KR20130133010A - Curable heat-dissipating composition - Google Patents
Curable heat-dissipating composition Download PDFInfo
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- KR20130133010A KR20130133010A KR1020137025713A KR20137025713A KR20130133010A KR 20130133010 A KR20130133010 A KR 20130133010A KR 1020137025713 A KR1020137025713 A KR 1020137025713A KR 20137025713 A KR20137025713 A KR 20137025713A KR 20130133010 A KR20130133010 A KR 20130133010A
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Abstract
This invention is urethane resin which has a carboxyl group obtained by making (A) (a) polyisocyanate compound, (b) polycarbonate diol compound, (c) dihydroxy compound which has a carboxyl group react, (B) epoxy resin, and (C) It contains an inorganic filler (except barium sulfate and titanium oxide), and it is related with the curable heat radiation composition whose content rate of an inorganic filler (C) is 50-96 mass%. As an inorganic filler (C), it is preferable to use flat boron nitride and particulate alumina, aluminum nitride, or boron nitride together. The curable heat dissipating resin composition of the present invention has high thermal conductivity and flexibility, and good adhesion to metals, power semiconductors, semiconductor devices including optical semiconductors, semiconductor devices, circuit metal plates, circuits made of the metal plates, circuit boards, Very useful in the field of hybrid integrated circuits.
Description
The present invention relates to a curable heat dissipating composition which is not only excellent in heat dissipation, stress relaxation, insulation reliability, but also excellent in adhesiveness during work and adhesiveness after curing, and is preferable for fixing heat dissipation electronic components.
Recently, how to dissipate heat generated from electronic components in a narrow space due to miniaturization and high power of electrical and electronic components has become a problem. As one of the means, an insulating adhesive and a sheet for conducting heat from the heat generating target portion of the electronic component to the heat radiating member are used. As these adhesives and sheets, compositions in which an inorganic high heat dissipation filler is highly filled with a thermosetting resin are used. However, the amount of heat generated from electronic devices and electronic components tends to increase, and new adhesives for the adhesives and sheets used therein are required to improve the thermal conductivity. In order to do so, it is necessary to fill the resin with an inorganic high heat radiation filler more than ever. As resin used for this use, epoxy resin was mainly used from the viewpoint of adhesiveness with a base material (for example, Unexamined-Japanese-Patent No. 2008-101227 (Patent Document 1), Unexamined-Japanese-Patent No. 2008-280436 (Patent Document)). 2) Japanese Unexamined Patent Publication No. 2010-109285 (Patent Document 3)). However, since the surface area of an epoxy resin increases as the compounding quantity of a filler increases, the amount of resin adsorption to a filler surface increases. As a result, there exists a problem that the adhesiveness to a base material and the adhesiveness after hardening fall significantly. The epoxy resin composition which filled the filler higher has a problem that moldability deteriorates remarkably.
In view of the above circumstances, an object of the present invention is to provide a composition that has adhesiveness when fixing electrical and electronic components even at a high concentration of a heat-dissipating filler and has good workability and can be fixed at high adhesive strength by curing afterwards. It is done.
The present inventors have intensively studied, and as a result of filling a high heat dissipation filler into a resin composition combining a urethane resin and an epoxy resin having a carboxyl group having a specific structure excellent in flexibility, filler filling property and fluidity upon heating, high heat dissipation properties, The present invention was completed by finding that a curable heat-dissipating composition excellent in adhesiveness at work, adhesiveness after curing, and long-term reliability after adhesion was obtained.
That is, the present invention provides the following curable heat dissipating composition and adhesive.
[1] (A) Urethane resin having carboxyl group, (B) Epoxy resin and (C) Inorganic filler (except barium sulfate and titanium oxide) are contained, The content rate of the said inorganic filler (C) is 50- It is 96 mass%, The curable heat radiation composition.
[2] The method according to the above [1],
The said inorganic filler (C) contains the inorganic filler which has a thermal conductivity of 20 W / m * K or more, The curable heat dissipation composition characterized by the above-mentioned.
[3] The method according to the above [2],
Curable heat dissipation composition containing at least 10 mass% of inorganic fillers which have a thermal conductivity of 20 W / m * K or more in the said inorganic filler (C).
[4] The method according to any one of [1] to [3],
The urethane resin (A) having a carboxyl group is obtained by reacting (a) a polyisocyanate compound, (b) a polycarbonate diol compound, (c) a dihydroxy compound having a carboxyl group, and (d) a monohydroxy compound as necessary. Curable heat radiation composition characterized by the above-mentioned.
[5] The method according to the above [4],
Curable heat dissipation composition, characterized in that the number average molecular weight of the polycarbonate diol compound (b) is 300 ~ 50000.
[6] The method according to the above [5],
At least 10 mol% or more of the diol which comprises the said polycarbonate diol compound whose number average molecular weights are 300-500000 is a C6-C30 alicyclic compound, The curable heat dissipation composition characterized by the above-mentioned.
[7] The method according to the above [4],
At least 10 mol% or more of a polyisocyanate compound (a) is a C6-C30 alicyclic compound other than an isocyanate group part, The curable heat radiation composition characterized by the above-mentioned.
[8] The method according to any one of [1] to [4],
The number average molecular weight of the urethane resin (A) which has a carboxyl group is 500-100000, and an acid value is 5-150 mgKOH / g, The curable heat radiation composition characterized by the above-mentioned.
[9] The method according to any one of [1] to [3],
The mass ratio of the urethane resin (A) and epoxy resin (B) which have a carboxyl group is 100: 10-100, The curable heat radiation composition characterized by the above-mentioned.
[10] The method according to any one of [1] to [3],
The inorganic filler (C) is a curable heat dissipating composition, characterized in that a mixture of a flat filler and a particulate filler.
[11] The method according to the above [10],
The mass ratio of the flat filler and the particulate filler is 90:10 to 10:90, wherein the curable heat dissipating composition.
[12] The method according to the above [10] or [11],
The particulate filler is alumina, aluminum nitride or boron nitride, and the flat filler is boron nitride.
[13] An adhesive comprising the curable heat dissipating composition according to any one of [1] to [12].
(Effects of the Invention)
The curable heat dissipating composition of the present invention may be an adhesive having high heat dissipation, adhesiveness at work, adhesiveness after curing, and long-term reliability, and include a power semiconductor, a semiconductor element containing an optical semiconductor, a semiconductor device, a metal plate for a circuit, and the metal plate. It can be used for fixing electrical components such as circuits, circuit boards, and hybrid integrated circuits.
1: is a top view (a) and X-X sectional drawing (b) of the flat inorganic filler C used for this invention.
Hereinafter, the present invention will be described in detail.
In this invention, the mixed resin which consists of a urethane resin (A) and an epoxy resin (B) which have a carboxyl group is used as matrix resin of curable heat radiation composition.
Urethane resin (A) which has a carboxyl group used for this invention is excellent in flexibility, and excellent in the fluidity | liquidity at the time of heating, has adhesiveness even if it fills a high thermal conductivity inorganic filler, and is excellent in adhesiveness at the time of thermosetting Do. Moreover, since it is flexible, it is excellent in stress relaxation property and excellent in moisture resistance reliability, and the hardened | cured material using the said resin (A) has high long-term reliability.
The urethane resin (A) having a carboxyl group used in the present invention may be (a) a polyisocyanate compound, (b) a polycarbonate diol compound, (c) a dihydroxy compound having a carboxyl group, and (d) monohydroxy as necessary. It is obtained by making a compound react.
Specific examples of the polyisocyanate compound (a) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1, 4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1 , 4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, diphenylmethane diisocyanate, (o, m, or p) -xylene diisocyanate, methylenebis (cyclohexyl isocyanate), cyclohexane-1 , 3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methyleneditolylene-4,4'-di SOCCIA may be a carbonate, 4,4'-diphenyl ether diisocyanate, tetrachloro phenylene diisocyanate, norbornane diisocyanate, such as Nadi isocyanate. These diisocyanate can be used 1 type or in combination of 2 or more types.
Moreover, a small amount of polyisocyanate compounds which have three or more isocyanate groups, such as triphenylmethane triisocyanate, can also be used in the range which does not gelatinize.
Among these, especially when the polyisocyanate compound which has a C6-C30 alicyclic compound other than an isocyanate group part is used, the outstanding performance regarding the long-term insulation reliability at high temperature, high humidity is expressed. Examples of the polyisocyanate compound having an alicyclic compound having 6 to 30 carbon atoms other than the isocyanate group moiety include cyclohexanediisocyanate, isophorone diisocyanate, methylenebis (cyclohexyl isocyanate), and cyclohexane-1,3-dimethylene. Diisocyanate and cyclohexane-1,4-dimethylene diisocyanate are mentioned.
In order to express desirable physical properties, it is preferable to use at least 10 mol% or more, more preferably 30 mol% or more of the polyisocyanate compound having an alicyclic compound having 6 to 30 carbon atoms other than these isocyanate group moieties. Do.
As the polycarbonate diol compound (b), for example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2 -Methyl-1,8-octanediol, 1,9-nonanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclohexanediol The polycarbonate diol compound which has a structure which connected diol components, such as a tricyclohexane dimethanol and pentacyclo pentadecane dimethanol, by a carbonate bond is preferable. These polycarbonate diol compounds can be used 1 type or in combination or 2 or more types.
Among these, when the diol which has a C6-C30 alicyclic compound is used, the outstanding performance is expressed especially about the long-term insulation reliability at the time of high temperature, high humidity. Examples of the diol having an alicyclic compound having 6 to 30 carbon atoms include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, Tricyclodecane dimethanol and pentacyclo pentadecane dimethanol are mentioned.
In order to express preferable physical properties, it is preferable to use the polycarbonate diol which has these C6-C30 alicyclic compound at least 10 mol% or more, more preferably 30 mol% or more of all the polycarbonate diol components.
The preferable number average molecular weight of the polycarbonate diol compound (b) used for this invention is 300-50000. If it is less than 300, long-term insulation reliability at the time of high temperature, high humidity will fall, and if it exceeds 50000, a urethane resin synthesis | combination will become difficult.
Examples of the dihydroxy compound (c) having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N, N-bishydroxyethylglycine, N, N-bishydroxyethylalanine, and the like. Among these, dimethylol propionic acid and dimethylol butanoic acid are especially preferable from the solubility in a solvent. The dihydroxy compound which has these carboxyl groups can be used 1 type or in combination of 2 or more types.
Although the urethane resin which has a carboxyl group can be synthesize | combined only by the three components of said (a), (b) and (c), it is a monohydroxy compound for the purpose of providing radical polymerizability, reactivity, or eliminating the influence of the terminal isocyanate residue. (d) can be reacted further.
As monohydroxy compound (d), for example, 2-hydroxyethyl (meth) acrylate which has a radically polymerizable double bond, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, said each ( Caprolactone or alkylene oxide adduct of meta) acrylate, glycerin di (meth) acrylate, trimethyloldi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Trimethylol propane tri (meth) acrylate, allyl alcohol, aryloxy ethanol, etc. are mentioned, The compound which has carboxylic acid, such as glycolic acid and hydroxy pivalic acid, is mentioned as a monohydroxy compound which gives reactivity. .
These monohydroxy compounds can be used 1 type or in combination of 2 or more types. Among these, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, allyl alcohol, glycolic acid, hydroxy pivalic acid are preferable, and 2-hydroxy Roxyethyl (meth) acrylate is more preferable.
In addition, monohydroxy compounds used for the purpose of eliminating the influence of terminal isocyanate residues are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, amyl alcohol, hexyl alcohol, octyl Alcohol etc. are mentioned.
500-100000 are preferable and, as for the number average molecular weight of the carboxyl group-containing urethane resin of this invention, 2000-30000 are especially preferable. The number average molecular weight is a polystyrene conversion value measured by gel permeation chromatography here. If the number average molecular weight is less than 500, the elongation, flexibility, and strength of the cured film are not impaired. If the number average molecular weight is more than 100000, the solubility in the solvent is lowered, and the viscosity becomes too high even when dissolved, thereby increasing the restriction in terms of use.
5-150 mgKOH / g is preferable and, as for the acid value of the carboxyl group-containing urethane resin of this invention, 10-120 mgKOH / g is especially preferable. If the acid value is less than 5 mgKOH / g, the reactivity with the epoxy resin decreases and the heat resistance may be impaired. If the acid value exceeds 150 mgKOH / g, there is a drawback that the cured film is excessively hard or receded.
The urethane resin (A) having a carboxyl group used in the present invention is a polyisocyanate compound (a) or a polycarbonate diol using an appropriate solvent in the presence or absence of a known urethanization catalyst such as dibutyl tin dilaurylate. It is obtained by making compound (b), the dihydroxy compound (c) which has a carboxyl group, and a monohydroxy compound (d) react as needed. Although there is no restriction | limiting in particular in reaction mode, A typical example in industrial implementation is demonstrated.
The organic solvent used for the reaction may be one having low reactivity with isocyanate. For example, toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, tetrahydrofuran, diethylene glycol dimethyl ether, and ethylene glycol diethyl ether , Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, methoxy propionate methyl, methoxy propionate ethyl, ethoxypropionate methyl, ethoxypropionate ethyl, ethyl acetate, N-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone , Dimethyl sulfoxide, chloroform, methylene chloride and the like. Moreover, it is not preferable that the solubility of the produced | generated carboxyl group-containing urethane is low. Moreover, it is not preferable that a solvent remains in hardened | cured material in order to express heat dissipation, and the solvent which is easy to volatilize from that viewpoint is preferable. Among these, solvents, such as toluene, tetrahydrofuran, ethyl acetate, acetone, and methyl ethyl ketone, are preferable. As a density | concentration of reaction liquid, 10-90 mass% is preferable, and, as for the urethane resin concentration which has a carboxyl group, 40-80 mass% is more preferable.
Although there is no restriction | limiting in particular about the order which inputs a raw material, Generally, a diol compound (a polycarbonate diol compound of (b) and a dihydroxy compound containing the carboxyl group of (c)) is added first, and it melt | dissolves in a solvent, and it is 20 It adds, dropping the polyisocyanate compound of (a) at -150 degreeC, More preferably, 60-120 degreeC, Then, it makes it react at 50-160 degreeC, More preferably, it is 70-130 degreeC.
The molar ratio of the raw material is controlled by the target number average molecular weight and the acid value. However, when the monohydroxy compound (d) is introduced, the polyisocyanate compound of (a) is converted to the diol compound ((b) It is necessary to use more than polycarbonate diol compound + the dihydroxy compound containing the carboxyl group of (c)).
When the reaction between the diol compound and the polyisocyanate compound is almost finished, in order to react the isocyanate remaining at both terminals with the monohydroxy compound of (d), the monohydrate is at 20 to 150 ° C, more preferably at 70 to 120 ° C. The oxy compound is added dropwise, and then maintained at the same temperature to complete the reaction.
In this invention, it is preferable that the epoxy resin (B) used as a hardening | curing agent of the urethane resin (A) which has a carboxyl group has at least 2 or more average epoxy groups in 1 molecule. Moreover, such an epoxy resin may have a silicone skeleton, a urethane skeleton, and a polyimide skeleton, for example.
Such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, water added bisphenol A type epoxy resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, biphenyl type epoxy resins, Glycidyl ether type epoxy resins, such as a biphenyl aralkyl type epoxy resin, a naphthalene type epoxy resin, a naphthalene aralkyl type epoxy resin, a triphenylmethane type epoxy resin, a trimethylol propane triglycidyl ether, and a pentaerythritol polyglycidyl ether Glycidylamine epoxy resins such as hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester, triglycidyl isocyanurate, and tetraglycidyl diaminodiphenylmethane; And linear aliphatic epoxy resins such as epoxidized polybutadiene and epoxidized soybean oil. The said epoxy resin can be used individually or in mixture of 2 or more types.
100: 10-100 are preferable and, as for the mass ratio of the urethane resin (A) and epoxy resin (B) which have a carboxyl group, 100: 20-80 are more preferable. When the ratio of an epoxy resin is less than 10, hardening reaction will not fully advance. When it exceeds 100, since moldability deteriorates, an inorganic filler cannot be filled high and adhesiveness and adhesiveness after hardening also fall.
Any inorganic filler (C) used in the present invention can be used as long as it has a function of thermal conduction. However, barium sulfate and titanium oxide are not contained in the inorganic filler (C) used by this invention.
Examples of the inorganic filler (C) include ceramics such as silica, alumina, boron nitride, aluminum nitride, and silicon carbide, carbon materials such as diamond and graphite, and metal powders such as copper, aluminum, iron, and silver. The silica includes, for example, fused silica produced by melting high purity silica and crystalline silica produced by grinding natural quartz.
The shape of the inorganic filler (C) may be either particulate or flat, or a mixture thereof. Examples of the particulate filler include alumina, aluminum nitride, boron nitride (for example cubic crystal), silica, diamond, metal powder, and the like. As the flat filler, boron nitride (for example hexagonal crystal), graphite, metal, etc. Powder and the like.
Inorganic filler (C) can contain at least 10 mass%, preferably at least 20 mass% of inorganic fillers whose thermal conductivity is 20 W / m * K or more. This further improves the function of thermal conduction. Examples of the inorganic filler having a thermal conductivity of 20 W / m · K or more include ceramic materials such as alumina, boron nitride, aluminum nitride, and silicon carbide, carbon materials such as diamond and graphite, and metal powders such as copper, aluminum, iron, and silver.
In addition, the thermal conductivity of the inorganic filler used for this invention is measured by the method prescribed | regulated to the thermal diffusivity, specific heat, and thermal conductivity test method by the laser flash method of fine ceramics: JISR 1611 (2010).
Inorganic filler (C) is 50-96 mass% in the composition containing a urethane resin (A) which has a carboxyl group, an epoxy resin (B), and an inorganic filler (C), More preferably, 55-92 mass% of this invention Can achieve the purpose. If it is less than 50 mass%, sufficient heat dissipation will not be expressed. When it exceeds 96 mass%, the adhesiveness of a composition, adhesiveness after hardening, etc. are not fully obtained.
In addition, the compounding quantity of an inorganic filler (C) can be expressed by the total sum of the surface area of the inorganic filler in curable heat radiation composition. 50-350 m <2> is preferable per 100 g of curable heat radiation compositions, and, as for the total of the surface area of the inorganic filler in this case, 70-300 m <2> is more preferable. If it is less than 50 m <2>, sufficient heat dissipation will not be expressed, and if it exceeds 350 m <2>, adhesiveness of a composition, adhesiveness after hardening, etc. will not fully be obtained.
The total sum of the surface areas of the inorganic fillers can be obtained by the following method. That is, for example, when only P1 mass% of the filler 1 of specific surface area S1 is contained in curable heat radiation composition, the surface area of a filler per 100 g of curable heat radiation composition will be (S1 * P1). Moreover, when P2 mass% of the filler 2 of specific surface area (S2) is contained in the said curable heat radiation composition, the surface area of the filler per 100 g of curable heat radiation compositions will be (S1 * P1 + S2 * P2). Therefore, the total sum of the surface area of the inorganic filler per 100 g of the curable heat dissipating composition containing the n-component inorganic filler is represented by the following general formula.
Here, the specific surface area of an inorganic filler is the value measured by the nitrogen gas adsorption method (BET method). BET method is a method of measuring specific surface area by adsorb | sucking nitrogen gas which knows the adsorption occupation area of a single molecule to powder under liquid nitrogen temperature.
In addition, in the composition of this invention, an inorganic filler (C) can use combining a particulate form and a flat form. The thermal conductivity of hardened | cured material can be improved compared with the case of using a particulate form alone, and isotropy can be provided to the thermal conductivity of hardened | cured material compared with the case of using a flat thing alone.
In addition, in this invention, as shown in FIG. 1, the inorganic filler particle 1 top view (a) and XX sectional view (b) show the ratio of the long diameter L and the thickness t of the particle 1 5: 1-20: It means one person. The measurement can be performed by a scanning electron microscope.
In addition, in this invention, a particulate form is typically spherical and means the form whose flatness is smaller than the said flat form.
Boron nitride (for example, hexagonal crystal) and graphite, which are representative examples of flat fillers, have anisotropy in thermal conductivity. It is known that the thermal conductivity of hexagonal boron nitride is about 60 to 63 W / mK in the plane direction, about one minute of the moisture in the plane direction in the direction perpendicular to the plane direction, and the thermal conductivity in the plane direction is several times higher. . The flat filler is excellent in heat dissipation in the planar direction because the flat filler has a property of being arranged parallel to the planar direction when the composition of the present invention is applied to a substrate or sheeted by applying pressure. However, since the heat dissipation function may be necessary not only in the plane direction but also in the thickness direction, it is necessary to arrange the flat filler in the random or thickness direction.
In the curable heat dissipation composition of this invention, by mix | blending a particulate filler in a fixed range, a flat filler can be orientated randomly and the thermal conductivity of a thickness direction can be improved.
In the present invention, when the flat filler and the particulate filler are mixed and used, the mass ratio is preferably 90:10 to 10:90, and more preferably 85:15 to 15:85.
When the mass ratio of the flat filler is 10 or more, the thermal conductivity becomes good, and when the mass ratio of the particulate filler is 10 or more, the thermal conductivity in the thickness direction becomes good.
The flat filler and the particulate filler used in the curable heat dissipating composition of the present invention have a preferable average particle size in view of moldability, smoothness of the cured product, and thermal conductivity, respectively. In the case of a flat filler, an average particle diameter of 0.5-50 micrometers is preferable, and 1-30 micrometers is more preferable. In the case of a particulate filler, an average particle diameter of 1-100 micrometers is preferable, and 5-80 micrometers is more preferable. The average particle diameter of the flat filler used at the same time is smaller than the average particle diameter of the particulate filler, and the flat filler is randomly oriented, and is advantageous in terms of the thermal conductivity in the thickness direction.
These average particle diameters are the values obtained by measuring particle size distribution by a laser diffraction scattering method. Specifically, Seishin Enterprise Co., Ltd. It can measure by using manufacture and a laser diffraction scattering particle size distribution analyzer (LMS-2000e).
In the curable heat dissipating composition of the present invention, boron nitride is preferable as the flat filler from the viewpoint of thermal conductivity, electrical insulation and economical efficiency, and alumina, aluminum nitride and boron nitride are preferable as the particulate filler. As the boron nitride of the flat filler, for example, Showa Denko K.K. The produced UHP-1K (L: t = 8: 1) is, for example, Showa Denko K.K. As manufactured CB-A50S (average particle diameter 50 micrometers) and aluminum nitride of a particulate filler, Tokuyama Corporation. Production FAN-f50J (average particle diameter 50 micrometers) can be used preferably.
A hardening accelerator can be added to the curable heat radiation composition of this invention for the purpose of promoting hardenability. As a specific example of a hardening accelerator, a tertiary amine, an imidazole compound, a phosphine compound, etc. are mentioned.
Specific examples of the tertiary amine compound include triethylamine, dimethylcyclohexylamine, N, N-dimethylpiperazine, benzyldimethylamine, 2- (N, N-dimethylaminomethyl) phenol, 2,4,6-tris ( N, N-dimethylaminomethyl) phenol, 1,8- diazabicyclo (5.4.0) undecene-1, etc. are mentioned.
Specific examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-methyl. Midazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyano Ethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino -6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2-methylimidazole isocyanuric acid adduct, 2-phenylimidazole isocyanur Acid adducts, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine-isocyanuric acid adducts;
Specific examples of the phosphine compound include triphenylphosphine, tritolylphosphine, and the like.
A coupling agent can be added to the curable heat radiation composition of this invention in order to raise the dispersibility of the inorganic filler to a resin component, and adhesiveness to a base material. As a coupling agent, a silane type, titanate type, aluminum type etc. are mentioned. In this invention, a silane coupling agent can be used preferably, As a preferable specific example, (gamma) -aminopropyl trimethoxysilane, (gamma) -aminopropyl triethoxysilane, (gamma)-(2-aminoethyl) aminopropyl trimeth Methoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxy Cyclohexyl) ethyl triethoxysilane etc. are mentioned.
Moreover, it is also possible to use the monomer or oligomer which has another polymerizable functional group for the purpose of adjusting viscosity, a physical property, curability, etc. for the composition of this invention. Specifically, styrene derivatives such as styrene and vinyltoluene having a radical polymerizable group, methyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate and isoamyl (meth) ) Acrylate, hexyl (meth) acrylate, 2-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) ) Acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanedioldi ( Meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol # 400 di (meth) acrylate, 2 , 2-bis (4- (meta) arc Oxypolyethyloxyphenyl) propane, bisphenol A di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, propylene oxide (PO) modified bisphenol A di (meth) acrylate, hydrogenated bisphenol A di (meth) ) Acrylate, isocyanuric acid ethylene oxide (EO) modified di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, trimethylolpropane PO modified tree Monofunctional epoxy compounds, such as (meth) acrylic acid ester, such as (meth) acrylate methacrylate, styrene oxide, and phenyl glycidyl ether 2-ethylhexyl glycidyl ether, allyl ester resin, unsaturated polyester resin, and vinyl Ester resin is mentioned.
Although the composition of this invention can mix | blend the additive for adjusting a physical property with the urethane resin (A) which has a carboxyl group, (B) epoxy resin, and (C) inorganic filler, it can be used as a curable heat radiation composition as it is, but at the temperature which hardening does not advance. It can also form as a sheet | seat by heating and pressurization, and can also be used as an adhesive sheet. Moreover, you may form in shapes other than sheet shape. After formation, it can bond by heating to the temperature which presses with a base material and advances.
The curable heat dissipating composition of the present invention comprises a power semiconductor, a semiconductor device including an optical semiconductor, a semiconductor device, a circuit metal plate, a circuit comprising the metal plate as an adhesive having high heat dissipation, adhesiveness at work, adhesiveness after curing, and long-term reliability; It can be used for fixing electrical components such as circuit boards and hybrid integrated circuit fields.
(Example)
Although a synthesis example, an Example, and a comparative example are given to the following, this invention is demonstrated, but this invention is not limited at all by these Examples.
The number average molecular weight, acid value, thermal conductivity, adhesive strength, and elastic modulus of the molded cured plate of the urethane resin having a carboxyl group were measured (evaluated) by the following method.
Number average molecular weight:
It calculated | required as the value converted into polystyrene using the gel permeation chromatography (Showa Denko K.K. make, Shodex (trademark) GPC SYSTEM-11).
Acid value:
About 0.2 g of a sample is precisely weighed by a precision balance in a 100 ml Erlenmeyer flask, and 10 ml of a mixed solvent of ethanol / toluene = 1/2 (mass ratio) is added and dissolved therein. 1 to 3 more phenolphthalein ethanol solutions are added to this container as an indicator, and it fully stirs until a sample becomes uniform. This is titrated with 0.1 N potassium hydroxide-ethanol solution, and the end point of neutralization is when the red color of the indicator continues for 30 seconds. From the result, the value obtained using the following formula is taken as the acid value of resin.
Thermal Conductivity of Curable Heat Dissipation Composition:
The thermal conductivity in the plane direction was measured by a hot disk method using a TPS-2500 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.) using a rectangular parallelepiped specimen of 30 mm (length) x 28 mm (width) x 8 mm (thickness). . In addition, the thermal conductivity in the thickness direction was measured by thermal wave diffraction using an ai-Phase Mobile (manufactured by ai-Phase Co., Ltd.) by thermal wave thermal analysis, and obtained from the specific heat and density obtained separately. It calculated | required by the following formula.
Thermal Conductivity = Thermal Diffusion × Specific Heat × Density
Adhesive strength:
Using a test piece of copper (manufactured by Nippon Testpanel Co., Ltd., C100P, one side # 240 polishing), the curable heat dissipating composition in a sheet form was inserted into the copper test piece and the polished surface, and heat adhesion at 130 ° C. for 20 minutes was performed. It measured in shear mode based on JISK6852 (1994) after performing. In addition, the size of the test piece was made into 14 mm in width, 9 mm in thickness, and 30 mm in length, and the adhesive area was made into 14 width x 25 mm in length.
Synthesis Example 1 Urethane Resin Having a Carboxyl Group
C-1015N (polycarbonate diol produced by Kuraray Co., Ltd., raw material diol molar ratio 1,9-nonanediol: 2-methyl-1,8-) as a polycarbonate diol compound in a reaction vessel equipped with a stirring device, a thermometer and a condenser. Octanediol = 15: 85, molecular weight 964) 330.2 g, 60.4 g of 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Chemical Co., Ltd.) as a dihydroxyl compound having a carboxyl group, tetrahydrofuran (Kanto Kagaku) as a solvent 571.2 g was prepared, and the temperature of the reaction solution was raised to 60 ° C., and 180.4 g of Desmodul-W (manufactured by Juka Bayer Urethane Co., Ltd.) was added dropwise over 30 minutes as a polyisocyanate compound by dropping lot. After completion of the dropwise addition, the reaction was further performed at 60 ° C. for 6 hours to confirm that most of the isocyanate disappeared, and then 5 g of isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to carry out the reaction at 60 ° C. for 2 hours.
The number average molecular weight of the obtained urethane resin which has a carboxyl group was 8600, and the acid value of solid content was 39.6 mgKOH / g.
Synthesis Example 2 Urethane Resin Having a Carboxyl Group
UM-CARB90 (manufactured by Ube Industries, Ltd., raw material diol molar ratio cyclohexanedimethanol: hexanediol = 1: 1, molecular weight 891) 315.7 g, carboxyl group as a polycarbonate diol compound in a reaction vessel equipped with a stirring device, a thermometer and a condenser 58.6 g of 2,2-dimethylolbutanoic acid (manufactured by Nippon Kasei Chemical Co., Ltd.) as a dihydroxyl compound having a compound and 554.7 g of tetrahydrofuran (manufactured by Kanto Kagaku.) As a solvent were added thereto, and the temperature of the reaction solution was adjusted. It raised to 60 degreeC, and 180.4 g of Desmodule-W (made by Juka Bayer Urethane Corporation) was dripped over 30 minutes as a polyisocyanate compound by the dropping lot. After completion of the dropwise addition, the reaction was further performed at 60 ° C for 6 hours to confirm that most of the isocyanate disappeared, and then 5 g of isobutanol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the reaction was further performed at 60 ° C for 2 hours.
The number average molecular weight of the obtained carboxyl group-containing polyurethane was 7900 and the acid value of solid content was 40.2 mgKOH / g.
Example 1:
The equivalent ratio of the urethane resin (carboxyl equivalent 1416) and bisphenol A epoxy resin (Nippon Steel Chemical Co., Ltd. make, YD-128: epoxy equivalent 189) which have a carboxyl group obtained by the synthesis example 1 was adjusted to be 1.05: 1.0. A flat inorganic filler UHP-1K (manufactured by Showa Denko KK, boron nitride thermal conductivity 60 W / mK) as an inorganic filler was used as an inorganic filler (85 mass%, composition 100 g). The total surface area in = 349 m 2) was blended and kneaded using a rotating / revolving mixer (manufactured by Thinky, defoaming kneading Thinky Mixer) to obtain a target curable heat dissipating resin composition.
The curable heat dissipating composition was heat-molded at 130 ° C. for 20 minutes using a heat press, a molded cured plate cured in a sheet shape was produced, and the thermal conductivity was measured. As a result, the thermal conductivity in the surface direction was 37.4 W / m · K. Very high value was shown.
Examples 2-4:
The carboxyl group which adjusted the equivalent ratio of the carboxyl group-containing urethane resin (carboxyl equivalent 1396) and bisphenol-A epoxy resin (YD-128, the Nippon Steel Chemical Co., Ltd. make, epoxy equivalent 189) obtained by the synthesis example 2 to be 1.05: 1.0. Except having changed the mass% ratio of containing urethane-epoxy resin preparation and an inorganic filler as Table 1, it carried out similarly to Example 1, and prepared the curable heat radiation resin composition of Examples 2-4, and produced the molded hardening board. Table 1 shows the thermal conductivity measurement results in these plane directions. High thermal conductivity of 8 W / m · K or more was obtained.
Comparative Example 1:
Inorganic filler (UHP-1K): The curable heat dissipation resin composition was prepared in the same manner as in Example 1 except that the proportion of the carboxyl group-containing urethane / epoxy resin preparation was 40% by mass, to prepare a molded cured plate. As a result of measuring the thermal conductivity of this molded hardened plate, the thermal conductivity of the surface direction was 3.6 W / m * K.
Examples 5-7:
As inorganic filler, spherical inorganic filler CB-A50S (manufactured by Showa Denko KK, alumina thermal conductivity 36W / mK), particulate inorganic filler FAN-f50J (manufactured by Tokuyama Corporation, aluminum nitride thermal conductivity 200W / mK) and flat phase A cured heat dissipating composition was prepared in the same manner as in Example 1 except that the inorganic filler UHP-1K (manufactured by Showa Denko KK, boron nitride) was used in combination to form the composition shown in Table 2, to prepare a molded cured plate. Table 2 shows the measurement results of the respective composition ratios, the thickness direction thermal conductivity, and the state adhesive strength of the curable heat dissipating composition.
Comparative Example 2:
Commercially available novolak-type phenolic resin BRG-556 (manufactured by Showa Denko KK, hydroxyl equivalent 103 (measured based on JIS K0070)) and bisphenol A-type epoxy resin YD-128 (Nippon Steel Chemical Co., Ltd. manufactured, epoxy equivalent Novolak-Epoxy resin preparation: The particle size aluminum nitride (FAN-f50J): Boron nitride UHP-1K was adjusted to 11.7: 71.6: 16.6 (mass% ratio), respectively. In the same manner as in 1, a curable heat dissipating composition was prepared to form a molded cured plate. Table 2 shows the measurement results of the respective composition ratios, the thickness direction thermal conductivity, and the state adhesive strength of the curable heat dissipating composition.
The value of the thermal conductivity in the thickness direction of this molded cured plate was relatively high at 6.3 W / m · K. However, as a result of measuring the adhesive strength, the sheet made of this resin composition was inferior in flexibility, Adhesiveness deteriorated and it could not adhere | attach.
Comparative Example 3:
Epoxy resin preparation which added 100 mass parts of bisphenol-A epoxy resin YD-128 (made by Nippon Steel Chemical Co., Ltd., epoxy equivalent 189) and 2.5 mass parts of 1-cyanoethyl-2-methylimidazole as a hardening | curing agent. : Granular aluminum nitride (FAN-f50J): The boron nitride UHP-1K was set to 11.7: 71.6: 16.6 (mass% ratio), respectively, in the same manner as in Example 1 to prepare a curable heat dissipating composition, to prepare a molded cured plate. Table 2 shows the measurement results of the respective composition ratios, the thickness direction thermal conductivity, and the state adhesive strength of the curable heat dissipating composition.
Comparative Example 4:
Commercially available novolak-type phenolic resin BRG-556 (manufactured by Showa Denko KK, hydroxyl equivalent 103 (measured based on JIS K0070)) and bisphenol A-type epoxy resin YD-128 (Nippon Steel Chemical Co., Ltd. manufactured, epoxy equivalent Novolak-epoxy resin preparation adjusted to an equivalent ratio of 189) to 1.05: 1.0: particulate aluminum nitride (FAN-f50J): boron nitride (UHP-1K) as 9.1: 73.8: 17.1 (mass% ratio), respectively. In the same manner as in Example 1, a curable heat dissipating composition was prepared to form a molded cured plate. Table 2 shows the measurement results of the respective composition ratios, the thickness direction thermal conductivity, and the adhesive strength of the curable heat dissipating composition.
The curable heat dissipating resin composition of the present invention formed by blending an epoxy and an inorganic filler using a carboxyl group-containing urethane resin has a high thermal conductivity, flexibility, and good adhesion to a metal, and includes a power semiconductor, a semiconductor device including an optical semiconductor, and a semiconductor. It is very useful in the field of an apparatus, a circuit metal plate, a circuit which consists of said metal plate, a circuit board, a hybrid integrated circuit, etc.
1 flat weapon filler
Claims (13)
The said inorganic filler (C) contains the inorganic filler which has a thermal conductivity of 20 W / m * K or more, The curable heat radiation composition characterized by the above-mentioned.
Curable heat dissipation composition containing at least 10 mass% of inorganic fillers which have a thermal conductivity of 20 W / m * K or more in the said inorganic filler (C).
The urethane resin (A) having a carboxyl group is obtained by reacting (a) a polyisocyanate compound, (b) a polycarbonate diol compound, (c) a dihydroxy compound having a carboxyl group, and (d) a monohydroxy compound as necessary. Curable heat radiation composition characterized by the above-mentioned.
Curable heat dissipation composition, characterized in that the number average molecular weight of the polycarbonate diol compound (b) is 300 ~ 50000.
At least 10 mol% or more of the diol which comprises the said polycarbonate diol compound whose number average molecular weights are 300-500000 is a C6-C30 alicyclic compound, The curable heat dissipation composition characterized by the above-mentioned.
At least 10 mol% or more of a polyisocyanate compound (a) is a C6-C30 alicyclic compound other than an isocyanate group part, The curable heat radiation composition characterized by the above-mentioned.
The number average molecular weight of the urethane resin (A) which has a carboxyl group is 500-100000, and an acid value is 5-150 mgKOH / g, The curable heat radiation composition characterized by the above-mentioned. ·
The mass ratio of the urethane resin (A) and epoxy resin (B) which have a carboxyl group is 100: 10-100, The curable heat radiation composition characterized by the above-mentioned.
The inorganic filler (C) is a curable heat dissipating composition, characterized in that a mixture of a flat filler and a particulate filler.
The mass ratio of the flat filler and the particulate filler is 90:10 to 10:90, wherein the curable heat dissipating composition.
The particulate filler is alumina, aluminum nitride or boron nitride, and the flat filler is boron nitride.
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KR20170062475A (en) * | 2014-10-01 | 2017-06-07 | 나믹스 가부시끼가이샤 | Resin composition |
KR20200038105A (en) * | 2018-10-02 | 2020-04-10 | 주식회사 이엠따블유 | Flexible printed circuit board module and manufacturing method for thereof |
KR20230045280A (en) * | 2021-09-28 | 2023-04-04 | 이기영 | Manufacturing method of heat-dissipating resin composite for secondary battery and curing method thereof |
Families Citing this family (12)
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Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4089636B2 (en) * | 2004-02-19 | 2008-05-28 | 三菱電機株式会社 | Method for manufacturing thermally conductive resin sheet and method for manufacturing power module |
FR2872820B1 (en) * | 2004-07-07 | 2008-09-05 | Conception & Dev Michelin Sa | ADHESIVE SYSTEM FOR THE DIRECT COLLECTION OF A POLYURETHANE COOKED WITH RAW RUBBER |
JP4994679B2 (en) * | 2005-03-04 | 2012-08-08 | 昭和電工株式会社 | Film material forming paste |
JP5233392B2 (en) * | 2008-04-30 | 2013-07-10 | 東洋インキScホールディングス株式会社 | Polyurethane polyurea adhesive, curable electromagnetic wave shielding adhesive film using the same, and method for producing the same |
JP5506010B2 (en) * | 2006-03-17 | 2014-05-28 | 昭和電工株式会社 | Resin composition |
JP5164090B2 (en) * | 2007-02-16 | 2013-03-13 | 太陽ホールディングス株式会社 | Thermosetting resin composition containing carboxylic group-containing urethane resin and cured product thereof |
JP2009001642A (en) * | 2007-06-20 | 2009-01-08 | Hitachi Chem Co Ltd | Thermosetting resin composition, flexible substrate using the same, and electronic component |
JP5043577B2 (en) * | 2007-09-27 | 2012-10-10 | 太陽ホールディングス株式会社 | Thermosetting resin composition and cured product thereof |
JP2009096915A (en) * | 2007-10-18 | 2009-05-07 | Hitachi Chem Co Ltd | Thermosetting resin composition, flexible substrate using the same, and electronic component |
WO2009090997A1 (en) * | 2008-01-15 | 2009-07-23 | Toyo Ink Manufacturing Co., Ltd. | Curable electromagnetic shielding adhesive film, method for producing the same, use of the same, method for producing electromagnetic shielding article, and electromagnetic shielding article |
DE102008007749A1 (en) * | 2008-02-05 | 2009-08-06 | Tesa Se | Thermally activatable and curable adhesive film, in particular for the bonding of electronic components and flexible printed conductors |
JP5176073B2 (en) * | 2008-05-21 | 2013-04-03 | 日立化成株式会社 | Thermosetting resin composition |
JP2010229282A (en) * | 2009-03-27 | 2010-10-14 | Toyo Ink Mfg Co Ltd | Polyurethane polyurea resin composition, curable adhesive film with electromagnetic wave-shielding property and method of manufacturing the same |
CN102460867B (en) * | 2009-06-17 | 2013-09-18 | 昭和电工株式会社 | Discharge-gap-filling composition, and electrostatic discharge-protector |
JP2011148862A (en) * | 2010-01-19 | 2011-08-04 | Hitachi Chem Co Ltd | Thermosetting resin composition, method for forming protective film of flexible wiring board and flexible wiring board |
JP5901141B2 (en) * | 2010-05-17 | 2016-04-06 | 昭和電工株式会社 | Light-emitting element mounting substrate, light-emitting element mounting substrate manufacturing method, light-emitting device, light-emitting device manufacturing method, and white resin composition |
-
2012
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20170062475A (en) * | 2014-10-01 | 2017-06-07 | 나믹스 가부시끼가이샤 | Resin composition |
KR20200038105A (en) * | 2018-10-02 | 2020-04-10 | 주식회사 이엠따블유 | Flexible printed circuit board module and manufacturing method for thereof |
KR20230045280A (en) * | 2021-09-28 | 2023-04-04 | 이기영 | Manufacturing method of heat-dissipating resin composite for secondary battery and curing method thereof |
Also Published As
Publication number | Publication date |
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JPWO2012157627A1 (en) | 2014-07-31 |
TWI534256B (en) | 2016-05-21 |
CN103562258A (en) | 2014-02-05 |
WO2012157627A1 (en) | 2012-11-22 |
TW201311875A (en) | 2013-03-16 |
KR101525487B1 (en) | 2015-06-03 |
CN103562258B (en) | 2016-06-29 |
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