CN101068846B

CN101068846B - Epoxy resin composition and semiconductor device

Info

Publication number: CN101068846B
Application number: CN2005800410378A
Authority: CN
Inventors: 小谷贵浩; 关秀俊; 前田将克; 滋野数也; 西谷佳典
Original assignee: Sumitomo Bakelite Co Ltd
Current assignee: Sumitomo Bakelite Co Ltd
Priority date: 2004-11-30
Filing date: 2005-11-25
Publication date: 2012-04-25
Anticipated expiration: 2025-11-25
Also published as: CN101068846A; JP2006152185A

Abstract

An epoxy resin composition for semiconductor encapsulation which comprises (A) a crystalline epoxy resin, (B) a phenol resin represented by the general formula (1), wherein R1 and R2 are each independently hydrogen or alkyl having 1 to 4 carbon atoms and R1's or R2's may be the same or different from each other; a is an integer of 0 to 4; b is an integer of 0 to 4; c is an integer of 0 to 3; and n is a number of 0 to 10 on average, (C) a (co)polymer comprising structural units derived from butadiene or a derivative of the (co)polymer, and (D) 80 to 95% by weight of an inorganic filler based on the composition.

Description

Composition epoxy resin and semiconducter device

Technical field

The present invention relates to a kind of composition epoxy resin and semiconducter device that is used for packaged semiconductor.Particularly; The present invention is applicable to surface mount type semiconductor device (area mounting typesemiconductor device); Wherein semi-conductor chip is installed in the one side of PC board or die-attach area, and basically only its through the one side of installing with resin package.

Background technology

Recently trend towards the market for electronic devices of size reduction, weight reduction and raising performance, make and lead to the higher semi-conductor of integrated level.Because the development rapidly of the surface mounting technique of semiconducter device makes and develops a kind of surface mount type semiconductor device recently, and it has been got and has replaced the semiconducter device with traditional structure.

The demand that the trend of the reduction of dimensions of semiconductor devices and the thinning of thickness thereof makes appearance reduce the viscosity of the composition epoxy resin that is used for packaged semiconductor significantly and increase considerably its intensity.In addition, based on environmental factors, the composition epoxy resin that is used for packaged semiconductor need have higher flame retardant resistance and don't contain the for example fire retardant of bromine-containing compound and sb oxide.Because these factors, recent composition epoxy resin trends towards comprising the lower resin of viscosity and a large amount of mineral fillers.

As new trend, fusing point is higher than the lead-free solder of the conventional scolder that uses and just is on the increase in the application that semiconducter device is installed.When using this scolder, mounting temperature must be compared with conventional device than high about 20 ℃ of the used temperature of traditional technology, and the safety through the semiconducter device installed is obviously reduced.In view of this situation, more and more need improve the safety of semiconducter device through the performance of improving composition epoxy resin.In order to meet this requirement, people study with a large amount of mineral fillers of interpolation reducing resin viscosity.

The exemplary of surface mount type semiconductor device comprises size BGA (BGA device) and CSP (chip size packages) more closely, and encapsulates than traditional Q FP or little QFN and the SON of SOP such as erection space.Developed such as QFN and SON encapsulation and drawn number and high speed demand to satisfy height.The limit of the surface mount type semiconductor device of expressions such as the approaching QFP of these demands, SOP by routine.

BGA and CSP have only installed semi-conductor chip on hard wiring board or elasticity PC board that one side encapsulates through composition epoxy resin; The representative example of hard wiring board is the wiring board that is made up of BT resin/Copper Foil (bismaleimide-triazine resin/spun glass substrate), the wiring board of the representative example of elasticity PC board for being made up of polyimide resin film/Copper Foil.And, to have installed at substrate on that opposite simultaneously of semi-conductor chip, two dimension forms soldered ball abreast, and through welding it is installed in the circuit board.

As stated, the structure of BGA or CSP is the single face encapsulating structure, wherein only encapsulates (that one side that forms soldered ball on the substrate is not packed) in that one side that semi-conductor chip has been installed on the substrate with composition epoxy resin.Therefore; This semiconducter device is easy to after be shaped (molding), immediately become bent (wraped); This is inconsistent by thermal expansion between the composition epoxy resin after organic substrate or metal substrate and the curing and thermal contraction, or be shaped solidify (molding curing) during composition epoxy resin cure shrinkage caused.And the warpage of semiconducter device makes the tie point of soldered ball can not horizontal location.Therefore, during these semiconducter device of encapsulation, through the solder joint on the wiring board, semiconducter device can be from perk on the wiring board, and the decay of the safety that causes being electrically connected.

On the contrary, QFN or the SON identical have been produced with the design of conventional QFP or SOP.Yet; Recently produce encapsulation through following method: (for example in metal substrate; The veneer sheet of copper lead frame, with the lead frame of the nickel-palladium+gold plate of polyimide film-stack) one side on the matrix (matrix) of semi-conductor chip is installed; The composition epoxy resin that use is used to encapsulate encapsulates in batch, then substrate is cut into the little lattice of desired size, thereby obtains independent encapsulation (below be called MAP-QFN and MAP-SON) (for example referring to patent document 1).

As BGA or CSP, MAP-QFN or MAP-SON are the structures of single face encapsulation, and that one side that semi-conductor chip wherein only has been installed on substrate encapsulates with composition epoxy resin.At this, the package area of MAP-QFN or MAP-SON is bigger than common article in package shape (commonpackage molding), and only its single face is packed.Therefore; It is bent that such semiconducter device is easy to after shaping, immediately become; This is because thermal expansion and the thermal contraction between the composition epoxy resin after metal substrate and the curing inconsistent, or shaping setting up period composition epoxy resin cure shrinkage caused.

The warpage of semiconducter device makes semiconducter device perk from the wiring board of its installation, the decay of the safety that causes being electrically connected.

In order only to reduce basically the warpage of the surface mount type semiconductor device that encapsulates through composition epoxy resin in the one side of organic substrate or metal substrate; Importantly make the thermal expansivity of thermal expansivity and solidified composition epoxy resin of substrate close, and reduce cure shrinkage at shaping setting up period composition epoxy resin.

In order to reach this purpose, following technology has been proposed: thus multi-functional epoxy resin and polyfunctional phenolic resin are made up the Tg that increases composition epoxy resin, and the content of adjustment mineral filler makes it cooperate with α 1.Yet the combination of multi-functional epoxy resin and polyfunctional phenolic resin can reduce flowability, thereby causes such as filling pore problems such as (unfilled voids) not.

When through as infrared again when weldprocedures such as stream, gas phase welding and immersed solder are welded, the moisture that exists in the semiconducter device at high temperature is evaporated fast, this moisture is owing to solidified composition epoxy resin (molding) moisture absorption forms.The pressure that in welding process, produces can cause in semiconducter device, cracking, perhaps cause in metal substrate, having installed between surface and the solidified epoxy resin of semi-conductor chip interface peel.Therefore, need to reduce the warpage of semiconducter device through the content that increases mineral filler.Need reduce pressure through the water absorbability that reduces molding.In addition, need improve the thermotolerance of molding and the cohesiveness between raising solidify material and the metal substrate.

Developed when forming process, made composition epoxy resin keep the technology of high workability, this composition epoxy resin is applied in for example traditional QFP and the surface mount type semiconductor device of SOP.For example, disclose: adopt the resin (for example) and the employing of low melting viscosity that silane coupling agent is arranged, mineral filler is carried out surface treatment to improve the content (for example, referring to patent document 3) of mineral filler referring to patent document 2.Any of these technology only can satisfy wherein in the required multifrequency nature.

As stated, need to add the high density mineral filler, to improve the characteristic of solidify material, as reducing the stress of warpage, minimizing molding, this molding is to be formed by the composition epoxy resin that is used for packaged semiconductor.And,, must improve its flowability in order to improve the filling characteristic of the composition epoxy resin that is used for packaged semiconductor.Yet when filling the mineral filler of high density, the flowability that is used for the composition epoxy resin of packaged semiconductor will reduce.Therefore, between the solidify material characteristic of the flowability of the composition epoxy resin that is used for packaged semiconductor and molding, there is a trade-off relation.

Still the demand that has the semiconducter device of processing for the demand and the use said composition of all good composition epoxy resin that is used for packaged semiconductor of the solidify material characteristic performance of mobile and molding.

Patent document 1: Japanese Patent Laid is opened 2003-109983

Patent document 2: Japanese Patent Laid is opened 1995-130919

Patent document 3: Japanese Patent Laid is opened 1996-20673

Summary of the invention

One object of the present invention is to solve the problem that exists in the prior art; Provide a kind of and in mobile and molding, all show composition epoxy resin good, that be used for packaged semiconductor in the characteristic of solidify material, and the semiconducter device that uses the said composition manufacturing.

According to the present invention, following content is provided.

Dress

The composition epoxy resin of semi-conductor chip, it comprises:

(A) crystal rings epoxy resins,

(B) resol of representing by general formula (1):

Wherein, R1 and R2 independently are hydrogen or the alkyl with 1 to 4 carbon atom, and two or more R1 or two or more R2 can be identical or different; A is the integer of 0-4; B is the integer of 0-4; C is the integer of 0-3; N is a MV, and is the numerical value of 0-10.

(C) contain (being total to) polymkeric substance or derivatives thereof of divinyl deutero-structural unit,

With

(D) mineral filler, its content in whole composition epoxy resin is 80wt%-95wt%, comprises two endpoint values.

(2), like (1) the described composition epoxy resin that is used for packaged semiconductor, wherein said resol (B) is represented by general formula (2):

Said (being total to) polymkeric substance or derivatives thereof (C) is an epoxidised polyhutadiene compound (C-1); And

The content of said mineral filler (D) in whole composition epoxy resin is 85wt%-95wt%, comprises two endpoint values.

(3), like (2) the described composition epoxy resin that is used for packaged semiconductor, the number-average molecular weight of wherein said epoxidised polyhutadiene compound (C-1) is 500-4000, comprises two endpoint values.

(4), like (2) the described composition epoxy resin that is used for packaged semiconductor, it further comprises curing catalyst (E).

(5), semiconducter device, wherein semi-conductor chip is to adopt one of any described composition epoxy resin encapsulation that is used for packaged semiconductor in (2)-(4).

(6), be used for the surface installing type composition epoxy resin of packaged semiconductor, said composition is one of any described composition epoxy resin that is used for packaged semiconductor in (2)-(4), it is used for package surface mounted semiconductor device,

Wherein semi-conductor chip is installed in the one side of substrate, and basically only substrate installed semi-conductor chip one side packed.

(7), surface mount type semiconductor device, wherein semi-conductor chip be by as (6) described surface installing type composition epoxy resin that is used for packaged semiconductor packaged.

(8), like (1) the described composition epoxy resin that is used for packaged semiconductor, wherein said resol (B) is represented by general formula (2):

Wherein said (being total to) polymkeric substance or derivatives thereof (C) is perbutan (C-2).

(9), like (8) the described composition epoxy resin that is used for packaged semiconductor, wherein said perbutan (C-2) is the perbutan of carboxy blocking, it is represented by general formula (3):

Wherein, Bu representes divinyl deutero-structural unit; ACN representes vinyl cyanide deutero-structural unit; X is the positive number less than 1; Y is the positive number less than 1; X+y=1; And z is the integer of 50-80.

(10), like (8) the described composition epoxy resin that is used for packaged semiconductor, the content of wherein said perbutan (C-2) in whole composition epoxy resin is 0.05wt%-0.5wt%, comprises two endpoint values.

(11), like (8) the described composition epoxy resin that is used for packaged semiconductor, the content of wherein said mineral filler (D) in whole composition epoxy resin is 85wt%-95wt%, comprises two endpoint values.

(12), like (8) the described composition epoxy resin that is used for packaged semiconductor, it further comprises curing catalyst (E).

(13), semiconducter device, wherein semi-conductor chip is packaged by one of any described composition epoxy resin that is used for packaged semiconductor in (8)-(12).

(14), be used for the surface installing type composition epoxy resin of packaged semiconductor, said composition is one of any described composition epoxy resin that is used for packaged semiconductor in (8)-(12), it is used for package surface mounted semiconductor device,

Wherein semi-conductor chip is installed in the one side of substrate, and it is packed only at substrate the one side of semi-conductor chip to be installed basically.

(15), surface mount type semiconductor device, wherein semi-conductor chip be by as (14) described surface installing type composition epoxy resin encapsulation that is used for packaged semiconductor.

(16), like (1) the described composition epoxy resin that is used for packaged semiconductor, wherein said crystal rings epoxy resins (A) is represented by general formula (4):

Wherein, X be selected from singly-bound ,-O-,-S-and-C (R2) ₂-group; R1 is the alkyl with 1 to 6 carbon atom; Two or more R1 can be identical or different; M is the integer of 0-4; R2 is hydrogen or the alkyl with 1 to 4 carbon atom; Two or more R2 can be identical or different,

Said resol (B) is represented by general formula (5):

Wherein, R1 and R2 independently are hydrogen or the alkyl with 1 to 4 carbon atom; Two or more R1 or two or more R2 can be identical or different; A is the integer of 0-3; B is the integer of 0-4; N is a MV, and is the positive number of 1-5,

Said (being total to) polymkeric substance or derivatives thereof (C) is the polyhutadiene (C-3) with intramolecularly ethylene oxide structure, and the oxygen level in its oxyethane is 3%-10%, comprise its two ends numerical value and

The content of said mineral filler (D) in whole composition epoxy resin is 85wt%-95wt%, comprises two endpoint values; And

Further comprise epoxy resin (F) by general formula (6) expression:

Wherein, R1 and R2 independently are hydrogen or the alkyl with 1 to 4 carbon atom; Two or more R1 or two or more R2 can be identical or different; A is the integer of 0-3; B is the integer of 0-4; N is a MV, and is the positive number of 1-5.

(17), like (16) the described composition epoxy resin that is used for packaged semiconductor, wherein said polyhutadiene (C-3) with intramolecularly ethylene oxide structure is that 25 ℃ viscosity is 20Pas-700Pas in temperature, comprises endpoints thereof.

(18), like (16) the described composition epoxy resin that is used for packaged semiconductor, it further comprises curing catalyst (E).

(19), semiconducter device, wherein semi-conductor chip is by one of any described composition epoxy resin encapsulation that is used for packaged semiconductor in (16)-(18).

(20), be used for the surface installing type composition epoxy resin of packaged semiconductor, said composition is one of any described composition epoxy resin that is used for packaged semiconductor in (16)-(18), it is used for package surface mounted semiconductor device,

(21), surface mount type semiconductor device, wherein semi-conductor chip be by as (20) described surface installing type composition epoxy resin encapsulation that is used for packaged semiconductor.

(22), like (1) the described composition epoxy resin that is used for packaged semiconductor, wherein said crystal rings epoxy resins (A) is represented by general formula (4):

Said resol (B) is represented by general formula (5):

Said (being total to) polymkeric substance or derivatives thereof (C) is an epoxidised polyhutadiene compound (C-1), and the content of said mineral filler (D) in whole composition epoxy resin is 80wt%-94wt%, comprises two endpoint values; And further comprise epoxy resin (F) by general formula (6) expression:

Wherein, R1 and R2 independently are hydrogen or the alkyl with 1 to 4 carbon atom; Two or more R1 or two or more R2 can be identical or different; A is the integer of 0-3; B is the integer of 0-4; N is a MV, and is the positive number of 1-5; And

Wherein said epoxy resin (F) is 10/90 to 90/10 with the weight ratio [(F)/(A)] of said crystal rings epoxy resins (A) by general formula (4) expression, comprises two endpoint values.

(23), like (22) the described composition epoxy resin that is used for packaged semiconductor, the number-average molecular weight of wherein said epoxidised polyhutadiene compound (C-1) is 500-4000, comprises two endpoint values.

(24), like (22) the described composition epoxy resin that is used for packaged semiconductor, it further comprises curing catalyst (E).

(25), semiconducter device, wherein semi-conductor chip is by one of any described composition epoxy resin encapsulation that is used for packaged semiconductor in (22)-(24).

(26), be used for the surface installing type composition epoxy resin of packaged semiconductor, said composition is one of any described composition epoxy resin that is used for packaged semiconductor in (22)-(24), it is used for package surface mounted semiconductor device,

Wherein semi-conductor chip is installed in the one side of substrate, and only packed in the one side that semi-conductor chip has been installed basically.

(27), surface mount type semiconductor device, wherein semi-conductor chip be by as (26) described surface installing type composition epoxy resin encapsulation that is used for packaged semiconductor.

(28), like (1) the described composition epoxy resin that is used for packaged semiconductor, wherein said crystal rings epoxy resins (A) is represented by general formula (4):

Said resol (B) is represented by general formula (5):

Wherein, R1 and R2 hydrogen or have the alkyl of 1 to 4 carbon atom independently; Two or more R1 or two or more R2 can be identical or different; A is the integer of 0-3; B is the integer of 0-4; N is a MV, and is the positive number of 1-5,

Said (being total to) polymkeric substance or derivatives thereof (C) is perbutan (C-2); And

Further comprise epoxy resin (F) by general formula (6) expression:

(29), like (28) the described composition epoxy resin that is used for packaged semiconductor, wherein said perbutan (C-2) is the perbutan of carboxy blocking, it is represented by general formula (3):

Wherein, Bu representes divinyl deutero-structural unit; ACN representes vinyl cyanide deutero-structural unit; X is the positive number less than 1; Y is the positive number less than 1; X+y=1; Z is the integer of 50-80.

(30), like (28) the described composition epoxy resin that is used for packaged semiconductor, the content of wherein said perbutan (C-2) in whole composition epoxy resin is 0.05wt%-0.5wt%, comprises two endpoint values.

(31), like (28) the described composition epoxy resin that is used for packaged semiconductor, wherein said epoxy resin (F) is 10/90 to 90/10 with the weight ratio [(F)/(A)] of said crystal rings epoxy resins (A) by general formula (4) expression, comprises two endpoint values.

(32), like (28) the described composition epoxy resin that is used for packaged semiconductor, it further comprises curing catalyst (E).

(33), semiconducter device, wherein semi-conductor chip is by one of any described composition epoxy resin encapsulation that is used for packaged semiconductor in (28)-(32).

(34), be used for the surface installing type composition epoxy resin of packaged semiconductor, said composition is one of any described composition epoxy resin that is used for packaged semiconductor in (28)-(32), it is used for package surface mounted semiconductor device,

(35), surface mount type semiconductor device, wherein semi-conductor chip be by as (34) described surface installing type composition epoxy resin encapsulation that is used for packaged semiconductor.

Compared with prior art, the epoxidation resin combination that is used for packaged semiconductor of the present invention can improve the filling ratio of mineral filler and the flowability that improves compsn.Therefore the composition epoxy resin that is used for packaged semiconductor of the present invention can show good solidify material characteristic, as the warpage in the molding reduce, stress reduces, good filling property.Therefore, especially be suitable as the surface installing type composition epoxy resin that is used for packaged semiconductor and semiconducter device.

Preferred forms of the present invention

The composition epoxy resin that is used for packaged semiconductor of the present invention comprises following component (A)-(D):

(A) crystal rings epoxy resins,

(B) resol of representing by general formula (1):

Wherein, R1 and R2 independently are hydrogen or the alkyl with 1 to 4 carbon atom, and two or more R1 or two or more R2 can be identical or different; A is the integer of 0-4; B is the integer of 0-4; C is the integer of 0-3; N is a MV, and is the numerical value of 0-10,

(C) contain divinyl deutero-structural unit (being total to) polymkeric substance or derivatives thereof and

(D) mineral filler.

The content of said mineral filler (D) in whole composition epoxy resin is 80wt%-95wt%, comprises two endpoint values.

The composition epoxy resin that is used for packaged semiconductor with this compsn can reduce coefficient of thermal expansion through high-load mineral filler (D), and makes the elasticity reduction through (be total to) polymkeric substance or derivatives thereof (C) that interpolation has a divinyl deutero-structural unit.Therefore, the composition epoxy resin that is used for packaged semiconductor shows the minimizing and the soldering resistance of improved flowability, solidify material warpage, and these performances all are that surface mount type semiconductor device is needed.Therefore, can obtain semiconducter device more reliably.

Below will elaborate to the composition epoxy resin that is used for packaged semiconductor of the present invention.

Crystal rings epoxy resins (A)

The example that is used for crystal rings epoxy resins of the present invention (A) comprises the glycidyl ether of quinhydrones, bisphenol-f type epoxy resin, by the biphenyl type epoxy resin of general formula (7) expression, by the stilbene type epoxy resin of general formula (8) expression and by the epoxy resin of general formula (4) expression.

Wherein, R3-R10 is hydrogen or has the alkyl of 4 carbon atoms at the most, and can be identical or different.

Wherein, R11-R20 is hydrogen or has the alkyl of 4 carbon atoms at the most, and can be identical or different.

Wherein, X be selected from singly-bound ,-O-,-S-and-C (R2) ₂-group; R1 is the alkyl with 1 to 6 carbon atom; Two or more R1 can be identical or different; M is the integer of 0-4; R2 is hydrogen or the alkyl with 1 to 4 carbon atom, and two or more R2 can be identical or different.

Resol (B)

Being used for resol of the present invention (B) is represented by general formula (1):

(being total to) polymkeric substance or derivatives thereof (C) with divinyl deutero-structural unit

Be used for (being total to) polymkeric substance or derivatives thereof (C) (following only abbreviate as sometimes " (being total to) polymkeric substance or derivatives thereof (C) ") with divinyl deutero-structural unit of the present invention by as monomeric divinyl prepared (being total to) polymkeric substance or derivatives thereof (C).

(being total to) polymkeric substance or derivatives thereof (C) can be epoxidised polyhutadiene compound (C-1), perbutan (C-2) or the polyhutadiene (C-3) with ethylene oxide structure.These compounds will be described following.

Mineral filler (D)

Be used for those mineral fillers that mineral filler of the present invention (D) can be selected from the composition epoxy resin that is generally used for packaged semiconductor.

These mineral fillers can comprise fused quartz, crystalline silica, secondary assembly quartz, alumina, titanium white, white lake, talcum powder, clay and spun glass, and also two or more unite use but these mineral fillers can be used separately.Fused quartz is especially preferred.The form of fused quartz can be ground particle or spheroid.More preferably, spherical quartz can be used for improving its content, and makes the increase of the melt viscosity of composition epoxy resin reduce to minimum.In order to improve the content of spherical quartz, it is desirable to regulate the size distribution of spherical quartz, make its distribution wideer.

If desired, can carry out surface treatment to mineral filler with coupling agent, epoxy resin or resol.Surface treatment can be adopted suitable technology, as removing solvent after in solvent, mixing again, directly additive is added into obtains mixture in the mineral filler, with stirrer this mixture is handled then.

The composition epoxy resin that is used for packaged semiconductor of the present invention also comprises curing catalyst (E), epoxy resin (F) and silane coupling agent (G) except that comprising said components (A)-(D).

Curing catalyst (E)

Curing catalyst (E) is not done any special restriction, its optional self energy promotes those curing catalysts of the reaction of epoxy group(ing) and phenolic hydroxyl group group, and it comprises Diazabicycloalkene and verivate thereof, as 1, and 8-diazabicyclo (5,4,0) hendecene-7; Organic phosphine and verivate thereof are like triphenylphosphine and methyldiphenyl base phosphine; With four Qu Dai Phosphonium-four substituted boracic acid salt, like tetraphenyl boron tetraphenylphosphoniphenolate, four phenylformic acid boron tetraphenylphosphoniphenolates-(tetraphenylphosphonium.tetrabenzoic acid borate), four naphthoic acid boron tetraphenylphosphoniphenolates (tetraphenylphosphonium.tetranaphthoic acid borate), four naphthoyl oxygen boron tetraphenylphosphoniphenolate/(tetraphenylphosphonium.tetranaphthoyloxy borate) and four naphthalene oxygen boron tetraphenylphosphoniphenolates (tetraphenylphosphonium.tetranaphthyloxy borate).These curing catalysts can use separately or two or more unite use.

Epoxy resin (F)

Epoxy resin (F) can be the epoxy resin by general formula (6) expression:

Silane coupling agent (G)

Silane coupling agent (G) can be the compound by general formula (9) expression:

R3-NH-R4-Si(OR5) _nR6 _3-n (9)

Wherein, R3 is the organic group with 1 to 12 carbon atom; R4, R5 and R6 are the hydrocarbon with 1 to 12 carbon atom; R3 to R6 is identical or different; N is the integer of 1-3.

Other component

When needing, except that said components (A) to (G), composition epoxy resin of the present invention also can suitably comprise various additives, said additive comprises:

Natural wax is like POLISHING WAX-103;

Synthetic wax is like polyethylene wax;

Higher fatty acid or its metal-salt are like Triple Pressed Stearic Acid and Zinic stearas;

Releasing agent is like paraffin;

Tinting material is like carbon black and reddle;

Fire retardant is like brominated epoxy resin, ANTIMONY TRIOXIDE SB 203 99.8 PCT, white lake, Marinco H, zinc borate, zinc molybdenum oxide, phosphine nitrile and phosphorus compound;

Inorganic ion exchanger is like the bismuth oxide hydrate; With

The low-stress component is like silicone oil and rubber; And

Inhibitor.

Composition epoxy resin of the present invention can be by following prepared: for example at room temperature utilizing, stirrer mixes component (A)-(G) and other additive; When heating, utilize kneading instrument such as cylinder to grind powder machine, kneader and extrusion machine etc. and mediate this mixture, this mixture then cools off, mills.

When using composition epoxy resin packaged electronic components of the present invention such as semi-conductor chip to make semiconducter device, can be cured shaping through conventional forming technology such as transfer mould, pressing mold and injection molding.It is optional from known method that other relates to the method for making semiconducter device.Especially, composition epoxy resin of the present invention is suitable for surface mount type semiconductor device most.

Will be in following explanation preferred implementation of the present invention.

Embodiment 1:

The composition epoxy resin that is used for packaged semiconductor of embodiment 1 comprises following component (A)-(E):

(A) crystal rings epoxy resins,

(B) resol of representing by general formula (2),

(C-1) epoxidized polybutadiene compound,

(D) mineral filler, its content in whole composition epoxy resin is 85wt%-95wt%, comprises two endpoint values.

(E) curing catalyst.

The content of epoxidized polybutadiene compound (C-1) in whole composition epoxy resin is 0.05wt%-5wt%, comprises two endpoint values.

This composition epoxy resin that is used for packaged semiconductor can reduce coefficient of thermal expansion through high-load mineral filler (D), can elasticity reduced through adding epoxidised polyhutadiene compound (C-1) again.Therefore,

Be used for the mobile height of the composition epoxy resin of packaged semiconductor, and therefore have improved filling properties.In addition, this composition epoxy resin that is used for packaged semiconductor can provide the molding of solidify material excellent performance, and said performance comprises the warpage properties that is able to reduce and has soldering resistance etc.Therefore said composition can significantly process the semiconducter device of high reliability effectively.As stated, the composition epoxy resin that is used for packaged semiconductor of this embodiment is applicable to surface mount type semiconductor device.

Embodiment 1 is specified.

Crystal rings epoxy resins (A)

The example that is used for the crystal rings epoxy resins (A) of embodiment 1 comprises the glycidyl ether of quinhydrones, bisphenol-f type epoxy resin, by the biphenyl type epoxy resin of general formula (7) expression with by the stilbene type epoxy resin of general formula (8) expression.

Wherein, R11-R20 is hydrogen or the alkyl that is at most 4 carbon atoms, can be identical or different.

These epoxy resin at room temperature are solids, therefore have good operability, and have low melting viscosity at shaping.Low melting viscosity can improve the flowability of the epoxy resin that is used for packaged semiconductor, and allows to such an extent that can be used for filling the mineral filler of high density.Therefore, can improve moisture resistance, and reduce the difference of coefficient of linear expansion, thereby improve the performance of molding.

Preferred embodiment by the biphenyl type epoxy resin of general formula (7) expression comprises 4,4 '-diglycidyl biphenyl, 3,3 '; 5; 5 '-tetramethyl--4, the molten mixture of 4 '-diglycidyl biphenyl and these compounds, they can obtain good balance aspect operability and the practicality.

Preferred embodiment by the stilbene type epoxy resin of general formula (8) expression comprises the 5-tertiary butyl-4,4 '-diglycidyl-2,3 '; 5 '-trimethylammonium stilbene, 4; 4 '-diglycidyl-3,3 ', 5; The molten mixture of 5 '-tetramethyl-stilbene and these compounds, they can obtain good balance aspect operability and the practicality.

These crystal rings epoxy resins (A) can be united use with other epoxy resin.

Uniting when using when it, the content of crystal rings epoxy resins (A) is preferably the 10wt% at least of epoxy resin total amount, more preferably 30wt% or more than, further be preferably 50wt% or more than.Can add the crystal rings epoxy resins (A) in the above-mentioned content range, thereby improve the flowability of the epoxy resin that is used for packaged semiconductor.

The instance that can be united the epoxy resin of use includes but not limited to the phenol aldehyde type epoxy resin of novolac epoxy resin, cresol-novolak type epoxy resin, tris-phenol type epoxy resin, phenol aralkyl-type epoxy resin, naphthol type epoxy resin, naphthylidene type epoxy resin, alkyl-modified tris-phenol type epoxy resin, the epoxy resin that contains the triazine parent nucleus and Dicyclopentadiene (DCPD) modification.Ideally, unite use epoxy resin have alap viscosity avoiding making the useful performance of epoxy resin crystalline, that is being worsened at shaping than low melting viscosity.

Resol (B)

The resol that uses in this embodiment (B) can be the resol by general formula (2) expression.

Resol by general formula (2) expression has hydrophobicity and inflexible biphenylene part between phenolic hydroxyl group.Therefore, has the warpage that biphenylene resol (B) partly can be used to reduce the cured prod (molding) of the epoxy resin that is used for packaged semiconductor.In addition, reduced the rate of moisture absorption of this molding, reduced the Young's modulus in being higher than the high temperature range of Tg, and semi-conductor chip, organic substrate and metal substrate have been shown good cohesiveness.In addition, even its cross-linking density is low, resol also has the characteristic of high flame retardant, high heat resistance.

In view of curing performance, by the resol of general formula (2) expression preferably by the resol of general formula (10) expression.

Wherein, n is a MV, and is the numerical value of 0-10.

In general formula (2) and (10), when n in above-mentioned scope, the flowability of resin combination can improve in solidification process, make to increase the content of mineral filler, this helps to reduce water absorbability, and reduces warpage.

The resol by general formula (2) expression that is used for embodiment 1 can be united use with other resol.When uniting when using, be preferably the 10wt% at least of resol total amount by the content of the resol (B) of general formula (2) expression, more preferably 30wt% or more than, further be preferably 50wt% or more than.Can add the resol (B) in the above-mentioned content range, thereby make the composition epoxy resin that obtains at high temperature show low elasticity, agent of low hygroscopicity, and good cohesiveness and flame retardant resistance.

The instance that can be united the resol of use includes but not limited to lacquer resins (phenolnovolac resins), cresol-novolak type resin (cresol novolac resins), naphthols aralkyl resin, tris-phenol resin, terpene resin modified phenol resin, Dicyclopentadiene (DCPD) resin modified phenol resin and the phenol aralkyl resin with phenylen moiety.These resol can use separately or two or more unite use.In order to improve the content of mineral filler, the same with epoxy resin, preferably have LV.

The epoxide group number in the used whole epoxy resin of embodiment 1 and the equivalence ratio of the phenolic hydroxyl group number in the whole resol are preferably 0.5-2, comprise two endpoint values; Especially be preferably 0.7-1.5, comprise two endpoint values.When equivalence ratio is in above-mentioned scope, can obtain being used for the composition epoxy resin of packaged semiconductor, said composition can provide the molding that shows good resistance dampness and curing characteristics.

Epoxidized polybutadiene compound (C-1)

The epoxidized polybutadiene compound (C-1) that uses in the embodiment 1 can be the compound by general formula (11) expression, but is not limited thereto.

Wherein, k, l, m and n are 1 to 50 integers; R21 has C _pH _qThe structure of expression; P is 0 to 10 integer; Q is 1 to 21 integer.

In whole composition epoxy resin, the content of epoxidized polybutadiene compound (C-1) is preferably 0.05wt%-5wt%, comprises two endpoint values; Be preferably 0.1wt%-2wt% especially, comprise two endpoint values.Content in the above-mentioned scope can cause the minimizing of the Young's modulus of composition epoxy resin, and further reduces its viscosity.

In addition, the number-average molecular weight that is used for the epoxidised polyhutadiene compound (C-1) of this embodiment is preferably 500 to 4000, comprises two endpoint values.Number-average molecular weight in the above-mentioned scope can cause the minimizing of the Young's modulus of composition epoxy resin, and the viscosity that obtains expecting.

Mineral filler (D)

The mineral filler (D) that is used for embodiment 1 can be above-mentioned mineral filler.In whole composition epoxy resin, the content that is used for the mineral filler of this embodiment is 85wt%-95wt%, comprises two endpoint values; Be preferably 87wt%-93wt%, comprise two endpoint values.When the content of mineral filler (D) is in above-mentioned scope, the water absorbability of prepared molding and thermal expansivity will reduce fully, make semiconducter device have good soldering resistance, and warpage is reduced.And the flowability that is used for the composition epoxy resin of packaged semiconductor can improve, and thus, it can be filled in forming process reliably, therefore can avoid such as problems such as gold thread distortion.

Curing catalyst (E)

The curing catalyst (E) that is used for embodiment 1 can be an above-claimed cpd.

Other component

Composition epoxy resin in this embodiment also can comprise except that said components (A), (B), (C-1), (D) and (E), other component.In addition; If desired; Compsn can suitably comprise various additives arbitrarily, and said additive comprises like silane coupling agents such as epoxy silane, hydrosulphonyl silane, aminosilane, urea groups silane and vinyl silanes, and like coupling agents such as titanate coupling agent, aluminum coupling agent and aluminium/zirconium coupling agents.

Composition epoxy resin in this embodiment 1 can be by following prepared: for example at room temperature utilizing, stirrer mixes component (A) to (E) and other additive; Then when heating, utilize kneading instrument such as cylinder to grind powder machine, kneader and extrusion machine etc. and mediate this mixture, this mixture then cools off, mills.

When using composition epoxy resin packaged electronic components of the present invention such as semi-conductor chip to make semiconducter device, can be cured shaping through conventional forming technology such as transfer mould, pressing mold and injection molding.It is optional from known method that other relates to the method for making semiconducter device.Especially, composition epoxy resin of the present invention is to be best suited for surface mount type semiconductor device.

Embodiment 2

The composition epoxy resin that is used for packaged semiconductor in the embodiment 2 comprises following component (A)-(C-2):

(A) crystal rings epoxy resins,

(B) resol of representing by general formula (2),

(C-2) perbutan.

Wherein, R1 and R2 be hydrogen or have the alkyl of 1 to 4 carbon atom independently, and two or more R1 or two or more R2 can be identical or different; A is the integer of 0-4; B is the integer of 0-4; C is the integer of 0-3; N is a MV, and is the numerical value of 0-10.

This composition epoxy resin can satisfy the condition of high-content mineral filler and high workability simultaneously.In addition, this composition epoxy resin that is used for packaged semiconductor can provide the molding of solidify material excellent performance, and said excellent properties comprises the warpage properties that is able to reduce and has soldering resistance etc.Therefore, said composition can significantly be processed the semiconducter device of high reliability effectively.As stated, the composition epoxy resin that is used for packaged semiconductor of this embodiment is applicable to surface mount type semiconductor device.

For embodiment 2 with specifying.

Crystal rings epoxy resins (A)

Crystal rings epoxy resins (A) used in the embodiment 2 can be as illustrated in the enforcement mode 1.

Crystal rings epoxy resins (A) in this embodiment can be united use with other epoxy resin of description in the embodiment 1.When uniting when using, the content of crystal rings epoxy resins (A) is preferably the 10wt% at least of epoxy resin total amount, more preferably 30wt% or more than, further be preferably 50wt% or more than.Can add the crystal rings epoxy resins (A) in the above-mentioned scope, thereby improve the flowability of composition epoxy resin.

Resol (B)

The resol (B) that uses in the embodiment 2 can be the compound like general formula (2) expression described in the enforcement mode 1.

Resol in the embodiment 2 (B) can be united use with other resol described in the embodiment 1.When uniting when using, the content of resol (B) is preferably the 10wt% at least of resol total amount, more preferably 30wt% or more than, further be preferably 50wt% or more than.Resol (B) in the above-mentioned scope can be added into the composition epoxy resin that is used for packaged semiconductor, shows low elasticity, agent of low hygroscopicity under the high temperature thereby be provided at, and also has the formation article of good cohesiveness and flame retardant resistance.

The epoxide group number in the used whole epoxy resin of this embodiment and the equivalence ratio of the phenolic hydroxyl group number in the whole resol are preferably 0.5-2, comprise two endpoint values; Especially be preferably 0.7-1.5, comprise two endpoint values.When equivalence ratio is in above-mentioned scope, can obtain being used for the composition epoxy resin of packaged semiconductor, said composition can provide the molding that shows good resistance dampness and curing characteristics.

Perbutan (C-2)

The perbutan (C-2) that uses in the embodiment 2 can be the compound by general formula (3) expression, but is not limited thereto, and two ends of these compounds all have a carboxyl.

Carboxyl in the perbutan (C-2) can be with mineral filler and the epoxy resin as the raw material of the composition epoxy resin that is used to encapsulate, and combines with semi-conductor chip and organic substrate as semiconductor apparatus assembly.

In whole composition epoxy resin, the content of used perbutan (C-2) is preferably 0.05wt%-5wt% in this embodiment, comprises two endpoint values; More preferably 0.1wt%-0.3wt% comprises two endpoint values.

Content in the above-mentioned scope can improve soldering resistance, has good cohesiveness because it can be used between cured prod and the substrate of composition epoxy resin of packaged semiconductor.And the flowability of composition epoxy resin can become fully, and said composition is filled in forming process reliably, thereby avoids the gold thread distortion in the semiconducter device.

The composition epoxy resin that is used for packaged semiconductor in this embodiment also comprises mineral filler (D) and/or curing catalyst (E) except that above-mentioned component (A)-(C-2).

Mineral filler (D)

Mineral filler in the embodiment 2 (D) can be the filler of explanation in the embodiment 1.The content that is used for the mineral filler of this embodiment is the 85wt%-95wt% of composition epoxy resin total amount, comprises two endpoint values; Be preferably 87wt%-93wt%, comprise two endpoint values.When the content of mineral filler (D) in above-mentioned scope, the water absorbability of prepared molding and thermal expansivity will reduce fully, make semiconducter device have good soldering resistance, and warpage is reduced.In addition, the flowability that is used for the composition epoxy resin of packaged semiconductor also can improve, and thus, it can be filled in forming process reliably, therefore can avoid such as problems such as gold thread distortion.

Curing catalyst (E)

The curing catalyst (E) that uses in the embodiment 2 can be the compound described in the embodiment 1.

Other component

Composition epoxy resin in the embodiment 2 can be selected from the composition epoxy resin described in the embodiment 1 or other.

Composition epoxy resin in the embodiment 2 can prepare described in enforcement mode 1.And this composition epoxy resin can be used for encapsulating electronic components such as semi-conductor chip, with preparation, the semiconducter device described in enforcement mode 1.

Embodiment 3

The composition epoxy resin that is used for packaged semiconductor in the embodiment 3 comprises following component (A)-(G):

(A) the crystal rings epoxy resins of general formula 4 expressions,

(B) resol of general formula (5) expression,

(C-3) have the polyhutadiene (C-3) of intramolecularly ethylene oxide structure,

(D) curing catalyst,

(E) mineral filler, its content in whole composition epoxy resin is 85wt%-95wt%, comprises two endpoint values,

(F) epoxy resin of general formula (6) expression and

(G) silane coupling agent of general formula (9) expression.

The oxygen level of the oxyethane in the polyhutadiene (C-3) is 3%-10%, comprises two endpoint values.

Wherein, X be selected from singly-bound ,-O-,-S-and-C (R2) ₂-group; R1 is the alkyl with 1 to 6 carbon atom; Two or more R1 can be identical or different; M is the integer of 0-4; R2 is hydrogen or the alkyl with 1 to 4 carbon atom; Two or more R2 can be identical or different.

R3-NH-R4-Si(OR5) _nR6 _3-n (9)

This composition epoxy resin can satisfy the condition of high-content mineral filler and high workability simultaneously.In addition, this composition epoxy resin that is used for packaged semiconductor can provide the molding of solidify material excellent performance, and the performance of said excellence for example is the warpage properties that is able to reduce and has soldering resistance etc.Therefore, said composition can significantly be processed the semiconducter device of high reliability effectively.As stated, the composition epoxy resin that is used for packaged semiconductor in this embodiment is applicable to surface mount type semiconductor device.

Will be to embodiment 3 with specifying.

Crystal rings epoxy resins (A)

Used crystal rings epoxy resins (A) can be the crystal rings epoxy resins by general formula (4) expression in the embodiment 3.Crystal rings epoxy resins (A) by general formula (4) expression at room temperature is a solid, at the next low liquid of viscosity pole that becomes of its temperature more than fusing point, can add the mineral filler of greater concn thus.Therefore the resin that contains this composition epoxy resin shows excellent soldering resistance.

Crystal rings epoxy resins (A) by general formula (4) expression can be bisphenol A type epoxy resin for example, but it is had no particular limits, as long as it has the structure of general formula (4).

If associating use, the content of uniting other epoxy resin of use are preferably the 70wt%-100wt% that the amount that makes epoxy resin (F) and crystal rings epoxy resins (A) reaches the epoxy resin total amount, comprise two endpoint values.When the total content of epoxy resin (F) and crystal rings epoxy resins (A) was in above-mentioned scope, cured prod can have low rate of moisture absorption, and had excellent splitting resistance.

The epoxy resin that can be united use can be monomer, oligopolymer or the polymkeric substance with intramolecularly epoxide group.The instance that can be united the epoxy resin of use comprises novolac epoxy resin; O-cresol formaldehyde type epoxy resin; Naphthol novolak type epoxy resin; Phenol aralkyl-type epoxy resin with phenylen moiety; Naphthols aralkyl-type epoxy resin (having for example phenylene or xenyl part); The phenol type epoxy resin of Dicyclopentadiene (DCPD) modification; Stilbene type epoxy resin; Tris-phenol type epoxy resin; Alkyl-modified tris-phenol type epoxy resin and the epoxy resin that contains the triazine parent nucleus.These epoxy resin that can be united use can use separately or two or more unite use.

Resol (B)

The resol (B) that uses in the embodiment 3 can be the resol by general formula (5) expression.

Resol by general formula (5) expression has hydrophobic between phenolic hydroxyl group and inflexible biphenylene part.Cured prod by the composition epoxy resin preparation that contains resol shows rate of moisture absorption and the Young's modulus that obtains reducing in being higher than the high temperature range of Tg.And semi-conductor chip, organic substrate and metal substrate are shown good cohesiveness.Even its cross-linking density is low, still has high flame retardant.Therefore, the semiconducter device with the resin combination encapsulation that contains resol has good splitting resistance.

In general formula (5), n is a MV, and it is the positive number of 1-5, is preferably the integer of 1-3.When the value of n was in above-mentioned scope, composition epoxy resin showed good curing characteristics and improved flowability.Resol by general formula (5) expression can use separately, perhaps with two or more than unite use.

By the resol of general formula (5) expression can, for example be phenol xenyl aralkyl resin, but do not have special restriction, as long as it has the structure of general formula (5).

In this embodiment, can unite and use other resol, as long as this resol can not make the resol that utilizes general formula (5) expression and the characteristic variation that obtains.The content of the additional resol that associating is used is preferably the content that makes resol (B) 70wt%-100wt% as the resol total amount, comprises two endpoint values.When the content of resol (B) was in above-mentioned scope, the cured prod rate of moisture absorption reduced.And, cured prod show and base material between soldering resistance after good cohesiveness and the welding.

Additional resol can be monomer, oligopolymer or the polymkeric substance with intramolecularly phenolic hydroxyl group, and it is desirably has alap viscosity.Instance comprises lacquer resins, cresol-novolak type resin, phenol aralkyl resin (having phenylen moiety), naphthols aralkyl resin, tris-phenol resin, terpene resin modified phenol resin and Dicyclopentadiene (DCPD) resin modified phenol resin.These resins can use separately or two or more unite use.In view of the safety that needs moisture resistance as the composition epoxy resin that is used for packaged semiconductor, preferred resin comprises answers the least possible sodium ion or the ionic impurity of cl ions.

The epoxide group number in the whole epoxy resin and the equivalence ratio of the phenolic hydroxyl group number in the resol, promptly epoxy group(ing) number/phenolic hydroxyl group number is preferably 0.7-1.5, comprises two endpoint values.When equivalence ratio was in above-mentioned scope, the epoxy resin that is used for packaged semiconductor showed good curing characteristics.And the glass transition temp of cured prod raises, and the safety of moisture resistance also improves.When epoxy resin (F) and crystal rings epoxy resins (A) and resol (B) are united when using, can obtain the effect of the best aspect the weldableness after splitting resistance and warpage and moisture absorption.

Polyhutadiene (C-3) with intramolecularly ethylene oxide structure

The polyhutadiene (C-3) that this embodiment uses has the intramolecularly ethylene oxide structure.The oxygen level of oxyethane influences cohesiveness.Mensuration according to the standard method that is used to analyze grease, oil and related substances (oxygen of oxyethane) is carried out learns that the oxygen level of oxyethane is 3%-10%, comprises two endpoint values; Be preferably 5%-8%, comprise two endpoint values.When the oxygen level of oxyethane was in above-mentioned scope, the cohesiveness between cured prod and the substrate was improved.And the flowability of composition epoxy resin can be improved, thereby is filled reliably.

Viscosity influence with polyhutadiene (C-3) of intramolecularly ethylene oxide structure is used for the viscosity of the resin combination of packaged semiconductor.According to JIS z-8803, be used for the composition epoxy resin that contains polyhutadiene (C-3) of packaged semiconductor, the viscosity of under 25 ℃ temperature, measuring is 20Pas to 700Pas, comprises two endpoint values; More preferably 50Pas to 500Pas comprises two endpoint values.When viscosity was in above-mentioned scope, the composition epoxy resin that is used for packaged semiconductor showed improved flowability.And, cured prod show and substrate between good cohesiveness, and the warpage of semiconducter device also is reduced to minimum.

Polyhutadiene (C-3) with intramolecularly ethylene oxide structure can be the compound by general formula (11) expression.In this embodiment, polyhutadiene (C-3) is necessary.

Polyhutadiene (C-3) can improve the cohesiveness between composition epoxy resin and the metal substrate (for example nickel-palladium or nickel-palladium-gold plate), thereby causes the high anti-heating power that flows again.

As long as use the effect of polyhutadiene (C-3) to be without prejudice, can unite the stress depressant that uses other.The instance that can be united the stress depressant of use comprises that rubber at room temperature is solid like the silicone oil of organic ZGK 5 etc. with like the rubber of silicone rubber and acrylic-nitrile rubber etc.

Its content is 0.05wt%-1.5wt%, comprises two endpoint values; Be preferably 0.1wt%-1wt%, comprise two endpoint values.When content is in above-mentioned scope, cured prod show and substrate between good cohesiveness.And the flowability of composition epoxy resin also can improve, thereby obtains filling more reliably.

Mineral filler (D)

The mineral filler (D) that embodiment 3 uses can be the filler described in enforcement mode 1.In whole composition epoxy resin, the content of mineral filler (D) is 85wt%-95wt%, comprises two endpoint values; Be preferably 87wt%-93wt%, comprise two endpoint values.When the content of mineral filler (D) was in the above-mentioned scope, the water absorbability of prepared molding and thermal expansivity can be reduced fully, make semiconducter device have good soldering resistance, and warpage is reduced.And the flowability that is used for the composition epoxy resin of packaged semiconductor can improve, and it can be filled in forming process reliably, therefore can avoid such as problems such as gold thread distortion.

Curing catalyst (E)

The curing catalyst (E) that embodiment 3 uses can be like enforcement mode 1 described compound.

Epoxy resin (F)

Epoxy resin (F) can be the epoxy resin by general formula (6) expression.

Shown in general formula (6), epoxy resin (F) has hydrophobic between epoxy group(ing) and inflexible biphenylene part.Therefore, the rate of moisture absorption of the cured prod that is prepared into by the composition epoxy resin that contains epoxy resin (F) reduces, and the Young's modulus in the high temperature range that is higher than glass transition temp (below be called Tg) also reduces.In addition, also show bonds well property with semi-conductor chip, organic substrate and metal substrate.And even its cross-linking density is low, epoxy resin (F) still shows higher thermotolerance.

Epoxy resin (F) can be, phenol xenyl aralkyl-type epoxy resin for example, but do not do special restriction, as long as it has the structure of general formula (6).

In general formula (6), in the time of in n is in above-mentioned scope, composition epoxy resin shows improved curing characteristics and flowability.

Silane coupling agent (G)

The silane coupling agent (G) that uses in the embodiment 3 can be the compound by general formula (9) expression.In this embodiment, silane coupling agent (G) is basic.

R3-NH-R4-Si(OR5) _nR6 _3-n (9)

Use can reduce the viscosity of composition epoxy resin by the silane coupling agent (G) of general formula (9) expression, and therefore its flowability is improved.In whole composition epoxy resin, the content of silane coupling agent (G) is 0.05wt%-1wt%, comprises two endpoint values; Be preferably 0.1wt%-0.8wt%, comprise two endpoint values; But be not limited only to above-mentioned scope.When the content of silane coupling agent (G) during between above-mentioned scope, cured prod show and substrate between good cohesiveness.In addition, composition epoxy resin performance aspect mobile and curing characteristics is excellent.Can use separately or two or more unite use by the silane coupling agent (G) of general formula (9) expression.

Only otherwise can cause the deleterious of employed silane coupling agent (G) by general formula (9) expression, also can unite and use other coupling agent.The instance that can unite the coupling agent of use comprises like silane coupling agents such as epoxy silane, hydrosulphonyl silane, aminosilane, urea groups silane and vinyl silanes, and coupling agents such as titanate coupling agent, aluminum coupling agent and aluminium/zirconium coupling agent.

Other component

The composition epoxy resin of embodiment 3 also can comprise above-mentioned other component except that component (A)-(G).

The composition epoxy resin of embodiment 3 can prepare described in enforcement scheme 1.And composition epoxy resin can be used for packaged electronic components such as semi-conductor chip with the preparation semiconducter device, described in enforcement scheme 1.

Embodiment 4:

The composition epoxy resin that is used for packaged semiconductor in the embodiment 4 comprises following component (A)-(F):

(A) the crystal rings epoxy resins of representing by general formula (4),

(B) resol of representing by general formula (5),

(C-1) epoxidized polybutadiene compound,

(D) mineral filler,

(E) curing catalyst and

(F) epoxy resin of representing by general formula (6).

Component (F) is 10/90 to 90/10 with the weight ratio [(F)/(A)] of component (A), comprises two endpoint values.The content of component (D) in whole composition epoxy resin is 80wt% to 94wt%, comprises two endpoint values.And the content of epoxidized polybutadiene compound (C-1) in whole composition epoxy resin is 0.05wt%-5wt%, comprises two endpoint values.

This composition epoxy resin can reduce the warpage of semiconducter device, and makes it have excellent anti-weldering fragility.Therefore, this composition epoxy resin is specially adapted to package surface mounted semiconductor device.

To specify embodiment 4.

Crystal rings epoxy resins (A)

Used crystal rings epoxy resins (A) can be the epoxy resin crystal described in enforcement scheme 3 in the embodiment 4.

In embodiment 4, epoxy resin (F) is 10/90 to 90/10 with the weight ratio [(F)/(A)] of crystal rings epoxy resins (A), comprises two endpoint values; Be preferably 20/80 to 70/30, comprise two endpoint values; Be preferably 30/70 to 50/50 especially, comprise two endpoint values.When weight ratio [(F)/(A)] was in above-mentioned scope, the cured prod that is prepared by composition epoxy resin had low rate of moisture absorption.And, can contain high-load mineral filler in the composition epoxy resin.Therefore, cured prod can have low rate of moisture absorption and HS.

In embodiment 4, only otherwise the characteristic variation that the use owing to epoxy resin (F) and crystal rings epoxy resins (A) is obtained can be added the additional ring epoxy resins described in enforcement mode 3.If added additional epoxy resin, the content of additional epoxy resin is preferably and makes the content of epoxy resin (F) and crystal rings epoxy resins (A) is the 70wt% to 100wt% of epoxy resin total amount, comprises two endpoint values.When the total amount of epoxy resin (F) and crystal rings epoxy resins (A) during between above-mentioned scope, cured prod shows rate of moisture absorption that obtains reducing and the splitting resistance of further improving.

Resol (B)

The resol (B) that uses in the embodiment 4 can be the resol by general formula (5) expression described in enforcement mode 3.

Only otherwise can make and in this embodiment, use the characteristic variation that obtains by the epoxy resin (B) of general formula (5) expression, can unite and use above-mentioned additional resol.The resol by general formula (2) expression that is used for embodiment 1 can be united use with other resol.If added other resol, the content of other resol is preferably and makes the content of resol (B) is the 70wt% to 100wt% of resol total amount, comprises two endpoint values.When the content of resol (B) was in the above-mentioned scope, cured prod had the rate of moisture absorption that has reduced, and showed the bonds well property with sill, and the soldering resistance after the welding.

The epoxide group number in the whole epoxy resin and the equivalence ratio of the phenolic hydroxyl group number in the whole resol, promptly epoxy group(ing) number/phenolic hydroxyl group number is preferably 0.7-1.5, comprises two endpoint values.In the time of in equivalence ratio is in above-mentioned scope, resin Composition shows the excellent in curing characteristic.And the glass transition temp of cured prod is improved, and the safety of moisture resistance aspect also is able to improve.When uniting use with the resol of representing by general formula (5) (B), can aspect the weldableness after splitting resistance and the warpage and the moisture absorption, obtain best effect by the epoxy resin (F) of general formula (6) expression with by the crystal rings epoxy resins (A) of general formula (4) expression.

Epoxidized polybutadiene compound (C-1)

The epoxidised polyhutadiene compound (C-1) that uses in this embodiment can be the compound described in the embodiment 1.Its content is preferably the 0.05wt%-5wt% of composition epoxy resin gross weight, comprises two endpoint values; Be preferably 0.1wt%-2wt% especially, comprise two endpoint values.When its content is in above-mentioned scope, can cause the Young's modulus of composition epoxy resin and viscosity to reduce.

The number-average molecular weight of the epoxidized polybutadiene compound (C-1) in this embodiment is preferably 500 to 4000, comprises two endpoint values.When number-average molecular weight was in above-mentioned scope, cured prod showed excellent soldering resistance, and can avoid the viscosity of composition epoxy resin to increase.

Mineral filler (D)

The mineral filler (D) that is used for embodiment 4 can be the filler described in the embodiment 1.When balance plasticity-and safety, the total content of mineral filler is preferably the 80wt%-94wt% of composition epoxy resin gross weight, comprises two endpoint values.The content of above-mentioned scope can be avoided in the cure shrinkage of shaping/setting up period and from the caused thermal contraction of forming temperature to room temperature, thereby makes warpage be able to reduce.And, reduced the rate of moisture absorption of cured prod, so anti-welding fragility is improved.In addition, flowability also is able to improve, thereby obtains good plasticity.

Curing catalyst (E)

Used curing catalyst (E) can be the compound described in enforcement mode 1 in the embodiment 4.

Epoxy resin (F)

Epoxy resin in the embodiment 4 (F) can be the epoxy resin described in enforcement mode 3.

Other component

Composition epoxy resin used in the embodiment 4 also can comprise additional component except that comprising said components (A)-(F).And if desired, compsn can suitably comprise arbitrarily various additive, and said additive comprises the coupling agent like the γ-glycidyl ether oxygen propyl trimethoxy silicane of silane coupling agent etc.

Used composition epoxy resin can be by being prepared as follows in this embodiment: component (A) to (F) and other additive are at room temperature mixed through stirrer; Then utilize like cylinder and grind these mixtures of kneading instruments kneading such as powder machine, kneader and forcing machine, cool off then and this mixture of milling.

The composition epoxy resin of embodiment 4 can be described in enforcement mode 1 manufacturing.And this composition epoxy resin can be used for packaged electronic components such as semi-conductor chip to make semiconducter device, described in enforcement scheme 1.

Embodiment 5

The composition epoxy resin that is used for packaged semiconductor of embodiment 5 comprise following component (A)-(C-2) with (F):

(A) the crystal rings epoxy resins of representing by general formula (4),

(B) resol of representing by general formula (5),

(C-2) perbutan and

(F) epoxy resin of representing by general formula (6).

In general formula (4), X be selected from singly-bound ,-O-,-S-and-C (R2) ₂-group; R1 is the alkyl with 1 to 6 carbon atom; Two or more R1 can be identical or different; M is the integer of 0-4; R2 is hydrogen or the alkyl with 1 to 4 carbon atom; Two or more R2 can be identical or different.

In general formula (5), R1 and R2 independently are hydrogen or the alkyl with 1 to 4 carbon atom; Two or more R1 or two or more R2 can be identical or different; A is the integer of 0-3; B is the integer of 0-4; N is a MV, and is the positive number of 1-5.

In general formula (6), R1 and R2 independently are hydrogen or the alkyl with 1 to 4 carbon atom; Two or more R1 or two or more R2 can be identical or different; A is the integer of 0-3; B is the integer of 0-4; N is a MV, and is the positive number of 1-5.

This composition epoxy resin can satisfy the condition of high-content mineral filler and high workability simultaneously.Therefore, said composition can significantly reduce the warpage of surface mount type semiconductor device effectively, also can improve safety, as soldering resistance is improved.

To specify embodiment 5.

Crystal rings epoxy resins (A)

Used crystal rings epoxy resins (A) can be the epoxy resin by general formula (4) expression described in enforcement mode 3 in the embodiment 5.

In embodiment 5, epoxy resin (F) is 10/90 to 90/10 with the weight ratio [(F)/(A)] of crystal rings epoxy resins (A), comprises two endpoint values; Be preferably 20/80 to 70/30, comprise two endpoint values; Be preferably 30/70 to 50/50 especially, comprise two endpoint values.When weight ratio [(F)/(A)] is in above-mentioned scope; The cured prod of being processed by composition epoxy resin can show lower rate of moisture absorption; And can add high-load mineral filler and can not damage the flowability of the composition epoxy resin of shaping, thereby obtain good soldering resistance.

In embodiment 5, only otherwise the characteristic variation that the use owing to epoxy resin (F) and crystal rings epoxy resins (A) is obtained can be added the additional epoxy resin described in enforcement mode 3.If added additional epoxy resin, the content of additional epoxy resin is preferably and causes the content of epoxy resin (F) and crystal rings epoxy resins (A) is the 70wt% to 100wt% of epoxy resin total amount, comprises two endpoint values.When the total amount of epoxy resin (F) and crystal rings epoxy resins (A) is in above-mentioned scope, can obtain gratifying agent of low hygroscopicity and enough soldering resistances.

Resol (B)

The resol (B) that uses in the embodiment 5 can be the resol by general formula (5) expression.

In this real formula scheme, only otherwise can cause using resol (B) and the characteristic variation that obtains, can unite use with other resol described in the embodiment 3.When uniting when using, the content of additional resol is preferably that to cause the content of resol (B) be the 40wt% to 100wt% of resol total amount, comprises two endpoint values.When resol (B) is in above-mentioned scope, can obtain gratifying agent of low hygroscopicity and enough soldering resistances.

Perbutan (C-2)

The perbutan (C-2) that uses in the embodiment 5 can be the compound by general formula (3) expression described in enforcement mode 2, but is not limited in this.The content of perbutan (C-2) is preferably the 0.05wt%-5wt% of composition epoxy resin gross weight, comprises two endpoint values; Be preferably 0.1wt%-0.3wt% especially, comprise two endpoint values.The content of above-mentioned scope can improve the cohesiveness between cured prod and the base material.And, improved the flowability of composition epoxy resin, it can be filled in forming process reliably.In addition, because the viscosity of composition epoxy resin diminishes, thereby can avoid the gold thread distortion in the semiconducter device for example.

Epoxy resin (F)

Epoxy resin in the embodiment 5 (F) can be the epoxy resin by general formula (6) expression described in enforcement mode 3.

The composition epoxy resin that is used for packaged semiconductor in this embodiment except comprise component (A)-(C-2) with (F), also can comprise mineral filler (D) and/or curing catalyst (E).

Mineral filler (D)

The mineral filler of using in the embodiment 5 (D) can be the filler of describing in the embodiment 1.The content of mineral filler is the 80wt%-95wt% of composition epoxy resin total amount, comprises two endpoint values; Be preferably 86wt%-93wt%, comprise two endpoint values.Content in the above-mentioned scope can prevent the soldering resistance variation that the increase owing to rate of moisture absorption and thermal expansivity causes.In addition, also can prevent the warpage of cured prod.And, improved the flowability of composition epoxy resin, it can be filled in forming process reliably.Viscosity is reduced, thereby can prevent to produce such as problems such as gold thread distortion in the semiconducter device.

Curing catalyst (E)

The curing catalyst (E) that uses in the embodiment 5 can be the compound described in the embodiment 3.

Except component (A)-(F), the epoxy resin of this embodiment also can comprise above-mentioned annexing ingredient.And; If desired; Compsn can suitably comprise any various additive, and said additive comprises like silane coupling agents such as epoxy silane, hydrosulphonyl silane, aminosilane, urea groups silane and vinyl silanes, and coupling agents such as titanate coupling agent, aluminum coupling agent and aluminium/zirconium coupling agent.

Composition epoxy resin in the embodiment 5 can prepare described in enforcement mode 1.And as stated, this composition epoxy resin can be used for encapsulating electronic components such as semi-conductor chip with the preparation semiconducter device.

Embodiment

The present invention will describe with reference to embodiment, but the present invention is not limited to embodiment.At this, any content is all represented with wt%.

Test Example A

Test Example a-1

Epoxy resin 1: biphenyl type epoxy resin (Japan Epoxy Resins Co., Ltd., YX4000K, fusing point: 105 ℃, epoxide equivalent: 185): 4.13wt%

Resol 1: have biphenylene part phenol aralkyl resin (Meiwa PlasticIndustries, Ltd., MEH7851SS, softening temperature: 65 ℃, hydroxyl equivalent: 203): 4.54wt%

Triphenylphosphine: 0.13wt%

Spherical fused quartz (median size: 30 μ m): 90.00wt%

Epoxidized polybutadiene compound 1 (Nippon Petrochemicals Company, E-1800-6.5, number-average molecular weight: 1800, viscosity (25 ℃): 350Pas): 0.50wt%

γ-glycidyl propyl trimethoxy silicane: 0.20wt%

POLISHING WAX-103: 0.20wt%

Carbon black: 0.30wt%

With stirrer these components are mixed.Mediate this mixture with two rollers then, the surface temperature of two rollers is 90 ℃ and 45 ℃.After the cooling, this mixture of milling obtains composition epoxy resin.Estimate the composition epoxy resin of gained through following method.The result is shown in Table 1.

Evaluation method

Eddy flow: the temperature of Measurement die is 175 ℃, and injection pressure is 6.9MPa, and be 2 minutes set time, according to the EMMI-1-66 swirl measurement.Its representation unit is centimetre.

The warpage of encapsulation: under following condition, form 352-pin BGA encapsulation with transfer moIding machine:

Forming temperature: 175 ℃, annotate and press: 6.9MPa, set time: 2 minutes;

Wherein substrate is bismaleimides-cyanate resin/spun glass substrate, and its thickness is 0.56mm; Size of semiconductor device is 30mm * 30mm (thickness is 1.17mm); Semiconductor chip size is 10mm * 10mm (thickness is 0.35mm); To be the gold thread of 25 μ m through diameter be connected with bond pad in the wiring board semi-conductor chip.Under 175 ℃, carry out 2 hours after fixing, obtain sample.Make ten semiconducter device of a cover that make thus be cooled to room temperature.Then, utilize surface roughness tester, measure displacement along short transverse from the diagonal of the door (gate) of encapsulation.The maximum displacement difference of measuring is an angularity, and its unit is a micron (μ m).

The gold thread deformation rate: observe the 352-pin BGA encapsulation that the warpage be used to estimate encapsulation forms through the soft X-ray scenograph, represent the gold thread deformation rate with flow/gold thread length ratio, its unit is %.

Soldering resistance: the 352-pin BGA that forms like said method is encapsulated under 175 ℃ the temperature carries out 2 hours post curing treatment, obtain being used to estimate the sample of warpage of packaging assembly.Ten encapsulation of a cover of gained are the processing 168 hours down of 60% atmosphere in 60 ℃ temperature, relative humidity; Be to handle 168 hours under 60% the atmosphere in 85 ℃ temperature, relative humidity; , 85 ℃ temperature, relative humidity handled 72 hours under being 85% atmosphere then.Afterwards, under 260 ℃ peak temperature (handling for 10 seconds under 255 ℃ or the higher temperature), make encapsulation stand IR and flow processing again.After the processing, inside is peeled off or the existence of crackle is observed, and calculate the substandard products number of semiconducter device through ultrasonic fault detector.When the substandard products number of semiconducter device is n, fraction defective is expressed as n/10.

Test Example a-2 to a-11 and b-1 to b-7

According to the composition in table 1 and the table 2, prepare composition epoxy resin, and it is estimated according to Test Example a-1.Evaluation result is shown in table 1 and the table 2.

Below be the component beyond the component of using among the Test Example a-1:

Epoxy resin 2: o-cresol formaldehyde type epoxy resin (epoxide equivalent: 196, softening temperature: 55 ℃)

Resol 2: have phenylen moiety phenol aralkyl resin (Mitsui Chemicals Inc., XLC-LL, softening temperature: 75 ℃, hydroxyl equivalent: 175)

Resol 3: lacquer resins (softening temperature: 80 ℃, hydroxyl equivalent: 105)

1,8-diazabicyclo (5,4,0) hendecene-7 (below be called " DBU ")

Epoxidized polybutadiene compound 2 (number-average molecular weight: 700, viscosity (25 ℃): 10Pas) epoxidized polybutadiene compound 3 (number-average molecular weight: 2000, viscosity (25 ℃): 550Pas).

Table 1

Table 2

Test Example B

Test Example a-1

Epoxy resin 1: biphenyl type epoxy resin (Japan Epoxy Resins Co., Ltd., YX4000K, fusing point: 105 ℃, epoxide equivalent: 185): 4.29 weight parts

Resol 1: have biphenylene part phenol aralkyl resin (Meiwa PlasticIndustries, Ltd., MEH7851SS, softening temperature: 65 ℃, hydroxyl equivalent: 203): 4.71 weight parts

Perbutan (Ube Industries, Ltd., HYCAR CTBN 1008-SP, x=0.82, y=0.18, z=62 (MV)): 0.15 weight part

Triphenylphosphine: 0.15 weight part

Fusion spherical quartz (median size: 30 μ m): 90.00 weight parts

γ-glycidyl propyl trimethoxy silicane: 0.20 weight part

POLISHING WAX-103: 0.20 weight part

Carbon black: 0.30 weight part

With stirrer these components are mixed.Mediate this mixture with two rollers then, the surface temperature of two rollers is 90 ℃ and 45 ℃.After the cooling, this mixture of milling obtains composition epoxy resin.Estimate the composition epoxy resin of gained through following method.The result is shown in Table 3.

Evaluation method

Eddy flow: under the condition described in Test Example A, measure.The sample that eddy flow is lower than 100cm is a unacceptable product.

The warpage of encapsulation: under the condition described in Test Example A, measure.Record downward protrusion 60 μ m or above sample and be rated as substandard products.

Gold thread deformation rate: under the condition described in Test Example A, measure.Observed value be 3% or above sample be rated as substandard products.

Soldering resistance: the 352-pin BGA that forms like said method is encapsulated under 175 ℃ the temperature carries out 2 hours post curing treatment, obtain being used to estimate the sample of warpage of packaging assembly.10 encapsulation of a cover of gained are the processing 168 hours down of 60% atmosphere in 60 ℃ temperature, relative humidity; Be to handle 168 hours under 60% the atmosphere in 85 ℃ temperature, relative humidity.Afterwards, under 260 ℃ peak temperature (handling for 10 seconds under 255 ℃ or the higher temperature), make encapsulation stand IR and flow processing again.After the processing, inside is peeled off or the existence of crackle is observed, and calculate the substandard products number of semiconducter device through ultrasonic fault detector.When the substandard products number of semiconducter device is n, fraction defective is expressed as n/10.

Test Example a-2 to a-10 and b-1 to b-4

According to the composition in the table 3,4 and 5, prepare composition epoxy resin, and it is estimated as Test Example a-1 is said.Evaluation result is shown in the table 3,4 and 5.

Epoxy resin 2: tris-phenol type epoxy resin (Japan Epoxy Resins Co.Ltd., E-1032H60, softening temperature: 59 ℃, epoxide equivalent: 169)

1,8-diazabicyclo (5,4,0) hendecene-7 (below be called " DBU ")

γ-Qiu Jibingjisanjiayangjiguiwan

Table 3

Table 4

Table 5

Test Example C

Test Example a-1

Epoxy resin 1: phenol xenyl aralkyl-type epoxy resin (Nippon Kayaku Co.Ltd., NC3000P, epoxide equivalent: 274, softening temperature: 58 ℃): 1.47 weight parts

Epoxy resin 2: bisphenol A-type crystal rings epoxy resins (Japan Epoxy Resins Co.Ltd., YL6810, epoxide equivalent: 171, fusing point: 45 ℃): 3.41 weight parts

Resol 1: phenol xenyl aralkyl resin (Meiwa Plastic Industries, Ltd., MEH-7851SS, hydroxyl equivalent: 203, softening temperature: 65 ℃): 5.12 weight parts

Triphenylphosphine: 0.15 weight part

Spherical fused quartz (median size: 30 μ m): 88.85 weight parts

Polyhutadiene 1 (viscosity in the time of 25 ℃: 350Pas, the oxygen level in the oxyethane: 6.5%): 0.30 weight part

N-phenyl-gamma-amino propyl trimethoxy silicane: 0.20 weight part

POLISHING WAX-103: 0.20 weight part

Carbon black: 0.30 weight part

At room temperature these components are mixed with stirrer.70 ℃ under 120 ℃, mediate these mixtures with two rollers.After the cooling, this mixture of milling obtains composition epoxy resin.Estimate the composition epoxy resin of gained through following method.Gained is the result be shown in Table 6.

Evaluation method

Eddy flow: under the condition described in Test Example A, measure.

MAP molding (not filling pore): under following condition; Utilize transfer moIding machine to make MAP-QFN (metal substrate: have the copper frame of nickel-palladium-gold plate, encapsulating face size: 45mm * 62mm, thickness: 0.65mm; Semiconducter device (QFN-16L) chip size: 4.0mm * 4.0mm; Semiconductor element size: 1.5mm * 1.5mm, thickness: 0.2mm, passivation type: SiN) be shaped:

Forming temperature: 175 ℃, annotate and press: 6.9MPa, curring time: 90 seconds.

Calculate not filling pore number.

The warpage of encapsulation: the MAP-QFN (not filling pore) that forms for being used to estimate the MAP molding, utilize surface roughness tester, measure displacement along the longitudinal direction along short transverse.The maximum displacement difference of measuring is the warpage of encapsulation, and its unit is a micron (μ m).

Soldering resistance: form above-mentioned MAP-QFN, make it under 175 ℃ temperature, carry out 4 hours post curing treatment.Be cut into independent small pieces then, obtain semiconducter device (QFN-16L) sample.20 samples of a cover that make are being handled under the following condition respectively: be to handle 120 hours under 60% the condition in 60 ℃ temperature, relative humidity, under 85 ℃ temperature, relative humidity is 60% condition, handled 168 hours then.Afterwards, make sample stand IR and flow 10 seconds of processing (260 ℃) again.Through ultrasonic fault detector the existence of the various interfacial separation of sample is observed.Encapsulation substandard products number when interfacial separation occurring is n, and fraction defective is expressed as n/20.

Test Example a-2 to a-12 and b-1 to b-9

According to the composition in table 6 and the table 7, prepare composition epoxy resin, and it is estimated as Test Example a-1 is said.Evaluation result is shown in table 6 and the table 7.Below be the component beyond the component utilized among the Test Example a-1:

Epoxy resin 3: biphenyl type epoxy resin (Japan Epoxy Resins Co.Ltd., YX4000K, softening temperature: 105 ℃, epoxide equivalent: 185)

Resol 2: phenol aralkyl resin (Mitsui Chemicals Inc., XLC-LL, softening temperature: 75 ℃, hydroxyl equivalent: 175)

γ-glycidyl propyl trimethoxy silicane

Polyhutadiene 2-6

Oxygen level in the oxyethane of polyhutadiene and the viscosity under 25 ℃ are shown in Table 8.

Table 6

Table 7

Note: ^*1; Owing to do not fill, do not obtain assess sample.

Table 8

Test Example D

Test Example a-1

Epoxy resin 1: phenol xenyl aralkyl-type epoxy resin (Nippon Kayaku Co.Ltd., NC3000P, epoxide equivalent: 274, softening temperature: 58 ℃): 1.90 weight parts

Epoxy resin 2: bisphenol A-type crystal rings epoxy resins (Japan Epoxy Resins Co.Ltd., YL6810, epoxide equivalent: 171, fusing point: 45 ℃): 2.85 weight parts

Resol 1: phenol xenyl aralkyl resin (Meiwa Plastic Industries, Ltd., MEH-7851SS, hydroxyl equivalent: 203, softening temperature: 65 ℃): 4.65 weight parts

Triphenylphosphine: 0.20 weight part

Spherical fused quartz (median size: 30 μ m): 89.00 weight parts

Epoxidised polyhutadiene compound 1:Nippon Petrochemicals Company, E-1800-6.5, number-average molecular weight: 1800, viscosity (25 ℃): 350Pas:0.50 weight part

γ-Qiu Jibingjisanjiayangjiguiwan: 0.40 weight part

POLISHING WAX-103: 0.20 weight part

Carbon black: 0.30 weight part

At room temperature these components are mixed with stirrer.70 ℃ under 120 ℃, mediate these mixtures with two rollers.After the cooling, this mixture of milling obtains composition epoxy resin.Estimate the composition epoxy resin of gained through following method.Gained is the result be shown in Table 9.

Evaluation method

Eddy flow: under the condition described in Test Example A, measure.When eddy flow during,, can cause during in package shape, occurring such as unfilled defective because flowability is too low less than 90cm.

The warpage of encapsulation: use transfer moIding machine under following condition, to form 352p BGA encapsulation:

Forming temperature: 175 ℃, annotate and press: 6.9MPa, set time: 2 minutes;

Wherein substrate is bismaleimides-cyanate resin/spun glass substrate, and its thickness is 0.56mm; Dimensions of semiconductor devices is 30mm * 30mm (thickness is 1.17mm); Semiconductor chip size is 15mm * 15mm (thickness is 0.35mm).Under 175 ℃, carry out 2 hours post curing treatment, be cooled to room temperature after, utilize surface roughness tester, measure displacement from the diagonal of the door of encapsulation along short transverse.The maximum displacement difference of measuring is the warpage of encapsulation, and its unit is micron (μ m).When the warpage of encapsulation is 70 μ m or when above, the inapplicable packaged material that acts on the encapsulation single face of said composition then.

Gold thread deformation rate: under the condition described in Test Example A, measure.When the gold thread deformation rate is 4% or when above,, the contact between the gold thread is short-circuited because can making.

Soldering resistance: will under 175 ℃ temperature, carry out 2 hours post curing treatment to obtain sample like the 352pBGA that said method being used to of forming estimated warpage of packaging assembly.Under following condition, make the sample of ten in a cover soak processing respectively then: 60 ℃ temperature, relative humidity 60%, handled 168 hours; 85 ℃ temperature, relative humidity 60% were handled 168 hours.Afterwards, through ultrasonic fault detector the internal fissure of sample and the existence of various interface peels being observed, is n when encapsulating the substandard products number, and fraction defective is expressed as n/10.When encapsulation substandard products number is 3 or still less the time, the then test estimated through soldering resistance of sample.

Test Example a-2 to a-26

According to the composition in the table 9,10 and 11, the preparation composition epoxy resin, and like Test Example a-1 to its said evaluation.Evaluation result is shown in the table 9,10 and 11.Below be the component beyond the component utilized among the Test Example a-1:

Epoxy resin 3: o-cresol formaldehyde type epoxy resin (Nippon Kayaku Co.Ltd., EOCN-1020-55, epoxide equivalent: 196, softening temperature: 55 ℃)

Resol 2: phenol phenyl aralkyl resin (Mitsui Chemicals Inc., XLC-LL, softening temperature: 75 ℃, hydroxyl equivalent: 175)

1,8-diazabicyclo (5,4,0) hendecene-7 (below be called " DBU ")

Epoxidized polybutadiene compound 2: by the compound of general formula (4) expression, wherein, k, l, m and n are 1 to 3 integer; R1 has by C _pH _qThe structure of expression; P is 0 to 3 integer; Q is 1 to 8 integer, number-average molecular weight: 400, and viscosity (25 ℃): 150Pas

Epoxidized polybutadiene compound 3: by the compound of general formula (4) expression, wherein, k, l, m and n are 1 to 100 integer; R1 has by C _pH _qThe structure of expression; P is 0 to 10 integer; Q is 1 to 21 integer, number-average molecular weight: 4500, and viscosity (25 ℃): 800Pas

Table 9

Table 10

Table 11

Test Example E

Test Example a-1

Epoxy resin 1: phenol biphenyl aralkyl-type epoxy resin (Nippon Kayaku Co., Ltd., NC3000, epoxide equivalent: 274, softening temperature: 58 ℃): 2.55 weight parts

Epoxy resin 2: bisphenol A-type crystal rings epoxy resins (Japan Epoxy Resins Co.Ltd., YL6810, epoxide equivalent: 171, fusing point: 45 ℃): 2.56 weight parts

Resol 1: phenol xenyl aralkyl resin (Meiwa Plastic Industries, Ltd., MEH-7851SS, hydroxyl equivalent: 203, softening temperature: 65 ℃): 4.89 weight parts

Perbutan 1 (Ube Industries, Ltd., HYCAR CTBN 1008-SP; In general formula (3), x=0.82, y=0.18, z=62 (MV)): 0.15 weight part

Triphenylphosphine: 0.15 weight part

Fusion spherical quartz (median size: 30 μ m): 89.00 weight parts

γ-glycidyl propyl trimethoxy silicane: 0.20 weight part

POLISHING WAX-103: 0.20 weight part

Carbon black: 0.30 weight part

With stirrer these components are mixed.Mediate this mixture with two rollers then, the surface temperature of two rollers is 90 ℃ and 45 ℃.After the cooling, this mixture of milling obtains composition epoxy resin.Estimate said composition epoxy resin through following method.Gained is the result be shown in Table 12.

Evaluation method

Eddy flow: under the condition described in Test Example A, measure.Picking out eddy flow is unacceptable product less than the sample of 90cm.

The warpage of encapsulation: under the condition described in Test Example A, measure.Warpage is that 60 μ m or above sample are substandard products.

Gold thread deformation rate: under the condition described in Test Example A, measure.The gold thread deformation rate be 3% or above sample be substandard products.

Soldering resistance: the 352-pin BGA that forms like said method is encapsulated in carry out under 175 ℃ the temperature 2 hours post curing treatment to obtain being used to estimate the sample of warpage of packaging assembly.Ten encapsulation of a cover of gained are that 60% atmosphere was handled 168 hours down or is processing 168 hours under 60% the condition 85 ℃ temperature, relative humidity in 60 ℃ temperature, relative humidity.Afterwards, 260 ℃ peak temperature (255 ℃ or or higher temperature under handled for 10 seconds) under make encapsulation stand IR to flow processing again.After the processing, inside is peeled off or the existence of crackle is observed, and calculate the substandard products number of semiconducter device through ultrasonic fault detector.When the substandard products number of semiconducter device was n, fraction defective was expressed as n/10.

Test Example a-2 to a-22

According to the composition in the table 12,13 and 14, prepare composition epoxy resin, and it is estimated according to Test Example a-1.Evaluation result is shown in the table 12,13 and 14.

Below be the component beyond the component utilized among the Test Example a-1:

Resol 2: by the resol of general formula (12) expression (Tohto Kasei Co., Ltd., SN-485, softening temperature: 87 ℃, hydroxyl equivalent: 210)

Resol 3: have phenylen moiety phenol aralkyl resin (Mitsui Chemicals Inc., XLC-LL, softening temperature: 75 ℃, hydroxyl equivalent: 175)

Resol 4: lacquer resins (softening temperature: 80 ℃, hydroxyl equivalent: 105)

Perbutan 2 (Ube Industries, Ltd., HYCAR CTBN 1300X13; In general formula (3), x=0.74, y=0.26, z=54 (MV)):

1,8-diazabicyclo (5,4,0) hendecene-7 (below be called " DBU ")

γ-Qiu Jibingjisanjiayangjiguiwan

Table 12

Table 13

Table 14

Claims

1. be used for the composition epoxy resin of packaged semiconductor, it comprises:

(A) crystal rings epoxy resins,

(B) resol of representing by general formula (1):

(C-2) perbutan of carboxy blocking, its content in whole composition epoxy resin is 0.1wt%-0.3wt%, comprise two endpoint values and

(D) mineral filler, its content in whole composition epoxy resin is 80wt%-95wt%, comprises two endpoint values,

Wherein, the perbutan of said carboxy blocking is represented by general formula (3):

2. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 1, wherein said resol (B) is represented by general formula (2):

3. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 2, the content of wherein said mineral filler (D) in whole composition epoxy resin is 85wt%-95wt%, comprises two endpoint values.

4. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 2, it further comprises curing catalyst (E).

5. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 1, wherein said crystal rings epoxy resins (A) is represented by general formula (4):

Wherein, X be selected from singly-bound ,-O-,-S-and-C (R2) ₂-group; R1 is the alkyl with 1 to 6 carbon atom; Two or more R1 can be identical or different; M is that the integer R2 of 0-4 is hydrogen or the alkyl with 1 to 4 carbon atom; Two or more R2 can be identical or different,

Said resol (B) is represented by general formula (5):

Further comprise epoxy resin (F) by general formula (6) expression:

6. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 5, wherein said perbutan (C-2) is the perbutan of carboxy blocking, it is represented by general formula (3):

7. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 5, the content of wherein said perbutan (C-2) in whole composition epoxy resin is 0.1wt%-0.3wt%, comprises two endpoint values.

8. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 5, wherein said epoxy resin (F) is 10/90 to 90/10 with the weight ratio [(F)/(A)] of said crystal rings epoxy resins (A) by general formula (4) expression, comprises two endpoint values,

9. the composition epoxy resin that is used for packaged semiconductor as claimed in claim 5, it further comprises curing catalyst (E).

10. semiconducter device, wherein semi-conductor chip is by one of any described composition epoxy resin encapsulation that is used for packaged semiconductor among the claim 2-4.

11. be used for the surface installing type composition epoxy resin of packaged semiconductor, said composition is one of any described composition epoxy resin that is used for packaged semiconductor among the claim 2-4, it is used for package surface mounted semiconductor device,

12. surface mount type semiconductor device, wherein semi-conductor chip is to be encapsulated by the described surface installing type composition epoxy resin that is used for packaged semiconductor of claim 11.

13. semiconducter device, wherein semi-conductor chip is by one of any described composition epoxy resin encapsulation that is used for packaged semiconductor among the claim 5-9.

14. be used for the surface installing type composition epoxy resin of packaged semiconductor, said composition is one of any described composition epoxy resin that is used for packaged semiconductor among the claim 5-9, it is used for package surface mounted semiconductor device,

15. surface mount type semiconductor device, wherein semi-conductor chip is to be encapsulated by the described surface installing type composition epoxy resin that is used for packaged semiconductor of claim 14.