WO2024190331A1 - ペースト - Google Patents
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- WO2024190331A1 WO2024190331A1 PCT/JP2024/006162 JP2024006162W WO2024190331A1 WO 2024190331 A1 WO2024190331 A1 WO 2024190331A1 JP 2024006162 W JP2024006162 W JP 2024006162W WO 2024190331 A1 WO2024190331 A1 WO 2024190331A1
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- paste
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
Definitions
- One embodiment of the present invention relates to a paste.
- Paste also called grease
- sliding components brake components, vibration suppression/absorption components, and other components to ensure the desired movement, wear resistance, seizure resistance, etc. of these components.
- heat dissipation (thermally conductive) materials are used between the heat generating element and the heat dissipation member in electronic components, etc., to efficiently transfer heat from the heat generating element to the heat dissipation member.
- electronic components such as power modules have become smaller and have higher output
- the amount of heat generated per unit area by these electronic components, etc. has become very large, and there is a demand for heat dissipation materials with excellent heat dissipation properties to ensure the normal operation of electronic components, etc. and long-term reliability.
- Heat dissipation materials are mainly available in two forms: sheet type and paste type.
- the sheet type has high thermal resistance due to poor compatibility with opposing surfaces such as heating elements and heat dissipation components, and the need for a certain thickness for the sheet itself.
- the paste type is used because it can be made thin, has good compatibility with opposing surfaces, and has excellent heat dissipation performance.
- the viscosity of the paste is low when applied, workability and productivity such as paintability are improved, and it is easy to place a specified amount of paste, especially a small amount, in a specified location.
- the paste layer can be made thinner, improving heat dissipation performance, so low viscosity when applied is required.
- the paste is also required to remain in a specified location (e.g., between the heating element and the heat dissipation member) in order to achieve the purpose required of the paste.
- a specified location e.g., between the heating element and the heat dissipation member
- the viscosity of the paste when applied is low, the flow resistance is low, and the paste is expelled from the specified location due to the thermal cycle applied to electronic components, etc., resulting in a problem of so-called pump-out, making it difficult to maintain heat dissipation performance over the long term.
- Patent Document 1 a method has been proposed for heat dissipation pastes that use a silicone-based material as the base oil, in which an addition reaction with a platinum catalyst is used to reduce viscosity when applied, and the base oil is hardened after application, thereby increasing flow resistance and suppressing pump-out.
- Patent Document 2 a method has been proposed in which a photoactive platinum complex curing catalyst is used to harden the paste by exposure to ultraviolet light (Patent Document 2), and an organic peroxide is used to harden the paste by heating (Patent Document 3).
- the addition reaction type compositions described in Patent Document 1 and the like include one-liquid compositions and two-liquid compositions, but when considering workability such as the complexity of mixing, one-liquid compositions are preferred, and Patent Document 1 also describes a one-liquid composition.
- the one-liquid compositions described in Patent Document 1 and the like require freezing or refrigeration, making it difficult to store and manage the compositions.
- UV-irradiation type and heat-curing type require an UV-irradiation process and a heating process, respectively, to cure, these processes must be incorporated into the production process for electronic parts, etc., which makes the process more complicated and lengthy, reducing production efficiency.
- One embodiment of the present invention provides an anaerobic paste that, despite its low initial viscosity, thickens (does not solidify but remains paste-like or rubber-like) at room temperature when in contact with a metal component and is isolated from air (anaerobic) conditions, and can suppress pump-out.
- the initial viscosity here refers to the viscosity at the time of preparation of the anaerobic paste, that is, the viscosity of the anaerobic paste before it is thickened, and usually the viscosity at the time of application.
- An example configuration of the present invention is as follows:
- a composition comprising a polysiloxane (A) having a mercapto group and a redox initiator (B),
- A polysiloxane
- B a redox initiator
- the anaerobic paste thickens at room temperature under anaerobic conditions and in contact with a metal member, and is in a paste or rubber form after thickening.
- anaerobic paste that, despite its low initial viscosity, thickens (does not solidify but remains paste-like or rubber-like) at room temperature under (anaerobic) conditions in which it is in contact with a metal member and air (oxygen) is blocked off, thereby suppressing pump-out.
- anaerobic paste according to one embodiment of the present invention between, for example, a heat generating body and a heat dissipating member (at least one of these that is in contact with the anaerobic paste is a metal member) and compressing it (blocking oxygen), it thickens in a short time without heating or light irradiation, increases the flow resistance, and suppresses pump-out.
- a heat dissipating member at least one of these that is in contact with the anaerobic paste is a metal member
- compressing oxygen it thickens in a short time without heating or light irradiation, increases the flow resistance, and suppresses pump-out.
- it is possible to provide an anaerobic heat dissipation paste with excellent heat dissipation performance.
- the anaerobic paste according to one embodiment of the present invention (hereinafter also referred to as “the paste") contains a polysiloxane (A) having a mercapto group (hereinafter also referred to as “component (A)". The same applies to the other components.) and a redox initiator (B),
- the viscosity increases at room temperature under anaerobic conditions in contact with a metal member (hereinafter also referred to as "anaerobic room temperature thickening"), and after the anaerobic room temperature thickening, the viscosity is paste-like or rubber-like.
- this paste between a heating element and a heat dissipation member (at least one of these that contacts the anaerobic paste is a metal member) and compressing it (blocking oxygen), the oxygen is blocked, and furthermore, the redox initiator is cleaved by the catalytic effect of metal ions and mercapto groups from the metal member, generating radicals.
- the generated radicals abstract protons from the mercapto groups, and a crosslinking reaction proceeds, which is thought to cause the viscosity of this paste to increase.
- the paste thickens in a short, simplified process without the steps previously required (e.g., heating or light irradiation), suppresses pump-out, and enables long-term performance (e.g., heat dissipation) to be maintained.
- the "paste” is defined as a paste having a thickness of 200 ⁇ m or less when 0.2 g of the paste is cut into a 5 mm square and compressed at 23° C. under a pressure of 1.0 MPa.
- the method for measuring the thickness is specifically as described in the following Examples.
- rubber is defined as a material that is not paste-like, has elasticity, and has a surface Martens hardness of 10 N/mm2 or less, measured with an ultra-microhardness tester using a triangular pyramidal indenter (edge angle 115°) as the measuring indenter at a maximum test force of 0.3 mN.
- solidified refers to a state that is neither pasty nor rubbery, and can be defined as a state in which the surface Martens hardness measured with an ultra-microhardness tester using a triangular pyramidal indenter (edge angle 115°) as the measuring indenter at a maximum test force of 0.3 mN exceeds 10 N/ mm2 .
- This paste does not solidify even after anaerobic room temperature thickening, and is in a paste or rubber-like state after anaerobic room temperature thickening.
- a paste is thickened at room temperature under anaerobic conditions in contact with a metal member, and specifically, 4 g of the paste is sandwiched between two copper plates at 23°C and compressed for 2.5 hours so that the paste has a thickness of 0.4 mm.
- the compressed body is then cut into a 5 mm square and compressed at 23°C under a pressure of 1.0 MPa, such that the thickness is 200 ⁇ m or less; or the surface of the compressed body has a surface Martens hardness of 10 N/mm2 or less , as measured at a maximum test force of 0.3 mN using an ultra-microhardness meter using a triangular pyramidal indenter (edge angle 115°) as the measuring indenter.
- the method for measuring the thickness is specifically as described in the following Examples.
- thickening refers to a viscosity increase after anaerobic room temperature thickening of at least 10% over the initial viscosity.
- the paste may be a two-component (e.g., two-liquid) or more-component composition that includes a first agent containing component (A) and a second agent containing component (B); however, taking into consideration workability such as the complexity of mixing, a one-component (e.g., one-liquid) composition is preferred.
- a two-component e.g., two-liquid
- a one-component e.g., one-liquid
- component (A) There are no particular limitations on component (A) as long as it is a polysiloxane having a mercapto group (-SH).
- component (A) may have a functional group other than a mercapto group (e.g., a group having an ethylenically unsaturated bond [e.g., a vinyl group, a (meth)acryloyl group]).
- a functional group other than a mercapto group e.g., a group having an ethylenically unsaturated bond [e.g., a vinyl group, a (meth)acryloyl group].
- the component (A) used in the present paste may be one type or two or more types.
- the bonding position of the mercapto group is not particularly limited, and may be a so-called side chain type, a terminal type (including one terminal type and both terminal types), or a side chain both terminal type, but a side chain type or both terminal type is preferable, and a side chain type is more preferable.
- Component (A) is an organopolysiloxane in which an organic group is bonded to a silicon atom, and preferably is a polysiloxane in which at least a portion of the organopolysiloxane has a mercapto group.
- Examples of the organic group bonded to a silicon atom include a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, and an alkoxy group.
- Examples of the linear alkyl group include groups having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, and a decyl group.
- Examples of the branched alkyl group include groups having 3 to 20 carbon atoms, preferably 3 to 6 carbon atoms, such as an isopropyl group, an isobutyl group, a t-butyl group, and a 2-ethylhexyl group.
- Examples of the cyclic alkyl group include groups having 3 to 20 carbon atoms, such as a cyclopentyl group and a cyclohexyl group.
- Examples of the aryl group include groups having 6 to 20 carbon atoms, such as a phenyl group and a tolyl group.
- Examples of the aralkyl group include groups having 7 to 20 carbon atoms, such as a benzyl group, a 2-phenylethyl group, and a 2-methyl-2-phenylethyl group.
- Examples of halogenated alkyl groups include groups having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, such as 3,3,3-trifluoropropyl group, 2-(nonafluorobutyl)ethyl group, and 2-(heptadecafluorooctyl)ethyl group.
- Examples of the alkoxy group include methoxy and ethoxy groups having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms.
- the organic group bonded to the silicon atom is preferably a linear alkyl group or an aryl group, more preferably a linear alkyl group or an aryl group having 1 to 6 carbon atoms, and particularly preferably a methyl group or a phenyl group.
- the structure other than the portion having a mercapto group in the organopolysiloxane preferably has at least one polysiloxane structure selected from dimethylpolysiloxane, methylphenylpolysiloxane, and diphenylpolysiloxane, and more preferably has a dimethylpolysiloxane structure.
- the mercapto group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via an organic group bonded to the silicon atom.
- component (A) is not particularly limited, and examples include linear, branched, partially branched linear, and dendritic (dendrimer) structures, with linear and partially branched structures being preferred.
- Component (A) may be a single polymer having these molecular structures, a copolymer having these molecular structures, or a mixture of two or more of these polymers.
- component (A) include polysiloxanes represented by the following formula (2).
- R 1 and R 2 are each independently an unsubstituted or substituted monovalent hydrocarbon group, a mercapto group, an alkoxy group, or -R-SH (R is a hydrocarbon group having 1 to 20 carbon atoms), and the sum of a and b is an integer from 2 to 500.
- R 1 and R 2 in formula (2) contains a mercapto group or -R-SH, and multiple R 1s present in formula (2) may be the same or different, and multiple R 2s present in formula (2) may be the same or different.
- the unsubstituted or substituted monovalent hydrocarbon group in R1 and R2 is preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include the same groups (other than alkoxy groups) as those exemplified as the organic group bonded to a silicon atom. Among these, a monovalent hydrocarbon group having 1 to 6 carbon atoms is preferred, and an alkyl group or aryl group having 1 to 6 carbon atoms is more preferred.
- Examples of the alkoxy group in R 1 and R 2 include the same alkoxy groups as those exemplified as the organic group bonded to a silicon atom.
- R in -R-SH is a hydrocarbon group having 1 to 20 carbon atoms, and examples of the R include groups in which one hydrogen atom has been removed from the groups (groups other than halogenated alkyl groups and alkoxy groups) exemplified above as organic groups bonded to silicon atoms.
- Component (A) may be synthesized by a conventional method or may be a commercially available product.
- the shear viscosity of component (A) at 23° C. measured with a cone-plate viscometer (rotation speed: 0.5 rpm) is preferably 0.005 to 60.00 Pa ⁇ s, more preferably 0.01 to 5.00 Pa ⁇ s.
- a thin paste layer can be easily formed in a predetermined location, such as between a heat generating body and a heat dissipation member, and a paste layer that is easily compatible with the opposing surface of a heat generating body or a heat dissipation member can be easily formed. Therefore, the thermal resistance of the paste layer can be reduced, and electronic components and the like having excellent heat dissipation properties can be easily obtained.
- the functional group equivalent of component (A) is preferably 1,000 to 50,000 g/mol, more preferably 1,500 to 35,000 g/mol, from the viewpoint of easily obtaining a paste that has a viscosity sufficient to suppress pump-out after anaerobic room-temperature thickening, does not solidify after anaerobic room-temperature thickening, and remains pasty or rubbery even after anaerobic room-temperature thickening.
- the functional group of component (A) refers to a group that reacts with a radical generated from the redox initiator, and specific examples thereof include a mercapto group and functional groups other than the above-mentioned mercapto group.
- component (A) it is desirable to use a polysiloxane (A1) having a functional group equivalent preferably in the range of 1000 to 5000 g/mol, more preferably 1500 to 5000 g/mol, and a polysiloxane (A2) having a functional group equivalent preferably in the range of 15000 to 50000 g/mol, more preferably 20000 to 35000 g/mol, from the viewpoint of easily obtaining a paste that has a viscosity sufficient to suppress pump-out after anaerobic room-temperature thickening, does not solidify even after anaerobic room-temperature thickening, and remains pasty or rubbery even after anaerobic room-temperature thickening.
- the proportion of polysiloxane (A2) relative to the total of these (100 mass %) is preferably 50.0 to 99.5 mass %, more preferably 75.0 to 99.0 mass %.
- the number average molecular weight (Mn) of component (A) measured by gel permeation chromatography (GPC) is preferably 3,000 to 50,000, more preferably 15,000 to 25,000, because it is easy to obtain a paste that can suppress pump-out after anaerobic room temperature thickening, despite its low initial viscosity.
- the content of component (A) in the paste is preferably 40.0 to 98.0 mass%, more preferably 60.0 to 95.0 mass%, relative to 100 mass% of the paste. If the paste contains the following component (D), the content of component (A) in the paste is preferably 5.0 to 40.0 mass%, more preferably 10.0 to 30.0 mass%, relative to 100 mass% of the paste.
- the content of component (A) in the paste is preferably 40.0 to 99.0 mass%, more preferably 70.0 to 99.0 mass%, and even more preferably 85.0 to 98.5 mass%, relative to 100 mass% of the total of components (A) and (C) in the paste, when the paste contains component (C) below, in order to easily obtain a paste that has a good balance between heat resistance, low initial viscosity, and pump-out suppression.
- component (B) There are no particular limitations on component (B) so long as it is a redox initiator, and any of the conventionally known redox initiators can be used. Since component (A) having a mercapto group acts as a reducing agent, component (B) is preferably a component (oxidizing agent) that can cause a redox reaction with component (A) to generate radicals.
- component (B) used in the present paste may be one type or two or more types.
- component (B) examples include organic peroxides, persulfates, permanganic acid, permanganates, manganese triacetate, cerium ammonium nitrate, cerium ammonium sulfate, bromic acid, bromates, and hydrogen peroxide. Among these, organic peroxides are preferred.
- organic peroxides examples include hydroperoxides such as t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, and diisopropylbenzene hydroperoxide; dihydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide; ketone peroxides such as acetylacetone peroxide and methyl ethyl ketone peroxide; peroxy esters such as t-butylperoxybenzoate; disuccinic acid peroxide; and diglutaric acid peroxide.
- hydroperoxides such as t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide,
- persulfates include ammonium persulfate, sodium persulfate, and potassium persulfate.
- permanganates include ammonium permanganate, alkali metal salts of permanganic acid (e.g., potassium permanganate), and alkaline earth metal salts of permanganic acid.
- bromates include ammonium bromate, alkali metal salts of bromate, and alkaline earth metal salts of bromate.
- the functional group ratio represented by the following formula (1) in the present paste is preferably 1.0 ⁇ 10 ⁇ 3 or less, more preferably 5.0 ⁇ 10 ⁇ 4 or less, and further preferably 3.0 ⁇ 10 ⁇ 4 or less.
- the paste is a one-component paste, it tends to thicken easily during storage, but by having the functional group ratio in the above range, it tends to be easy to obtain a paste with excellent storage stability. If the functional group ratio exceeds the above range, it may not be easy to obtain a paste with excellent storage stability (storage stability).
- the functional group ratio represented by the following formula (1) in this paste is preferably 1.0 x 10 -6 or more, more preferably 1.0 x 10 -5 or more.
- Functional group ratio (amount of component (A)/functional group equivalent of component (A)) ⁇ (amount of component (B)/active oxygen equivalent of component (B)) (1)
- the amount of component (A) is 100 parts by mass
- the amount of component (B) is the amount of component (B) relative to 100 parts by mass of component (A).
- the "amount of component (A)/functional group equivalent of component (A)" in the above formula (1) is "(x1/a+x2/b)". The same applies when two or more types of components (A) and/or (B) are used.
- the "amount of component (A)” is, for example, 100 ⁇ z/100 when a commercially available product with a purity (amount of active ingredient) of z% by mass is used as component (A) at 100% by mass. The same applies to the “amount of component (B)".
- the content of component (B) in this paste is preferably an amount that satisfies the above formula (1), but from the viewpoints of easily obtaining a paste that thickens at room temperature under anaerobic conditions, suppresses pump-out, and has excellent storage stability, the content is preferably 0.05 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 10 parts by mass, per 100 parts by mass of component (A) in this paste.
- the paste may contain components other than the components (A) and (B) as long as the effects of the present invention are not impaired.
- the other components include a compound (C) having two or more ethylenically unsaturated bonds in one molecule other than the component (A); a thermally conductive filler (D); a stabilizer; a catalyst; a plasticizer such as a fluorine-based or silicone-based oil; a silane coupling agent; a surfactant; a solvent; a dispersant; a flame retardant; and a pigment.
- the other components may each be used alone or in combination of two or more.
- the paste of the present invention does not contain a platinum-based catalyst, for example, in view of being able to easily obtain a paste with a long pot life.
- Conventional pastes use platinum-based catalysts, but the use of platinum-based catalysts results in a short pot life, making it impossible to store the paste for long periods of time.
- not containing a platinum-based catalyst means that the content of the platinum-based catalyst per 100 parts by mass of component (A) is, for example, 0.0001 parts by mass or less, and the lower limit is preferably 0 parts by mass.
- Component (C) having two or more ethylenically unsaturated bonds in one molecule is not particularly limited as long as it is a compound other than component (A) having two or more ethylenically unsaturated bonds in one molecule, and a conventionally known compound (co-crosslinking agent) can be used.
- a paste having excellent pump-out suppression properties after anaerobic room temperature thickening can be easily obtained.
- the component (C) used in the present paste may be one type or two or more types.
- the number of ethylenically unsaturated bonds in component (C) may be two, but from the viewpoint of being able to further suppress pump-out, etc., it is preferably three or more, and more preferably three to six.
- the two or more ethylenically unsaturated bonds contained in the component (C) may be the same or different, that is, the component (C) may have two or more types of ethylenically unsaturated bonds.
- the group having an ethylenically unsaturated bond includes, for example, alkenyl groups having 2 to 8 carbon atoms, such as vinyl groups, methylvinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, pentenyl groups, hexenyl groups, and heptenyl groups, vinylphenyl groups, (meth)acryloyl groups, allyloxy groups, styryl groups, propargyl groups, and maleimide groups.
- alkenyl groups having 2 to 8 carbon atoms such as vinyl groups, methylvinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, pentenyl groups, hexenyl groups, and heptenyl groups, vinylphenyl groups, (meth)acryloyl groups, allyloxy groups, styryl groups, propargyl groups, and maleimide groups.
- alkenyl groups having 2 to 8 carbon atoms and (meth)acryloyl groups are preferred, alkenyl groups having 2 to 4 carbon atoms and (meth)acryloyl groups are more preferred, and vinyl groups and (meth)acryloyl groups are particularly preferred.
- component (C) examples include polysiloxanes having two or more ethylenically unsaturated bonds in one molecule; Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glyceryl tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythrito
- polyfunctional (meth)acrylate compounds, polyfunctional allyl compounds, and polyfunctional (meth)acrylamide compounds are preferred, as they are easy to obtain pastes with excellent reactivity and heat resistance, and trifunctional or higher polyfunctional (meth)acrylate compounds and trifunctional or higher polyfunctional allyl compounds are more preferred, with triallyl isocyanurate and trimethylolpropane tri(meth)acrylate being particularly preferred.
- Examples of the polysiloxane having two or more ethylenically unsaturated bonds per molecule include dimethylpolysiloxanes capped at both molecular terminals with dimethylvinylsiloxy groups, dimethylpolysiloxanes capped at both molecular terminals with methylphenylvinylsiloxy groups, dimethylsiloxane-methylphenylsiloxane copolymers capped at both molecular terminals with dimethylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymers capped at both molecular terminals with dimethylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymers capped at both molecular terminals with silanol groups, dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymers capped at both molecular terminals with silanol groups
- polysiloxane having two or more ethylenically unsaturated bonds in one molecule is the compound represented by the following formula (3).
- R 3 's are each independently an unsubstituted or substituted monovalent hydrocarbon group
- R 4 's are each independently an alkyl group, an alkoxyalkyl group, an alkenyl group, or an acyl group
- the sum of c and d is an integer of 2 to 1000
- e is an integer of 1 to 3.
- at least two of R 3's and R 4 's in formula (3) contain the above-mentioned ethylenically unsaturated bond, and the multiple R 3 's present in formula (3) may be the same or different, and the multiple R 4 's present in formula (3) may be the same or different.
- Each R3 is independently an unsubstituted or substituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, examples of which include the same groups (other than halogenated alkyl groups and alkoxy groups) as exemplified above as the organic group bonded to a silicon atom, and alkenyl groups. Of these, monovalent hydrocarbon groups having 1 to 6 carbon atoms are preferred, and alkenyl groups, aryl groups, and alkyl groups having 1 to 3 carbon atoms are more preferred.
- Examples of the alkyl group for R4 include the same straight-chain alkyl groups, branched-chain alkyl groups, and cyclic alkyl groups as those exemplified as the organic groups bonded to silicon atoms.
- Examples of the alkoxyalkyl group in R 4 include groups having 2 to 10 carbon atoms, such as a methoxyethyl group and a methoxypropyl group.
- Examples of the alkenyl group in R3 and R4 include the same alkenyl groups as those exemplified above as the ethylenically unsaturated bond.
- Examples of the acyl group in R 4 include groups having 2 to 10 carbon atoms, such as an acetyl group and an octanoyl group. The sum of c and d is preferably an integer of 10 to 50, and e is preferably 1.
- the functional group (ethylenically unsaturated bond) equivalent of component (C) is preferably 4 to 25,000 g/mol, more preferably 50 to 25,000 g/mol, and even more preferably 75 to 130 g/mol, from the viewpoints of easily obtaining a paste that has a viscosity sufficient to suppress pump-out after anaerobic room-temperature thickening, does not solidify after anaerobic room-temperature thickening, and remains pasty or rubbery even after anaerobic room-temperature thickening.
- Component (C) has a viscosity sufficient to suppress pump-out after anaerobic room-temperature thickening, but does not solidify even after anaerobic room-temperature thickening, and a paste that remains pasty or rubbery even after anaerobic room-temperature thickening can be easily obtained.
- the functional group ratio represented by the following formula (4) is preferably 3 or less, more preferably 0.01 to 3, even more preferably 0.01 to 2, even more preferably 0.015 to 1, and particularly preferably 0.02 to 0.8.
- Functional group ratio (amount of component (A)/functional group equivalent of component (A))/(amount of component (C)/functional group equivalent of component (C)) (4)
- the amount of component (A) is 100 parts by mass
- the amount of component (C) is the amount of component (C) relative to 100 parts by mass of component (A).
- the "amount of component (A)/functional group equivalent of component (A)” in the above formula (4) is "(x1/a+x2/b)". The same applies when two or more types of components (A) and/or (C) are used.
- the blending amount of the component (A) is, for example, 100 mass% of a commercially available product with a purity (amount of active ingredient) of z mass% as the component (A) is used, and the blending amount of the component (C) is 100 ⁇ z/100.
- the content of component (C) is preferably an amount that satisfies the above formula (4), but the content of component (C) in this paste is preferably as small as possible.
- the content of component (C) relative to 100% by mass of this paste is preferably 0.2 to 50% by mass, more preferably 0.3 to 15% by mass, and even more preferably 0.5 to 5.5% by mass.
- the present paste When the present paste is used as a heat dissipation paste, the present paste preferably contains component (D).
- component (D) When component (D) is used in the present paste, the component (D) may be one type or two or more types. When two or more types of component (D) are used, two or more types of component (D) having different materials may be used, or two or more types of component (D) having different shapes, average particle sizes, etc. may be used.
- component (D) it is preferable to use a filler having a thermal conductivity of 1 W/m ⁇ K or more.
- component (D) include metal powder, metal oxide powder, metal nitride powder, metal hydroxide powder, metal oxynitride powder, metal carbide powder, and carbon materials, and specific examples include aluminum oxide ( Al2O3 ), silicon oxide ( SiO2 ), magnesium oxide (MgO), beryllium oxide (BeO), zinc oxide (ZnO), silicon nitride ( Si3N4 ), boron nitride (e.g., hexagonal BN and cubic BN), aluminum nitride (AlN), silicon carbide (SiC), graphite, diamond, and carbon nanotubes.
- Al2O3 aluminum oxide
- SiO2 silicon oxide
- MgO magnesium oxide
- BeO beryllium oxide
- ZnO zinc oxide
- Si3N4 silicon nitride
- boron nitride e.g., hexagon
- the shape of component (D) is not particularly limited and may be, for example, granular, scaly, or needle-like, with granular being preferred as this allows for higher density packing.
- the average particle size of the granular component (D) is, for example, 0.1 to 100 ⁇ m, and preferably 0.5 to 50 ⁇ m.
- the average particle size is the d50 value in the particle size distribution obtained by a laser diffraction/scattering method (Microtrack method).
- the content of component (D) is preferably 30 to 80% by volume, and more preferably 30 to 70% by volume, relative to 100% by volume of the paste, in order to easily obtain a paste with low initial viscosity and excellent heat dissipation properties.
- the amount of component (D) blended was increased, the initial viscosity increased and workability decreased (it became difficult to form the paste in a specified location by painting, pouring, etc.), and therefore it was not possible to blend a large amount of component (D) in conventional pastes.
- the present paste has a low initial viscosity, even if the amount of component (D) blended is increased, the workability of the present paste is not likely to decrease. Therefore, according to one embodiment of the present invention, in order to obtain a paste having particularly excellent thermal properties, even if component (D) is blended in an amount of preferably 40 to 80 volume %, more preferably 50 to 70 volume %, relative to 100 volume % of the paste, a paste having low initial viscosity and excellent workability can be obtained.
- the stabilizer is not particularly limited, but it is preferable to use a stabilizer that enhances the storage stability of the paste.
- the stabilizer may be used in a single type or in a combination of two or more types.
- the stabilizer may, for example, be a metal ion-sealing agent or a polymerization inhibitor.
- chelating agents such as disodium ethylenediaminetetraacetate dihydrate (EDTA2Na) and tetrasodium ethylenediaminetetraacetate tetrahydrate (EDTA4Na); dibutylhydroxytoluene (BHT), p-hydroxytoluene, hydroquinone (HQ), di-tert-butylhydroquinone (DTBHQ), mono-tert-butylhydroquinone (MTBHQ), 1,4-naphthoquinone, tert-butylhydroxyanisole, p-hydroxyanisole, benzoic acid, and 2,5-dihydroxybenzoic acid.
- BHT dibutylhydroxytoluene
- HQ hydroquinone
- DTBHQ di-tert-butylhydroquinone
- MTBHQ mono-tert-
- Polymerization inhibitors such as ethyl acetate, 2,5-dihydroxyterephthalic acid, toluic acid, catechol, t-butylcatechol, 4-allylcatechol, 4-acetylcatechol, 2-methoxyphenol, p-methoxyphenol, 2-ethoxyphenol, 2-methoxy-4-(2-propenyl)phenol, 3,4-dihydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, tert-butylhydroxyaniline, p-hydroxyaniline, and propyl gallate;
- the content of the stabilizer is preferably 0.01 to 3.0 parts by mass, and more preferably 0.1 to 2.0 parts by mass, per 100 parts by mass of component (A), in order to easily obtain a paste with excellent storage stability.
- the catalyst is not particularly limited, but it is preferable to use a catalyst that promotes anaerobic reactions.
- the catalyst used may be one type or two or more types.
- Examples of the catalyst include metal ions and catalysts that promote the generation of radicals by the component (B), and specific examples include acids and reducing agents. Specific examples of the catalyst include saccharin, maleic acid, amine compounds, mercaptan compounds, and hydrazine derivatives.
- amine compound examples include heterocyclic secondary amines such as 1,2,3,4-tetrahydroquinoline and 1,2,3,4-tetrahydroquinaldine; heterocyclic tertiary amines such as quinoline, methylquinoline, quinaldine and quinoxalinephenazine; aromatic tertiary amines such as N,N-dimethyl-anisidine, N,N-dimethylaniline and N,N-dimethyl-p-toluidine (DMPT); aromatic secondary amines such as N,N'-1,4-phenylenebis(5-methyl-2-hexaneamine); and azole compounds such as 1,2,4-triazole, oxazole, oxadiazole, thiadiazole, benzotriazole, hydroxybenzotriazole, benzothiazole, benzoxazole, 1,2,3-benzothiadiazole and 3-mercaptobenzotriazole.
- heterocyclic secondary amines such as 1,2,
- Examples of the mercaptan compound include linear mercaptans such as n-dodecyl mercaptan, ethyl mercaptan, butyl mercaptan, and 2-mercaptoethanol.
- Examples of hydrazine derivatives include methyl carbazate, 1-acetyl-2-phenylhydrazine (APH), nitrophenylhydrazine (NPH), and p-trisulfonylhydrazide.
- the content of the catalyst is preferably 0.01 to 1.0 parts by mass, and more preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of component (A), from the viewpoint of easily obtaining a paste that is prone to thickening at room temperature in an anaerobic atmosphere.
- the paste can be prepared, for example, by mixing the components (A) and (B) and the other components used as necessary, and kneading and dispersing the mixture using a mixer, a roll or the like.
- the initial shear viscosity of this paste at 23°C (this viscosity refers to the initial viscosity) measured with a cone-plate viscometer (rotation speed: 0.5 rpm) is preferably low, specifically, preferably 500 Pa ⁇ s or less, more preferably 100 Pa ⁇ s or less, particularly preferably 50 Pa ⁇ s or less, and preferably 1 Pa ⁇ s or more.
- this viscosity of the paste is within the above range, a paste with excellent workability (easily formed in a predetermined location by painting, pouring, etc.) can be easily obtained.
- a paste with a low initial viscosity is a heat dissipation paste
- a thin paste layer can be easily formed in a predetermined location, such as between a heat generating body and a heat dissipation member, and since it is easily compatible with the mating surfaces of the heat generating body, the heat dissipation member, etc., the thermal resistance due to the paste layer can be reduced, and electronic components with excellent heat dissipation characteristics can be easily obtained.
- a paste with a low initial viscosity is prone to pumping out even when thickened.
- even a paste with a low initial viscosity can be prevented from pumping out after anaerobic room temperature thickening.
- the shear viscosity of the compressed body (viscosity after anaerobic room temperature thickening) is preferably 1.5 times or more, more preferably 3 times or more, and even more preferably 10 times or more, the shear viscosity of the paste before anaerobic room temperature thickening (initial viscosity).
- the shear viscosity of the compressed body (viscosity after anaerobic room temperature thickening) is substantially infinitely many times the initial viscosity, so it can be said to satisfy this range.
- the ratio of the viscosity after anaerobic room temperature thickening to the initial viscosity is within the above range, a paste having a good balance between a low initial viscosity and an excellent pump-out suppression property can be easily obtained.
- the viscosity after the anaerobic room temperature thickening is preferably such that the ratio of the viscosity after anaerobic room temperature thickening to the initial viscosity is in the above-mentioned range; specifically, from the viewpoint of being able to suppress pump-out, the viscosity is preferably 20 Pa ⁇ s or more, more preferably 40 Pa ⁇ s or more, and even more preferably 50 Pa ⁇ s or more.
- an example of a specific value of the viscosity after anaerobic room temperature thickening is preferably 500 Pa ⁇ s or more, more preferably 1000 Pa ⁇ s or more, and particularly preferably 1500 Pa ⁇ s or more.
- viscosity after anaerobic room temperature thickening is within the above range, pump-out can be easily suppressed due to flow resistance after anaerobic room temperature thickening.
- the viscosity after anaerobic room temperature thickening is specifically measured by the method described in the examples below.
- the present paste can be used without limitation in applications in which conventional pastes have been used, but in terms of better exerting the effects of the present invention, it can be suitably used in applications in which it may be exposed to high temperatures (e.g., 200°C or higher), applications in which it is difficult to heat or irradiate a paste placed in a specified location, and in particular applications in which it is required that the viscosity is low when the paste is formed in a specified location by painting, pouring, or the like, and that it remains in a paste or rubber-like state in the specified location after anaerobic room temperature thickening.
- high temperatures e.g. 200°C or higher
- applications in which it is difficult to heat or irradiate a paste placed in a specified location e.g. 200°C or higher
- it is required that the viscosity is low when the paste is formed in a specified location by painting, pouring, or the like, and that it remains in a paste or rubber-like state in the specified location after ana
- the applications include sliding members, brake members, vibration suppressing/absorbing members, etc.
- the paste containing the component (D) can be used as a heat dissipating paste between a heat generating body and a heat dissipating member in an electronic component, etc.
- An example of an application in which the suppression of pump-out is extremely important is the heat dissipating paste.
- at least a portion of the components that come into contact with this paste e.g., sliding components, braking components, vibration suppressing/absorbing components, heating elements, heat dissipating components
- the paste containing the component (D) has a low initial viscosity, and after anaerobic thickening, pump-out, base oil loss, solidification, dripping, etc. are suppressed, and heat dissipation (thermal conductivity) can be maintained for a long period of time, so it can be suitably used in devices, equipment, parts, etc. that have a heat generating body.
- heat dissipation thermal conductivity
- the paste has a low initial viscosity and is compatible with the heat generating body and heat dissipation member, so a thin paste layer can be formed between the heat generating body and the heat dissipation member, and the thermal resistance due to the paste layer can be reduced, so it is suitably used as a heat dissipation paste provided between the heat generating body and the heat dissipation member, and further, since it does not solidify, is not easily cracked, and can absorb (suppress) vibrations, it is suitably used as a heat dissipation paste for semiconductor devices such as power modules, and for vehicles such as automobiles, and is particularly suitably used as a heat dissipation paste for power modules.
- Methods for forming the paste at a predetermined location include, for example, applying the paste to the predetermined location using a conventionally known painting method, or pouring the paste into the predetermined location.
- a conventionally known painting method When forming the paste between two components, it is preferable to apply pressure after applying or pouring the paste between the components. In this case, heating may be performed if necessary.
- the thickness of the paste (layer) formed is thin. Therefore, in this case, it is preferable to form the paste between the heating element and the heat dissipation element, and then apply pressure to spread the paste.
- the compression conditions, etc. are as follows.
- the surface Martens hardness was measured at a maximum test force of 0.3 mN using an ultra-microhardness tester (DUH-211 [manufactured by Shimadzu Corporation]) using a triangular pyramidal indenter (inter-edge angle 115°) as the measuring indenter.
- the thickness of the compressed body measured using the anaerobic pastes prepared in Examples 2, 4 to 15, and 17 and Comparative Examples 1 to 3 was 200 ⁇ m or less, it was evaluated as ⁇ (paste-like), and when the thickness of the compressed body measured exceeded 200 ⁇ m, it was evaluated as ⁇ (not paste-like).
- the anaerobic paste was compressed by spreading 0.2 g of anaerobic paste onto a metal disk to a size of 5 mm square, then clamping it between another metal disk and tightening the screws with a torque wrench to apply a specified load to the sample.
- the thickness was measured by first stacking two metal discs and applying a load of 1 MPa to both ends of the two metal discs (length without the sample), then measuring the length of both ends of the two metal discs with the sample sandwiched between them (length with the sample), and then subtracting the length without the sample from the length with the sample. In consideration of the change in thickness due to compression, the thickness was measured 3 minutes after compression.
- the pressure was applied using a Pressure sample holder (Flash Analyzer LFA467 accessory, manufactured by Netsch Japan KK) and a torque wrench, and the thickness was measured using a Litematic VL-50 (manufactured by Mitutoyo Corporation).
- a copper plate thin pitch copper C1100P [manufactured by Hakudo Co., Ltd.] was used in the property test after anaerobic room temperature thickening, and a plate made of SUS304 with a diameter of 14 mm, a thickness of 3 mm, and a surface roughness Ra of 0.2 was used in the storage stability test.
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Abstract
Description
なお、ここで初期粘度とは、嫌気性ペースト調製時の粘度であり、嫌気性ペーストを増粘する前の粘度であり、通常、塗装時の粘度である。
金属製部材に接する条件下、かつ、嫌気条件下で、常温で増粘し、増粘後はペースト状またはゴム状である、嫌気性ペースト。
官能基比=(前記ポリシロキサン(A)の配合量/前記ポリシロキサン(A)の官能基当量)×(前記レドックス開始剤(B)の配合量/前記レドックス開始剤(B)の活性酸素当量) ・・・(1)
また、本発明の一実施形態によれば、放熱性能に優れる嫌気性放熱ペーストを提供することもできる。
本発明の一実施形態に係る嫌気性ペースト(以下「本ペースト」ともいう。)は、メルカプト基を有するポリシロキサン(A)[以下「成分(A)」ともいう。他の成分についても同様。]と、レドックス開始剤(B)とを含み、
金属製部材に接する条件下、かつ、嫌気条件下で常温で増粘(以下「嫌気常温増粘」ともいう。)し、嫌気常温増粘後はペースト状またはゴム状である。
従って、本ペーストは、使用時に、従来必要であった工程(例:加熱、光照射)を行うことなく、短時間、簡略した工程で増粘し、ポンプアウトを抑制し、長期の性能(例:放熱性)の維持が可能となる。
前記厚みの測定方法は、具体的には、下記実施例に記載の通りである。
なお、本発明において「固化」とは、前記ペースト状でもゴム状でもない状態をいい、測定圧子として三角錐圧子(稜間角115°)を用いた超微小硬度計により、最大試験力0.3mNにて測定される表面マルテンス硬度が10N/mm2を超えるものとして定義することができる。
このような本ペーストは、金属製部材に接する条件下、かつ、嫌気条件下で、常温で増粘を行った後、具体的には、本ペースト4gを、23℃において、2枚の銅板で挟み、該ペーストの厚みが0.4mmになるように、2.5時間圧縮した後の圧縮体0.2gを5mm角にした後、23℃下、1.0MPaの圧力で圧縮した際の厚みが200μm以下になる、または、該圧縮体表面を、測定圧子として三角錐圧子(稜間角115°)を用いた超微小硬度計により、最大試験力0.3mNにて測定された表面マルテンス硬度が10N/mm2以下になる。
前記厚みの測定方法は、具体的には、下記実施例に記載の通りである。
成分(A)は、メルカプト基(-SH)を有するポリシロキサンであれば特に制限されない。なお、成分(A)は、メルカプト基以外の官能基(例:エチレン性不飽和結合を有する基[例:ビニル基、(メタ)アクリロイル基])を有していてもよい。
このような成分(A)を用いることで、耐熱性に優れ、嫌気常温増粘後においても固化せず、嫌気常温増粘後はペースト状またはゴム状であるペーストを容易に得ることができる。
本ペーストに用いる成分(A)は、1種でもよく、2種以上でもよい。
直鎖状アルキル基としては、例えば、メチル基、エチル基、プロピル基、ヘキシル基、オクチル基、デシル基等の炭素数1~20、好ましくは炭素数1~6の基が挙げられる。
分岐鎖状アルキル基としては、例えば、イソプロピル基、イソブチル基、t-ブチル基、2-エチルヘキシル基等の炭素数3~20、好ましくは炭素数3~6の基が挙げられる。
環状アルキル基としては、例えば、シクロペンチル基、シクロヘキシル基等の炭素数3~20の基が挙げられる。
アリール基としては、例えば、フェニル基、トリル基等の炭素数6~20の基が挙げられる。
アラルキル基としては、例えば、ベンジル基、2-フェニルエチル基、2-メチル-2-フェニルエチル基等の炭素数7~20の基が挙げられる。
ハロゲン化アルキル基としては、例えば、3,3,3-トリフルオロプロピル基、2-(ノナフルオロブチル)エチル基、2-(ヘプタデカフルオロオクチル)エチル基等の炭素数1~20、好ましくは炭素数1~6の基が挙げられる。
アルコキシ基としては、例えば、メトキシ基、エトキシ基等の炭素数1~20、好ましくは炭素数1~6の基が挙げられる。
つまり、前記オルガノポリシロキサンにおけるメルカプト基を有する部分以外の構造としては、ジメチルポリシロキサン、メチルフェニルポリシロキサンおよびジフェニルポリシロキサンから選ばれる少なくとも1種のポリシロキサン構造を有することが好ましく、ジメチルポリシロキサン構造がより好ましい。
成分(A)の粘度が前記範囲にあると、初期粘度が低く、塗装性に優れるペーストを容易に得ることができる。また、このような初期粘度の低いペーストが放熱ペーストである場合、例えば、発熱体と放熱部材との間などの所定の場所に厚みの薄いペースト層を容易に形成することができ、発熱体や放熱部材などの相手面と馴染みやすいペースト層を容易に形成することができる。このため、該ペースト層による熱抵抗を低減することができ、放熱特性に優れる電子部品等を容易に得ることができる。
なお、成分(A)の官能基とは、レドックス開始剤から生じたラジカルにより反応する基のことをいい、具体的には、メルカプト基および前記メルカプト基以外の官能基が挙げられる。
このようなポリシロキサン(A1)と(A2)とを用いる場合、これらの合計100質量%に対する、ポリシロキサン(A2)の割合は、好ましくは50.0~99.5質量%、より好ましくは75.0~99.0質量%である。
成分(B)はレドックス開始剤であれば特に制限されず、従来公知のレドックス開始剤を用いることができる。
メルカプト基を有する成分(A)は、還元剤として作用するため、成分(B)としては、該成分(A)によりレドックス反応を起こし、ラジカルを発生することができる成分(酸化剤)であることが好ましい。
本ペーストに用いる成分(B)は、1種でもよく、2種以上でもよい。
有機過酸化物としては、例えば、t-ブチルハイドロパーオキサイド、t-アミルハイドロパーオキサイド、クメンハイドロパーオキサイド、1,1,3,3-テトラメチルブチルハイドロパーオキサイド、p-メンタンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイドなどのハイドロパーオキサイド;2,5-ジメチルヘキサン-2,5-ジハイドロパーオキサイドなどのジハイドロパーオキサイド;アセチルアセトンパーオキサイド、メチルエチルケトンパーオキサイドなどのケトンパーオキサイド;t-ブチルペルオキシベンゾエートなどのパーオキシエステル;ジコハク酸パーオキサイド;ジグルタル酸パーオキサイド;が挙げられる。
過硫酸塩としては、例えば、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウムが挙げられる。
過マンガン酸塩としては、例えば、過マンガン酸アンモニウム、過マンガン酸のアルカリ金属塩(例:過マンガン酸カリウム)、過マンガン酸のアルカリ土類金属塩が挙げられる。
臭素酸塩としては、例えば、臭素酸アンモニウム、臭素酸のアルカリ金属塩、臭素酸のアルカリ土類金属塩が挙げられる。
本ペーストを、1成分型のペーストとする場合、貯蔵時に増粘しやすい傾向にあるが、官能基比が前記範囲にあることで、貯蔵安定性に優れるペーストを容易に得ることができる傾向にある。官能基比が前記範囲を超えると、貯蔵安定性(貯蔵保管性)に優れるペーストを容易に得ることができない場合がある。
また、嫌気常温増粘し、ポンプアウトを抑制できるペーストを容易に得ることができる等の点から、本ペーストにおける下記式(1)で表される官能基比は、好ましくは1.0×10-6以上、より好ましくは1.0×10-5以上である。
官能基比=(成分(A)の配合量/成分(A)の官能基当量)×(成分(B)の配合量/成分(B)の活性酸素当量) ・・・(1)
なお、成分(A)として、例えば、官能基当量ag/molの成分(A)を配合量x1質量%で用い、官能基当量bg/molの成分(A)を配合量x2質量%で用いる場合(但し、x1+x2=100)、前記式(1)における「成分(A)の配合量/成分(A)の官能基当量」は、「(x1/a+x2/b)」となる。成分(A)や(B)として2種類以上を用いる場合も同様である。
なお、前記「成分(A)の配合量」は、例えば、成分(A)として、純度(有効成分量)z質量%の市販品を100質量%用いる場合、100×z/100となる。前記「成分(B)の配合量」も同様である。
本ペーストは、必要に応じて、本発明の効果を損なわない限り、前記成分(A)および(B)以外のその他の成分を含んでいてもよい。
該その他の成分としては、例えば、前記成分(A)以外の、1分子中に2個以上のエチレン性不飽和結合を有する化合物(C);熱伝導性フィラー(D);安定剤;触媒;フッ素系やシリコーン系オイル等の可塑剤;シランカップリング剤;界面活性剤;溶剤;分散剤;難燃剤;顔料が挙げられる。
該その他の成分はそれぞれ、1種を用いてもよく、2種以上を用いてもよい。
従来のペーストは、白金系触媒を用いていたが、白金系触媒を用いると、ポットライフが短く、ペーストの長期保存ができなかった。
なお、白金系触媒を含まないとは、成分(A)100質量部に対する白金系触媒の含有量が、例えば0.0001質量部以下であることをいい、下限は好ましくは0質量部である。
成分(C)は、前記成分(A)以外の、1分子中に2個以上のエチレン性不飽和結合を有する化合物であれば特に制限されず、従来公知の化合物(共架橋剤)を用いることができる。
成分(C)を用いることで、嫌気常温増粘後にはポンプアウトの抑制性により優れるペーストを容易に得ることができる。
本ペーストに用いる成分(C)は、1種でもよく、2種以上でもよい。
前記成分(C)に含まれる2個以上のエチレン性不飽和結合は、それぞれ同一でも異なっていてもよい。つまり、成分(C)は、2種以上のエチレン性不飽和結合を有していてもよい。
エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ブチレングリコールジ(メタ)アクリレート、ヘキサンジオールジ(メタ)アクリレート、シクロヘキサンジメタノールジ(メタ)アクリレート、ビスフェノールAアルキレンオキシドジ(メタ)アクリレート、ビスフェノールFアルキレンオキシドジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、グリセリントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリペンタエリスリトールヘプタ(メタ)アクリレート、トリペンタエリスリトールオクタ(メタ)アクリレート、エチレンオキシド付加トリメチロールプロパントリ(メタ)アクリレート、エチレンオキシド付加ジトリメチロールプロパンテトラ(メタ)アクリレート、エチレンオキシド付加ペンタエリスリトールテトラ(メタ)アクリレート、エチレンオキシド付加ジペンタエリスリトールヘキサ(メタ)アクリレート、プロピレンオキシド付加トリメチロールプロパントリ(メタ)アクリレート、プロピレンオキシド付加ジトリメチロールプロパンテトラ(メタ)アクリレート、プロピレンオキシド付加ペンタエリスリトールテトラ(メタ)アクリレート、プロピレンオキシド付加ジペンタエリスリトールヘキサ(メタ)アクリレート、ε-カプロラクトン付加トリメチロールプロパントリ(メタ)アクリレート、ε-カプロラクトン付加ジトリメチロールプロパンテトラ(メタ)アクリレート、ε-カプロラクトン付加ペンタエリスリトールテトラ(メタ)アクリレート、ε-カプロラクトン付加ジペンタエリスリトールヘキサ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレートコハク酸変性物、ペンタエリスリトールトリ(メタ)アクリレートコハク酸変性物、ジペンタエリスリトールペンタ(メタ)アクリレートフタル酸変性物、ペンタエリスリトールトリ(メタ)アクリレートフタル酸変性物、トリ((メタ)アクリロイルオキシエチル)イソシアヌレート、アルキレンオキシド付加トリ((メタ)アクリロイルオキシエチル)イソシアヌレート等の多官能(メタ)アクリレート化合物;
エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、ポリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ブチレングリコールジビニルエーテル、ヘキサンジオールジビニルエーテル、ビスフェノールAアルキレンオキシドジビニルエーテル、ビスフェノールFアルキレンオキシドジビニルエーテル、トリメチロールプロパントリビニルエーテル、ジトリメチロールプロパンテトラビニルエーテル、グリセリントリビニルエーテル、ペンタエリスリトールテトラビニルエーテル、ジペンタエリスリトールペンタビニルエーテル、ジペンタエリスリトールヘキサビニルエーテル、エチレンオキシド付加トリメチロールプロパントリビニルエーテル、エチレンオキシド付加ジトリメチロールプロパンテトラビニルエーテル、エチレンオキシド付加ペンタエリスリトールテトラビニルエーテル、エチレンオキシド付加ジペンタエリスリトールヘキサビニルエーテル等の多官能ビニルエーテル類;
(メタ)アクリル酸2-ビニロキシエチル、(メタ)アクリル酸3-ビニロキシプロピル、(メタ)アクリル酸1-メチル-2-ビニロキシエチル、(メタ)アクリル酸2-ビニロキシプロピル、(メタ)アクリル酸4-ビニロキシブチル、(メタ)アクリル酸4-ビニロキシシクロヘキシル、(メタ)アクリル酸5-ビニロキシペンチル、(メタ)アクリル酸6-ビニロキシヘキシル、(メタ)アクリル酸4-ビニロキシメチルシクロヘキシルメチル、(メタ)アクリル酸p-ビニロキシメチルフェニルメチル、(メタ)アクリル酸2-(ビニロキシエトキシ)エチル、(メタ)アクリル酸2-(ビニロキシエトキシエトキシエトキシ)エチル等のビニルエーテル基含有(メタ)アクリル酸エステル類;
エチレングリコールジアリルエーテル、ジエチレングリコールジアリルエーテル、ポリエチレングリコールジアリルエーテル、プロピレングリコールジアリルエーテル、ブチレングリコールジアリルエーテル、ヘキサンジオールジアリルエーテル、ビスフェノールAアルキレンオキシドジアリルエーテル、ビスフェノールFアルキレンオキシドジアリルエーテル、トリメチロールプロパントリアリルエーテル、ジトリメチロールプロパンテトラアリルエーテル、ジアリルフタレート、グリセリントリアリルエーテル、ペンタエリスリトールテトラアリルエーテル、ジペンタエリスリトールペンタアリルエーテル、ジペンタエリスリトールヘキサアリルエーテル、エチレンオキシド付加トリメチロールプロパントリアリルエーテル、エチレンオキシド付加ジトリメチロールプロパンテトラアリルエーテル、エチレンオキシド付加ペンタエリスリトールテトラアリルエーテル、エチレンオキシド付加ジペンタエリスリトールヘキサアリルエーテル、トリアリルイソシアヌレート、トリアリルシアヌレート、トリアリルホルマール、トリアリルトリメリテート、テトラアリルテレフタルアミド等の多官能アリル化合物;
(メタ)アクリル酸アリル等のアリル基含有(メタ)アクリル酸エステル類;
N,N-エチレンビス(メタ)アクリルアミド等の多官能(メタ)アクリルアミド化合物;
ジプロパルギルテレフタレート等の多官能プロパルギル化合物;
N,N'-m-フェニレンビスマレイミド等の多官能マレイミド化合物;
トリレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート等の多官能イソシアネートと、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル等の水酸基含有(メタ)アクリル酸エステル類との反応で得られる多官能ウレタン(メタ)アクリレート類;
ジビニルベンゼン等の多官能芳香族ビニル類;
が挙げられる。
R4におけるアルコキシアルキル基としては、例えば、メトキシエチル基、メトキシプロピル基等の炭素数2~10の基が挙げられる。
R3およびR4におけるアルケニル基としては、例えば、前記エチレン性不飽和結合として例示した基と同様のアルケニル基が挙げられる。
R4におけるアシル基としては、例えば、アセチル基、オクタノイル基等の炭素数2~10の基が挙げられる。
cとdとの和は、好ましくは10~50の整数であり、eは、好ましくは1である。
官能基比=(成分(A)の配合量/成分(A)の官能基当量)/(成分(C)の配合量/成分(C)の官能基当量) ・・・(4)
なお、成分(A)として、例えば、官能基当量ag/molの成分(A)を配合量x1質量%で用い、官能基当量bg/molの成分(A)を配合量x2質量%で用いる場合(但し、x1+x2=100)、前記式(4)における「成分(A)の配合量/成分(A)の官能基当量」は、「(x1/a+x2/b)」となる。成分(A)や(C)として2種類以上を用いる場合も同様である。
なお、前記成分(A)の配合量は、例えば、成分(A)として、純度(有効成分量)z質量%の市販品を100質量%用いる場合、100×z/100となる。前記成分(C)の配合量も同様である。
本ペーストを放熱ペーストとして用いる場合、本ペーストは、成分(D)を含有することが好ましい。
本ペーストに成分(D)を用いる場合、用いる成分(D)は、1種でもよく、2種以上でもよい。2種以上の成分(D)を用いる場合、材質の異なる2種以上の成分(D)を用いてもよく、形状や平均粒子径等の異なる2種以上の成分(D)を用いてもよい。
このような成分(D)としては、例えば、金属粉、金属酸化物粉、金属窒化物粉、金属水酸化物粉、金属酸窒化物粉、金属炭化物粉、炭素材料が挙げられ、具体的には、酸化アルミニウム(Al2O3)、酸化ケイ素(SiO2)、酸化マグネシウム(MgO)、酸化ベリリウム(BeO)、酸化亜鉛(ZnO)、窒化ケイ素(Si3N4)、窒化ホウ素(例:六方晶BNや立方晶BN)、窒化アルミニウム(AlN)、炭化ケイ素(SiC)、グラファイト、ダイヤモンド、カーボンナノチューブが挙げられる。
粒状である成分(D)の平均粒子径は、例えば0.1~100μmであり、好ましくは0.5~50μmである。該平均粒子径は、レーザー回折・散乱法(マイクロトラック法)により得られる粒径分布におけるd50の値である。
一方、本ペーストは、初期粘度が低いため、本ペーストによれば、成分(D)の配合量を多くしても、作業性が低下し難い。
従って、本発明の一実施形態によれば、熱特性に特に優れるペーストを得ることを目的として、本ペースト100体積%に対し、成分(D)を、好ましくは40~80体積%、より好ましくは50~70体積%配合しても、初期粘度が低く、作業性に優れるペーストを得ることができる。
前記安定剤としては特に制限されないが、本ペーストの貯蔵安定性を高める安定剤を用いることが好ましい。
本ペーストに安定剤を用いる場合、用いる安定剤は、1種でもよく、2種以上でもよい。
前記触媒としては特に制限されないが、嫌気性反応を促進する触媒を用いることが好ましい。
本ペーストに触媒を用いる場合、用いる触媒は、1種でもよく、2種以上でもよい。
前記触媒の具体例としては、サッカリン、マレイン酸、アミン化合物、メルカプタン化合物、ヒドラジン誘導体が挙げられる。
アミン化合物としては、例えば、1,2,3,4-テトラヒドロキノリン、1,2,3,4-テトラヒドロキナルジンなどの複素環第2級アミン;キノリン、メチルキノリン、キナルジン、キノキサリンフェナジンなどの複素環第3級アミン;N,N-ジメチル-アニシジン、N,N-ジメチルアニリン、N,N-ジメチル-p-トルイジン(DMPT)などの芳香族第3級アミン類;N,N'-1,4-フェニレンビス(5-メチル-2-ヘキサンアミン)などの芳香族第2級アミン類;1,2,4-トリアゾール、オキサゾール、オキサジアゾール、チアジアゾール、ベンゾトリアゾール、ヒドロキシベンゾトリアゾール、ベンゾチアゾール、ベンゾオキサゾール、1,2,3-ベンゾチアジアゾール、3-メルカプトベンゾトリアゾールなどのアゾール系化合物;が挙げられる。
メルカプタン化合物としては、例えば、n-ドデシルメルカプタン、エチルメルカプタン、ブチルメルカプタン、2-メルカプトエタノールなどの直鎖型メルカプタンが挙げられる。
ヒドラジン誘導体としては、例えば、メチルカルバゼート、1-アセチル-2-フェニルヒドラジン(APH)、ニトロフェニルヒドラジン(NPH)、p-トリスルホニルヒドラジドが挙げられる。
本ペーストは、例えば、前記成分(A)~(B)および必要により用いられる前記その他の成分を混合し、ミキサーやロール等を用いて混練分散させることにより調製することができる。
本ペーストのコーンプレート型粘度計(回転数:0.5rpm)で測定した23℃における初期剪断粘度(この粘度は、初期粘度のことである。)は、低いことが好ましく、具体的には、好ましくは500Pa・s以下、より好ましくは100Pa・s以下、特に好ましくは50Pa・s以下であり、好ましくは1Pa・s以上である。
本ペーストの初期粘度が前記範囲にあると、作業性に優れる(塗装や流し込みなどにより所定の場所にペーストを形成しやすい)ペーストを容易に得ることができる。また、このような初期粘度が低いペーストが放熱ペーストである場合、例えば、発熱体と放熱部材との間などの所定の場所に厚みの薄いペースト層を容易に形成することができ、発熱体や放熱部材などの相手面と馴染みやすいため、該ペースト層による熱抵抗を低減することができ、放熱特性に優れる電子部品等を容易に得ることができる。
通常、初期粘度の低いペーストは、増粘したとしてもポンプアウトしやすかったが、本発明の一実施形態によれば、初期粘度の低いペーストであっても、嫌気常温増粘後にはポンプアウトを抑制することができる。
初期粘度に対する嫌気常温増粘後の粘度の比が前記範囲にあると、低い初期粘度と、ポンプアウトの抑制性とにバランスよく優れるペーストを容易に得ることができる。
嫌気常温増粘後の粘度が前記範囲にあると、流動抵抗により、嫌気常温増粘後にはポンプアウトを容易に抑制することができる。
なお、前記嫌気常温増粘後の粘度は、具体的には、下記実施例に記載の方法で測定した粘度である。
本ペーストは、従来のペーストが用いられてきた用途に制限なく用いることができるが、本発明の効果がより発揮される等の点から、高温(例:200℃以上)下に曝される可能性のある用途、所定の場所に配置したペーストに加熱や光照射し難い用途、特に、塗装や流し込みなどにより所定の場所にペーストを形成する際には粘度が低く、嫌気常温増粘後には、該所定の場所にペースト状またはゴム状で留まることが求められている用途に好適に用いることができる。
なお、本ペーストと接する部材(例:摺動部材やブレーキ部材、振動抑制・吸収部材、発熱体、放熱部材)の少なくとも一部(本ペーストと接する箇所の少なくとも一部)は、金属製であることが好ましい。
表1に示す配合比率(数値の単位は質量部である)で、表1の各配合成分を混合することで嫌気性ペーストを調製した。
表1中の各成分の詳細は、表2の通りである。
なお、表1中の「官能基比」は、下記式(5)から算出した値である。例えば、「E-04」は、「10-4」のことを示す。
官能基比=(ポリシロキサンの配合量/該ポリシロキサンの官能基当量)×(開始剤の配合量/該開始剤の活性酸素当量) ・・・(5)
[式(5)におけるポリシロキサンの配合量は100質量部であり、開始剤の配合量は、ポリシロキサンの配合量100質量部に対する開始剤の配合量である。なお、2種類のポリシロキサンを用いる場合、これらの合計の配合量が100質量部である。]
調製した嫌気性ペーストを、物性安定化のため、1日間、空気中、常温で静置した後、23℃における粘度(初期粘度)を、コーンプレート型粘度計(HBDVNextCP[ブルックフィールド社製])を用い、回転数0.5rpmの条件で測定した。結果を表1に示す。
調製した嫌気性ペーストを、物性安定化のため、1日間、空気中、常温で静置した後、該嫌気性ペースト4gを、23℃において、2枚の銅板(タフピッチ銅 C1100P[白銅(株)製])で挟み、該ペーストの厚みが0.4mmになるように、シムを用いて2.5時間圧縮した。次いで、圧縮後の嫌気性ペーストの剪断粘度を、コーンプレート型粘度計(HBDVNextCP[ブルックフィールド社製])を用いて回転数0.5rpmで測定した。なお、コーンプレート型粘度計を用いて回転数0.5rpmで測定した際に、測定上限粘度を超えた場合には、回転数を0.1rpmに変更して測定した。結果を表1に示す。
なお、回転数を0.1rpmに変更した場合であっても、測定上限粘度を超えた場合、表1では、「>8000」と示す。
調製した嫌気性ペーストを、物性安定化のため1日間常温で静置した後、該嫌気性ペースト4gを、23℃において、2枚の銅板(タフピッチ銅 C1100P[白銅(株)製])で挟み、該ペーストの厚みが0.4mmになるように、シムを用いて2.5時間圧縮することで圧縮体を得た。実施例2、4~15、17および比較例1~3で調製した嫌気性ペーストを用いて得られた圧縮体0.2gを5mm角にし、23℃において、1.0MPaの圧力で圧縮した際の厚みを測定した。この圧縮の条件等は、以下の通りである。
また、実施例1、3および16で調製した嫌気性ペーストを用いて得られた圧縮体については、測定圧子として三角錐圧子(稜間角115°)を用いた超微小硬度計(DUH-211[(株)島津製作所製])により、最大試験力0.3mNにてその表面マルテンス硬度を測定した。
実施例2、4~15、17および比較例1~3で調製した嫌気性ペーストを用いて測定した圧縮体の厚みが200μm以下である場合を○(ペースト状である)とし、測定した圧縮体の厚みが200μmを超えた場合を×(ペースト状ではない)とした。
また、実施例1、3および16で調製した嫌気性ペーストを用いて得られた圧縮体については、表面マルテンス硬度が10N/mm2以下である場合を○(ゴム状である)とし、測定した圧縮体の表面マルテンス硬度が10N/mm2を超えた場合を×(固化(=ゴム状ではない))とした。
結果を表1に示す。
調製した嫌気性ペーストを、5日間、空気中、常温で静置した後、該嫌気性ペースト0.2gを5mm角にし、23℃において、1.0MPaの圧力で圧縮した際の厚みを測定した。この圧縮の条件等は、以下の通りである。
測定した嫌気性ペーストの厚みが200μm以下である場合を○(ペースト状である)とし、測定した嫌気性ペーストの厚みが200μmを超えた場合を×(ペースト状ではない)とした。結果を表1に示す。
嫌気性ペーストの圧縮は、金属円盤上に、0.2gの嫌気性ペーストを5mm角に引き延ばした後、もう一枚の金属円盤によって挟み込み、トルクレンチでねじを締めこむことによって所定の荷重をサンプルに負荷することで行った。
なお、圧縮による厚みの変化を考慮し、厚みの測定は、圧縮から3分経過後に実施した。
前記金属円盤としては、嫌気常温増粘後の性状試験では、銅板(タフピッチ銅 C1100P[白銅(株)製])を用い、貯蔵保管性試験では、材質がSUS304であり、直径14mm、厚み3mm、表面粗さRa0.2の板を使用した。
Claims (5)
- メルカプト基を有するポリシロキサン(A)と、レドックス開始剤(B)とを含み、
金属製部材に接する条件下、かつ、嫌気条件下で、常温で増粘し、増粘後はペースト状またはゴム状である、嫌気性ペースト。 - 23℃における初期剪断粘度が500Pa・s以下である、請求項1に記載の嫌気性ペースト。
- 下記式(1)で表される官能基比が1.0×10-3以下である、請求項1に記載の嫌気性ペースト。
官能基比=(前記ポリシロキサン(A)の配合量/前記ポリシロキサン(A)の官能基当量)×(前記レドックス開始剤(B)の配合量/前記レドックス開始剤(B)の活性酸素当量) ・・・(1) - 熱伝導性フィラー(D)を含む、請求項1~3のいずれか1項に記載の嫌気性ペースト。
- 前記熱伝導性フィラー(D)の含有量が、嫌気性ペースト100体積%に対し、30~80体積%である、請求項4に記載の嫌気性ペースト。
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5331902B2 (ja) * | 1976-03-03 | 1978-09-05 | ||
| JPS5335985B2 (ja) * | 1976-03-03 | 1978-09-29 | ||
| JPS5443025B2 (ja) * | 1977-01-03 | 1979-12-18 | ||
| JPS5539262B2 (ja) * | 1977-01-03 | 1980-10-09 | ||
| JPS56501607A (ja) * | 1979-12-03 | 1981-11-05 | ||
| JPS61218660A (ja) * | 1985-03-25 | 1986-09-29 | Toray Silicone Co Ltd | メルカプト官能性オルガノポリシロキサン流体組成物 |
| WO2023182414A1 (ja) * | 2022-03-25 | 2023-09-28 | 株式会社バルカー | ペースト |
-
2024
- 2024-02-21 WO PCT/JP2024/006162 patent/WO2024190331A1/ja not_active Ceased
- 2024-02-21 CN CN202480016861.0A patent/CN120826447A/zh active Pending
- 2024-02-21 JP JP2025506640A patent/JPWO2024190331A1/ja active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5331902B2 (ja) * | 1976-03-03 | 1978-09-05 | ||
| JPS5335985B2 (ja) * | 1976-03-03 | 1978-09-29 | ||
| JPS5443025B2 (ja) * | 1977-01-03 | 1979-12-18 | ||
| JPS5539262B2 (ja) * | 1977-01-03 | 1980-10-09 | ||
| JPS56501607A (ja) * | 1979-12-03 | 1981-11-05 | ||
| JPS61218660A (ja) * | 1985-03-25 | 1986-09-29 | Toray Silicone Co Ltd | メルカプト官能性オルガノポリシロキサン流体組成物 |
| WO2023182414A1 (ja) * | 2022-03-25 | 2023-09-28 | 株式会社バルカー | ペースト |
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| CN120826447A (zh) | 2025-10-21 |
| JPWO2024190331A1 (ja) | 2024-09-19 |
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