CN109415608A - Electric conductivity adhesion agent composition and electric conductivity adhesive tape - Google Patents
Electric conductivity adhesion agent composition and electric conductivity adhesive tape Download PDFInfo
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- CN109415608A CN109415608A CN201680086775.2A CN201680086775A CN109415608A CN 109415608 A CN109415608 A CN 109415608A CN 201680086775 A CN201680086775 A CN 201680086775A CN 109415608 A CN109415608 A CN 109415608A
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- Prior art keywords
- electric conductivity
- agent composition
- acrylic acid
- adhesion agent
- adhesive tape
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0064—Earth or grounding circuit
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Electromagnetism (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Dispersion Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
The present invention provides a kind of electric conductivity adhesion agent composition, it contains acrylic acid series copolymer (A) and electroconductive particle (B), the 00 type hardness tester meter hardness as defined in ASTM D 2240 is 15 or more at 85 DEG C, it is stretched even in a high temperature environment by the screen resilience for the object that is stuck, also it is difficult to generate peeling, wire drawing, electric conductivity reduction, the present invention also provides a kind of electric conductivity adhesive tapes, have the adhering agent layer formed by the electric conductivity adhesion agent composition in the one or both sides of conductive substrate.
Description
Technical field
The present invention relates to even in a high temperature environment by the object that is stuck screen resilience stretching, it is also difficult to generate peeling, wire drawing,
The electric conductivity adhesion agent composition that electric conductivity reduces；And the electric conductivity adhesive tape of the electric conductivity adhesion agent composition is used.
In more detail, it is related to electric conductivity adhesion useful in terms of the purposes of the electromagnetic wave shielding of such as electronic equipment internal or ground connection
Band.
Background technique
In the electronic device, due to electrostatic, electromagnetic wave adverse effect and the delaying work of generating means, material are broken sometimes
It is bad.Based on such dysgenic purpose is prevented, there is the component inside for equipment to use the method for electric conductivity adhesive tape.Tool
For body, it is known to use metal foil is as the electric conductivity adhesive tape added with electroconductive particle in substrate and adhering agent layer in electromagnetism
It is useful in terms of the purposes that wave screen covers, is grounded.For such electric conductivity adhesive tape, electric conductivity and adherence are important
Performance, propose the various schemes for improving the performance.
A kind of electric conductivity adhesive tape of adhering agent layer with specific thicknesses, the adhering agent layer are disclosed in patent document 1
Spherical and/or spike 14~45 parts by weight of electroconductive stuffing for being 1.0~1.5 containing length-width ratio.And think, the adhesive tape
It is different from the adhesive tape of each comparative example of the electroconductive stuffing for having used long filiform, laminar electroconductive stuffing etc., even if
In the case where making adhering agent layer filming, adherence and electric conductivity are also excellent, further have ladder absorbability.
A kind of slim adhesive sheet of the electric conductivity with the adhering agent layer with a thickness of 6~12 μm is disclosed in patent document 2, it should
Adhering agent layer contains the electroconductive particle that partial size d50 is 4~12 μm and d85 is 6~15 μm.And think, even if the adhesive sheet
To be slim, cementability and electric conductivity are also excellent, and then productivity is also excellent.
A kind of electric conductivity adhesive tape, thickness t (μm) and the electroconductive particle of adhering agent layer are disclosed in patent document 3
The relationship of partial size d50 (μm) with t < d50, the adhesion strength of adhering agent layer are 4N/20mm or more.And think, which is
Make to be used for a long time, be used under harsh environmental condition, it may have stable electric conductivity, and then can keep in view of operability
Adhesion strength.
The ratio t/ of the thickness t (μm) of adhering agent layer and the partial size d50 (μm) of electroconductive particle are disclosed in patent document 4
D50 is 0.2 or more 4.0 electric conductivity adhesive tape below.And think, even if the adhesive tape is used for a long time, in harsh environment
Under the conditions of use, it may have stable electric conductivity.
However, in recent years, there is electronic equipment to miniaturise, thin layer tendency.Such as mobile phone, smart phone,
The information equipments such as wearable terminal gradually become thin and small.Therefore, each component for constituting them also becomes smaller, the adhesive surface of adhesive tape
Product also more narrows.In turn, for miniaturization, thin layer electronic equipment, such as the FPC of one of component
(Flexible Printed Circuits, flexible print circuit) is bent configuration, bending angle in extremely narrow space
The case where as acute angle, is more.
If bonding area is narrow and the bending angle of FPC is acute angle, there is adhesive tape to cannot stand the screen resilience of FPC and generate
The worry of peeling or wire drawing (adhering agent layer is stretched and partly generates a large amount of state such as silky shape).And
If the heat as caused by electronic equipment internal (such as fever of battery) and adhering agent layer soften, the stripping of adhesive tape is generated
Fall, wire drawing a possibility that further increase.Further, it even if not generating peeling, wire drawing, is slightly drawn only by adhering agent layer
It stretches, also results in that the mutual contact of electroconductive particle is reduced and resistance value becomes unstable, conductive reduced worry.
On the other hand, if persistently applying load to the electric conductivity adhesive tape inside equipment using components such as gaskets,
Then such problems can be difficult to generate.If adhering agent layer is compressed, the mutual contact of electroconductive particle increases and shows
Show stable resistance value.However, the size of each component is small and is difficult to for equipment for miniaturising, thin layer
The components such as gasket are set, and in the case where surface has concave-convex, it is difficult to apply load.In addition, in the case where component is thin,
If applying strong load, there is damaged worry.
The project that the screen resilience of the object that is stuck when in Patent Documents 1 to 4 for generating heat inside equipment due to generates is simultaneously
Do not carry out any research.Such as in patent document 1, used spike or spherical electroconductive particle in embodiment, than
(patent is determined with normality to the resistance value for the adhesive tape for having used long Filamentous or laminar electroconductive particle compared in example
[0067] section of document 1).In patent document 2, the electricity of adhesive sheet is measured while applying the load of face pressure 20N at 23 DEG C
Resistance value ([0078] section of patent document 2).In patent document 3 and 4, the resistance value of sample is added with 85 DEG C × 85%RH
It is determined after speed, under conditions of after -40 DEG C~85 DEG C of ranges repeatedly heating and cooling, but the sample is that will have stickup
There is the evaluation of adhesive tape to be suppressed under the pressure of 0.1MPa with substrate/EVA film/glass plate composition laminated body, then makes EVA
Product obtained by heat cure, it can be said that evaluation is state to be compressed by glass plate with the adhesive tape on substrate and is fixed
([0117] section, [0107] section of patent document 4 of patent document 3).
Any research is not carried out for following project in Patent Documents 1 to 4: in electric conductivity adhesive tape with narrow
Area is glued to produce heat inside miniaturization, thin layer electronic equipment internal and equipment in the case where, can be because of FPC etc.
Be stuck object screen resilience and generate peeling, wire drawing；Or can because FPC etc. be stuck object screen resilience due to lead to adhering agent layer quilt
Slightly stretching will make resistance value become unstable.Moreover, being solved in this way for previous general electric conductivity adhesive tape
Project be difficult.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2009-79127 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2013-245234 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2015-10109 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2015-10110 bulletin
Summary of the invention
Problems to be solved by the invention
The purpose of the present invention is to provide a kind of electric conductivity adhesion agent compositions, and have used the electric conductivity sticker group
The adhesive tape for closing object, is stretched because of the screen resilience for the object that is stuck even in a high temperature environment, it is also difficult to generate and peel off, draws
Silk, electric conductivity reduce.
The method used for solving the problem
The present invention relates to a kind of electric conductivity adhesion agent compositions, contain acrylic acid series copolymer (A) and electroconductive particle
(B), the 00 type hardness tester meter hardness as defined in ASTM D 2240 is 15 or more at 85 DEG C.
Further the present invention relates to a kind of electric conductivity adhesive tapes, have in the one or both sides of conductive substrate by above-mentioned
The adhering agent layer that electric conductivity adhesion agent composition is formed.
The effect of invention
It is stretched even in a high temperature environment because of the screen resilience for the object that is stuck in accordance with the invention it is possible to provide one kind,
It is difficult to generate the electric conductivity adhesion agent composition of peeling, wire drawing, electric conductivity reduction.The electric conductivity adhesion agent composition is used as and is used for
It is highly useful for forming the material of the adhering agent layer of electric conductivity adhesive tape.Electric conductivity adhesive tape with such adhering agent layer
Even if heat is generated inside equipment being for example glued to miniaturization, thin layer electronic equipment internal with narrow area, and
In the case where being stretched because of the screen resilience for the object that is stuck, it is also difficult to generate peeling, wire drawing, electric conductivity reduction.Moreover, being not required to
Adhesive tape to be compressed using components such as gaskets, thus for realize the miniaturising of electronic equipment, it is thin layer and
Speech is also highly useful.
Detailed description of the invention
Fig. 1 is the electron micrograph of long Filamentous nickel powder used in embodiment.
Fig. 2 is the electron micrograph of spike nickel powder used in embodiment.
Fig. 3 is the schematic perspective view for illustrating the measuring method of the resistance to rebound resistance value in embodiment.
Fig. 4 is the schematic sectional view for illustrating the measuring method of the resistance to rebound resistance value in embodiment.
Specific embodiment
< electric conductivity adhesion agent composition >
Electric conductivity adhesion agent composition of the invention is the 00 type hardness tester meter hardness as defined in ASTM D 2240 at 85 DEG C
It is 15 or more, preferably 20~90, more preferably 25~70 composition.Specifically, the durometer hardness is as be described hereinafter
Documented by embodiment like that, the sample of thickness 6mm is saved 1 hour in 85 DEG C of drying machine, be and then measured and
Obtained value.
The durometer hardness of electric conductivity adhesion agent composition of the invention under high temperature (85 DEG C) is more viscous than previous electric conductivity
Agent composition it is high, therefore be stretched even in a high temperature environment because of the screen resilience for the object that is stuck, it is also difficult to generate stripping
It falls, wire drawing.And be difficult to generate as previous electric conductivity adhesive tape, adhering agent layer is slightly stretched and leads to conduction
Property the mutual contact of particle reduce, resistance value becomes unstable, and electric conductivity significantly reduces such problems.
In general, durometer hardness when durometer hardness and high temperature (85 DEG C) at room temperature might not be in ratio
Relationship.This is because the phenomenon that being reduced by heating hardness, is specifically according to the difference of material category and in varied
's.Therefore, in order to improve durometer hardness when high temperature (85 DEG C), it is important that the kind of each ingredient of appropriate adjustment constituent material
Class, use level, and in high temperature (85 DEG C) Shi Jinhang practical measurement, and durometer hardness when being not merely using room temperature as
Standard.The durometer hardness of electric conductivity adhesion agent composition of the invention at high temperature (85 DEG C) for example can be by suitably setting
The vitrifying of the type, ratio, acrylic acid series copolymer (A) of the constituent of the polymer chain of acrylic acid series copolymer (A) turns
The various conditions such as height (Tg), molecular weight, the shape of electroconductive particle (B), use level, type, the use level of crosslinking agent (C) are come
Adjustment.Further, it is possible to be adjusted by the type of additive, use level.More specifically, for example, if make relatively largely
The constituent for using glass transition point (Tg) to get higher as acrylic acid series copolymer (A) polymer chain constituent, or
The molecular weight for improving acrylic acid series copolymer (A), or keeps electroconductive particle (B), the amount of crosslinking agent (C) more, or make to be easy to because
Hot and the ingredient of softening additive amount is less, then the tendency that there is durometer hardness when high temperature (85 DEG C) to get higher.However, these
Method only illustrates, and the present invention is not limited to electric conductivity sticker groups obtained from adjusting durometer hardness as these methods
Close object.
Electric conductivity adhesion agent composition of the invention contains acrylic acid series copolymer (A) and electroconductive particle (B).It is preferred that containing
There is acrylic acid series copolymer (A) as the base polymer in composition.For example, if organic silicon-type sticker is heated,
Low molecular weight compositions ooze out and the operability such as welding are hindered to be easy to deteriorate if rubber series sticker is heated sometimes.And it is another
On the one hand, acrylic acid series sticker is difficult to generate such problems.Electroconductive particle (B) is for assigning to adhesion agent composition
The ingredient of electric conductivity.
The type of acrylic acid series copolymer (A) used in the present invention is not particularly limited, and preferably includes following ingredient
The acrylic acid series copolymer of constituent as polymer chain: (methyl) acrylic acid with the alkyl that carbon atom number is 1~3
Arrcostab (A1), with carbon atom number be 4~12 (methyl) alkyl acrylate (A2) of alkyl, carboxyl group-containing monomer (A3),
Hydroxyl monomer (A4) and vinyl acetate (A5).By specific kind that suitably changes these each ingredient (A1)~(A4)
Class, ratio can adjust the durometer hardness of electric conductivity adhesion agent composition of the invention at high temperature (85 DEG C).
As the concrete example of (methyl) alkyl acrylate (A1), (methyl) methyl acrylate, (methyl) propylene can be enumerated
Acetoacetic ester, (methyl) propyl acrylate.Wherein, preferably (methyl) methyl acrylate.(methyl) alkyl acrylate (A1)
Content is in the 100 mass % of constituent (monomeric unit) of acrylic acid series copolymer (A), and preferably 20 mass % are hereinafter, more
Preferably 16 mass % are hereinafter, particularly preferably 2~15 mass %.
As the concrete example of (methyl) alkyl acrylate (A2), (methyl) butyl acrylate, (methyl) propylene can be enumerated
Sour isobutyl ester, (methyl) 2-EHA, (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) third
The different nonyl ester of olefin(e) acid, (methyl) lauryl acrylate.Wherein, preferably (methyl) butyl acrylate, (methyl) acrylic acid 2- ethyl
Own ester.Constituent (monomeric unit) 100 matter of the content of (methyl) alkyl acrylate (A2) in acrylic acid series copolymer (A)
It measures in %, preferably 50~97 mass %, more preferably 65~90 mass %.
As the concrete example of carboxyl group-containing monomer (A3), acrylic acid, methacrylic acid, itaconic acid, crotonic acid, Malaysia can be enumerated
Acid, fumaric acid, 2- carboxyl -1- butylene, 2- carboxyl -1- amylene, 2- carboxyl -1- hexene, 2- carboxyl -1- heptene.Wherein, preferably
Acrylic acid, methacrylic acid, more preferably acrylic acid.Structure of the content of carboxyl group-containing monomer (A3) in acrylic acid series copolymer (A)
At in 100 mass % of ingredient (monomeric unit), preferably 3 mass % or more, more preferably 3.5~15 mass %, particularly preferably
For 7~12 mass %.
As the concrete example of hydroxyl monomer (A4), (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid can be enumerated
3- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl.Structure of the content of hydroxyl monomer (A4) in acrylic acid series copolymer (A)
At in 100 mass % of ingredient (monomeric unit), preferably 0.01~2 mass %, more preferably 0.05~0.5 mass %.
Constituent (monomeric unit) 100 mass % of the content of vinyl acetate (A5) in acrylic acid series copolymer (A)
In, preferably 5 mass % are hereinafter, more preferably 1~4 mass %.
Polymerization for obtaining acrylic acid series copolymer (A) is not particularly limited, and readily sees from polymer design
Point sets out, preferably free radical solution polymerization.In addition it is also possible to which modulation includes acrylic acid series copolymer (A) and monomer first
Acrylic acid series slurry, in the acrylic acid series slurry cooperate crosslinking agent (B) and addition Photoepolymerizationinitiater initiater make its polymerization.
In the manufacture of acrylic acid series copolymer (A), within the scope of the effect of the invention, ingredient can be made
(A1) the monomer copolymerization other than~(A5).
The weight average molecular weight of acrylic acid series copolymer (A) is preferably 450,000 or more, and more preferably 500,000~1,800,000, especially
Preferably 550,000~1,500,000.The weight average molecular weight is the value measured by GPC method.It is total by suitably changing acrylic acid series
The weight average molecular weight of polymers (A) can adjust the hardometer of electric conductivity adhesion agent composition of the invention at high temperature (85 DEG C)
Hardness.
The theory T g of acrylic acid series copolymer (A) is preferably -55 DEG C hereinafter, more preferably -75 DEG C~-57 DEG C.The theory
Tg is the value calculated by the formula of FOX.By suitably changing the Tg of acrylic acid series copolymer (A), can adjust of the invention
Durometer hardness of the electric conductivity adhesion agent composition at high temperature (85 DEG C).
In the present invention, it at least uses acrylic acid series copolymer (A) as resin component, but is not damaging effect of the invention
In the range of fruit, can also and with the addition resin component of other types.As concrete example, rosin based tackifiers, terpene can be enumerated
The tackifying resins such as olefine resin, petroleum line resin, terpenes phenolic aldehyde system resin, phenylethylene resin series.
Electroconductive particle (B) used in the present invention is not particularly limited, and the combination of known conductive sticker can be used
The well known electroconductive particle being able to use in object.As concrete example, can enumerate by the metals such as nickel, copper, chromium, gold, silver or its
Metallic, the carbon particle, graphite particle that alloy or modifier are formed.In addition it is also possible to be coated with gold using in resin surface
The electroconductive resin particle of category.Also two kinds or more of electroconductive particle can be used together.Wherein, preferably metallic, more preferably
For nickel particles, copper particle, most preferably nickel particles.
The shape of electroconductive particle (B) is not particularly limited, and can be used known in long filiform, spike, flake, spherical etc.
Shape electroconductive particle.Wherein, it is easy to become more from the mutual contact of electroconductive particle, from the perspective of resistance value is stablized,
Preferably long filiform, spike, flake, more preferably long Filamentous, spike.The size of electroconductive particle (B) is not particularly limited,
Use the electroconductive particle (B) of well known size.
The use level of electroconductive particle (B) relative to 100 mass parts of acrylic acid series copolymer (A), preferably 2 mass parts with
On, more preferably 3~100 mass parts, particularly preferably 5~75 mass parts.By the cooperation for suitably changing electroconductive particle (B)
Amount, can adjust the durometer hardness of electric conductivity adhesion agent composition of the invention at high temperature (85 DEG C).
Electric conductivity adhesion agent composition of the invention preferably further contains crosslinking agent (C).Crosslinking agent (C) is in order to third
Olefin(e) acid based copolymer (A) reacts and forms cross-linked structure and the compound that cooperates.It particularly preferably can be with acrylic copolymer
The compound of carboxyl and/or the hydroxyl reaction of object (A), more preferably isocyanates system crosslinking agent.It is crosslinked as isocyanates system
The concrete example of agent can enumerate toluene di-isocyanate(TDI), xylene diisocyanate, 1, hexamethylene-diisocyanate, isophorone two
The modified prepolymers etc. of isocyanates and they.They can be used together two kinds or more.
The use level of crosslinking agent (C) is relative to 100 mass parts of acrylic acid series copolymer (A), preferably 0.02~2 mass parts
More than, more preferably 0.03~1 mass parts, particularly preferably 0.3~0.9 mass parts.By suitably changing matching for crosslinking agent (C)
Resultant can adjust the durometer hardness of electric conductivity adhesion agent composition of the invention at high temperature (85 DEG C).
Electric conductivity adhesion agent composition of the invention can according to need further containing silane coupling agent, antioxidant,
The additives such as antirust agent.
It particularly preferably include the silane coupling agent of glycidyl as silane coupling agent.As concrete example, can enumerate
2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- glycidoxypropyltrime,hoxysilane, 3- glycidoxy
Hydroxypropyl methyl diethoxy silane, 3- epoxy propoxy propyl triethoxysilane, three-(trimethoxy-silylpropyls) are different
Cyanurate etc..They can be used together two kinds or more.The use level of silane coupling agent is relative to acrylic acid series copolymer (A) 100
Mass parts, preferably 0.01~0.5 mass parts, more preferably 0.02~0.5 mass parts, particularly preferably 0.03~0.3 mass
Part.
As antioxidant, particularly preferably hindered phenolic antioxidant.The use level of antioxidant is relative to acrylic acid
100 mass parts of based copolymer (A), preferably 0.01~1 mass parts, more preferably 0.02~0.5 mass parts.
As antirust agent, such as imidazole compound, three azole compounds, four azole compounds, thiadiazoles can be used
Based compound.Wherein, preferably three azole compounds.As the concrete example of three azole compounds, benzotriazole, 1- ammonia can be enumerated
Base benzotriazole, 5- amino benzotriazole.Particularly preferably benzotriazole.The use level of antirust agent (F) is relative to acrylic acid series
100 mass parts of copolymer (A), preferably 0.1~10 mass parts, more preferably 0.3~5 mass parts, particularly preferably 0.5~3
Mass parts.
Electric conductivity adhesion agent composition of the invention also can according to need comprising silane coupling agent described above, antioxygen
Other additives other than agent, antirust agent.Specifically, the electric conductivity adhesion for being known to make an addition to the type can be added
Such as tackifier, plasticizer, softening agent, matal deactivator, pigment in agent composition.Moreover, by suitably changing various add
It is hard can to adjust the hardometer of electric conductivity adhesion agent composition of the invention at high temperature (85 DEG C) for type, the additive amount for adding agent
Degree.
< electric conductivity adhesive tape >
Electric conductivity adhesive tape of the invention has in the one or both sides of conductive substrate is adhered by electric conductivity of the invention
The adhering agent layer that agent composition is formed.The electric conductivity of the substrate also contributes to the effect for inhibiting the effect of static electrification, shielding electromagnetic wave
Fruit.As conductive substrate, preferably made of metal substrate (especially metal foil), electric conductivity nonwoven substrate, electric conductivity cloth
Substrate.As the concrete example for the metal for constituting conductive substrate, copper, aluminium, nickel, stainless steel, iron, chromium, titanium can be enumerated.Wherein, excellent
It is selected as copper, aluminium, most preferably copper.The thickness of conductive substrate is preferably 3~50 μm, and more preferably 5~35 μm, particularly preferably
6~20 μm.
The thickness of adhering agent layer is preferably 2~100 μm, more preferably 3~50 μm, particularly preferably 5~30 μm, most preferably
It is 7~20 μm.Adhering agent layer can only be formed in the one side of conductive substrate, can also be formed in two sides and two-sided adhesion is made
Band.
Adhering agent layer can be formed by making electric conductivity adhesion agent composition of the invention carry out cross-linking reaction.For example,
Electric conductivity adhesion agent composition can be coated on conductive substrate, so that it is carried out cross-linking reaction by heating, in electric conductivity
Adhering agent layer is formed on substrate.In addition it is also possible to which electric conductivity adhesion agent composition is coated on processing release paper or other films, pass through
Heating makes it carry out cross-linking reaction, forms adhering agent layer, the adhering agent layer is made to fit in the one or both sides of conductive substrate.It leads
The coating of electrical adhesion agent composition can be used for example, roll coater, die coating machine, lip coating machine (lip coater) etc.
Apparatus for coating.In the case where being heated after coating, it also can use heating and carry out removing electric conductivity while cross-linking reaction
Solvent in adhesion agent composition.
As described above, electric conductivity adhesion agent composition of the invention is used as and is used to form conductive substrate
Material with the adhering agent layer of the electric conductivity adhesive tape of adhering agent layer is highly useful.However, electric conductivity of the invention is adhered
The purposes of agent composition is without being limited thereto.For example, electric conductivity adhesion agent composition of the invention can be shaped to sheet, as nothing
The adhesive sheet of occurring matrix type comes using can also make it dissolve and be coated as liquid sticker or bonding agent in solvent to make
With.
Embodiment
Hereinafter, enumerating embodiment and comparative example, illustrate the present invention in further detail.In the following record, " part " table
Show mass parts, " % " indicates quality %.
< Production Example 1~5 (modulation of acrylic acid series copolymer (A)) >
Into the reaction unit for having blender, thermometer, reflux cooler and nitrogen ingress pipe, it is added shown in table 1
Ingredient (A1)~(A5) of amount (%), ethyl acetate, as the n-dodecane mercaptan of chain-transferring agent and as peroxide system
0.1 part of the lauryl peroxide of radical polymerization initiator.Nitrogen is enclosed in reaction unit, exist nitrogen while stirring
At 68 DEG C under air-flow, 3 hours polymerization reactions are carried out, then at 78 DEG C, carry out 3 hours polymerization reactions.Then it cools down up to room temperature,
Additional ethyl acetate.The acrylic acid series copolymer of theory T g shown in table 1, weight average molecular weight (Mw) and concentration are obtained as a result,
(A)。
The weight average molecular weight (Mw) of acrylic acid series copolymer (A) is to be gathered the standard of acrylic acid series copolymer by GPC method
The value that the molecular weight of styrene conversion is measured by following measurement device and condition.
Device: LC-2000 series (Japan Spectroscopy Corporation's system)
Column: KF-806M × 2 piece Shodex, KF-802 × 1 piece Shodex
Elutriant: tetrahydrofuran (THF)
Flow velocity: 1.0mL/ minutes
Column temperature: 40 DEG C
Sample volume: 100 μ L
Detector: index meter (RI)
Measurement sample: making acrylic acid series polymeric compounds be dissolved in THF, and the concentration for making acrylic acid series polymeric compounds is 0.5 matter
The solution for measuring % is filtered using filter and removes the sample after waste.
Theory T g is the value calculated by the formula of FOX.
[table 1]
Table 1 (Production Example 1~5 of ingredient (A))
Abbreviation in table 1 indicates following compound.
" MA ": methyl acrylate
" 2-EHA ": 2-EHA
" BA ": n-butyl acrylate
" AA ": acrylic acid
" 4-HBA ": acrylic acid 4- hydroxybutyl
" HEMA ": 2-hydroxyethyl methacrylate
" 2-EHA ": acrylic acid 2- hydroxy methacrylate
" Vac ": vinyl acetate
1 > of < embodiment
Relative to 100 parts of solid component of the acrylic acid series copolymer (A) obtained by Production Example 1, adds and measured shown in table 2
The electroconductive particle (B1), crosslinking agent (C) of (part) are mixed, and electric conductivity adhesion agent composition is modulated.
By the electric conductivity adhesion agent composition by the thickness of the adhering agent layer after drying become 16 μm in a manner of be coated on through
It crosses on the release liner (liner) of organosilicon processing.Then, solvent is removed at 110 DEG C, is dry, and carrying out cross-linking reaction,
Form adhering agent layer.The adhering agent layer is set to fit in electrolytic copper foil (Bo Fen industrial group, FUKUDA METAL system, the commodity of 18 μ m-thicks
Name CF-T9FZ-STD-18) gloss surface side.Then, it is conserved 3 days at 40 DEG C, obtains electric conductivity adhesive tape.
2 > of < embodiment
Relative to 100 parts of solid component of the acrylic acid series copolymer (A) obtained by Production Example 2, adds and measured shown in table 2
The electroconductive particle (B1), crosslinking agent (C) of (part) are mixed, and electric conductivity adhesion agent composition is modulated.Then, with embodiment
1 operates in the same way, and obtains electric conductivity adhesive tape (but adhering agent layer with a thickness of 15 μm).
3 > of < embodiment
Relative to 100 parts of solid component of the acrylic acid series copolymer (A) obtained by Production Example 3, adds and measured shown in table 2
The electroconductive particle (B1), crosslinking agent (C) of (part) are mixed, and electric conductivity adhesion agent composition is modulated.Then, with embodiment
1 operates in the same way, and obtains electric conductivity adhesive tape.
4 > of < embodiment
Relative to 100 parts of solid component of the acrylic acid series copolymer (A) obtained by Production Example 4, adds and measured shown in table 2
The electroconductive particle (B1), crosslinking agent (C) of (part) are mixed, and electric conductivity adhesion agent composition is modulated.Then, with embodiment
1 operates in the same way, and obtains electric conductivity adhesive tape (but adhering agent layer with a thickness of 17 μm).
5 > of < embodiment
Relative to 100 parts of solid component of the acrylic acid series copolymer (A) obtained by Production Example 5, adds and measured shown in table 2
The electroconductive particle (B1), crosslinking agent (C) of (part) are mixed, and electric conductivity adhesion agent composition is modulated.Then, with embodiment
1 operates in the same way, and obtains electric conductivity adhesive tape (but adhering agent layer with a thickness of 17 μm).
6 > of < embodiment
Relative to 100 parts of solid component of the acrylic acid series copolymer (A) obtained by Production Example 1, adds and measured shown in table 2
The electroconductive particle (B2), crosslinking agent (C) of (part) are mixed, and electric conductivity adhesion agent composition is modulated.Then, with embodiment
1 operates in the same way, and obtains electric conductivity adhesive tape.
7 > of < embodiment
Relative to 100 parts of solid component of the acrylic acid series copolymer (A) obtained by Production Example 1, adds and measured shown in table 2
The electroconductive particle (B3), crosslinking agent (C) of (part) are mixed, and electric conductivity adhesion agent composition is modulated.Then, with embodiment
1 operates in the same way, and obtains electric conductivity adhesive tape (but adhering agent layer with a thickness of 17 μm).
1 > of < comparative example
Relative to 100 parts of solid component of the acrylic acid series copolymer (A) obtained by Production Example 5, adds and measured shown in table 2
The electroconductive particle (B1), crosslinking agent (C) of (part) are mixed, and electric conductivity adhesion agent composition is modulated.Then, with embodiment
1 operates in the same way, and obtains electric conductivity adhesive tape (but adhering agent layer with a thickness of 17 μm).
The hardometer of each electric conductivity adhesion agent composition of above embodiments 1~7 and comparative example 1 is measured in accordance with the following methods
Hardness.It shows the result in table 2.
(durometer hardness of electric conductivity adhesion agent composition)
Electric conductivity adhesion agent composition is coated in such a way that the thickness after drying becomes 50 μm and is handled by organosilicon
Release liner on.Then, in 110 DEG C of removing solvents and dry while carries out cross-linking reaction, adhering agent layer is formed, at 40 DEG C
Maintenance 3 days.After maintenance, thickness is stacked to as 6mm, as measurement sample.Ring by the sample of thickness 6mm at 23 DEG C
It is saved under border, measures the 00 type hardness tester meter hardness (23 DEG C) as defined in ASTM D 2240.Further, sample is dry at 85 DEG C
It is saved 1 hour in dry machine, measures the 00 type hardness tester meter hardness (85 DEG C) as defined in ASTM D 2240.
[table 2]
Table 2
Abbreviation in table 2 indicates following electroconductive particle or compound.
" B1 ": (NOVAMET corporation, trade name nickel by powder 525LD, Fig. 1 are length filiform nickel powder B1's to long filiform nickel powder
Electron micrograph.)
" B2 ": (VALE corporation, trade name nickel by powder TYPE123, Fig. 2 are the electronics of spike nickel powder B2 to spike nickel powder
Microscope photo.)
" B3 ": laminar nickel powder (NOVAMET corporation, trade name HCA-1)
" C1 ": isocyanates system crosslinking agent (Tosoh corporation, trade name Coronate (registered trademark) L-45E (solid at
Divide concentration 45%))
< evaluation test >
In accordance with the following methods come evaluate by embodiment and comparative example acquisition electric conductivity adhesive tape resistance value.Result is shown
In table 3.
(resistance to rebound resistance value)
As shown in Fig. 3 (A), the electric conductivity adhesive tape 1 for cutting into width 20mm, length 60mm is made into adhering agent layer 1b
Side is fixed on upward on the resin plate 2 of 40mm × 40mm square.The fixation has used double faced adhesive tape (not shown).Then as schemed
Shown in 3 (B) like that, the protrusion (20mm) of electric conductivity adhesive tape 1 is turned back to upside.In the part of the fold-back, electric conductivity
Substrate 1a (copper foil) is upward.Then as shown in Fig. 3 (C), the exhausted of 10mm wide is pasted in the top half of electric conductivity adhesive tape 1
Marginal zone 3.Then as shown in Fig. 3 (D), by width 10mm, length 80mm tape laminate body 4 in a manner of each prominent 20mm
It is fixed under resin plate 2.The tape laminate body 4 is that 50 μm of thickness of aluminium foil and 125 μm of thickness of polyimide film is made to utilize thickness
Product obtained from the double faced adhesive tape fitting of 50 μm of degree.The fixation uses double faced adhesive tape (not shown), so that the side aluminium foil 4a is upward
Mode fixed.Then, it as shown in Fig. 3 (E), will turn back on the upside of a direction of tape laminate body 4, it will be band-like folded
The end of the aluminium foil 4a of layer body 4 is pasted on the adhering agent layer 1b (bonding area=5mm × 10mm) of electric conductivity adhesive tape 1, utilizes
2kg roller is crimped.Then, by the conductive substrate 1a (copper foil) of the aluminium foil 4a of tape laminate body 4 and electric conductivity adhesive tape 1
It is connected to each testing machine terminal 5.
As described above in test body obtained from operation production, as shown in Figure 4, the aluminium foil 4a of tape laminate body 4
End and electric conductivity adhesive tape 1 adhering agent layer 1b paste.And the bending angle of tape laminate body 4 is big, therefore in logical
It crosses the screen resilience and is applied with the state of the power stretched upwards to adhering agent layer 1b.
After the end of aluminium foil 4a is just pasted with adhering agent layer 1b (after just being crimped using 2kg roller), to flow through 0.1A's
The mode of electric current adjusts voltage, calculates the adhering agent layer 1b after just pasting by R (resistance value)=V (voltage)/I (electric current) formula
Resistance value (m Ω).Then, in 85 DEG C of progress, 24 hours accelerated tests, resistance value (m Ω) is calculated using same procedure.However,
At the time of behind 24 hours of accelerated test, the crimping using 2kg roller is not carried out.
[table 3]
Table 3
Even if result as shown in Table 3 is it is found that the electric conductivity adhesive tape of Examples 1 to 7 is passing through returning for tape laminate body 4
Elastic force and adhering agent layer 1b is applied in the state of the power of through-thickness stretching with 85 DEG C of progress, 24 hours accelerated tests, it is electric
The rising of resistance value is also small.That is, when even if the electric conductivity adhesive tape of Examples 1 to 7 is long with narrow bonding area (5mm × 10mm)
Between (24 hours) expose to the open air under high temperature (85 DEG C), do not generate peeling, wire drawing, the reduction of electric conductivity is also small yet.
On the other hand, the electric conductivity adhesive tape of comparative example 1 is since adhering agent layer is low by the durometer hardness at 85 DEG C
Electric conductivity adhesion agent composition formed, therefore adhering agent layer after accelerated test generates wire drawing, and the rising of resistance value becomes larger,
Electric conductivity is greatly reduced.
Industry utilizability
Electric conductivity adhesion agent composition of the invention is as the material for the adhering agent layer for being used to form electric conductivity adhesive tape
Highly useful.Electric conductivity adhesive tape with such adhering agent layer for example for prevent electronic equipment internal electrostatic,
It is useful in terms of the dysgenic electromagnetic wave shielding of electromagnetic wave, the purposes of ground connection.Even and if being suitable for requiring by inside
Screen resilience and be stretched, it is also difficult to generate peelings, wire drawing, electric conductivity reduction purposes.Specifically, can be very suitably
For such as mobile phone, smart phone, wearable terminal, tablet computer, auto-navigation system, camera, audio-video device, trip
In the various portable electronic devices such as gaming machine, information equipment, carried out miniaturization, filming electronic equipment component.
Symbol description
1: electric conductivity adhesive tape, 1a: conductive substrate, 1b: adhering agent layer, 2: resin plate, 3: insulating tape, 4: tape laminate
Body, 4a: aluminium foil, 5: testing machine terminal.
Claims (7)
1. a kind of electric conductivity adhesion agent composition, containing acrylic acid series copolymer (A) and electroconductive particle (B), by ASTM D
00 type hardness tester meter hardness as defined in 2240 is 15 or more at 85 DEG C.
2. electric conductivity adhesion agent composition according to claim 1, the shape of electroconductive particle (B) is long Filamentous, spike
Or flake.
3. electric conductivity adhesion agent composition according to claim 1, the weight average molecular weight of acrylic acid series copolymer (A) is 45
Ten thousand or more.
4. electric conductivity adhesion agent composition according to claim 1, acrylic acid series copolymer (A) includes 3 mass % or more
Constituent of the carboxyl group-containing monomer as polymer chain.
5. electric conductivity adhesion agent composition according to claim 1, the theory T g of acrylic acid series copolymer (A) is -55 DEG C
Below.
6. a kind of electric conductivity adhesive tape has in the one or both sides of conductive substrate by electric conductivity described in claim 1
The adhering agent layer that adhesion agent composition is formed.
7. electric conductivity adhesive tape according to claim 6, it to be used for electromagnetic wave shielding or the ground connection of electronic equipment internal
Purposes.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2016/068056 WO2017216947A1 (en) | 2016-06-17 | 2016-06-17 | Electroconductive pressure-sensitive adhesive composition and electroconductive pressure-sensitive adhesive tape |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109415608A true CN109415608A (en) | 2019-03-01 |
| CN109415608B CN109415608B (en) | 2021-11-23 |
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| CN201680086775.2A Active CN109415608B (en) | 2016-06-17 | 2016-06-17 | Conductive adhesive composition and conductive adhesive tape |
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| Country | Link |
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| JP (1) | JP6748203B2 (en) |
| KR (1) | KR102306299B1 (en) |
| CN (1) | CN109415608B (en) |
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| JP2018035286A (en) * | 2016-09-01 | 2018-03-08 | パナソニックＩｐマネジメント株式会社 | Conductive resin composition and electronic circuit member using the same |
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| CN101440263A (en) * | 2007-10-10 | 2009-05-27 | 日东电工株式会社 | Double-sided pressure-sensitive adhesive tape or sheet for wiring circuit board and wiring circuit board |
| CN101809105A (en) * | 2007-09-26 | 2010-08-18 | 日东电工株式会社 | Electroconductive pressure-sensitive adhesive tape |
| CN102725369A (en) * | 2010-01-26 | 2012-10-10 | 日东电工株式会社 | Conductive adhesive tape |
| JP2014136778A (en) * | 2013-01-18 | 2014-07-28 | Dic Corp | Conductive adhesive sheet |
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| CN107636106A (en) * | 2015-06-15 | 2018-01-26 | 株式会社寺冈制作所 | Adhesion agent composition and adhesive tape |
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| KR101373569B1 (en) | 2008-01-16 | 2014-03-13 | 한라비스테온공조 주식회사 | Front End Module for Automobile |
| JP5924123B2 (en) | 2012-05-23 | 2016-05-25 | Dic株式会社 | Conductive thin adhesive sheet |
| KR20150010110A (en) | 2013-07-18 | 2015-01-28 | 한국산업기술대학교산학협력단 | Book Dust Removing Apparatus of Stable Book Transfer |
| KR20150010109A (en) | 2013-07-18 | 2015-01-28 | (주) 케이엠팩 | Polymer product for food packaging having bread roasting flavour and the manufacturing method thereof |
| JP6516473B2 (en) | 2014-02-28 | 2019-05-22 | 日東電工株式会社 | Conductive adhesive tape and display device with conductive adhesive tape |
| JP2015196741A (en) * | 2014-03-31 | 2015-11-09 | デクセリアルズ株式会社 | conductive shield tape |
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- 2016-06-17 KR KR1020187036086A patent/KR102306299B1/en active IP Right Grant
- 2016-06-17 JP JP2018523136A patent/JP6748203B2/en active Active
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101809105A (en) * | 2007-09-26 | 2010-08-18 | 日东电工株式会社 | Electroconductive pressure-sensitive adhesive tape |
| CN101440263A (en) * | 2007-10-10 | 2009-05-27 | 日东电工株式会社 | Double-sided pressure-sensitive adhesive tape or sheet for wiring circuit board and wiring circuit board |
| CN102725369A (en) * | 2010-01-26 | 2012-10-10 | 日东电工株式会社 | Conductive adhesive tape |
| JP2014136778A (en) * | 2013-01-18 | 2014-07-28 | Dic Corp | Conductive adhesive sheet |
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| CN107636106A (en) * | 2015-06-15 | 2018-01-26 | 株式会社寺冈制作所 | Adhesion agent composition and adhesive tape |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201800531A (en) | 2018-01-01 |
| JP6748203B2 (en) | 2020-08-26 |
| WO2017216947A1 (en) | 2017-12-21 |
| JPWO2017216947A1 (en) | 2019-04-04 |
| KR102306299B1 (en) | 2021-09-28 |
| CN109415608B (en) | 2021-11-23 |
| TWI756215B (en) | 2022-03-01 |
| KR20190007472A (en) | 2019-01-22 |
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