JPH04314723A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in heat resistance, crack resistance, mold release characteristics, adhesiveness and hydrophobic properties by compounding an epoxy resin with a specific polyallylphenol, etc., as a curing agent and a silicone-modified epoxy resin as a modifier. CONSTITUTION:The title compsn. is prepd. by compounding 100 pts.wt. epoxy resin with 30-120 pts.wt. curing agent consisting of a polyallylphenol having 1-6 repeating units each having a group of formula I (e.g. a polymer of formula III) or a partially propenylated polyallylphenol having 1-6 repeating units each having a group of formula II (e.g. a polymer of formula IV) and 25-80 pts.wt. silicone-modified epoxy resin as a modifier. In formulas II and IV, R is CH2-CH =CH2 or CH=CHCH3.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to an epoxy resin composition, and more specifically, to an epoxy resin composition that has excellent heat resistance, flexibility, crack resistance, mold releasability, adhesion, and hydrophobicity. . Because the epoxy resin composition of the present invention has these excellent properties, it can be used in various fields, especially in the fields of multilayer lamination resins, conductive pastes, electronic device protective films, adhesives, paints, sealing materials, and molding materials. It can be used advantageously.

0002

BACKGROUND OF THE INVENTION In recent years, electronic and electrical equipment, transportation equipment, etc. have become smaller and lighter, and their performance has improved, and along with this, materials with excellent heat resistance and moisture resistance are desired.

Polyimide resin is generally known as a heat-resistant resin, but since it is a dehydration condensation type, voids are likely to occur in the cured product due to condensation water generated during the reaction, and the reliability of the cured product may be reduced. Decreases sex. On the other hand, since polyimide itself is insoluble and infusible, it is difficult to mold it.

[0004] Bismaleimide resin is known as a polyimide with improved moldability, but molding requires a temperature of 200°C.
It requires higher temperatures and has poor workability. Furthermore, bismaleimide resin has poor hydrophobicity, which significantly reduces the reliability of the cured product.

[0005] For epoxy resins with good moldability, acid anhydrides and phenols are usually used as curing agents, but all of these cured products are somewhat insufficient in terms of heat resistance. For example, the glass transition temperature of epoxy/phenol curing systems is typically 140-170°C.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the drawbacks of the conventional techniques as described above, in other words, to provide a method that can be advantageously used in a wide range of fields.
An object of the present invention is to provide an epoxy resin composition having excellent heat resistance, flexibility, crack resistance, mold releasability, adhesion, and hydrophobicity.

[0007]

[Means for Solving the Problems] The above-mentioned problems of the present invention are achieved by using an epoxy resin as a base resin,

[Image Omitted] Polyallylphenol having 1 to 6 repeating units containing a group represented by formula (1), or

[Chemical formula 12] 30 to 120 parts by weight of a partially propenylated polyallylphenol having 1 to 6 repeating units containing a group represented by formula (2) as a curing agent based on 100 parts by weight of an epoxy resin
This can be achieved by an epoxy resin composition containing 5 to 80 parts by weight of a silicone-modified epoxy resin as a modifier per 100 parts by weight of the epoxy resin.

[0008]

[Operation] Any epoxy resin can be used as the base resin in the composition of the present invention. However, according to the findings of the inventors, examples of epoxy resins that can be advantageously used include glycidyl ethers such as bisphenol A epoxy resin, cresol novolac epoxy resin, phenol novolak epoxy resin, and tetramethylbiphenyl epoxy resin. Examples include epoxy resins having two or more epoxy groups in one molecule, such as type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, and halogenated epoxy resins. These epoxy resins may be used alone or in a mixed system of two or more.

[0009] Polyallylphenol as a curing agent

[
embedded image A polymer represented by formula (3), or

[Chemical formula 14] A polymer represented by formula (4) can be used.

[0010] Also, as partially propenylated polyallylphenol,

[Chemical formula 15] A polymer represented by formula (5), or

[Chemical formula 16] A polymer represented by formula (6) can be used.

By using polyallylphenol or partially propenylated polyallylphenol as a curing agent, the glass transition temperature of the cured resin product can be adjusted to 180 to 22.
It is possible to improve the temperature to 0°C, thereby improving heat resistance, and further improving hydrophobicity. This is the effect of the allyl group,
Further, the propenyl group has self-polymerizability and further improves curability. Partially propenylated polyallylphenol is usually produced by converting some of the allyl groups of polyallylphenol into 2-
It is obtained by isomerizing to a propenyl group, and the propenylation rate is preferably less than 50% because the propenyl group itself has self-polymerizability. Further, the number of repeating units is preferably 1 to 6. This is because if it is 7 or more, the toughness of the cured product will be impaired.

[0012] The blending amount of polyallylphenol or partially propenylated polyallylphenol is
It is desirable to use 30 to 120 parts by weight per 100 parts by weight. If it is less than 30 parts by weight, the curing reaction will not proceed sufficiently, and if it exceeds 120 parts by weight, the heat resistance of the cured product will decrease.

[0013] In the epoxy resin composition of the present invention, the silicone-modified epoxy resin as a modifier simultaneously improves, in particular, crack resistance, flexibility, and mold releasability. This silicone-modified epoxy resin can take a variety of forms,
For example, it is available as SIN-620 (Dainippon Ink Chemical). Generally, it is desirable that the silicone-modified epoxy resin be used in an amount of 5 to 80 parts by weight per 100 parts by weight of the epoxy resin. This is because, as will be described in detail in the examples below, if it is less than 5 parts by weight, the effect of addition will not be apparent, and if it exceeds 80 parts by weight, the properties of the resin composition as a heat-resistant resin will deteriorate.

[0014] In order to improve the heat resistance and adhesion of the cured product, the following (1) and (2) can be added, and further, by adding a silicone-modified epoxy resin, flexibility is imparted to the cured product. However, if the flexibility is insufficient with silicone-modified epoxy resin alone, the following (3) ~
The flexibility imparting agent (6) can be added. (1) Epoxy-modified polyallylphenol (2) Maleimide resin (3) Polystyrene/polybutadiene/polystyrene terminal block copolymer (4) Ethylene/propylene ternary copolymer (5) Ethylene/α-olefin copolymer ( 6) Silicone rubber powder characterized by containing an epoxy group as a functional group The above flexibility imparting agent can have various structures.

[0015] Epoxy-modified polyallylphenol is

[
A polymer having 1 to 6 repeating units containing a group represented by formula (7),

[Chemical formula 18] Formula (9) or

embedded image A polymer represented by formula (10) can be used.

It has been discovered that the addition of epoxy-modified polyallylphenol improves the adhesion with silicon chips, which is important in semiconductor encapsulation. This is an effect due to the epoxy group. Epoxy-modified polyallylphenol is obtained by glycidylating the hydroxyl group of polyallylphenol, and the substitution rate is 5 to 100%. If it is less than 5%, the effect of the epoxy group will not be apparent. The amount of the epoxy-modified polyallylphenol added is 5 to 80 parts by weight per 100 parts by weight of the epoxy resin. If the amount is less than 5 parts by weight, no effect will be exhibited, and if it exceeds 80 parts by weight, it may bleed out onto the surface of the cured product or impair heat resistance.

[0017] The maleimide resin is

embedded image A polymer represented by formula (8) can be used. Maleimide resin improves bending strength at high temperatures; if it is less than 5 parts by weight based on 100 parts by weight of the epoxy resin, the effect is small, and if it exceeds 30 parts by weight, moisture resistance is impaired.

The ethylene/propylene ternary copolymer is composed of ethylene/propylene/an unsaturated compound, and examples of the unsaturated compound include dicyclopentadiene and ethylidene norbornene. These modifiers are commercially available in a variety of forms. To give an example, the polystyrene/polybutadiene/polystyrene terminal block copolymer is Kraton G-1652 (Shell Chemical), the ethylene/propylene rubber is JSR 57P (Japan Synthetic Rubber), and the ethylene/α-olefin copolymer is Tafmer PP. -0280 (Mitsui Petrochemical), a silicone rubber powder characterized by containing an epoxy group as a functional group is called Torefill E601 (Toray Dow Corning),
Each is available. In either case, it is desirable to add 5 to 80 parts by weight to 100 parts by weight of the epoxy resin as the base material. If it is less than 5 parts, no effect will be exhibited, and if it exceeds 80 parts, the heat resistance will decrease.

[0019] Furthermore, the following components can be added to the composition of the present invention as required. (1) Curing accelerator (2) Inorganic filler (3) Coupling agent (4) Mold release agent (5) Colorant, pigment, flame retardant

(1) A curing accelerator for accelerating the curing reaction between the epoxy resin and polyallylphenol or partially propenylated polyallylphenol. As a curing accelerator, imidazole type such as 2-methylimidazole,
DBUs such as phenol salts of phosphine-based diazabicycloundecene (DBU) such as triphenylphosphine;
systems etc. are used. Furthermore, when adding a maleimide resin, a radical polymerization initiator such as a peroxide may be added.

(2) Powdered inorganic fillers such as fused silica, crystalline silica, alumina, calcium carbonate, and glass fiber. The amount of filler added is preferably in the range of 30 to 85% by weight of the entire composition. If it is less than 30% by weight, mechanical strength will not be improved, and if it is more than 85% by weight, flowability will be lowered, leading to a possibility that workability will be lowered.

(3) When adding an inorganic filler, a coupling agent is used to improve compatibility with the resin. Examples include silane coupling agents such as 3-aminopropyltriethoxysilane, and titanium coupling agents such as tetraoctyl bis(phosphite) titanate. The amount of the coupling agent added depends on the type and amount of the inorganic filler used, the specific surface area, and the minimum area covered by the coupling agent, but in the present invention, it is preferably 0.1 to 15% by weight of the entire composition. .

(4) Carnauba wax, stearic acid and its metal salts, montan wax, etc. can be added as a mold release agent. (5) Brominated epoxy resin, antimony trioxide, titanium dioxide, etc. may be added as a flame retardant, and carbon black or the like may be added as a pigment.

The resin composition of the present invention can be prepared by heating the above-mentioned components at a temperature of about 60 to 120°C using a means such as a roll, kneader, or extruder. Further, in the present invention, after-curing after molding is preferably performed in order to complete the curing reaction of the uncured epoxy resin in the cured product. For after-curing after molding, heat treatment may be performed for a predetermined period of time in a constant temperature layer at approximately the same temperature as that during molding.

[0025]

EXAMPLES Next, the present invention will be explained with reference to Examples and Comparative Examples. The following raw materials were used. Base resin: Cresol novolac type epoxy resin Nippon Kayaku EOCN-1025 Curing agent: Polyallylphenol represented by formula (3) or partially propenylated phenol represented by formula (5) Modifier: Silicone modified epoxy resin Large Nippon Ink Kagaku SIN-620 In each example, other modifiers described for each example were also added.

The compositions of the Examples and Comparative Examples were prepared by kneading the raw materials together in a pressure kneader. In addition, the test pieces were prepared as follows. First, the composition obtained by kneading was made into an 8 mesh pass powder, this powder was transferred to a press mold, and heated at 200°C.
, 80 kg/cm2 for 20 minutes, and was further after-cured at 200°C for 8 hours.

Regarding the composition thus obtained,
Characteristic evaluation was performed as follows. Glass transition temperature: Measured using a thermomechanical analyzer (Shinku Riko). Bending strength: According to JIS K6911. Cracks: Sample after molding and cooling (10×
A cross section of 5 x 30 mm) was evaluated using a microscope. Water absorption rate: According to JIS K6911. Mold releasability: Measured the number of moldings and adhesive strength when repeatedly molded on a chrome plated plate. Adhesion: Resin was molded onto a 5 x 5 mm silicon chip, and the adhesion between the chip and the cured product was measured. Bleedout: Visually inspect the surface of the molded product using a stereomicroscope.

<Experiment A> Polyallylphenol represented by formula (3) was used as a curing agent.

Examples 1 to 13 The following epoxy-modified polyallylphenol was also added as a modifier. Epoxy modification rate 3 shown by formula (9)
The composition ratio and properties of 0% epoxy-modified polyallylphenol are shown in Tables 1 and 2.

[Table 1]

[Table 2] Comparative Examples 1 to 6 Comparative Examples 1 to 6 were carried out in the same manner as Examples 1 to 13 except that the composition ratio was changed. Table 3 shows the composition ratio and properties.

[Table 3] The flexibility of the cured product is improved by adding silicone-modified epoxy resin, and the amount added is preferably 5 to 80 parts by weight.
By using polyallylphenol as a curing agent, a resin composition with excellent hydrophobicity can be obtained. Furthermore, by adding 5 to 80 parts by weight of epoxy-modified polyallylphenol, an epoxy resin composition with excellent adhesiveness can be obtained.

<Experiment B> Partially propenylated phenol represented by formula (5) and having a propenylation rate of 10% was used as a curing agent. In addition, moisture resistance is added as a characteristic value,
This is shown as the defective rate in the attached Figures 1-8. Moisture resistance: Evaluation of defective rate after pressure cooker test (125°C, 2.3 atm) using aluminum wiring simulator.

Examples 14-22 The composition ratio and properties are shown in Tables 4 and 5.

[Table 4] Comparative Examples 7 to 10 The same procedures as Examples 14 to 22 were carried out except that the composition ratio was changed. Table 5 shows the composition ratio and properties.

[Table 5] From Examples 14 to 22 and Comparative Examples 7 to 10, the toughness of the cured products was improved by adding silicone-modified epoxy resin.
The mold releasability and flexibility are improved, and the addition amount is preferably 5 to 80 parts by weight.By using 30 to 120 parts by weight of partially propenylated polyallylphenol as a curing agent, a resin composition with excellent hydrophobicity can be obtained. Obtainable.

Examples 23 to 26 Experiments 14 to 22 were conducted in the same manner as in Experiments 14 to 22, except that a maleimide resin was further added as a modifier and the composition ratios of other components were changed. Maleimide resin: Bismaleimide Mitsui Toatsu Comparative Example 1
1, 12 The same procedure as Examples 23 to 26 was carried out except that the composition ratio was changed. Table 6 shows the compositions and properties of Examples 23 to 26 and Comparative Examples 11 and 12.

[Table 6] From Examples 23 to 26 and Comparative Examples 11 and 12, the heat resistance of the cured product was improved by adding maleimide resin, and the addition amount was preferably 5 to 30 parts by weight, and partially propenylated as a curing agent. By using polyallylphenol,
A resin composition with relatively excellent hydrophobicity can be obtained.

Examples 27-31 Polystyrene/polybutadiene/polystyrene end block copolymer Shell Chemical Kraton G-1
The same procedure as Examples 23 to 26 was conducted except that 652 was added and package crack was added as a characteristic. Package crack: 84-pin QFP is molded, 12
After moisture absorption treatment at 1°C for 24 hours, the occurrence of cracks was examined when immersed in solder at 260°C. Comparative Examples 13 and 14 The same procedures as Examples 27 to 31 were carried out except that the composition ratio was changed. The composition ratio and performance are shown in Table 7 together with Examples 27-31.

[Table 7] From Examples 27 to 31 and Comparative Examples 13 and 14, the flexibility of the cured product was improved by adding the polystyrene/polybutadiene/polystyrene end block copolymer, and the amount added was 5 to 80 parts by weight. By using partially propenylated polyallylphenol as a curing agent,
A resin composition with excellent hydrophobicity can be obtained.

Examples 32 to 36 As a modifier, an ethylene/propylene ternary copolymer was used instead of the terminal block copolymer. Japan Synthetic Rubber JS
Examples 27 to 31 except that R 57P was added.
I did the same thing. Comparative Examples 15 and 16 The same procedures as Examples 32 to 36 were carried out except that the composition ratio was changed. The composition ratio and properties are shown in Table 8 together with Examples 32-36.

[Table 8] From Examples 32 to 36 and Comparative Examples 15 and 16, the flexibility of the cured product was improved by adding the ethylene/propylene ternary copolymer, and the amount added was 5 to 80 parts by weight. By using partially propenylated polyallylphenol as a curing agent, a resin composition with excellent hydrophobicity can be obtained.

Examples 37 to 41 Ethylene/α-olefin copolymer instead of ternary copolymer Mitsui Petrochemical Tafmer PP-0280
The same procedure as Examples 32 to 36 was carried out except that . Comparative Examples 17 and 18 The same procedures as Examples 37 to 41 were carried out except that the composition ratio was changed. The composition ratio and properties are shown in Table 9 together with Examples 37-41.

[Table 9] From Examples 37 to 41 and Comparative Examples 17 and 18, the flexibility of the cured product was improved by adding the ethylene/α-olefin copolymer, and the addition amount was preferably 5 to 80 parts by weight. By using partially propenylated polyallylphenol as a curing agent, a resin composition with excellent hydrophobicity can be obtained.

Examples 42 to 46 Examples 37 to 4 except that epoxy group-containing silicone powder Toray Dow Corning Torefill E-601 was added instead of the α-olefin copolymer.
This was done in the same manner as in step 1. Comparative Examples 19 and 20 The same procedures as Examples 42 to 46 were carried out except that the composition ratio was changed. The composition ratio and characteristic values are shown in Table 10 together with Examples 42 to 46.

[Table 10] From Examples 42 to 46 and Comparative Examples 19 and 20, the flexibility of the cured product was improved by adding the epoxy group-containing silicone powder, and the addition amount was preferably 5 to 80 parts by weight.
By using partially propenylated polyallylphenol as a curing agent, a resin composition with excellent hydrophobicity can be obtained.

Examples 47 to 51 Silica Ryumori RD- was used instead of silicone powder.
The same procedure as in Examples 42 to 46 was conducted except that 8 was added and the viscosity was measured as a characteristic value by the flow tester method. Comparative Examples 21 and 22 The same procedures as Examples 47 to 51 were carried out except that the composition ratio was changed. The composition ratios and characteristic values are shown in Table 11 together with Examples 47 to 51.

[Table 11] From Examples 47 to 51 and Comparative Examples 21 and 22, the mechanical strength of the cured product is improved by adding silica, and the addition amount is preferably 30 to 85% by weight, and partially propenylated as a curing agent. By using polyallylphenol, a resin composition with excellent hydrophobicity can be obtained.

[0038]

[Effect of the invention] In the epoxy resin composition according to the present invention,
Polyallylphenol or partially propenylated polyallylphenol used as a curing agent effectively works to improve the heat resistance and hydrophobicity of the cured product, and silicone-modified epoxy resin is added to the epoxy resin used as the base resin. This improves flexibility and crack resistance.

[0039] Adhesion can be improved by adding epoxy-modified polyallylphenol, and furthermore, polystyrene/polybutadiene/polystyrene terminal block copolymer, ethylene/propylene rubber, ethylene/α as a flexibility imparting agent can be added. - By adding silicone rubber powder characterized by containing an olefin copolymer and an epoxy group as a functional group, crack resistance and mold releasability are improved, and heat resistance, flexibility, mold releasability and Simultaneously improving crack resistance and adding inorganic fillers also improves mechanical strength.

[Brief explanation of drawings]

[Figure 1] Examples 14 to 18 of Experiment B and Comparative Examples 7 and 8
In this section, the defective rate versus time when pressure cooker test (PCT) is performed is shown, and the moisture resistance of Examples and Comparative Examples is compared.

FIG. 2 shows a comparison similar to FIG. 1 in Examples 19 to 22 and Comparative Examples 9 and 10.

FIG. 3 shows a comparison similar to FIG. 1 in Examples 23 to 26 and Comparative Examples 11 and 12.

FIG. 4 shows a comparison similar to FIG. 1 in Examples 27 to 31 and Comparative Examples 13 and 14.

FIG. 5 shows a comparison similar to FIG. 1 in Examples 32 to 36 and Comparative Examples 15 and 16.

FIG. 6 shows a comparison similar to FIG. 1 in Examples 37 to 41 and Comparative Examples 17 and 18.

FIG. 7 shows a comparison similar to FIG. 1 in Examples 42 to 46 and Comparative Examples 19 and 20.

FIG. 8 shows a comparison similar to FIG. 1 in Examples 47 to 51 and Comparative Examples 21 and 22.

Claims (9)

[Claims] Claim 1: An epoxy resin is used as a base resin, [Chemical formula 1]
] A polyallylphenol having 1 to 6 repeating units containing a group represented by formula (1), or a partial propenyl having 1 to 6 repeating units containing a group represented by formula (2) polyallylphenol as a curing agent, 30 to 12 parts by weight per 100 parts by weight of epoxy resin.
0 parts by weight, and using silicone-modified epoxy resin as a modifier, 5 to 80 parts by weight per 100 parts by weight of epoxy resin.
An epoxy resin composition comprising parts by weight. 2. The composition according to claim 1, wherein the polyarylphenol is a polymer represented by formula (3). 3. The composition according to claim 1, wherein the polyarylphenol is a polymer represented by formula (4). 4. The composition according to claim 1, wherein the partially propenylated polyallylphenol is a polymer represented by formula (5). 5. The composition according to claim 1, wherein the partially propenylated polyallylphenol is a polymer represented by formula (6). [Claim 6] 5 to 80 parts by weight of an epoxy-modified polyallylphenol having 1 to 6 repeating units containing a group represented by formula (7), or [ 5 to 30 parts by weight of maleimide resin represented by formula (8),
or polystyrene/polybutadiene/polystyrene end block copolymer, or ethylene/propylene/
Unsaturated compound-based ternary copolymer or ethylene/α
- The composition according to claim 1, further comprising 5 to 80 parts by weight of an olefin copolymer or an epoxy group-containing silicone powder as a modifier. 7. The composition according to claim 6, wherein the epoxy-modified polyallylphenol is a polymer represented by formula (9). 8. The composition according to claim 6, wherein the epoxy-modified polyallylphenol is a polymer represented by formula (10). 9. The composition according to claim 1, further comprising 30 to 85% by weight of an inorganic filler based on the epoxy resin composition.