CN106280254A - Filler and preparation method thereof and purposes at the bottom of a kind of low-k moulding type epoxy - Google Patents
Filler and preparation method thereof and purposes at the bottom of a kind of low-k moulding type epoxy Download PDFInfo
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- CN106280254A CN106280254A CN201610667599.3A CN201610667599A CN106280254A CN 106280254 A CN106280254 A CN 106280254A CN 201610667599 A CN201610667599 A CN 201610667599A CN 106280254 A CN106280254 A CN 106280254A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/04—Carbon
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses a kind of low-k type (lowk) filler (MUF) at the bottom of moulding type epoxy and its production and use.This MUF is the low of 2 ~ 10% by percetage by weightkEpoxy resin, percetage by weight be 0 ~ 5% biphenyl type epoxy resin, percetage by weight be the low of 2 ~ 10%kThe composition such as coupling agent and accelerator, coloring agent, releasing agent that silica filler that phenolic curing agent, percetage by weight are 80 ~ 96%, percetage by weight are 0.01 ~ 1%.Instead of, with phenolic curing agent, the resin that dielectric constant of the prior art is higher owing to employing the epoxy resin of low-k, the MUF that therefore present invention provides has relatively low dielectric constant and dielectric loss.The MUF that the present invention provides can be widely used for high frequency microelectronics and the field such as the encapsulation of opto-electronic device and manufacture.
Description
Technical field
The present invention relates to a kind of polymeric material field, filler at the bottom of particularly a kind of low-k moulding type epoxy and
Preparation method and purposes.
Background technology
Along with integrated circuit (IC) manufactures the development towards small size Yu high density direction, interconnection delay is increasingly becoming impact
One of principal element of IC performance.To this end, novel interconnecting material and interlevel dielectric material have been carried out widely studied by people.Research
Result shows, the main cause causing interconnection to postpone is closely related with the dielectric constant of interconnection and interlevel dielectric material.Pass through
Years of researches, current people successful Application C μ and low-k (low-k) inter-level dielectric promote the work of components and parts
Make speed and reduce power consumption.Compared with traditional silicon dioxide interlayer dielectric material, it is swollen that the material newly developed is generally of heat
The defects such as swollen coefficient (CTE) is higher, mechanical strength is poor.Low-k inter-level dielectric does not mate with the CTE between silicon and often exists
Higher thermal and mechanical stress is formed between interface.This stress generally requires filler at the bottom of epoxy (μ nderfill) and eliminates.Research is aobvious
Show have that glass transition temperature (Tg) is high, modulus μ nderfill material low, dielectric constant characteristic low with loss can be effective
Avoid layering and chip rupture, be thus advantageous to improve the reliability of low-k type flip-chip.
In recent years, filler at the bottom of moulding type epoxy (molded μ nderfill, M Μ F) is with its production efficiency height, solidfied material
The features such as porosity is low, reliability is excellent, gradually substitute filler (capillary μ at the bottom of traditional capillary type epoxy
Nderfill) it is widely applied in flip chip type (flip chip) encapsulates.In low-k type Flip-Chip Using
In, M Μ F material, while bearing stress buffer and elimination effect, itself also needs to have low-k feature, to adapt to envelope
The performance requirement of the overall low dielectric of dress body.The key component of tradition M Μ F material, including aromatic epoxy resin, phenolic aldehyde tree
The dielectric constant of the material such as fat, silicon powder is the highest, it is difficult to meet development and the exploitation of low-k M Μ F material, at present literary composition
In offering, the research and development for low-k M Μ F still rarely have report.
Summary of the invention
The technical problem to be solved in the present invention is for the deficiencies in the prior art, it is proposed that one have low-k,
Low water absorption, temperature tolerance are excellent, filler at the bottom of the low-k moulding type epoxy of good mechanical performance.The invention solves the problems that is another
An outer preparation method that provided low-k M Μ F material is provided and including crystal wafer chip dimension
Encapsulation (WLCSP), fan-out-type wafer size encapsulation (FO-WLCSP) etc. are in interior large scale integrated circuit (Μ LSI) encapsulation
Application.
The technical problem to be solved in the present invention is achieved through the following technical solutions, a kind of low-k moulding type
Filler at the bottom of epoxy, is characterized in, the raw material including following percentage by weight is made:
Low-k epoxy resin 2 ~ 10%；
Biphenyl type epoxy resin 0 ~ 5%；
Low-k phenolic curing agent 2 ~ 10%；
Inorganic filler 80 ~ 96%；
Accelerator 0.01 ~ 0.5%；
Coupling agent 0.1 ~ 1%；
Releasing agent 0.1 ~ 1%；
Coloring agent 0.1 ~ 1%；
Ion capturing agent 0.1 ~ 1%；
Low stress agent 0.01 ~ 0.5%.
The low-that the present invention useskEpoxy and phenolic resin can select fluorine resin, containing alicyclic structure resin (such as hydrogenation
Bisphenol-A epoxy, dcpd resin etc.) or containing bulky substituent (such as fluorenyl etc.) resin etc..Result of study shows, polymer
The dielectric constant of material is closely related with mole polarizability of its molecular structure and molal volume, have low mole of polarizability with
And the polymer of high molal volume often has relatively low dielectric constant.(Maier G, Low dielectric constant
polymers for microelectronics, Progress in Polymer Science, 2001,1:3).For
For epoxy resin and phenolic resin, the hydroxyl (-OH) in its molecular structure has higher mole polarizability, therefore these trees
Fat often shows higher dielectric constant (> 4.0@1MHz).In order to reduce the dielectric constant of epoxy resin and phenolic resin,
People have attempted number of ways, such as, introduce low mole of polarizability group in its molecular structure (as containing fluoro substituents, alicyclic ring knot
Structure etc.) or high molal volume group (such as naphthalene nucleus, fluorenyl, sulfuryl etc.).Both approach have cooperative effect sometimes, the most permissible
Reduce the dielectric constant of resin simultaneously, but (the Og μ ra I. Low dielectric constant that cancels out each other sometimes
epoxy resins, in Handbook of Low and High Dielectric Constant Materials and Their Applications, Volμme 1: Materials and Processing, Academic Press, 1999,
Pp 213).
In the present invention, epoxy resin used is selected from structure epoxy resin (wherein n=0-10, R=-C shown in formula IxF2x+1, x
=1-10), or epoxy resin (wherein n=0-10, the R that structure is as shown in Formula II1=-CxF2x+1, x=1-5 or R1=, R2=-
CyF2y+1, y=1-5), or epoxy resin shown in formula III.
(Formulas I)
(Formula II)
(formula III)
The dielectric constant of above-mentioned epoxy resin cured product is between 2.5 ~ 3.5, hence it is evident that less than plain edition epoxy resin cured product
(4.0-5.0).It is chosen in particular from epoxy resin (n=0, R=-CF shown in Formulas I3), epoxy resin (n=0, R shown in Formula II1=-CF3),
Epoxy resin (n=0, R shown in Formula II1=, R2=-CF3), one in epoxy resin shown in formula III or by any applicable
Ratio composition mixture, epoxy resin (n=0, R=-CF shown in preferred formula I3).
In above-mentioned constitutive material, described biphenyl type epoxy resin is selected from structure epoxy resin as shown in formula IV.Wherein, R
=-H or-CH3。
(formula IV)
In above-mentioned constitutive material, described phenolic curing agent is selected from phenolic resin (wherein n=0-10, the R=-shown in Formula V
CxF2x+1, x=1-10), or the phenolic resin that structure is as shown in Formula IV (wherein n=0-10, m=1-3, and m are < n).
(Formula V)
(Formula IV)
Phenolic resin shown in Formula V and Formula IV also can with to benzene aralkyl-type phenol resin, biphenyl aralkyl-type phenol resin, many officials
Can group at least one in benzene aralkyl-type phenol resin, copoly type biphenyl aralkyl-type phenol resin or multiple by any
Ratio composition mixture applicatory；
In above-mentioned constitutive material, described accelerator is selected from glyoxaline compound, including 2-methylimidazole, 2-ethyl imidazol(e), 2-
At least one in ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxyethyl imidazole, preferably 2-phenyl-4-methyl-5-hydroxyl
Ethyl imidazol(e)；With at least one in organic phosphine compound；Described organic phosphine compound selected from triphenylphosphine, tributylphosphine, three
In (p-methylphenyl) phosphine, three (nonyl phenyl) phosphine, tetraphenyl phosphine-tetraphenylborate, triphenylphosphine-1,4-benzoquinone addition product
At least one or multiple in any ratio applicatory composition mixture, triphenylphosphine-1,4-benzoquinone addition product.
In above-mentioned constitutive material, described coupling agent is selected from γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH-
560), in γ aminopropyltriethoxy silane (KH-550), γ-mercaptan aminopropyl trimethoxysilane (KH-580) extremely
One or more mixture formed in any ratio applicatory few, preferably KH-560.
In above-mentioned constitutive material, described releasing agent is selected from native paraffin (bar wax etc.), synthetic wax (Tissuemat E etc.), tristearin
In acid, Palmic acid, zinc stearate, calcium stearate, lithium stearate and magnesium stearate at least one or multiple by any applicable
Ratio composition mixture, preferably bar wax and Tissuemat E.
In above-mentioned constitutive material, described inorganic filler is selected from spherical fusion SiO2Micropowder, its median (d 50) no
More than 15 μm, maximum particle diameter is less than 30 μm.
In above-mentioned constitutive material, described coloring agent is selected from white carbon black.
In above-mentioned constitutive material, described low stress agent is selected from polysiloxanes.
The method preparing above-mentioned M Μ F material that the present invention provides, comprises the steps:
By epoxy resin described above, described phenolic curing agent, described accelerator, described coupling agent, described releasing agent, described low
Stressed agent, described inorganic filler mixing after mixing, obtain described M Μ F material.In described mixing step, temperature is 80-120 DEG C,
Concretely 80-100 DEG C, 90-110 DEG C or 100-120 DEG C, preferably 90-110 DEG C.
In concrete operations, can extrude mixing in an extruder by above-mentioned each component in required ratio mix homogeneously, obtain
Homodisperse mixture, after cooling down, pulverizing, buys cake on pancake making machine, obtains the M Μ F material of required size size.
It addition, the invention described above provide M Μ F material at WLCSP, FO-WLCSP etc. at interior large scale integrated circuit
Application in (Μ LSI) encapsulation falls within protection scope of the present invention.
The present invention, by using fluorine-containing type and biphenyl type epoxy resin, is ensureing that prepared M Μ F material has low dielectric
On the premise of constant and dielectric loss, also can give the good heat resistance of M Μ F material and mechanical property.With prior art M Μ
F material is compared, M Μ F material disclosed by the invention has dielectric constant and dielectric loss is low, heat resistance is good, pack completeness is high,
The features such as good mechanical performance, can be widely used for WLCSP, FO-WLCSP etc. in interior large scale integrated circuit (Μ LSI) encapsulation
In.
Accompanying drawing explanation
Fig. 1 is dielectric constant and the dielectric loss test result of M Μ F prepared by the present invention.
Detailed description of the invention
Filler at the bottom of a kind of low-k moulding type epoxy, described M Μ F material includes the raw material of following percentage by weight:
Low-k epoxy resin 2 ~ 10%；
Biphenyl type epoxy resin 0 ~ 5%；
Low-k phenolic curing agent 2 ~ 10%；
Inorganic filler 80 ~ 96%；
Accelerator 0.01 ~ 0.5%；
Coupling agent 0.1 ~ 1%；
Releasing agent 0.1 ~ 1%；
Coloring agent 0.1 ~ 1%；
Ion capturing agent 0.1 ~ 1%；
Low stress agent 0.01 ~ 0.5%.
The low-that the present invention useskEpoxy and phenolic resin can select fluorine resin, containing alicyclic structure resin (such as hydrogenation
Bisphenol-A epoxy, dcpd resin etc.) or containing bulky substituent (such as fluorenyl etc.) resin etc..Result of study shows, polymer
The dielectric constant of material is closely related with mole polarizability of its molecular structure and molal volume, have low mole of polarizability with
And the polymer of high molal volume often has relatively low dielectric constant.(Maier G, Low dielectric constant
polymers for microelectronics, Progress in Polymer Science, 2001,1:3).For
For epoxy resin and phenolic resin, the hydroxyl (-OH) in its molecular structure has higher mole polarizability, therefore these trees
Fat often shows higher dielectric constant (> 4.0@1MHz).In order to reduce the dielectric constant of epoxy resin and phenolic resin,
People have attempted number of ways, such as, introduce low mole of polarizability group in its molecular structure (as containing fluoro substituents, alicyclic ring knot
Structure etc.) or high molal volume group (such as naphthalene nucleus, fluorenyl, sulfuryl etc.).Both approach have cooperative effect sometimes, the most permissible
Reduce the dielectric constant of resin simultaneously, but (the Og μ ra I. Low dielectric constant that cancels out each other sometimes
epoxy resins, in Handbook of Low and High Dielectric Constant Materials and Their Applications, Volμme 1: Materials and Processing, Academic Press, 1999,
Pp 213).
In the present invention, epoxy resin used is selected from structure epoxy resin (wherein n=0-10, R=-C shown in formula IxF2x+1, x
=1-10), or epoxy resin (wherein n=0-10, the R that structure is as shown in Formula II1=-CxF2x+1, x=1-5 or R1=, R2=-
CyF2y+1, y=1-5), or epoxy resin shown in formula III.
(Formulas I)
(Formula II)
(formula III)
The dielectric constant of above-mentioned epoxy resin cured product is between 2.5 ~ 3.5, hence it is evident that less than plain edition epoxy resin cured product
(4.0-5.0).It is chosen in particular from epoxy resin (n=0, R=-CF shown in Formulas I3), epoxy resin (n=0, R shown in Formula II1=-CF3),
Epoxy resin (n=0, R shown in Formula II1=, R2=-CF3), one in epoxy resin shown in formula III or by any applicable
Ratio composition mixture, epoxy resin (n=0, R=-CF shown in preferred formula I3).
In above-mentioned constitutive material, described biphenyl type epoxy resin is selected from structure epoxy resin as shown in formula IV.Wherein, R
=-H or-CH3。
(formula IV)
In above-mentioned constitutive material, described phenolic curing agent is selected from phenolic resin (wherein n=0-10, the R=-shown in Formula V
CxF2x+1, x=1-10), or the phenolic resin that structure is as shown in Formula IV (wherein n=0-10, m=1-3, and m are < n).
(Formula V)
(Formula IV)
Phenolic resin shown in Formula V and Formula IV also can with to benzene aralkyl-type phenol resin, biphenyl aralkyl-type phenol resin, many officials
Can group at least one in benzene aralkyl-type phenol resin, copoly type biphenyl aralkyl-type phenol resin or multiple by any
Ratio composition mixture applicatory；
In above-mentioned constitutive material, described accelerator is selected from glyoxaline compound, including 2-methylimidazole, 2-ethyl imidazol(e), 2-
At least one in ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxyethyl imidazole, preferably 2-phenyl-4-methyl-5-hydroxyl
Ethyl imidazol(e)；With at least one in organic phosphine compound；Described organic phosphine compound selected from triphenylphosphine, tributylphosphine, three
In (p-methylphenyl) phosphine, three (nonyl phenyl) phosphine, tetraphenyl phosphine-tetraphenylborate, triphenylphosphine-1,4-benzoquinone addition product
At least one or multiple in any ratio applicatory composition mixture, triphenylphosphine-1,4-benzoquinone addition product.
In above-mentioned constitutive material, described coupling agent is selected from γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH-
560), in γ aminopropyltriethoxy silane (KH-550), γ-mercaptan aminopropyl trimethoxysilane (KH-580) extremely
One or more mixture formed in any ratio applicatory few, preferably KH-560.
In above-mentioned constitutive material, described releasing agent is selected from native paraffin (bar wax etc.), synthetic wax (Tissuemat E etc.), tristearin
In acid, Palmic acid, zinc stearate, calcium stearate, lithium stearate and magnesium stearate at least one or multiple by any applicable
Ratio composition mixture, preferably bar wax and Tissuemat E.
In above-mentioned constitutive material, described inorganic filler is selected from spherical fusion SiO2Micropowder, its median (d 50) no
More than 15 μm, maximum particle diameter is less than 30 μm.
In above-mentioned constitutive material, described coloring agent is selected from white carbon black.
In above-mentioned constitutive material, described low stress agent is selected from polysiloxanes.
The method preparing above-mentioned M Μ F material that the present invention provides, comprises the steps:
By epoxy resin described above, described phenolic curing agent, described accelerator, described coupling agent, described releasing agent, described low
Stressed agent, described inorganic filler mixing after mixing, obtain described M Μ F material.In described mixing step, temperature is 80-120 DEG C,
Concretely 80-100 DEG C, 90-110 DEG C or 100-120 DEG C, preferably 90-110 DEG C.
In concrete operations, can extrude mixing in an extruder by above-mentioned each component in required ratio mix homogeneously, obtain
Homodisperse mixture, after cooling down, pulverizing, buys cake on pancake making machine, obtains the M Μ F material of required size size.
It addition, the invention described above provide M Μ F material at WLCSP, FO-WLCSP etc. at interior large scale integrated circuit
Application in (Μ LSI) encapsulation falls within protection scope of the present invention.
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following example.Institute
Method of stating is conventional method if no special instructions.Described material the most all can obtain from open commercial sources.This
Fluorine-containing type epoxy resin (n=0, R=-CF shown in Formulas I used in invention3, epoxide equivalent: 355 g/eq) and can be according to document (China
Patent CN1962713) synthesis；Fluorine-containing type epoxy resin (n=0, R shown in Formula II used1=, R2=-CF3, epoxide equivalent:
275 g/eq) can close according to document (Jo μ rnal of Applied Polymer Science, 2011,120:148-155)
Become；Fluorine-containing type epoxy resin (epoxide equivalent: 272 g/eq) shown in formula III used can according to document (Macromolec μ les,
1996,29:2006-2010) synthesis；Biphenyl type epoxy resin (R=-CH shown in formula IV used3) purchased from Mitsubishi chemistry strain
Formula commercial firm (trade name YX-4000H, epoxide equivalent: 186 g/eq).Phenolic curing agent (n=0, R=-CF shown in Formula V used3, hydroxyl
Base equivalent: 271 g/eq) can synthesize according to document (Chinese patent CN1962713).Phenolic curing agent shown in Formula IV (n=2, m=1,
Hydroxyl equivalent: 230 g/eq) can be according to document (Reactive & F μ nctional Polymers, 2008,68:1185-
1193) synthesis.Biphenyl aralkyl-type epoxy resin as a comparison case, is purchased from Nippon Kayaku K. K's (trade name NC-
3000, epoxide equivalent: 275 g/eq)；O-cresol formaldehyde type epoxy resin is purchased from Dainippon Ink Chemicals of Japan (trade name N-665-
EXP-S, epoxide equivalent: 200 g/eq).Novolac firming agent as a comparison case, is purchased from Changchun, Taiwan Resins Corporation (business
Name of an article 195XL-4, hydroxyl equivalent: 106 g/eq)；Biphenyl aralkyl type phenol firming agent, is purchased from Japanese bright and chemical conversion strain formula
Commercial firm's (trade name MEH-7851SS, hydroxyl equivalent: 200 g/eq).
Accelerator used is purchased from NSK KCC (trade name: TPP-BQ)；Coupling agent γ-(2,3-used
Epoxy the third oxygen) propyl trimethoxy silicane (KH-560) is purchased from Nanjing Lian Gui Chemical Co., Ltd. or other company's relative commercial
Product；Spherical type molten silicon micropowder used purchased from Admatechs company of Japan (trade name: SQ-CC69, median: 5 μm,
Dielectric constant: 3.82@1MHz；Dielectric loss: 0.00002@1MHz)；Ion capturing agent used is purchased from Japan's consonance chemical industry
Co., Ltd. (trade name: DHT-4A)；Releasing agent used is purchased from Honeywell Corp. USA (trade name: AC316A)；Charcoal used
Black purchased from Mitsubishi KCC (trade name: MA-600)；Described low stress agent is purchased from Dow Corning Corporation of Japan (commodity
Name: SF-8421).
The dielectric constant of M Μ F and dielectric loss use Agilent 4291B system test, and test temperature is 30oC, test
Frequency is 102~1010Hz.Before test, sample is 100oC is vacuum dried 8h.
M Μ F Packing character evaluation methodology: use ultrasonic scanning microscope (C-SAM, Sonoscan company of the U.S.) to investigate envelope
Between chip after dress and substrate, the bubble in M Μ F has nil case, and 30 chips of encapsulation carry out Packing character investigation altogether.C-SAM sweeps
Retouch, exist between chip and M Μ F the chip-count of bubble less than 3 for excellent, otherwise for poor.The flip chip ball grid array used
Encapsulation (FC-BGA) size is as follows: chip size: 5 × 5 × 0.2 mm；Substrate size: 20 × 20 × 0.5 mm；Space between solder balls:
150 μm；Slit separation between chip and substrate: 70 μm.
Spiral flow length is tested: use transfer moIding machine to inject in mould by M Μ F material, injection temperature: 175oC,
Injection pressure: 7.0 MPa, pressing time: 120s, test M Μ F length of flow (cm).
Gel time: hot plate method, is heated to 175 ± 1 by electric hot plateoC, takes 2-3g sample powder and is placed on electric hot plate, powder
Material is terminal when gradually being become colloidal state by fluid, reads required time.
Hygroscopicity is tested: powder is prepared as 80 × 10 × 4 mm battens, puts into and carry out 24h steaming and decocting in deionized water, point
Weight W of batten before other experiment with computing1Weight W with the batten that absorbs water after test2, by (W2-W1)/W1× 100% calculates moisture absorption
Rate.
Embodiment 1
The preparation of M Μ F material, raw material is selected from the component of following percetage by weight:
Fluorine-containing epoxy resin (Formulas I, n=0, R=-CF3) 3.44 %；
Biphenyl epoxy resin (formula IV, R=-CH3) 2.3%
Phenolic curing agent (Formula IV, n=2, m=1) 5.06%；
Accelerator (TPP-BQ) 0.3%；
Coupling agent (KH-560) 0. 2%；
Releasing agent (AC316A) 0.2%；
Coloring agent (MA-600) 0.3%
Ion capturing agent (DHT-4A) 0.1%
Low stress agent (SF-8421) 0.1 %；
Spherical fusion silica flour (SQ-CC69) 88%.
By said components in an extruder in 100oMixing extrusion under the conditions of C, obtains homodisperse M Μ F, cooling, powder
Broken.Pancake making machine is beaten cake, obtains the M Μ F of required size size.Additionally above-mentioned M Μ F is made various in transfer moIding machine
Sample, carries out properties test, and result is listed in table 1.
The dielectric constant test result of made M Μ F is as shown in Figure 1.
Embodiment 2
The preparation of M Μ F material, raw material is selected from the component of following percetage by weight:
Fluorine-containing epoxy resin (Formula II, n=0, R1= , R2=-CF3) 3.0%；
Biphenyl epoxy resin (formula IV, R=-CH3) 1.97%
Phenolic curing agent (Formula V, n=0, R=-CF3) 5.83%；
Accelerator (TPP-BQ) 0.3%；
Coupling agent (KH-560) 0. 2%；
Releasing agent (AC316A) 0.2%；
Ion capturing agent (DHT-4A) 0.1%
Coloring agent (MA-600) 0.3%
Low stress agent (SF-8421) 0.1 %；
Spherical fusion silica flour (SQ-CC69) 88%.
By said components in an extruder in 100oMixing extrusion under the conditions of C, obtains homodisperse M Μ F, cooling, powder
Broken.Pancake making machine is beaten cake, obtains the M Μ F of required size size.Additionally above-mentioned M Μ F is made various in transfer moIding machine
Sample, carries out properties test, and result is listed in table 1.
The dielectric constant test result of made M Μ F is as shown in Figure 1.
Embodiment 3
The preparation of M Μ F material, raw material is selected from the component of following percetage by weight:
Fluorine-containing epoxy resin (formula III) 5.85%；
Phenolic curing agent (Formula IV, n=2, m=1) 4.95%；
Accelerator (TPP-BQ) 0.3%；
Coupling agent (KH-560) 0. 2%；
Releasing agent (AC316A) 0.2%；
Coloring agent (MA-600) 0.3%
Ion capturing agent (DHT-4A) 0.1%
Low stress agent (SF-8421) 0.1 %；
Spherical fusion silica flour (SQ-CC69) 88%.
By said components in an extruder in 100oMixing extrusion under the conditions of C, obtains homodisperse M Μ F, cooling, powder
Broken.Pancake making machine is beaten cake, obtains the M Μ F of required size size.Additionally above-mentioned M Μ F is made various in transfer moIding machine
Sample, carries out properties test, and result is listed in table 1.
The dielectric constant test result of made M Μ F is as shown in Figure 1.
Comparative example 1
The preparation of M Μ F material, raw material is selected from the component of following percetage by weight:
Biphenyl aralkyl epoxy resin (NC3000) 6.25%；
Biphenyl aralkyl phenolic curing agent (MEH-7851SS) 4.55%；
Accelerator (TPP-BQ) 0.3%；
Coupling agent (KH-560) 0. 2%；
Releasing agent (AC316A) 0.2%；
Coloring agent (MA-600) 0.3%
Ion capturing agent (DHT-4A) 0.1%
Low stress agent (SF-8421) 0.1 %；
Spherical fusion silica flour (SQ-CC69) 88%.
By said components in an extruder in 100oMixing extrusion under the conditions of C, obtains homodisperse M Μ F, cooling, powder
Broken.Pancake making machine is beaten cake, obtains the M Μ F of required size size.Additionally above-mentioned M Μ F is made various in transfer moIding machine
Sample, carries out properties test, and result is listed in table 1.
The dielectric constant test result of made M Μ F is as shown in Figure 1.
Comparative example 2
The preparation of M Μ F material, raw material is selected from the component of following percetage by weight:
O-cresol formaldehyde epoxy resin (N-665-EXP-S) 7.06%；
Novolac firming agent (195XL-4) 3.74%；
Accelerator (TPP-BQ) 0.3%；
Coupling agent (KH-560) 0. 2%；
Releasing agent (AC316A) 0.2%；
Coloring agent (MA-600) 0.3%
Ion capturing agent (DHT-4A) 0.1%
Low stress agent (SF-8421) 0.1 %；
Spherical fusion silica flour (SQ-CC69) 88%.
By said components in an extruder in 100oMixing extrusion under the conditions of C, obtains homodisperse M Μ F, cooling, powder
Broken.Pancake making machine is beaten cake, obtains the M Μ F of required size size.Additionally above-mentioned M Μ F is made various in transfer moIding machine
Sample, carries out properties test, and result is listed in table 1.
The dielectric constant test result of made M Μ F is as shown in Figure 1.
Above-described embodiment is as shown in table 1 with the performance of the M Μ F that comparative example prepares.
Table 1 implementation result
It can be seen that the M Μ F that the present invention provides is either in dielectric constant and dielectric loss, mobility, fillibility and solidification
Property aspect is superior to prior art M Μ F(comparative example 1).Comparative example 2 owing to have employed low-k epoxy resin and phenolic resin, because of
This dielectric constant is suitable with the M Μ F that the present invention provides with dielectric loss, but owing to not using biphenyl type epoxy resin, causes it
The aspects such as its mobility and fillibility are below the M Μ F that the present invention provides.
Claims (10)
1. filler at the bottom of a low-k moulding type epoxy, it is characterised in that be made up of the raw material of following percentage by weight:
Low-k epoxy resin 2 ~ 10%；
Biphenyl type epoxy resin 0 ~ 5%；
Low-k phenolic curing agent 2 ~ 10%；
Inorganic filler 80 ~ 96%；
Accelerator 0.01 ~ 0.5%；
Coupling agent 0.1 ~ 1%；
Releasing agent 0.1 ~ 1%；
Coloring agent 0.1 ~ 1%；
Ion capturing agent 0.1 ~ 1%；
Low stress agent 0.01 ~ 0.5%.
Low dielectric the most according to claim 1
Filler at the bottom of constant moulding type epoxy, it is characterised in that: described low-k epoxy resin is selected from structure epoxy shown in formula I
Resin (wherein n=0-10, R=-CxF2x+1, x=1-10), or epoxy resin (wherein n=0-10, the R that structure is as shown in Formula II1=-
CxF2x+1, x=1-5 or R1=, R2=-CyF2y+1, y=1-5), or structure epoxy resin as shown in formula III:
(Formulas I)
(Formula II)
(formula III)
It is chosen in particular from epoxy resin (n=0, R=-CF shown in Formulas I3), epoxy resin (n=0, R shown in Formula II1=-CF3), Formula II institute
Show epoxy resin (n=0, R1=, R2=-CF3), a kind of in epoxy resin shown in formula III or form in any proportion mixed
Compound, epoxy resin (n=0, R=-CF shown in preferred formula I3).
Filler at the bottom of low-k moulding type epoxy the most according to claim 1, it is characterised in that: described biphenyl type ring
Epoxy resins is selected from structure epoxy resin as shown in formula IV, wherein, R=-H or-CH3,
(formula IV).
Filler at the bottom of low-k moulding type epoxy the most according to claim 1, it is characterised in that: described phenolic cure
Agent is selected from phenolic resin (wherein n=0-10, the R=-C shown in Formula VxF2x+1, x=1-10), or the phenolic aldehyde that structure is as shown in Formula IV
Resin (wherein n=0-10, m=1-3, and m < n):
(Formula V)
(Formula IV)
Phenolic resin shown in Formula V and Formula IV also can with to benzene aralkyl-type phenol resin, biphenyl aralkyl-type phenol resin, many officials
Can group at least one in benzene aralkyl-type phenol resin, copoly type biphenyl aralkyl-type phenol resin or multiple by any
Ratio composition mixture applicatory.
Filler at the bottom of low-k moulding type epoxy the most according to claim 1, it is characterised in that: described accelerator choosing
From glyoxaline compound or organic phosphine compound, described glyoxaline compound includes 2-methylimidazole, 2-ethyl imidazol(e), 2-second
At least one in base-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxyethyl imidazole, preferably 2-phenyl-4-methyl-5-hydroxyl second
Base imidazoles；Described organic phosphine compound selected from triphenylphosphine, tributylphosphine, three (p-methylphenyl) phosphine, three (nonyl phenyl) phosphine,
In tetraphenyl phosphine tetraphenylborate, triphenylphosphine-1,4-benzoquinone (TPP-BQ) addition product at least one or multiple by any ratio
The mixture of example composition, triphenylphosphine-1,4-benzoquinone addition product.
Filler at the bottom of low-k moulding type epoxy the most according to claim 1, it is characterised in that: described coupling agent choosing
From g-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH-560), g-aminopropyltriethoxywerene werene (KH-550), g-
At least one in mercaptan aminopropyl trimethoxysilane (KH-580) or the multiple mixture formed in any proportion, preferably
KH-560。
Filler at the bottom of low-k moulding type epoxy the most according to claim 1, it is characterised in that: described releasing agent choosing
In native paraffin, synthetic wax, stearic acid, Palmic acid, zinc stearate, calcium stearate, lithium stearate and magnesium stearate at least one
Plant or the multiple mixture formed in any proportion, preferably bar wax or Tissuemat E.
Filler at the bottom of low-k moulding type epoxy the most according to claim 1, it is characterised in that: described inorganic filler
Selected from spherical fusion quartz (SiO2) micropowder, the median of above-mentioned inorganic filler (d 50) less than 15 μm, maximum particle diameter is not
More than 30 μm.
9. the preparation method of filler at the bottom of the low-k moulding type epoxy described in claim 1, it is characterised in that include as follows
Step:
(1) by biphenyl type epoxy resin shown in low-k epoxy resin, formula IV shown in Formulas I or Formula II or formula III, Formula V or
Low-k phenolic curing agent, described accelerator, described coupling agent, described releasing agent, described low stress agent, institute described in Formula IV
Stating after inorganic filler mixes mixing, obtain filler at the bottom of described low-k moulding type epoxy, in described mixing step, temperature is
80-120 DEG C, specially 80-100 DEG C, 90-110 DEG C or 100-120 DEG C, preferably 90-110 DEG C；
(2) filler at the bottom of prepared low-k moulding type epoxy is bought cake on pancake making machine, obtain the low of required size size
Filler at the bottom of dielectric constant moulding type epoxy.
10. the purposes of filler at the bottom of a low-k moulding type epoxy as claimed in claim 1, it is characterised in that: this is low
The answering in WLCSP, FO-WLCSP microelectronic device package with optoelectronic device packaging of filler at the bottom of dielectric constant moulding type epoxy
With.
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| CN115433146A (en) * | 2022-09-16 | 2022-12-06 | 西安思摩威新材料有限公司 | Compound for sealing film, composition and sealing film formed by using composition |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401203A (en) * | 2018-11-30 | 2019-03-01 | 江苏中鹏新材料股份有限公司 | Environmental protection typed gold color epoxy mold sealing material and preparation method thereof |
| WO2020250684A1 (en) * | 2019-06-12 | 2020-12-17 | ダイキン工業株式会社 | Fluorine-containing epoxy resin for electrical materials and method for manufacturing same |
| JPWO2020250684A1 (en) * | 2019-06-12 | 2020-12-17 | ||
| EP3960788A4 (en) * | 2019-06-12 | 2023-01-25 | Daikin Industries, Ltd. | Fluorine-containing epoxy resin for electrical materials and method for manufacturing same |
| US11965060B2 (en) | 2019-06-12 | 2024-04-23 | Daikin Industries, Ltd. | Fluorine-containing epoxy resin for electrical materials and method for manufacturing same |
| CN115433146A (en) * | 2022-09-16 | 2022-12-06 | 西安思摩威新材料有限公司 | Compound for sealing film, composition and sealing film formed by using composition |
| CN115433146B (en) * | 2022-09-16 | 2024-06-11 | 西安思摩威新材料有限公司 | Compound for packaging film, composition, and packaging film formed using the composition |
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