JPH04145128A - Silicon-modified propargyl resin composition and resin composition containing the same for sealing semiconductor - Google Patents

Abstract

PURPOSE:To obtain the subject composition, excellent in moisture resistance, compatibility and flame retardancy, good in solder heat resistance with low stress and suitable as resins for sealing semiconductors by reacting a propargyl ether compound of brominated polyphenols with a polysiloxane. CONSTITUTION:The objective resin composition is obtained by reacting (A) brominated polyphenols expressed by formula I (R is H, etc.; R1 is H, etc.; R2 is CF3, etc.; n is 0-30; m is 0-4; m' is 0-3) with (B) propargyl chloride, providing a propargyl ether compound and further reacting 100 pts.wt. resultant compound with (C) preferably 2-100 pts.wt. polysiloxane expressed by formula II (X is H, etc.; R3 is CH3, etc.; j is 1-100).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a silicone-modified propargyl resin composition and a silicone-modified propargyl resin composition containing the same, which has a high glass transition point (hereinafter referred to as Tg), moisture resistance, compatibility, and flame retardancy. The present invention relates to a resin composition for semiconductor encapsulation that has excellent properties and low stress properties.

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

However, as electronic components are becoming more mass-producible, more highly integrated, and more surface-mounted, demands on sealing resins are becoming more severe.

In particular, chips become larger due to higher integration, packages become thinner, and solder immersion (200 to 3f) O' during surface mounting.
Due to C), cracks are likely to occur in the equipment,
In order to improve reliability, low stress characteristics and heat resistance are strongly desired for semiconductor encapsulation resins.

Epoxy resin is currently the mainstream resin for semiconductor encapsulation, but there are limits to its improvement in terms of heat resistance as long as epoxy resin is used, and it is difficult to obtain a highly reliable product after solder immersion during surface mounting. Not yet.

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

Maleimide resins are attracting attention as a resin with high heat resistance to replace epoxy resins, but amine-modified maleimide resins obtained by the reaction of bismaleimide and aromatic diamines have excellent heat resistance during drying. but,
It has a high water absorption rate, and cracks occur when immersed in solder when moisture is absorbed, resulting in poor reliability.

Other maleimide resins include examples in which polymaleimide and alkenylphenols or alkenyl phenyl ethers are reacted in the presence of a polymerization catalyst (Japanese Patent Application Laid-open No.
2-994.58-117219.61-95012.
62-11716.63-230728), but like the amine-modified maleimide resin, the cured product is hard, so it has the disadvantage of poor low stress properties.

Attempts have been made to add various silicone compounds as a measure to improve low stress properties, but they suffer from poor compatibility, low strength, high water absorption, lack moisture resistance and reliability, and have many practical problems. remain.

(Problem M to be Solved by the Invention) The object of the present invention is to provide a silicone-modified propargyl resin composition and a silicone-modified propargyl resin composition containing the same, which has good compatibility, moisture resistance, and flame retardancy without deteriorating general properties. The object of the present invention is to provide a resin composition for semiconductor encapsulation, which has excellent properties such as high heat resistance and low stress properties, high heat resistance, and extremely high reliability after being immersed in solder.

(Means for Solving the Problems) The first invention provides (A) a propargyl ether compound of brominated polyphenols represented by the following formula CI), and CR:H or -CH2-C=CH where H/-CH2 -C=CH is θ~3.0R1: -H
, -CH3, -CF3, = (), also C + OHR2 knee H
1-CH3, or -CF3 0≦n<30 m, m' are the average values of the number of bromines bonded to each benzene ring, and 0<m<4.0<m'<3 means the total number of bromines The average value t is 0<1≦2. ) (B) A polysiloxane represented by the following formula (II) and
or -+CH2)30cH2cH-CHa, ゝ0/each independently selected group j: 1 to 10o) is reacted, and the second invention is a silicone-modified propargyl resin composition, characterized in that it is formed by reacting (A) A propargyl ether compound of brominated polyphenols represented by the following formula CI) and
, -CH3, -CF3, = (), also bar Q-OHR, n H1-CH3, also i, t-cF30≦n<30 m, m' is the average value of the number of bromines bonded to each benzene ring 0<m<4, o<m'<3, and the average value t of the total number of bromines is 0<1≦2. ) (B) Polysiloxane represented by the following formula [TI] and (X: -H
In addition, wrinkle cone-modified propargyl resin ( A
A resin composition for semiconductor encapsulation characterized by containing or reacting B) and (C) a thermosetting resin.

(Function) The propargyl ether compound of brominated polyphenols used in the present invention is obtained by reacting the brominated polyphenol represented by formula CI) with propargyl chloride or propargyl bromide to convert it into propargyl ether.

When the brominated polyphenol is a compound, n is
Indicates the number of repetitions of the structural level shown within 0, and when composed of two or more types of compounds with different molecular weights, indicates the average number of repetitions, and 0≦n<30. Preferably 0
≦n≦10 is good. If the molecular weight is too large, the melting point and melt viscosity will also become high, making work difficult.

m and m' are the average values of the number of bromines bonded to each benzene ring, and if 0<m<4 and O<m'<3, the average value t of the total number of bromines is 0<t''≦2 It is.

If the number of bromines is too small, flame retardancy will not improve, so preferably 0.5≦t≦2.

The propargyl etherification rate is preferably 50% or more and 100% or less based on the phenolic OH group. If it is less than 50%, a large amount of phenolic OH groups remain, resulting in a high water absorption rate and no improvement in moisture resistance and solder crack resistance.

The propargyl ether compound of the present invention has the following formula (m)
It may be used in combination with propargyl ether compounds of polyphenols.

(R1 knee H1-CH3, -CF3, =(), or -J
oHR2 knee H5-CH3, or -CF3 0≦n<3
0) The polysiloxane used in the present invention has two or more reactive groups in the molecule, and has the formula (II
), and its degree of polymerization j is in the range of 1 to 100. If the degree of polymerization is greater than 100, compatibility will decrease.

Polysiloxane is globargyl ether compound 100
It is preferably 2 to 100 parts by weight. If it is too small, low stress properties cannot be obtained. If there is too much, the mechanical strength, T
g decreases and cracks occur during solder immersion.

It is essential that the propargyl ether compound and the polysiloxane are reacted in advance using a catalyst, if necessary, to obtain a silicone-modified propargyl resin. Since polysiloxane has poor compatibility, if it is not reacted in advance, the silicone will bleed and the appearance of the molded product will be poor and the strength will be significantly reduced. The catalyst for the above reaction is not particularly limited, but for example, when X in formula (II) is -H, chloroplatinic acid, which is a catalyst used for the reaction between a hydrosilyl group and an olefin, is used. In such cases, tertiary amines, imidazoles, phosphines, etc., which are catalysts used for the reaction between epoxy groups and phenol, can be used. In particular, the former siloxane in which X is -H has excellent moisture resistance.

Examples of the thermosetting resin used in the present invention include epoxy resin, cyanate resin, maleimide resin, unsaturated polyester resin, diallyl phthalate resin, or a combination of two or more of these resins.

Epoxy resins have at least two or more epoxy groups in their molecules, such as bisphenol A
epoxy resins, bisphenol F-based epoxy resins, brominated epoxy resins, phenol-novolac-based epoxy resins, cresol novolac-based epoxy resins, and other polyfunctional epoxy resins can be used.

The cyanate resin has at least two or more cyanate groups (-0CEN) in its molecule, such as dicyanate benzene, bis(4-cyanatophenyl)methane, and bis(365-dimethyl).

4-cyanatophenyl)methane, 2,2-bis(4-
Usable examples include cyanatophenyl)propane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, tricyanatebenzene, and phenol novolac polycyanates.

By blending an epoxy resin, a cyanate resin, or both, and more preferably reacting them in advance, workability, curability, and adhesion to the element and the υ-deframe are further improved. However, if the amount is too high, heat resistance, flame retardance, and solder crack resistance will deteriorate.

Maleimide resin is a compound having at least two or more maleimide groups in the molecule, such as N,N'--phenylene bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-m-)- Luylene bismaleimide, N,N'-4,4'-biphenylene bismaleimide,
N, N'-4,4'-(3,3'-dimethyl-biphenylene bismaleimide, N, N'-4,4'-(3,3'
-dimethyldiphenylmethane] bismaleimide, N, N
'-4,4'-(3,3'-diethyldiphenylmethane)bismaleimide, N.

N'-4,4'-diphenylmethane bismaleimide, N
, N'-4,4'-diphenylpropane bismaleimide, N, N'-4,4'-diphenyl ether bismaleimide, N, N'-3,3'-diphenylsulfone bismaleimide, N, N'-4, 4'-diphenylsulfone bismaleimide, -a polymaleimide represented by formula (IV) or (V), etc. (R, knee H, alkyl group or phenyl group 0<F
<10) (0<4<10) Alternatively, modified maleimide resins obtained by reacting these compounds with aromatic amines, aromatic cyanates, or allyl etherified phenols can be mentioned. There is no problem even if two or more of these are included.

By blending a maleimide resin, more preferably by reacting it in advance, curability and workability are further improved. However, if the amount is too large, the bending elastic modulus and water absorption rate will increase, resulting in poor solder crack resistance and reliability.

The amount of these thermosetting resins is preferably 20 to 500 parts by weight per 100 parts by weight of the silicone-modified propargyl resin.

The silicone-modified propargyl resin composition of the present invention and the semiconductor encapsulation resin composition containing the same may optionally contain other flame retardants such as antimony trioxide, tertiary amines,
Curing accelerators such as imidazoles, phosphines, and organic peroxides can also be used in combination.

(Example) Examples 1 to 2 In a reaction vessel equipped with a stirring device, a reflux condenser, a thermometer, and a dropping funnel, IJum hydroxide and water/acetone (1,/1 ) was added and dissolved, and brominated polyphenols were added and dissolved. This solution was heated, propargyl chloride was added dropwise, and the mixture was reacted under reflux for 3 hours. Thereafter, acetone and unreacted propargyl chloride were distilled off, and 1 u of toluene was added. The mixture was transferred to a separating funnel, washed with water three times, and the solvent was removed using an evaporator. Table 1 shows the reaction rate (reaction rate of phenolic hydroxyl group) of the obtained propargyl ether compound.

Example 3 Into a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer, put the propargyl ether compound of Example 1 and toluene according to the recipe in Table 2, dissolve them uniformly, and then add the chloroplatinic acid solution. Added. Dihydropolysiloxane was added to this and reacted at 80°C for 2 hours. Thereafter, the reflux condenser was replaced with a vacuum distillation apparatus to remove the solvent, and the mixture was further heated at 180°C under reduced pressure (approximately 20111 !L Hg) for 4 hours.
The reaction was carried out at 200'C for 4 hours. The resulting resin was homogeneous and the melting point is shown in Table 2.

Examples 4 to 5 The propargyl ether compounds of Examples 1 and 2 and toluene were placed in a reaction vessel equipped with a stirring device, a vacuum distillation device, and a thermometer according to the recipe in Table 2, and the mixture was uniformly dissolved.
A chloroplatinic acid solution was added.

Dihydropolysiloxane was added to this and reacted at 80°C for 2 hours. Thereafter, the reflux condenser was replaced with a vacuum distillation apparatus to remove the solvent. Further heat to 150°C, add N,
N'-4,4'-diphenylmethane bismaleimide or epoxy resin was added and reacted for 35 minutes in Example 4 and 100 minutes in Example 5. The resulting resin was homogeneous and the melting point is shown in Table 2.

Examples 6 to 8 According to the formulations shown in Table 3, the resins of Examples 3 to 5 were kneaded using hot rolls to obtain molding materials. The obtained molding material was molded by transfer molding at 180° C. for 53 minutes to obtain a glossy molded product without blisters. This molded article was further cured at 180° C. for 18 hours and its properties were evaluated.

The results are shown in Table 3.

The molding materials of Examples 6 to 8 using the resins of Examples 3 to 5 have a small bending modulus and low stress.

Moreover, it has a high glass transition temperature, high bending strength at 260°C, excellent heat resistance, solder crack resistance, and flame retardancy, and low water absorption.

Comparative Example 1 The same procedure as in Example 6 was carried out using maleimide resin. Although the appearance, hot bending strength, and glass transition temperature of the molded product were good, the bending elastic modulus and water absorption in normal and hot conditions were large, and the solder crack resistance was insufficient. Flame retardancy was V-1.

Comparative Example 2 Dihydropolysiloxane was blended with maleimide resin,
The same procedure as in Example 6 was carried out. Although the flexural modulus under normal conditions and when heated was small, the silicone component separated on the surface of the molded product, and the appearance of the molded product was not good.

The bending strength was decreased, the water absorption rate was high, and the solder crack resistance was also poor.

Comparative example 3 The same procedure as in Example 8 was carried out using an epoxy resin.

Although the molded product had good appearance and normal bending strength, its solder crack resistance was poor.

(Effects 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 is excellent in flame retardancy, moisture resistance, and strength under heat, so it is resistant to solder cracks in the encapsulation. It has good properties, low stress, and excellent heat cycle resistance, making it an excellent and highly reliable resin composition for semiconductor encapsulation.

Table 1 (old) *l: 7x/-le resin (resident dure XTIH
PR-51470) was brominated by stripping. n-3,
= 10 Table 2 Sip +, = ,, 01st: 322 (41ml: Made by Nippon Polyimide ■ Kelimide 601*
20th Octopus Kouyu FIICN-102 *3 Ito υDure Stone Made PR-5147ON-'=
y-i-+r, -mFl(125'Cl00g!1(t
II>(@TAQ water"".

6: fjL-91 ni 1;
'Lou...Top t: Mount composite of 61 corner 4f, t7
Buffer t+kJ l, 111 molded bodies were subjected to moisture absorption treatment (65°C, 959
Immediately after immersing the molded body in the Tabata bath for 10 seconds, the surface of the molded body was coated with 999
4 Show the number

Claims (4)

[Claims] (1) (A) There are propargyl ether compounds of brominated polyphenols represented by the following formula [I] and ▲mathematical formulas, chemical formulas, tables, etc.▼[I] (R:H or -CH_2-C≡CH where H /-CH_2-C≡CH is 0 to 3.0R_1:-
H, -CH_3, -CF_3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼R
_2: -H, -CH_3, or -CF_30≦n<30 m, m' are the average values of the number of bromines bonded to each benzene ring, and 0<m<4, 0<m'<3, , and the average value t of the total number of bromines expressed as (2m+nm')/(2+n)=t satisfies 0<t≦2. )(
B) Polysiloxane represented by the following formula [II] and ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[II] (X: -H or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_3: -CH_3, -CF_3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or groups j: 1 to 100) each independently selected from Resin composition. (2) (A) Propargyl ether compound of brominated polyphenols represented by the following formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (R: H or -CH2-C≡CH where H/ -CH_2-C≡CH is 0 to 3.0R_1:-
H, -CH_3, -CF_3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼R
_2: -H, -CH_3, or -CF_30≦n<30 m, m' are the average values of the number of bromines bonded to each benzene ring, and 0<m<4, 0<m'<3, , and the average value t of the total number of bromines, expressed as (2m+nm')/(2+n)=t, satisfies 0<t≦2. ) (B) Polysiloxane represented by the following formula [II] and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・・・・・・[II] (X: -H or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R_3: Silicone-modified propargyl resin (A
A resin composition for semiconductor encapsulation, characterized by containing or reacting B) with (C) a thermosetting resin. (3) The composition according to claim 2, wherein the thermosetting resin is an epoxy resin. (4) The composition according to claim 2, wherein the thermosetting resin is a maleimide resin.