TW200920779A - Composition with thermally-treated silica filler for performance enhancement - Google Patents

Abstract

A curable composition comprising a curable resin and a thermally-treated silica filler, when used as an underfill material in semiconductor packages provides improved flow behavior, reduction in CTE, and enhancement of modulus, leading to reduced warpage. In one embodiment, the curable composition comprises (a) a thermally-treated silica filler, (b) a curable resin (c) an initiator, and (d) optionally, adhesion promoters and/or wetting agents. The curable resins can be cyanate ester resins, epoxy resins, maleimide resins, or acrylate or methacrylate resins.

Description

200920779 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a composition comprising a curable resin and a heat-treated cerium oxide. In particular, it relates to a composition comprising a cyanate ester and/or an epoxy resin and a heat-treated cerium oxide. [Prior Art] 10 15 20 The ruthenium filler is used for a variety of chemical compositions for the manufacture of semiconductor packages and microelectronic devices, particularly as a caulking composition. Semiconductor packages and microelectronic devices contain a large number of electronic circuit components that are electrically connected to each other and to the carrier or substrate. Applying a polymer or metal solder to the bumps of the part or substrate contacts to interconnect the parts and the substrate, these are aligned and in contact with each other, and the resulting components are subjected to an addendum to make the metal or polymer solder back. Weld _〇W) to connect the 岐. ...... Within the life of the 'electronic components to include solder joints, reflow process two ... after the test of the temperature rise and fall cycle. Due to the difference in coefficient of thermal expansion (CTE) between the electronic components and the substrate, this thermal cycle can cause the group to fail due to compression or distortion. In order to avoid parts == polymer sealant (a type of filler) base i t expansion coefficient difference 'reduced part curvature. The second material = the curved force is used to prepare the sealant composition to fill the resin::: the normal filler filled with a variety of resin systems can be used to form the sealant composition, the inclusion compound, 5 200920779 cis-butane diacid Bismueimides and acrylates' are also ideal resins because they form a back-to-parent density and high cross-linking density provides low moisture absorption and high glass transition temperature. (Tg). High glass transition temperature (usually higher than 125. 〇 allows polymer 1 to maintain polymer integrity during thermal cycling. 10 15 20 $, because the material becomes non-flexible due to cross-linking, high cross-linking density allows parts to be ^ Warpage. Using a large amount of filler can not only reduce warpage, but also reduce the thermal expansion coefficient, increase the strength of the material, and change its rheological properties. The problem with Dadong filler is to increase the viscosity and slow down the flow rate. One of the methods of using a caulk is to apply a measured amount of caulking agent along a boundary of one or more electronic components, and the gap between the part and the substrate is used to introduce the caulking agent. It can be preheated as needed to achieve the package viscosity required for the nucleus capillary action. After the gap is filled, the additional gap == additional seaming can be used to reduce the stress and delay the zero:,,,, and the fatigue Dp. Caulking or moisture absorption is a time consuming step, and the magic flow is not suitable for the caulking agent / 1 degree of material because it will slow down the capillary and therefore 'adding the curable filling composition to the vinegar' When using caulk material: use two actions to reduce zero Ί 翻 Ί Ί 备 备 备 备 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【于一6 200920779=The material comprises (4)-heat treated cerium oxide filler cerium, (c) an initiator, and (d) optionally added eucalyptus, the curable $m^ 刎 and/or wetting

UiG is a resin of horse macadamine, epoxy resin, imine resin or (10) acid ester or f-based acrylic acid. — [2:::,,:: or 'curable resin is - cyanate ester resin or - epoxy resin or combination of phthalate resin and epoxy resin, cerium oxide filler, and initiator And choose σ,, ',,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The heat treatment of the oxidized oxidized stone significantly reduces the base concentration on the surface - 10 15 20 = which results in an improvement in compatibility with the resin, and in particular, compatibility with odor acid = hydrazine, improved The flow behavior reduces cte and enhances modulus. = This improves the quality of the raw material, and the lightness of the wafer package using the resin and the heat-treated oxide oxide is reduced. In other words, the Oxide Oxide Filler is supplied by the manufacturer, and its surface is widely distributed with a high concentration of several bases. Some of the resin (for example, cyanate vinegar resin) will release volatile substances through the action of the base and the reaction. When the caulking agent is solidified, the volatile matter that escapes from the composition of the filling agent generates pores, which can cause frequent electronic equipment to occur frequently. Sexual failure. Removing the warp group can improve the problem. In addition, how the interaction between the filler and the resin determines the viscosity of the composition. By removing the i-base, the oxidation can be reduced; The viscosity of the specific resin (especially cyanuric acid vinegar) is reduced by the surface energy. This phenomenon allows a large amount of oxidized stone to be added to reduce the component's curvature without increasing the viscosity of the group. The good phase between Shixi and the scented resin also affects the thermal expansion coefficient and modulus of the composite, so that it can significantly reduce the curvature of the surface compared with the untreated oxidized oxide. 7 200920779 Applicable as a caulk material The cyanate esters include those having a general structure fNSC-, wherein η is greater than or equal to 1, and X is a hydrocarbyl group, the LJ η root ester is suitable as a caulking material. For example, X represents Not limited to): bisphenol hydrazine, bisphenol F, bisphenol S, bisphenol oxime, bisphenol 0, 5 phenol or nonanophenol novolac resin (novolac), dicyclopentadiene, polybutadiene, polycarbonate Ester, polyamino phthalate, polyether or polyester. Commercially available cyanate ester materials include: AROCY L-10, AROCYXU366, AROCYXU371, AROCYXU378, XU71787.02L, and XU 71787.07L from Huntsman LLC; PRIMASET PT30, PRIMASET PT30 S75, PRIMASET PT60 > PRIMASET PT60S > PRIMASET BADCY 'PRIMASETDA230S, PRIMASETMethylCy and PRIMASET LECY from Lonza Group i〇Limited; 2-propylpropyl benzoate from Oakwood Products, Inc. , 4-decyloxyphenol cyanate, 2,2-bis(4-cyanylbenzene 15phenol)-1,1,1,3,3,3-hexafluoropropane, bisphenol ocyanate, Bisallyl bisphenol A cyanate, 4-phenylphenol cyanate, 1,1,1-tris(4-cyanylphenyl)ethane, 4-isopropylphenol cyanate, ι , ι_bis(4-cyanylphenyl)ethane, 2,2,3,4,4,5,5,6,6,7,7-dodecafluorooctanediol dicyanate, and 4,4-bisphenol is cool.

The structural cyanate 'wherein R1 to R4 each independently represent anthracene, CrC1()alkyl, C3-C8 cycloalkyl, alkoxy, halogen, phenyl, phenoxy and partially or fully fluorinated alkyl Or aryl (for example: stupid base-1,3-dicyanate 8 200920779

a structural cyanate wherein R1 to R5 are each oxy, _, phenyl, phenoxy and partially or fully fluorinated alkyl or

Aryl; with Μ θ θ Θ

a cyanate of the NSC-O-O-CSN structure, wherein R1 to R4 each independently represent H'c^-c alkyl, C3-C8 cycloalkyl, q-Cioalkoxy, halogen, phenyl, benzene An oxy group and a partially or fully fluorinated alkyl or aryl group; Z) is a chemical bond 10 S〇2, CF2, CH2, CHF, CHCH3, isopropyl, hexafluoroisopropyl, ίν〇10 alkyl, hydrazine , N=N, R8OCR8 (wherein R8 represents H, CVC10 alkyl, or aryl), R8COO, R8C=N, R8ON-C(R8)=N, CVCk) alkoxy, S, Si(CH3)2 or One of the following structures: 15

C*— ί cf3 (eg 4,4′ ethylene diphenyl phenyl cyanate,

Its trade name from Vantico is AroCyL-10); a cyanate having a structure of 20, wherein η is a number from 〇 to 20, R_6 represents Η, Cl-Cl0 alkyl group and Χ represents one of CH2 or the following structure: 9 200920779

(Example: Commercial products XU366 and XU71787.07 from Vantico); a nitrite having a NSC-〇-R7-0-CSN structure and a cyanate having a structure of N^GO-R7, wherein R7 represents 3 A non-aromatic hydrocarbon chain of up to 12 carbon atoms, which may be selectively partially or fully fluorinated. Suitable epoxy resins include bisphenols, naphthalenes and aliphatic epoxides. Commercially available materials include: bisphenol type epoxy resins, manufactured by DainipponInk & ίο Chemicals, Inc. (EPICLON 830LVP, 830CRP, 835LV, 850CRP); naphthalene type epoxy resin, manufactured by DainipponInk & Chemicals, Inc. (EPICLON HP4032) The lipid epoxy resin is manufactured by Ciba Specialty Chemicals (ARALDITE CY179, 184, 192, 175, 179), Dow Corporation (Epoxy 1234, 249, 206) as 15 and Daicel Chemical Industries, Ltd (EHPE-3150). Other suitable epoxy resins include cycloaliphatic epoxy resins, bisphenol-A epoxy resins, bisphenol-F epoxy resins, epoxy novolac resins, bisphenyl epoxy resins, naphthalene epoxy resins. Resin, dicyclopentadiene phenol type epoxy resin. Suitable maleimide resins have the following general structure:

20, wherein η is 1 to 3, X1 is an aliphatic or aromatic functional group, and examples of X1 include: poly(butadiene), poly(carbonate), poly(amino phthalate), poly(ether), Poly 200920779 (ester), simple hydrocarbons, and simple hydrocarbons containing functional groups such as carbonyl carboxyl, guanyl, urethane, urea, ester or ether. This type of resin is commercially available and can be obtained, for example, from Dainippon

Ink and Chemicals, Inc. and other companies. 5 Other suitable maleimide resins include, but are not limited to, solid aromatic bis-butylene imidate (BMI) resins, especially

11 200920779

5 10 15 "'With this, the Q-bridged functional group of the maleimide resin has been commercialized' and is available from Sart〇mer (USA) or HOS-Technic GmbH (Austria). Other suitable maleimide resins include: 〇 〇 20 Ο Ο # + a hydrocarbon group representing a straight or branched hydrocarbon chain of 36 carbon atoms (with or without a ring moiety), 12 200920779 and

ο · Suitable acrylate and methacrylate resins include those consisting of the general structure 10 (where η is 1 to 6, R1 represents -Η or -CH3, and X is an aromatic or aliphatic functional group) Examples of Χ2 include: poly(succinic acid vinegar), poly(amino carboxylic acid vinegar), poly(趟), poly(5), simple hydrocarbon = 15 and functional groups (eg silk, silk, St amine) Simple hydrocarbons of amines/acids, ureas, esters or ethers. Commercially available = :=KyoeishaChemicalc〇,, LTD's (methyl)propene's butyl sulfonate , (ethyl)ethyl 2-ethylhexyl)isodecyl acrylate, (mercapto) acrylic acid, acid sulphuric acid, (meth) acrylic acid, thirteenth hydrazine, (mercapto) propylene (four) ^硬土月^: (A, acid ring hexahydrate, (mercapto) acrylic acid four-gas sweet and sour vinegar, (methyl) propyl 妒 2 stupid oxyacetic acid, (meth) acrylic acid Borneol vinegar, di(methyl)propanoid acid, 4, butanediol vinegar, di(methyl)propionic acid hexanediol vinegar, mono (meth) acrylic acid!, 9-nonanediol vinegar, (meth)acrylic acid perfluoro Base 13 200920779 Ethyl ester, bis(indenyl)acrylic acid 1,1〇~ decyl glycol ester, (mercapto)acrylic acid decyl phenol based polypropoxylated ester and polypentoxylated ester tetrahydrofurfuryl acrylate ; bis-mercaptoacrylic acid polybutadienyl decanoate (CN302, NTX6513) and bis-decyl-propionic acid polybutadiene 5 (CN301, NTX6039, PRO6270) from Sartomer Company, Inc; obtained from Negami Chemical

Polyacrylic acid amide phthalate (Art Resin UN9200A) from Industries Co., LTD; acrylated aliphatic amino phthalate oligomers from Radcure Specialities, Inc. (Ebecryl 230, 264, 265, 270 , 284, 4830, 4833, 4834, 4835, 4866, 4881, 4883, ί 8402, 8800-20R, 8803, 8804); poly S acrylate oligomers from Radcure Specialities (Ebecryl 657, 770, 810, 830, 1657, 1810, 1830); epoxy based acrylic resins (CN 104, 111, 112, 115, 116, 117, 118, 119, 120, 124, 136) available from Sartomer Company, Inc. In one embodiment, the acrylic resin is selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, dodecyl acrylate, dodecyl methacrylate, and poly(butyl) having an acrylic functional group. Alkene), a poly(butylene) having a methacrylic acid functional group. Suitable cerium oxide particles are spheres having an average particle size of from 0.1 micron to 10 microns, such as the products SOE5 and SOE2 available from Admatechs. 2 In one embodiment, a mixture of particles of different sizes can be used to increase the loading of the total filler while maintaining the viscosity within a manageable range. The heat treatment process is carried out by placing a quantity of cerium oxide powder obtained from a supplier (generally 10 g to 50 g) in a porcelain crucible and heating in an oven preheated to 400 ° C to 450 C for 72 hours. The applicable oven is Thermolyne 14 200920779 F-A1740 high temperature furnace. Remove the crucible from the furnace and cool to 80 ° C in dry air or nitrogen. The treated cerium oxide is transferred from dry heat (80 ° C) to a polymer-based airtight storage container (for example, a 250 ml Nalgene bottle) under dry air. Containers filled with heat-treated yttrium oxide can be stored in '5 ventable packages (eg food storage bags) to provide additional protection against the effects of moisture around them for long-term storage. [Examples] Example 1. Flow rate ίο The composition was prepared and tested for flowability using a resin composition as described in the above detailed description and a cerium oxide filler consisting of: 60% by weight of cyanate ester (obtained from Lonza LTD's PRIMASET LECY) and 40% by weight of Bis-F-epoxy resin (available from EPON 828 Resolution Performance Products). The oxidized stone enamel filler 15 had a maximum particle size of 5 μm (SE5050 ruthenium oxide available from Admatechs) was added to the resin system at 40% by weight and 70% by weight. The control group does not contain fillers. The resin was combined with a filler in a polypropylene cup with 3 mm glass or zirconia grinding media to prepare a filled sample. Place the cups into the Flaktek 2〇 Speed Mixer and mix at 1800 RPM, 2100 RPM, 2700 RPM for three 30 seconds. The flow rate of the filled cyanate/epoxy resin composition is measured by a custom-made device consisting of a rectangular capillary channel, a temperature-controlled flow chamber, and an optical configuration and digital imaging system to measure the flow front. Rectangular capillary channel 15 200920779 consists of two upper and lower substrates 'connected along the long sides of the two sides of the substrate, separated by a certain distance. The results of this recording were obtained using two slides (75 X 25 mm) with a gap of 50 μm. The fox-controlled flow chamber holds the capillary channel as described above and maintains the sample and the test machine 5 as a whole at a uniform temperature. This system can be explored 2〇. Flow phenomena within the range. One end of the temperature control chamber is connected to the opening of the capillary channel to inject the sample, and the sample is injected into the 〇5 to 〇12 ml with the injection needle. The flow of the sample under the pipe = observed from above the temperature control chamber, and the digital image capture system records the flow of material in the bureaucracy. Flow front position, speed and estimate 10 fill time can be found by digital image analysis. The results of this test are reported in Table i, and the results are shown in the flow rate measured at 90 C without the addition of filler and cyanate/epoxy resin added with the above apparatus and method. Table 1 T=90°C Untreated cerium oxide heat treated gas 彳 .. Shijie Tang warehousing 4 oxidized eve Wt% flow rate / S) (UL / S) 执 / 虚虚瑰 0 2294 2294 1.00 40 322 328 1.02 70 22 — I·丨丨-—一一一。 Π9 ----- 5,40, the filler treatment concentration of the filler exceeds the surface property of the filler. The results of thermal expansion and mold flow rate are shown in Low filler loading has no significant effect on flow rate. However, the percolation point (about 35 weight 〇/〇) apparently becomes viscous, thus slowing its flow rate. 16 200920779 Number performance, the proportion of bismuth oxide must be less than 40%. The above table shows that when the filler loading is 70%, the flow rate of the heat-treated filler is at least increased by a factor of five. The use of heat treated fillers in cyanate/epoxy systems allows for a high loading (without flow rate). 5 Example 2. Warpage Warpage is measured by comparing the height difference between the highest and lowest points of the caulk package relative to the substrate. The resin system was prepared and tested for warpage using a resin system as described in the above detailed description, and the formulation of the resin was 55.8 parts by weight of cerium cyanide (available from PRIMASET LECY of Lonza LTD), 37.2% by weight. Bis-F-Epoxy Resin (by National Starch and

Chemical Company prepared in situ) with 7 wt% of 3,3' diamine diphenyl sulfonone (available from Aldrich). The resin component was mixed prior to the addition of the filler. The maximum particle size of the cerium oxide filler was 5 μm (SOE 2 obtained from 15 Admatechs), and was added to the resin system at 4% by weight and 60% by weight, respectively. The resin and the filler were centrifuged at 3 Torr > M at high speed for 5 minutes' and then degassed to remove the air contained in the formulation. The New Curve test was carried out on a flip-chip platform with a grain size of 15 X 15 , = error-free solder bonded to a 42 x 42 mm 基板τ substrate, and a die-to-cho 2 lead-free reflow process. Before the caulking, the test was carried out by preheating the box for 2 hours to remove the absorbed moisture, and the test head caliber 0 33 was maintained at U &> C. The caulk formulation was filled with a needle after filling with a needle and applied by hand along the edge of the die to fill in C for 90 minutes. 20 200920779 The degree of interest in the test platform was measured on the back of the substrate with a Cobra 3D (Optical Gaging Product) along two diagonal directions. The average height of the two curves can be calculated as the degree of enchantment of the package, and the melody degree is measured before the filling and immediately after the package is cooled to 25 °C. The degree of softness added after solidification can be used to compare the effect of the filler on the degree of distortion. The results are recorded as shown in Table 2. Table 2 % change in filler loading S0E2-MRCE treatment (micron) The surface curvature of SOE2-MRCE(micron) increased by 40% wt 23.2±3.0 19.7±2.0 -15% 60% wt 38.6±4.2 28.1± 2.0 -21% 10 The results show that with the heat-treated cerium oxide, the degree of warpage of the composition for caulking can be reduced, and the degree of reduction increases with the amount of filler, when the filler loading is 60% by weight. The degree of warpage after curing is reduced by .27% °. Prediction of viscosity with temperature change 15 The viscosity change rate of the material affects its performance, such as overflow, sagging and flow. This effect has been applied to the design of capillary sealants, printing inks, and adhesive materials for electronic component packaging. Viscosity changes may or may not be desirable for these materials. Therefore, it would be very helpful to predict the viscosity change of the filled resin system. 20 The rate of reaction of the filled resin system to temperature is not exactly the same as that of the resin system without filler addition. Partially filled resin is much slower than the resin without added filler. The rate of thinning with temperature changes is much slower, even with Pick up, pounds of strange viscosity. ® 1 shows a plot of viscosity versus temperature for a series of surface treated oxidized stone materials in a poly(integrated) p-group (4) (Pqms) fluid. Surface treatment = phenyl triacetoxy oxime (phenyl in the figure), phenylamine-based tri-burning 5-milyl-wei (the phenyl wire of the towel), and the end (four) trifilite It is carried out based on the oligomer (the steel in the figure). The load capacity and particle size of this series of materials are the same. The graph shows that the viscosity decreases with increasing temperature, but different fillers have different reduction ratios. For the effect of temperature on viscosity, the behavior of the tree-filled system is a process of activation by energy. The activation energy can be plotted against the logarithm of the viscosity versus the reciprocal of the temperature, measured as the slope of the resulting line. Taking P0MS as an example, when the shear variability (Shearrate) is 1 rad/s, the activation energy of p〇MS (4) is t〇〇OK, and the general Bis_F_ epoxy resin is 9l9〇K. The activation energy (Ea) of the oxidized stone and alumina filler is determined by a series of surface treatments of epoxy resin, poly U (phenylmethyl) linaloate (PPMS) and POMS. The difference in activation energy between different filler types and resins is shown in Figure 2 (the value of the activation energy is derived from the natural logarithm of viscosity and the inverse of temperature (1/τ)). The performance of different resin systems varies widely; some systems are similar to resins without fillers; some systems remain invariant to temperature changes; others swell slightly with increasing temperature. Another example of activation energy dependence of resin and filler combination, cyanate ester, lipid _MASETL-10) combined with oxidized stone with the following surface modification: treatment with hexamethyldioxane (HMDZ), ring Oxane treatment, heat treatment (calcination) and untreated. Untreated, epoxy decane treatment and calcination filling 19 200920779 5 10 15 20 ^The quality is thinned with the temperature rise, but the ship μ: the rise 'first thinning and then expanding (see item 3) with temperature or expected to occur Species are unpredictable, filled with trees (4) Temperature dependence and independence ^ ^ ^ ^ ^ # ^ (m:g^;alf; (^ ^ ^ coatmg), dry coating method of MAIc lmpact in two: Table: Degree The viscosity change affected =:; =, the viscosity of the chemical energy and the temperature. The degree of surface modification is changed to achieve the required other examples. In the filled resin system, different amounts of wax system are added to contain phase filling] The results of Figure 5 show that the activation energy (10) agent _ amount, as the amount increases, the activation energy of the polymer approaches zero: the surface of the tree and the surface properties of the filler change with temperature Viscosity; quasi-capacity: (9) interaction with standard interface (F) J = relationship between the two; where Q is the activation energy of the filled resin and the unfilled tree 匕 匕 = = = = = =:;;;; adhesion; The ratio of the sum of the two surface energies made; that is, the parameter of the standard activation energy is Q-

The parameter of Jymtr 'and the standard interface interaction force is calculated by the surface tension of the resin multiplied by β (1 + filler particles do 20 200920779 cosine (c〇s) with resin contact angle) °F and Q Two parameters can normalize rheology and interaction to the nature of the unfilled resin, thus directly comparing the independence of the interfacial effects of the resin and filler in the filled resin system. Figures 6A and 6B graphically show the meaning of F and Q. 10 15 20 In fact, engineering this effect helps to apply caulk to electronic parts packages to control edge or resin overflow. The caulking agent with an activation energy (Ea) close to zero does not become thinner or spread as the temperature of the reflow or curing oven increases. The material used as the capillary sealant must be applied at room temperature and thin and flow below the grains as the temperature rises. The combination of resin and filler must be selected to be thin enough to be flowable as the temperature increases, but does not overflow the material content at which it should be. Next, two types of caulk formulations (JKL and MN〇) are exemplified, and both JKL and MNO are POMS resins containing cerium oxide in an amount of 35% by volume as a filler. The formulation JKL cerium oxide is surface treated with fluorenone, and the preparation MNO cerium oxide is surface treated with phenyl decane; the activation energy of JKL is positive, and MNO is close to zero. Applying these two formulations to the wafers and the glass-based wipes at room temperature for a few hours to achieve equilibrium, can completely fill the volume under the wafer, and have similar The edge lead angle is 2 degrees. After the preparation is placed on the hot plate and heated at a surface temperature of 12 〇t, the MN0 formulation remains below the wafer and the activation energy remains close to zero. JKL, *屮Benefits a % ^ Dance test observation freshly observed rheological behavior, obviously! The activation energy of the piece and the material, its own overflow control characteristics have - the interface and rheological properties of POMS filled resin have the following characteristics 21 200920779 JKL MNO Filler Type SE-5050-SQ SE-5050-SPD Filler Surface Treatment Anthrone Phenyldecane Resin POMS POMS Loading 35.1 34.6 Viscosity (mz, 25°C) 30.0 49.7 Filled Sample Surface Tension 25.7 25.9 Ea (K /1000)@lHz 2.6 -0.4 Viscosity index -α 7.1 9.0 Resin surface tension (mN/m) 24.9 24.9 Filler surface tension (raN/m) 36.1 54.1 When the Q value approaches zero, the observed F value The range is marked to predict the pairing of various types of resin fillers will be produced The nature of the figure, as shown in Figure 7, shows that the two blocks represent the range that approaches zero after experimental observation: one zone has an F value of 5 to 2.5, and the other zone has an F value of less than 15. High F value The area represents the adhesion force is greater than the liquid surface tension, which occurs when the energy of the filler is higher than the resin. When F = 2, the contact angle = 〇., the high F value area represents good wetting conditions; low The F value region represents a decrease in work performed by the adhesive force, and is more favorable for the formation of a charge and a resin than the interface formed by the resin itself. This occurs when the energy of the filler is lower than that of the liquid phase, and the filler The energy is not enough to interfere with the behavior of the liquid interface. The combination of fillers falls in the high F value zone, because of the material of the stone 阙 resin, which is lower (~25mN/m). The formulation MN〇 compound is such a system 22 200920779 ,弋 Table, a combination of fat 矽鲷 and high energy yttrium oxide (~5〇mN/m) ^^'^2; cyanic resin (~45 ((4) 贞 low energy filling two" for example. HMD2, ~ The combination of 2 〇 mN/m) falls in the low ρ value region. The propanol and aliphatic ΒΜι materials fall between the two regions, and the predicted enthalpy becomes thinner as the temperature rises. Thus, the inventors' value of the F-value relationship approaching zero can be used to help predict and design ... a resin/filler system that exhibits near zero behavior. For example, the relationship between the Q value and the carrying capacity of the maleimide resin and the cycloaliphatic epoxy resin is a function of the surface treatment and the filler addition amount, and the two materials are pre-etched by the relationship diagram. Under the amount, it should be thinned as the temperature rises. BRIEF DESCRIPTION OF THE DRAWINGS Fig. / is a graph showing the relationship between viscosity and temperature of a series of surface treated cerium oxide materials in polyoctylmethyl silicone fluids. Figure 15 is a graph showing the change in activation energy of different fillers and resins. Figure 3 is a graph of activation energy dependence of a resin in combination with a filler. Figure 4 „,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The meaning of the standardized activation energy parameter (q) is shown in the figure and the standardized inter-interface interaction parameter (F). Figure 7 Resin and filler combination when the Q value approaches zero, the range of F value. 200920779 [Explanation of main component symbols] No 24

Claims (1)

200920779 X. Patent application scope: L:=r, which contains curable wax and heat-treated oxidized fossil horn filler. 2. The curable composition according to the scope of the invention, wherein the resin is selected from the group consisting of cyanate esters, epoxides, cis-imine resins, acrylates, and combinations of these resins. A method of heat treating cerium oxide, which comprises subjecting cerium oxide to a temperature range of -40 C to 450 ° C for 72 hours. Further, a curable composition comprising a curable resin and a filler, wherein a standard interface interaction parameter of the 10 curable resin and the filler is j/ and F is less than or equal to 1.5 or greater than or equal to 2· 5, of which Bu Bu) 15 20 25