WO2017090759A1 - 熱硬化性組成物およびそれを用いた導電性接着剤 - Google Patents
熱硬化性組成物およびそれを用いた導電性接着剤 Download PDFInfo
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- WO2017090759A1 WO2017090759A1 PCT/JP2016/085071 JP2016085071W WO2017090759A1 WO 2017090759 A1 WO2017090759 A1 WO 2017090759A1 JP 2016085071 W JP2016085071 W JP 2016085071W WO 2017090759 A1 WO2017090759 A1 WO 2017090759A1
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- meth
- thermosetting composition
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- acrylate
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Classifications
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
Definitions
- the present invention relates to a thermosetting composition that cures at a high temperature for a short time (within 100 to 150 ° C. within 1 minute) and an isotropic conductive adhesive using the thermosetting composition.
- Patent Document 1 describes an invention relating to a two-pack type acrylic sealing material, and describes that a viscosity is set low in order to suppress bumping during heating.
- thermosetting composition of the prior art has sufficient rapid curability while suppressing bumping during curing at a high temperature for a short time (within 100 to 150 ° C. within 1 minute). There was a problem that it could not be demonstrated.
- an object of the present invention is to provide a thermosetting composition that does not cause sudden boiling during curing at a high temperature in a short time and has rapid curability.
- Another object of the present invention is to provide a conductive adhesive using the thermosetting composition.
- thermosetting composition and a conductive adhesive using the composition, and have reached the present invention.
- the first embodiment of the present invention is a thermosetting composition
- the first embodiment of the present invention is a thermosetting composition
- the second embodiment of the present invention is the thermosetting composition according to the first embodiment, wherein the melting point of the component (B) is lower than 225 ° C.
- a third embodiment of the present invention provides the thermosetting composition according to the first or second embodiment, wherein the component (A) includes the following components (A-1) and (A-2): (A-1) Component: Urethane-modified oligomer having (meth) acryl group; (A-2) Component: A monomer having one or more (meth) acryl groups in the molecule.
- a fourth embodiment of the present invention is the thermosetting composition according to any one of the first to third embodiments, wherein the component (C) is an organic peroxide having a structure of Formula 2. is there.
- the fifth embodiment of the present invention is the thermosetting composition according to any one of the first to fourth embodiments, further comprising conductive particles surface-treated with stearic acid as component (D). It is.
- a sixth embodiment of the present invention is the thermosetting composition according to the fifth embodiment, wherein the conductive particles are silver powder or silver plating powder surface-treated with stearic acid.
- a seventh embodiment of the present invention is a conductive adhesive containing the thermosetting composition described in the fifth or sixth embodiment.
- the eighth embodiment of the present invention is an electrical / electronic component including the cured product of the conductive adhesive described in the seventh embodiment.
- thermosetting composition comprising components (A) to (C): (A) Component: Compound having (meth) acrylic group (B) Component: Phenol compound having a molecular weight of 230 or more and dissolved in (A) component: Organic peroxide having the structure of Formula 1 .
- R 1 represents an independent hydrocarbon group.
- X to Y are used to mean that the numerical values (X and Y) described before and after that are included as the lower limit value and the upper limit value. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%. Also, the term “(meth) acrylate” includes both methacrylate and acrylate.
- the component (A) that can be used in the present invention is a compound having a (meth) acryl group.
- a urethane-modified oligomer having a (meth) acryl group and a monomer having one or more (meth) acryl groups in the molecule preferably includes the following components (A-1) and (A-2): (A-1) Component: Urethane-modified oligomer having (meth) acryl group; (A-2) Component: A monomer having one or more (meth) acryl groups in the molecule.
- a monomer having one or more (meth) acrylic groups in the molecule of the component (A-2) a monomer having two or more (meth) acrylic groups in the molecule is added within a range not impairing the characteristics of the present invention.
- Monomers having one or more (meth) acrylic groups include (meth) acrylic acid, lauryl (meth) acrylate, stearyl (meth) acrylate, ethyl carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone modified Tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (Meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, nonylphenoxyethyl (meth) acrylate, nonylphenoxytetrae Lenglycol (meth) acrylate, methoxy
- the mass ratio of the urethane-modified oligomer having a (meth) acrylic group as the component (A-1) and the monomer having one or more (meth) acrylic groups in the molecule of the component (A-2) is 20:80 to 80 :
- the range of 20 is preferable. Thereby, it is easy to express low temperature curability.
- the component (B) that can be used in the present invention is a phenol compound having a molecular weight of 230 or more and dissolved in the component (A).
- (B) 1 or more phenol groups should just exist in a component.
- a thermosetting composition that does not contain the component (B)
- if it is heated in the coated state it will foam inside and the bubbles will pop and harden into a crater shape. In the present invention, this phenomenon is expressed as bumping.
- the appearance of the cured product is good by suppressing bumping at the time of heat-curing, and no bubbles remain at the interface during surface bonding, and shear bonding strength Can be improved.
- the resistance value at the interface between the adherend and the cured product of the present invention can be stabilized.
- dissolution means that the component (B) is dissolved in an appropriate amount of the component (A), and the original form of the component (B) is not recognized by visual or tactile sense at an appropriate temperature, and is in a uniform state.
- the appropriate amount corresponds to the amount of component (B) added to component (A) described below.
- the appropriate temperature refers to a temperature at which the thermosetting composition of the present invention is stored, and here is room temperature (25 ° C.).
- the melting point of the component (B) is more preferably 120 to 220 ° C., and particularly preferably 180 to 215 ° C.
- 1,3,5-tris [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -1,3,5-triazine-2,4, 6 (1H, 3H, 5H) -trione (melting point: 221 ° C., molecular weight: 784), 4,4′-butylidenebis (6-tert-butyl-m-cresol) (melting point: 212 ° C., molecular weight: 383), 3 Stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (melting point: 52 ° C., molecular weight: 531), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate] (melting point: 115 ° C., molecular weight: 1178), and the like, but is not limited thereto. Specific examples of
- the component (B) is preferably added in an amount of 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, with respect to 100 parts by mass of the component (A). By adding 0.01 part by mass or more of the component (B), the resin does not bump during heat curing. On the other hand, when the component (B) is 5 parts by mass or less, the curability is not lowered.
- the component (C) that can be used in the present invention is an organic peroxide having the structure of Formula 1.
- each R 1 represents an independent hydrocarbon group and may be linear or cyclic. It is considered that the organic peroxide having the structure of the formula (1) is more effective for low temperature curability and quick curability.
- Particularly preferred R 1 is a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, and more preferred R 1 is a substituted or unsubstituted cyclic hydrocarbon group having 3 to 8 carbon atoms.
- Examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.
- the most preferred hydrocarbon group (R 1 ) is a substituted or unsubstituted cyclohexyl group.
- examples of the substituent in the case where the hydrocarbon group as R 1 is substituted include a hydrocarbon group having 1 to 7 carbon atoms, preferably an alkyl group having 1 to 7 carbon atoms, Examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, iso-butyl group and the like.
- Particularly preferred component (C) is an organic peroxide having the structure of Formula 2 in view of low volatility.
- each R 2 represents an independent hydrocarbon group, and may be linear or cyclic.
- Particularly preferred R 2 is a hydrocarbon group having 1 to 7 carbon atoms, and more preferred R 2 is an alkyl group having 1 to 7 carbon atoms. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an iso group.
- -Propyl group, n-butyl group, sec-butyl group, tert-butyl group, iso-butyl group and the like are mentioned, among which the most preferred hydrocarbon group (R 2 ) is t-butyl group.
- (C) component is a solid at 25 degreeC from a viewpoint of maintaining the storage stability at the time of adding electroconductive particle to a thermosetting composition.
- Component (C) includes di-n-propyl-peroxydicarbonate, di-iso-propyl-peroxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, and di (2-ethylhexyl) percarbonate. Examples thereof include, but are not limited to, oxydicarbonate and di-sec-butyl-peroxydicarbonate.
- thermosetting composition The quick curability of a thermosetting composition can be improved by adding a component.
- the temperature at the time when the half-life is reached in a specific time is a standard. Specific examples include a 1 minute half-life temperature, a 1-hour half-life temperature, and a 10-hour half-life temperature.
- the 1 minute half-life temperature refers to a temperature at which the concentration of the organic peroxide becomes half of the initial concentration in 1 minute.
- the 1-minute half-life temperature of the component (C) is preferably 100 ° C. or lower.
- component (C) examples include NPP (1-minute half-life temperature: 94.0 ° C.), IPP (1-minute half-life temperature: 88.3 ° C.), SBP (manufactured by NOF Corporation). 1 minute half-life temperature: 92.4 ° C., TCP (1 minute half-life temperature: 92.1 ° C.), OPP (1 minute half-life temperature: 90.6 ° C.), etc. is not.
- the component (C) is preferably contained in an amount of 1 to 10 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B).
- the component (C) is 1 part by mass or more, low temperature curability is exhibited.
- the component (C) is 10 parts by mass or less, the storage stability can be maintained when conductive particles are added to the thermosetting composition of the present invention.
- thermosetting composition of the present invention may further contain a component (D) in order to realize isotropic conductivity.
- the component (D) that can be used in the present invention is conductive particles surface-treated with stearic acid.
- thermosetting composition In the prior art, conductive particles are sometimes added to the thermosetting composition in order to achieve conductivity, but the organic peroxide in the thermosetting composition is caused by metal ions generated from the conductive particles. Degradation is promoted and gelation easily occurs, the viscosity changes with time, and the storage stability of the thermosetting composition is lacking, so that the handleability is poor. Therefore, the inventors' research has revealed that the silver powder treated with stearic acid has the effect of improving the storage stability, although the specific reason is unknown. If conductive particles of component (D) are added to the thermosetting composition, the storage stability in an atmosphere at 25 ° C. can be maintained. In addition to exhibiting adhesion strength to a difficult-to-adhere metal adherend such as gold or nickel, stable conductivity can be exhibited.
- the conductive particles only have to exhibit electrical conductivity, and the material of the particles and the shape of the particles are not limited.
- the material for the conductive particles include silver powder, nickel powder, palladium powder, carbon powder, tungsten powder, and plating powder. Silver powder is particularly preferable.
- examples of the shape of the conductive particles include a spherical shape, an indeterminate shape, a flake shape (scale shape), a filament shape (needle shape), and a dendritic shape. A plurality of types may be mixed and used.
- conductive particles obtained by silver-plating insulating metal oxide, nickel powder, or insulating powder can also be used.
- the insulating metal oxide include copper powder, aluminum powder, iron powder, and the like, and a passive state is formed on the metal surface and conductivity is not exhibited.
- the average particle size is preferably 100 ⁇ m or less.
- the conductive particles of component (D) are preferably silver powder or silver-plated powder surface-treated with stearic acid in consideration of cost and conductivity.
- a surface treatment method using stearic acid there is known a method of drying a solvent after treating stearic acid diluted in a solvent together with conductive particles with a ball mill or the like, but is not limited thereto.
- the component (D) is preferably contained in an amount of 100 to 1000 parts by mass, more preferably 200 to 800 parts by mass with respect to 100 parts by mass of the component (A).
- the component (D) is 100 parts by mass or more, conductivity is exhibited.
- the component (D) is 1000 parts by mass or less, there is no occurrence of stringing and the workability is good.
- a stabilizer may be added as long as the characteristics of the present invention are not impaired.
- examples of the stabilizer include a polymerization inhibitor and a chelating agent.
- a polymerization inhibitor can also be used.
- a chelating agent can also be used to capture the generated metal ions.
- the polymerization inhibitor include quinone polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, Alkyl phenol polymerization inhibitors such as 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, alkylated diphenylamine N, N′-diphenyl-p-phenylenediamine, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1, 4-dihydroxy-2,2,6,6-tetramethylpiperidine, Amine-based polymerization inhibitors such as -hydroxy-4-benzoyloxy-2,2,6,6
- chelating agent examples include EDTA ⁇ 2Na and EDTA ⁇ 4Na manufactured by Doujin Chemical Laboratory Co., Ltd., and examples of the chelating agent which is liquid at 25 ° C. include MZ-8 manufactured by Kirest Co., Ltd. However, it is not limited to these.
- the amount of the stabilizer added is preferably 0.001 to 1.0% by mass based on the entire composition.
- a filler can be added within a range not impairing the characteristics of the present invention.
- Fillers are classified into inorganic fillers and organic fillers.
- inorganic fillers include metal powder that does not exhibit electrical conductivity (metal powder whose powder surface has formed a passive state due to oxidation), alumina powder, calcium carbonate powder, talc powder, silica powder, fumed silica powder, and the like.
- organic filler include acrylic particles, rubber particles, and styrene particles, but are not limited thereto.
- the powder characteristics such as the average particle diameter and shape are not particularly limited, but the average particle diameter is preferably 0.001 to 50 ⁇ m in consideration of ease of dispersion in the composition and nozzle clogging.
- the addition of fumed silica powder imparts thixotropy and maintains storage stability.
- Specific examples of fumed silica powder include AEROSIL R805, R972 manufactured by Nippon Aerosil Co., Ltd., but are not limited thereto.
- 0.1 to 10 parts by mass of the filler is added to 100 parts by mass of the total of the components (A) and (B).
- the amount of the filler is more than 0.1 parts by mass, the fluidity can be stabilized and workability can be improved.
- the amount of the filler is less than 10 parts by mass, the storage stability can be maintained.
- an appropriate amount of additives such as pigments, dyes and other colorants, flame retardants, antioxidants, antifoaming agents, coupling agents, leveling agents, rheology control agents and the like are included within the range not impairing the properties of the present invention. You may do it. By adding these, an adhesive having excellent conductivity, resin strength, adhesive strength, workability, storage stability, or the like, or a cured product thereof can be obtained.
- thermosetting composition of the present invention comprising the component (D).
- the conductive adhesive may further contain other components as long as the characteristics of the conductive adhesive are not impaired.
- the conductive adhesive is (D) It consists of the thermosetting composition of this invention containing a component.
- Another embodiment of the present invention is an electrical / electronic component including a cured product of the conductive adhesive. That is, in the electrical / electronic component, a conductive adhesive is used for assembling a semiconductor element and various electrical / electronic components or bonding them to a substrate. Specifically, as the electric / electronic component, a semiconductor element, a solar panel, a thermoelectric element, a chip component, a discrete component, or a combination thereof is mounted on a substrate by the conductive adhesive of the present invention, or the present invention.
- the conductive adhesive include a film antenna, a keyboard membrane, a touch panel, an RFID antenna formed with wiring and connected to a substrate.
- the present invention realizes a thermosetting composition having rapid curability without sudden boiling during curing at a high temperature for a short time (within 100 to 150 ° C. within 1 minute), and the thermosetting composition is electrically conductive. If particles are added, the storage stability in an atmosphere at 25 ° C. can be maintained, and adhesion strength and stable conductivity can be exhibited with respect to a metal adherend that is difficult to adhere such as gold or nickel. .
- thermosetting composition is also simply referred to as a composition.
- Component Compound having (meth) acrylic group / hexafunctional aliphatic urethane acrylate oligomer (EBECRYL8301R manufactured by Daicel Ornex Co., Ltd.) ⁇ 2-Hydroxyethyl methacrylate (manufactured by Nippon Shokubai Co., Ltd.)
- Component (B) a phenol compound having a molecular weight of 230 or more and dissolved in component (A).
- Comparative Example 1 uses a phenol compound having a molecular weight of 230 or more, but did not dissolve in the component (A), and could not confirm bumping confirmation and curing time measurement. Further, when Examples 1 to 6 and Comparative Example 2 were compared, Comparative Example 2 used BHT having a reaction suppressing effect, but could not suppress bumping. Furthermore, in Comparative Example 3 using an organic peroxide other than the component (C), it can be seen that the curing time is long. From these, in the composition containing the organic peroxide, if the reactivity of the organic peroxide is increased too much, bumping will occur, and if the reactivity is lowered too much, the curing time tends to become longer. In Examples 1 to 6, it is possible to shorten the reactive curing time and suppress bumping.
- (A) Component: Compound having (meth) acrylic group / hexafunctional aliphatic urethane acrylate oligomer (EBECRYL8301R manufactured by Daicel Ornex Co., Ltd.) ⁇ 2-Hydroxyethyl methacrylate (manufactured by Nippon Shokubai Co., Ltd.)
- Component (B) Phenol compound dissolved in component (A) having a molecular weight of 230 or more.
- component (C) was weighed, put into a stirring vessel, and stirred for 30 minutes.
- component (D) was weighed and put into a stirring vessel and stirred for 1 hour.
- Table 3 Detailed preparation amounts are in accordance with Table 3, and all numerical values are expressed in parts by mass.
- the viscosity is measured under the following measurement conditions to obtain the initial viscosity. Thereafter, the sample is allowed to stand in an atmosphere of 25 ° C., measured every 12 hours, and measured until the initial viscosity is increased by 20%, and “storage stability” is judged according to the following evaluation criteria.
- the storage stability is preferably “ ⁇ ”. When the storage stability is “x”, the resistance value measurement and the shear bond strength measurement are not performed.
- Adhesive is applied to one nickel plate that is exposed, and the other nickel plate of the same size is attached to the cross and pressed.
- the protruding adhesive is wiped off and fixed with a fixing jig.
- the test piece is taken out from the hot air drying furnace after being put into a hot air drying furnace at 140 ° C. and left for 10 seconds. After the sample has dropped to 25 ° C., using a dual display multimeter having needle-like electrodes, the needle-like electrodes are brought into contact with the top and bottom of the exposed portion of the nickel plate, and “resistance ( ⁇ )” is measured. From the viewpoint of ensuring conductivity, the resistance value is preferably 0.5 ⁇ or less.
- a masking tape was affixed on a nickel plate having a thickness of 1.6 mm, a width of 25 mm, and a length of 100 mm to a thickness of 50 ⁇ m, and the adhesive was squeezed to form a uniform coating film.
- the digital force gauge with a contact is moved at 50 mm / min, and the tip is pushed with the contact to measure “maximum strength (N)”.
- the adhesive strength (MPa) was calculated.
- the case where a ceramic chip is used is referred to as “adhesion strength 1 (MPa)”
- the case where a gold-plated chip is used is referred to as “adhesion strength 2 (MPa)”.
- the adhesive strength is preferably 0.5 MPa or more.
- Comparative Example 4 does not contain the component (B). Since bumping occurred inside the test piece, it can be seen that the resistance value increases and the adhesive strength decreases. It can be seen that Examples 7 to 14, which are conductive adhesives, are cured at a high temperature for a short time and have good results with respect to storage stability, resistance value and adhesive strength.
- the present invention can be used as a structural adhesive because it achieves both storage stability in an atmosphere at 25 ° C. and fast curability at a high temperature for a short time (within 1 minute at 100 to 150 ° C.) without bumping. .
- it exhibits high adhesive strength for difficult-to-adhere metallic adherends such as gold and nickel, and stable electrical conductivity even in conductive adhesives with conductive particles added. Connection can be made. From these characteristics, it can be used for assembling various electronic parts and the like, and may be widely used.
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Abstract
Description
(A)成分:(メタ)アクリル基を有する化合物
(B)成分:分子量が230以上であって、且つ(A)成分に溶解するフェノール化合物
(C)成分:式1の構造の有機過酸化物。
本発明の第二の実施態様は、前記(B)成分の融点が225℃より低い第一の実施態様に記載の熱硬化性組成物である。
(A-1)成分:(メタ)アクリル基を有するウレタン変性オリゴマー;
(A-2)成分:分子内に(メタ)アクリル基を1つ以上有するモノマー。
本発明の第五の実施態様は、(D)成分としてステアリン酸により表面処理された導電性粒子をさらに含む、第一から第四の実施態様のいずれか一つに記載の熱硬化性組成物である。
(A)成分:(メタ)アクリル基を有する化合物
(B)成分:分子量が230以上であって、且つ(A)成分に溶解するフェノール化合物
(C)成分:式1の構造の有機過酸化物。
本発明の詳細を次に説明する。
(A-1)成分:(メタ)アクリル基を有するウレタン変性オリゴマー;
(A-2)成分:分子内に(メタ)アクリル基を1つ以上有するモノマー。
・6官能の脂肪族ウレタンアクリレートオリゴマー(EBECRYL8301R ダイセル・オルネクス株式会社製)
・2-ヒドロキシエチルメタクリレート(HEMA 株式会社日本触媒製)
(B)成分:分子量が230以上であって、且つ(A)成分に溶解するフェノール化合物
・1,3,5-トリス[[3,5-ビス(1,1-ジメチルエチル)-4-ヒドロキシフェニル]メチル]-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン(融点:221℃、分子量:784)(アデカスタブAO-20 ADEKA株式会社製)
・4,4’-ブチリデンビス(6-tert-ブチル-m-クレゾール)(融点:212℃、分子量:383)(アデカスタブAO-40 ADEKA株式会社製)
・3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリル(融点:52℃、分子量:531)(アデカスタブAO-50 ADEKA株式会社製)
・ペンタエリトリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナート](融点:115℃、分子量:1178)(アデカスタブAO-60 ADEKA株式会社製)
(B’)成分:(B)成分以外のフェノール化合物
・1,1,3-トリス(2-メチル-4-ヒドロキシ-5-tert-ブチルフェニル)ブタン(融点:184℃、分子量:545)(アデカスタブAO-30 ADEKA株式会社製)
・ジブチルヒドロキシトルエン(BHT)(融点:70℃、分子量:220)(試薬)
(C)成分:式1の構造の有機過酸化物
・ビス(4-tert-ブチルシクロヘキシル)パーオキシジカーボネート(25℃で固体、1分間半減期温度:92.1℃)(パーロイルTCP 日油株式会社製)
(C’)成分:(C)成分以外の有機過酸化物
・ジラウロイルパーオキサイド(25℃で固体、1分間半減期温度:116.4℃)(パーロイルL 日油株式会社製)
(A)成分および(B)成分(または(B’)成分)を秤量して攪拌釜に投入し1時間攪拌した。その後、(C)成分(または(C’)成分)を秤量して攪拌釜に投入して30分攪拌した。詳細な調製量は表1に従い、数値は全て質量部で表記する。
組成物を調製する際に、以下の評価基準に従い、(B)成分(または(B’)成分)が溶解しているか目視にて確認を行い、「溶解性」とする。溶解すれば突沸の抑制に効果を発現する可能性があることから「○」であることが好ましい。
○:完全溶解
×:溶解せず
[突沸確認]
ノズル付きシリンジに入った組成物を10mg秤量しガラス板上に塗出して、110℃に設定したホットプレートの上に10分間静置する。目視で外観を以下の評価基準に従って確認し、「突沸」とする。貼り合わせで使用する場合、内部に突沸が発生すると接着強さに影響を与えることから「◎」、「○」であることが好ましい。
◎:突沸無し
○:突沸は無いが硬化物の表面が少し荒れている
×:突沸有り
[硬化時間測定]
ノズル付きシリンジに入った組成物を10mg秤量しガラス板上に塗出して、110℃に設定したホットプレートの上に放置して、組成物をポリテトラフルオロエチレン製の棒の先端で押して、棒を引いた時に糸曳きが無くなり、硬化するまでの時間を「硬化時間(秒)」とする。被着体に対して熱によるダメージを低減させるためには、低温硬化性は20秒以内であることが好ましい。
・6官能の脂肪族ウレタンアクリレートオリゴマー(EBECRYL8301R ダイセル・オルネクス株式会社製)
・2-ヒドロキシエチルメタクリレート(HEMA 株式会社日本触媒製)
(B)成分:分子量が230以上の(A)成分に溶解するフェノール化合物
・1,3,5-トリス[[3,5-ビス(1,1-ジメチルエチル)-4-ヒドロキシフェニル]メチル]-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン(融点:221℃、分子量:784)(アデカスタブAO-20 ADEKA株式会社製)
・4,4’-ブチリデンビス(6-tert-ブチル-m-クレゾール)(融点:212℃、分子量:383)(アデカスタブAO-40 ADEKA株式会社製)
・3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリル(融点:52℃、分子量:531)(アデカスタブAO-50 ADEKA株式会社製)
・ペンタエリトリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナート](融点:115℃、分子量:1178)(アデカスタブAO-60 ADEKA株式会社製)
(C)成分:式1の構造の有機過酸化物
・ビス(4-tert-ブチルシクロヘキシル)パーオキシジカーボネート(25℃で固体)(パーロイルTCP 日油株式会社製)
(D)成分:ステアリン酸により表面処理された導電性粒子
・銀粉1:下記の粉体特性を有するステアリン酸処理されたフレーク状銀粉
タップ密度:3.17g/cm3
50%平均粒径:5.0μm
BET比表面積:0.67m2/g
・銀粉2:下記の粉体特性を有するステアリン酸処理されたフレーク状銀粉
タップ密度:3.57g/cm3
50%平均粒径:1.2μm
BET比表面積:2.01m2/g
(A)成分、(B)成分を秤量して攪拌釜に投入し1時間攪拌した。その後、(C)成分を秤量して攪拌釜に投入して30分攪拌した。最後に、(D)成分を秤量して攪拌釜に投入して1時間攪拌した。詳細な調製量は表3に従い、数値は全て質量部で表記する。
接着剤を2ml使用して、下記の測定条件で粘度を測定して初期粘度とする。その後、25℃雰囲気下で放置して、12時間毎に測定し初期粘度の20%増まで粘度測定を行い、下記の評価基準により「保存安定性」について判断する。接着剤の吐出時に吐出量を変化させないために、保存安定性は「○」であることが好ましい。保存安定性が「×」の場合、抵抗値測定と剪断接着強さ測定を行わない。
コーンローター:3°×R2.4
せん断速度:1.0(1/s)
測定温度:25℃(温調装置使用)
評価基準
○:25℃で48時間以上
×:25℃で48時間未満
[抵抗値測定]
厚さ1.6mm×幅25mm×長さ10mmのニッケル板上に、ニッケル板の幅方向の両端部から10mm分を100μm厚のポリイミドテープでマスクして、幅5mm分ニッケル板が剥き出しになったものを2枚用意する。一方のニッケル板が剥き出しになっているところに接着剤を塗布して、もう一方の同寸法のニッケル板を十字に貼り合わせて押さえつけ、はみ出た接着剤を拭き取って固定治具で固定する。140℃雰囲気の熱風乾燥炉に投入して10秒間放置した後、熱風乾燥炉からテストピースを取り出す。サンプルが25℃に下がった後に、針状電極を有するデュアルディスプレイマルチメータを用いて、針状電極をニッケル板の剥き出し部の上下に触れさせ、「抵抗値(Ω)」を測定する。導電性を確保する観点から、抵抗値は0.5Ω以下であることが好ましい。
厚さ1.6mm×幅25mm×長さ100mmのニッケル板上に、厚さ50μmになる様にマスキングテープを貼り付け、接着剤をスキージーして均一な塗膜を形成した。マスキングテープを剥がした後、塗膜上に2φ×1mmの円筒形のセラミックチップまたは金メッキチップを塗膜から1cm上から垂直に落下させてテストピースを作成した(n=5)。テストピースを5分以内に、140℃雰囲気の熱風乾燥炉に投入して、10秒間放置してから熱風乾燥炉からテストピースを取り出す。25℃に戻った後に、ニッケル板を固定した状態で、接触子付きのデジタルフォースゲージを50mm/分で移動させて、接触子でチップを押して「最大強度(N)」を測定する。接着面積から換算して、接着強さ(MPa)を計算した。セラミックチップを使用した場合を「接着強さ1(MPa)」とし、金メッキチップを使用した場合を「接着強さ2(MPa)」とする。部品の脱落等を考慮すると、接着強さは0.5MPa以上であることが好ましい。
Claims (8)
- 前記(B)成分の融点が225℃より低い、請求項1に記載の熱硬化性組成物。
- 前記(A)成分が、下記(A-1)成分および(A-2)成分を含む請求項1または2に記載の熱硬化性組成物:
(A-1)成分:(メタ)アクリル基を有するウレタン変性オリゴマー;
(A-2)成分:分子内に(メタ)アクリル基を1つ以上有するモノマー。 - (D)成分としてステアリン酸により表面処理された導電性粒子をさらに含む、請求項1~4のいずれか1項に記載の熱硬化性組成物。
- 前記導電性粒子は、ステアリン酸により表面処理された銀粉または銀メッキ粉である、請求項5に記載の熱硬化性組成物。
- 請求項5または6に記載の熱硬化性組成物を含む、導電性接着剤。
- 請求項7に記載の導電性接着剤の硬化物を含む、電気電子部品。
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