KR101898757B1 - Thermally conductive, moisture-curable resin composition - Google Patents
Thermally conductive, moisture-curable resin composition Download PDFInfo
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- KR101898757B1 KR101898757B1 KR1020147007477A KR20147007477A KR101898757B1 KR 101898757 B1 KR101898757 B1 KR 101898757B1 KR 1020147007477 A KR1020147007477 A KR 1020147007477A KR 20147007477 A KR20147007477 A KR 20147007477A KR 101898757 B1 KR101898757 B1 KR 101898757B1
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3737—Organic materials with or without a thermoconductive filler
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
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Abstract
The present invention relates to a thermally conductive moisture curable composition capable of efficiently conducting heat to a component accompanied by heat generation. (A) an organic polymer containing at least two crosslinkable hydrolyzable silyl groups, (B) a thermally conductive filler, and (C) a polyether compound having only a crosslinkable hydrolyzable silyl group at one terminal end, in a thermally conductive moisture curable resin composition .
Description
The present invention relates to a thermally conductive moisture curable composition capable of efficiently conducting heat to a component accompanied by heat generation. Further, the thermally conductive moisture curing composition of the present invention is excellent in coating workability and free from bleeding out.
Heat-generating electronic components such as transistors and thyristors used in electronic devices are required to remove heat since they generate heat during use. Conventionally, heat dissipation fins or metal plates, such as copper or aluminum, are provided on these components to diffuse heat and remove heat from the components. Since the heat dissipation fin or the metal plate (hereinafter, collectively referred to as a heat dissipation member) is solid and a fine gap is generated even when adhered to an electronic component such as a transistor, a heat conductive silicone rubber sheet or the like is interposed therebetween, there was.
2. Description of the Related Art In recent years, there has been a demand for high performance and miniaturization of electronic devices. In order to achieve high density and high functionality of semiconductors, the circuit board on which the semiconductor is mounted also needs to be miniaturized, and it is important to design the circuit board to take out heat generated from the circuit board. Therefore, it is desired that the thermally conductive resin or sealing material used for the circuit board has high thermal conductivity.
On the other hand, a curable composition having an alkoxysilyl group, a curable composition containing a so-called modified silicone as a main component has been proposed variously. These curable compositions are crosslinked by moisture in an atmospheric environment, resulting in a cured product having excellent durability and weather resistance. Accordingly, the curable composition is used for various applications such as paints, coatings, adhesives, pressure-sensitive adhesives, sealants and sealants.
In order to obtain a thermally conductive curable resin using the curable composition, it is common to add a filler having high thermal conductivity in the composition. For example, Patent Document 1 discloses adding a thermally conductive filler to a modified silicone having polyisobutylene as a main skeleton.
On the other hand, Patent Document 2 discloses that by adding an organic solvent, the viscosity of the composition is reduced and the coating operation and adhesion are improved.
Patent Document 3 discloses a composition in which polypropylene glycol having a hydrolyzable silyl group at the molecular chain end is added to improve adhesion and curability.
However, in the technique described in Patent Document 1, it is necessary to add a large amount of filler in order to exhibit high thermal conductivity of the thermally conductive curable resin, and the viscosity of the composition becomes very high. However, it is difficult to apply a composition having a high viscosity to a small component. Therefore, it is required to improve the viscosity of the composition and the flow property. In order to lower the viscosity of such a composition, a liquid having a low viscosity such as a plasticizer may be added. However, there is a problem that the plasticizer bleeds out from the cured product.
Also, in the technique described in Patent Document 2, since the diluent is a solvent, the adherend is invaded when the adherend is plastic or the like, but the hardening shrinkability and volatility are large, and storage stability and the like are still problematic.
Further, in the technique described in Patent Document 3, there is a problem that the viscosity of the composition is excessively low and the coating workability is poor, and bleeding-out easily occurs from the cured product.
In order to solve the problems described above, the present invention is characterized by adding a low molecular weight one-terminal reactive silylated polyether as a reactive diluent, whereby a high degree of thermal conductivity can be obtained even when a large amount of thermally conductive filler is added, The present invention has been completed based on the discovery that the application workability is excellent and the occurrence of bleed-out can be suppressed without adversely affecting the electronic parts.
(A) an organic polymer containing at least two crosslinkable hydrolyzable silyl groups, (B) a thermally conductive filler, and (C) a polyether compound having only a crosslinkable hydrolyzable silyl group at one end only And a thermosetting moisture-curable resin composition.
In the present specification, the terms "mass part", "weight part", "mass ratio" and "weight ratio" are synonyms.
In a preferred embodiment of the present invention, the mixing ratio of the component (A) to the component (C) is 70:30 to 1:99 in terms of the mass ratio, and the component (B) Is 150 to 3,000 parts by mass based on 100 parts by mass of the thermosetting moisture-curable resin composition.
The thermally conductive moisture-curing resin composition of the present invention has high thermal conductivity and does not adversely affect electric and electronic parts, so that the coating workability is excellent and the occurrence of bleed-out can be suppressed.
The organic polymer (A) used in the present invention is not particularly limited as long as it has two or more crosslinkable hydrolyzable silyl groups in one molecule. In the component (A), the hydrolyzable silyl group is hydrolyzed to form a siloxane bond, so that the organic polymer is crosslinked to form a cured product on the rubber.
The hydrolyzable silyl group is one in which 1 to 3 hydrolysable groups are bonded to silicon atoms. Examples of the hydrolyzable group include hydrogen, halogen atoms, alkoxy groups such as methoxy and ethoxy groups, acyloxides, Preferred examples thereof include an alkoxy group, an alkoxy group, a methoxy group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group and an alkenyloxy group. Especially preferred is an alkoxy group which does not produce harmful byproducts during the reaction.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, a tert-butoxy group, a phenoxy group and a benzyloxy group. And may be a combination of different types.
Examples of the alkoxysilyl group in which an alkoxy group is bonded to a silicon atom include trialkoxysilyl groups such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group and a triphenoxysilyl group; Dialkoxysilyl groups such as a dimethoxymethylsilyl group and a diethoxymethylsilyl group; And a monoalkoxysilyl group such as a methoxydimethoxysilyl group and an ethoxydimethylsilyl group. A plurality of these may be used in combination, or a plurality of different alkoxy groups may be used in combination.
The main chain structure of the component (A) is not particularly limited as long as it is a main chain skeleton of a so-called modified silicone, and may be a polyether main chain structure, Structure, a polyimide backbone structure, and a vinyl-based polymer main chain structure obtained by polymerizing a polymerizable unsaturated group. The component (A) may have the main chain structure thereof in a molecule alone, or may have a main chain structure obtained by combining a plurality of these components. It may also be a mixture of two or more compounds having these structures. Among the above-described main chain structures, at least one of a vinyl-based polymer main chain structure and a polyether main chain structure is particularly suitable. That is, the main chain structure may be a vinyl polymer main chain structure, a polyether main chain structure, or both of a polyether main chain structure portion and a vinyl polymer main chain structure portion.
Examples of the polyether main chain structure include a main chain structure such as polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol; derivatives thereof having these copolymer structures and substituents. MS Polymers S-203, S-303 and S-903 as commercially available MS Polymers, which are commercially available from Kabushiki Kaisha Chemical Co., Ltd., Cyryl SAT-200 as a cryol polymer, MA-403, MA-447, and the like, available from Asahi Glass Co., Ltd., ESS-2410, ESS-2420 and ESS-3630.
Examples of the polyester main chain structure include a polyester obtained by condensing a glycol such as ethylene glycol, propylene glycol, neopentyl glycol or tetramethylene glycol with a dicarboxylic acid such as terephthalic acid, isophthalic acid, sebacic acid, succinic acid, phthalic acid or adipic acid And a polyester backbone structure.
Examples of the main chain structure of the polyurethane include a polyurethane such as a polyether polyol and a polyester polyol, and a polyurethane main chain obtained by adding a diisocyanate such as xylene diisocyanate, isophorone diisocyanate, methylene diphenyl diisocyanate, Structure and the like.
Examples of the polyamide main chain structure include a polyamide main chain structure obtained by condensation of a diamine and a dicarboxylic acid or ring-opening polymerization of caprolactam. As the polyurea backbone structure, there may be mentioned a polyurea backbone structure obtained by adding a diamine and diisocyanate in the middle. Examples of the polyimide backbone structure include a polyimide backbone structure obtained by imidization of a diamine and a compound having two cyclic acid anhydride structures in one molecule.
The vinyl-based polymer main chain structure obtained by polymerizing a polymerizable unsaturated group is not particularly limited as long as it is a vinyl-based polymer structure obtained by polymerizing a compound having a polymerizable unsaturated group. The vinyl-based polymer obtained by polymerizing the compound having a polymerizable unsaturated group may be a polymer obtained by polymerizing a vinyl monomer, and examples thereof include polyethylene, polypropylene, polyisobutylene, poly (meth) acrylate, polystyrene, Vinyl, polyvinylidene chloride, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl ether, and the like. It may also be a copolymer having these vinyl polymer moieties.
The thermally conductive filler of component (B) is a component for imparting thermal conductivity to the composition. As the component (B), known ones can be used. Inorganic oxides such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina powder and silica; nitrogen inorganic compounds such as aluminum nitride, boron nitride and silicon nitride; , Graphite, and silicon carbide; metallic materials such as silver, copper, and aluminum; and the like. These may be used alone or in combination of two or more.
The thermally conductive filler may be any shape such as spherical, powder, fibrous, acicular, and scaly, and has an average particle size of about 1 to 100 탆. The amount of the thermally conductive filler to be used varies depending on the shape and kind of the filler to be used but is preferably from 150 to 3,000 parts by mass based on 100 parts by mass of the total amount of the component (A) and the component (C) When the amount is more than 3,000 parts by mass, the adhesive strength when the resin composition is cured is weakened, and there is a possibility that the adhesiveness between the heat radiation member and the heat generating component is weakened.
The component (C) of the present invention is a polyether compound having only a crosslinkable hydrolyzable silyl group at one end. The crosslinkable hydrolyzable silyl group is the same as the crosslinkable hydrolyzable silyl group in the above-mentioned component (A). The polyether which is the main chain portion of the component (C) is also the same as described above. The viscosity of the component (C) is preferably from 100 to 1000 mPa · s. The molecular weight (weight average molecular weight) of the component (C) is preferably about 1000 to 5,000. The industrially available component (C) is CYLYL SAT-115 as a cryol polymer, which is a trade name of KANEKA KABUSHIKI CO., LTD. The weight average molecular weight means a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography.
The component (C) contributes to lowering of the viscosity of the product at a low viscosity, but does not cause bleed-out because it is included in the reaction. In addition, in view of the fact that the functional group is at one end, the physical properties of the resin are not lost and mechanical properties can be maintained. It is also conceivable to use a resin having a low viscosity as the component (A) for the purpose of simply lowering the viscosity of the composition. However, this method causes a problem that the resin properties after the curing are discarded. Further, if a low viscosity is attempted by using a plasticizer or an organic solvent, problems such as poor curing, bleeding-out and deterioration of hardening shrinkage are caused. However, these problems can be solved by using the component (C) of the present invention.
The mixing ratio of the component (A) to the component (C) is not particularly limited, but is preferably from 70: 30 to 1:99, more preferably from 50: 3:97, particularly preferably from 35:65 to 5:95. The mixing ratio of the component (A) to the component (C) is in this range because it is possible to improve the heat radiation characteristics while maintaining the coating workability.
Various additives may be added to the thermally conductive moisture curable resin composition of the present invention as necessary. Examples of the additive include a wetting agent, a water absorbent, an adhesion-imparting agent, a curing catalyst, a filler, a flame-retardant aid, a light stabilizer, an antioxidant, a colorant and the like.
The water absorbent is not particularly limited as long as it absorbs moisture of the composition or reacts with moisture. Examples thereof include silicate compounds represented by methyl silicate, ethyl silicate, propyl silicate and butyl silicate, and oligomers thereof, vinyl silanes, calcium oxide, and the like. These may be used alone, or two or more of them may be used in combination.
Examples of the tackifier include vinyl silane, epoxy silane, styryl silane, methacryloxy silane, acryloxy silane, aminosilane, ureido silane, chloropropyl silane, mercaptosilane, sulfide silane, phenyl silane and isocyanate Silane, and the like. These may be used alone, or two or more of them may be used in combination.
The curing catalyst is not particularly limited as long as it is a catalyst for crosslinking the polymer (A). Specific examples thereof include dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin distearate, dibutyltin laurate oxide, dibutyltin diacetylacetonate, dibutyltin dioleyl Tin compounds such as maleate, dibutyltin octoate, dioctyltin oxide, dioctyltin dilaurate and the like; Examples of the metal complexes include titanate compounds such as tetra-n-butoxytitanate and tetraisopropoxide titanate; Carboxylic acid metal salts such as lead octylate, lead naphthenate, nickel naphthenate, cobalt naphthenate, zinc compounds, iron compounds, and bismuth; A metal acetylacetonate complex such as an aluminum acetylacetonate complex, a vanadium acetylacetonate complex and the like. In addition, amine salts such as dibutylamine-2-ethylhexoate, organic phosphoric acid compounds such as monomethylphosphoric acid and di-n-butylphosphoric acid, other acidic catalysts and basic catalysts can also be used. These may be used alone, or two or more of them may be used in combination.
Examples of the filler include organic and inorganic fillers of various shapes, but inorganic fillers such as talc, clay, magnesium carbonate, silicic anhydride, hydrated silicon, calcium silicate, shirasu balloon and glass balloon are preferable. When such an inorganic material is added , Flame retardancy and workability may be improved.
The flame-retardant aid is not particularly limited, but a commercially available silicone compound is preferably used as the flame retardant, and it can be used as a flame-retardant auxiliary for non-halogen.
Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl- ) Sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert- butyl-4-hydroxyphenyl) propionyl Oxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, Pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) [[3,5- 1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) N, N ', N' '' - tetrakis- (4,6-bis- (butyl- (N-methyl- 6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N , 2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) ) Butylamine, a polycondensate of poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate and 4-hydroxy-2, 2,6,4-tetramethyl-20- (? - lauryloxycarbonyl) ethyl-7-oxa-3,20- Diazatispyro [5,1,11,2] hennaic acid-21-one,? -Alanine, N- (2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / tetra Decyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine- Tetra-methyl-7-oxa-3,20-diazadispyro [5,1,11,2] heneic acid-21-one, 2,2,4,4-tetramethyl- Diazadicyclo- [5,1,11,2] -Henaco -Propane dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) Esters, higher fatty acid esters of 2,2,6,6-tetramethyl-4-piperidines, 1,3-benzenedicarboxyamide, N, N'-bis (2,2,6,6- 4-piperidinyl); Benzophenone compounds such as octabenzone; 4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [ Methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl Benzotriazol-2-yl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di- 2-yl) -6-dodecyl-4-methylphenol and the like, a reaction product of benzyltriazole with 5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol compound; Benzoate-based compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; And triazine-based compounds such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 - [(hexyl) oxy] phenol. Particularly preferred are hindered amine compounds.
Examples of the antioxidant include antioxidants such as? -Naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, quinone compounds such as tert-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, and 2,5-di-tert-butyl-p-benzoquinone; (4-methyl-6-tert-butylphenol), catechol, tert-butylcatechol, 2-butyl-4-hydroxyanisole, 2,6- 2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxyphenyl) Tert-butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4'-butylidenebis (6-tert- 3-methylphenol), 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, pentaerythritol tetrakis [3- (3,5- Hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl- butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis [3- (3,5- Propanamide], benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 branched alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) , 3,3 ', 3 ", 5,5', 5" -hexa-tert-butylphenyl) methylphosphonate, and diethyl [[3,5-bis (1,1- -Butyl-, a ', a "- (mesitylene-2,4,6-tolyl) tri-p-cresol, calcium diethylbis [ Butylphenyl] methyl] phosphonate, 4,6-bis (octylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis 3- [5- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris 3, 5H) -triene, 1,3,5-tris [(4-tert-butyl- 2,4,6 (1H, 3H, 5H) -triene, N, N-phenylbenzeneamine and 2,4,6- Reaction of 6-trimethylpentene Phenols such as 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine-2-ylamino) phenol, picric acid and citric acid; Tris (2,4-di-tert-butylphenyl) phosphite, tris [2- [[2,4,8,10-tetra-tert- butyldibenzo [d, f] (2,4-bis (1,1-dimethylethyl) -6, 6-dihydroxypropyl) -Methylphenyl] ethyl ester phosphoric acid, tetrakis (2,4-di-tert-butylphenyl) [1,1-bisphenyl] -4,4'-diylbisphosphonite, 6- 3- -Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyl dibenz [d, f] [1,3,2] dioxaphosphper compound; Diaryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3- Lauryl thiopropionate), and 2-mercaptobenzimidazole; Amine-based compounds such as phenothiazine; Lactone-based compounds; Vitamin E-based compounds, and the like. Among them, phenol compounds are suitable.
The thermally conductive moisture-curable resin composition of the present invention can be cured by moisture in the air.
The thermally conductive moisture curable resin composition of the present invention may be of a one-component type or a two-component type, if necessary. The thermally conductive moisture-curable resin composition of the present invention can be applied to a computing circuit such as a CPU (Central Processing Unit) or an MPU (Micro-Processing Unit), an electronic component such as a transistor or a thyristor, And is used between the members. In addition, it can be used as long as it is necessary for heat conduction.
Example
Hereinafter, the present invention will be described in more detail with reference to examples, but it should be understood that these examples are illustrative and should not be construed as limiting.
(Examples 1 to 5 and Comparative Examples 1 to 7)
Components (A) to (C) were mixed in the blend (unit: parts by mass) shown in Table 1, and phenyltrimethoxysilane as an adhesion-imparting agent and 1 part by weight of dibutyltin acetate as a curing catalyst were added and mixed To prepare a moisture-curable composition.
The compounding compounds in Table 1 are as follows.
Kane-Kasai Reel SAT200: Kaneka Co., Ltd., a polyether containing a total of two hydrolyzable silyl groups at both ends, a viscosity of 23 Pa at 25 캜
· Ganexa reel SAT115: Kaneka Co., Ltd., a polyether having only a hydrolyzable silyl group at one end, a viscosity of 0.5 Pa · s at 23 ° C
Ganexa Reil SAT350: Kaneka Co., Ltd. Polyethers containing a total of two hydrolyzable silyl groups at both ends, a viscosity of 23 Pa at 4 ° C
ARUFON UP-1000: manufactured by Doagosei Co., Ltd., acrylic polymer having no reactive functional group
Alumina powder 1: Crushed alumina powder having an average particle diameter of 0.5 mu m
Alumina powder 2: a spherical alumina powder having an average particle diameter of 30 mu m
Alumina powder 3: A spherical alumina powder having an average particle diameter of 10 mu m
Each of the compositions obtained above was used to perform the following performance evaluation. The results are shown in Table 2.
The various test items in Table 2 were performed as follows.
1) Viscosity
The viscosities at frequencies 1 Hz and 10 Hz were measured using a rheometer under the following measurement conditions.
Measuring instrument: DAR-100 manufactured by Rheologica Co., Ltd. Viscoelasticity measurement,
Pleshare shear rate: 5.0 (1 / S) 20 seconds, equilibration time 200 seconds,
Distortion: 1 x E-2, integration count: 3 times, measurement count: 20 times, interval 10 seconds,
Measurer: Parallel 25, gap 1 mm, temperature 25 캜
2) Dischargeability
The cartridge was charged into a polyethylene-made cartridge equipped with a plunger, and a nozzle having an inner diameter of 5 mm was attached to the cartridge. The cartridge was attached to an air gun and extruded at a pressure of 0.5 MPa for 10 seconds.
3) Heat dissipation characteristics
Various compositions were measured using a thermal conductivity meter (QTM-D3, manufactured by Kyoto Denshi Kogyo Co., Ltd.) according to the hot wire method (thin film).
4) presence or absence of bleed-out
2.2 g of each composition was discharged on an aluminum plate (A1050P) in a circular shape, and after standing for 24 hours, the composition was observed and it was confirmed whether or not the liquid material bleed-out on the outer periphery of the composition.
5) Hardness of the cured product
Various compositions were injected into a sheet-like fluorine formulation and cured at 23 DEG C, 50% RH for 168 hours. The hardness (unit) of the obtained sheet-like cured product of 2 mm in thickness was measured using a C2 type hardness durometer. For details, see JIS K 6253 (2006).
As apparent from the results of Table 2, the composition of the present invention has a low viscosity, excellent workability in coating, and high heat conductivity. Further, there is no problem that the properties of the resin after curing, which are generated when diluting with a solvent or a plasticizer as in the prior art, are discarded, curing defects, bleed-out occur, and the viscosity is increased.
Although the present invention has been described in detail with reference to specific embodiments, it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. The present application is based on Japanese Patent Application (Japanese Patent Application No. 2011-205534) filed on September 21, 2011, the contents of which are incorporated herein by reference.
≪ Industrial applicability >
The thermally conductive moisture curable resin composition of the present invention is applied to an electronic circuit such as a CPU or an MPU, an electronic circuit such as a transistor or a thyristor, and is used between a heat dissipation member such as a heat dissipation fin or a Peltier element. In addition, it can be used as long as it is necessary for heat conduction.
Claims (2)
(B) component: a pulverized thermally conductive filler and a precursory thermally conductive filler, and
Component (C): Polyether compound having only a crosslinkable hydrolyzable silyl group at one terminal end
≪ / RTI >
Wherein the blend amount of the component (B) is 900 to 3,000 parts by mass relative to 100 parts by mass of the total amount of the component (A) and the component (C) as the thermoconductive moisture-
Wherein the composition has a viscosity at a frequency of 1 Hz of 101 to 174 Pa · s.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011205534 | 2011-09-21 | ||
| JPJP-P-2011-205534 | 2011-09-21 | ||
| PCT/JP2012/073736 WO2013042638A1 (en) | 2011-09-21 | 2012-09-14 | Thermally conductive, moisture-curable resin composition |
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| Publication Number | Publication Date |
|---|---|
| KR20140063722A KR20140063722A (en) | 2014-05-27 |
| KR101898757B1 true KR101898757B1 (en) | 2018-09-13 |
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| KR1020147007477A KR101898757B1 (en) | 2011-09-21 | 2012-09-14 | Thermally conductive, moisture-curable resin composition |
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|---|---|
| JP (1) | JPWO2013042638A1 (en) |
| KR (1) | KR101898757B1 (en) |
| CN (1) | CN103998528B (en) |
| WO (1) | WO2013042638A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111615539B (en) * | 2018-02-15 | 2022-08-02 | 三键有限公司 | Heat-conductive moisture-curable resin composition and cured product thereof |
| WO2020002257A1 (en) * | 2018-06-25 | 2020-01-02 | Sika Technology Ag | Catalyst-free curable compositions based on silane-functional polymers |
| CN109135247A (en) * | 2018-07-17 | 2019-01-04 | 平湖阿莱德实业有限公司 | High thermal conductivity calking boundary material and preparation method thereof |
| JP2022520317A (en) * | 2019-02-13 | 2022-03-30 | シーカ テクノロジー アクチェンゲゼルシャフト | Thermally conductive curable composition |
| US11873423B2 (en) * | 2019-02-28 | 2024-01-16 | Kaneka Americas Holding, Inc. | Moisture curable adhesive compositions |
| JP7256944B2 (en) * | 2019-08-08 | 2023-04-13 | 株式会社スリーボンド | Moisture-curable resin composition and cured product |
| WO2022197726A1 (en) * | 2021-03-15 | 2022-09-22 | Henkel Ag & Co. Kgaa | One component thermally conductive ambient temperature curable materials |
| FR3136238A1 (en) * | 2022-06-03 | 2023-12-08 | Bostik Sa | Two-component thermally conductive composition of silylated polymer |
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| JP2004224985A (en) * | 2003-01-24 | 2004-08-12 | Kanegafuchi Chem Ind Co Ltd | Cold-setting composition |
| WO2005073276A1 (en) * | 2004-01-30 | 2005-08-11 | Kaneka Corporation | Method for producing hydrolyzable silicon group-containing oxyalkylene polymer and curing composition thereof |
| CN101166773A (en) | 2005-04-29 | 2008-04-23 | Sika技术股份公司 | Moisture-curable composition featuring increased elasticity |
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| JPH04335086A (en) | 1991-05-10 | 1992-11-24 | Three Bond Co Ltd | Thermally conductive filler composition |
| JP2002363429A (en) | 2001-06-07 | 2002-12-18 | Three Bond Co Ltd | Heat-conductive composition |
| JP2008088318A (en) * | 2006-10-03 | 2008-04-17 | Momentive Performance Materials Japan Kk | Thermoconductive silicone composition and semiconductor device comprised of the same |
| KR20090074039A (en) * | 2006-10-10 | 2009-07-03 | 다우 코닝 코포레이션 | Extenders for organosiloxane compositions |
| JP5300232B2 (en) * | 2007-09-12 | 2013-09-25 | 三井・デュポンポリケミカル株式会社 | Heat dissipation resin composition |
| JP4656339B2 (en) * | 2008-02-14 | 2011-03-23 | 信越化学工業株式会社 | Condensation reaction curable silicone rubber composition |
| GB0806820D0 (en) * | 2008-04-16 | 2008-05-14 | Dow Corning | Polymeric compositions |
| JP2011256214A (en) | 2008-10-08 | 2011-12-22 | Denki Kagaku Kogyo Kk | Heat-conductive moisture curable resin composition |
| JP2011032344A (en) * | 2009-07-31 | 2011-02-17 | Kaneka Corp | Curable resin composition for semiconductor package |
| WO2011125636A1 (en) * | 2010-04-08 | 2011-10-13 | 電気化学工業株式会社 | Thermally conductive moisture curable resin composition |
| JP2011225695A (en) * | 2010-04-19 | 2011-11-10 | Three Bond Co Ltd | Fire-retardant moisture-curable resin composition |
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2012
- 2012-09-14 KR KR1020147007477A patent/KR101898757B1/en active IP Right Grant
- 2012-09-14 WO PCT/JP2012/073736 patent/WO2013042638A1/en active Application Filing
- 2012-09-14 CN CN201280046308.9A patent/CN103998528B/en active Active
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|---|---|---|---|---|
| JP2004224985A (en) * | 2003-01-24 | 2004-08-12 | Kanegafuchi Chem Ind Co Ltd | Cold-setting composition |
| WO2005073276A1 (en) * | 2004-01-30 | 2005-08-11 | Kaneka Corporation | Method for producing hydrolyzable silicon group-containing oxyalkylene polymer and curing composition thereof |
| CN101166773A (en) | 2005-04-29 | 2008-04-23 | Sika技术股份公司 | Moisture-curable composition featuring increased elasticity |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103998528B (en) | 2017-06-23 |
| WO2013042638A1 (en) | 2013-03-28 |
| KR20140063722A (en) | 2014-05-27 |
| JPWO2013042638A1 (en) | 2015-03-26 |
| CN103998528A (en) | 2014-08-20 |
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