JP2513378B2 - Thermosetting resin - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is effectively used as an epoxy resin or a phenol resin as a component of various resin compositions and a modifier of various resins, and is excellent in processability and heat resistance.
The present invention relates to a fluorine-modified thermosetting resin which has a high strength, a high glass transition temperature, a low coefficient of thermal expansion, and gives a cured product having particularly low water absorption and high adhesiveness.

[0002]

2. Description of the Related Art Thermosetting resins have been used in various electrical materials, structural materials, etc. as materials for casting, impregnation, lamination and molding. The usage conditions of materials tend to be strict in applications, and heat resistance and low water absorption of materials are important characteristics.

Among thermosetting resins, epoxy resins and phenol resins have been highly useful, but as a heat-resistant polyepoxy compound, an epoxy compound of phenol novolac (for example, manufactured by Yuka Shell Epoxy Co., Ltd.) is used. Ep), epoxide of cresol novolac (for example, EOCN manufactured by Nippon Kayaku Co., Ltd.), methylene dianiline tetraepoxide, and epoxides of tri- and tetra (hydrmexoxyphenyl) alkane. As the phenol resin, resins such as phenol novolac resin, orthocresol novolac resin, bisphenol A and triphenol methane are known.

However, all of the cured products using the above-mentioned resins show relatively high heat resistance, but the heat resistance is not sufficiently satisfactory, and at the time of high temperature for a long time to develop practical strength. It has the drawback that it needs to be heated, and its workability is not sufficient. In addition, especially in semiconductor encapsulation applications, in addition to heat resistance, low water absorption, workability, low thermal expansion coefficient and high adhesiveness are also required.

The present invention has been made in view of the above circumstances, and is suitably used as an epoxy resin or a phenol resin as a component of various resin compositions and a modifier of various resins, and has good processability and heat resistance. An object of the present invention is to provide a thermosetting resin which gives a cured product having excellent strength, low thermal expansion coefficient, low water absorption coefficient and high adhesiveness.

[0006]

Means for Solving the Problems and Actions The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, have shown that fluorine-modified bisphenol A represented by the following formula (3) and mono-functional compounds represented by the following formula (4). , Di-, tri-, or tetrahydroxynaphthalene, and by reacting an aldehyde compound to form a novolak, as a phenol resin, and by further epoxidizing this phenol resin as an epoxy resin, the following general formula (1) or ( In addition to finding that the novel fluorine-modified thermosetting resin shown in 2) can be obtained, this thermosetting resin has good processability, excellent moldability, heat resistance, and long-term heat resistance. Phenolic resin which is excellent in deteriorating property, gives a cured product with high strength, low thermal expansion coefficient, low water absorption coefficient and high adhesiveness, and is particularly used for a thermosetting resin composition for semiconductor encapsulation. , It found to be excellent as an epoxy resin, in which the present invention has been accomplished.

[0007]

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[0008]

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Therefore, the present invention provides a thermosetting resin represented by the above general formula (1) or (2).

The present invention will be further described below. The thermosetting resin of the present invention is represented by the following general formula (1) or (2) as described above.

[0011]

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[0012]

[Chemical 6]

As described above, the thermosetting resin of the present invention uses, for example, the fluorine-modified bisphenol A represented by the formula (3) and the mono-, di-, tri- or tetrahydroxynaphthalene represented by the formula (4), A phenol resin can be easily synthesized by reacting an aldehyde compound in the presence of a catalyst to form a novolak.

In this case, commercially available fluorine-modified bisphenol A and hydroxynaphthalene as raw materials can be used.
The use ratio of these is not particularly limited, but fluorine-modified bisphenol A / hydroxynaphthalene = 0.
It is preferably from 01 to 100, particularly preferably from 0.1 to 10.

Specific examples of aldehyde compounds include formaldehyde and salicylaldehyde. The amount of the aldehyde compound used is not particularly limited, but the ratio of the raw material aldehyde compound / phenol compound is preferably 0.05 to 1, particularly 0.11 to 0.7 in terms of molar ratio. If the molar ratio of aldehyde compound / phenol compound is less than 0.05, the molecular weight of the obtained polymer may be small, and if the molar ratio exceeds 1, gelation may occur.

Further, a known alkali or acid catalyst can be used as the catalyst, and KO is used as the alkali catalyst.
H, NaOH and the like, and the acid catalyst includes hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, paratoluenesulfonic acid, acetic acid,
Examples include butyric acid and propionic acid. The amount of these alkali catalysts or acid catalysts used is a catalytic amount, but it can be usually used in the range of 0.5 to 2% by weight with respect to the phenol compound.

The reaction conditions for the above-mentioned novolak-forming and polymerizing reaction are not particularly limited, but the fluorine-modified resin and the aldehyde compound are resolized in an alkaline aqueous solution and then acidified, and hydroxynaphthalene is further added to 100.
It is preferable to carry out the reaction at ˜150 ° C. for 4 to 8 hours to obtain a novolak.

Thus, the phenol resin according to the present invention can be obtained, and if necessary, it can be epoxidized to obtain the epoxy resin according to the present invention.

The thermosetting resin of the present invention (phenolic resin,
The epoxy resin) is used as a resin component of a thermosetting resin composition, particularly a semiconductor encapsulating composition. For example, in the case of an epoxy resin composition, the thermosetting resin of the present invention can be used as an epoxy resin and a phenol resin as a curing agent for the epoxy resin. In this case epoxy resin,
All of the phenolic resin may be composed of the thermosetting resin of the present invention, a part thereof may be the thermosetting resin of the present invention, and either or both of the epoxy resin and the phenolic resin may be used. The thermosetting resin of the present invention can be used. When the thermosetting resin according to the present invention is used to prepare a thermosetting resin composition, as other components, conventional components can be used depending on the type, purpose and the like.

[0020]

EXAMPLES Hereinafter, the present invention will be specifically shown by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Example 1 In a 1-liter four-necked flask equipped with a condenser, a thermometer and a stirrer under an N ₂ atmosphere, 2,2, -bis- (4-hydroxyphenyl) hexafluoropropane 168 g, 37 % Formaldehyde aqueous solution 48.7 g and water 100 g were added. While stirring, 1.0 g of potassium hydroxide was added, and the mixture was reacted under reflux for 6 hours. After cooling, 3.3 g of oxalic acid, 140 g of toluene,
80 g of 2,6-dihydroxynaphthalene was added, and the mixture was heated and dehydrated for 2 hours under reflux of toluene. After reacting for further 2 hours, toluene was extracted under reduced pressure and reacted at 150 ° C. for 1 hour. After cooling, the reaction product was diluted with methyl isobutyl ketone, washed with water, and the solvent was distilled off to obtain 218 g of the following compound A having an OH equivalent of 131 (theoretical amount 127) (yield: 85.9%). The compound A was identified by NM
It was confirmed by R and IR.

[0022]

[Chemical 7]

Next, 197 g of Compound A was placed in a 1-liter four-necked flask equipped with a condenser, a thermometer and a stirrer.
800 g of epichlorohydrin and 1.5 g of cetyltrimethylammonium were added, and the mixture was stirred under reflux for 3 hours. After that, 120 g of sodium hydroxide aqueous solution (50% aqueous solution)
Was added dropwise under reduced pressure (80 to 90 ° C./100 to 130 mmHg). After completion of the dropping, the mixture was aged for 3 hours, then filtered, the solvent was removed, hydrolyzable chlorine was removed with an aqueous sodium hydroxide solution (10% aqueous solution), and the product was washed with water. As a result, epoxy equivalent 189 (theoretical amount 183 g) of the following compound B250 was obtained.
g was obtained (yield 91%).

[0024]

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Example 2 In a 1-liter four-necked flask equipped with a condenser, a thermometer and a stirrer, under N ₂ atmosphere, 2,2, -bis- (4-hydroxyphenyl) hexafluoropropane 168 g, 37 % Formaldehyde aqueous solution 48.7 g and water 100 g were added. While stirring, 1.0 g of potassium hydroxide was added, and the mixture was reacted under reflux for 6 hours. After cooling, 3.3 g of oxalic acid, 140 g of toluene,
72 g of α-naphthol was added, and the mixture was heated and dehydrated for 2 hours under reflux of toluene. After reacting for further 2 hours, toluene was extracted under reduced pressure and reacted at 150 ° C. for 1 hour. After cooling, the reaction product was diluted with methyl isobutyl ketone, washed with water, and the solvent was distilled off. As a result, OH equivalent 169 (theoretical amount 1
64 g of the following compound C214 was obtained (yield 87.
0%). The identification of compound C was confirmed by NMR and IR.

[0026]

[Chemical 9]

Then, in a 1-liter four-necked flask equipped with a condenser, a thermometer and a stirrer, 177 g of Compound C,
800 g of epichlorohydrin and 1.5 g of cetyltrimethylammonium were added, and the mixture was stirred under reflux for 3 hours. After that, 120 g of sodium hydroxide aqueous solution (50% aqueous solution)
Was added dropwise under reduced pressure (80 to 90 ° C./100 to 130 mmHg). After the completion of the dropping, the mixture was aged for 3 hours, then filtered, the solvent was removed, hydrolyzable chlorine was removed with a sodium hydroxide aqueous solution (10% aqueous solution), and the mixture was washed with water. As a result, epoxy equivalent 228 (theoretical amount 220 g) of the following compound D236 was obtained.
g was obtained (yield 90.5%).

[0028]

[Chemical 10]

The IR of the above compounds (A) to (D) are shown in FIGS. 1 to 4, respectively. In addition, N of the compounds (A) to (D)
The attribution of the MR peak is as follows.

[0030]

[Chemical 11]

Example 3 A 1 liter four-necked flask equipped with a condenser, a thermometer and a stirrer was charged with 2,2, -bis- (4-hydroxyphenyl) hexafluoropropane (168 g, 37) under N ₂ atmosphere. % Formaldehyde aqueous solution 48.7 g and water 100 g were added. While stirring, 1.0 g of potassium hydroxide was added, and the mixture was reacted under reflux for 6 hours. Apart from this, in the same way, 2,2, -bis- (4
-Hydroxyphenyl) hexafluoropropane 84 g,
37% formaldehyde aqueous solution 48.7 g, water 100
g and 1.0 g of potassium hydroxide were reacted. After cooling, these were put together in a 2 liter flask and oxalic acid 6.
6 g, 300 g of toluene and 160 g of 2,6-dihydroxynaphthalene were added, and the mixture was heated and dehydrated for 2 hours under reflux of toluene. After reacting for further 2 hours, toluene was extracted under reduced pressure and reacted at 150 ° C. for 1 hour. Then cool down,
The reaction product was diluted with methyl isobutyl ketone, washed with water and the solvent was distilled off to obtain 395 g of the following compound E having an OH equivalent of 144 (theoretical amount of 138) (yield: 84.5%).
The identification of compound E was confirmed by NMR and IR.

[0032]

[Chemical 12]

Next, in a one-liter four-necked flask equipped with a condenser, a thermometer, and a stirrer, compound E216g,
800 g of epichlorohydrin and 1.5 g of cetyltrimethylammonium were added, and the mixture was stirred under reflux for 3 hours. After that, 120 g of sodium hydroxide aqueous solution (50% aqueous solution)
Was added dropwise under reduced pressure (80 to 90 ° C./100 to 130 mmHg). After completion of the dropping, the mixture was aged for 3 hours, then filtered, the solvent was removed, hydrolyzable chlorine was removed with an aqueous sodium hydroxide solution (10% aqueous solution), and the product was washed with water. As a result, epoxy equivalent 205 (theoretical amount 194 g) of the following compound F265 was obtained.
g was obtained (yield 88.5%).

[0034]

[Chemical 13]

[Examples 4 to 6, Comparative Example 1] Examples 1 to 3
Fluorine-modified epoxy resin B, D, F synthesized in
Fluorine-modified phenolic resins A, C, E, curing catalyst, quartz powder, flame retardant, etc. were used in the compounding amounts shown in Table 1, and the resulting compound was uniformly melt-mixed with a two-roll heat and three types were mixed. A thermosetting resin composition was prepared.

For comparison, a thermosetting resin composition was prepared in the same manner as in Examples using the phenol novolac resin (Compound G) and the epoxidized orthocresol novolac resin (Compound H) shown below.

[0037]

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The following tests (a) to (d) were conducted on these thermosetting resin compositions. The results are also shown in Table 1. (A) Spiral flow value Using a mold conforming to the EMMI standard, 175 ° C, 70
It was measured under the condition of kg / cm ² . (B) Mechanical strength (flexural strength and flexural modulus) 180 ° C., 70 kg / cm according to JIS-K6911
^{2. A} bending rod of 10 × 4 × 100 mm was molded under the conditions of a molding time of 2 minutes, and post-cured at 180 ° C. for 4 hours. (C) 5 under the conditions of expansion coefficient, glass transition temperature 180 ° C., 70 kg / cm ² , molding time 2 minutes
A test piece of × 5 × 15 mm was molded, post-cured at 180 ° C. for 4 hours, and the value when the temperature was raised at a rate of 5 ° C./min was measured by a dilatometer. (D) Water absorption rate: 180 ° C., 70 kg / cm ² , molding time: 2 minutes 5
A disk of 0φ × 3 mm was molded, post-cured at 180 ° C. for 4 hours, left in an atmosphere of 121 ° C./100% RH for 24 hours, and the water absorption was measured.

[0039]

[Table 1] * Γ-glycidoxypropyltrimethoxysilane was used as the silane coupling agent. ** Carnauba wax was used as the release agent.

From the results shown in Table 1, the thermosetting resin composition using the thermosetting resin of the present invention is compared with the conventional one using orthocresol novolac epoxy resin and phenol novolac resin (comparative example). It is recognized that a cured product having high flexural strength and flexural modulus, particularly high glass transition temperature, low linear expansion coefficient, and low water absorption coefficient is obtained.

[0041]

As described above, the thermosetting resin of the present invention has excellent processability, high reactivity with other epoxy resins, phenolic resins, etc., good heat resistance, and high temperature mechanical properties. Excellent in characteristics and long-term heat resistance, high hardness, low coefficient of thermal expansion,
It gives a cured product with low water absorption and excellent adhesion. Therefore, the thermosetting resin of the present invention can be effectively used as a component of various resin compositions and a modifier of various resins.

[Brief description of drawings]

FIG. 1 is an IR chart of the phenol resin according to the present invention obtained in Example 1.

2 is an IR chart of the epoxy resin according to the present invention obtained in Example 1. FIG.

FIG. 3 is an IR chart of the phenol resin according to the present invention obtained in Example 2.

4 is an IR chart of the epoxy resin according to the present invention obtained in Example 2. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location H01L 23/31

Claims (1)

(57) [Claims] 1. A thermosetting resin represented by the following general formula (1) or (2). Embedded image Embedded image