JPS61264018A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition for the sealing of semiconductor, having decreased internal stress in the sealing material and excellent heat-shock resistance, reliability in moist state and moldability, by compounding an epoxy resin composition with a specific phenol-modified silicone compound. CONSTITUTION:The objective composition can be produced by (1) reacting (A) an organic silicone compound of formula I (R1 is H, methyl, etc.; R2 is 1-5C alkylene; X is epoxy-containing organic group; Y is functional group containing recurring units and is oxyethylene polymer, oxypropylene polymer, etc.; l, m and n are integer) or a combination of the silicone compound with an organic silicone compound of formula II (o and p are integer) with (B) an organic Si compound of formula III (Z is functional group reactive with epoxy, e.g. mercapto, amino, etc.; R3 is 2-5C alkylene; R4 is methyl or ethyl; q is 0-2) and (C) a phenolic resin and, (2) compounding the resultant phenol-modified silicone compound with an epoxy resin, phenolic resin and inorganic filler.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides an epoxy resin composition comprising an epoxy resin, a phenol resin, and an inorganic filler, which contains at least one organosilicon compound, an organosilicon compound, and a phenol resin. The mixture is made with a phenol-modified silicone compound that has been reacted in advance, and is excellent in reducing the internal stress of sealed molded products and improving moisture resistance reliability.Moreover, there is no decrease in moldability or strength of the composition, and it is suitable for use in electronic components such as semiconductors. The present invention relates to an epoxy resin composition for semiconductor encapsulation with excellent sealing properties.

(Prior art) In recent years, most semiconductors (hereinafter referred to as process 0) have been encapsulated with resin, and epoxy resin compositions have become mainstream in terms of adhesiveness with elements and cost. It becomes. These require technical improvements necessary to maintain the characteristics of semiconductors. Among these, two important issues are improving moisture resistance reliability and reducing internal stress generated from distortion due to (3') curing shrinkage of the resin and the difference in thermal expansion coefficient between the resin and the element.

In particular, due to the recent increase in the integration of ICs, the size of devices has increased, and cracks in the resin due to internal stress and internal stress during thermal shock have become a major problem.

For this reason, various studies have recently been conducted with the aim of reducing this internal stress, and methods for reducing internal stress include: - lowering the coefficient of thermal expansion of the resin to be close to the coefficient of thermal expansion of the element; ■ increasing the modulus of elasticity. Examples include lowering.

The former is generally done by adding an inorganic filler with a low coefficient of thermal expansion to the resin, but since the elastic modulus increases, internal stress cannot be sufficiently reduced, and if the filling is increased, molding becomes difficult. This results in problems of poor properties and reduced fluidity. The latter is achieved by adding a flexibility imparting agent to the resin. This can be done by adding a rubber component (Japanese Unexamined Patent Publication No. 57
-131223 publication, etc.), series with flexibility
□ Addition of corn compounds is practiced.

In particular, silicone compounds hold great promise as they have superior heat resistance and less impurities than ordinary rubber.

The conventional technology for silicone compounds is to add silicone compounds that are not reactive with resins (Japanese Patent Laid-Open No. 58
-219218, etc.) or a silicone compound having a functional group reactive with the resin (Japanese Unexamined Patent Application Publication No. 56-1989).
145942, JP-A-58-138730, etc.). However, these results do not show a significant reduction in internal stress, which is thought to be due to the following problems. In other words, silicone compounds that are not reactive with resins have a weak bonding force at the interface with the resin, and silicone compounds and resins are inherently poorly compatible, so it is thought that this is a major cause of their inability to disperse well. It is thought that the silicone compound having the reactive functional group Z also had poor compatibility with the resin, and therefore did not produce a significant effect.

(Problems to be Solved by the Invention) The present invention solves these drawbacks, and provides a phenol-modified silicone compound, which is obtained by reacting at least one specific organosilicon compound, a specific organosilicon compound, and a phenol resin. To provide an epoxy resin composition for semiconductor encapsulation which greatly reduces the internal stress of the encapsulation material by incorporating it into the epoxy resin composition, and which also has excellent heat shock resistance, moisture resistance reliability, and moldability. It is something.

(Means for solving the problems) 1. That is, the present invention consists of: (a) Epoxy resin (1)) Phenol resin (Q) An organic silicone compound represented by the following formula [1] or the following formula] and [ A phenol-modified silicone compound which has been reacted in advance with a combination of an organic silicone compound represented by [2], a silane coupling agent represented by the following formula [6], and a phenol resin.

Z-R3-8i -noR,) 3-9
Formula [3] (R4)q (In formula [1] or formula (2), R represents hydrogen, a methyl group, an ethyl group, or a phenyl group, R2 represents an alkylene group having 1 to 5 carbon atoms, and X is an epoxy group-containing organic group, Y is a functional group having a repeating unit, and indicates an oxyethylene polymer, an oxypropylene polymer, or an oxyalkylene polymer that is a copolymer thereof.Also, Y is a direct functional group. represents a mercapto group, an amino group, or a ureido group; R3 represents an alkylene group having 2 to 5 carbon atoms; R4 represents a methyl group or an ethyl group; q represents an integer from 1 to 6; d) It is characterized by containing an inorganic photostimulant.

The present invention will be explained in detail below.

The organic silicone compound used in the phenol-modified silicone compound of the present invention has the general formula % where R is hydrogen, a methyl group, an ethyl group, or a phenyl group, and X represents an organic group containing an epoxy group; There are no particular restrictions as long as it has the following.

For example, etc. At this time, it is necessary that at least one epoxy group exists in one molecule of the organic silicone compound, and , m, n, o, and p are integers.

Next, R2 represents an alkylene group with a P prime number of 1 to 5, and Y represents a functional group having a repeating unit and represents an oxyethylene polymer, an oxypropylene polymer, or an oxyalkylene polymer that is a copolymer thereof. . Also, Y is R
It may be directly bonded to the silicon atom without bonding to 2.

The degree of polymerization of these oxyalkylene polymers is 5 to 500.
Preferably it is 10-300. If the degree of polymerization is less than 5, no compatibility effect will be observed, and if it exceeds 500, the strength of the epoxy resin itself will decrease, and the moisture resistance reliability will also deteriorate, causing problems. The ratio of these polymers to the total organic silicone compound represented by formula (2) or a combination of formulas (1) and [2] is 2 to 50% by weight. If it is less than this, the compatibility with the resin will deteriorate, and if it exceeds this, the strength and moisture resistance of the resin itself will decrease, which poses a problem.

Further, the epoxy equivalent of the organic silicone compound represented by formula [1] or formula (2) of the present invention is 500 to 2000.
A value of 0 is preferable; if it is less than this, R-ru formation may occur during the preliminary reaction with the 7-enol resin, and if it exceeds this, the adhesion at the interface with the resin will be weakened, resulting in a decrease in heat shock resistance. In addition, the molecular weight of these organic silicone compounds is preferably 2000 to 20.0000; if it is less than this, the effects of stress reduction and heat shock resistance will not be recognized, and if it exceeds this, the strength of the resin itself will decrease, causing problems. arise.

Furthermore, the terminal groups of the organosilicone compound of formula [1] or formula [2] are not limited to %, but include -OR and -R.

-03i(ft)3 and ・81(R)3 (R is hydrogen,
Those represented by an alkyl group such as a methyl group or an ethyl group, an allyl group such as a phenyl group, an epoxy group-containing organic group, or a male-nyl group-containing organic group are preferred.

Next, when using the organosilicone compounds of formula [1] and formula [2] together, as long as the above ratio of oxyalkylene polymer is satisfied, there is no problem even if they are mixed in the following ratios. It is not a restriction.

The amount of the phenol-modified silicone compound added is 5 to 50 parts by weight, preferably 7 to 4'0 parts by weight, per 100 parts by weight of the epoxy resin. If the amount added is less than 5 parts by weight, the effect of reducing internal stress and improving moisture resistance reliability cannot be sufficiently obtained, and if it exceeds 50 parts by weight, it is not preferable because it will adversely affect the strength and moldability of the resin itself.

The organosilicon compound to be added to the diphenol-modified silicone compound is not particularly limited as long as it is represented by the formula [■]. 2 represents a functional group that reacts with an epoxy group, such as a mercapto group, an amino group, or a ureido group; Rr5 represents an alkylene group having 2 to 5 carbon atoms; and R4 represents a methyl group or an ethyl group.

q represents an integer from 0 to 2. The ratio of formula [3] to the organic silicone compound of formula (1) and formula [2] is not limited as long as it is based on the stoichiometry of the epoxy groups of these organic silicone compounds, but preferably these It is preferable to add the silane coupling agent in an amount of 0.2 to 10 times, more preferably 0.5 to 5 times, the number of moles of the epoxy group.

If the amount added is less than this, the effect on the spreading properties of the silicone compound will be small, so moldability will not be improved, and the effect on stress reduction and heat shock resistance will also be weakened. If it exceeds this, problems arise such as a decrease in moisture resistance reliability and an increase in the occurrence of flash during molding.

The method for producing the thunol-modified silicone compound is as follows.

Solvent 8・1°1 dissolution 1 system T h tx b h 7),
Melted egg j series 0 place.

If the organic silicone compound of formula [1] or formula [2], the organosilicon compound of formula [3]'', and the phenol resin are dissolved in a solvent such as methyl ethyl ketone, methyl isobutyl ketone, etc. , Preferably, a catalyst such as triphenylphosphine is added to this, and after heating and stirring for a predetermined period of time at a rapid flow temperature of the solvent, the solvent is distilled off. In the case of no solvent, the phenol resin is heated at 120 to 160°C. Preferably, a catalyst such as triphenylphosphine is added thereto, and then the organosilicone compound and the organosilicon compound are added and reacted for a predetermined period of time with stirring.At this time, the epoxy group of the organosilicone compound is It is preferable to react with a phenolic resin or an organosilicon compound in an amount of 50 or more in terms of heat shock resistance, low stress, and resistance to bleeding into a molded article or mold.

The phenol-modified silicone compound obtained in this way is well dispersed in the epoxy resin, is well compatible with the resin at the interface, and has strong adhesion to the resin due to chemical bonds, and when molded, the surface of the molded product The ability to lead into the mold is reduced.

The epoxy resin used in the present invention is not particularly limited in molecular structure, molecular weight, etc., as long as it has at least two or more epoxy bonds in its molecule.

Examples include bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc., but in this case, it is preferable to use one with less impurities and hydrolyzable chlorine.

Next, examples of the phenol resin used in the pre-reaction with the organic silicone compound or as a curing agent include phenol novolac resins and cresol novolac resins. Although there are no particular limitations on the amounts used, it is necessary to add the epoxy group and the curing agent in a stoichiometric amount of 2.

Examples of inorganic photonic agents include powders such as crystalline silica, fused silica, calcium silicate, alumina, calcium carbonate, talc, and barium sulfate, or glass fibers, but usually crystalline silica or fused Silica is used. Furthermore, spherical silica can be used to improve the fluidity of the composition and wear resistance of molds during molding, and low α-ray silica can be used to prevent soft errors when sealing memories etc. It is also possible to use The blending ratio of these inorganic photonic agents to the entire composition varies depending on the selected resin content, but generally it may be about 150 to 450 parts by weight based on 100 parts by weight of the resin content. If it is less than 150 parts by weight, the coefficient of thermal expansion and molding shrinkage will be low, and the thermal conductivity will be low, and if it exceeds 450 parts by weight, there will be disadvantages of decreased fluidity and increased mold wear.

Other ingredients that may be added as necessary include a silane coupling agent such as γ-glycidoxypropyltrimethoxysilane, a curing accelerator such as imidazoles, phosphines, preferably triphenylphosphine, and pigments such as carbon black. , a mold release agent such as Montana wax, carnauba wax or Hoechst wax, and a flame retardant such as brominated epoxy resin or antimony trioxide.

The resin composition of the present invention can be obtained by stirring and mixing each component and additives in a lamixer, kneading with heated rolls, cooling, and pulverizing.

(Example) Examples 1 to 8 Organosilicone compounds and organosilicon compounds having the structures shown in the table were added in the amounts shown in the table, 40 parts by weight of phenol novolak resin and 2 parts by weight of triphenylphosphine skin, respectively. The reaction was carried out in a solvent or without a solvent. As a solvent, the above was added to 40 parts by weight of methyl isyptyl ketone, and after reacting at 120°C for 3 hours, the solvent was removed by distillation.
The mixture was allowed to react for 3 hours. After grinding the resulting product with a Henschel mixer, mix it with other ingredients in the proportions shown in the table (parts by weight).
They were mixed together using a mixer. As for the phenol resin, the insufficient amount was added to the amount shown in the table. This mixture is then kneaded with heated rolls,
After cooling, it was crushed to produce eight types of molding materials.

Comparative Examples 1 to 7 Seven types of molding materials were produced using the various organic silicone compounds shown in the table in the proportions shown in the table in the same manner as in the examples, and evaluated. At that time, for comparison purposes, as shown in the table, the production method was also conducted without pre-reacting with the phenol resin.

1) Stress evaluation In order to evaluate the internal stress applied to the semiconductor element, a piezoresistive element (the resistance value changes due to stress - formed on a 2D resistor 7 semiconductor chip) was set in a frame of a 16-bin D type P type C type. Each composition was then transfer molded, and the stress applied to the element was measured from the change in resistance.

2) Heat shock resistance evaluation A 16-bin lead frame with an island size of 4 x 7.5 m was transfer molded using each composition.
Pin D type P type molded body with liquid at -196°C and +260°C
The molded product was repeatedly immersed in a liquid for 30 seconds at a time, and the crack occurrence rate on the surface of the molded product was determined from 50 samples.

3) Moisture resistance evaluation Using each composition, a device having aluminum wire electrodes facing each other was transfer molded, and the sealed sample was subjected to a direct current of 20°C between the electrodes at a temperature of 125°C and under a steam pressure of 2.5 atm. A bias voltage of (2) was applied, and the open failure rate of the aluminum wire over time was determined from 50 samples. This test is called y, -BPOT (bias pressure test). In the same way, testby was conducted under non-bias conditions, and this test) Y PC
It is called T (pressure test).

To +o ward (a) a) +o - II II II II II II
II Theory S Field Theory Item q(
−−〇−) (−〜−１) .

(Effects of the Invention) As explained above, the present invention provides a sealed molded product by using a composition of an epoxy resin, a phenol resin, a filler, and a phenol-modified silicone compound. In addition, there is no decrease in moldability or strength of the composition, and it exhibits excellent effectiveness in sealing electronic components such as semiconductors.

Patent Applicant Denki Kagaku Kogyo Co., Ltd. Procedural Amendment June 19, 1985 Director General of the Patent Office Manabu Shiga 1, Indication of Case 1985 Patent Application No. 1 or 691 2, Name of Invention Epoxy Resin Composition 6 , Relationship with the person making the amendment Patent applicant address 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Name (3
29) Detailed explanation of the invention column 5 of Denki Kagaku Kogyo Co., Ltd. specification, contents of amendment 1) "Silane coupling agent" in lines 5-6 on page 7 and line 2 on page 13 of the specificationヲCorrect to ``organosilicon compound.''

2) Lines 16-17 of page 12 of the specification are corrected as follows.

"q represents an integer from 0 to 2. Formula [1] and formula [
The ratio of the organosilicon compound of formula [3] to the organosilicon compound of formula [2] is as follows.'' Procedural Amendment November 2G, 1985 □ - Commissioner of the Japan Patent Office
Michibe Uga 1. Indication of the case 1985 Patent Application No. 103691 □2. Name of the invention Epoxy resin composition 3. Person making the amendment Relationship to the case Patent applicant 100 Address 1 Yurakucho, Chiyoda-ku, Tokyo Claims column and Detailed description of the invention column 5 of the specification of Chome No. 4-1, Attachment 1 of the content of the amendment, page 9 of the specification, formula [2] bottom 2nd line (7) r 'R
Correct it to j k rRlj.

2. Change "such as" to "1" in the first line of page 12 of the specification.
And, in the 19th line, ``Academic theory'' is corrected to ``Academic theory''.

6. "Silicone compound" in the first line of page 12 of the specification is corrected to "organosilicone compound," and in the fifth line of the specification, "简" and "to" are corrected.

4. The property column [Heat shock resistance] in the table on page 21 of the specification has been corrected to read "Heat shock resistance."

Do uterus name eirikoro-, Yb criminal, y5・口, 屹っっりりりえょうう6 Claims r (1) (a) Epoxy resin (b) Phenol resin (c) Organic resin represented by the following formula [1] A phenol-modified silicone compound obtained by reacting a silicone compound or a combination of organic silicone compounds represented by the following formulas [1] and [2], an organic silicon compound represented by the following formula [3], and a phenol resin in advance.

(In formula [1] or formula [2], R represents hydrogen, methyl group, ethyl group, or phenyl group, R3 represents an alkylene group having 1 to 5 carbon atoms, ■ is an epoxy group-containing organic group, Y is a functional group having a repeating unit, and represents an oxyethylene polymer, an oxyzolopyrene polymer, or an oxyalkylene polymer that is a copolymer thereof.Y may also be directly bonded to a silicon atom. +
m+ n+ 0+ p each represent an integer. ceremony〔ro〕
In the organosilicon compound represented by 2, 2 is a functional group that reacts with a modified oxygen group, such as a mercapto group, an amino group, or a ureido group, R3 is an alkylene group having 2 to 5 carbon atoms, and R4 is a methyl group or an ethyl group. shows. q represents an integer from 0 to 2. ) (dl An epoxy resin composition for semiconductor encapsulation, which contains an inorganic photonic agent.

(2) The oxyalkylene polymer contained in the organosilicone compound represented by formula [1] is 2 to 2 of the entire organosilicone compound represented as formula [1] or a combination of formula [1] and formula [2]. The epoxy resin composition for semiconductor encapsulation according to claim 1, characterized in that it has a weight ratio of 50% by weight.

(3) The epoxy equivalent of the organic silicone compound represented by formula [1] is 500 to 20. The epoxy resin composition for semiconductor encapsulation according to claim 1, which is ODO.

(4) The epoxy equivalent of the organic silicone compound represented by formula [2] is 500 to 20. The epoxy resin composition for semiconductor encapsulation according to claim 1, which is DOO.

(5) The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the organic silicone compound represented by formula [1] has a molecular weight of 2000 to 200 [100].

(6) The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the organic silicone compound represented by formula [2] has a molecular weight of 2,000 to 200,000. ” -1^

Claims (6)

[Claims] (1) (a) Epoxy resin (b) Phenol resin (c) An organic silicone compound represented by the following formula [1] or a combination of organic silicone compounds represented by the following formulas [1] and [2], and the following formula A phenol-modified silicone compound obtained by reacting the organosilicon compound represented by [3] with a phenol resin in advance. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Formula [1] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Formula [2] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Formula [3] (Formula [1] or Formula [ 2], R_1 represents hydrogen, methyl group, ethyl group or phenyl group, R_2 represents an alkylene group having 1 to 5 carbon atoms, X is an epoxy group-containing organic group, Y is a functional group having a repeating unit,
Indicates an oxyalkylene polymer that is an oxyethylene polymer, an oxypropylene polymer, or a copolymer thereof. Further, Y may be directly bonded to the silicon atom. l,
m, n, o, and p each represent an integer. In the organosilicon compound represented by formula [3], Z is a functional group that reacts with an epoxy group, and represents a mercapto group, an amino group, or a ureido group;
_3 represents an alkylene group having 2 to 5 carbon atoms, and R_
4 represents a methyl group or an ethyl group. q represents an integer from 0 to 2. ) (d) An epoxy resin composition for semiconductor encapsulation containing an inorganic filler. (2) The oxyalkylene polymer contained in the organosilicone compound represented by formula [1] is the 2- to 50% by weight of the epoxy resin composition for semiconductor encapsulation according to claim 1. (3) The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the organic silicone compound represented by formula [1] has an epoxy equivalent of 500 to 20,000. (4) The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the organic silicone compound represented by formula [2] has an epoxy equivalent of 500 to 20,000. (5) The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the organic silicone compound represented by formula [1] has a molecular weight of 2,000 to 200,000. (6) The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the organic silicone compound represented by formula [2] has a molecular weight of 2,000 to 200,000.