shell Chemical Co., Ltd.) is combined as a curing agent, an epoxy resin containing bisphenol Δ as a four-way chain (trade name: Epicure-1-828, Compared to Shell Chemical (manufactured by Shell Chemical), the cured product does not show much superior performance in mechanical properties such as tensile strength, elongation, bending strength, and bending modulus, as well as heat resistance such as heat distortion temperature.

Furthermore, since the epoxy resin of the present invention can be used to select the molecular weight and softening point of the aromatic amine resin over a wide range, it can be made to any molecular weight or softening point depending on the application without reducing or reducing the content of epoxy groups. It is possible to obtain a softening point.

Next, the method for producing Evo-Toshi resin of the present invention will be described.

First, the aromatic amine resin represented by type N) was discovered and filed by the present inventors (Japanese Patent Application No. 62-28204).
No. 8).

A specific example for obtaining this will be described below.

First, for 1 mole of a bishalogenomethyl derivative represented by the form (TI) (wherein, X represents a halogen atom),
Aniline is added in an amount of 1 to 15 moles, preferably 1.1 to 10 moles, and the mixture is heated as it is to react at the temperature described below. In addition, in order to speed up the reaction, a suitable acid catalyst may be added in advance or during the reaction.

Note that X in the bishalogenonotyl derivative represented by the general formula (II) used in the present invention is a chlorine atom, a bromine atom, a fluorine atom, or an iodine atom.

Therefore, the substances used in the present invention include α,α''-dichloro-p-kilne, α,α'-dibromo-p-4-silene, α,α''-difluoro-p-xylene, α,α'-short- p-xylene, among which preferred are α,
α゛-dichloro-p-xylene.

In the method of the present invention, an acid catalyst may be used for the purpose of accelerating the reaction as described above. Inorganic acid catalysts,
or organic acids, especially mineral acids, such as hydrochloric acid, phosphoric acid, sulfuric acid, or nitric acid; or Friedelta-Track type catalysts such as zinc chloride, stannic chloride, aluminum chloride, ferric chloride; methanesulfonic acid or P -Organic sulfonic acids such as 1-luenesulfonic acid; and super strong acids such as 1-lifluoromethanesulfonic acid and Nafion 1-1 (trade name; manufactured by DuPont) alone or in combination. Good too. Industrially preferred is inexpensive hydrochloric acid. The amount of catalyst used is 10 mol% or more based on the aromatic amine compound,
Preferably it is 20 to 100 mol%.

Below this range, the reaction progresses slowly and complete conversion to primary amines is difficult to achieve. Above this range, there is no problem of reaction or it is not economical.

The reaction temperature needs to be 130°C or higher; if it is lower than 130°C, the reaction will be extremely slow.

In addition, in order to shorten the reaction time as much as possible, approximately 170 ~
A temperature range of 240'C is preferred. Reaction time is 10-4
It is 0 hours.

Although an inert solvent may be used in the reaction in the method of the present invention, the reaction is usually carried out without a solvent.

After the reaction is completed, the acid used as a catalyst is neutralized with a dilute alkali aqueous solution such as a caustic soda aqueous solution, a potassium hydroxide aqueous solution, or an aqueous ammonia solution, and then separated.

If an unreacted aromatic amine compound remains in the following reaction, it is distilled off under vacuum or by steam distillation.

The aromatic amine resin of the present invention is obtained in the following manner.

The molecular weight range of this aromatic amine resin is 300 to 5000.
The softening point range of the resin is from liquid at room temperature to about 150 (ring and ball softening point according to JIS-2548). A known method can be applied to evolute the reaction product containing the aromatic amine resin thus obtained.

That is, the ebonization is an addition reaction between an aromatic amine resin and epihalohydrin, preferably epichlorohydrin, to produce a halo-phosphorus amine (first step reaction);
The reaction is carried out in two steps: formation of glycidylamine by dehydrohalogenation from halohydrinamine (second stage).

First, mix aromatic amine resin and shrimp halohydrin,
The mixture is dissolved and stirred for several hours at 40 to 120°C, preferably 40 to 80°C, in the presence of water or alcohols, if necessary, to complete the first-stage addition reaction. Even if excess shrimp halohydrin is distilled off at this stage, it will not affect the following reaction.

The epihalohydrin used in the reaction is usually used in an amount of 2.0 to 30 equivalents based on the active hydrogen, but in consideration of the performance of the target product and economical efficiency, it is preferably about 3.5 to 8 equivalents.

The second step reaction is dehydrohalogenation from halohydrin amine using a hydrogen halide acceptor to generate an oxirane ring.

As the hydrogen halide acceptor used, alkali metals and hydroxides such as potassium hydroxide and thorium hydroxide are suitable, and these are added as an aqueous solution or a solid. The concentration as an aqueous solution may be arbitrary, but in consideration of efficiency, a concentration of 40% or more is desirable. Any means such as filtration or washing with water may be used to remove by-product inorganic salts from the reaction product.

The epoxy resin of the present invention has a softening point from liquid to 130°C and an epoxy equivalent weight ranging from 130 g/eQ to 200 g/eq.

Additionally, the epoxy resin produced by the method of the present invention can be cured with a conventional curing agent.

A typical example of a hardener is a chemical hardener for epoxy resins, his(4-aminophenyl)methane/aniline/
Pol-11aldehy+” resin, bis(4-aminophenyl)sulfone, propane-1,3-diamine, hexamethylenediamine, diethylenetriamine, triethylenetheramine, 2,2゜4-trimethylhexamine 1
．． 6-diamine, m-xylylenediamine, bis(4-
Aliphatic, cycloaliphatic, aromatic and Heterocyclic amines, polyaminoamides such as those obtained from aliphatic polyamines and trimerized or trimerized fatty acids, polyphenols such as redulucinol, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane and phenol/aldehyde resins, “ Polythiols such as those commercially available as Thiocholspa, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, he-1-zachloroentomylenetetrahydrophthalic anhydride, piIcomelidic acid 7jjj water Things, 3.3
',4,4'-Hensephenonetetracarboxylic dianhydride, the aforementioned anhydrides, and polycarboxylic acids such as isophthalic acid and terephthalic acid and their anhydrides.

〔Example〕

EXAMPLES Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto in any way.

Example 1 Aniline 111 was added to a reaction vessel equipped with a stirrer and a thermometer.
．． 6 g (I, 2 moles), 70.0 g (0.71 moles) of α,α゛-dichloro-p-xylene as a bishalogenomethyl derivative represented by the -form (TI) were charged, and nitrogen gas was introduced. The temperature was increased with ventilation. Internal temperature 30°
Fever was observed at about C, but the temperature continued to rise until 8.
It was kept constant at 5-100°C for 3 hours (first stage reaction). Thereafter, the temperature was raised continuously and the reaction was carried out at 90 to 200°C for 200 hours (second stage reaction).

Then, the internal temperature was lowered to 95°C by cooling, and 15%
230 g of aqueous caustic soda solution was added, followed by stirring and neutralization. After standing still, the aqueous layer of the F layer was separated and removed, and 30% of saturated saline solution was added.
0g was added and washing and liquid separation was performed. Next, the mixture was heated and dehydrated under a nitrogen stream, and then filtered under pressure to remove inorganic salts and the like. This was vacuum concentrated under a vacuum of 2 to 3 mmHg to recover 48.5 g of unreacted aniline. After removing the residual odor, 100 g of a pale yellowish brown aniline resin was obtained.

As a result of compositional analysis of the aromatic amine resin obtained by the method of the present invention as described above by high performance liquid chromatography, n=0 of -form (I) was 27.8, n=1 was 19.
2, n=2 is 14. O, n=3 is 11,8, n≧4 is 2
It was 7.2 (area%).

In addition, the amine equivalent (perchloric acid-glacial acetic acid method) of this resin is 0.65 equivalent/(I00g), and it is -2 in JIS-2.
The softening point measured using a ring and ball softening point measuring device manufactured by No. 548 was 64°C. Moreover, the average molecular weight was 880.

100 g of this amine resin was charged into a reaction vessel equipped with a stirrer and a thermometer, and 601.25 g of epichlorohydrin was added.
g (6.5 mol) and dissolved.

This mixture was heated to 80°C while stirring, and then heated to 70°C.
The reaction was carried out for 4 hours while maintaining the temperature at 80°C.

Next, this reaction solution was cooled to 60°C and heated to 50-60°C.
156g of 40% NaOH aqueous solution (Na
1.56 mol) was added dropwise over 3 hours. After stirring at the same temperature for 1 hour, 150 cc of water was added and stirred to dissolve the inorganic salt. After the inorganic salt is completely dissolved, at room temperature
The mixture was allowed to stand for a minute to separate into an organic phase and an aqueous phase, and the aqueous layer (2) was discharged. Further, 100 cc of water was added, stirred at room temperature for 30 minutes, allowed to stand for 15 minutes, and the upper aqueous layer was discharged. Next, 100 cc of ionized water was added and the same washing operation was performed to remove inorganic ions.

Excess epichlorohydrin was removed from the reaction product thus obtained under reduced pressure to obtain 155 g of the desired black-brown ebony tree.

The epoxy equivalent of this epoxy resin is 145 g/eq
The softening point was 42°C.

Example 2 Aniline 372.2% was added to a reaction vessel equipped with a stirrer and a temperature controller.
4 g (4,0-t-nyl), --- 70 g (0.4 mol) of α, α°-cyclop-xylene as a bis-octa-methyl derivative represented by the format (IT) was charged, and nitrogen gas was introduced. The temperature was increased with ventilation. Although heat generation was observed from an internal temperature of about 30°C, the temperature was raised and kept constant at 70 to 80°C for 5 hours.

Next, add 35% hydrochloric acid solution to this reaction solution in a container 125.2.
g (I, 2 mol) was charged, and the temperature was raised as it was. temperature 1
The reaction was carried out at 80-190'C for 16 hours. Then, the same cold treatment as in Example 1 (4) neutralization, liquid separation, washing, dehydration, filtration,
After performing each concentration operation, a light brown oily aniline resin of 10
0 g was obtained.

As a result of compositional analysis of the aromatic amine resin obtained by the above method by high performance liquid chroma I/graphy,
-Form (I) rl-0 is 79,0, n=1 is 17.7
, n=2 was 2.7, and r1≧3 was 0.6 (area %).

The amine equivalent of this amine resin is 0.674 equivalent/
(I, oog) and the average molecular weight was 330.

100 g of this amine resin was charged into a reaction vessel equipped with a stirrer and a thermometer, and 623.6 g of epichlorohydrin was added.
(6.74 mol) and dissolved.

Add 40g of water to this mixture and stir at 80° (
2. After raising the temperature to ゛, keep it at 70-80°C.
5 Ayuma reaction was carried out. The reaction solution was then cooled to 60°C, and 161.76 g (I, 6176 mol) of a 40% aqueous sodium hydroxide solution was added dropwise over 1 hour while maintaining the temperature at 50 to 60°C, followed by stirring at the same temperature for 1 hour. did.

After the reaction was completed, 150 g of water was added and stirred to dissolve the inorganic salt. The mixture was allowed to stand at room temperature for 30 minutes, separated, and the lower aqueous layer was discharged, and the organic phase was further washed with 200 cc of water.

Next, inorganic ions in the organic phase were removed using 200 cc of ionized water.
Removed halogen ions.

Excess epichlorohydrin was distilled off under reduced pressure from the main reaction component obtained in this way, and brown, oily epoxy resin 15
2g was obtained. The epoxy equivalent of this epoxy resin is 142
g/eq.

-15 Example 3 Aniline et al.
g (0.75 mol), -87.5 g (0.5 mol) of α,α''-dichloroI:I-p-xylene as a bishalogenomethyl derivative of the form (I1), The temperature was raised while aerating nitrogen gas.Indoor bath 30
Fever was observed from position C, but the temperature continued to rise to 80.
It was kept constant at ~100°C for 4 hours. After heating, the temperature was raised to 190-200°C for 20 hours, then cooled to lower the internal temperature to 95°C, and the same operation as in Example 1 was performed to obtain 125 g of a light brown aniline resin.

As a result of compositional analysis of the aromatic amine resin obtained by the above method using high-speed liquid lithography,
-Form (I), n=o is 10.1, n=1 is 6.8, n
≧2 was 83.1 (area%).

In addition, the amine equivalent of this amine resin is 0.535 equivalent/
(I00g), and the average molecular weight was 2300.

100 g of this amine resin was charged into a reaction vessel equipped with a stirrer and a thermometer, and 507.8 g of epichlorohydrin was added.
g (5,49 moles) and nkon? I made a container.

Add 35g of water to this mixture and heat to 80°C without stirring.
After raising the temperature to 70-80°C, the reaction was continued for 3 hours.

Next, the mixture was cooled to 60°C, and 131.8 g (I, 32 mol) of a 40% aqueous solution of 40% sodium hydroxide (I, 32 mol) was added dropwise at 50 to 60°C, followed by stirring at the same temperature for 1 hour. After the reaction was completed, 300 g of water was added and stirred to dissolve the inorganic salt.

Thereafter, the organic phase was washed and concentrated in the same manner as in Example 1 to obtain 147 g of a brown epoxy resin. The epoxy equivalent of this epoxy resin is 161 g/eq, and the softening point is 72°.
It was C.

The results of the IR analysis are shown in Figure 1.

Usage Example The epoxy resins produced in Examples 1.2 and 3 were blended with liquefied MPPA (trade name: Epicure Z, manufactured by Shell Chemical) as a curing agent as shown in Table 1, and melted and kneaded at 80°C for 5 minutes. A formulation was obtained.

The formulations were cast according to the curing schedule in Table 1 and the thermal and mechanical properties were measured.

The results are shown in Table 1.

As a comparative example, general-purpose epoxy resins Epicote 828 (bisphenol A skeleton epoxy resin, manufactured by Shell Chemical Co., Ltd.) and Epicure Z were cast in the same manner as in the usage example using the formulations shown in Table 1, and their thermal and mechanical properties were evaluated. The properties were measured.

[Effects of the Invention] As explained above, the epoxy resin of the present invention can have any desired molecular weight and softening point without reducing the epoxy content by changing the manufacturing method of the aromatic amine resin. be. Therefore, it can be used in any form, from liquid to powder, depending on the application.

Moreover, the cured product has a well-balanced combination of mechanical properties, oxidation resistance, heat resistance, etc.

The epoxy resin of the present invention, which has the above-mentioned advantages, can be expected to be used in various applications, and is particularly promising for use in fields such as heat-resistant composite materials and heat-resistant adhesives, which have been traditionally desired.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the IR analysis results (liquid film method) of the epoxy resin obtained in Example 3. Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1) An aromatic amine resin represented by the general formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, n represents an integer from 0 to 50] Amino An epoxy resin in which 50 to 100% of the hydrogen atoms in the group are substituted with glycidyl groups. 2) The method for producing an epoxy resin according to claim 1, wherein the aromatic amine resin represented by the general formula (I) and epihalohydrin are reacted in the presence of a hydrogen halide acceptor.