JP5107177B2 - Die bond agent composition - Google Patents

Description

The present invention relates to a die-bonding agent composition that includes a silicone polymer and has a cured product excellent in flexibility and impact resistance when having two kinds of functional groups having different reactivities, and a semiconductor device using the composition. On how to make.

A die bond agent for a semiconductor device is an adhesive that fixes a chip on a substrate, and is an indispensable member for assembling the semiconductor device. The die bond agent bonds a chip mainly composed of single crystal silicon and a substrate mainly composed of plastic, and further protects them with a sealing material mainly composed of plastic and an inorganic filler. A large stress is generated at the interface between the die bond agent and the peripheral member due to the difference in characteristics of these constituent members, that is, thermal expansion and elastic modulus. In order to absorb such stress, it is known to use a silicone-modified resin (Patent Document 1).

A method is often used in which a die bond agent is applied on a substrate and then heated at a relatively low temperature so as to be in a B-stage state, semi-solid or cured state, and a chip is mounted thereon and then completely cured. This B-staging method includes (1) a method for forcibly stopping the curing reaction in the middle, and (2) two reaction systems having different curing temperature regions coexist to cure a reaction system that cures at a low temperature. There is a method (for example, Patent Document 2). Among these, the method (1) is an easy method with many types of reaction systems that can be applied, but the stability of the B stage state is insufficient. On the other hand, the method (2) has a problem that the types are limited so that the two reaction systems do not cause phase separation or the like.
JP 2002-249484 A JP 2005-513192 A

Then, this invention aims at providing the die-bonding agent composition which does not have said problem and gives the hardened | cured material which is excellent in a softness | flexibility and a thermal shock resistance.

［Ｒ^１は、下記式（ａ−１）で表される基と（ａ−２）表される基の組合せ又は下記式（ｂ−１）表される基と（ｂ−２）表される基の組合せであり、（ａ−２）／（ａ−１）のモル比が１／９〜９であり、（ｂ−２）／（ｂ−１）のモル比が１／９〜９であり、

（Ｒ^５は水素原子もしくはメチル基である）
Ｒ^２は、夫々独立に、炭素数１〜１０の飽和炭化水素基、
Ｒ^３は、夫々独立に、炭素数１〜１０の飽和炭化水素基、
Ｒ^４は、炭素数２〜４のアルキレン基、
ｎは０〜２の整数、ｍは０〜１００の整数である。］ That is, the present invention
A curing agent having R ¹ and the reactive group of 100 parts by weight of a polymer containing a repeating unit of the formula (A) (1) (B) Component (A), the equivalent of the reactive groups, R ¹ A die bond agent composition comprising 0.1 to 10 parts by weight of (C) a polymerization initiator and 0.1 to 10 parts by weight of (D) a curing accelerator so that the ratio to the equivalent of 0.8 is 1.2. It is a thing.

[R ¹ is a combination of a group represented by the following formula (a-1) and a group represented by (a-2) or a group represented by the following formula (b-1) and (b-2) It is a combination of groups, the molar ratio of (a-2) / (a-1) is 1/9 to 9, and the molar ratio of (b-2) / (b-1) is 1/9 to 9. Yes,

(R ⁵ is a hydrogen atom or a methyl group)
R ² each independently represents a saturated hydrocarbon group having 1 to 10 carbon atoms,
R ³ each independently represents a saturated hydrocarbon group having 1 to 10 carbon atoms,
R ⁴ is an alkylene group having 2 to 4 carbon atoms,
n is an integer of 0 to 2, and m is an integer of 0 to 100. ]

The die-bonding agent composition of the present invention includes a silicone polymer having two types of functional groups with different reactivities, thereby giving a cured product excellent in flexibility and thermal shock resistance without causing phase separation and the like. The yield of semiconductor products can be improved.

Component (A) polymer The first feature of this polymer, specifically an alternating copolymer, is an aromatic skeleton that is a rigid part, as shown in formula (1), and flexible It is to contain a silicone skeleton that is a site. As a result, the thermal shock resistance is excellent. By adjusting the type, molecular weight, and content of the rigid part and the flexible part, it is possible to provide performance according to the application.

As for the molecular weight of the polymer, the weight average molecular weight is preferably 1,000 to 1,000,000, particularly 5,000 to 500,000. The molecular weight of this polymer can be achieved by adjusting the type, molecular weight, content, and polymer synthesis conditions described below. Here, when the weight average molecular weight is less than the lower limit, the thermal shock resistance of the cured product is lowered, and curing by heating or ultraviolet irradiation is not sufficient, and in the step (iii) in the method described later, the composition is dicered. May cause problems such as sticking to the blade. On the other hand, when the weight average molecular weight is larger than the upper limit, the compatibility with the (B) curing agent and (E) (meth) acrylic compound decreases, and the method according to claim 7 or 8 is used. In addition, the composition may be excessively solid by heating or ultraviolet irradiation, and may be excessively cured by heating or ultraviolet irradiation, which may cause problems such as the composition not being sufficiently bonded to the substrate or other chips.

（Ｒ^５は水素原子もしくはメチル基である） The second feature of this polymer is a radical represented by the following formula (a-2) (hereinafter, “group represented by” is omitted) or a radical (b-2) caused by light, heat, or the like. It has a polymerizable group. As a result, the polymer can further form a high molecular weight polymer to form a B-stage state.

(R ⁵ is a hydrogen atom or a methyl group)

The molar ratio of (a-2) / (a-1), or the molar ratio of (b-2) / (b-1) is 1/9 to 9, preferably 2/8 to 8. . When the ratio is less than 1/9, curing by heating or ultraviolet irradiation is not sufficient, and in the step (iii) in the method to be described later, there is a risk of causing trouble such as adhesion of the composition to the blade of the dicer. . On the other hand, when the ratio is more than 9, the composition may be excessively cured by heating or ultraviolet irradiation, and the composition may not be sufficiently bonded to the substrate or other chips.

  The third feature of this polymer is that it has (a-1) or (b-1). As a result, the polymer further forms a polymer having a high molecular weight. If an acrylic group or a methacryl group is polymerized in advance and then an epoxy group or a phenolic hydroxyl group is polymerized, a stronger cross-linked structure is formed.

In Formula (1), R ² is each independently a saturated hydrocarbon group having 1 to 10 carbon atoms, such as an alkyl group, and n is an integer of 0 to 2. R ³ is each independently a saturated hydrocarbon group having 1 to 10 carbon atoms, preferably a methyl group. R ⁴ is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group and a propylene group, and m is an integer of 0 to 100, preferably an integer of 0 to 30.

下記式で示される両末端にＳｉＨ結合を有するオルガノハイドロジェンポリシロキサンを付加反応に付した後、

（ｍ及びＲ^３は上述のとおりである。）
（メタ）アクリル酸を、塩基性触媒、例えばトリフェニルホスフィン、１，８−ジアザジシクロ（５，４，０）ウンデセン−７等、の存在下で、反応させることによって、作ることができる。付加反応は、例えば特許文献１（特開２００２−２４９５８４号公報）記載の方法により行なうことができる。 (A) The polymer is, for example, the following epoxy group or phenol group-containing compound,

After subjecting an organohydrogenpolysiloxane having SiH bonds at both ends represented by the following formula to an addition reaction,

(M and R ³ are as described above.)
(Meth) acrylic acid can be made by reacting in the presence of a basic catalyst such as triphenylphosphine, 1,8-diazadicyclo (5,4,0) undecene-7, and the like. The addition reaction can be performed, for example, by the method described in Patent Document 1 (Japanese Patent Application Laid-Open No. 2002-249484).

（ｑは０以上の整数、好ましくは１〜８の整数。）
Component (B) Curing agent When R ^{1 of} component (A) is a combination of (a-1) and (a-2), an epoxy resin curing agent can be used, for example, phenol resin, acid Examples include anhydrides and amines. Among these, a phenol resin is preferable. Examples of the phenol resin include novolak type, bisphenol type, trishydroxyphenylmethane type, naphthalene type, cyclopentadiene type, phenol aralkyl type and the like, and these may be used alone or in combination of two or more. Of these, bisphenol A type and bisphenol F type shown in the following formula are preferable.

(Q is an integer of 0 or more, preferably an integer of 1 to 8.)

（ｐは０以上の整数、好ましくは１〜８の整数。） When R ^{1 of the} component (A) is a combination of (b-1) and (b-2), an epoxy resin can be used. Examples thereof include novolac type, bisphenol type, biphenyl type, phenol aralkyl type, dicyclopentadiene type, naphthalene type, amino group-containing type, silicone-modified epoxy resin described later, and mixtures thereof. Among these, bisphenol A type, bisphenol F type, and novolak type shown in the following formula are preferable.

(P is an integer of 0 or more, preferably an integer of 1 to 8.)

Since the above phenol resin has two or more phenolic hydroxyl groups and the epoxy resin has two or more epoxy groups, it reacts with two or more polymer molecules to form a crosslinked structure.

Another function of the component (B) is to improve the bonding property of the composition to a substrate or another chip. When an epoxy resin or a phenol resin is used as the component (B), the viscosity of these resins decreases at the chip bonding temperature and oozes out from the semi-solid network structure obtained by heating or ultraviolet irradiation. Bondability of the resin composition is improved by wetting and spreading on the surface of the substrate or other chip.

The content of component (B), relative to the equivalents of ^{R 1} in component (A), in an amount such that ^{R 1} and reactive groups of component (B) is 0.8 to 1.2 equivalents of is there. Here, when the content of the component (B) is less than the lower limit, a crosslinked structure is not sufficiently formed, or the bonding property of the above resin composition does not sufficiently appear, and is sufficient for a substrate or another chip. There is a risk of causing problems such as non-bonding. On the other hand, when the content of the component (B) is larger than the upper limit, the content of (A) is relatively small, and thus sufficient flexibility and thermal shock resistance may not be obtained.

Component (C) Polymerization Initiator This polymerization initiator is the component (E) that is optionally blended in the semi-solidification step in (a-2) or (b-2) with an acrylic or methacrylic group. It is blended for the purpose of promoting the polymerization of the acrylic group or methacryl group.

Examples of the polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, benzophenone, -{4- (2-hydroxyethoxy) -phenyl} -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, oligo [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl } Propanone] (trade name: ESACURE KIP-150, manufactured by LAMBERTI SpA), KR-04 (trade name, Kagawa Chemical Co., Ltd.) And the like; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, (2, And benzoylphosphine oxides such as 4,6-trimethylbenzoyl) diphenylphosphine oxide. These can be used singly or in combination of two or more. Among these, the above-mentioned ESACURE KIP-150, KR-04, and the like, which are phenyl ketone compounds, are preferable since the generation of volatile components during polymerization is small.

(C) Content of a polymerization initiator is 0.1-10 weight part with respect to 100 weight part of (A), Preferably it is 0.2-2 weight part. Here, when the content of the polymerization initiator is less than 0.1 weight, it is not sufficiently solid by heating or ultraviolet irradiation, and when the content of the polymerization initiator is more than 10 parts by weight, the storage stability is high. The composition may be damaged and excessively cured by heating or ultraviolet irradiation, and the composition may not be sufficiently bonded to the substrate or other chips.

（Ｒ^６及びＲ^７は、夫々独立に、水素原子、炭素数１〜１０の炭化水素基及びハロゲン原子から選択される１価の基である。）

（Ｒ^８及びＲ^９は炭素数１〜１０の有機基である。） Component (D) Curing accelerator The curing accelerator is blended to accelerate the curing of the component (A) and the component (B). As a hardening accelerator, the hardening accelerator of an epoxy resin and a phenol resin can be used, for example, Basic organic compounds, such as organic phosphorus, an imidazole, a tertiary amine, are mentioned, for example. Examples of organic phosphorus include triphenylphosphine, tributylphosphine, tri (p-toluyl) phosphine, tri (p-methoxyphenyl) phosphine, tri (p-ethoxyphenyl) phosphine, triphenylphosphine / triphenylborate derivatives, tetra Examples thereof include phenylphosphine and tetraphenylborate. Examples of imidazole include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxy Examples thereof include triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo (5,4,0). ) Undecene-7 and the like. Preferably, it is a tetraphenylphosphine / tetraphenylborate derivative represented by the following formula (2) or an imidazole derivative represented by the formula (3).

(R ⁶ and R ⁷ are each independently a monovalent group selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and a halogen atom.)

(R ⁸ and R ⁹ are organic groups having 1 to 10 carbon atoms.)

More preferably, 2-phenyl-4-hydroxymethylimidazole of the following formula (4), 2-phenyl-4, 5-dihydroxymethylimidazole of the formula (5), tetraphenylphosphine tetraphenylborate of the formula (6) Alternatively, tetraphenylphosphine tetratoluyl borate of the formula (7) is used.

The curing accelerator has an active temperature for the reaction of (A) the epoxy group or phenolic hydroxyl group and (B) the curing agent in the vicinity of 180 ° C. to 200 ° C., which is higher than normal organophosphorus or imidazole derivatives. Therefore, the composition has excellent storage stability. In addition, once the reaction starts, it shows the same activity as a normal organic phosphorus or imidazole derivative. That is, when the composition is made semi-solid by heating, the temperature or time condition is wide, the storage stability in the B-stage state is excellent, and the hardness of the composition is further increased.

The content of the curing accelerator is 0.1 to 10 parts by weight, preferably 0.2 to 2 parts by weight with respect to 100 parts by weight of (A). Here, the content of the curing accelerator is 0.1. If it is less than the weight, the curing reaction may not proceed sufficiently. On the other hand, when there is more content of a hardening accelerator than 10 weight part, there exists a possibility that storage stability may be impaired.

Component (E) (Meth) acrylic compound A (meth) acrylic compound can be mix | blended with the composition of this invention. As the compound, an epoxy acrylate obtained by reacting an epoxy resin and acrylic acid, and an epoxy methacrylate obtained by reacting an epoxy resin and methacrylic acid are preferable. Examples of the raw material epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin and the like. These can be used singly or in combination of two or more. Among these, a reaction product of an epoxy resin such as bisphenol A type epoxy resin or bisphenol F type epoxy resin and acrylic acid and / or methacrylic acid is preferable.

Content of a component (E) is 5-500 weight part with respect to 100 weight part of (A), Preferably it is 10-100 weight part. Here, when the content of the component (E) is less than the lower limit, the composition does not solidify sufficiently by heating or ultraviolet irradiation, and the composition adheres to the blade of the dicer in step (iii) in the method described later. There is a risk of causing trouble. On the other hand, when the content of the component (E) is more than the above upper limit value, it may be excessively solid by heating or ultraviolet irradiation, and the composition may not be sufficiently bonded to the substrate or other chips. is there.

Other components In addition to the above-mentioned components, the resin composition of the present invention is an adhesion promoter such as an insulating filler such as silica and alumina, an inorganic filler such as a conductive powder such as silver powder, and alkoxysilane. An agent, a viscosity adjusting diluent, a flame retardant aid, an ion trapping agent, and the like can be arbitrarily blended depending on the purpose and application.

Method for preparing composition The composition of the present invention is obtained by mixing the above-described components using a known method, for example, a mixer, a roll, or the like. Conditions such as mixing order, time, temperature, and atmospheric pressure can be controlled as necessary.

When a semiconductor device is manufactured using the above composition, it is applied on a substrate (Method 1) or applied to a wafer (Method 2) as described below.
Method 1
(Step 1) The die-bonding agent composition of the present invention is applied onto a substrate,
(Step 2) The applied die bond agent composition is made into a B-stage by heating or ultraviolet irradiation,
(Process 3) A semiconductor chip is mounted on a semi-solid die bond agent composition,
(Step 4) The semi-solid die bond agent composition is cured.
Method 2
(Step i) Applying the resin composition of the present invention on a silicon wafer,
(Step ii) The applied die bond agent composition is made into a B-stage by heating or ultraviolet irradiation,
(Step iii) The wafer and the die bond agent composition are cut into chip-shaped pieces,
(Step iv) The pieces are mounted on a substrate or another chip via a die bond agent composition,
(Step v) The die bond agent composition is cured.

Here, in step 1 or step i, the resin composition is provided on the substrate or wafer by a dispenser, printer, spin coater or the like, and in step 2 or step ii, heating by a batch or continuous oven, or by an ultraviolet irradiation device, Raises radical polymerization to make it semi-solid. In step iii of method 2, the wafer and the resin composition coated and solidified thereon are simultaneously cut into chips using a dicer usually used for wafer separation.

In step 3 or step iii, the chip is mounted with a die bonder, and in step 4 or step iv, the resin composition is cured in a batch or continuous oven. Further, in step 4 or step v, the epoxy group or phenolic hydroxyl group (A) or (E) containing epoxy group or phenolic hydroxyl group reacts by heating in the presence of (C).

Examples The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
Raw material used Polymer A (Synthesis Example 1)
Polymer B (Synthesis Example 2)
Polymer D (Synthesis Example 4)
Polymer F (Synthesis Example 6)
Epoxy resin H (bisphenol type epoxy resin, equivalent 180, Nippon Kayaku RE310S),
Phenol resin I (phenol novolac resin, equivalent 110, Meiwa Kasei DL-92),
Methacryl compound J (bisphenol A type epoxy methacrylate, epoxy ester 3000M manufactured by Kyoeisha Chemical)
Polymerization initiator K (oligo [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone], ESACURE KIP-150 manufactured by LAMBERTI SpA)
Curing accelerator L (tetraphenylphosphine / tetraphenylborate, TPP-K, manufactured by Hokuko Chemical)
Curing accelerator M (2-phenyl-4,5-dihydroxymethylimidazole, 2PHZ manufactured by Shikoku Kasei)
Silica N (Spherical fused silica, average particle size 0.8 microns, maximum particle size 3 microns, Admatex SE2030)
Adhesion aid O (γ-glycidoxypropyltrimethoxysilane, KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)
Polymer used in Comparative Example Polymer C (Synthesis Example 3)
Polymer E (Synthesis Example 5)
Polymer G (Synthesis Example 7)

(Synthesis Example 1)
In a flask equipped with a stirring blade, dropping funnel, thermometer, ester adapter and reflux tube, 42.0 g (0.10 mol) of epoxy resin (diallyl bisphenol A type epoxy resin, Nippon Kayaku RE810NM) of the following formula (10) And 168.0 g of toluene were added, and azeotropic dehydration was performed at 130 ° C./2 hours. This was cooled to 100 ° C., 0.2 g of a catalyst (CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.) was dropped, and immediately, 36.3 g (0.05 mol) of an organopolysiloxane of the following formula (12) and 145.2 g of toluene. The mixture was added dropwise over 1 hour and further aged at 100 ° C./6 hours. This was cooled to room temperature, 8.6 g (0.10 mol, conversion rate 50%) of methacrylic acid and 0.2 g of triphenylphosphine were added and reacted at 100 ° C./12 hours. From this, toluene was removed to obtain a yellow transparent liquid (weight average molecular weight 1780, siloxane content 42 parts by weight). This is designated as Polymer A.

(Synthesis Example 2)
In a flask equipped with a stirring blade, dropping funnel, thermometer, ester adapter and reflux tube, 42.0 g (0.10 mol) of epoxy resin of formula (10) (diallyl bisphenol A type epoxy resin, Nippon Kayaku RE810NM) 168.0 g of toluene was added and azeotropic dehydration was performed at 130 ° C./2 hours. This was cooled to 100 ° C., 0.2 g of a catalyst (CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.) was dropped, and immediately a mixture of 36.3 g (0.05 mol) of organopolysiloxane of formula (12) and 145.2 g of toluene. Was dripped in 1 hour and further aged at 100 ° C./6 hours. This was cooled to room temperature, 4.3 g (0.05 mol, conversion rate 25%) of methacrylic acid and 0.2 g of triphenylphosphine were added and reacted at 100 ° C./12 hours. From this, toluene was removed to obtain a yellow transparent liquid (weight average molecular weight 1690, siloxane content 44 parts by weight). This is designated as Polymer B.

(Synthesis Example 3)
In a flask equipped with a stirring blade, dropping funnel, thermometer, ester adapter and reflux tube, 42.0 g (0.10 mol) of epoxy resin of formula (10) (diallyl bisphenol A type epoxy resin, Nippon Kayaku RE810NM) Add 168.0 g of toluene and perform azeotropic dehydration at 130 ° C./2 hours. This was cooled to 100 ° C., 0.2 g of a catalyst (CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.) was dropped, and immediately a mixture of 36.3 g (0.05 mol) of organopolysiloxane of formula (12) and 145.2 g of toluene. Was dripped in 1 hour and further aged at 100 ° C./6 hours. This was cooled to room temperature, 0.86 g (0.01 mol, conversion rate 5%) of methacrylic acid and 0.2 g of triphenylphosphine were added and reacted at 100 ° C./12 hours. From this, toluene was removed to obtain a yellow transparent liquid (weight average molecular weight 1610, siloxane content 46 parts by weight). This is designated as Polymer C.

(Synthesis Example 4)
In a flask equipped with a stirring blade, dropping funnel, thermometer, ester adapter and reflux tube, 42.0 g (0.10 mol) of epoxy resin of formula (10) (diallyl bisphenol A type epoxy resin, Nippon Kayaku RE810NM) Add 168.0 g of toluene and perform azeotropic dehydration at 130 ° C./2 hours. This was cooled to 100 ° C., 0.2 g of a catalyst (CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.) was dropped, and immediately a mixture of 36.3 g (0.05 mol) of organopolysiloxane of formula (12) and 145.2 g of toluene. Was dripped in 1 hour and further aged at 100 ° C./6 hours. This was cooled to room temperature, 12.9 g (0.15 mol, conversion rate 75%) of methacrylic acid and 0.2 g of triphenylphosphine were added and reacted at 100 ° C./12 hours. From this, toluene was removed to obtain a yellow transparent liquid (weight average molecular weight 1830, siloxane content 40 parts by weight). This is designated as Polymer D.

(Synthesis Example 5)
In a flask equipped with a stirring blade, dropping funnel, thermometer, ester adapter and reflux tube, 42.0 g (0.10 mol) of epoxy resin of formula (10) (diallyl bisphenol A type epoxy resin, Nippon Kayaku RE810NM) Add 168.0 g of toluene and perform azeotropic dehydration at 130 ° C./2 hours. This was cooled to 100 ° C., 0.2 g of a catalyst (CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.) was dropped, and immediately a mixture of 36.3 g (0.05 mol) of organopolysiloxane of formula (12) and 145.2 g of toluene. Was dripped in 1 hour and further aged at 100 ° C./6 hours. This was cooled to room temperature, 16.3 g (0.19 mol, conversion rate 95%) of methacrylic acid and 0.2 g of triphenylphosphine were added and reacted at 100 ° C./12 hours. From this, toluene was removed to obtain a yellow transparent liquid (weight average molecular weight 1920, siloxane content 38 parts by weight). This is designated as Polymer E.

(Synthesis Example 6)
In a flask equipped with a stirring blade, a dropping funnel, a thermometer, an ester adapter and a reflux tube, 30.8 g (0.100 mol) of phenol resin of formula (11) (diallyl bisphenol A, BPA-CA-S manufactured by Konishi Kayaku) And 123.2 g of toluene are added, and azeotropic dehydration is performed at 130 ° C./2 hours. This was cooled to 100 ° C., 0.2 g of a catalyst (CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.) was dropped, and immediately a mixture of 36.3 g (0.05 mol) of organopolysiloxane of formula (12) and 145.2 g of toluene. Was dripped in 1 hour and further aged at 100 ° C./6 hours. This was cooled to room temperature, 8.6 g (0.10 mol, conversion rate 50%) of methacrylic acid and 0.2 g of triphenylphosphine were added and reacted at 100 ° C./12 hours. From this, toluene was removed to obtain a yellow transparent liquid (weight average molecular weight 1530, siloxane content 48 parts by weight). This is designated as Polymer F.

(Synthesis Example 7)
In a flask equipped with a stirring blade, a dropping funnel, a thermometer, and a reflux tube, 36.0 g (0.05 mol) of epoxy resin F (bisphenol type epoxy resin, equivalent of 180, RE310S manufactured by Nippon Kayaku) and 8.6 g of methacrylic acid ( 0.10 mol, conversion rate 50%), 0.2 g of triphenylphosphine and 144.0 g of toluene were added and reacted at 100 ° C./12 hours. From this, toluene was removed to obtain a yellow transparent liquid (weight average molecular weight 450, siloxane content 0 part by weight). This is designated as polymer G.

Examples 1-4, Comparative Examples 1-4
Each component was mixed with a blending amount shown in Table 1 or 2 with a planetary mixer at 25 ° C, passed through three rolls at 25 ° C, and mixed again with a planetary mixer at 25 ° C to obtain a composition. . These compositions were subjected to the following tests (a) to (d), and the results shown in Tables 1 and 2 were obtained.

(A) Young's modulus of cured product Each composition was cured by ultraviolet irradiation at 365 nm / 100 mW / 30 seconds, then heated at 125 ° C./1 hour + 165 ° C./2 hours, and at −55 ° C., 25 ° C., 125 according to JIS6911. The Young's modulus at ℃ was measured.

(B) Moisture resistance and solder resistance test 20 test pieces shown in FIG. 1 were prepared by the following method, left in a constant temperature and humidity chamber of 85 ° C./85% RH for 168 hours, and the maximum temperature was 260 ° C. After passing through the IR reflow oven three times, the presence or absence of defects such as peeling or cracking was observed with an ultrasonic flaw detector, and the number of test pieces / total number of test pieces (20) in which defects were found was counted.
Preparation of semiconductor device test piece 1) Application of composition The composition was applied to one side of a silicon wafer (8-inch diameter, 0.3 mm) using a printing machine, and a resin composition layer of 45 to 55 microns was formed on the entire surface of the wafer. Formed. This was irradiated with ultraviolet rays under the condition of 365 nm / 100 mW / 30 seconds to obtain a wafer with a semisolid resin composition.

2) Wafer individualization and chip mounting A dicing film was stuck on the upper surface of the wafer composition layer obtained in 1), and the wafer was separated into 12 mm × 12 mm chips. The chip was picked up and mounted on a BT substrate (200 micron thickness, 35 mm × 35 mm) coated with a solder resist (20 micron thickness) on the surface via a composition layer. The chip mounting conditions here are 150 ° C. (chip) / 100 ° C. (substrate) / 1 kg / 0.1 second. This was cured under the conditions of 125 ° C./1 hour + 165 ° C./2 hours / nitrogen flow.

3) Resin sealing The substrate with a chip obtained in 2) was sealed with KMC-2520 (epoxy sealing material manufactured by Shin-Etsu Chemical Co., Ltd.). The molding conditions are a mold temperature of 175 ° C., an injection time of 10 seconds, an injection pressure of 70 KPa, a molding time of 90 seconds, and a post-curing condition of 180 ° C./2 hours. The entire test piece after molding is 1000 microns thick and 35 mm × 35 mm. is there.

(C) Temperature cycle test The test piece having no cracks or the like after the moisture resistance and solder resistance test of (b) was continuously put into a temperature cycle tester. The test conditions here are -55 ° C / 30 minutes + (-55 ° C → 125 ° C) / 5 minutes + 125 ° C / 30 minutes + (125 ° C → -55 ° C) / 5 minutes, 500 cycles or 1000 cycles. After the cycle, the presence or absence of defects such as peeling and cracking was observed with an ultrasonic flaw detector, and the number of test pieces / total number of test pieces (20) in which defects were found was counted.
(D) Regarding both the pass / fail judgment test method (b) and the test method (c), the test result was 0/20, and the others were rejected.

In the examples, in order for the polymer to form a sufficient cross-linked structure via the epoxy resin or phenol resin, the elastic modulus is balanced above room temperature, and the moisture and solder resistance test and the temperature cycle test are performed. Good results were obtained.
On the other hand, in Comparative Example 1, the amount of the radical polymerizable group is too small, and it is not sufficiently semi-solid after irradiation with ultraviolet rays, so that the wafer cannot be singulated. In Comparative Example 2, the radical polymerizable group is Since there was too much amount, and it solidified too much by ultraviolet irradiation and chip mounting was impossible, neither a moisture-proof / solder-proof test and a temperature cycle test were possible.
In addition, since the polymer used in Comparative Example 3 did not contain a silicone chain, the elastic modulus of the cured product was high, and defects were found in the moisture / solder resistance test and the temperature cycle test.
Since Comparative Example 4 did not contain (B), the crosslinked structure was not sufficiently formed, and the moisture resistance / solder resistance test and the temperature cycle test could not be performed.

It is sectional drawing of the semiconductor device test piece created in the Example.

Claims (9)

(A) 100 parts by mass of a polymer containing a repeating unit of formula (1) (B) a curing agent having a reactive group with R ^{1 of} component (A), an equivalent of R ¹ of the reactive group A die-bonding agent composition containing 0.1 to 10 parts by weight of (C) a polymerization initiator and 0.1 to 10 parts by weight of (D) a curing accelerator, such that the ratio to the equivalent is 0.8 to 1.2. .

[R ¹ is a combination of a group represented by the following formula (a-1) and a group represented by (a-2) or a group represented by the following formula (b-1) and (b-2) It is a combination of groups, the molar ratio of (a-2) / (a-1) is 1/9 to 9, and the molar ratio of (b-2) / (b-1) is 1/9 to 9. Yes,

(R ⁵ is a hydrogen atom or a methyl group)
R ² each independently represents a saturated hydrocarbon group having 1 to 10 carbon atoms,
R ³ each independently represents a saturated hydrocarbon group having 1 to 10 carbon atoms,
R ⁴ is an alkylene group having 2 to 4 carbon atoms,
n is an integer of 0 to 2, and m is an integer of 0 to 100. ] The composition of Claim 1 whose molar ratio of (a-2) / (a-1) or (b-2) / (b-1) is 2 / 8-8. The composition according to claim 1, wherein R ¹ is a combination of (a-1) and (a-2), and (B) is a phenol resin. The composition according to claim 1, wherein R ¹ is a combination of (b-1) and (b-2), and (B) is an epoxy resin. The composition according to any one of claims 1 to 4, wherein (C) is a phenyl ketone compound. The composition according to any one of claims 1 to 5, wherein (D) is a tetraphenylphosphine-tetraphenylborate derivative of the formula (2) or an imidazole derivative of the formula (3).

(R ⁶ and R ⁷ are each independently a monovalent group selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and a halogen atom.)

(R ⁸ and R ⁹ are organic groups having 1 to 10 carbon atoms.) (E) The composition of any one of Claims 1-6 which further contains a (meth) acryl compound. A manufacturing method of a semiconductor device including the following steps 1 to 4.
(Step 1) Applying the die bond agent composition according to any one of claims 1 to 7 on a substrate,
(Step 2) The applied die bond agent composition is made into a B-stage by heating or ultraviolet irradiation,
(Process 3) A semiconductor chip is mounted on the B-stage die bond composition,
(Step 4) B-stage die bond composition is cured. A method for manufacturing a semiconductor device, comprising the following steps i to v.
(Step i) The die bond agent composition according to any one of claims 1 to 7 is applied onto a silicon wafer,
(Step ii) The applied die bond agent composition is made into a B-stage by heating or ultraviolet irradiation,
(Step iii) The wafer and the die bond agent composition are cut into chip-shaped pieces,
(Step iv) The pieces are mounted on a substrate or another chip via a die bond agent composition,
(Step v) The die bond agent composition is cured.

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