JP3436794B2 - Epoxy resin, epoxy resin composition and cured product thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various kinds of insulating materials such as highly reliable semiconductor encapsulating materials for electric and electronic parts, and laminated boards (printed wiring boards) and CFRP (carbon fiber reinforced plastic). The present invention relates to an epoxy resin useful for composite materials, adhesives, paints, etc., a resin composition containing the same, and a cured product thereof.

[0002]

2. Description of the Related Art Epoxy resins are used in electric and electronic parts, structural materials, adhesives, paints, etc. due to their excellent workability and cured products having excellent electrical characteristics, heat resistance, adhesiveness, moisture resistance (water resistance), etc. Widely used in.

However, in recent years, particularly with the development of electric and electronic fields, further improvement of various characteristics such as heat resistance, moisture resistance, adhesiveness, and low viscosity for high filling of filler has been demanded in addition to purification. ing. Further, as structural materials, lightweight materials having excellent mechanical properties such as aerospace materials and leisure / sports equipment are required. Many proposals have been made for epoxy resins and their compositions to meet these requirements, but they are still insufficient.

[0004]

DISCLOSURE OF THE INVENTION The present invention has various properties such as a highly reliable semiconductor encapsulation showing excellent adhesiveness and low water absorption in its cured product, and a laminated board (printed wiring board) and CFRP. The present invention provides an epoxy resin, a composition and a cured product thereof, which are useful for composite materials, adhesives, paints and the like.

[0005]

The present inventors have completed the present invention as a result of earnest research on a method for imparting and improving the above characteristics. That is, the present invention provides (1) the following formula (1)

[0006]

[Chemical 4]

(In the formula, a plurality of A's each independently represent the formula (2) or (3) below.

[0008]

[Chemical 5]

(In the formula, a plurality of Rs each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a methoxy group). Further, a plurality of Bs independently exist in the following formula (4) or (5).

[Chemical 6]

(In the formula, a plurality of R's each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a methoxy group). n shows the positive number of 0-10. In the epoxy resin composition containing the epoxy resin represented by the formula (2), (2) the epoxy resin, the curing agent and, if necessary, the curing accelerator and the filler, the epoxy resin containing the epoxy resin described in (1) above as the epoxy resin. A composition, (3) a cured product obtained by curing the epoxy resin composition as described in (2) above.

The method for synthesizing the epoxy resin of the present invention includes:
The following methods are available. That is, the following formula (6)

[0012]

[Chemical 7]

(In the formula, a plurality of A's each independently represent the following formula (7) or (8)

[0014]

[Chemical 8]

(In the formula, a plurality of Rs each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a methoxy group). ) Also, a plurality of existing B's are each independently represented by the following formula (9) or (10).

[0016]

[Chemical 9]

(In the formula, a plurality of R's each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a methoxy group). n shows the positive number of 0-10. The epoxy resin of the present invention can be obtained by reacting the compound represented by (4) with epihalohydrin to form a glycidyl ether.

The compound represented by the formula (6) can be obtained by dehydration condensation of 2-hydroxy-3-methoxybenzaldehyde with phenols or naphthols. Specific examples of usable phenols include phenol, cresol, dimethylphenol, trimethylphenol,
tert-butylphenol, 3-methyl-6-tert
Examples thereof include butylphenol, methoxyphenol, phenylphenol, cumylphenol, and examples of naphthols include 1-naphthol and 2-naphthol, but are not limited thereto. These may be used alone or in combination of two or more. As a catalyst for condensation,
Hydrochloric acid, oxalic acid, sulfuric acid, p-toluenesulfonic acid and the like are suitable, but not limited to these. The amount of phenols and naphthols used is preferably 1. per mol of 2-hydroxy-3-methoxybenzaldehyde.
It is in the range of 1 to 30 mol, more preferably 1.2 to 20 mol. The reaction may be solvent-free or solvent-based. Suitable solvents that can be used include, but are not limited to, toluene, xylene, methyl isobutyl ketone, and the like. The amount of the solvent used is usually 200 to 500 parts by weight with respect to 100 parts by weight of phenols or naphthols.

The epihalohydrin used in the glycidyl etherification reaction includes epichlorohydrin, epibromhydrin, epiiodohydrin and the like, and industrially available and inexpensive epichlorohydrin is preferable. This reaction can be performed according to a conventionally known method.

For example, a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a mixture of the compound of the formula (6) and epichlorohydrin, while adding 0.5 at a temperature between 20 and 120 ° C. Allow to react for 10 hours. At this time, an aqueous solution may be used as the alkali metal hydroxide, and in that case, water and epichlorohydrin are continuously added under reduced pressure or normal pressure from the reaction system while continuously adding the alkali metal hydroxide. Distillation may be performed, and liquid separation may be performed to remove water, and epichlorohydrin may be continuously returned to the reaction system.

In the above-mentioned method, the amount of epichlorohydrin used is usually 0.5 to 20 mol, preferably 0.7 to 10 mol, based on 1 equivalent of hydroxyl group in the compound represented by the formula (6).
It is a mole. The amount of alkali metal hydroxide used is calculated by the formula (6)
The amount is usually 0.5 to 1.5 mol, preferably 0.7 to 1.2 mol per 1 equivalent of the hydroxyl group in the compound. Further, in order to make the reaction proceed smoothly, it is preferable to add an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone. The amount of the aprotic polar solvent used is 5 to 200 relative to the weight of epichlorohydrin.
%, Preferably 10 to 100%. This production method using an aprotic polar solvent is remarkably improved in easiness of reaction and purity such as hydrolyzable chlorine concentration as compared with the conventional method of adding alcohols such as methanol and ethanol. This reaction is usually performed for 1 to 20 hours. In addition to the above solvents, toluene, xylene and the like can be used.

Further, a mixture of the compound represented by the formula (6) and an excess of epihalohydrin is used at a temperature of 50 ° C. by using a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride as a catalyst. To halohydrin ether obtained by adding a solid or aqueous solution of an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide to the resulting halohydrin ether, and again reacting at a temperature between 20 and 120 ° C to react with halohydrin. The glycidyl ether can be obtained by ring-closing the phosphorus ether. In this case, the amount of the quaternary ammonium salt used is 1 hydroxyl group of the compound of formula (6).
0.001-0.2 mol, preferably 0.1.
It is in the range of 05 to 0.1 mol.

Usually, these reaction products are washed with water or without washing with water to remove excess epihalohydrin under heating and reduced pressure, and then again dissolved in a solvent such as toluene or methyl isobutyl ketone to obtain sodium hydroxide, potassium hydroxide or the like. An aqueous solution of alkali metal hydroxide is added and the reaction is carried out again. In this case, the amount of the alkali metal hydroxide used is 0.01 to 0.2 mol, preferably 0.05 to 0.1 mol, relative to 1 equivalent of the hydroxyl group of the compound of formula (6). Reaction temperature is usually 5
It is carried out between 0 to 120 ° C., and the reaction time is usually 0.5 to 2
It's time.

After completion of the reaction, the by-produced salt is removed by filtration, washing with water and the like, and the solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain an epoxy resin having a small amount of hydrolyzable halogen. .

The epoxy resin composition of the present invention will be described below. When the epoxy resin of the formula (1) is used in the epoxy resin composition of the present invention, the epoxy resin of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, and particularly preferably 40% by weight or more.

Specific examples of other epoxy resins which can be used in combination with the epoxy resin of the present invention include novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin. , Biphenyl type epoxy resin,
Examples thereof include glycidyl amine epoxy resin and glycidyl ester epoxy resin, but are not limited thereto. These may be used alone or in combination of two or more.

Examples of the curing agent that can be used in the epoxy resin or the epoxy resin composition of the present invention include amine curing agents such as aliphatic polyamines, aromatic polyamines and polyamide polyamines, hexahydrophthalic anhydride, and methyl tetrahydro anhydride. Examples include, but are not limited to, acid anhydride type curing agents such as phthalic acid, phenolic novolacs, phenolic curing agents such as cresol novolacs, Lewis acids such as boron trifluoride or salts thereof, and curing agents such as dicyandiamides. It is not something that will be done. These may be used alone or in combination of two or more.

In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, particularly 0.6 to 1.2 equivalents, relative to 1 equivalent of the epoxy groups of the epoxy resin.
Equivalent weights are preferred.

In curing the epoxy resin or the epoxy resin composition of the present invention, a curing accelerator is used as necessary, and imidazole compounds such as 2-methylimidazole and 2-ethylimidazole, tris- (dimethylaminomethyl). ) Tertiary amine compounds such as phenol,
Various known curing accelerators such as triphenylphosphine compounds can be used and are not particularly limited. When a curing accelerator is used, its amount is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the epoxy resin,
The range of 0.1 to 10 parts by weight is particularly preferable.

The epoxy resin composition of the present invention may further contain known additives, if desired. Examples of the additives include inorganic fillers such as silica, alumina, talc and glass fiber, surface treatment agents for fillers such as silane coupling agents, release agents, pigments and the like.

The epoxy resin composition of the present invention is obtained by uniformly mixing the components, and is usually 130 to 170.
Pre-cure in the range of 30 to 500 seconds at a temperature of ℃,
By post-curing at a temperature of 150 to 200 ° C. for 2 to 15 hours, a sufficient curing reaction proceeds to obtain the cured product of the present invention. It is also possible to uniformly disperse or dissolve the components of the epoxy resin composition in a solvent, remove the solvent and then cure.

The cured product thus obtained has high adhesiveness and low water absorption. Therefore, the epoxy resin of the present invention can be used in a wide range of fields where adhesiveness and low water absorption are required. Specifically, it is useful as a compounding component of all electric / electronic materials such as insulating materials, laminated plates, and sealing materials.
In addition to molding materials and composite materials, they can also be used in fields such as coating materials and adhesives.

[0033]

EXAMPLES The present invention will be described below with reference to examples. In addition, the epoxy equivalent in an Example shows g / eq. In addition, hydrolyzable chlorine is 1N KOH ethanol solution in dioxane.
It is the amount of chlorine (titrated) which is generated when the substance is decomposed under reflux for 0 minutes. The present invention is not limited to these examples.

Example 1 (a) A flask was charged with 152 parts by weight of 2-hydroxy-3-methoxybenzaldehyde, 1128 parts by weight of phenol and 1.5 parts by weight of p-toluenesulfonic acid, and reacted at a reflux temperature for 4 hours. After completion of the reaction, p by washing with water
-Toluenesulfonic acid was removed, and excess phenol was distilled off by heating under reduced pressure and steam distillation to obtain a resin. (B) To 107 parts by weight of this resin, 370 parts by weight of epichlorohydrin and 60 parts by weight of dimethylsulfoxide were added and dissolved, and then heated at 40 ° C., 41 parts by weight of flaky sodium hydroxide (99% pure) for 100 minutes. Then, the mixture was further added at 50 ° C. for 2 hours and then at 70 ° C. for 1 hour. Then, after repeatedly washing with water until the washing liquid became neutral, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 330 parts by weight of methyl isobutyl ketone was added and dissolved in the residue. (C) Further, add 7 parts of this solution of methyl isobutyl ketone.
Heated to 0 ° C. and added 30 wt% sodium hydroxide solution 13
After adding 1 part by weight and reacting for 1 hour, washing with water was repeated until the washing solution became neutral. Then, 160 parts by weight of the epoxy resin (A) of the present invention was obtained by distilling off methyl isobutyl ketone from the oil layer under heating and reduced pressure. The obtained epoxy resin (A) had an epoxy equivalent of 178 and a hydrolyzable chlorine content of 380 ppm.

Comparative Example 1 The same procedure as in Example 1 was repeated except that 2-hydroxy-3-methoxybenzaldehyde was replaced with 4-hydroxy-3-methoxybenzaldehyde, and 155 parts by weight of epoxy resin (B) was obtained. This epoxy resin (B) has an epoxy equivalent of 180 and hydrolyzable chlorine of 42.
It was 0 ppm.

Example 2 In Example 1 (a), phenol was replaced with o-cresol 1
Change to 300 parts by weight, the amount of resin used in (b) 10
When the same operation was performed except that 7 parts by weight was changed to 117 parts by weight, 162 parts by weight of the epoxy resin (C) of the present invention was obtained. The epoxy equivalent of this epoxy resin (C) is 1
80, hydrolyzable chlorine was 390 ppm.

Comparative Example 2 The same procedure as in Example 2 was repeated except that 2-hydroxy-3-methoxybenzaldehyde was changed to 4-hydroxy-3-methoxybenzaldehyde, whereby 160 parts by weight of epoxy resin (D) was obtained. This epoxy resin (D) has an epoxy equivalent of 185 and hydrolyzable chlorine of 42.
It was 0 ppm.

Example 3 Except that the phenol was changed to 1500 parts by weight of o-methoxyphenol in (a) of Example 1 and the amount of resin used in (b) was changed from 107 parts by weight to 133 parts by weight. When the same operation was performed, the epoxy resin (E) 168 of the present invention
Parts by weight were obtained. The epoxy equivalent of this epoxy resin (E) was 201, and hydrolyzable chlorine was 410 ppm.

Comparative Example 3 160 parts by weight of an epoxy resin (F) was obtained in the same manner as in Example 3 except that 2-hydroxy-3-methoxybenzaldehyde was changed to 4-hydroxy-3-methoxybenzaldehyde. This epoxy resin (E) has an epoxy equivalent of 205 and hydrolyzable chlorine of 43.
It was 0 ppm.

Example 4 In Example 1 (a), 2 naphthol 1 was added to phenol.
Change to 728 parts by weight, the amount of resin used in (b) 10
When the same operation was performed except that 7 parts by weight was changed to 141 parts by weight, 180 parts by weight of the epoxy resin (G) of the present invention was obtained. The epoxy equivalent of this epoxy resin (G) is 2
12. Hydrolyzable chlorine was 400 ppm.

Comparative Example 4 The same procedure as in Example 4 was repeated except that 2-hydroxy-3-methoxybenzaldehyde was replaced with 4-hydroxy-3-methoxybenzaldehyde to obtain 185 parts by weight of epoxy resin (H). This epoxy resin (H) has an epoxy equivalent of 215 and hydrolyzable chlorine of 40.
It was 0 ppm.

Example 5 Phenol was changed to 2000 parts by weight of 2-tert-butyl-5-methylphenol in (a) of Example 1,
201 parts by weight of the epoxy resin (I) of the present invention was obtained by the same operation except that the amount of the resin used in (b), 107 parts by weight, was changed to 154 parts by weight. The epoxy equivalent of this epoxy resin (I) was 227, and hydrolyzable chlorine was 390 ppm.

Comparative Example 5 The same procedure as in Example 5 was repeated except that 2-hydroxy-3-methoxybenzaldehyde was replaced with 4-hydroxy-3-methoxybenzaldehyde, and 205 parts by weight of epoxy resin (J) was obtained. This epoxy resin (J) has an epoxy equivalent of 224 and hydrolyzable chlorine of 39.
It was 0 ppm.

Example 6 Except that the phenol was changed to 2500 parts by weight of 4-quamylphenol in (a) of Example 1 and 107 parts by weight of the resin used in (b) was changed to 192 parts by weight. When the same operation was performed, 230 parts by weight of the epoxy resin (K) of the present invention was obtained. This epoxy resin (K) had an epoxy equivalent of 265 and hydrolyzable chlorine of 430 ppm.

Comparative Example 6 The same procedure as in Example 6 was repeated except that 2-hydroxy-3-methoxybenzaldehyde was replaced with 4-hydroxy-3-methoxybenzaldehyde, and 235 parts by weight of epoxy resin (L) was obtained. This epoxy resin (L) has an epoxy equivalent of 266 and hydrolyzable chlorine of 44.
It was 0 ppm.

Examples 7 to 12, Comparative Examples 7 to 13 Epoxy resins (A) to (L) obtained in Examples 1 to 6 and Comparative Examples 1 to 6 and EPPN-501 (Nippon Kayaku Co., Ltd.)
Epoxy Equivalent 165, softening point 52 ° C. (hereinafter referred to as (M)) is used, and a curing agent (phenol novolac resin (manufactured by Nippon Kayaku Co., Ltd., PN-80, 150) per epoxy equivalent of these epoxy resins is used. ICI viscosity of 1.5 ps at ℃, softening point of 86 ℃, OH equivalent of 106) 1 hydroxyl group equivalent compounded, curing accelerator (triphenylphosphine)
1 part by weight per 100 parts by weight of an epoxy resin was mixed, and a resin molded body was prepared by transfer molding, and cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.

The results of measuring the physical properties of the cured product thus obtained are shown in Tables 1 to 3. The measurement was performed by the following method. -Copper foil peeling strength: 180 degree peeling test of a test piece. Tensile tester; Toyo Baldwin Tensilon RTM
-500 (tensile mode) Measurement temperature: 30 ° C Crosshead speed: 200 mm / min. Copper foil; JTC foil manufactured by Nikko Gourde Co., Ltd. 70 μm Water absorption: Weight increase (%) after boiling a test piece (5 cm diameter × 4 mm thick disc) in warm water at 100 ° C. for 24 hours

[0048]

[Table 1]                                   Table 1   Example 7 8 9 10 11 12   Epoxy resin AC E G I K   Copper foil peel strength (Kg / cm) 3.5 3.3 3.8 3.3 3.5 3.4   Water absorption rate (%) 1.8 1.7 1.9 1.5 1.6 1.6 1.6

[0049]

[Table 2]                                   Table 2   Comparative Examples 7 8 9 10 11 12   Epoxy resin BD F H J L   Copper foil peeling strength (Kg / cm) 3.1 2.9 3.3 3.0 3.1 3.1   Water absorption rate (%) 2.2 2.1 2.4 1.9 1.9 2.0

[0050]

[Table 3]

As described above, the cured product of the epoxy resin of the present invention has a small water absorption rate and a large copper foil peeling strength as compared with the conventionally known cured product of the epoxy resin, and therefore,
Excellent adhesion.

[0052]

Since the epoxy resin and the epoxy resin composition of the present invention show excellent water resistance and adhesiveness in the cured product, the insulating material for electric / electronic parts including semiconductor encapsulant, and laminated plate ( It is extremely useful when used as a material such as a printed wiring board), various composite materials including CFRP, adhesives, paints and the like.

Continuation of the front page (56) Reference JP-A-2-189326 (JP, A) JP-A-2-58523 (JP, A) JP-A-1-252624 (JP, A) JP-A-62-25116 (JP , A) JP 57-141419 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 59/06-59/08 C08G 59/32

Claims (3)

(57) [Claims] 1. The following formula (1): (In the formula, a plurality of A's each independently represent the following formula (2) or (3): (In the formula, a plurality of Rs are each independently a hydrogen atom,
A hydrocarbon group having 1 to 10 carbon atoms and a methoxy group are shown. ) Is shown. ) In addition, a plurality of Bs independently exist in the following formula (4) or (5): (In the formula, a plurality of Rs are each independently a hydrogen atom,
A hydrocarbon group having 1 to 10 carbon atoms and a methoxy group are shown. ) Is shown. n shows the positive number of 0-10. ) Epoxy resin represented by. 2. An epoxy resin composition containing an epoxy resin, a curing agent, and optionally a curing accelerator and a filler, the epoxy resin composition containing the epoxy resin according to claim 1 as the epoxy resin. 3. A cured product obtained by curing the epoxy resin composition according to claim 2.