JPH06248056A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin suitable for embedding materials of coatings, adhesives, molding materials, laminated sheet materials and electric parts and excellent in heat resistance, impact resistance and thermal shock resistance. CONSTITUTION:The objective epoxy resin composition having thermal shock resistance and heat resistance is composed of (1) 100 pts.wt. tris(2,3-epoxypropyl) isocyanurate, (2) 130-470 pts.wt. liquid rubbery compound obtained by reacting 50-350 pts.wt. carboxyl-containing liquid acrylonitrile butadiene rubber with 80-120 pts.wt. liquid bifunctional epoxy resin and (3) a liquid polycarboxylic acid anhydride of 0.8-1 equivalent based on 1 equivalent total epoxy compounds and (4) 0.001-2 pts.wt. triphenylphosphine or its salt or 0.001-2 pts.wt. tertiary amine as a curing accelerator.

Description

Detailed Description of the Invention

[0001]

[Industrial application] Excellent heat resistance, shock resistance, and heat shock resistance suitable for paints, adhesives, molding materials, laminated board materials (printed circuit boards, CFRP and GFRP matrix) and embedded materials for electrical parts. And an epoxy resin composition.

[0002]

BACKGROUND OF THE INVENTION Epoxy resin compositions generally exhibit excellent physical, electrical and chemical properties. That is, it exhibits excellent properties such as low curing shrinkage, high mechanical strength, high heat resistance, high dimensional stability, high chemical resistance and high corrosion resistance, and also excellent electrical properties such as insulation resistance. Epoxy resin compositions are used in various fields due to these excellent properties. Examples thereof include paints, adhesives, FRP matrices, semiconductor encapsulation materials, insulating structural materials for heavy electrical equipment, and various molding materials. Recently, required properties of epoxy resin compositions for these various uses have become strict, and demands for satisfying both contradictory properties such as heat resistance and toughness have become stronger.

However, the heat resistance of a cured product made of a general typical epoxy resin is not sufficient, and the flexibility and toughness are relatively lacking, and there are problems in heat shock resistance, shock resistance and breaking strength. Japanese Patent Laid-Open No. 4-180956 discloses a CTBN with little stress concentration and cavitation between the boundary between the rubber phase and the epoxy phase.
(Carboxyl group-containing acrylonitrile butadiene rubber)
A modified epoxy resin composition is disclosed. This resin composition increases the mechanical strength of the resin but has low heat resistance.
Japanese Unexamined Patent Publication No. 3-244626 discloses an epoxy resin powder composition having excellent coating properties and penetrability as well as excellent thermal shock resistance and adhesiveness, but this resin composition also has poor heat resistance. Further, Japanese Patent Application No. 4-331826 has significantly improved heat resistance by adding tris (2,3-epoxypropyl) isocyanurate (hereinafter abbreviated as TEPIC) to a typical epoxy resin composition. A resin composition is disclosed. However, this resin composition is inferior in impact resistance. Japanese Patent Application Laid-Open No. 4-110320 discloses spherical epoxy resin particles having heat resistance, high toughness, and spherical shape. A plate-shaped cured product having the same composition as this resin composition has the same performance as spherical epoxy resin particles, but the heat resistance is not sufficient. JP-A-58-91755 discloses an epoxy resin composition in which a vulcanized rubber is uniformly dispersed in an epoxy resin to improve the flexibility of a cured product, but there is no description concerning heat resistance. Further, JP-A-59-51910 and JP-A-56-122823 disclose powdery epoxy resin compositions which have good preservability and do not lose flexibility even in a low temperature range. Has not touched.

[0004]

The object of the present invention is to find an epoxy resin composition which has a high glass transition temperature and gives a cured product which simultaneously satisfies the contradictory performances of thermal shock resistance and impact resistance. It is in. That is, in general, a cured product in which the rubber phase is completely compatible with the matrix phase has a slightly improved impact resistance due to the rubber phase, but on the other hand, it often follows the additive rule that the rubber phase lowers the heat resistance. The present invention, the rubber particles are microphase-separated in the epoxy resin during the heat curing process, and by giving a cured product having an appropriate particle size, for example, 0.1 μm to 30 μm, a thermal shock resistance without lowering the heat resistance. It is intended to provide a rubber-modified epoxy resin composition which gives a cured product with significantly improved impact resistance.

[0005]

In the present invention, a liquid rubber compound obtained from a carboxyl group-containing acrylonitrile butadiene rubber and a liquid difunctional epoxy resin is dissolved in a matrix composed of TEPIC and an acid anhydride, and then, in a curing process. By forming a microphase-separated structure of a flexible fine particle rubber elastomer, thermal shock resistance and impact resistance are imparted without impairing the heat resistance inherent in the epoxy resin. It is important to control the compatibility of the liquid rubber compound in order to obtain an appropriate particle size, and the liquid rubber compound, the epoxy matrix, the type of the curing accelerator and the amount added thereof are selected,
It has become possible to obtain a cured product having excellent heat resistance, heat shock resistance, shock resistance and water absorption resistance.

That is, the present invention is as follows: High thermal shock resistance / high heat resistance epoxy resin composition composed of the following four components: (1) 100 parts by weight of tris (2,3-epoxypropyl) isocyanurate (2) Liquid carboxyl group-containing acrylonitrile butadiene rubber 130 to 470 parts by weight of a liquid rubber compound obtained by reacting 50 to 350 parts by weight with a liquid bifunctional epoxy resin 80 to 120 parts by weight (3) Liquid polycarboxylic acid based on 1 equivalent of all epoxy compounds 0.8-1 equivalent of anhydride (4) 0.001-2 parts by weight of curing accelerator 1. Liquid carboxyl group-containing acrylonitrile-butadiene rubber having an acrylonitrile content of 15 to 20% by weight, 50 to 350 parts by weight, and liquid difunctional epoxy resin 80
2. 130 to 470 parts by weight of the liquid rubber compound obtained by reacting 120 parts by weight to 120 parts by weight is used, and the epoxy resin composition according to 1 above, Liquid carboxyl group-containing acrylonitrile butadiene rubber 25 having an acrylonitrile content of 8 to 12% by weight
0 to 350 parts by weight and liquid bifunctional epoxy resin 80 to 1
33 of a liquid rubber compound obtained by reacting 20 parts by weight
3. The epoxy resin composition according to the above item 1, characterized in that 0 to 470 parts by weight is used. Liquid carboxyl group-containing acrylonitrile butadiene rubber having an acrylonitrile content of 25 to 30% by weight 1
50-250 parts by weight and liquid difunctional epoxy resin 80-
2 of a liquid rubber compound obtained by reacting 120 parts by weight
1 characterized in that 30 to 370 parts by weight are used
4. The epoxy resin composition described in 5. Liquid carboxyl group-containing acrylonitrile butadiene rubber having an acrylonitrile content of 15 to 20% by weight
0 to 80 parts by weight and liquid difunctional epoxy resin 30 to 40
80-1 of liquid rubber compound obtained by reacting parts by weight
20 parts by weight and 50 to 80 parts by weight of a liquid carboxyl group-containing acrylonitrile butadiene rubber having an acrylonitrile content of 25 to 30% by weight, and 100 to 100 parts of a liquid rubber compound obtained by reacting 50 to 80 parts by weight of a liquid difunctional epoxy resin. 6. The epoxy resin composition as described in 1 above, which is used by mixing 160 parts by weight. 6. The epoxy resin composition according to 1 above, wherein the liquid bifunctional epoxy resin is a bisphenol epoxy resin (epoxy equivalent 180 to 300 g / eq.). 7. The epoxy resin composition according to the above 1, wherein the liquid difunctional epoxy resin is a diglycidyl ether-based epoxy resin of a propylene oxide adduct of bisphenol A. 8. The epoxy resin composition according to 1 above, wherein the liquid difunctional epoxy resin is a glycidyl ester of dimer acid. 10. 0.02 to 2 parts by weight of triphenylphosphine or a salt thereof is used as a curing accelerator, and the epoxy resin composition according to 2 above, As a curing accelerator, a tertiary amine of 0.001 to 0.
The epoxy resin composition as described in 2 above, wherein 2 parts by weight is used.

Next, the components constituting the composition of the present invention will be explained step by step. The liquid rubber compound is produced by heating and mixing a liquid carboxyl group-containing acrylonitrile butadiene rubber and a liquid difunctional epoxy resin. The two components will be described in detail below.

Liquid Rubber Compound The liquid rubber compound used in the present invention is a liquid carboxyl group-containing acrylonitrile butadiene rubber (50 to 300 parts by weight) and a liquid difunctional epoxy resin (80 to 120 parts by weight).
It is obtained by reacting with. The liquid carboxyl group-containing acrylonitrile butadiene rubber and the liquid difunctional epoxy resin will be described below. Liquid carboxyl group-containing acrylonitrile butadiene rubber (a) Examples of commercially available liquid carboxyl group-containing acrylonitrile butadiene rubber include BFGoodrich C
hemical Hycar CTBN (Acrylonitrile content approx.
10 to 30% by weight). The types of Hycar CTBN are CTBN1300 × 3 with carboxyl groups at both ends as shown in the table below.
1, CTBN1300 × 8, CTBN1300 × 13, and CTBNX1300 × 9 (having an acrylonitrile content of about 17% by weight) having a carboxyl group other than at both ends, and these may be used alone or in combination of two or more. The types and properties of CTBN are shown in the table below.

[0009]

[Table 1] Table 1 Types and properties of CTBN ────────────────────────────── CTBN types AN content (wt%) -COOH / mol Acid value Mw SP ────────────────────────────── CTBN 1300 × 31 10 1.9 0.53 3500 8.45 CTBN 1300 × 8 17 1.85 0.53 3500 8.77 CTBN 1300 × 13 27 1.85 0.53 3500 9.14 CTBNX 1300 × 9 17 2.3 0.66 3500 −− ────────────────────────── ───── AN: Acrylonitrile SP: Solubility parameter Acid value: COOH equivalent / kg

The CTBN content is 5 to 50% by weight of the total composition.
Is preferable, and more preferably 10 to 45% by weight. If it is less than that, the modifying effect is small, and if it is too large, the amount dissolved in the matrix increases and the heat resistance decreases.

(B) Liquid Bifunctional Epoxy Resin The reason why the liquid difunctional epoxy resin is used in the production of the liquid rubber compound is that it is a reaction product of a flexible bifunctional epoxy resin and a carboxyl group-containing acrylonitrile butadiene rubber. This is to form an appropriately flexible domain during the curing process to obtain a microphase-separated structure having excellent impact resistance and thermal shock resistance.

Another function of the liquid bifunctional epoxy resin is a function as a matrix component. That is, the bifunctional epoxy resin that did not react with the carboxyl group-containing acrylonitrile butadiene rubber was TEPIC
/ The effect of lowering the crosslink density of the cured product of an acid anhydride and sufficiently exhibiting the stress absorbing action in the microphase-separated structure by the fine particle rubber elastomer.

The kind of the bifunctional epoxy resin which is liquid at room temperature used in the present invention is a bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd .: epoxy equivalent 180 to 300 g / e).
q.), bisphenol F type epoxy resin, and other hydrogenated bisphenol A type epoxy resin (eg Tohto Kasei)
ST-1000 manufactured by K.K., diglycidyl ester of dimer acid (for example, YD-171 manufactured by Tohto Kasei Co., Ltd.), or diglycidyl ether of bisphenol A with propylene oxide (for example, Eporite 3002 manufactured by Kyoeisha Yushi Co., Ltd.) ) And the like are suitable, and these may be used alone or in combination of two or more kinds.

The amount of the liquid bifunctional epoxy resin used is preferably 10 to 25% by weight based on the whole composition, and the mechanical strength
Gives the most balanced properties in terms of thermal properties, electrical properties, and water resistance. If the amount added is too large, the thermal properties of the cured product will be deteriorated, and if the amount is too small, excellent mechanical properties will not be exhibited.

The amount of the liquid rubber compound obtained by reacting the liquid carboxyl group-containing acrylonitrile butadiene rubber with the liquid difunctional epoxy resin is 130 to 470 parts by weight per 100 parts by weight of TEPIC.

Tris (2,3-epoxypropyl) isocyanurate It is added as a matrix resin component of a cured product in order to improve heat resistance. Since TEPIC has three epoxy groups in one molecule, the cured product obtained has a high crosslink density and excellent heat resistance. This TEPIC includes general-purpose grade TEPIC-G, high-purity grade TEPIC-S, and high-solubility grade TEPIC-L (both manufactured by Nissan Chemical Industries, Ltd.). There is no difference in physical properties. However, TEPIC-G is inferior in operability because it gradually reacts with an acid anhydride in the step of preparing a composition.

The amount of TEPIC used is 10 to 2 with respect to the total composition.
5% by weight is preferable, and it provides the most well-balanced properties in mechanical strength, thermal properties, electrical properties, and water resistance. If the amount added is too large, the mechanical properties of the cured product will be deteriorated, and if it is too small, excellent thermal properties will not be exhibited.

Liquid polycarboxylic anhydride Used as a matrix component for curing the epoxy resin. Examples of the type of liquid polycarboxylic acid anhydride include methylhymic acid anhydride (Hitachi Chemical Co., Ltd.
MHAC), methyl hexahydrophthalic anhydride (MHH
PA; MH-700 manufactured by Shin Nippon Rika Co., Ltd., methyl tetrahydrophthalic anhydride (MTHPA; MT-500 manufactured by Shin Nippon Rika Co., Ltd.) and the like are suitable. These are used singly or as a mixture of two or more kinds, and the amount of the polycarboxylic acid anhydride equivalent to the total epoxy equivalent is preferably 0.8 to 1.0, and particularly 0.85 to 1.0 brings further good results.

Curing Accelerator Although used as a curing accelerator for the composition, it also serves as a catalyst for producing a liquid rubber compound. Examples of the curing accelerator include triphenylphosphine (TPP), various salts of TPP (for example, SA-5003 manufactured by San-Apro Co., Ltd.), and tris- (2,4,6) -dimethylaminomethylphenol ( DMP-30 manufactured by Tokyo Kasei Co., Ltd., benzyldimethylamine, imidazoles and the like are suitable.

The amount used varies depending on the type of curing accelerator and the type of liquid rubber compound, and will be described in detail later, but 0.001 to 2 parts by weight is usually used per 100 parts by weight of TEPIC.

Filler The filler may be used for improving moisture resistance reliability, hardness, or linear expansion coefficient, and examples thereof include fused silica, carbon fiber, glass fiber and a mixture thereof. To be If necessary, these may be surface-treated with a surface treatment agent or a coupling agent before use.

Next, the method for producing the liquid rubber compound will be described in detail. The present invention is achieved by a method in which a carboxyl group-containing acrylonitrile-butadiene rubber is once reacted with a liquid bifunctional epoxy resin to produce a liquid rubber compound, and the liquid rubber compound is added to a matrix. The charge equivalent ratio of the liquid difunctional epoxy resin to the carboxyl group-containing acrylonitrile butadiene rubber is preferably 1 to 10 times.

In the production of the liquid rubber compound, the curing accelerator may be omitted, but if it is added at this stage, it promotes the production of the liquid rubber compound and also has the action of promoting the curing of the present composition. It is convenient to add the minimum amount required for the curing process at this stage. The reaction between the carboxyl group-containing acrylonitrile butadiene rubber and the liquid difunctional epoxy resin is carried out by heating and mixing at 120 ° C. for about 2 hours in the presence of a curing accelerator. The end point of the reaction is confirmed by measuring the acid value and epoxy value of the reaction product.

Next, the characteristics of the present composition using a liquid rubber compound and the method for modifying the composition will be described. The prerequisites for obtaining a good microphase-separated structure by spinodal decomposition are as follows. That is, before curing, the liquid rubber compound has a compatibility relationship capable of maintaining a uniform composition with the matrix, and an appropriate compatibility relationship that the liquid rubber compound causes microphase separation from the high molecular weight matrix during the process of heat curing. Is preferred. As a result, the final cured product forms a sea-island structure, whereby a product having excellent heat resistance, thermal shock resistance, impact resistance, and water absorption resistance can be obtained.

This suitable compatibility relationship varies depending on the types and blending amounts of TEPIC, liquid difunctional epoxy resin and acid anhydride, which are the components of the composition, but the most influential factor is the carboxyl group-containing acrylonitrile butadiene rubber. Is the acrylonitrile content of. Hereinafter, a method for modifying a liquid rubber compound prepared from various carboxyl group-terminated acrylonitrile-butadiene rubbers having different acrylonitrile contents and a liquid difunctional epoxy resin will be described.

[Modification with Liquid Rubber Compound A] As a general carboxyl group-containing acrylonitrile-butadiene rubber having an acrylonitrile content of about 17%, for example, commercially available Hycar CTBN1300 × 8 was used and reacted with a liquid bifunctional epoxy resin. A modification method using a liquid rubber compound (hereinafter, abbreviated as liquid rubber compound A) will be described.

As described above, the liquid rubber compound A and TEPI
The composition, which is a mixture with the matrix components, consisting of C and an acid anhydride, must be a homogeneous compatible system before curing. A matrix comprising a mixture of the liquid rubber compound A, TEPIC, and methylhymic acid anhydride as a polycarboxylic acid anhydride (hereinafter, abbreviated as MHAC manufactured by Hitachi Chemical Co., Ltd.) in a temperature range of room temperature or higher before curing. Although it is a homogeneous compatible system at all mixing ratios, it undergoes spinodal decomposition in the heat curing process and undergoes microphase separation.

Further, as a result of diligent studies, the present inventors have found that in the modified system using the liquid rubber compound A, the impact property is remarkably improved by controlling the curing rate. This can be achieved by setting the addition amount of the curing accelerator to the necessary minimum amount. The amount of the curing accelerator added varies depending on the type, but when triphenylphosphine is used, it is preferably 0.01 to 1 phr based on the total epoxy resin. More preferably, it was 0.02-0.1 phr. When a tertiary amine is used, it is preferably 0.001 to 0.1 phr, more preferably 0.002 to 0.05 phr, based on the total epoxy resin.

If the amount of the curing accelerator added is too large, the formation of a microphase-separated structure due to spinodal decomposition during the heat curing process will be insufficient, and if it is too small, insufficient curing and reduced thermal shock resistance will result.

The types and preferable blending ratios of the liquid carboxyl group-containing acrylonitrile-butadiene rubber, TEPIC, liquid difunctional epoxy resin, curing accelerator and acid anhydride are as follows. If the compounding ratio deviates from this range, the compatibility relationship for achieving the present invention cannot be obtained. (1) 50-300 parts by weight of acrylonitrile-butadiene rubber containing a carboxyl group having an acrylonitrile content of about 17% by weight, 80-120 parts by weight of a bifunctional epoxy resin liquid at room temperature, and 0.002-0.2 phr of a tertiary amine as a curing accelerator. 130 to 420 parts by weight of the liquid rubber compound obtained by the reaction (2) TEPIC: 100 parts by weight (3) MHAC: 0.8 to 1 equivalent

[Modification with Liquid Rubber Compound B] Carboxyl group-terminated acrylonitrile butadiene rubber with low acrylonitrile content For example, Hycar CTBN1300 × 31 (acrylonitrile content of about 10 wt%) and a liquid rubber which is a reaction product of a liquid bifunctional epoxy resin. A modification method using a compound (hereinafter referred to as liquid rubber compound B) will be described.

CTBN, which has a low content of acrylonitrile, has the advantage of excellent electrical properties of the cured product because it has few polar groups, but on the other hand, its compatibility with epoxy resin is extremely poor.
Liquid rubber compound B, which is a reaction product of CTBN with low acrylonitrile content and liquid difunctional epoxy resin, is also used.
The compatibility with the TEPIC / MHAC matrix is remarkably poor, and further, the entire cured product undergoes macroscopic two-phase separation during the curing process.

As a result of diligent studies, the present inventors have found that when a large amount of the liquid rubber compound B having a low compatibility due to the low content of acrylonitrile is mixed, for example, C is added to the entire composition.
It has been found that, when compounded at about 40 wt% in terms of TBN, it surprisingly becomes a compatible system at room temperature, causes moderate spinodal decomposition in the curing process, and forms a microphase-separated structure in which particles are dispersed in several μm. This makes it possible to improve thermal shock resistance while maintaining high heat resistance.

Typical blending ratios are as follows. (1) A liquid rubber compound obtained by reacting 250 to 350 parts by weight of acrylonitrile-butadiene rubber containing a carboxyl group with an acrylonitrile content of about 10% by weight, 80 to 120 parts by weight of a bifunctional epoxy resin which is liquid at room temperature, and a curing accelerator. 33
0 to 470 parts by weight (2) TEPIC: 100 parts by weight (3) MHAC: 0.8 to 1 equivalent

[Modification with liquid rubber compound C] Carboxyl group-containing acrylonitrile-butadiene rubber having a high content of acrylonitrile, for example, Hycar CTBN1300 × 13
A modification method using (acrylonitrile content of 27 wt%) and a liquid rubber compound (hereinafter abbreviated as liquid rubber compound C) which is a reaction product of a liquid difunctional epoxy resin will be described.

The composition of the liquid rubber compound C and the TEPIC / MHAC matrix is a homogeneous compatible system at all mixing ratios in the temperature range of room temperature or higher, but the cured product does not form a micro phase separation structure even in the curing process. It becomes a homogeneous system. Since the rubber component is dissolved in the matrix, this cured product has insufficient heat resistance and insufficient improvement in thermal shock resistance. However, the amount of liquid rubber compound C added was about 40 wt% in CTBN conversion based on the total composition.
By increasing the amount above, there is an effect that the thermal shock resistance is remarkably improved although the heat resistance is slightly lowered.

Typical blending ratios are as follows. (1) of a liquid rubber compound obtained by reacting 150-250 parts by weight of acrylonitrile-butadiene rubber containing a carboxyl group with an acrylonitrile content of about 27% by weight, 80-120 parts by weight of a bifunctional epoxy resin liquid at room temperature and a curing accelerator
230 to 370 parts by weight (2) TEPIC: 100 parts by weight (3) MHAC: 0.8 to 1 equivalent Also, liquid rubber compound A, liquid rubber compound C and TEPIC / M
The composition in which the HAC matrix is blended in an appropriate ratio is a homogeneous compatible system at all mixing ratios in the temperature range of room temperature or higher before curing, but spinodal decomposition occurs in the heat curing process,
It becomes possible to perform micro phase separation.

Typical blending ratios are as follows. (1) a liquid rubber compound obtained by reacting 80-120 parts by weight of acrylonitrile-butadiene rubber containing a carboxyl group with an acrylonitrile content of about 17% by weight, 30-70 parts by weight of a bifunctional epoxy resin which is liquid at room temperature, and a curing accelerator. 11
0 to 190 parts by weight and 80 to 120 parts by weight of acrylonitrile butadiene rubber containing a carboxyl group having an acrylonitrile content of about 27% by weight and a difunctional epoxy resin liquid at room temperature 8
160 to 240 parts by weight of liquid rubber compound obtained by reacting 0 to 120 parts by weight and a curing accelerator (2) TEPIC: 100 parts by weight (3) MHAC: 0.8 to 1 equivalent

[Evaluation of Physical Properties of Cured Product] Cured product state: A liquid epoxy resin composition was obtained in the same manner as in the examples.
Approximately 24mm in diameter with spring washer No. 2 standardized in JIS B1251
A 50 mm silicon mold release agent-treated aluminum cup was cast and cured under predetermined conditions to give cracks in the cured product. The symbols used in the examples are based on the following criteria.

∘: No cracks exist even after storage after curing. ◯: No cracks occurred immediately after curing, but cracks occurred during storage. C: Cracks occurred during cooling after curing. Sep .... A cured product that has been completely separated into two phases, a rubber phase and a matrix phase, without undergoing microphase separation. Glass transition temperature (Tg): Thermomechanical analysis (TMA) method (compression load method)
Was determined from the change in thermal expansion of the cured product. Test piece: approx. 5 mm x 5 mm x 3 mm, load: 10 g, heating rate: 10
℃ / min. IZOD impact strength: JIS-K7110 Linear expansion coefficient: TMA method Measured below glass transition temperature Confirmation of sea-island structure: Observation of fracture surface of cured product obtained by IZOD impact test by scanning electron microscope (SEM) The existence of sea-island structure and the shape of dispersed particles were confirmed. Thermal shock resistance: The following cooling / heating cycle was added to the cured product containing the spring washer prepared according to the above procedure, and the thermal shock resistance was evaluated by the number of cracked cycles.

[0041]

[Table 2] Table 2 Conditions for thermal cycle ───────────────────────────── Number of cycles Low temperature range (℃ / min.) High temperature Range (℃ / min.) ───────────────────────────── 1-10 / 30 105/30 2-20 / 30 105 / 30 3-30 / 30 105/30 4-40 / 30 105/305 5-50 / 30 105/30 ──────────────────────── ─────

[0042]

[Table 3]

[0043]

The present invention will now be described with reference to examples, but the present invention is not limited to these examples. The description of the curing conditions in the table is as follows. Curing condition A: Hold at 100 ° C for 2 hours, heat up to 180 ° C in 7 hours, and allow to cool. Curing condition B: Hold at 100 ° C for 2 hours, raise to 180 ° C in 7 hours, and heat at 180 ° C for 3 hours. After holding, let cool. Curing condition C: Hold at 140 ° C for 2 hours, hold at 180 ° C for 3 hours, and let cool.

Examples 1 to 3 and Comparative Examples 1 and 2 (modified with liquid rubber compound B) Epicoat # 828, CTBN
Liquid rubber compound B was prepared by mixing 1300 × 31 and triphenylphosphine in the weight parts shown in Table 4 and stirring at 120 ° C. for 2 hours. It was confirmed that the acid value was about 0 and the reaction was completed.

This liquid rubber compound B and parts by weight of TEPIC-S listed in Table 4 (manufactured by Nissan Chemical Industries, Ltd., high purity product,
An epoxy equivalent of 100) and an acid anhydride curing agent MHAC were mixed and dissolved at about 90 ° C., and the resulting composition was added and degassed under reduced pressure to obtain a liquid epoxy resin composition. This was treated with a silicone release agent
A glass casting tool with a silicon rubber spacer with a thickness of about 3 mm sandwiched between two glass plates and a spring washer No. 2 24S standardized in JIS B1251 into an aluminum cup with a diameter of about 50 mm. It was cured under the curing conditions shown in 1 and the physical properties were measured. The results are shown in Table 4.

[0046]

[Table 4] Table 4 Modification with liquid rubber compound B ────────────────────────────── Actual example ratio Comparative example 1 2 3 1 2 ────────────────────────────── <Manufacture of liquid rubber compound B> Heavy epoxy coat # 828 100 100 100 100 100 quantity CTBN 1300 × 31 300 300 300 100 200 parts Triphenylphosphine 1 1 1 1 1 ───────────────────────────── ─ <Curing reaction> Heavy TEPIC-S 100 100 100 100 100 Amount MHAC 220 220 220 237 237 part Triphenylphosphine 1 1 ー ー Curing conditions> AABAA ─────────────── ─────────────── <Cured product condition> ◎ ◎ ◎ Sep. Sep. ─────────────────────── ──────── <Cured physical properties> Tg (TMA) (° C) 170 185 196--Linear expansion coefficient (× 10-5 36 27 27--IZOD Notched (kg.cm/cm2) 13 14 13--Thermal shock resistance ◎ ◎ ◎--Boiling water absorption (%) 100hr 1.6 1.4 1.3--────────── ────────────────────

Examples 4 to 8 (Modification with liquid rubber compound A) Epicoat # 828, CTBN
Liquid rubber compound A was prepared by mixing 1300 × 8 and triphenylphosphine in the weight parts shown in Table 5 and stirring at 120 ° C. for 2 hours. It was confirmed that the acid value was about 0 and the reaction was completed.

This liquid rubber compound A, a composition prepared by mixing TEPIC-S and the acid anhydride curing agent MHAC in parts by weight shown in Table 5 by mixing at about 90 ° C. were added, degassed under reduced pressure, and liquid An epoxy resin composition was obtained. This was treated with a silicone release agent
A glass casting tool with a silicon rubber spacer with a thickness of about 3 mm sandwiched between two glass plates and a spring washer No. 2 24S standardized to JIS B1251 are cast into an aluminum cup with a diameter of about 50 mm. It was cured under the curing conditions shown in 1 and the physical properties were measured. The results are shown in Table 5.

[0049]

[Table 5] Table 5 Modification by liquid rubber compound A ────────────────────────────── Example 4 5 6 7 8 ────────────────────────────── <Manufacture of liquid rubber compound A> Heavy epoxy coat # 828 100 100 100 100 100 Amount CTBN 1300 × 8 100 100 200 300 300 parts Triphenylphosphine 1 1 1 1 1 <Curing reaction> Heavy TEPIC-S 100 100 100 100 100 100 amount MHAC 237 237 237 220 220 parts <Curing conditions> ACAAB ──────── ─────────────────────── <Cured state> ○ ○ ○ ◎ ◎ <Cured physical properties> Tg (TMA) (° C) 190 186 175 170 183 Linear expansion coefficient (× 10-5) 25 34 31 35 38 IZOD Notched (kg.cm/cm2) 5 5 5 16 15 Thermal shock resistance---◎ ◎ Boiled water absorption rate (%) 100hr 2.4 1.5 1.7-1.4 ──────────────────────────────

Examples 9 to 12 (Modification with liquid rubber compound A; influence of curing accelerator) As a preliminary reaction, Epicoat # 828, CTBN1300 × 8, and triphenylphosphine were mixed in a weight ratio shown in Table 6. hand
Liquid rubber compound A was manufactured by stirring at 120 ° C. for 2 hours. It was confirmed that the acid value was about 0 and the reaction was completed.

This liquid rubber compound A, and a composition prepared by mixing TEPIC-S in parts by weight shown in Table 6 and acid anhydride curing agent MHAC at about 90 ° C. and dissolving were added, degassed under reduced pressure, and liquid An epoxy resin composition was obtained. This was treated with a silicone release agent
A glass casting tool with a silicon rubber spacer with a thickness of about 3 mm sandwiched between two glass plates and a spring washer No. 2 24S standardized in JIS B1251 into an aluminum cup with a diameter of about 50 mm. It was cured under the curing conditions shown in 1 and the physical properties were measured. The results are shown in Table 6.

[0052]

[Table 6] Table 6 Modification with liquid rubber compound A (influence of curing accelerator) ───────────────────────────── Example 9 10 11 12 ──────────────────────────── <Manufacture of Liquid Rubber Compound A> Heavy Epcoat # 828 100 100 100 100 Amount CTBN 1300 × 8 100 100 100 100 parts Triphenylphosphine 0.5 0.2 0.1 0.04 <Curing reaction> Heavy TEPIC-S 100 100 100 100 100 MHAC 237 237 237 237 parts <Curing conditions> A A A A ──────────────────────────── <Cured product state> ○ ◎ ◎ ◎ <Cured physical properties> Tg (TMA) (° C) 187 168 170 165 Linear expansion coefficient (× 10-5) 29 40 27 31 IZOD Notched (kg.cm/cm2) 4 6 6 5 ──────── ─────────────────────

Examples 13 to 17 Modification with liquid rubber compound A (influence of curing accelerator) Epicoat # 828, CTBN1300 × 8,
Liquid rubber compound A was prepared by mixing tris- (2,4,6) -dimethylaminomethylphenol (DMP-30 manufactured by Tokyo Kasei Co., Ltd.) in a weight ratio shown in Table 7 and stirring at 120 ° C. for 2 hours. Was manufactured. It was confirmed that the acid value was about 0 and the reaction was completed.

This liquid rubber compound A, a composition prepared by mixing TEPIC-S and the acid anhydride curing agent MHAC in parts by weight shown in Table 7 by mixing at about 90 ° C. were added, degassed under reduced pressure, and liquid An epoxy resin composition was obtained. This was treated with a silicone release agent
A glass casting tool with a silicon rubber spacer with a thickness of about 3 mm sandwiched between two glass plates and a spring washer No. 2 24S standardized in JIS B1251 into an aluminum cup with a diameter of about 50 mm. It was cured under the curing conditions shown in 1 and the physical properties were measured.
The results are shown in Table 7.

[0055]

[Table 7] Table 7 Modification by liquid rubber compound A (effect of curing accelerator) ─────────────────────────────── Example 13 14 15 16 17 ─────────────────────────────── <Production of Liquid Rubber Compound A> Heavy Equacoat # 828 100 100 100 100 100 volume CTBN 1300 × 8 100 100 100 100 100 parts DMP-30 0.1 0.02 0.01 0.005 0.1 <Curing reaction> Heavy TEPIC-S 100 100 100 100 100 volume MHAC 237 237 237 237 237 237 parts <Curing conditions> AAAAC ─────────────────────────────── <Cured product state> ○ ○ ○ ○ ○ <Cured property> Tg (TMA ) (° C) 185 190 177 177 175 Linear expansion coefficient (× 10-5) 21 19 24 29 36 ──────────────────────────── ─────

Example 18 and Comparative Examples 3 and 4 (modified with liquid rubber compound C) Epicoat # 828, CTBN
Liquid rubber compound C was prepared by mixing 1300 × 13 and triphenylphosphine in the weight parts shown in Table 8 and stirring at 120 ° C. for 2 hours. It was confirmed that the acid value was about 0 and the reaction was completed.

The liquid rubber compound C, a composition prepared by mixing and dissolving TEPIC-S and the acid anhydride curing agent MHAC in parts by weight shown in Table 8 at about 90 ° C. were added, degassed under reduced pressure, and liquid An epoxy resin composition was obtained. A glass casting tool with a silicon rubber spacer with a thickness of about 3 mm sandwiched between two glass plates treated with a silicone release agent and a spring washer No. 2 24S standardized to JIS B1251 with a diameter of about 50 mm. After casting in an aluminum cup of No. 3, the composition was cured under the curing conditions shown in Table 8 and the physical properties were measured. The results are shown in Table 8.

[0058]

[Table 8] Table 8 Modification with liquid rubber compound C ───────────────────────────── Example Comparative Example 18 34 ──────────────────────────── <Manufacture of liquid rubber compound C> Heavy epoxy coat # 828 100 100 100 amount CTBN 1300 × 13 200 300 100 parts Triphenylphosphine 1 1 1 <Curing reaction> Heavy TEPIC-S 100 100 100 Amount MHAC 228 220 237 parts <Curing conditions> AAA ──────────────────── ────────── <Cured product state> ◎ ◎ × <Cured property> Tg (TMA) (° C) 170 158 175 Linear expansion coefficient (× 10-5) 28 31 25 IZOD Notched ( kg.cm/cm2) 10 15 5 Thermal shock resistance ◎ ◎-────────────────────────────────

Examples 19 and 20 (Modification with a mixture of liquid rubber compounds A and C) Epicoat # 828, CTBN1300 × 8, and triphenylphosphine were mixed in a weight ratio shown in Table 9 and mixed at 120 ° C. for 2 hours. Liquid rubber compound A was manufactured by stirring for a period of time. It was confirmed that the acid value was about 0 and the reaction was completed. Separately from this, Epicote # 82
8, CTBN1300 × 13 and triphenylphosphine were mixed in the weight parts shown in Table 9 and stirred at 120 ° C. for 2 hours to prepare a liquid rubber compound C. It was confirmed that the acid value was about 0 and the reaction was completed.

After mixing both of these liquid rubber compounds, parts by weight of TEPIC-S and acid anhydride curing agent MHAC listed in Table 9 were used.
Was mixed at about 90 ° C. and dissolved, and the resulting composition was degassed under reduced pressure to obtain a liquid epoxy resin composition. A glass casting tool that has a silicon rubber spacer with a thickness of about 3 mm sandwiched between two glass plates treated with a silicone-based mold release agent and JIS B1251
After casting in an aluminum cup with a diameter of about 50 mm containing the spring washer No. 2 24S standardized in 1., it was cured under the curing conditions shown in Table 9 and the physical properties were measured. The results are shown in Table 9.

[0061]

[Table 9] Table 9 Modification with a mixture of liquid rubber compounds A and C ──────────────────────────── Example 19 20 ── ───────────────────────── <Manufacture of liquid rubber compounds> Heavy Epcoat # 828 33.3 66.7 33.3 66.7 Amount CTBN 1300 × 8 66.7 ー 66.7 CTBN 1300 × 13 ー 66.7 ー 66.7 Triphenylphosphine 0.33 0.33 0.33 0.33 <Curing reaction> Heavy TEPIC-S 100 100 Amount MHAC 228 228 parts <Curing conditions> AB ─────────────── ───────────── <Cured product state> ◎ ○ <Cured property> Tg (TMA) (° C) 175 200 Linear expansion coefficient (× 10-5) 25 31 IZOD With notch ( kg.cm/cm2) 10 6 ───────────────────────────

Examples 21 and 22 (Modification with liquid rubber compound A) Diglycidyl ester of dimer acid (eg YD-171 manufactured by Tohto Kasei Co., Ltd.), CTBN1
Liquid rubber compound A was prepared by mixing 300 × 8 and triphenylphosphine in the weight parts shown in Table 10 and stirring at 120 ° C. for 2 hours. It was confirmed that the acid value was about 0 and the reaction was completed.

This liquid rubber compound A, a composition obtained by mixing TEPIC-S in parts by weight shown in Table 10 and acid anhydride curing agent MHAC at about 90 ° C. and dissolving were added, degassed under reduced pressure, and liquid An epoxy resin composition was obtained. A glass casting tool with a silicon rubber spacer with a thickness of about 3 mm sandwiched between two glass plates treated with a silicone release agent and a spring washer 2 24S standardized to JIS B1251 with a diameter of about 50 mm. After casting in an aluminum cup of No. 3, the composition was cured under the curing conditions shown in Table 10, and the physical properties were measured. The results are shown in Table 10.

[0064]

[Table 10] Table 10 Modification by liquid rubber compound A (effect of YD-171) ───────────────────────────── Example 21 22 ───────────────────────────── <Production of liquid rubber compound A> Heavy YD-171 62 93 Quantity CTBN 1300 × 8 100 100 parts Triphenylphosphine 0.6 0.9 ───────────────────────────── <Curing reaction> Heavy TEPIC-S 100 100 Amount # 828 79 70 parts MHAC 236 236 <Curing conditions> AA ───────────────────────────── <Cured product condition> ○ ○ ───────────────────────────── <Cured physical properties> Tg (TMA) (° C) 177 170 Linear expansion coefficient (× 10 ー5) 29 23 ──────────────────────────────

Examples 23 and 24 (Modification with liquid rubber compound A) A diglycidyl ether of a bisphenol A propylene oxide adduct (for example, Epolite 3002 manufactured by Kyoeisha Oil & Fat Co., Ltd.), CTBN1300 × 8, and triphenylphosphine are shown. The liquid rubber compound A was manufactured by mixing in the amount of 11 parts by weight and stirring at 120 ° C. for 2 hours. It was confirmed that the acid value was about 0 and the reaction was completed.

This liquid rubber compound A, and a composition prepared by mixing TEPIC-S and the acid anhydride curing agent MHAC in parts by weight shown in Table 11 at about 90 ° C. and dissolving were added, degassed under reduced pressure, and liquid An epoxy resin composition was obtained. A glass casting tool with a silicon rubber spacer with a thickness of about 3 mm sandwiched between two glass plates treated with a silicone release agent and a spring washer 2 24S standardized to JIS B1251 with a diameter of about 50 mm. After casting in an aluminum cup of No. 3, the composition was cured under the curing conditions shown in Table 11, and the physical properties were measured. The results are shown in Table 11.

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Table 11 Table 11 Modification with liquid rubber compound A (effect of Epolite 3002) ─────────────────────── Example 23 24 ──── ─────────────────── <Manufacture of liquid rubber compound A> Heavy epholite 3002 100 100 amount CTBN 1300 × 8 100 100 parts Triphenylphosphine 1 1 ──── ─────────────────── <Curing reaction> Heavy TEPIC-S 100 100 amount MHAC 203 203 parts <Curing conditions> AB ─────────── ──────────── <Cured state> ○ ○ ─────────────────────── <Cured physical properties> Tg (TMA ) (° C) 170 178 Linear expansion coefficient (× 10-5) 28 31 IZOD Notched (kg.cm/cm2) 3.5 3.7 ───────────────────── ─── The type of CTBN used in the production of liquid rubber compounds is a micro phase separation structure (sea island structure) Table 11 summarized the impact of thermal shock resistance (12), was as 12 (13).

[0068]

[Table 12] Table 12 Microphase-separated structure (sea-island structure) and thermal shock resistance (CTBN content 19 wt% based on the total composition) ────────────────────── Comparative Example 1 Example 4 Comparative Example 4 ─────────────────────────────────────────────── ────Types of CTBN CTBN1300 × 31 CTBN1300 × 8 CTBN1300 × 13 Thermal shock resistance Two-phase separation ○ × Dispersed particle size (μm) −10 to 50 None Tg (℃) − 190 175 ───────── ─────────────────────────

[0069]

[Table 13] Table 13 Micro phase-separated structure (sea-island structure) and thermal shock resistance (CTBN content of 41 wt% based on the total composition) ────────────────────── ───────────── Example 1 Example 7 Comparative Example 3 ───────────────────────────── ────── Type of CTBN CTBN1300 × 31 CTBN1300 × 8 CTBN1300 × 13 Thermal shock resistance ◎ ◎ ◎ Dispersion particle size (μm) 5 to 6 15 to 25 None Tg (℃) 170 170 158 ────── ────────────────────────────

When the CTBN content was 19 wt% with respect to the total composition, the use of CTBN1300 × 31 resulted in complete two-phase separation of the cured product. The cured product modified by CTBN1300 × 8 has high heat resistance and high thermal shock resistance because it has a sea-island structure with an appropriate dispersed particle size. On the other hand, the cured product modified with CTBN1300 × 13 is a homogeneous compatible system and the modification effect due to the sea-island structure does not appear, so the heat resistance decreases and the thermal shock resistance is also poor.

When the CTBN content is 41 wt% with respect to the total composition, the system modified with CTBN1300 × 31 and CTBN1300 × 8 undergoes homogeneous compatibility before curing, causes spinodal decomposition in the curing process, and has an appropriate dispersed particle size. Form a sea island structure.
Therefore, it has high thermal shock resistance while maintaining high heat resistance.
However, when CTBN1300 × 13 is used, it has a high thermal shock resistance because it is a homogeneous compatible system, but the heat resistance decreases.

Claims (10)

[Claims] 1. An epoxy resin composition having high thermal shock resistance and high heat resistance, which comprises the following four components. (1) 100 parts by weight of tris (2,3-epoxypropyl) isocyanurate (2) Reaction of 50-350 parts by weight of liquid carboxyl group-containing acrylonitrile butadiene rubber with 80-120 parts by weight of difunctional epoxy resin 130 to 470 parts by weight of the obtained liquid rubber compound (3) 1 to 1 equivalent of all epoxy compounds, 0.8 to 1 equivalent of liquid polycarboxylic acid anhydride (4) 0.001 to 2 of curing accelerator Parts by weight 2. The epoxy resin composition according to claim 1, wherein a liquid carboxy group-containing acrylonitrile-butadiene rubber having an acrylonitrile content of 15 to 20% by weight is used. 3. Acrylonitrile content of 8-12% by weight
3. A liquid rubber compound, 330 to 470 parts by weight, which is obtained by reacting 250 to 350 parts by weight of a liquid carboxyl group-containing acrylonitrile butadiene rubber, which is the above, with 80 to 120 parts by weight of a liquid difunctional epoxy resin is used. The epoxy resin composition described. 4. A liquid rubber compound obtained by reacting 150 to 250 parts by weight of a liquid carboxyl group-containing acrylonitrile butadiene rubber having an acrylonitrile content of 25 to 30% by weight with a liquid difunctional epoxy resin 80 to 120 parts by weight. 230 to 370 parts by weight are used, The epoxy resin composition of Claim 1 characterized by the above-mentioned. 5. A liquid rubber compound obtained by reacting 50 to 80 parts by weight of a liquid carboxyl group-containing acrylonitrile butadiene rubber having an acrylonitrile content of 15 to 20% by weight with a liquid difunctional epoxy resin of 30 to 40 parts by weight. Liquid rubber compound obtained by reacting 80 to 120 parts by weight and 50 to 80 parts by weight of a liquid carboxyl group-containing acrylonitrile butadiene rubber having an acrylonitrile content of 25 to 30% by weight with a liquid difunctional epoxy resin 50 to 80 parts by weight The epoxy resin composition according to claim 1, which is used by mixing 100 to 160 parts by weight thereof. 6. A liquid bifunctional epoxy resin is a bisphenol epoxy resin (epoxy equivalent 180 to 300 g /
eq.), The epoxy resin composition according to claim 1. 7. The epoxy resin composition according to claim 1, wherein the liquid difunctional epoxy resin is a diglycidyl ether epoxy resin of a propylene oxide adduct of bisphenol A. 8. The epoxy resin composition according to claim 1, wherein the liquid difunctional epoxy resin is a glycidyl ester of dimer acid. 9. The epoxy resin composition according to claim 2, wherein 0.02 to 2 parts by weight of triphenylphosphine or a salt thereof is used as a curing accelerator. 10. A tertiary amine as a curing accelerator is 0.0
The epoxy resin composition according to claim 2, wherein 01 to 0.2 part by weight is used.