CN110128780B - Low dielectric constant epoxy resin composition - Google Patents
Low dielectric constant epoxy resin composition Download PDFInfo
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- CN110128780B CN110128780B CN201810126955.XA CN201810126955A CN110128780B CN 110128780 B CN110128780 B CN 110128780B CN 201810126955 A CN201810126955 A CN 201810126955A CN 110128780 B CN110128780 B CN 110128780B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
Abstract
The present invention relates to a low dielectric constant epoxy resin composition comprising: (a) an epoxy resin, (b) a curing agent, (c) a curing accelerator, (d) an inorganic filler, and (e) optionally one or more additives selected from the group consisting of: flame retardant, coupling agent, release agent and colorant; wherein the curing agent has the structure of formula (I);
wherein R is 1 、R 2 Each independently is alkyl substituted with one or more halogen atoms, R 3 ‑R 10 Each independently is hydrogen, halogen, C 1 ‑C 10 Alkyl, C 3 ‑C 20 Cycloalkyl, C 6 ‑C 14 Aryl, C 5 ‑C 14 Heteroaryl, said C 1 ‑C 10 Alkyl, C 3 ‑C 20 Cycloalkyl, C 6 ‑C 14 Aryl, C 5 ‑C 14 Heteroaryl groups are optionally substituted with one or more halogen atoms. The invention also relates to a preparation method and application of the epoxy resin composition.
Description
Technical Field
The present invention relates to the technical field of electronic chip packaging, and in particular relates to an epoxy resin composition, particularly an epoxy resin composition containing a specific curing agent, which has a low dielectric constant. The invention also relates to a preparation method and application of the epoxy resin composition.
Background
With the advancement of integrated circuit technology, chips with high speed, high device density, low power consumption, and low cost are becoming the primary products of very large scale integrated circuit fabrication. As the density of wires in a chip increases, the width and pitch of wires decrease, and parasitic effects caused by resistors and capacitors in the interconnect become more and more apparent, such parasitic effects may cause signal propagation delays, power dissipation, and the like. The use of the low dielectric constant epoxy molding compound can reduce the effect caused by parasitic effect, and overcome signal propagation delay, line-to-line interference, power dissipation and the like caused by resistance-capacitance hysteresis. Therefore, low dielectric constant electronic material development is receiving more and more attention.
Epoxy resins, curing agents and inorganic fillers are the three major components of epoxy molding compounds, and these three types of components are currently being investigated to reduce the dielectric constant of epoxy molding compounds. For example, epoxy resins having a certain structure may be synthesized or blended with the remaining resin, curing agents of a specific structure may be designed, or specific types of inorganic fillers may be selected. Since fluorocarbon bonds have a small dipole moment and have a very low polarizability, introduction of fluorine atoms or fluorine-containing groups into a polymer material can effectively lower the dielectric constant of the material. CN106795259a relates to an epoxy resin composition comprising an epoxy resin (a) and a triazine ring-containing phenolic resin (B) having a dielectric constant of 3.5 to 4.1.CN104479293a relates to a mesoporous silicon filled epoxy resin composite material, which is obtained by polymerizing the following raw materials in parts by weight: 100 parts of epoxy resin, 1-20 parts of fluorine-containing polymer modified mesoporous silicon, 60-90 parts of curing agent and 0.1-1 part of accelerator; the preparation method comprises the following steps: synthesizing mesoporous silicon; grafting and modifying mesoporous silicon; then adding the modified mesoporous silicon into the epoxy resin, stirring and mixing uniformly, and adding the curing agent and the accelerator. The dielectric constant of the resulting epoxy resin composite may be 2.65.
There remains a need to design and select the components of epoxy resin compositions to obtain epoxy resin compositions that are simple in process, low in cost, and have low dielectric constants.
Disclosure of Invention
In one aspect, the present invention relates to an epoxy resin composition comprising:
(a) An epoxy resin is used to cure the epoxy resin,
(b) The curing agent is used for curing the resin,
(c) A curing accelerator is used to cure the cured product,
(d) Inorganic filler
(e) Optionally one or more additives selected from the group consisting of: flame retardant, coupling agent, release agent and colorant;
wherein the curing agent has the structure of formula (I);
wherein R is 1 、R 2 Each independently is an alkyl group substituted with one or more halogen atoms,
R 3 -R 10 each independently is hydrogen, halogen, C 1 -C 10 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 14 Aryl, C 5 -C 14 Heteroaryl, said C 1 -C 10 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 14 Aryl, C 5 -C 14 Heteroaryl groups are optionally substituted with one or more halogen atoms.
In one embodiment, R in the curing agent in the epoxy resin composition of the present invention 1 、R 2 Each independently is C 1 -C 3 Alkyl groups, which are one or moreFluorine atom substitution;
R 3 -R 10 is hydrogen.
In a preferred embodiment, the curing agent in the epoxy resin composition of the present invention is
In one embodiment, wherein the curing agent is present in an amount of 3 to 10 wt%, preferably 4 to 8 wt%, based on the total weight of the epoxy resin composition.
In another embodiment, wherein the epoxy resin is selected from the group consisting of ortho-cresol novolac epoxy resins, epoxy resins having a naphthalene backbone, dicyclopentadiene type epoxy resins, triphenolmethane type epoxy resins, biphenyl type epoxy resins, and combinations thereof.
In yet another embodiment, wherein the inorganic filler is selected from the group consisting of spherical silica, crystalline silica, fused silica, aluminum oxide, titanium dioxide, aluminum hydroxide, talc, clay, glass fibers, and combinations thereof, preferably spherical silica.
In one embodiment, the epoxy resin composition possesses one or more of the following properties:
(1) A gelation time of about 80s or less at about 160-200 ℃;
(2) A spiral flow length of about 10 to 60 inches within about 200 seconds of curing at about 160 to 200 ℃;
(3) Volume resistivity of 15X 10 15 -50×10 15 Ω.cm；
(4) Dielectric loss is below 10;
(5) The dielectric constant is 3 or less.
In a preferred embodiment, the epoxy resin composition comprises, based on the total weight of the epoxy resin composition:
(a) An epoxy resin in an amount of 3 to 10 wt%;
(b) A curing agent in an amount of 3 to 10 wt%;
(c) A curing accelerator in an amount of 0.01 to 5 wt%;
(d) An inorganic filler in an amount of 60 to 90 wt%; and
(e) 0.03-35 wt% of one or more additives selected from the group consisting of: flame retardant, coupling agent, release agent and colorant.
In another aspect, the present invention relates to a method of preparing an epoxy resin composition comprising the steps of:
(1) Each component is weighed and mixed to obtain a pre-mixed powder,
(2) The premixed powders are heat mixed and extruded to obtain a product,
wherein the heating temperature in the step (2) is 70-100 ℃.
In a further aspect, the present invention relates to the use of the epoxy resin composition of the present invention for electronic chip packaging.
In a further aspect, the invention relates to the use of a compound of formula (I) as a curing agent for epoxy resins,
wherein R is 1 、R 2 Each independently is an alkyl group substituted with one or more halogen atoms,
R 3 -R 10 each independently is hydrogen, halogen, C 1 -C 10 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 14 Aryl, C 5 -C 14 Heteroaryl, said C 1 -C 10 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 14 Aryl, C 5 -C 14 Heteroaryl groups are optionally substituted with one or more halogen atoms.
In one embodiment, in the compound of formula (I), R 1 、R 2 Each independently is C 1 -C 3 Alkyl groups substituted with one or more fluorine atoms; r is R 3 -R 10 Is hydrogen.
In a preferred embodiment, the compounds of formula (I) are
Detailed Description
General definition and terminology
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
All percentages, parts, ratios, etc. are by weight unless otherwise specified.
When an amount, concentration, or other value or parameter is expressed as a range, a preferred range, or an upper preferable range value, and a lower preferable range value, this is to be understood as equivalent to any range specifically disclosed by combining any pair of upper range values or preferred range values with any lower range value or preferred range value, regardless of whether the range is specifically disclosed. Unless otherwise indicated, the numerical ranges set forth herein are intended to include the endpoints of the ranges, and all integers and fractions within the range. For example, "1-8" encompasses 1, 2, 3, 4, 5, 6, 7, 8 and any subrange comprised of any two values therein, e.g., 2-6, 3-5.
The terms "about," "approximately," when used in conjunction with a numerical variable, generally refer to the value of the variable and all values of the variable within experimental error (e.g., within a confidence interval of 95% for an average value) or within + -10% of the specified value, or a wider range.
The expression "comprising" or similar expressions "including", "containing" and "having" etc. synonymously therewith are open ended and do not exclude additional unrecited elements, steps or components. The expression "consisting of …" excludes any element, step or ingredient not specified. The expression "consisting essentially of …" means that the scope is limited to the specified elements, steps, or components, plus any elements, steps, or components that are optionally present that do not materially affect the basic and novel characteristics of the claimed subject matter. It should be understood that the expression "comprising" encompasses the expressions "consisting essentially of …" and "consisting of …".
The term "optional" or "optionally" as used herein means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
"a" and "an" are used to describe elements and components of the invention. This is merely for convenience and to give the usual meaning of the invention. Such description should be understood to include one or at least one, and also include plural forms unless it is obvious to the contrary.
As used herein, one (or more) means 1, 2, 3, 4, 5, 6, 7, 8, 9, 10(s) or more.
Similarly, two (species) or more may represent 2, 3, 4, 5, 6, 7, 8, 9, 10 (species) or more.
The term "any combination thereof" as used herein means that the elements described above may be used singly or in combination of one or more.
Except in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, or parameters of defined ingredients herein are to be understood as being defined in all instances by the term "about".
The term "Room Temperature (RT)" as used herein refers to about 25 ℃.
The term "(substituted") means that any one or more hydrogen atoms on a particular atom is replaced by a substituent, provided that the valence of the particular atom is normal and the substituted compound is stable. The groups or structures herein may be optionally substituted with one or more substituents, for example with one, two or three substituents. The substituents may be, for example, halogen, alkyl, aryl, cycloalkyl, heteroaryl, and the like.
The term "alkyl" refers to a straight or branched saturated aliphatic hydrocarbon group consisting of carbon and hydrogen atoms, which is attached to the remainder of the molecule by a single bond. The alkyl groups described herein generally have from about 1 to about 20 carbon atoms, preferably from about 1 to about 10 carbon atoms, and more preferably from about 1 to about 3 carbon atoms. Non-limiting examples thereof include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and the like.
The term "aryl" refers to a cyclic aromatic hydrocarbon that does not contain heteroatoms in the ring. Aryl groups thus include, but are not limited to, phenyl, biphenyl, fluorenyl, phenanthryl, triphenylyl, tetracenyl, anthracenyl, and naphthyl. In some embodiments, the aryl group contains about 6 to 14 carbons, preferably about 6 to 10 carbons, in the ring portion of the group. Aryl groups may be unsubstituted or substituted. Representative substituted aryl groups may be mono-or poly-substituted, such as, but not limited to, 2-, 3-, 4-, 5-or 6-substituted benzene or 2-8 substituted naphthyl, which may be substituted with carbon or non-carbon groups such as those listed herein, e.g., with halogen.
The term "heteroaryl" refers to a monovalent monocyclic, bicyclic or tricyclic aromatic ring system having 5 to 14 ring atoms ("5-to 14-membered heteroaryl"), particularly 5 to 10 ring atoms, and which contains at least one heteroatom, which may be the same or different, such as oxygen, nitrogen or sulfur. Benzo-fused heteroaryl groups are also possible. Heteroaryl groups are, for example, thienyl, furyl, pyrrolyl, oxazolyl, and the like, as well as their benzo derivatives, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, and the like. Heteroaryl groups may be substituted or unsubstituted, and may be monosubstituted or polysubstituted. Which may be substituted with carbon or non-carbon groups such as those listed herein, such as with halogen.
The term "cycloalkyl" refers to a non-aromatic saturated cyclic compound containing 3 or more carbon ring atoms, which may be monocyclic or polycyclic. Cycloalkyl groups contain about 3 to 20 carbon ring atoms, preferably about 3 to 10 carbon ring atoms, more preferably about 3 to 8 carbon ring atoms. Which may be substituted or unsubstituted.
The term "halogen", by itself or as part of another substituent, refers to fluorine, chlorine, bromine or iodine unless otherwise indicated.
The term "epoxy molding compound" as used herein, i.e., epoxy molding compound. The epoxy resin composition is used herein as a molding compound, and thus "epoxy molding compound" is also referred to as "epoxy resin composition".
Unless defined otherwise, all terms used in the disclosure of the present invention, including technical and scientific terms, have the meaning commonly understood by one of ordinary skill in the art to which this invention belongs. By way of further example, term definitions are included herein to better understand the teachings of the present invention.
Each component in the epoxy resin composition of the present invention will be described in detail below.
Epoxy resin
As used herein, the term "epoxy resin" refers to a polymer that typically contains two or more epoxy groups per molecule.
In the epoxy resin composition of the present invention, the type of epoxy resin is not particularly limited, but it is preferable to use an epoxy resin having a small dielectric constant, for example, an epoxy resin having a linear, small polarity and high symmetry as a basic unit. Examples of epoxy resins useful in the present invention include, but are not limited to, bisphenol type glycidyl ether epoxy resins such as bisphenol a type epoxy resins and bisphenol F type epoxy resins; biphenyl type glycidyl ether epoxy resins such as biphenyl type epoxy resin and tetramethyl biphenyl type epoxy resin; polyphenol type glycidyl ether epoxy resins such as phenol novolac epoxy resin, o-cresol novolac epoxy resin; triphenol methane type epoxy resin; tetraphenylethane epoxy resin; dicyclopentadiene type epoxy resins; phenol aralkyl epoxy resin; an epoxy resin having a naphthalene skeleton. These epoxy resins may be used singly or in combination of two or more.
Among the above epoxy resins, the epoxy resin is preferably selected from the group consisting of o-cresol novolac epoxy resins, epoxy resins having a naphthalene skeleton, dicyclopentadiene type epoxy resins, triphenol methane type epoxy resins, biphenyl type epoxy resins, and combinations thereof, more preferably selected from the group consisting of epoxy resins having a naphthalene skeleton, dicyclopentadiene type epoxy resins, and combinations thereof, and most preferably epoxy resins having a naphthalene skeleton.
The epoxy resin may be used in a liquid form or in a solid form. The viscosity of the epoxy resin at 150 ℃ is typically about 0.6 to 4.9 poise, for example about 0.7 poise. The amount of epoxy resin in the epoxy resin composition of the present invention may be about 3 to 10 wt.%, preferably about 5 to 8 wt.%, for example about 6.15 wt.%, 7.5 wt.%, based on the total weight of the epoxy resin composition.
Curing agent
As used herein, "curing agent" has the same meaning as "hardener". Which can react with the functional groups of the epoxy resin to expand the crosslinking of the resin and to obtain a thermosetting resin.
The curing agent of the epoxy resin composition of the present invention has the structure of the following formula (I);
wherein R is 1 、R 2 Each independently is an alkyl group substituted with one or more halogen atoms,
R 3 -R 10 each independently is hydrogen, halogen, C 1 -C 10 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 14 Aryl, C 5 -C 14 Heteroaryl, said C 1 -C 10 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 14 Aryl, C 5 -C 14 Heteroaryl groups are optionally substituted with one or more halogen atoms.
In one embodiment, R3, R5, R8, R10 are each independently hydrogen, halogen, C 1 -C 10 Alkyl optionally substituted with one or more halogen atoms.
In a preferred embodiment, R 1 、R 2 Each independently is C 1 -C 3 Alkyl groups, more preferably methyl groups, substituted with one or more fluorine atoms.
In another preferred embodiment, R 3 -R 10 Is hydrogen.
In a more preferred embodiment, R 1 、R 2 Each independently is C 1 -C 3 Alkyl groups, more preferably methyl groups, substituted with one or more fluorine atoms; r is R 3 -R 10 Is hydrogen.
In a further preferred embodiment, the curing agent is
(also known as 2, 2-bis (4-hydroxyphenyl) hexafluoropropane).
In the curing agent of the formula (I), the-OH connected with the benzene ring is used for reacting with the functional group of the epoxy resin, R 1 And R is 2 The groups are selected such that the-OH attached to the benzene ring has suitable reactivity to make the epoxy curing reaction milder and lower the dielectric constant. R is R 1 And R is 2 The groups are also chosen such that the molecular van der Waals volume is not significantly changed compared to 2, 2-bis (4-hydroxyphenyl) propane.
R 3 -R 10 The selection of (3) is such that the-OH attached to the benzene ring has a certain reactivity, the volume of the hardener molecule is not much changed compared to 2, 2-bis (4-hydroxyphenyl) propane, and the curing reaction of the-OH with the epoxy groups of the epoxy resin is not adversely affected. For example, R 3 、R 5 、R 8 、R 10 The functional group van der waals volume of (a) should not be excessively large to avoid affecting the curing reaction of-OH with the epoxy groups of the epoxy resin.
The amount of curing agent is critical in order to obtain an epoxy resin composition having desired properties such as low dielectric constant, gelation time, spiral flow length, etc. Too low an amount of the curing agent does not easily achieve the desired effect, and too high an amount of the curing agent reduces the gelation time and the spiral flow length. The amount of curing agent in the epoxy resin composition of the present invention may be about 3 to 10 wt.%, preferably about 4 to 8 wt.%, e.g., about 5.5 wt.%, 6.7 wt.%, based on the total weight of the epoxy resin composition.
Phenolic resin may also optionally be added as a second curing agent. Wherein the phenolic resin used in the present invention contains two or more phenolic hydroxyl groups capable of forming a crosslinked structure upon reaction with the epoxy resin. Phenolic resins useful in the present invention include, but are not limited to: phenol novolac resins, cresol novolac resins, phenol aralkyl novolac resins, phenolic resins having a naphthalene skeleton, terpene-modified phenolic resins, dicyclopentadiene-modified phenolic resins, which may be used alone or in combination. In one embodiment, the epoxy resin composition of the present invention comprises a phenolic resin. In another embodiment, phenolic resin is not included in the epoxy resin composition of the present invention.
Curing accelerator
As used herein, the term "cure accelerator" has the same meaning as "catalyst" that catalyzes or accelerates the curing reaction between an epoxy resin and a curing agent.
The curing accelerator of the present invention is not particularly limited, and various compounds such as an organic phosphorus compound, an amine, an amidine compound, an imidazole compound, a metal salt of an organic acid, a lewis acid, an amine complex salt, and the like may be included as the curing accelerator in the epoxy resin composition. Any of the above-listed curing accelerators may be used alone or in combination of two or more. The curing accelerators of the invention can be, for example, 2-ethyl-4-methylimidazole, organophosphorus compounds such as triphenylphosphine, 1, 8-diazabicyclo- [5.4.0] -undecene, preferably triphenylphosphine.
The amount of the curing accelerator should be such as to facilitate proper crosslink density, hardness, viscosity, etc. of the epoxy resin after curing. The amount of cure accelerator in the epoxy resin composition of the present invention may be from about 0.01 to 5 weight percent, preferably from about 0.05 to 2 weight percent, such as about 0.1 weight percent, 0.15 weight percent, based on the total weight of the epoxy resin composition.
Inorganic filler
Inorganic fillers may be used to improve certain properties of the molded product, such as abrasion resistance, moisture resistance, thermal conductivity, or electrical properties.
The inorganic filler used in the present invention may be one or more selected from the group consisting of: spherical silica, crystalline silica, fused silica, alumina, titania, aluminum hydroxide, talc, clay and glass fibers. Any of the above-listed fillers may be used alone or in combination of two or more. In order to obtain better flowability, spherical silica is preferably used. One kind of filler may be selected, or a combination of two or more kinds of fillers may be selected. The particle size of the inorganic filler is not particularly limited, but should be such that it can be uniformly dispersed in the epoxy resin composition, and should be such that it is suitable for physical devices such as a mold or the like used for the epoxy resin composition, for example, about 15 to 25 micrometers, about 3 to 8 micrometers, such as 20 micrometers, 5 micrometers. The ratio between the inorganic fillers of different particle sizes is such that they are well dispersed in the epoxy resin composition and such that the epoxy resin composition has good flowability and viscosity. In one example, the ratio between the inorganic filler having a particle size of 20 microns and the inorganic filler having a particle size of 5 microns is about 42.
The amount of inorganic filler in the epoxy resin composition of the present invention may be about 60 to 90 wt.%, preferably about 70 to 90 wt.%, for example about 86 wt.%, 84 wt.%, based on the total weight of the epoxy resin composition.
Other additives
The present invention may also optionally include one or more other additional ingredients including, but not limited to, flame retardants, coupling agents, mold release agents, colorants.
The flame retardant is a functional auxiliary agent that can impart flame retardancy to an epoxy resin composition having a polymer matrix, and includes reactive flame retardants and additive flame retardants. The present invention may optionally comprise a flame retardant. Flame retardants suitable for the epoxy resin composition of the present invention include, but are not limited to, brominated epoxy resins, zinc oxide, antimony oxide, and phosphine-containing compounds, preferably zinc oxide. The flame retardant is present in an amount of about 0 to 20 weight percent, preferably 0.1 to 5 weight percent, more preferably 0.1 to 1 weight percent, for example about 0.25 weight percent, based on the total weight of the epoxy resin composition.
Coupling agents can be used as additives to improve the interfacial properties of polymers with inorganic fillers, also known as surface modifiers. The composite material can form an interface layer between the inorganic filler and the polymer, transfer stress, strengthen the bonding strength between the inorganic filler and the polymer, improve the dispersibility of the inorganic filler and improve the performance of the composite material. Coupling agents of the present invention include, but are not limited to, organochromium complexes, silanes, titanates and aluminate compounds, preferably silane coupling agents such as 3-mercaptopropyl trimethoxysilane. The coupling agent is present in an amount of about 0.01 to 5 wt%, preferably about 0.1 to 2 wt%, for example about 1 wt%, 0.65 wt%, based on the total weight of the epoxy resin composition.
The colorant is a substance for imparting color to the epoxy resin composition, and should have good dispersibility, weather resistance, thermal stability, and chemical stability. Colorants for epoxy resin compositions mainly include inorganic and organic pigments. Colorants include, but are not limited to, carbon black, titanium dioxide, iron oxide yellow, chrome yellow, phthalocyanine blue, and the like, with carbon black being preferred. The colorant is present in an amount of about 0.01 to 5 weight percent, preferably about 0.1 to 1 weight percent, for example about 0.25 weight percent, based on the total weight of the epoxy resin composition.
The mold release agent is an additive that facilitates separation of the prepared material from the mold. The release agent should have good heat resistance and be not easily decomposed, and includes, but is not limited to, silicon series, wax series, surfactant series, polyether series, and the like. Mold release agents suitable for the present invention are natural waxes, synthetic waxes, and the like, for example selected from montan waxes, fatty acid ester waxes, fatty acid waxes, aliphatic ester waxes, polyethylene waxes, polypropylene waxes, alkyl oligomer waxes, amide waxes, and combinations thereof, for example polyethylene waxes. The release agent is present in an amount of about 0.01 to 5 weight percent, preferably about 0.1 to 2 weight percent, such as about 0.75 weight percent, 0.5 weight percent, based on the total weight of the epoxy resin composition.
Preparation method
The invention also relates to a method for preparing the epoxy resin composition, which comprises the following steps:
(1) Each component is weighed and mixed to obtain a pre-mixed powder,
(2) The premixed powders are heat mixed and extruded to obtain a product,
wherein the heating temperature in the step (2) is 70-100 ℃.
The mixing time in step (1) is required to allow the components to be uniformly mixed. In one embodiment, the time of mixing in step (1) is about 15 to 25 minutes, for example about 20 minutes. For the same reasons, the speed of mixing is generally about 1500-3000r/min, for example about 2000r/min. In one example, a mixer, such as a high speed mixer, is used for mixing.
The heating and mixing equipment in the step (2) needs to enable the components to be heated uniformly and mixed uniformly, and an extruder is usually used, and can be a single-screw extruder or a double-screw extruder, preferably a double-screw extruder. The heating temperature in the step (2) is higher than the melting temperature of the epoxy resin, so that the epoxy resin has good fluidity and reactivity. The temperature of the heating should also be such that all components entering the extruder do not decompose or degrade, and there is good reactivity between the components of the epoxy resin. In one embodiment, the heating in step (2) is at a temperature of about 70-100 ℃, such as about 90 ℃. In another embodiment, the heating of step (2) is for a period of about 1 to 3 minutes, for example about 2 minutes.
In one embodiment, the extrusion further comprises a cooling, comminuting step.
Epoxy resin composition
The present invention relates to an epoxy resin composition comprising:
(a) An epoxy resin is used to cure the epoxy resin,
(b) The curing agent is used for curing the resin,
(c) A curing accelerator is used to cure the cured product,
(d) Inorganic filler
(e) Optionally one or more additives selected from the group consisting of: flame retardant, coupling agent, release agent and colorant;
wherein the curing agent is as described above.
In a preferred embodiment of the present invention, the epoxy resin composition comprises, based on the total weight of the epoxy resin composition:
(a) An epoxy resin in an amount of about 3 to 10 wt%, preferably about 5 to 8 wt%, for example about 6.15 wt%, 7.5 wt%;
(b) A curing agent in an amount of about 3 to 10 wt%, preferably about 4 to 8 wt%, such as about 5.5 wt%, 6.7 wt%;
(c) A curing accelerator in an amount of about 0.01 to 5 wt%, preferably about 0.05 to 2 wt%, for example about 0.1 wt%, 0.15 wt%;
(d) An inorganic filler in an amount of about 60 to 90 wt%, preferably about 70 to 90 wt%, for example about 86 wt%, 84 wt%; and
(e) 0.03-35 wt%, preferably about 1-15 wt%, more preferably about 1-10 wt%, for example about 2.25 wt%, of an additive selected from the group consisting of: flame retardant, coupling agent, release agent and colorant.
It will be appreciated that the amounts of the components should be reasonably selected so that the sum of the components in the product is 100%.
In one embodiment, the epoxy resin is preferably an epoxy resin having a naphthalene skeleton. The curing agent is preferably 2, 2-bis (4-hydroxyphenyl) hexafluoropropane. The curing accelerator is preferably triphenylphosphine. The inorganic filler is preferably spherical silica. The flame retardant is preferably zinc oxide. The coupling agent is preferably a silane coupling agent, such as 3-mercaptopropyl trimethoxysilane. The release agent is preferably a polyethylene wax. The colorant is preferably carbon black.
The epoxy resin composition of the present invention has a suitable gelation time, a spiral flow length and a high volume resistivity. The gelation time can be measured, for example, by the following method: the epoxy resin composition was placed on a curing plate heated to 175℃and the sample was uniformly stirred using a doctor blade at the front end of the plate, and the stop of the stop watch was stopped until the sample gel, which was the gelation time. The gelation time of the epoxy resin composition of the present invention is about 80s or less, preferably about 70s or less, more preferably 50s or less, for example, about 26s or 27s at a temperature of about 160 to 200 ℃.
The spiral flow length can be determined by the following method: the mold was measured by spiral flow at a molding temperature of 175℃and 70kg/cm 2 Under the conditions of injection molding pressure and 90s curing timeMeasurements were made. The epoxy resin composition of the present invention has a spiral flow length of about 10 to 60 inches, e.g., about 22 inches, 40 inches, within about 200 seconds of curing at about 160 to 200 ℃.
Volume resistivity is used to represent the electrical properties of a material. Generally, the higher the volume resistivity, the higher the effectiveness of the material in functioning as an electrical insulation component. The volume resistivity of the epoxy resin composition of the present invention can be measured by the following method: the epoxy resin composition powder was fabricated into a module and cured at 175℃for 6 hours, and the volume resistivity was measured at 25 ℃. The test instrument is an instrument commonly used in the art, for example, edwan TR8601. The volume resistivity of the epoxy resin composition of the present invention is about 15X 10 15 -50×10 15 Omega cm, preferably about 15X 10 15 -30×10 15 Omega cm, e.g. 20X 10 15 Ω.cm，25×10 15 Ω.cm。
The epoxy resin composition of the invention has lower dielectric loss and dielectric constant.
The dielectric properties of polymers refer to the property of polymers to exhibit storage and loss of electrostatic energy under the action of an electric field, commonly expressed in terms of dielectric loss and permittivity. Dielectric loss is the loss of energy caused by a voltage. The smaller the dielectric loss, the better the insulation of the material. If the dielectric loss is too large, the dielectric temperature increases too high, which accelerates thermal decomposition and aging of the dielectric, and greatly reduces the insulating performance of the material. The epoxy resin composition with relatively low dielectric constant can reduce the effect caused by parasitic effect, and overcome signal propagation delay, line-to-line interference, power dissipation and the like caused by resistance-capacitance hysteresis. The dielectric constant and dielectric loss of the epoxy resin composition of the present invention can be measured, for example, using the following methods: the epoxy resin composition powder was fabricated into a module and cured at 175℃for 6 hours, and tested at 25 ℃. The dielectric constant and dielectric loss tester can be, for example, an love QBG-3D tester. The dielectric constant of the epoxy resin composition of the present invention is about 3 or less, for example about 2.8 or less and 2.72 or less. The epoxy resin composition of the present invention has a dielectric loss of about 10 or less, preferably 8 or less, more preferably 6 or less, for example, about 3.75, about 5.63.
The epoxy resin composition of the present invention possesses one or more of the following properties:
(1) A gelation time of about 80s or less at about 160-200 ℃;
(2) A spiral flow length of about 10 to 60 inches within about 200 seconds of curing at about 160 to 200 ℃;
(3) Volume resistivity of 15X 10 15 -50×10 15 Ω.cm；
(4) Dielectric loss is below 10;
(5) The dielectric constant is 3 or less.
In a preferred embodiment, the epoxy resin composition of the present invention has the properties of (1) to (5) described above.
The epoxy resin composition of the present invention can be used as a molding compound for the field of semiconductor packaging, particularly for the field of packaging of electronic chips, such as transistor outline packaging, quad flat non-leaded packages, and small flat packages.
The invention also relates to the use of a compound of the structure of formula (I) as a curing agent, preferably for epoxy resins.
Wherein R is 1 、R 2 Each independently is an alkyl group substituted with one or more halogen atoms,
R 3 -R 10 each independently is hydrogen, halogen, C 1 -C 10 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 14 Aryl, C 5 -C 14 Heteroaryl, said C 1 -C 10 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 14 Aryl, C 5 -C 14 Heteroaryl groups are optionally substituted with one or more halogen atoms.
In one embodiment, R 3 、R 5 、R 8 、R 10 Each independently is hydrogen, halogen, C 1 -C 10 Alkyl optionally substituted with one or more halogen atoms.
In a preferred embodiment, R 1 、R 2 Each independently is C 1 -C 3 Alkyl groups, more preferably methyl groups, substituted with one or more fluorine atoms.
In another preferred embodiment, R 3 -R 10 Is hydrogen.
In a more preferred embodiment, R 1 、R 2 Each independently is C 1 -C 3 Alkyl groups, more preferably methyl groups, substituted with one or more fluorine atoms; r is R 3 -R 10 Is hydrogen.
In a further preferred embodiment, the curing agent is
Advantageous effects
The epoxy resin composition has the advantages of excellent gelation time, spiral flow length, fluidity, volume resistivity, lower dielectric loss, lower dielectric constant, strong compressive capacity, low water absorption, simple and convenient preparation process and low cost, and is suitable for packaging electronic chips.
Examples
The present invention is described in further detail with reference to the following examples, which are not intended to limit the scope of the invention. All values in the examples are expressed as parts by weight.
Sample preparation
Raw materials:
epoxy resin: epoxy resins having naphthalene skeleton (Nippon Kayaku Co., ltd.) have a viscosity of 0.7 poise at 150℃and generally have the following structure:
curing agent:
2, 2-bis (4-hydroxyphenyl) propane (Shanghai national medicine group)
2, 2-bis (4-hydroxyphenyl) hexafluoropropane (Boschiza chemical industry development Co., ltd.)
Curing accelerator: triphenylphosphine, shanghai national medicine group;
spherical silica (particle size 20 μm, 5 μm): all purchased from Jiangsu-associated New Material stock Co., ltd; flame retardant: zinc oxide, you Niwei l chemicals (Shanghai);
coupling agent: 3-mercaptopropyl trimethoxysilane, dow Corning, USA;
and (3) a release agent: polyethylene wax, dow Corning, usa;
coloring agent: carbon black, palmer Holland.
Preparation:
as shown in Table 1, the raw materials of the epoxy resin compositions of each of examples 1-2 and comparative examples 1-2 of the present invention were weighed. All the raw materials were stirred uniformly in a high-speed mixer at 2000r/min for 20 minutes to obtain a premixed powder, and the premixed powder was put into a twin-screw extruder to be heated and mixed at about 90 ℃ for 2 minutes and extruded, followed by cooling and pulverizing to obtain a product.
TABLE 1
Testing
The obtained epoxy resin composition was tested for various properties according to the following test methods, and the results are shown in table 2 below.
Gelation time: the epoxy resin composition was placed on a curing plate heated to 175℃and the sample was uniformly stirred using a doctor blade at the front end of the plate, and the stop of the stop watch was stopped until the sample gel, which was the gelation time.
Spiral flow length: the mold was measured at 175℃molding temperature, 70kg/cm using a spiral flow according to EMI-1-66 2 The measurements were made under injection molding pressure and 90s cure time conditions.
Volume resistivity: the epoxy resin composition powder was fabricated into a module having a diameter of 11cm and a thickness of 5mm, and cured at 175℃for 6 hours, and the volume resistivity was measured at 25℃using a tester of Aide Wan TR8601.
Dielectric constant: epoxy resin composition powder was fabricated into a module having a diameter of 11cm and a thickness of 5mm, and cured at 175℃for 6 hours, and tested for dielectric constant and dielectric loss at 25 ℃. The dielectric constant and dielectric loss tester is ai QBG-3D.
TABLE 2
As shown in Table 2, the epoxy resin compositions of examples and comparative examples each had a suitable spiral flow length and gelation time. The epoxy resin compositions of examples 1-2 have lower dielectric constants and dielectric losses, as well as higher volume resistivities, than comparative examples 1-2.
Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. The following claims are intended to cover such equivalents. It will be apparent to those skilled in the art that many modifications and variations of the present invention can be made without departing from its spirit and scope. The specific embodiments described herein are offered by way of example only and are not meant to be limiting in any way. The true scope and spirit of the invention is indicated by the following claims, which are exemplary only.
Claims (8)
1. An epoxy resin composition comprising:
(a) An epoxy resin is used to cure the epoxy resin,
(b) The curing agent is used for curing the resin,
(c) A curing accelerator is used to cure the cured product,
(d) Inorganic filler
(e) Optionally one or more additives selected from the group consisting of: flame retardant, coupling agent, release agent and colorant;
wherein the curing agent is
Wherein the curing agent is present in an amount of 3 to 10 weight percent, based on the total weight of the epoxy resin composition; the epoxy resin is an epoxy resin with a naphthalene skeleton.
2. The epoxy resin composition of claim 1, wherein the curing agent is present in an amount of 4 to 8 weight percent, based on the total weight of the epoxy resin composition.
3. The epoxy resin composition of claim 1, wherein the inorganic filler is selected from the group consisting of spherical silica, crystalline silica, fused silica, aluminum oxide, titanium dioxide, aluminum hydroxide, talc, clay, glass fibers, and combinations thereof.
4. The epoxy resin composition of claim 1, wherein the inorganic filler is spherical silica.
5. The epoxy resin composition of claim 1, characterized in that the epoxy resin composition has one or more of the following properties:
(1) The gelation time is below 80s at 160-200 ℃;
(2) Curing at 160-200 ℃ for less than 200 seconds with an internal spiral flow length of 10-60 inches;
(3) Volume resistivity of 15X 10 15 -50×10 15 Ω·cm；
(4) Dielectric loss is below 10;
(5) The dielectric constant is 3 or less.
6. The epoxy resin composition of claim 1, wherein the epoxy resin composition comprises, based on the total weight of the epoxy resin composition:
(a) An epoxy resin in an amount of 3 to 10 wt%;
(b) A curing agent in an amount of 3 to 10 wt%;
(c) A curing accelerator in an amount of 0.01 to 5 wt%;
(d) An inorganic filler in an amount of 60 to 90 wt%; and
(e) 1-15 wt% of one or more additives selected from the group consisting of: flame retardant, coupling agent, release agent and colorant.
7. A method of preparing the epoxy resin composition of any one of claims 1-6, comprising the steps of:
(1) Each component is weighed and mixed to obtain a pre-mixed powder,
(2) The premixed powders are heat mixed and extruded to obtain a product,
wherein the heating temperature in the step (2) is 70-100 ℃.
8. Use of the epoxy resin composition according to any one of claims 1 to 6 for electronic chip packaging.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05140274A (en) * | 1991-11-25 | 1993-06-08 | Nippon Kayaku Co Ltd | Resin composition, method for forming transparent thin film, and transparent thin film |
| CN101495533A (en) * | 2005-03-18 | 2009-07-29 | 大日本油墨化学工业株式会社 | Epoxy resin composition and cured article thereof, novel epoxy resin and production method thereof, and novel phenol resin |
| CN103450632A (en) * | 2012-05-28 | 2013-12-18 | 汉高华威电子有限公司 | Epoxy resin composition for electronic packaging and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05140274A (en) * | 1991-11-25 | 1993-06-08 | Nippon Kayaku Co Ltd | Resin composition, method for forming transparent thin film, and transparent thin film |
| CN101495533A (en) * | 2005-03-18 | 2009-07-29 | 大日本油墨化学工业株式会社 | Epoxy resin composition and cured article thereof, novel epoxy resin and production method thereof, and novel phenol resin |
| CN103450632A (en) * | 2012-05-28 | 2013-12-18 | 汉高华威电子有限公司 | Epoxy resin composition for electronic packaging and preparation method thereof |
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