JP3100662B2 - Modified epoxy resin and epoxy resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified novolak type epoxy resin, an epoxy resin composition having improved toughness by adding the same, and a cured product thereof.

[0002]

2. Description of the Related Art Epoxy resins have been particularly actively modified, and the range of application thereof has been expanded. Epoxy resins have excellent electrical properties, adhesive properties, thermal properties, and the like, but are generally brittle and have a problem that cracks easily occur due to stress strain during curing or use, heat or mechanical impact. To solve this problem, use a curing agent having a long-chain aliphatic group or rubber-like properties, add a compound having an elastomeric property, add a plasticizer such as an asphalt substance, glycols, etc., glass fiber, aramid fiber, carbon The toughness of the epoxy compound is enhanced by the addition of fibers such as fibers and the introduction of a molecular group exhibiting rubber elasticity of the epoxy compound itself (Koichi Ochi, Polymer 38 (3), 200 (1989)).

[0003]

However, novolak type epoxy resins widely used as encapsulants for semiconductor devices are polyfunctional epoxy resins having a high crosslinking density, and are hard and brittle. For this problem,
Attempts have been made to solve the problem by adding the rubbery substance described above, but the sufficient effect cannot be obtained because sufficient compatibility is not obtained, and the excellent heat resistance and adhesion of the epoxy resin There is a problem that the characteristics such as the above are impaired and the cost becomes extremely high. The present invention has been made in view of these problems, and an object of the present invention is to provide a novolak-type epoxy resin composition that provides improved toughness without reducing the heat resistance characteristics of the novolak-type epoxy resin.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a novolak type epoxy resin represented by the general formula (I), a curing agent and a general formula (I)
By compounding the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer shown in (I) as a main component, it is possible to improve the toughness of the epoxy resin without reducing the properties of the epoxy resin and its cured product. We have found and completed the present invention.

Embedded image R—CHR ² — (— R—CHR ² —) n—R (I) (wherein, R is a group of formula 6 or 7; R ¹ is a hydrogen atom, a bromine atom or a methyl group, R ² _{- (CH 2) 3 CH 3} , -C
_{H 2 CH (CH 3) 2} , -C (CH 3) 2 CH 2 C
_{H 3, -CH = CH 2,} -C 6 H 6 or a hydrogen atom, n =
Represents an integer of 1 to 40)

Embedded image (Wherein, R ¹ is a hydrogen atom, a bromine atom or a methyl group, and the dotted line indicates that there is no terminal R)

Embedded image (Wherein, R ¹ is a hydrogen atom, a bromine atom or a methyl group, and the dotted line indicates that there is no terminal R)

Embedded image (Where x is an integer of 3 to 7, y is an integer of 1 to 4, y /
(X + y) = 0.1 to 0.3, z = integer of 5 to 15, m
= An integer of 1 to 400, n / (m + n) = 0.01 to 0.
50, l = an integer of 1 to 50, Ar ¹ and Ar ³ are divalent aromatic groups, and Ar ² is a divalent aromatic group containing a phenolic hydroxyl group.)

The modified epoxy resin of the present invention can be obtained by reacting a novolak type epoxy resin (I) with a block copolymer (II) in an amide solvent. N, N-dimethylacetamide, N-
Methyl-2-pyrrolidone and the like are used. The amount of the epoxy resin (I) used is based on the block copolymer (II).
It is 1 to 20 equivalents, preferably 5 to 15 equivalents. The reaction temperature is 50 ° C. or higher, preferably 70 ° C. or higher.

In the epoxy resin composition of the present invention,
The amount of the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer (II) is as follows:
0.1 to 1 for novolak type epoxy resin (I)
5 by weight% is preferred.

In the present invention, the reason why the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile copolymer represented by the general formula (II) promotes the toughening of the epoxy resin represented by the general formula (I) is not clear, but it is not clear. By reacting the hydroxyl group of the hydrophilic hydroxyl group-containing aramid-polybutadiene-acrylonitrile copolymer with the epoxy resin, compatibilization with the epoxy resin is promoted, and an epoxy resin composition in which the aramid component is uniformly molecularly dispersed in the epoxy resin can be obtained. . Further, by heating and curing the epoxy resin composition, the polybutadiene-acrylonitrile component causes microphase separation, and the aramid component is fixed in a state of molecular dispersion in the epoxy component. By this mechanism, aramid chains with high rigidity and high glass transition point are molecularly dispersed in the epoxy resin, and not only the heat resistance and toughness of the epoxy resin are improved, but also the uniformly dispersed polybutadiene-acrylonitrile component has a stress moderating action. Therefore, it is estimated that the toughening is efficiently performed without lowering the heat resistance of the cured epoxy resin. The phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer has a toughening modifying effect,
This is achieved with a small amount of these copolymers. As a result, the heat resistance can be improved without impairing the excellent properties of the epoxy resin composition and the cured product thereof.

The block copolymer (I) used in the present invention
I) can be synthesized by the following method. A dicarboxylic acid having a phenolic hydroxyl group-containing divalent aromatic group Ar ² in the general formula (I) and a divalent aromatic group Ar in the general formula (I)
^An excess amount of diamine having a divalent aromatic group Ar ³ in the general formula (I) is added to the dicarboxylic acid having ¹ , and these are added to N 2 in the presence of a phosphite and a pyridine derivative.
Heating and stirring in an organic solvent represented by -methyl-2-pyrrolidone under an inert atmosphere such as nitrogen. As a result, the resulting phenolic hydroxyl group-containing polyaramid oligomer solution in which both ends became an aminoaryl group,
A block copolymer (II) can be obtained by adding a polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends and performing polycondensation.

As the Ar ² -containing dicarboxylic acid having a phenolic hydroxyl group, 4-hydroxyisophthalic acid, 5
-Hydroxyisophthalic acid, 2-hydroxyphthalic acid,
2-hydroxyterephthalic acid, Ar ¹ -containing dicarboxylic acids having no phenolic hydroxyl group include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, 3,3′-methylene dibenzoic acid, 4'-
Methylene dibenzoic acid, 4,4'-oxydibenzoic acid,
4,4'-thiodibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 4,4'-
Carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the like, but are not limited thereto. is not.
These aromatic dicarboxylic acids can be used alone or in combination.

The above-mentioned Ar ³ -containing diamine includes, for example, m-phenylenediamine, p-phenylenediamine,
3,3'-oxydianiline, 3,4'-oxydianiline, 4,4'-oxydianiline, 3,3'-diaminobenzophenone, bis (4-aminophenyl) sulfone, bis (3-aminophenyl ) Sulfone, bis (4-
Aminophenyl) sulfide, 1,4-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-bis (4-phenoxy) diphenylsulfone, 4,4'-bis (3-phenoxy) diphenylsulfone, 2,2 '-
Examples include (4-aminophenyl) propane, bis (4-aminophenyl) methane, o-tolidine, o-dianiline, and the like, but are not limited thereto. These aromatic diamines can be used as a mixture.

A polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends is commercially available from Goodrich as Hycar CTBN, and these can be used.

Novolak type epoxy resins include orthocresol novolak type, phenol novolak type,
Novolak-type naphthols and their methylated or brominated products are exemplified. In the present invention, these epoxy resins can be mixed and used.

As the curing agent used in the present invention, for example, bis (4-aminophenyl) sulfone, bis (4-aminophenyl) methane, 1,5-diaminonaphthalene, p-
Aromatic amine compounds such as phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,6-dichloro-1,4-benzenediamine, 1,3- (p-aminophenyl) propane, and m-xylenediamine;
Aliphatic amines such as ethylenediamine, diethylenetriamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, polymethylenediamine and polyetherdiamine -Based compounds, polyaminoamide-based compounds, aliphatic acid anhydrides such as dodecyl succinic anhydride, polyadipic anhydride, and polyazeleic anhydride; alicyclic acid anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic anhydride Phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, aromatic anhydrides such as ethylene glycol bis trimellitate, glycerol tristrimellitate, dicyandiamide, organic acid dihydrazide Basic active hydrogen compounds and the like,
Examples include, but are not limited to, imidazole compounds, Lewis acids and Breasted acid salts, polymercaptan compounds, phenolic resins, urea resins, melamine resins, isocyanates and blocked isocyanate compounds.

The epoxy resin composition of the present invention may contain a curing accelerator, a reaction diluent for epoxy resin, a dye, an oxidation stabilizer, a coupling agent, other resins, and the like, if necessary. Examples of the curing accelerator include phosphorus-based compounds such as triphenylphosphine and tertiary amine compounds such as triethanolamine, tetraethylamine, 1,8-diaza-bicyclo [5,4,0] -7-undecene (DBU), N, N −
Dimethylbenzylamine, 1,1,3,3-tetramethylguanidine, 2-ethyl-4-methylimidazole,
Boron-based compounds such as N-methylpiperazine and the like, for example, 1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate and the like are used.

The epoxy resin composition of the present invention preferably comprises 0.1 to 10% by weight of a copolymer of the formula (II) and 2% of a curing agent based on the novolak type epoxy resin of the formula (I).
~ 60% by weight, preferably 5-40% by weight, and obtained by mixing. The epoxy resin composition of the present invention includes a composition comprising a modified epoxy resin, a novolak type epoxy resin and a curing agent in a state before heat curing and a cured product after heat curing. In this case, the composition after heat curing can be supplied as various formed bodies. This heat curing is generally performed at 250 ° C. or lower for several hours, but in the present invention, this condition is not affected.

[0016]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 Synthesis of phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer (phenolic hydroxyl group contained in aramid portion is 2 mol%): 19.60 g (118 mmol) of isophthalic acid, 3,4'-oxydi 26.4 g (132 mmol) of aniline, 0.41 g (2.3 mmol) of 5-hydroxyisophthalic acid, 3.9 g of lithium chloride, 12.1 g of calcium chloride, 240 ml of N-methyl-2-pyrrolidone and 54 ml of pyridine were added to 11-4. After placing it in a round-bottomed flask and stirring and dissolving, 74 g of triphenyl phosphite was added.
The reaction was carried out for a period of time to produce a phenolic hydroxyl group-containing aramid oligomer. A polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends (Hy
car CTBN, manufactured by BF Goodrich. A solution prepared by dissolving 48 g of acrylonitrile component contained in polybutadiene acrylonitrile part at 17 mol% and having a molecular weight of about 3600) in 240 ml of pyridine was added, and the mixture was further reacted for 4 hours.
The reaction solution is cooled to room temperature, and the reaction solution is poured into methanol 201, and an aramid-polybutadiene-acrylonitrile block containing about 2 mol% of a phenolic hydroxyl group containing 50 wt% of a polybutadiene-acrylonitrile copolymer part used in the present invention. The copolymer was precipitated. The precipitated polymer was further purified by washing with methanol and refluxing methanol. The intrinsic viscosity of this polymer is 0.85 dl
/ G (dimethylacetamide, 30 ° C). Was measured infrared spectrum by diffusion reflection method polymer powder, the amide carbonyl group to 1674cm ^-1, 285
The absorption based on C-H bonds of the butadiene part in 6-2975cm ^-1, revealed absorption based on nitrile group in 2245 cm ^-1.

Synthesis Example 2 Synthesis of phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer (phenolic hydroxyl group contained in aramid portion is 14 mol%): Synthesis Example 1
19.60 g (118 mmol) of isophthalic acid of 3,
26.4 g (132 mmol) of 4'-oxydianine,
0.41 g (2.3 mmol) of 5-hydroxyisophthalic acid
1) and polybutadiene having carboxyl groups at both terminals
48 g of the acrylonitrile copolymer was charged with 19.93 g (120 mmol) of isophthalic acid, 30.63 g (153 mmol) of 3,4'-oxydianiline and 3.64 (20 mmol) of 5-hydroxyisophthalic acid and carboxyl at both ends. Polymerization by the same procedure except that the polybutadiene-acrylonitrile copolymer having a group was changed to 55.5 g (Hycar CTBN, manufactured by BF Goodrich Co., Ltd .; acrylonitrile contained in the polybutadiene acrylonitrile portion was 17 mol% and the molecular weight was about 3600). After the same post-treatment, an aramid-polybutadiene-acrylonitrile block copolymer containing about 14 mol% of phenolic hydroxyl groups used in the present invention was precipitated. The intrinsic viscosity of this polymer is 0.82 dl / g (dimethylacetamide, 3
0 ° C). It was measured infrared spectrum by diffusion reflection method polymer powder, based amide carbonyl group 1675 cm ^-1, the absorption based on C-H bonds of the butadiene part in 2854-2971Cm ^-1, the nitrile group to 2243cm ^-1 absorption Admitted.

Example 1 After dissolving 24 g of a phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer containing 2 mol% of phenolic hydroxyl groups obtained in Synthesis Example 1 in 200 g of dimethylformamide, orthocresol novolak was obtained. 4.5 g of a type epoxy resin (EOCN-103S, average degree of polymerization: 5 to 7, epoxy equivalent: 210 to 230, manufactured by Nippon Chemical Co., Ltd.) and 0.08 g of triphenylphosphine as a reaction accelerator are added, and the mixture is added at 90 ° C. For 2 hours. This was added to water to precipitate the resin, washing with warm water was repeated, and further tetrahydrofuran was added to azeotropically evaporate these solvents under reduced pressure, followed by vacuum drying, and the epoxy resin reacted with the aramid part. A resin composition was obtained. In a solution of 1 mg of this product dissolved in about 30 ml of pyridine,
Color indicator liquid for phenolic hydroxyl group (anhydrous iron (III) chloride 1
g in 100 ml of chloroform.
After the addition of a few ml, the precipitate was filtered and a red solution was prepared), and several drops were added, followed by stirring, but no discoloration was observed, and the phenolic hydroxyl group was completely changed to glycidyl group in this resin. It reacted and confirmed that it was not contained.

Comparative Example 1 Orthocresol novolak type epoxy resin (EOCN-10)
3S, average degree of polymerization: 5 to 7, epoxy equivalent: 210 to 23
0, manufactured by Nippon Chemical Co., Ltd.) 100 g, a curing accelerator triethanolamine 1.0 g, and a curing agent bis (4-
After adding 22 g of (aminophenyl) methane, stirring and mixing uniformly, the mixture was dried under vacuum to obtain an epoxy resin sample for comparison.

Example 2 3.6 g of the product obtained in Example 1 and the epoxy resin 9
6.4 g, 21.3 g of bis (4-aminophenyl) methane as a curing agent, and 1 g of tetraethylamine as a curing accelerator were melted and added, followed by stirring and uniform mixing to obtain an epoxy resin composition of the present invention. .

Example 3 5.9 g of the product obtained in Example 1 and the epoxy resin 9
4.1 g, 20.9 g of bis (4-aminophenyl) methane as a curing agent, and 1 g of triethanolamine as a curing accelerator are melted, added, and stirred and uniformly mixed to obtain an epoxy resin composition of the present invention. Was.

Example 4 The phenolic hydroxyl group obtained in Synthesis Example 2 contained about 14 mol%
24 g of the contained aramid-polybutadiene acrylonitrile block copolymer, 11.4 g of epoxy resin, and 0.64 g of triphenylphosphine as a reaction accelerator were dissolved in 200 g of dimethylformamide, and the same operation as in Example 1 was carried out. A reaction product of a polybutadiene acrylonitrile block copolymer and an epoxy resin was obtained. To a solution of 1 mg of this product dissolved in about 30 ml of pyridine, dissolve 1 g of a phenolic hydroxyl group color indicator (anhydrous iron (III) chloride in 100 ml of chloroform,
Further, 8 ml of pyridine was added, and the precipitate was filtered to prepare a red solution. A few drops of the mixture were added and stirred, but no discoloration was observed, and the resin contained no glycidyl hydroxyl groups. It reacted with the group and was confirmed not to be contained.

Example 5 4.4 g of the product obtained in Example 4, 95.6 g of the epoxy resin, and bis (4-aminophenyl) as a curing agent
21.3 g of methane and 1 g of tetraethylamine as a curing accelerator were melted, added, stirred, and uniformly mixed to obtain an epoxy resin composition of the present invention.

Example 6 7.4 g of the product obtained in Example 4 and the epoxy resin 9
2.6 g, 20.9 g of bis (4-aminophenyl) methane as a curing agent, and 1 g of tetraethylamine as a curing accelerator were melted and added, followed by stirring and uniform mixing to obtain an epoxy resin composition of the present invention. .

After molding the epoxy resin compositions of Comparative Example 1 and Examples 2, 3, 5, and 6 at 120 ° C. for 2 hours and 200 ° C.
For 5 hours to prepare a test piece. Using this test piece, the impact toughness was measured by the following method.
Summarized in Measurement of impact strength: Dynestst Feinm
echanic Ralf Kogel) using DIN-53453.
It went according to. The test piece was 15 × 10 × 2 (mm).

[0026]

[Table 1] a) Addition amount of block copolymer to epoxy resin b) In block copolymer, indicates mol% of hydroxyl group contained in aramid portion.

[0027]

The epoxy resin composition of the present invention exhibits, without impairing the heat resistance of the novolak type epoxy resin cured product can be produced a molded body with improved toughness.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification code FI H01L 23/31 (56) References JP-A-2-222444 (JP, A) JP-A-2-133422 (JP, A) JP-A-2-135217 (JP, A) JP-A-1-188521 (JP, A) JP-A-1-174519 (JP, A) JP-A-63-230725 (JP, A) JP-A-63-37116 JP, A) JP-A-62-273224 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/14 C08G 59/20-59/38 C08G 81/00-81 / 02 C08L 63/00-63/10 H01L 23/29

Claims (3)

(57) [Claims] 1. A modified epoxy resin obtained by reacting a novolak type epoxy resin represented by the general formula (I) with a phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer represented by the general formula (II). Embedded image R—CHR ² — (— R—CHR ² —) n—R (I) (wherein R is a group of formula 2 or 3 and R ² is — (CH ₂ ) _{3
CH 3, -CH 2 CH (CH} 3) 2, -C (CH 3) 2
CH ₂ CH ₃ , —CH ＝ CH ₂ , —C ₆ H ₆ or a hydrogen atom, n = 1 to 40. (In the formula, R ¹ is a hydrogen atom, a bromine atom or a methyl group, and a dotted line indicates that there is no terminal R.) (In the formula, R ¹ is a hydrogen atom, a bromine atom or a methyl group, and a dotted line indicates that there is no terminal R.) (Where x is an integer of 3 to 7, y is an integer of 1 to 4, y /
(X + y) = 0.1 to 0.3, z = integer of 5 to 15, m
= An integer of 1 to 400, n / (m + n) = 0.01 to 0.
50, l = an integer of 1 to 50, Ar ¹ and Ar ³ are divalent aromatic groups, and Ar ² is a divalent aromatic group containing a phenolic hydroxyl group.) 2. An epoxy resin composition comprising the modified epoxy resin according to claim 1, a novolak epoxy resin, and a curing agent. 3. The phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer represented by the general formula (II) is contained in an amount of 0.1 to 15% by weight based on the novolak type epoxy resin represented by the general formula (I). 3. The epoxy resin composition according to claim 2, wherein