JP2823654B2 - Resin composition for semiconductor encapsulation - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a resin composition for semiconductor encapsulation having a high glass transition point (hereinafter referred to as Tg), excellent moisture resistance, excellent compatibility, and excellent low stress characteristics. It is about.

(Prior Art) In recent years, epoxy resin compositions are generally used for sealing semiconductor elements such as ICs, LSIs, transistors, diodes, and the like, electronic circuits, and the like, from the viewpoint of characteristics, cost, and the like.

However, the trend toward mass production of electronic components, high integration, and surface mounting has been progressing, and accordingly, the demand for sealing resin has become strict.

In particular, cracks are likely to occur in the equipment due to chip enlargement due to high integration, thinning of packages and solder immersion (200 to 300 ° C) during surface mounting, and semiconductors are required to improve reliability. As a sealing resin, low stress characteristics and heat resistance are strongly desired.

Epoxy resin is currently the mainstream resin for semiconductor encapsulation, but in terms of heat resistance, improvement is limited as long as epoxy resin is used, and a highly reliable resin after solder immersion during surface mounting can be obtained. Not.

In order to cope with these solder heat resistances, it is desired that the resin has low stress, high Tg, and a temperature higher than the solder bath temperature.

As a resin having high heat resistance in place of an epoxy resin, a maleimide resin has been attracting attention, but an amine-modified maleimide resin obtained by a reaction between a bismaleimide and an aromatic diamine has excellent heat resistance during drying. However, there is a disadvantage that the water absorption is large, cracks are generated by solder immersion during moisture absorption, and the reliability is poor.

Other examples of the maleimide resin include an example in which a polymaleimide is reacted with an alkenylphenol or an alkenylphenyl ether in the presence of a polymerization catalyst (Japanese Patent Application Laid-Open No.
52-994, 58-117219, 61-95012, 62-11716, 63-230
No. 728), but there is a drawback that the cured product is inferior in low stress characteristics because the cured product is hard like the amine-modified maleimide resin.

Attempts have been made to add various silicone compounds to improve low-stress properties, but compatibility is remarkably poor, strength is reduced, water absorption is large, moisture resistance and reliability are poor, and there are many practical problems. Remains.

(Problems to be Solved by the Invention) The object of the present invention is to have good compatibility, without deteriorating general properties, excellent in moisture resistance and low stress properties,
Another object of the present invention is to provide a resin composition for semiconductor encapsulation which has high heat resistance and very excellent reliability after solder immersion.

(Means for Solving the Problems) The present invention provides (A) a propargyl and glycidyl etherified resin represented by the following formula [I] or / and [II]: (R ₁ : a group independently selected from -H or -CH ₃ 0 <a, b <100, 0 ≦ c <100 and a + b + c = 100 a, b, c represents the percentage of each structural unit .) (0 <d, e <100, 0 ≦ f <100 and d + e + f = 100 d, e, f indicate the percentage of each structural unit.) (B) Polysiloxane represented by the following formula [III]; _{(X: -H, CH 2 3} NH 2, -CH = CH ₂ or -CH ₂ -CH = CH ₂ R ₂ : -CH ₃ , Or a group n: 1 to 100 independently selected from X) (C) a resin composition for semiconductor encapsulation, which comprises (C) a curing agent for an epoxy resin.

(Action) The propargyl and glycidyl etherified resins used in the present invention are resins having a phenolic hydroxyl group, specifically, phenol resins, phenol / aromatic hydrocarbon resins, for example, phenol-modified xylene resins (Mitsubishi Gas Chemical Co., Ltd.) Nikonol P-100, etc.) and phenol aralkyl resin (Mirex XL-22, Mitsui Toatsu Co., Ltd.)
5), vinylphenol resin (Maruzen Petrochemical Co., Ltd.)
Marukalinker M, etc.) or vinyl phenol / styrene copolymer resin (Maruzerin Kagaku Co., Ltd. Marukalinker CS)
T) is reacted with propargyl chloride and glycidyl chloride to form propargyl and glycidyl ether, and is represented by the following formula [I] or [II].

(R ₁ : a group independently selected from —H or —CH ₃ ) a, b, c and d, e, f indicate the percentage (%) of each structural unit in the formulas [I] and [II], respectively, and the portion having each structural unit in the resin as a whole [I] In the formula, a, b,
c and [II] exist in the ratio of d, e, f.
0 <a, b <100, 0 ≦ c <100 and a + b + c = 100 0 <d, e <100, 0 ≦ f <100 and d + e + f = 100. Preferably, 30 ≦ a, b ≦ 90, 10 ≦ b, e ≦ 50, 0 ≦
c, f ≦ 50 is good.

The components a and b are effective in properties such as heat resistance, toughness, moisture resistance, and reliability. If the content is too small, these characteristics are weakened.
Conversely, if the amount is too large, the curability deteriorates.

The b and e components are effective in improving curability and moldability,
If the amount is too large, heat resistance, moisture resistance and reliability deteriorate.

The c and f components have the effect of further improving the characteristics of the a and d components such as moisture resistance and reliability. However, if the amount is too large, the curability and the moldability are significantly deteriorated.

The polysiloxane used in the present invention has two or more reactive groups in the molecule, and has the following formula [II
And the degree of polymerization n is in the range of 1 to 100.

_{(X: -H, CH 2 3} NH 2, -CH = CH ₂ or -CH ₂ -CH = CH ₂ R ₂ : -CH ₃ , Or a group independently selected from X: n: 1 to 100) When the degree of polymerization is larger than 100, the compatibility is reduced.

The polysiloxane is preferably 2 to 100 parts by weight based on 100 parts by weight of propargyl and glycidyl etherified resin. If the amount is too small, low stress characteristics cannot be obtained. If it is too large, the mechanical strength and Tg decrease, and cracks occur during solder immersion.

It is desirable that the polysiloxane be reacted in advance with a propargyl and a curing agent for glycidyl etherified resin or epoxy resin, using a catalyst if necessary, until the melting point is in the range of 50 to 120 ° C. The catalyst for the above reaction is not particularly limited, but as an example, when X in the formula (III) is -H, chloroplatinic acid which is a catalyst used for the reaction between a hydrosilyl group and an olefin Can be used, and X is In the case of, tertiary amines, imidazoles, phosphines and the like, which are catalysts used for the reaction between the epoxy group and phenol, can be used, and X is -CH = CH ₂ , -CH _2-
For CH = CH _2, it may be an organic peroxide. When X is CH _{2 3} NH _2, the reaction can be carried out by heating without using a catalyst.

The epoxy resin curing agent used in the present invention,
What is usually used for an epoxy resin sealing material may be used. For example, a phenol resin can be used. In addition,
Bis (4-cyanatephenyl) methane, bis (3,5-
Polycyanates such as dimethyl-4-cyanatephenyl) methane and 2,2-bis (4-cyanatephenyl) propane can also be used.

The amount of the curing agent for an epoxy resin is appropriately determined according to the epoxy equivalent in the resin. If necessary, curing accelerators such as tertiary amines, imidazoles, phosphines, and organic peroxides can be used in combination.

In order to form a molding material using the resin composition for semiconductor encapsulation of the present invention, a curing accelerator, an inorganic filler, a lubricant, a flame retardant, a release agent, a silane coupling agent, etc. are appropriately added as needed. It can be made into a material by heating and kneading.

(Example) [Synthesis of propargyl and glycidyl etherified resin] Synthesis Examples 1 to 3 A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel was mixed with potassium hydroxide according to the formulation in Table 1; A mixed solvent of water / acetone (1/1) was added and dissolved, and a phenol resin, a phenol / aromatic hydrocarbon resin, or a vinyl phenol resin was added and dissolved therein.

This solution was heated, propargyl chloride and glycidyl chloride were added dropwise, and the mixture was reacted at 50 ° C. to reflux for 3 hours. Thereafter, the mixture was neutralized with hydrochloric acid, acetone was distilled off, and 1 liter of toluene was added. It was transferred to a separating funnel, washed three times with water, and the solvent was removed with an evaporator.

 The composition of the obtained resin is shown in Table 1.

Examples 1-2 In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, the propargyl and glycidyl etherified resin of Synthesis Example 1 or Synthesis Example 2 and toluene were charged according to the formulation in Table 2 and uniformly dissolved. Then, the chloroplatinic acid solution was added.
Dihydropolysiloxane or diaminopolysiloxane was added thereto and reacted at 80 ° C. for 2 hours. Thereafter, the reflux condenser was replaced with a reduced pressure upstream device to remove the solvent, and further reacted at 180 ° C. under reduced pressure (about 20 mmHg) for 4 hours. The resulting polysiloxane-modified resin was homogeneous and the melting points are shown in Table 2.

Example 3 A phenol resin and triphenylphosphine were added to a reaction vessel equipped with a stirrer, a vacuum distillation apparatus and a thermometer in a second vessel.
It was added according to the recipe in the table, and heated to dissolve uniformly. Diglycidyl polysiloxane is added to this, and under reduced pressure (about
The reaction was performed at 180 ° C. for 3 hours. The resulting polysiloxane-modified phenolic resin was homogeneous and the melting points are shown in Table 2.

Examples 4 to 6 According to the composition shown in Table 3, a curing agent, a silica powder, a curing accelerator, an aminosilane, a coloring agent and a release agent were added to the resin, and kneaded with a hot roll to obtain a molding material. The resulting molding material was molded by transfer molding at 180 ° C. for 3 minutes to obtain a glossy molded product without blisters. This molded article was further cured at 180 ° C. for 8 hours, and the characteristics were evaluated. The results are shown in Table 3.

The molding materials of Examples 4 to 6 have low flexural modulus at room temperature, low stress, and low internal stress. Moreover, the glass transition temperature is high, the bending strength at 260 ° C is large,
Excellent solder crack resistance and low water absorption.

Comparative Example 1 The procedure of Example 4 was repeated except that the propargyl and glycidyl etherified resin of Synthesis Example 1 were used without adding polysiloxane. The appearance, bending strength and heat resistance of the molded product are good, but the bending elastic modulus is large and the solder crack resistance is not sufficient.

Comparative Example 2 An epoxy resin was used as a resin component, and the same procedure as in Example 4 was performed with the composition shown in Table 3. Due to poor heat resistance, solder crack resistance is very poor.

Comparative Example 3 Using a maleimide resin as a resin component, the same procedure as in Example 4 was performed with the composition shown in Table 3. Although the heat resistance is excellent, the flexural modulus and the water absorption are large, and the solder crack resistance is not sufficient.

Comparative Example 4 A maleimide resin was used as a resin component, and polysiloxane was added. Poor compatibility between maleimide resin and polysiloxane,
The appearance of the molded article was not good. The water absorption was large and the solder crack resistance was poor.

(Effect of the Invention) The cured product of the composition using the resin for semiconductor encapsulation according to the present invention has a high Tg, and has excellent moisture resistance and strength at the time of heating, so that the sealing body has good solder crack resistance, In addition, it has low stress and excellent heat cycle resistance, and is a highly reliable and excellent resin composition for semiconductor encapsulation.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08F 299/00 (56) References JP-A-2-227423 (JP, A) JP-A-2-208314 (JP, A JP-A-2-3411 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 63/00-63/10 C08L 83/04-83/06 C08G 59/20 H01L 23 / 29

Claims (1)

(57) [Claims] (A) a propargyl and glycidyl etherified resin represented by the following formula [I] and / or [II]: (R ₁ : a group independently selected from -H or -CH ₃ 0 <a, b <100, 0 ≦ c <100 and a + b + c = 100 a, b, c represents the percentage of each structural unit .) (0 <d, e <100, 0 ≦ f <100 and d + e + f = 100 d, e, f indicate the percentage of each structural unit.) (B) Polysiloxane represented by the following formula [III]; _{(X: -H, CH 2 3} NH 2, -CH = CH ₂ or -CH ₂ -CH = CH ₂ R ₂ : -CH ₃ , Or a group n: 1 to 100 independently selected from X) (C) a resin composition for semiconductor encapsulation, comprising: a curing agent for an epoxy resin.