JPH03157417A - Brominated epoxy composition and flame-retardant epoxy resin composition for sealing semiconductor - Google Patents

Abstract

PURPOSE:To obtain a brominated epoxy compound suitable as a flame-retardant for resins, having excellent thermal stability by reacting a specific bisphenol type epoxy resin with a specific brominated polycarbonate oligomer in a specific ratio. CONSTITUTION:A bisphenol type epoxy resin (e.g. 4,4'-dihydroxybiphenyl) shown by formula I (X1 and X2 are H, halogen or 1-5C alkyl; m is 0-5) is reacted with a brominated polycarbonate oligomer shown by formula II (n is 1-10) containing a phenolic hydroxyl group at the end in a ratio of 0.05-0.5 phenolic hydroxyl group of the oligomer based on 1 epoxy group of the epoxy resin to give a brominated epoxy compound. 100 pts.wt. epoxy resin is blended with 3-50 pts.wt. of the compound to give an epoxy resin composition suitable for sealing semiconductors, providing cured materials having a small amount of extractable bromine content, excellent thermal stability and flame retardance.

Description

Detailed Description of the Invention (JL) Purpose of the Invention (Field of Industrial Application) The present invention provides a brominated epoxy compound that has excellent thermal stability and is useful as a flame retardant for hexagonal resin, and a tetrabrominated epoxy compound. The present invention relates to a flame retardant epoxy resin composition for semiconductor encapsulation, which contains a compound.

(Prior art) In recent years, JIII combustion of polymer materials has become one of the most important methods.

JIS standards, standards for automobile products, standards for electrical products.

Regulations are also established in UL standards, etc.

There are many flame retardants for ivy molecular materials.

Brominated epoxy compounds are suitable for use with epoxy resins, etc., from the viewpoint of compatibility with the base resin, reactivity, and not reducing the physical properties of the base resin.

It is widely used as a flame retardant for various synthetic resins such as phenol resins, polyester resins, and ABS resins.

However, generally commercially available brominated epoxy compounds such as tetrabromobisphenol diglycidyl ether and brominated phenol diglycidyl ether have a low thermal decomposition initiation temperature of 230 to 250°C; Sometimes generates large amounts of hydrogen bromide gas and bromine gas.

Therefore, a resin composition containing such a brominated epoxy compound as a flame retardant can be used at the time of mixing the paste resin and the brominated epoxy compound, and at the time of molding the resin composition after the mixing.
Or during heating when using the molded resin,
The bromine chemical compound causes thermal decomposition, and the generated gas causes deterioration or discoloration of the resin before or after molding, or gold bullion parts that are close to molding equipment or molded products can be manufactured at low cost. For sealing, a thermosetting resin molding compound is used instead of ceramic sealing or metal studs. So-called resin sealing has come to be used, and low-pressure molding epoxy resin has become the most commonly used resin molding material for the sealing.

However, such sealing resins have strict requirements regarding reliability, especially moisture resistance reliability.

In general, the moisture resistance of resin sealing greatly depends on the resin composition, and moisture absorption is caused by bulk moisture permeation, water intrusion from the interface,
Factors based on impurity levels, electrical characteristics, etc. are thought to be the dominant factors, and among these, the influence of impurities is thought to be extremely large.

Impurities that cause M wiring corrosion in moisture resistance tests of sealing resins include sodium, chlorine, and bromine, but sodium and chlorine are moisture resistant depending on the manufacturing method and purification of the raw materials. I have now been able to reduce the amount of time I listen to sex to a level where I almost never hear it. but,
Conventional brominated flame retardants, such as the above-mentioned tetrapromobisphelene A diglycidyl ether and brominated epoxy compounds such as brominated phenol-ac polyglycidyl ether, have poor stability and are susceptible to hydrolysis upon moisture absorption.・Bromide compounds such as beautifying hydrogen are likely to be generated due to thermal decomposition during powder flow.

There are also proposals to use flame retardants with good thermal stability such as 5' capromodiphenyl ether, brominated polycargenate oligomers, or their epoxy compounds, but these flame retardants do not work well with the paste resin. Due to poor compatibility, high melting point, and high viscosity.

Since it is difficult to mix uniformly with the paste resin, the flame retardant bleeds out during molding, and the physical properties of the paste resin deteriorate.

There are also proposals to use flame retardants other than brominated epoxy compounds to make the sealing resin flame retardant, but there are problems with moldability.

From the viewpoint of reliability, price, etc., the current situation is good.

Is bromine chemical a flame retardant for semiconductor encapsulation resin? The xyl resin/antimony trioxide system is numerically used as the best one.

(Problems to be solved by the invention) The present invention provides a brominated epoxy compound that is highly stable and excellent as a flame retardant, and contains an assimilated adduct, has excellent moisture resistance and thermal stability, and contains hot water extractable bromine. The object of the present invention is to provide a flame-retardant epoxy resin composition for semiconductor encapsulation in a small amount.

(bl Structure of the Invention (Means for Solving Problem 11!)) As a result of repeated research in order to solve the above-mentioned problems, the present inventors discovered that brominated polycarbons, which themselves have excellent thermal stability, can be used as nate oligomers. This objective was achieved using a brominated epoxy resin obtained by reacting a biphenol type epoxy resin that has excellent compatibility with a paste resin.

In other words, the bromine chemical technology of the present invention? Oxygen compounds are.

- Numerical formula (in the formula) (+ and X2 are each a hydrogen atom, a logan atom, or an alkyl group having 1 to 5 carbon atoms, and m is a number of 0 to 5 on average.) a brominated polycargenate oligomer having 1 phenolic hydroxyl group at the end of the bed represented by (where n is a number from 1 to 10 on average), and t''11 the biphenol. The phenolic hydroxyl group of the brominated polycargenate oligomer per 11 epoxy resins in the type epoxy resin is 0.
．． It is a compound formed by reacting at a ratio of 0.05 to 0.5.

Specific examples of the biphenol type epoxy resin represented by the above general formula (I), which is a raw material for obtaining the brominated epoxy compound of the present invention, include 4,4'-dihydroxybiphenyl, 3,3', 5. 5'-tetramethyl-4,4'-dihydroxybiphenyl, 3.3'.

5.5'-tetramethyl-4,47-dihydroxybiphenyl, 3.3',5.5'-tetraethyl-4,4
Dalicidyl ethers of biphenyls such as '-dihydroxybiphenyl and 3,3',5,5'-tetraguapyr-4,4'-dihydroxybiphenylnato are prepared.

In addition, in order to obtain the brominated polycarbonate oligomer of the present invention, the brominated polycarbonate oligomer represented by the above-mentioned formula, which is reacted with the biphenol type epoxy resin (I), can be synthesized by the following method. can.

That is, in the presence of an inert organic solvent and amines,
Tetrabromobisphenol A dissolved in an alkali metal hydroxide aqueous bath solution was reacted with phosdan while adjusting its − to 10 to IIKN. If hydrolyzed with water and an alkali metal hydroxide water bath, the -
A brominated polycarbonate oligomer of formula I is obtained.

In the above formula, when the value of n is smaller than l, the thermal stability of the compound decreases.

If the brominated epoxy compound becomes larger than 10, the softening point of the compound becomes too high, which not only makes it difficult to mix with, for example, a flame-retardant resin, but also reduces the production reaction of the brominated epoxy compound itself [i.e., - If the value of n is 1 to 1, the reaction with biphenol type epoxy resin will be difficult.
Those within the range of 0 are the best.

The reaction between the biphenol-type epoxy resin (I) and the brominated polycarbonate oligomer to produce the brominated epoxy compound of the present invention is performed using a biphenol-type epoxy resin (for one epoxy group of I+). , the proportion of phenolic hydroxyl groups in the brominated polycarnate oligomer is 0.05 to 0.5.If the reaction proportion of the A-purified polycarnate oligomer is too small,
The epoxy resin produced will have a low bromine content, reducing its flame retardant effect, and if the reaction rate is too high.

The produced niboxy resin has too high an epoxy equivalent.

In addition, it has a high softening point and viscosity, making it difficult to handle.

In addition, the reaction between the biphenol-type epoxy resin fl and the brominated polycarbonate oligomer.

It can be done according to the usual law. That is,
- Numerically speaking, a quaternary ammonium salt catalyst such as tetramethylammonium hydroxide or tetramethylano7nium chloride, or an imidazole catalyst, which is a reaction catalyst between an epoxy group and a 7-enolic hydroxyl group, is added to an epoxy resin with 7jt, Using 50-11000pp, Wr51i
! When Mayuzumi's biphenol-type epoxy resin +I+ and odor-accumulated polycarbonate oligomer are melted and stirred for 1 to 5 hours at a temperature of 100 to 200°C, the desired odor 51 epoxy compound of the present invention is obtained. It will be done.

The brominated epoxy compound of the present invention obtained in this way has excellent thermal stability in itself and is excellent in compatibility with the paste resin of the plant, and does not impair the heat resistance (glass transition point, etc.) of the paste resin. There is no O, 8! Excellent as a flame retardant for various thermosetting resins and thermoplastic resins.

In particular, the bromine chemical of the present invention per 100 parts by weight of epoxy resin? 3 to 501 lids, preferably 5 to 4
Epoxy resin compositions containing 0 parts by weight have outstanding flame retardancy and can be advantageously used in various applications requiring low flammability.

It is particularly excellent as a flame-retardant epoxy resin composition for semiconductor encapsulation.

In addition to epoxy resins, there are various other paste resins suitable for incorporating the brominated epoxy compound of the present invention as a flame retardant. example is.

Thermosetting resins such as phenolic resins; polyesters.

Polyolefin, polystyrene, acrylonitrile-butadiene-styrene resin (i.e. ABS resin), acrylonitrile-styrene resin (i.e. As resin), acrylic resin, vinyl acetate resin, polycargonate, polysulfone, polyenylene sulfide, yuzu nylon, polyurethane, etc. Thermoplastic resins are suitable, but Nixy resin is most preferred.

When blending the brominated epoxy compound of the present invention as a flame retardant into a paste resin other than these epoxy resins, the blending ratio is also 3 to 50 parts by weight, preferably #15 to 40 parts by weight based on the paste resin 1001 Department. In addition, when the brominated epoxy resin of the present invention is blended as a flame retardant into various paste resins such as epoxy resins, for example, antimony trioxide, antimony tetroxide, antimony pentoxide,
Pyroantimony soda, barium metaborate, zinc boron, aluminum hydroxide, zirconium oxide.

When an inorganic flame retardant aid such as molybdenum oxide is used in combination, the flame retardant effect can be further enhanced.

The epoxy resin for paste used to make 1 #l of the flame retardant epoxy resin composition for semiconductor encapsulation containing the brominated epoxy compound of the present invention as a flame retardant is ya
There are various things. For example, bisphenol As bisphenol F, resorcinol, hydroquinone, methylresorcinol, phenol nodelac, cresol nogolac,
An epoxy resin prepared from phenols such as resorcinol gelac and shrimp/-rohydro/- formula (where m is an integer of 3 or 4, R1 and R2 each have a carbon number of 1
~10 hydrocarbon groups. ) and trifunctional or tetrafunctional epoxy resins.

The epoxy*fat composition for semiconductor encapsulation containing the brominated epoxy compound of the present invention contains a curing agent, a curing accelerator, an inorganic filler, a mold release agent, and a coupling agent.

Flame retardant aids and the like can be appropriately blended.

As the curing agent, curing agents for epoxy resins used for drinking can be used, such as nogelac type phenolic resins such as novolac type phenol resins and nogelac type cresol resins; tetrahydrophthalic anhydride,
Examples include dispersed anhydrides such as pyromellitic anhydride; amines such as diaminodiphenyl meta/ and noamino diphenyl sulfone.

Examples of the curing accelerator include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; 2.4.6-) amines such as lis(tumethylaminomethyl)phenol and benzylmethylamine; Tributylphosphine.

Organic phosphorus compounds such as triphenylphosphine can be used.

Examples of the inorganic filler include fused silica.

Examples include crystalline silica, glass powder, alumina, zircon, etc. As mold release agents, natural wax,
Synthetic wax, higher fatty acids, gold II4 salts of higher fatty acids,
/f roughin, etc., and examples of combustion aids include antimony trioxide, phosphorus M, and phosphorus compounds.

The epoxy resin composition for semiconductor encapsulation of the present invention is prepared by blending the 44 wood chemical poxy compound of the present invention and various additives including the above-mentioned curing agent into the epoxy side fat for the paste.
Although various methods can be used for the expression, a method of melt-mixing using a mixing roll, an extractor, etc. is simple and preferable for the synthesis.

(Examples, etc.) Examples and comparative examples will be explained in detail below.

In addition, Examples 1 and 2 #i are examples of fabrication of the brominated epoxy compound of the present invention, and Examples 3 and 4 are similar to Examples 1 and 2.
This is an example of an epoxy resin composition for semiconductor encapsulation using each of the brominated epoxy compounds produced in .

Example 1 In a reactor equipped with a stirrer and a thermometer, 3.3<s, s
Glycidyl ether of '-tetramethyl-4,4'-dihydroxybiphenyl (trade name: Epicor, Yuka Shell Epoxy Co., Ltd.) YX-4000H, epoxy equivalent: 190
1/eq, - m=o in formula fl, 13]20
0Ii and 100j' of brominated polycarbonate oligomer [phenolic hydroxyl group equivalent xoooI//eq--n=3.8 in formula 12
After heating and stirring at 0°C, 0.4 I of a 1.0% aqueous solution of tetramethylammonium hydroxide was added, and the mixture was reacted at 160°C for 3 hours.

The ratio of the number of phenolic hydroxyl groups/the number of epoxy groups in this reaction was 0.095.

The obtained brominated nixy compound has an epoxy equivalent of 33
01/・qo, softening point 68℃, bromine content 18.8
%Met.

Example 2 3,3',5.5'-tetramethyl- in Example 1
Diglycidyl ether of 4,4'-dihydroxybiphenyl 200. For PO, diglycidyl ether of 4,4'-dihydroxybiphenyl (epoxy equivalent: 161
#/*q--n in general formula I formula = 0.15) 1
20.9 was used, and the reaction was carried out in the same manner as in Example 1. Number of phenolic hydroxyl groups in this reaction/
The ratio of epoxy bases is 0.134, which is 9.

The nine epoxy compounds obtained have an epoxy equivalent of 356 j
i/・q,, softening point is 76℃, bromine content is 25.7%
Met.

Comparative Example 1 Diglycidyl ether of bisphenol A (oiled shell epoxy Co., Ltd. Product name: Epicote 828, epoxy equivalent: 18611/・q,)
The reaction was carried out in the same manner as in Example 1 except that 200& was used.

The obtained epoxy resin has an epoxy equivalent of 3261//
@q, The softening point was 64°C, and the bromine content was 18.7%. Examples 3 and 4 Comparative Examples 2 to 4 As shown in Table 1, epoxy resin 1 various brominated epoxy compounds ( flame retardants), curing agents, curing accelerators, fillers,
Antimony trioxide, Shishimen treatment agent.

and a mold release agent were added. The blending amount of each brominated epoxy compound in this case was such that the amount of bromine was 1.011% by weight based on the entire composition in all cases except Comparative Example 4. Each of the formulations was then heated to 90°C using a mixing roll.
After melt-mixing for 5 minutes at a temperature of , each of the resulting molten mixtures was taken out in the form of a sheet, cooled, and pulverized to obtain each molding material.

The amount of extractable halodan, jf lath transition point, and thermal stability of each of the molding materials obtained were tested. The results are as shown in No. 1N, and each of the molding materials of Examples 3 and 4 had a small amount of extractable halogen, a high glass transition point, excellent thermal stability, and an epoxy resin for semiconductor encapsulation. I found it to be an excellent composition.

In particular, strong hydrogen bromide was generated from the molding material of Comparative Example 2 in the thermal stability test.

Although it was confirmed that beautifying hydrogen was generated by the force of the brominated epoxy compound (fuel agent), no hydrogen bromide was generated from the molding materials of Examples 3 and 4.

111 ≦-1'1 Notes to Table 1 *1... Yuka Shell Epoxy Co., Ltd. Product name Epicoat 180H65, Cresolno is a rack type epoxy resin, epoxy equivalent 201 *2... Yuka Shell Epoxy Co., Ltd. Product name: Tetrapromobinphenol A type yf? xy resin.

Epoxy fi385. Bromine content 49%*3...Phenol novolac manufactured by Gunei Chemical Co., Ltd., softening point 85°C *4...Triphenylphosphine*5...Tatsumorisha brand name RD-8 (bath-fused silica powder)
*6...Shin-Etsu Chemical Co., Ltd. product name KBM-403 (
Epoxysilane thread cutting agent) *7 Carnauba wax *θ... After hot water extraction at 125°C for 24 hours, it was quantified by ion chromatography analysis.

*9: Determined from the transition point of fever blood relatives.

Book 10: A vertical combustion test was carried out according to the VL 94 standard using Seiki test specimens.

tel Effects of the Invention The brominated epoxy compound of the present invention has excellent thermal stability and generates little hydrogen bromide during heating or moisture absorption, making it useful as a flame retardant. Furthermore, an epoxy resin composition containing this brominated epoxy compound has a small amount of extractable bromine and provides a cured product with excellent thermal stability and flame retardancy, so it is particularly excellent for semiconductor encapsulation.

Claims (2)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, X^1 and X^2 are each a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, and m is the average There are biphenol type epoxy resins represented by the general formula ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (where n is a number from 1 to 10 as an average value). A brominated polycarbonate oligomer having a phenolic hydroxyl group at the end thereof is reacted with a brominated polycarbonate oligomer having a phenolic hydroxyl group at the end thereof in a ratio of 0.05 to 0.5 phenolic hydroxyl groups of the brominated polyoligomer per epoxy group of the biphenol type epoxy resin. Brominated epoxy compounds. (2) A flame-retardant epoxy resin composition for semiconductor encapsulation, comprising 3 to 50 parts by weight of the brominated epoxy compound according to claim 1, based on 100 parts by weight of the epoxy resin.