JPH0867746A - Phenol aralkyl resin, method for producing the same, and epoxy resin composition - Google Patents

Abstract

(57) [Summary] [Purpose] Allyl etherified phenol aralkyl resin and allylated phenol aralkyl resin having low melt viscosity, and a method for producing them, and an epoxy resin composition giving a cured product excellent in heat resistance and moisture resistance. Stuff. [Structure] A phenol aralkyl resin and an allyl halide are reacted at room temperature to 100 ° C. in an organic solvent in the presence of a base to obtain an allyl etherified phenol aralkyl resin. This is subjected to Claisen rearrangement at 160 to 250 ° C. to obtain an allylated phenol aralkyl resin.
Next, an epoxy resin composition containing this allylated phenol aralkyl resin is obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an allyl etherified phenol aralkyl resin, an allylated phenol aralkyl resin, an allyl etherified phenol aralkyl resin, and a method for producing the allylated phenol aralkyl resin,
And an epoxy resin composition using an allylated phenol aralkyl resin as a curing agent. The phenol aralkyl resin of the present invention is an intermediate for producing an epoxy resin for an IC encapsulating material, a laminate material, a heat resistant adhesive, a paint or a resist, a molding material, a curing agent for an epoxy resin or a maleimide resin. Is useful as

[0002]

2. Description of the Related Art Allyl etherified phenolic resins and allylated phenolic resins obtained by reacting phenols with allyl halides are well known, and are widely used as curing agents for epoxy resins and maleimide resins. For example, JP-A-4-23824 discloses a resin composition using polyallylphenol as a curing agent for epoxy resin. Cured products of these known allylated phenolic resins have excellent strength and rigidity at room temperature and high temperature, and are relatively inexpensive and stable. However, it has a drawback that it absorbs a relatively large amount of water and the mechanical properties are deteriorated under humid conditions.

Further, JP-A-4-4212 discloses an allylated phenol / aromatic hydrocarbon resin as a component of a resin composition for semiconductor encapsulation having improved hygroscopicity and low stress characteristics. However, this publication makes no mention of an allyl etherified phenol aralkyl resin, an allylated phenol aralkyl resin, and a method for producing them. A water / acetone mixed solvent was also used in the examples, and as a result, the obtained resin was a copolymer type resin in which allyl etherification and allylation of the phenol nucleus proceeded at the same time. Allyl etherified phenol aralkyl resins and allylated phenol aralkyl resins have not been obtained selectively. The copolymer-type resin has the following formula (4)
Allylated Phenol / Aromatic Hydrocarbon Resins

[0004]

[Chemical 5] (R _3, R _4: -H or a methyl group 0 <a, b, c, d <100 and a + b + c + d =
100a, b, c, d shows the percentage of each resin component. ).

With the recent remarkable progress of the technology in the electric and electronic fields, the performance required for resin has been required to be small and excellent in performance. For example I
For the C encapsulant, a low viscosity resin that is excellent in moldability and that can be highly filled with a filler is required. It is important to reduce the viscosity while maintaining properties such as heat resistance and moisture resistance that meet the required performance.

[0006]

An object of the present invention is to provide an allyl etherified phenol aralkyl resin and an allylated phenol aralkyl resin having a low viscosity, and a cured product excellent in their production method, heat resistance and moisture resistance. An object is to provide an epoxy resin composition.

[0007]

That is, the present invention provides an allyl etherified phenol aralkyl resin represented by the following general formula (1).

[0008]

[Chemical 6] (However, n in the formula represents an integer of 0 to 10, and A represents an allyl group.)

And an allylated phenol aralkyl resin represented by the following general formula (2)

[0010]

[Chemical 7] (However, n in the formula represents an integer of 0 to 10, and A represents an allyl group.)

And the following general formula (3)

[0012]

Embedded image (However, in the formula, n represents an integer of 0 to 10) and an allyl halide phenol aralkyl resin characterized by reacting an allyl halide in the presence of a base in an organic solvent. Manufacturing method of

And the following general formula (3)

[0014]

[Chemical 9] (However, n in the formula represents an integer of 0 to 10) and an allyl etherified phenol aralkyl resin obtained by reacting an allyl halide in the presence of a base are subjected to Claisen rearrangement. A method for producing an allylated phenol aralkyl resin,

Also, the present invention relates to an epoxy resin composition comprising an epoxy resin and the above-mentioned allylated phenol aralkyl resin.

Production of Phenol Aralkyl Resin The present invention will be described in detail below. The phenol aralkyl resin is a resin obtained by condensing a phenol and an aralkyl compound by a Friedel-Crafts reaction and is also called a Friedel-Crafts resin.

To obtain the phenol aralkyl resin of the present invention, the phenol compound is usually used in the range of 1.0 to 4.0 mol, preferably 1.5 to 3.5 mol, based on 1 mol of the aralkyl compound. In the presence of an acid catalyst, the temperature is raised as it is and the reaction is carried out at the temperature described below. After the reaction,
As a matter of course, unreacted phenol remains, but the resin obtained by distilling this off under vacuum is the phenol aralkyl resin represented by the above general formula (3).

The phenol compound used in this reaction may be any compound having a phenolic hydroxyl group, for example, phenol, o-cresol, p-cresol, m-cresol, p-ter.
alkyl-substituted phenols such as t-butylphenol,
Aromatic substituted phenols such as p-phenylphenol may be mentioned.

As the aralkyl compound used in this reaction, an aromatic ring compound having a divalent halomethyl group, a hydroxymethyl group, an alkoxymethyl group or the like capable of condensation addition is used. For example, dihalomethyl aromatic ring compounds such as α, α′-dichloro-p-xylene, p
-Dihydroxymethyl aromatic ring compounds such as xylylene glycol, α, α'-dimethoxy-p-xylene, α,
Examples include dialkoxymethyl aromatic ring compounds such as α′-diethoxy-p-xylene.

As the catalyst, stannic chloride, zinc chloride, ferric chloride, cupric chloride, cupric sulfate, mercuric sulfate, mercuric sulfate, mercuric chloride, mercuric chloride, Inorganic compounds such as silver sulfate, silver chloride, sodium hydrogen sulfate, sulfuric acid compounds such as sulfuric acid, monoethyl sulfuric acid, dimethyl sulfuric acid and diethyl sulfuric acid, organic compounds such as p-toluenesulfonic acid, p-phenolsulfonic acid and methanesulfonic acid Sulfonic acids are used. These catalysts may be used alone or in combination. The amount of the catalyst used is 0.01 to 5% by weight based on the total weight of the phenol compound and the aralkyl compound.

The reaction temperature is usually 110 ° C. or higher. 11
If the temperature is lower than 0 ° C, the reaction becomes extremely slow. Also, in order to shorten the reaction time, a temperature range of about 130 to 240 ° C. is desirable. The reaction time is usually 1 to 20 hours.

Further, if desired, an organic solvent having a relatively high boiling point is used. For example, methanol, ethanol, n
-Propanol, isopropanol, n-butanol,
Examples thereof include alcohols such as tert-butanol, and aromatic compounds such as toluene, xylene and mesitylene.

Production of Allyl Etherified Phenol Aralkyl Resin The allyl etherified phenol aralkyl resin containing the phenol aralkyl resin obtained by the above method as a base resin can be obtained by a known method of allylating phenols.

That is, after dissolving a phenol aralkyl resin as a base resin in an organic solvent, a base is added,
Then, an allyl halide such as allyl chloride, allyl bromide, and allyl iodide is added and reacted at room temperature to 100 ° C. for 1 to 5 hours to obtain an allyl etherified phenol aralkyl resin represented by the general formula (1).

The organic solvent used here includes alcohols such as n-propanol, 2-propanol and n-butanol, ketones such as acetone and methyl ethyl ketone, aprotic polar compounds such as dimethyl sulfoxide and N, N-dimethylformamide. Solvents may be mentioned. The yield of the reaction product changes depending on the organic solvent used, but when the above-mentioned organic solvent is used, the reaction rate is usually 95% or more. Since the organic solvent may be changed depending on the purpose of use of the resin to be obtained, the phenol aralkyl resin and the reaction product are soluble, and the organic solvent itself is decomposed by the base,
Any substance that does not cause a reaction can be used. Alcohols are preferable.

Examples of the base include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide. The amount used is 1. for the phenolic hydroxyl group to be allylated.
Use 0 to 3.0 equivalents of base. Preferably 1.0-
This is the case when 1.2 equivalents of base are used.

The amount of allyl halide added is at least equivalent to the base.

Production of Allylated Phenol Aralkyl Resin The allylated phenol aralkyl resin represented by the general formula (2) of the present invention is obtained by heating the obtained product, that is, allyl etherified phenol aralkyl resin to about 160 to 250 ° C. By doing so, the allyl group that had been ether-bonded can be rearranged and obtained.

As described above, the allyl etherified phenol aralkyl resin obtained by using the phenol aralkyl resin as the base resin and the allylated phenol aralkyl resin obtained by the heat rearrangement thereof have a low viscosity and a cured product. It has excellent heat resistance and moisture resistance. This is because this allylated phenol aralkyl resin has a heat resistance, as understood from its structure, as compared with the conventional, for example, novolak type phenolic resin and the like.
This is because it has a chemical structural feature that phenol is bonded via an aralkyl group that contributes to moisture resistance.

Epoxy Resin Composition An epoxy cured product is an epoxy resin composition comprising the above allylated phenol aralkyl resin and an epoxy resin,
It is usually obtained by treating in the temperature range of 100 to 250 ° C. in the presence of a curing accelerator.

The epoxy resin may be any epoxy resin having two or more epoxy groups in one molecule, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin. Examples thereof include resins, glycidyl ether type epoxy resins such as tetramethylbiphenyl type epoxy, and alicyclic epoxy resins such as (3 ′, 4′-epoxycyclohexylmethyl) -3,4-epoxycyclohexanecarboxylate. These epoxy resins may be used alone or in combination of two or more.

The amount of the allylated phenol aralkyl resin used is 20 to 25 relative to 100 parts by weight of the epoxy resin.
The amount is 0 part by weight, preferably 30 to 200 parts by weight.

Examples of the curing accelerator include organic phosphine compounds such as triphenylphosphine, imidazole compounds such as 2-ethyl-4-methylimidazole, and 1,8-diazabicyclo (5,4,0) undec-7-ene. Examples thereof include bicyclic nitrogen-containing compounds. The amount of addition was 0. 1 of the total weight of allylated phenol aralkyl resin and epoxy resin.
It is 01 to 5%, preferably 0.05 to 1%.

Further, if necessary, a filler such as silica, alumina, talc, or clay, a flame retardant such as antimony trioxide, a coloring agent such as carbon black, and a flexible agent such as acrylonitrile-butadiene rubber or silicone oil. It can be added.

[0035]

The present invention will be described in more detail with reference to Examples and Comparative Examples. The evaluation or measurement of various characteristic values in the examples was carried out by the following methods (1) to (5). (1) Melt viscosity The melt viscosity of the resin was measured using an ICI cone & plate viscometer (Research Equipment Co., Ltd .: London).
It was measured at 80 ° C. (2) Glass transition temperature (Tg) The Tg of the cured product was determined by measuring the linear expansion coefficient by the thermomechanical analysis (TMA) method using TMA8146 manufactured by Rigaku Corporation. (3) Infrared absorption spectrum (IR) analysis IR analysis of the resin was performed using Shimadzu FT-IR4200. (4) Gel permeation chromatography (GP
C) Analysis Resins are composed of multiple types of molecules or components, each component having its own number of repeating units. The GPC chart shows the distribution of each component. The content of each component is obtained from the height of each peak and the like. Number of columns: 2, column type: G4000HXL + G2
500HXL + G2000HXL (trade name, manufactured by Tosoh Corporation), eluent: tetrahydrofuran (5) Water absorption rate and water absorption rate The water absorption rate of the cured product is the boiling water absorption rate, and each sample is boiled at 100 ° C / 2 hours, and its weight Indicated by the rate of increase.
The calculation formula F is shown below. A = weight of cured product after water absorption B = weight of cured product before water absorption F = [(A−B) / B] × 100 (%) The water absorption ratio of each sample to the water absorption of Comparative Example 2 was calculated. It is the ratio of water absorption.

Production Example 1 (Production of Phenol Aralkyl Resin) 904.3 g (9.64 mol) of phenol and 31.8
70 g of methanol and 0.853 g of diethylsulfate
The mixture was charged into a reactor equipped with a condenser through which cooling water at ℃ was passed, and the temperature was raised in an oil bath while stirring. When the liquid temperature reached 140 ° C, charging of α, α'-dimethoxy-p-xylene was started. 800 g (4.81 mol) of α, α'-
After dimethoxy-p-xylene was continuously charged for 4 hours, an aging reaction was further performed at a liquid temperature of 140 ° C. for 90 minutes. Then, the liquid temperature was raised to 160 ° C. and unreacted phenol was removed under reduced pressure to obtain 1025 g of phenol aralkyl resin.

Production Example 2 (Production of Phenol Aralkyl Resin) 1582 g (16.84 mol) of phenol and 31.8
70 g of methanol and 0.853 g of diethylsulfate
The mixture was charged into a reactor equipped with a condenser through which cooling water at ℃ was passed, and the temperature was raised in an oil bath while stirring. When the liquid temperature reached 140 ° C, charging of α, α'-dimethoxy-p-xylene was started. 800 g (4.81 mol) of α, α'-
After dimethoxy-p-xylene was continuously charged for 4 hours, an aging reaction was further performed at a liquid temperature of 140 ° C. for 90 minutes. Then, the liquid temperature was raised to 160 ° C. and unreacted phenol was removed under reduced pressure to obtain 1008 g of phenol aralkyl resin.

Production Example 3 (Production of Novolac Phenolic Resin) Phenol 200 was added to a 5000 ml reactor equipped with a stirrer, a temperature controller, a reflux condenser, a total pressure reducer, a decompressor and the like.
0 g and 1150 g of 37% formalin aqueous solution are mixed,
5.6 g of oxalic acid dihydrate was added, and a condensation reaction was carried out at 70 ° C. for 4 hours. The reaction product mixture was then heated to 160 ° C. under atmospheric pressure to remove water and a small amount of phenol, and further heated to 170 ° C. at 20 mmHg to separate unreacted phenol. Then, it was heated to 210 ° C. at 6 mmHg to remove phenol. Next, distillation was performed by raising the temperature to a final temperature of 220 ° C. at a final pressure of 3 mmHg by using an apparatus equipped with a packing such as McMahon packing having a diameter of 15 mm and a height of 20 mm to obtain a novolac type phenolic resin.

Example 1 10 equipped with a stirrer, a thermometer, a cooler, and a dropping funnel
In a 00 ml four-necked separable flask, 360 g of 2-propanol was used as a reaction solvent, 103 g of the phenol aralkyl resin obtained in Production Example 1 was dissolved, and potassium hydroxide 4
5.6 g was added and stirred until uniform. To this, 56.7 g of allyl chloride was added dropwise over 10 minutes, and then the reaction solution was added to 40
The mixture was stirred at 0 ° C for 1 hour and further heated and stirred at 70 ° C for 5 hours to complete the allyl etherification reaction. Then, the reaction solution was filtered to remove by-produced potassium chloride, and then 2-propanol was distilled off and recovered. The residue was dissolved in ethyl acetate and washed with water, and then ethyl acetate was distilled off to obtain an allyl etherified phenol aralkyl resin. The result of IR analysis of the obtained allyl etherified phenol aralkyl resin was that absorption of ether was observed at around 1100 cm ^-1 and 340
Almost no absorption of phenolic hydroxyl groups near 0 cm ^-1 was observed. Further, the carbon derived from the allyl group near 1640cm ^-1 - absorbed carbon double bond was observed, which indicates that the allyl etherification. The chart of IR analysis of the obtained allyl etherified phenol aralkyl resin is shown in FIG. A GPC analysis chart of the resin is shown in FIG.

120 g of the obtained allyl etherified phenol aralkyl resin was placed in a 300 ml separable flask and heated to 195 ° C. and stirred for 5 hours for thermal rearrangement to obtain an allylated phenol aralkyl resin (yield 9
8%). The IR analysis result of the obtained resin showed that the absorption of ether was lost and the absorption of phenolic hydroxyl group was significantly increased as compared with the result of the allyl etherified phenol aralkyl resin. It shows that the group undergoes a thermal rearrangement into an allylated phenol aralkyl resin. The viscosity of the resin thus obtained is shown in Table 1. The chart of IR analysis of the obtained allylated phenol aralkyl resin is shown in FIG. A GPC analysis chart of the resin is shown in FIG.

Comparative Example 1 Phenol aralkyl resin obtained in Production Example 2

Comparative Example 2 A 1000 ml four-neck separable flask equipped with the same stirring device, thermometer, condenser and dropping funnel as in Example 2
-320 g of propanol and 106 g of the novolak-type phenol resin obtained in Production Example 3 were dissolved, and an allyl etherification reaction was carried out under the same conditions as in Example to obtain an allyl etherified novolak-type phenol resin. 130 g of the obtained allyl etherified novolak type phenol resin
Then, it was transferred to a 300 ml separable flask and an allylated phenol resin was obtained in the same manner as in the example (yield 96
%). The viscosity of the obtained resin is shown in Table 1. Also,
As a result of IR analysis, the same chart as in Example 1 was obtained,
The absorption of the phenolic hydroxyl group was large and the absorption of the ether was almost gone, indicating that the allyl group was thermally rearranged to become an allylated product.

Preparation of Epoxy Cured Product Using Allylated Product as Curing Agent Using the resins obtained in Examples and Comparative Examples 1-2 as a curing agent, the epoxy resin and the catalyst were dissolved in as little acetone as possible, and the thickness was about 2 mm. The casting plate of was prepared and provided for evaluation. The compounding ratio of the epoxy resin, the curing agent and the curing accelerator is 49 parts by weight of the curing agent and 1 part by weight of the curing accelerator with respect to 100 parts by weight of the epoxy resin. Epoxy resin (EOCN-102S manufactured by Nippon Kayaku Co., Ltd.) was used as the main agent, and triphenylphosphine (TPP) was used as the curing accelerator. Curing was performed at 175 ° C. for 5 hours. Table 1 shows the physical properties of the obtained cured product.

[0044]

[Table 1] (Note) Resin of Example 1: Allylated phenol aralkyl resin of the present invention Resin of Comparative Example 1: Phenol aralkyl resin obtained in Production Example 2 Resin of Comparative Example 2: Allyl of novolac-type phenol resin obtained in Production Example 3 Resin. Melt viscosity: The melt viscosity of the resin. Curing conditions: Conditions for obtaining an epoxy cured product.

[0045]

The resin of the present invention has a lower melt viscosity than the conventional phenol aralkyl resin (Comparative Example 1). The glass transition temperature of the cured product containing the resin of the present invention is equal to the glass transition temperature of the cured product containing the conventional phenol aralkyl resin (Comparative Example 1) or the conventional allylated novolac type phenol resin (Comparative Example 2). In some cases, since the cured product containing the resin of the present invention has a lower water absorption rate, the use of the resin of the present invention causes problems such as cracks in the molded product during the curing reaction of the epoxy resin. The application is wide, such as semiconductor encapsulation materials, laminated materials, paints, adhesives, and molding materials.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of the allyl etherified phenol aralkyl resin of Example 1.

FIG. 2 is a GPC chart of the resin of Example 1.

FIG. 3 is an infrared absorption spectrum of the allylated phenol aralkyl resin of Example 1.

FIG. 4 is a GPC chart of the resin of Example 1.

[Explanation of symbols]

The integers 0, 1, 2, 3 represent the numbers 0, 1, 2, 3 of the repeating units of the respective components.

Claims (10)

[Claims] 1. An allyl etherified phenol aralkyl resin represented by the following general formula (1). Embedded image (However, n in the formula represents an integer of 0 to 10, and A represents an allyl group.) 2. An allylated phenol aralkyl resin represented by the following general formula (2). Embedded image (However, n in the formula represents an integer of 0 to 10, and A represents an allyl group.) 3. The following general formula (3): (However, n in the formula represents an integer of 0 to 10) and an allyl halide are reacted with an allyl halide in the presence of a base in an organic solvent. Process for producing etherified phenol aralkyl resin. 4. The organic solvent is at least one selected from the group consisting of n-propanol, 2-propanol, n-butanol, acetone, methyl ethyl ketone, dimethyl sulfoxide, and N, N-dimethylformamide. Item 4. A method for producing an allyl etherified phenol aralkyl resin according to Item 3. 5. The method for producing an allyl etherified phenol aralkyl resin according to claim 3, wherein the organic solvent is 2-propanol. 6. The method for producing an allyl etherified phenol aralkyl resin according to claim 3, wherein the base is potassium hydroxide. 7. The method for producing an allyl etherified phenol aralkyl resin according to claim 3, wherein the allyl halide is allyl chloride. 8. The following general formula (3): (However, n in the formula represents an integer of 0 to 10) and an allyl etherified phenol aralkyl resin obtained by reacting an allyl halide in the presence of a base are subjected to Claisen rearrangement. The method for producing an allylated phenol aralkyl resin according to claim 2. 9. The temperature for the Claisen rearrangement reaction is 1
The method for producing an allylated phenol aralkyl resin according to claim 8, wherein the heating is performed in the range of 60 to 250 ° C. 10. An epoxy resin composition comprising an epoxy resin and the allylated phenol aralkyl resin according to claim 2.