JPS5821417A - Curable epoxy composition - Google Patents

Abstract

PURPOSE:The titled composition, prepared by incorporating a curable epoxy resin with a specific block copolymer of an aromatic polymer with a specific organopolysiloxane and an inorganic filler, having improved crack resistance and thermal conductivity, and suitable for semiconductor element sealing materials, etc. CONSTITUTION:A composition prepared by uniformly incorporating (A) 100pts.wt curable epoxy resin with (B) 5-100pts.wt. block copolymer of (i) an organopolysiloxane of the formula[R<1> is H or monofunctional organic group; (a) is 1.8- 2.3; n is an integer 3-200], e.g. copolymer of dimethylsiloxane with methylphenylsiloxane and/or diphenylsiloxane, with (ii) an aromatic polymer e.g. phenolic novolak resin or epoxy novolic resin, and (C) 0-1,000pts.wt. preferably 150-400pts.wt., based on 100pts.wt. component (B). EFFECT:Improved mechanical and water resistance characteristics without reducing the glass transition temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin composition that can provide a cured product with improved crack resistance without impairing mechanical properties, electrical properties, or water resistance properties or lowering the glass transition point. 7-・411 To obtain an epoxy resin compound with excellent thermal conductivity (heat dissipation) required for packaging electronic and electrical parts, low stress, and excellent crack resistance. This provides a preferred basic composition.

Resins used for packaging electronic and electrical parts include epoxy resin, silicone resin, polybutadiene,
In addition to thermosetting resins such as polyurethane and phenolic resins, a wide variety of thermosetting resins are known depending on the use and purpose.

Among these, epoxy resin has mechanical properties, electrical properties,
It has heat resistance, adhesive properties, moldability, etc.

In particular, it has an overwhelming position as a resin sealing material for semiconductor elements such as diodes, transistors, ICs, and 1.8I, which have experienced remarkable technological growth in recent years, due to their excellent properties.

However, recently, with the trend toward thinner layers and miniaturization of electronic components, as well as an increase in the degree of integration, packaging materials have changed to 1! The required properties are also becoming more and more severe, and the situation is such that conventional materials of this type cannot fully satisfy them.

In other words, such fjW properties provide higher purity, advanced electrical properties, shorter molding cycles to improve productivity, high thermal conductivity for heat dissipation, and to reduce physical stress on elements. low stress, excellent crack resistance that can withstand severe thermal cycles and impacts, and especially high thermal conductivity and crack resistance (low stress) without reducing or improving other properties ) is extremely difficult to achieve. At present, no material has been obtained that combines the properties described above. Most of the epoxy resin materials known today for encapsulating semiconductor devices are bisphenol-based epoxy resins or novolac-type epoxy resins, non-crystalline epoxy resins, etc. It is made by filling a large amount of silica powder or crystalline silica powder, and is cured by heat using a crosslinking agent and a curing agent. Although things are known,
In each case, it is often necessary to sacrifice some or most of the other physical properties (in particular, it has been judged that it is no longer possible to satisfy contradictory properties at the same time by extending conventional technology). For example, to improve low stress and crack resistance, various flexibilizers (1,4-butanediol, polyoxyalkylene ether glycol, glycerin, polysulfide polymer, polyoxyalkylene glycidyl ether) are added. However, products made by blending these materials show a decrease in glass transition point, water resistance, heat resistance, etc.Also, large amounts of crystalline silica alone are used to improve thermal conductivity, but this does not improve heat resistance. There are problems in that not only the cracking resistance is decreased but also the stress or expansion coefficient is increased.

In short, in order to achieve both high thermal conductivity and crack resistance, which are currently the main objectives of the present inventors, the above-mentioned drawbacks have more or less appeared in the conventional techniques, and it has been extremely difficult to solve them.

In order to solve these difficult problems, the inventors of the present invention have conducted intensive research and found that a block copolymer with a moderate molecular structure consisting of an aromatic polymer and an organopolysiloxane is used as an epoxy resin. It has been found that dispersion or dispersion co-crosslinking is extremely effective, and in fact, the initial objective can be reliably achieved by this method, leading to the completion of the present invention.

In general, the siloxane bond energy that forms the skeleton of organopolysiloxane is extremely high (106 KcaJf/moj), and the siloxane bond has excellent heat resistance, and the free rotation of the siloxane bond not only provides excellent flexibility but also reduces the volume occupied by space. In addition, linear organopolysiloxane has stable properties over a wide temperature range, and can be fully expected to be effective as a flexibility imparting agent for epoxy resins. filed an application for permission regarding the technical ideas of Jinno Tane (#Gan-Sho 55-3360)
(Refer to No. 1) 0 Unlike other examples, namely Jubei Kaichi's flexibility-imparting agents, organopolysiloxane hardly melts into epoxy resins even at high temperatures, which makes it difficult to use for other flexibility-imparting agents. This is the basis for its characteristic that it does not cause a decrease in the glass transition point as seen in other agents.

However, if organopolysiloxane is used as it is, a sea-island structure with excellent dispersibility cannot be obtained.
In addition, because the sea-island structure is easily changed, problems such as a decrease in mechanical strength and easy moisture permeation are likely to occur.However, compared to other organic polymers, siloxane bonds are present on the silica surface. Since it has much better binding properties, it is quite possible to obtain products that can be put to practical use.

In order to more effectively utilize the excellent properties of organopolysiloxanes, the present inventors have carried out various research studies and found that block copolymers of aromatic polymers and organopolysiloxanes have excellent dispersibility and mechanical properties. The objective was achieved by developing an excellent modifier that shows almost no decrease in physical strength and has no change in moisture permeability.

That is, the present invention includes (a) 100 parts by weight of a curable epoxy resin (b)
An aromatic polymer is represented by the formula (in the formula, R is a hydrogen atom or a monovalent organic group, and 慇 is a positive number taking an average value of 1.8 to z3), and n is 3 to 2.
This relates to a curable epoxy resin composition comprising 5 to 100 parts by weight of a block copolymer comprising organopolysiloxane, which is an integer of 00, and (c) 0 to 1000 parts by weight of an inorganic photonic agent.
The present invention provides a composition suitable for packaging electronic components that simultaneously has high thermal conductivity, crack resistance, and low stress properties.

The organopolysiloxane-containing block copolymer that achieves the object of the present invention preferably has at least one functional group capable of reacting with an epoxy resin or a crosslinking agent in its molecule, and The bond between both segments is easy to hydrolyze, in order to obtain stability and long-term moisture resistance.
-5s-o-c-: bond needs to be removed. This is presumed to be suitable, for example, for packaging materials for conductor elements that require extremely high reliability over long periods of time even under high temperatures.

The composition according to the present invention will be explained in detail below. This epoxy resin is a curable epoxy resin consisting of epoxy resin and various curing agents, and there are no particular restrictions on the molecular structure, molecular weight, etc., as long as this epoxy resin can be cured with various curing agents as described below. For example, epoxy resins synthesized from various novolac resins including epichlorohydrin and bisphenol, alicyclic epoxy resins, or epoxy resins containing halogen atoms such as chlorine or bromine atoms can be used. Examples include epoxy resins.

In addition, 1. Due to the heat of use of the above-mentioned component (a), there is no problem in using a monoepoxy compound as appropriate, and examples of the monoepoxidized metal include styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, and ethyl glycidyl ether. , phenylglycidyl ether, allylglycidyl ether, octylene oxide, dodeceneoxy Y, etc. 〇The component (a) is not necessarily limited to only one type in its use (or a mixture of two or more types). In addition, as a curing agent, amine curing agents represented by diaminodiphenylmethane, diaminodiphenylsulfone, metaphenylene diamine, etc., phthalic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, etc. Examples include acid anhydride curing agents, or phenol novolac curing agents having two or more hydroxyl groups in one molecule such as phenol novolac and cresol novolac. There is no problem in using various curing accelerators such as imidazole or its derivatives, tertiary amine derivatives, phosphine derivatives, cycloamidine derivatives, etc. in combination for the purpose of accelerating the reaction between the epoxy resin and the epoxy resin. It goes without saying that it is essential to use the curing agent in the required amount to cure the epoxy resin.Next, the block copolymer as a component used in the present invention Coalescence has a remarkable effect on improving crack resistance, which is the main objective of the present invention, and this is a combination of an aromatic polymer and an organopolysiloxane represented by the above formula (1). It is what it is.

Regarding the crack resistance of JL1, a considerable effect is expected by adding and blending a block copolymer of a non-aromatic heavy metal body and an organopolysiloxane. On the other hand, the block copolymer, which is the component of the present invention, has the disadvantage that it tends to gradually migrate to the surface of the molded product over time due to its poor compatibility. Because it uses a combination, it has the advantage that compatibility with the epoxy resin is appropriately controlled.

The aromatic polymer constituting the block copolymer of component (b) is, for example, the general formula % formula %) 2 in this formula is the formula C, H, VqR, X, ・=-= (ll+ ``) group or a monovalent to divalent organic group containing a monovalent group derived from a benzene ring represented by the formula %().

R in formulas (li+) to (V) has 1 to 1 carbon atom
6 substituted or unsubstituted monovalent organic group (however, this R
does not contain an acid atom, a sulfur atom, a silicon atom, or a nitrogen atom). Specifically, R represents a methyl group, an ethyl group, a propyl group, a t-butyl group, a vinyl group, an allyl group, OR is a water atom or a carbon atom number of 1 to 6, exemplified by a phenyl group or a cyclohexyl group.
Examples of the group include the same groups as those exemplified for R above.

(2) is a monovalent organic group containing an oxygen atom, a sulfur atom, a silicon atom, or a nitrogen atom, such as an alkoxy group such as a methoxy group or an ethoxy group, ÷CR,
OH% +CB 2s i8H.

+C SuzumeCoo)I, 1000C Suzume-)-NCOlo
We can give υ etc.

In the above formula, R1, R2 and R3 each have the same meaning as described above, W is a hydroxyl group, an alkoxy group, an acyloxy group, etc., and U is an integer of 0 to 6.

X is a chlorine atom, a bromine atom, or a halogen atom of an iodine atom.

ps Qs rs ”s p's q's r', II
'G! Each integer from θ to 5, where p+q+r+s
= z ~ 5, p'+ q/+ r'10s' = 5 O
Q is +CB"□su" (here R3 is the same as above, t is the number of ships from 1 to 6), -〇-1-8-1-SO, -1CH.

cloudy (where R and t are the same as above) and (where,
R, X, r and S are groups selected from (same as above), etc.

X in formula (11) is an integer of 0 to 30.

In the above, aromatic polymers represented by the formula Z-Q-= were exemplified, but in the present invention, the aromatic polymer is
, ・=-=-Q-Z, Z-Z-, ,,,,,-Z-Z
.

Needless to say, those shown in 1 are also included.
Furthermore, 2 and Q may be the same group, but this does not go beyond the scope of the present invention, i.e., formula (It)
') Z-Qa-(Z-Q/-), -Z When expressed as TE, when 2 and Q are the same, α and β are each 0.

Examples of such aromatic polymers include those shown below.

X.

In the above 4r formula, 'EL s RSV% X% I)% 9
%rlm and R is the same or different monovalent organic group, including unsubstituted-valent hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, vinyl group, allyl group, phenyl group, etc. A group in which the hydrogen atom of is partially clouded or substituted with an alkyl group, mercapto group, amino group, aminoalkyl group, hydroxyl group, etc., such as -OH, OH, -CH, NHCH, CH2NH,, -O
H, CH, CH, NH, -CH, CH, 8H.

Examples include -C'H20H, OH, 8H, etc., hydroxyl groups, alkoxy groups such as methoxy groups, ethoxy groups, etc. O a is a number that takes an average value of 1.8 to 23.

In the present invention, this siloxane has a degree of polymerization of 3 to 20.
It is required that the degree of polymerization is in the range of 0.
It is difficult to impart sufficient crack resistance to a block copolymer obtained by using a material smaller than
On the other hand, siloxanes with a degree of polymerization greater than 200 have poor reactivity with aromatic polymers, making it difficult to obtain a uniform reaction product (block copolymer).

If you expect other properties, such as sufficient flexibility, by using this (-) component,
The siloxane is preferably linear, but
There may be no problem even if there is some degree of branching. There is no particular limitation on the bonding mode between the above-mentioned aromatic polymer and organopolysiloxane, but when reactivity etc. are taken into account, the reaction mode shown below is acceptable. can be given.

(W: halogen atom or a hydrolyzable group such as an alkoxy group, acyloxy group, amino group, amide group) (X: halogen atom) (3) H is -N-) (h: 0 to 6 (integer) The reaction examples listed here are examples of reactive groups and bonding modes for obtaining a copolymer of an aromatic polymer and an organopolysiloxane, but are not limited thereto.

In addition, since the copolymer having the type of bond shown in reaction example (1) has the disadvantage of being weak (unstable) against moisture, in the present invention, the aromatic polymer and the organopolysiloxane are It is preferable that the bonding be done in a bonding manner other than 5i-o-c9.

The block copolymers obtained here include those with the structure shown below. However, the person in the formula below is an aromatic polymer, B-4-A-B- person → 7
, B-AmB.

In addition, for the purpose of further preventing the migration of this copolymer to the surface of the molded product, it is preferable to introduce at least one reactive functional group into the copolymer. The group can be any group that can react with an epoxy resin, an amine type, a phenol type, or an acid anhydride type curing agent, and is not limited in type.

The siloxane content in the copolymer varies depending on the degree of polymerization of the siloxane and the blending ratio of the aromatic polymer and the organopolysiloxane, but is generally in the range of 15 to 80 qb.

Such copolymers can be obtained in various forms, from resin-like to rubber-like, depending on the degree of polymerization of siloxane and the content of siloxane.

It is essential to use this copolymer in an amount of 5 to 100 parts by weight per 100 parts by weight of the curable epoxy resin as component (a).

This is because if the amount of the copolymer used is less than 5 parts by weight, it becomes difficult to provide crack resistance and low stress properties, whereas if the amount is 100 parts by weight or more, the crack resistance and low stress properties become poor. However, on the other hand, the mechanical strength decreases.As the inorganic filler, which is the component (c), crystalline or amorphous silica can be cited as a typical filler. @mouth (manufactured by Degutsusa), Cab
-0-sil (Cabot Co., Ultrasil
Ultrafine powdered silica (usually has an average particle size of 1 to 30μ bait) commercially available under the trade name of (manufactured by Degutsusa)
, Ce1ite (manufactured by John Manville), lm5i
(manufactured by Illinois Minerals) Crystalline or amorphous quartz powder (usually having an average particle size of 1 to 30 μm) is an example. In general, ultrafine powdered silica has excellent reinforcing properties. However, since it tends to thicken and impede fluidity, it is not widely used for casting or molding, so when using it for these moldings, it is best to use quartz-based powder. Accordingly, various excellent properties can be imparted.

Additionally, fillers other than silica may be used depending on the use and purpose of the composition of the present invention, such as talc, mica, clay, kaolin, calcium carbonate, alumina, zinc, etc. Flower, baryta, glass balloon,
Glass fiber, aluminum hydroxide, calcium hydroxide,
Examples include asbestos, titanium oxide, iron oxide, etc.

These fillers are not limited to being used alone.
It goes without saying that more than one type of siloxane bond may be used in combination. The present invention is particularly effective in systems highly filled with silica fillers, since it not only has a function of improving dispersibility, but also has a positive effect on improving various physical properties of the compound when a large amount is blended.

This (/→ inorganic filler with an acid component is described in (4) above.
The iE content is preferably 1000 parts by weight or less per 100 parts by weight, preferably 150 to 400 parts by weight per 100 parts by weight of the total amount of components (a) and (b). If more than 500 parts by weight is used, dispersion becomes difficult, and rx <, processability, low stress,
This is because satisfactory results cannot be obtained in terms of physical properties such as crack resistance.

It should be noted that the curing formulation 644 consisting only of a polymer does not include the addition of (b) M to achieve the object of the present invention.

The composition according to the present invention may contain various additives depending on the use, purpose, etc., as long as it does not impede the purpose of the present invention, such as carbon black, lead-free, wollastonite, etc. fillers, release agents such as fatty acids and waxes, coloring agents such as carbon black, coupling agents such as epoxy silane, vinyl silane, boronic compounds, and alkyl titanates, and flame release agents such as antimony compounds. I can do it.

The cough composition is dry kneaded using a roll, niegu or screw set continuous mixer.
It can be mixed uniformly by kneading or solution method, etc., and this compound is used for compression, transfer, and injection molding, so-called molding compound, liquid, solution, or powder coating material.
It can be used in a wide range of manufacturing methods and applications such as botting materials.

Molded articles obtained from the composition of the present invention have excellent crack resistance and excellent electrical properties, heat resistance, and moisture resistance, and are therefore suitable for use as sealing materials for electrical parts, various paints, etc.・Next, examples of NN of the present invention will be given, and all parts in each example indicate parts by weight.・However, %Me is all OH, − and O6 reference example
! Refragment sensor, thermometer, stirring bar.

and a phenolic novolac tree 115 containing 1 tulphenol in the proportions shown in Table 1 (b) from 4 pro flasks C2 with an internal volume of 5001114 and a dripping σ-t.
Add 0.01 g of 2-ethylhextinol-modified chloroplatinic acid solution (abbreviated as P-1) with a concentration of 0F, 111 and 200 g of methyl isobutylchloride, dissolve the complete g ninovolak resin, and azeotropically desorb for 1 hour. Drop 5011 CI-
)! The dropwise addition took 0.20 minutes.

After the completion of the dropwise addition, the reaction was continued for another 2 hours, followed by washing with water and distilling off the solvent to obtain the desired product (prolag copolymer). (v9 Hoon modified novolak resin AS in Table 1).

Thereafter, prolag copolymers were obtained in the same manner using the novolac resins shown in Tables 1 and 25.

Reference example 2 Internal volume 3 equipped with temperature needle, nitrogen gas inlet tube and stirring bar
00-3 flask 62, -OHrO1irOIf
r8H 1gII, epoxy cresol novolac resin (Eoo
) f-102, manufactured by Nippon Kayaku) 26.5,9, 0.4 g of tovethylamine and 50 g of N,N-dimethylformamide were charged as a catalyst, and reacted at 80°C for 2 hours and 30 minutes under a nitrogen gas atmosphere. . After the reaction was completed, the solvent was distilled off to obtain a transparent high viscosity fluid (copolymer 41
2) a The solution viscosity of sO methyl ethyl keto ν is 23o8
(25°C) Reference Example 3 A reaction apparatus similar to Reference Example 1 was used.

-0HrOHrOH female, 32L epoxy cresol novolac resin (KOON-102
)53. ? , 5 g of methanol, and N,N-dimethylformamin ysop were charged into two reaction vessels C.

After reacting at 100°C for 5 hours, the solvent was distilled off to obtain a light brown transparent solid.
.

Note that the solution viscosity of this 501G methyl ethyl ketone was 35o8 (25°C).

Reference example 44 Reaction similar to Reference Example 1 [using 11].

-OH, -OH,0OOH209 Epoxy cresol novolak resin (KOON-102
) 53L N,N-Dimethylformamide under a nitrogen atmosphere at 130°C for 5 hours, and then the solvent was distilled off to obtain a pale yellow translucent resin (copolymerization period 14
).

The solution viscosity of this 504 methyl ethyl ketone is 25
o8 (25° C.) Reference Example 5 Various block copolymers were obtained by reacting with an epoxy cresol novolac resin using the amino Vakit ν of the tanks shown in Table 31.

Reference Example 6 Brominated phenol novolac resin 539 was dissolved in 1G011g of methyl ethyl ketone, and NaOH11,5,f
The sodium salt was synthesized by reacting with

After that, it was exchanged with 200% of dimethylformamide in a solvent tube,
Add this mixture dropwise to 130c (while holding and stirring).
-) from -O)! rOHr (88L of 5HrO1) was added dropwise over 30 minutes.Then the temperature was lowered to 150
The mixture was reacted with I for 8 hours. After the reaction, the precipitate was separated and neutralized by washing with water to obtain a block copolymer (A, 19). The resulting product was a brown, transparent, rubbery substance. The viscosity of this 5011 methylated methyl ketone solution is 16.5o11 (25°C) Reference Example 7 Pumified Phenol Novolac Resin 53I? 8577 was dissolved in methyl ethyl ketone 20011/, and 8577 was added dropwise from the dropping funnel over 30 minutes under the reflux WL temperature of methyl ethyl ketone with stirring for 11 minutes, and then methyl ethyl ketone y was distilled off. Raise the a degree to 150℃, 30
The reaction was carried out under reduced pressure of 7 mHIi for 5 hours.

After the reaction is complete and methyl ethylke)y is removed.

Neutralization by washing with water a: A browner translucent rubbery block copolymer (A20) was obtained.Reference Example 8 Phenol novolac resin (however, phenol molding material M1 obtained in Example 1 and Comparative Example 1 above) A thermal cycle test and general physical property measurements were carried out using two -12g samples as described below, and the results are shown in Table 4 below.

Cooling and heat cycle test〉 Thickness 0.35 - To glue cone - 1-16m x 4.5
- The pieces were cut into rectangles and glued to a 14-bi yIo frame (4210), and then transfer-molded using the molding materials obtained above at 160°C for 2 minutes, and then at 180°C for 4 hours. Bot cure, then cool at t-55℃ for 30 minutes, heat at 150℃ for 30 minutes, a so-called cold-heat cycle, and calculate the number of cycles until the defect rate due to cracks in the molding resin reaches 50. It was measured.

Film properties> Two molding materials obtained above were used to measure the bending strength, coefficient of expansion, glass transition point, water absorption, and resin stress. Transfer molding was performed at 60° C. and a pressure cuff of 0 Kf/i. The results were as shown in the table. However,
The measurement conditions for each physical property are as shown in C below.

Mechanical strength (measurement of bending strength: , TI8 K 6911 l double-layer, molding temperature 16
0℃.

Under the conditions of molding pressure cuff 0 Kf/cd, molding time 3 minutes, width 1
O-1 length! 00-1 Fully molded 4-thick bar, then 1
Measurements were made using test pieces that were after-cured for 4 hours in a constant temperature bath at 80°C.

Measurement of linear expansion coefficient: ASTM D696 using a test piece for measuring bending strength
Measured according to.

Measurement of Glass Transition Point A square column of 51 squares and 20 wm in length was cut out from the test piece for bending strength measurement, and measured using a dictometer (manufactured by Shinku Riko) to measure the linear expansion when the temperature was raised at a rate of 5°C per minute. The point of bending was defined as the glass transition point.

Measurement of water absorption rate: Molding temperature 160℃, molding pressure cuff G! /ai, after molding a disk with a thickness of 2-1 and a diameter of 70-10 mm under the conditions of 52 for a molding time of 3 minutes, the specimen was after-cured for 4 hours in a 180°C constant temperature oven section 2, and was subjected to a pressure Kutsuka test. 1
The sample was taken out at 21°C, 2 atm, and 500 hours, and the increase in weight from the initial stage was taken as the water absorption rate.

Measurement of resin stress: Piezoresistor whose resistance value changes due to stress Molded on a t-3-angle semiconductor chip f14 bin IO frame C double bonded, wire bonded with Au wire, external electrode C:
Measure the initial resistance value (Ro) of the connected element, add the resistance value (R) t- after sealing the solid element with resin under the molding conditions of 160°C, 7oKr/aJ, and molding time 3 minutes, R.R.
e) /Re? Resin stress @ Example 2 The molding material of Example 1 is 45 g2, and the amount of block copolymer used 1 is 5.0.50 mm each, y5 is 100 IEiI
Molding materials AI3-15 were obtained by treating molding materials AI3-15 in the same manner using the same composition except that IIs was changed by two (all products of the present invention).・Example 3 Epoxy cresol novolak resin with epoxy equivalent weight 220 (!eOON-1021 manufactured by Nippon Kayaku Pharmaceutical Co., Ltd. 4.3s, 35.5 parts of tetrahydro-phthalic anhydride, 5.25 parts of block copolymer, silane captsig) agent (KBM-403
, Shin-Etsu Chemical Department) 1.6 parts, crystalline quartz powder 375 parts, carbon black 1.21B.

Carnauba wax 1.0! In, stearic acid 1.5
IIs and 01. After uniformly mixing 1.0 part of azine, the mixture was kneaded in a heated two-bar at 90 to 100°C to obtain a molding material Al 6t-ye (product of the present invention).

Comparative Example 2 Epoxy cresol novolak resin with epoxy equivalent weight 220 (EOON-1021 manufactured by Nippon Kayaku) 6A, 5illi
, latosahydrophthalic anhydride 35.5! ! Is.

Silane coupling agent (KBM403, Shin-Etsu Chemical 111
) 1.3 parts, crystalline quartz powder 300 evil, carbon black 1! fB% carnauba wax 1! ! 1% stearic acid 1
．． 5th part and e,, z horse mackerel yo, 8!1st? A molding material Al 71r was obtained by processing in the same manner as in Example 3 (product of the present invention).

Example 4 Epoxy cresol novolac resin (KOON-1021 manufactured by Nippon Kayaku) 6A with an epoxy equivalent weight of 220, 20 parts of diaminodiphenylmethane, block copolymer A5,25
111. A molding material AI Ill was obtained by sufficiently kneading 1 part of a silane coupling agent (KBM403. product).

Comparative Example 3 Epoxy cresol novolak resin with epoxy equivalent of 220 (IlooN-102, manufactured by Nippon Kayaku)! 00 parts, diaminodiphenyl meta y 25 parts, silane coupling agent (
KBM403, Shin-Etsu Ka handmade) 1m, crystalline quartz powder 230
and stearic acid 2WAS were treated in the same manner as in Example 4 to obtain a molding material A19? (control product).

Molding material C obtained in Examples 2 to 4 and Comparative Examples 2 to 3 above
A cooling and heating cycle test was then carried out using the method described above and the results are shown in Table 5 of Tc.

Example 5 Epoxy cresol novolak resin (100N-1021 manufactured by Nippon Kayaku) 6γm with an epoxy equivalent weight of 220, 33 parts of phenol novolac resin (MP-120, manufactured by Gunei Chemical), block copolymer synthesized in Reference Examples 2 to 5 (A12~
! 8) with ZSS and silane coupling agent (KB), respectively.
M-403, Shin-Etsu Chemical Handmade) 1.6 parts, crystalline quartz powder, 3
75! ! B. Mix well 1.2 parts of carbon black, 1.2 parts of carnauba wax, and 1.0 part of 2-phenylimidal as a hardening accelerator, and knead with two rolls at 80 to 95°C. 5: , molding resin (A20-426
) were obtained (all products of the present invention).

Comparative Example 4 Miyako, 33 parts of phenol novolac resin (MP-120,
Gunei Chemical) Silane coupling agent (IBM-403,
1.3 parts (made by Shin-Etsu Chemical), 300 parts of crystalline quartz powder, 1 part of carbon black, carnauba wax x, 0.8 ffllt- of 2-phenylimidazole as a hardening accelerator
Mix well and knead in a hot two-bar at 80-95°C to obtain molding material A27 (control product).

Example 6 67 parts of epoxy cresol novolak resin (EOC!N-102, manufactured by Nippon Kayaku) with an epoxy equivalent weight of 220, 331 parts of phenol bresol novolac resin (MP-120, manufactured by Gunei Chemical), block copolymer ( Al 3) 5
．． 3! IIS, silane coupling agent (KBM-403
(Handmade by Shin-Etsu Chemical) 1, 4 parts, crystalline Ruimidag Zo, 8 parts were thoroughly mixed and kneaded with two rolls heated at 80 to 95°C. .

Example 7 62 parts of epoxy cresol novolak resin (100N-102, Nippon Kayaku Layer) with an epoxy equivalent weight of 220, 38 parts of phenol novolac resin (MP-120, manufactured by Gunei Chemical Co., Ltd.)
1B, block copolymer (Al 3) 43.3 parts, silane coupling agent (IBM-403, Shin-Etsu Kagaku Bag) 1
．． 91B, crystalline quartz powder 430s, carbon black 1
．． Molding material A29 was obtained by kneading 4 parts of carnauba rags, 1.4 parts of carnauba rags, and 1.1 ffls of 2-phenylimidazole in the same manner as in Example 6 to obtain molding material A29 (product of the present invention).

Example 8 75.6 parts of epoxy cresol novolac resin (KOON-102% manufactured by Nippon Kayaku) with an epoxy equivalent weight of 220, 2 parts of phenol novolac resin (MP-120, manufactured by Gunei Chemical)
4.4 parts, 100 parts of block copolymer (A13), silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical)2.
6ffll, crystalline quartz powder 600! flll, 2 parts of carbon black, carnauba wax Za, and 1.6 parts of 2-phenylimidazole were kneaded in the same manner as in Example 6. A molded molding material 30 was obtained (Invention product X).

Example 9 Block copolymer (419) I: synthesized from the block copolymer of Example 5 in Reference Example 6.

Molding materials were manufactured with exactly the same composition.

This molding material was subjected to a thermal cycle test; the result was 50
The number of cycles resulting in a failure rate of 1 was 0. Kaha,
``Molding materials were obtained with exactly the same blending composition.

The result of a cold/heat cycle test for this molding material was 509.
The number of cycles with a defective rate of 6 is 2,501.

Example 11 Epoxy cresol novolac resin (BOON-102
% Nippon Kayaku) 6jli, Phenolnoporatsuyuki MF
j (MP-120, manufactured by Kagaku Kagaku) 22 parts% a-bumized epoxy V resin (XP-8094, manufactured by Dow Chemical Company)
1211S, block copolymer (All) 25s, crystallinity strength 400B, 6.5 parts of acymon trioxide, silane coupler jig 1 (KBM-403, Shin-Etsu Chemical) 1.
7fflS, 1 carbon black, 1.3 carnauba wax! ilS, 2-phenylimidazole 1.0ff
i1f Two heat lamps are sufficient C: A molding material was obtained by kneading.

The properties of this molding material are as follows.

! ) 41 Tension coefficient 2.5X10 1/C (room temperature ~ 120
℃) 2) Bending strength at room temperature) 121/-# (1
50°C) 61cf/- 3) Glass transition temperature 175°C 4) Cold and hot Nikletes) (Nikle Lord 2ooψiguru until 150φ failure occurs) Example 12 Epoxy cresol novolac resin (E OON-10
2, Nippon Kano 6711S, phenol novolac resin (MP, -120, manufactured by Kagaku Kagaku) 32, block copolymer represented by the following formula 20111゜Me 〇H鵞-OH*-81-0HI o-o 0ONH −
0-OH snow-■ °Me Me -0-NHOO-O-00H, -81nH*-01ls
-Me Me Me M・ Crystalline quartz powder 350! IB, carbon black 1.2!
II.

A molding material was obtained from C2 by thoroughly kneading 1.2 parts of carnauba wax and 1.3 parts of o11Z Ami ν (manufactured by Shikoku Kasei).This molding material had a failure rate of 504 in the cold cycle test and a failure rate of 200. Example 13 Epoxy cresol novolak resin (BOON-10
2, Nippon Kayaku W) 67 parts, phenol novolac resin (
MP-120 Gunei Chemical) 331! Is.

Contains 20 parts of a block copolymer represented by the following formula: MeMe M・MeM6Me Crystalline quartz powder 35081s, OP-wa 7'lx 1
．． 5g! A molding material t* was prepared by thoroughly kneading IS* and 1.0 part of 2-phenylimidazole.

In the cooling heat cycle test of this molding material, the number of cycles until 50 failures occurred was 150 cycles.Patent applicant: Shin-Etsu Chemical Co., Ltd. Procedural amendment September 21, 1932 Patent Office Official Haruki Shimada 1, Incident Indication of Akebono @ 1 $ 4-year Tatami Patent Application No. 1184704 #2, ``Curable Epoxy resin composition 3'', relationship with the case of the person making the amendment Patent applicant name (! @ 4) Shin-Etsu Chemical Industrial Co., Ltd. 4, Agent Address: Nagai Building, 4-9 Nihonbashi Honmachi, Chuo-ku, Tokyo 103 [Telephone Tokyo (27G) 011511
．． 0@59) Contents of the amendment 1) @The "Claims" on pages 1 to 6 of the specification shall be amended as shown in the attached sheet.

2) 11th m [3rd row f) rt8~2-5J to ``t8-4
Correct it to 7J.

3) Page 19, line 7 and correct it.

4) Page 2s, lines 1-2 ” and correct it.

S) Correct [CHs C11=-C1l-8%-CHr-] on page 26, line 1 to C1,J "CHs-ICH-III-CH,-...".

CHs J 6) Change “18~1isJ” to “ts~” in the 6th line from the bottom of page 51.
2.7”.

7) On page 47, the entire leftmost column of Table 1 is corrected as follows: Correct column A10J.

On the same page, in the same table, in the row for "Style Novolac Resin", in the column for "Pushoku Copolymer Cliff 11", correct it with "".

10) Page s6, line 11 f) rwp-120J as “MP
-120''.

11) "Molding" on page 59, line 13 is corrected to "diffusion."

12) The rows of Example 4, Comparative Examples 2 and 5 in the rightmost column of Table 5 on page 65 are corrected as follows.

15) Correct "phenol cresol novolac resin" on page 67, line 11 of llE to "phenol novolak resin."

14) Change rxp-8094J on page 72, line 2 to “XD-8
Correct it to 0?4J.

15) Change l"2.5X10 1/℃J in line 11 of the same page to "2
．． 5×10 1/℃”.

that's all Scope of claims tfo Curable epoxy resin 100 parts by weight.

←) Aromatic polymer and formula (in the formula, R1 is a hydrogen atom or a monovalent organic group, 1 is a positive number with an average value of 18 to 2.7), and the percentage is an integer of 5 to 200. Curable epoxy resin composition 2 comprising 5 to 100 parts by weight of a block copolymer consisting of an organoborisitetraxane and (to) 0 to 1000 parts by weight of an inorganic filler. The curable epoxy resin composition according to claim 1, which is a block epoxy resin, has the aromatic polymer constituting the block copolymer having the general formula %) [in the formula %2] Formula C@HpvqR1rX.

(Here, R1 is a substituted or unsubstituted monovalent organic group having 1 to 6 carbon atoms, ■ is a monovalent organic group containing an oxygen atom, a sulfur atom, a silicon atom, or a nitrogen atom, and X is a Gen atoms s psql r and l are each O ~ 50
a mono- to tetravalent organic group or formula derived from a benzene ring represented by p+q+r+sx2~S (where R1, V and X have the same meanings as above,
Rs is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 6 carbon atoms.

C'1. #1. # and 1' are each an integer of Q-5,
However, p' + q' + r' + s' m 5)
A monovalent or divalent organic group containing a monovalent group derived from a benzene ring represented by Q is CRm, ÷1 (
Here KR" is the same as above, t is an integer from 1 to 6), -0-
1-S-, -SO嘗-1-O-C-, -0-C-0-,
-N-C-.

(herein, R1, and t are the same as above) and (herein, K R1%X, r and - are the same as above), X is an integer of O to gof)] Curable epoxy resin composition according to claim 1 or 2.Claim 1, wherein the aromatic polymer constituting the block copolymer is substituted or unsubstituted phenol novolac. The curable ebony resin composition according to claim 1 or 2, wherein the aromatic polymer constituting the block copolymer is substituted or unsubstituted epoxy resin composition. Curable epoxy resin composition according to Item 2.Claims 1, 2, and 5, wherein the organopolysiloxane constituting the block copolymer is dimethylpolysoxane.

The curable epoxy resin composition according to Item 4 or Item 5, wherein the organopolysiloxane constituting the block copolymer is composed of nan units in dimethylsiloxane and ν units in methylphenylsiloxane and/or diphenylsiloxane. The curable epoxy resin composition according to Claims 1, 2, 3, 4, or 5, which is a copolymer. Claim I! and organoborisi E1 are bonded with 3gt, ce! The curable epoxy resin composition according to claim 1, wherein the block copolymer is a copolymer having at least one functional group capable of reacting with the &) component in its molecule, The curable epoxy resin composition 1a block copolymer according to item 2, 3, 4, 5, j16, 7, or 8 is,! The curable epoxy resin composition 1t according to claim 1, which is a lute block copolymer. Curable epoxy resin composition

Claims (1)

[Claims] L(a) curable epoxy resin 100 parts by weight, (→
An aromatic polymer is represented by the formula (in the formula, R is a hydrogen atom or a monovalent organic group, and Maro is a positive number with an average value of 1.8 to 23), and n is 3 to 2.
Curable epoxy resin composition 2 comprising 5 to 100 parts by weight of a block copolymer comprising organopolysiloxane, which is an integer of 00, and 0 to 1000 parts by weight of an inorganic filler (/-).The epoxy resin is a novolac deaf epoxy resin. and/or a bisphenol type epoxy resin, wherein the aromatic polymer constituting the block copolymer has the general formula %) [wherein, 2 is the formula C, H, VqRrX. (Here, R6 is a substituted or unsubstituted monovalent organic group having 1 to 6 carbon atoms, generally a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 6 carbon atoms, and ■ is an oxygen atom. , a monovalent organic group containing a sulfur atom, a silicon atom, or a nitrogen atom; A mono- to tetravalent organic group derived from the shown benzene ring (here, 8, ■ and X are the same monomers as above, and R
is a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 6 carbon atoms, p', q', r' and S' are each an integer of 0 to 5, provided that p' + Q' + r' +
s' = 5), a monovalent or 2-valent organic group containing a monovalent group derived from a benzene ring represented by same,
t is an integer from 1 to 6), -〇-1-S-1-SO, -1(
Here, R edict and t are the same as above) and (here R'',
X, r and S are the same as above), and X is an integer of 0 to 30. 2. The curable epoxy resin composition according to claim 1 or 2, wherein the aromatic polymer constituting the block copolymer is substituted or unsubstituted phenol novola. Curable epoxy resin composition The curable epoxy resin composition according to claim 1 or 2, wherein the aromatic polymer constituting the block copolymer is a mono-substituted or unsubstituted epoxy novolak. & The curable epoxy resin composition according to claim 1, 2, 3, 4, or 5, wherein the organopolysiloxane constituting the block copolymer is dimethylpolysiloxane. 7. Claims 1, 2, and 3, wherein the organopolysiloxane constituting the block copolymer is a copolymer consisting of dimethylsiloxane units and methylphenylsiloxane and/or diphenylsiloxane units.
In the curable epoxy resin composition a according to item 4, item 4 or item 5, the aromatic polymer and organopolysiloxane in the block copolymer are bonded by -1;81-C; The curable epoxy resin composition i according to claim 1, wherein the block copolymer is a copolymer having at least one functional group capable of reacting with component (a) in its molecule. Claims 1, 2, and 3
Term, 4th term, 5th term, jl! Curable epoxy resin composition IL according to claim 1, wherein the curable epoxy resin composition lα block copolymer according to claim 6, 7 or 8 is a multi-block copolymer. The curable epoxy resin composition according to claim 1, wherein the inorganic filler is fused (anatomical) silica monocrystalline silica.