CN103764780A - Conductive adhesive tape - Google Patents

Conductive adhesive tape Download PDF

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Publication number
CN103764780A
CN103764780A CN201280042413.5A CN201280042413A CN103764780A CN 103764780 A CN103764780 A CN 103764780A CN 201280042413 A CN201280042413 A CN 201280042413A CN 103764780 A CN103764780 A CN 103764780A
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CN
China
Prior art keywords
sensitive adhesive
adhesive tape
binder layer
electroconductive
electroconductive pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201280042413.5A
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Chinese (zh)
Inventor
大学纪二
中尾航大
武藏岛康
古田喜久
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
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Nitto Denko Corp
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Publication date
Priority claimed from JP2011187683A external-priority patent/JP2013049764A/en
Priority claimed from JP2011187682A external-priority patent/JP2013049763A/en
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of CN103764780A publication Critical patent/CN103764780A/en
Pending legal-status Critical Current

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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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/163—Metal in the substrate

Abstract

Provided is a conductive adhesive tape capable of exhibiting stable electrical conductivity even when used over the long-term or in a severe environment. This conductive adhesive tape having an adhesive layer on one surface of a metal foil is characterized in that the proportion of gel in the adhesive layer is 5-69 wt%, and the adhesive layer does not contain a conductive filler. In addition, this conductive adhesive tape having an adhesive layer on one surface of a metal foil is characterized in that the proportion of gel in the adhesive layer is 5-69 wt%, and the adhesive layer does contain a conductive filler. When the conductive adhesive tape is subjected to a heat cycle test, the largest resistance value measured in the first cycle is 1 ohm or less, while the largest resistance value measured in the two-hundredth cycle is not more than five times as large as the largest resistance value measured in the first cycle.

Description

Electroconductive pressure-sensitive adhesive tape
Technical field
The present invention relates to electroconductive pressure-sensitive adhesive tape.More specifically, the present invention relates to the electroconductive pressure-sensitive adhesive tape of purposes of conducting between two positions for making interval etc.
Background technology
Electroconductive pressure-sensitive adhesive tape has electrical conductivity (the particularly electrical conductivity on thickness direction), for by the purposes conducting between two positions at interval, electromagnetic wave shielding purposes etc.As such electroconductive pressure-sensitive adhesive tape, in the past for example known: to comprise tinsel and be arranged on the binder layer (formation of pressure-sensitive adhesive layer) of one side of this tinsel, the binder layer of described tinsel cover side be provided with run through described binder layer and its front end have portion of terminal conducting portion electroconductive pressure-sensitive adhesive tape (for example, referring to patent documentation 1～4), in tinsel, be provided with the electroconductive pressure-sensitive adhesive tape (for example,, referring to patent documentation 5,6) of the binder layer that is dispersed with the electroconductive stuffings such as nickel powder etc.
Prior art document
Patent documentation
Patent documentation 1: the real public clear 63-46980 communique of Japan
Patent documentation 2: Japanese kokai publication hei 8-185714 communique
Patent documentation 3: Japanese kokai publication hei 10-292155 communique
Patent documentation 4: Japanese kokai publication hei 11-302615 communique
Patent documentation 5: TOHKEMY 2004-263030 communique
Patent documentation 6: TOHKEMY 2005-277145 communique
Summary of the invention
Invent problem to be solved
Along with the multifunction of electronics in recent years and the variation of use-pattern, for the electroconductive pressure-sensitive adhesive tape using in such electronics etc., even the electrical conductivity that requires longer-term also to play stably using under harsher envrionment conditions.But in the situation by above-mentioned electroconductive pressure-sensitive adhesive tape for the internal wiring of described electronics etc., the contact resistance that is pasted with the part of electroconductive pressure-sensitive adhesive tape slowly raises, thus produce electrical conductivity through time the problem that declines.Visible, present situation is the electroconductive pressure-sensitive adhesive tape of the electrical conductivity that can play stably when not yet obtaining life-time service or using under harsh envrionment conditions.
Therefore, even the electroconductive pressure-sensitive adhesive tape of the electrical conductivity that also can play stably when the object of the present invention is to provide life-time service or using under harsh envrionment conditions.
For the means of dealing with problems
Therefore, the inventor has carried out research extensively and profoundly, found that, for the electroconductive pressure-sensitive adhesive tape that there is the binder layer that contains electroconductive stuffing or do not contain electroconductive stuffing for the one side side in tinsel, by the gel fraction of above-mentioned binder layer is controlled in specified range, even the electroconductive pressure-sensitive adhesive tape of the electrical conductivity that also can play stably when can obtain life-time service or using, and completed the present invention under harsh envrionment conditions.
That is, the invention provides a kind of electroconductive pressure-sensitive adhesive tape, it is characterized in that, in the one side side of tinsel, have binder layer, described binder layer has the gel fraction of 5～69 % by weight and does not contain electroconductive stuffing.
In addition, sometimes this electroconductive pressure-sensitive adhesive tape is called to " electroconductive pressure-sensitive adhesive tape of first method ".
The electroconductive pressure-sensitive adhesive tape of above-mentioned first method, preferably: the maximum resistance of the 1st circulation of measuring in following thermal cycling test is below 1 Ω and the maximum resistance of the 200th circulation is below 5 times of maximum resistance of the 1st circulation.
Thermal cycling test:
Electroconductive pressure-sensitive adhesive tape is pasted on silvering and makes adhesive portion be of a size of 5mm × 6mm(area 30mm 2), in the electroconductive pressure-sensitive adhesive tape that comprises adhesive portion and silvering, pass into the constant current of 2A, put it into repeat to carry out cooling and heating in thermostatic bath that the mode of following circulation sets, measure continuously the resistance value of described adhesive portion therebetween,
Described circulation is:
Design temperature in groove is cooled to-40 ℃ from 25 ℃, at-40 ℃, keep 10 minutes, then, at 85 ℃, keep 10 minutes after being warmed up to 85 ℃, and cooling reaches 25 ℃ again, using this process as a circulation.
The electroconductive pressure-sensitive adhesive tape of above-mentioned first method, preferably: there is the portion of terminal of exposing on the surface of described binder layer side, the every 30mm of described binder layer 2the total area of the portion of terminal of middle existence is 0.15～5mm 2.
The electroconductive pressure-sensitive adhesive tape of above-mentioned first method, preferably: described portion of terminal is, by offering through hole from described tinsel side, at the protuberance of the surface of described binder layer side formation tinsel, then this protuberance to be folded and the portion of terminal of formation.
The electroconductive pressure-sensitive adhesive tape of above-mentioned first method, preferably: with respect to average area through hole described in each, portion of terminal, be 50,000～500,000 μ m 2.
In addition, the invention provides a kind of electroconductive pressure-sensitive adhesive tape, it is characterized in that, in the one side side of tinsel, have binder layer, described binder layer has the gel fraction of 5～69 % by weight and contains electroconductive stuffing.
In addition, sometimes this electroconductive pressure-sensitive adhesive tape is called to " electroconductive pressure-sensitive adhesive tape of second method ".
The electroconductive pressure-sensitive adhesive tape of above-mentioned second method, preferably: the maximum resistance of the 1st circulation of measuring in following thermal cycling test is below 1 Ω and the maximum resistance of the 200th circulation is below 5 times of maximum resistance of the 1st circulation.
Thermal cycling test:
Electroconductive pressure-sensitive adhesive tape is pasted on silvering and makes adhesive portion be of a size of 5mm × 6mm(area 30mm 2), in the electroconductive pressure-sensitive adhesive tape that comprises adhesive portion and silvering, pass into the constant current of 2A, put it into repeat to carry out cooling and heating in thermostatic bath that the mode of following circulation sets, measure continuously the resistance value of described adhesive portion therebetween,
Described circulation is:
Design temperature in groove is cooled to-40 ℃ from 25 ℃, at-40 ℃, keep 10 minutes, then, at 85 ℃, keep 10 minutes after being warmed up to 85 ℃, and cooling reaches 25 ℃ again, using this process as a circulation.
The electroconductive pressure-sensitive adhesive tape of above-mentioned second method, preferably: it is 2%～5% that rate is exposed on the surface of electroconductive stuffing described in the described adhesive layer surface of measuring by following method.
Rate measuring method is exposed on surface:
Use the 0.5 % by weight ruthenic acid aqueous solution, at room temperature by the described adhesive layer surface steam dyeing of electroconductive pressure-sensitive adhesive tape 30 minutes; Then, use sputter equipment " E-3200 " (Hitachi Ltd.'s system), carry out the Pt-Pd sputter process of described adhesive layer surface, make observation sample;
Use scanning electron microscope (FE-SEM) " S-4800 " (Hitachi Ltd.'s system), at acceleration voltage 5kV, measure under the condition of 200 times of multiplying powers, measure the backscattered electron image (range of observation: 450 × 575 μ m of observing by the described adhesive layer surface side of sample 2);
For obtained backscattered electron image, use image processing software " Winroof " (three paddy business Co., Ltd. systems) to carry out binaryzation, calculate the area ratio of the inorganic layer part that belongs to electroconductive stuffing, thereby measure surface, expose rate.
The electroconductive pressure-sensitive adhesive tape of above-mentioned second method, preferably: the thickness of described binder layer is 10～100 μ m.
The electroconductive pressure-sensitive adhesive tape of above-mentioned second method, preferably: with respect to all solids composition (100 weight part) of the binder layer except electroconductive stuffing, the content of described electroconductive stuffing is 25～250 weight parts.
Above-mentioned electroconductive pressure-sensitive adhesive tape, preferably: described binder layer is served as reasons and contained the binder layer that acrylic polymers forms as the binder composition of base polymer.
Invention effect
Even electroconductive pressure-sensitive adhesive tape life-time service of the present invention or the electrical conductivity that also can play stably while using under harsh envrionment conditions.
Accompanying drawing explanation
Fig. 1 represents the electroconductive pressure-sensitive adhesive tape of the present invention (schematic diagram (sectional view of portion of terminal) of electroconductive pressure-sensitive adhesive tape example a).
Fig. 2 represents the electroconductive pressure-sensitive adhesive tape of the present invention (schematic diagram (vertical view) of electroconductive pressure-sensitive adhesive tape example a).
Fig. 3 partly represents the electroconductive pressure-sensitive adhesive tape of the present invention (schematic diagram of an example of electroconductive pressure-sensitive adhesive tape manufacture method a).
Fig. 4 represents the electroconductive pressure-sensitive adhesive tape of the present invention (schematic diagram (vertical view) of an example of the pin using in electroconductive pressure-sensitive adhesive tape manufacture a).
Fig. 5 represents the electroconductive pressure-sensitive adhesive tape of the present invention (schematic diagram (side-view) of an example of the pin using in electroconductive pressure-sensitive adhesive tape manufacture a).
Fig. 6 partly represents the electroconductive pressure-sensitive adhesive tape of the present invention (schematic diagram (vertical view) of an example of the configuration of the pin using in electroconductive pressure-sensitive adhesive tape manufacture a).
Fig. 7 represents the electroconductive pressure-sensitive adhesive tape of the present invention (schematic diagram (sectional view) of an example of the cylindrical bore of using in electroconductive pressure-sensitive adhesive tape manufacture a), form on the surface of former.
Fig. 8 represents the electroconductive pressure-sensitive adhesive tape of the present invention (schematic diagram (sectional view) of pin and an example of the position relationship of cylindrical bore in electroconductive pressure-sensitive adhesive tape manufacture a), while using formpiston and negative electrode to carry out stamping-out (formation through hole).
Fig. 9 represents that electroconductive pressure-sensitive adhesive tape of the present invention (in the operation 1 of electroconductive pressure-sensitive adhesive tape manufacture method a), has the formpiston of pin of rhombus rectangular pyramid shape and the former with cylindrical bore and form the schematic diagram of one example of protuberance shape during through hole in use.
Figure 10 represents that electroconductive pressure-sensitive adhesive tape of the present invention (in the operation 2 of electroconductive pressure-sensitive adhesive tape manufacture method a), is used scraper plate that protuberance is folding and form the schematic diagram of an example of the mode of portion of terminal.
Figure 11 is illustrated in the manufacture method of existing electroconductive pressure-sensitive adhesive tape, forms the schematic diagram of an example of the mode of portion of terminal by protuberance is carried out to press process.
Figure 12 is the schematic diagram that represents an example of the evaluation substrate using in the thermal cycling test of electroconductive pressure-sensitive adhesive tape.
Figure 13 is the schematic diagram that represents the evaluation equivalent circuit of the circuit in substrate using in the thermal cycling test of electroconductive pressure-sensitive adhesive tape.
Figure 14 is the schematic diagram (sectional view of the adhesive portion 43 of Figure 12) that represents an example of the resistance evaluation sample using in the thermal cycling test of electroconductive pressure-sensitive adhesive tape.
Figure 15 represents that design temperature (thermal cycle conditions) in the thermal cycling test of electroconductive pressure-sensitive adhesive tape is till the curve of second circulation.
Figure 16 is the figure of an example of the curve of the surface temperature (adhesive tape temperature) of envrionment temperature in the chamber that partly represents to measure in the thermal cycling test of embodiment (temperature in groove) and electroconductive pressure-sensitive adhesive tape.
Figure 17 is the schematic diagram (vertical view) that represents an example of the evaluation substrate using in the thermal cycling test of electroconductive pressure-sensitive adhesive tape.
Embodiment
Electroconductive pressure-sensitive adhesive tape of the present invention is to have binder layer in the one side side of tinsel, and the gel fraction of described binder layer is controlled to the one side self adhesive tape in specified range.More specifically, electroconductive pressure-sensitive adhesive tape of the present invention is " in the one side side of tinsel, having binder layer; described binder layer has the gel fraction of 5～69 % by weight and do not contain the electroconductive pressure-sensitive adhesive tape of electroconductive stuffing " or " in the one side side of tinsel, having binder layer, the electroconductive pressure-sensitive adhesive tape that described binder layer has the gel fraction of 5～69 % by weight and contains electroconductive stuffing ".Sometimes above-mentioned " the one side side in tinsel has binder layer, and described binder layer has the gel fraction of 5～69 % by weight and do not contain the electroconductive pressure-sensitive adhesive tape of electroconductive stuffing " is called to " electroconductive pressure-sensitive adhesive tape of first method ".In addition, sometimes above-mentioned " the one side side in tinsel has binder layer, the electroconductive pressure-sensitive adhesive tape that described binder layer has the gel fraction of 5～69 % by weight and contains electroconductive stuffing " is called to " electroconductive pressure-sensitive adhesive tape of second method ".In addition, while in this specification sheets, mentioning " electroconductive pressure-sensitive adhesive tape ", also comprise flap, i.e. " electroconductive adhesive sheet ".In addition, in this specification sheets, sometimes adhesive layer surface is called " adhesive face ".
Below, for the electroconductive pressure-sensitive adhesive tape of the first method in electroconductive pressure-sensitive adhesive tape of the present invention and the electroconductive pressure-sensitive adhesive tape of second method, describe.
[electroconductive pressure-sensitive adhesive tape of first method]
It is 5～69 % by weight and the binder layer that does not contain electroconductive stuffing that the electroconductive pressure-sensitive adhesive tape of first method has gel fraction in the one side side of tinsel.In this specification sheets, sometimes by the binder layer of the electroconductive pressure-sensitive adhesive tape of first method, gel fraction in specified range and the binder layer that does not contain electroconductive stuffing be called " the first binder layer ".
(tinsel)
The tinsel that forms the electroconductive pressure-sensitive adhesive tape of first method is not particularly limited, as long as having the tinsel of self-supporting and demonstration electrical conductivity.As above-mentioned tinsel, for example can enumerate: the tinsel of copper, aluminium, nickel, silver, iron, lead and their alloy etc.Wherein, from the viewpoint of electroconductibility, cost, processibility, consider, preferably aluminium foil, Copper Foil, more preferably Copper Foil.
In addition, above-mentioned tinsel can be implemented various surface treatments.For example, can implement the metallic surface plating processing that utilizes such as zinc-plated, silver-plated, gold-plated.Particularly, from the viewpoint that suppresses to corrode the resistance value rising causing, consider, preferably implement zinc-plated.
As above-mentioned tinsel, particularly preferably implement the Copper Foil (zinc-plated Copper Foil) after zinc-plated.
As the thickness of above-mentioned tinsel, be not particularly limited preferably 10 μ m～100 μ m, more preferably 20 μ m～80 μ m, further preferred 30 μ m～60 μ m.More than thickness being set as to 10 μ m, there is sufficient intensity, therefore workability improves.On the other hand, by thickness being set as below 100 μ m, aspect cost, be favourable.In addition, thickness is 100 μ m when following, and particularly at the electroconductive pressure-sensitive adhesive tape with through hole described later, (electroconductive pressure-sensitive adhesive tape easily forms through hole a), and therefore productivity improves.
(the first binder layer)
As the kind of tackiness agent that forms the first binder layer, be not particularly limited, for example can enumerate: acrylic adhesives, rubber adhesive, vinyl alkyl ethers class tackiness agent, polysiloxane-based tackiness agent, polyester tackiness agent, polyamide-based tackiness agent, polyurethane binding, fluorine-containing type tackiness agent, epoxy adhesive etc.Above-mentioned tackiness agent can be used separately, or is used in combination.In addition, above-mentioned tackiness agent can be the tackiness agent with any form, for example, can be active energy ray curable tackiness agent, solvent-borne type (solution-type) tackiness agent, Emulsion Adhesive, hot-melt type tackiness agent (Hotmelt Adhesive) etc.
Wherein, as the tackiness agent that forms the first binder layer, from the viewpoint of the easiness of thermotolerance, weathering resistance and polymer design, preferably acrylic adhesives.That is, the first binder layer is preferably acrylic adhesives layer.In addition, in this specification sheets, sometimes the acrylic adhesives layer as the first bonding coat is called on " the first acrylic adhesives layer ".
The first binder layer is formed by binder composition.In addition, in this specification sheets, binder composition is the composition that forms binder layer, and its concept comprises the composition that forms tackiness agent.In addition, sometimes the binder composition that forms the first binder layer is called to " the first binder composition ".
Acrylic adhesives layer (the first acrylic adhesives layer) as the first binder layer preferably forms by containing the binder composition (the first acrylic pressure-sensitive adhesive compositions) of acrylic polymers as neccessary composition.The content of the acrylic polymers in the first acrylic adhesives layer (100 % by weight) is not particularly limited, and is preferably 65 % by weight above (for example, 65～100 % by weight), more preferably 70～99 % by weight.In addition, in above-mentioned the first acrylic pressure-sensitive adhesive compositions, except acrylic polymers, can also contain as required other composition (additive) etc.
(methyl) alkyl acrylate that in the first acrylic adhesives layer, contained acrylic polymers is preferably to have straight or branched alkyl is as necessary monomer component (monomer component) and the acrylic polymers forming.In addition, form in the monomer component of aforesaid propylene acids polymkeric substance, can also contain polar functionalities monomer, polyfunctional monomer or other copolymerisable monomer as comonomer composition.By using these comonomer compositions, for example, can improve the adhesive power to adherend, or can improve the cohesive force of binder layer.In addition, the monomer component that forms aforesaid propylene acids polymkeric substance can be only a kind of, can be also two or more.In addition, in this specification sheets, " (methyl) vinylformic acid " refers to " vinylformic acid " and/or " methacrylic acid ".
(following as above-mentioned (methyl) alkyl acrylate with straight or branched alkyl, sometimes referred to as " (methyl) alkyl acrylate "), for example can enumerate: (methyl) alkyl acrylate that the carbonatoms of alkyl is 1～20, as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) aliphatic acrylate, (methyl) vinylformic acid heptadecyl ester, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid nonadecyl ester, (methyl) vinylformic acid eicosyl ester etc.Wherein, (methyl) alkyl acrylate that the carbonatoms of preferred alkyl is 1～12.In addition, above-mentioned (methyl) alkyl acrylate may be used singly or two or more in combination.
Wherein, from considering with the viewpoint of the binding property of substrate surface and the volumetric modulus of elasticity of tackiness agent, as above-mentioned (methyl) alkyl acrylate, (methyl) alkyl acrylate that the carbonatoms of (methyl) alkyl acrylate that is preferably 1～4 by the carbonatoms of alkyl and alkyl is 5～12 is used in combination.That is, the first binder layer is preferably the acrylic adhesives layer of the acrylic polymers that the carbonatoms that contains (methyl) alkyl acrylate using the carbonatoms of alkyl as 1～4 and alkyl forms as necessary monomer component as (methyl) alkyl acrylate of 5～12.Particularly, (methyl) alkyl acrylate that is 1～4 as the carbonatoms of alkyl, preferably n-butyl acrylate.In addition, (methyl) alkyl acrylate that is 5～12 as the carbonatoms of alkyl, preferably 2-EHA, vinylformic acid ester in the different ninth of the ten Heavenly Stems.
As above-mentioned (methyl) alkyl acrylate, when (methyl) alkyl acrylate that the carbonatoms of (methyl) alkyl acrylate that is 1～4 by the carbonatoms of alkyl and alkyl is 5～12 is used in combination, the ratio of (methyl) alkyl acrylate that (methyl) alkyl acrylate that is 1～4 as the carbonatoms of alkyl and the carbonatoms of alkyl are 5～12 [the former: the latter] (weight ratio), be not particularly limited, when but the ratio of (methyl) alkyl acrylate that the carbonatoms of alkyl is 1～4 is too much, sometimes viscosity dies down, binding property declines, on the other hand, the carbonatoms of alkyl is that the ratio of (methyl) alkyl acrylate of 5～12 is when too much, sometimes binder layer is excessively soft, therefore preferred 50:50～90:10, more preferably 60:40～80:20.
Above-mentioned (methyl) alkyl acrylate is not particularly limited with respect to the ratio of the monomer component total amount (100 % by weight) that forms aforesaid propylene acids polymkeric substance, is preferably 50～100 % by weight, more preferably 60～99.9 % by weight.
As above-mentioned polar functionalities monomer, for example can enumerate: carboxyl group-containing monomer (comprising containing anhydride group monomer, as maleic anhydride, itaconic anhydride etc.), as (methyl) vinylformic acid, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid, iso-crotonic acid etc.; Hydroxyl (hydroxy) monomer, as (methyl) hydroxyalkyl acrylate, vinyl alcohol, vinyl carbinols etc. such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, the own esters of (methyl) vinylformic acid 6-hydroxyl; Amide-containing monomer, as (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, N-hydroxyethyl acrylamide etc.; Emulsion stability, as (methyl) acrylic-amino ethyl ester, (methyl) dimethylaminoethyl acrylate, the tertiary fourth amino ethyl ester of (methyl) vinylformic acid etc.; Containing glycidyl monomer, as (methyl) glycidyl acrylate, (methyl) vinylformic acid methyl glycidyl ester etc.; Cyano-containing monomer, as vinyl cyanide, methacrylonitrile etc.; Containing heterocycle vinyl monomer, as NVP, (methyl) acryloyl morpholine, N-vinyl piperidone, N-vinyl piperazine, N-vinyl pyrrole, N-vinyl imidazole etc.; (methyl) alkoxyalkyl acrylate class monomer, as (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid ethoxy ethyl ester etc.; Containing sulfonic group monomer, as sodium vinyl sulfonate etc.; Phosphorous acidic group monomer, as acryloyl phosphoric acid 2-hydroxy methacrylate etc.; Containing imide monomer, as N-cyclohexylmaleimide, sec.-propyl maleimide etc.; Containing isocyanate group monomer, as 2-methylacryoyloxyethyl isocyanic ester etc.Wherein, preferred carboxyl group-containing monomer, hydroxyl monomer, more preferably vinylformic acid, vinylformic acid 4-hydroxyl butyl ester.In addition, above-mentioned polar functionalities monomer may be used singly or two or more in combination.
Above-mentioned polar functionalities monomer is not particularly limited with respect to the ratio of the monomer component total amount (100 % by weight) that forms aforesaid propylene acids polymkeric substance, is preferably 1～30 % by weight, more preferably 3～20 % by weight.More than the ratio of polar functionalities monomer is set as to 1 % by weight, the cohesive force of binder layer improves.On the other hand, by the ratio of polar functionalities monomer is set as below 30 % by weight, the cohesive force of binder layer can be not too high, and binding property improves.
As above-mentioned polyfunctional monomer, for example can enumerate: hexylene glycol two (methyl) acrylate, butyleneglycol two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane three (methyl) acrylate, (methyl) allyl acrylate, (methyl) vinyl acrylate, Vinylstyrene, epoxy acrylate, polyester acrylate, urethane acrylate etc.In addition, above-mentioned polyfunctional monomer may be used singly or two or more in combination.
Above-mentioned polyfunctional monomer is not particularly limited with respect to the ratio of the monomer component total amount (100 % by weight) that forms aforesaid propylene acids polymkeric substance, is preferably 0.5 % by weight following (for example, 0～0.5 % by weight), more preferably below 0～0.3 % by weight.By the ratio of polyfunctional monomer is set as below 0.5 % by weight, the cohesive force of binder layer can be not too high, and binding property improves.In addition, use in the situation of linking agent, can not use polyfunctional monomer, do not use in the situation of linking agent, the ratio of polyfunctional monomer is preferably 0.001～0.5 % by weight, more preferably 0.002～0.1 % by weight.
In addition, as other copolymerisable monomer (being sometimes referred to as below " other copolymerisable monomer ") beyond polar functionalities monomer and polyfunctional monomer, for example can enumerate: there is (methyl) acrylate of alicyclic hydrocarbon radical, as (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate etc.; (methyl) vinylformic acid aryl ester, as (methyl) phenyl acrylate etc.; Vinyl ester, as vinyl-acetic ester, propionate etc.; Aromatic ethenyl compound, as vinylbenzene, Vinyl toluene etc.; Alkene or dienes, as ethene, divinyl, isoprene, iso-butylene etc.; Vinyl ethers, as vinyl alkyl ethers etc.; Vinylchlorid etc.
As the making method of aforesaid propylene acids polymkeric substance, be not particularly limited, can enumerate known or usual polymerization process.For example, aforesaid propylene acids polymkeric substance can be by utilizing known or usual polymerization process that above-mentioned monomer component polymerization is obtained.As above-mentioned polymerization process, for example can enumerate: solution polymerization process, emulsion polymerisation process, bulk polymerization, the polymerization process (active energy beam polymerization process) etc. that utilizes active energy beam to irradiate.Wherein, from viewpoints such as the transparency, water tolerance, costs, consider preferred solution polymerization process, active energy beam polymerization process, more preferably solution polymerization process.
During above-mentioned solution polymerization, can use various common solvents.As such solvent, can enumerate organic solvent, for example: ester class, as ethyl acetate, n-butyl acetate etc.; Arene, as toluene, benzene etc.; Fat hydrocarbon, as normal hexane, normal heptane etc.; Alicyclic hydrocarbon type, as hexanaphthene, methylcyclohexane etc.; Ketone, as methylethylketone, methyl iso-butyl ketone (MIBK) etc.; Deng.In addition, solvent may be used singly or two or more in combination.
The polymerization starter using during the polymerization of aforesaid propylene acids polymkeric substance is not particularly limited, and can from known or usual polymerization starter, suitably select.Can preferably enumerate oil-soluble polymerization initiator, for example: azo polymerization starter, as 2,2 '-Diisopropyl azodicarboxylate, 2, two (4-methoxyl group-2 of 2 '-azo, 4-methyl pentane nitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitriles), 1,1 '-azo two (hexanaphthene-1-formonitrile HCN), 2,2 '-azo two (2,4,4-trimethylpentane), 2, two (2 Methylpropionic acid) dimethyl esters of 2 '-azo etc.; Peroxide polymerization starter, as benzoyl peroxide, tertbutyl peroxide, di-t-butyl peroxide, t-butyl per(oxy)benzoate, dicumyl peroxide, 1, two (the tert-butyl peroxy bases)-3 of 1-, 3,5-trimethyl-cyclohexane, 1, two (tert-butyl peroxy base) cyclododecanes of 1-etc.In addition, polymerization starter may be used singly or two or more in combination.In addition, the usage quantity of polymerization starter is not particularly limited, as long as in the past as the operable scope of polymerization starter.
The weight-average molecular weight of aforesaid propylene acids polymkeric substance is not particularly limited, and is preferably 300,000～1,200,000, and more preferably 350,000～1,000,000, further preferably 400,000～900,000.By the weight-average molecular weight of acrylic polymers is adjusted to more than 300,000, binding property improves.On the other hand, by being adjusted to below 1,200,000, coating improves.The temperature when weight-average molecular weight of acrylic polymers can be by the kind of polymerization starter or its usage quantity, polymerization or time and monomer concentration, monomer dropping speed etc. are controlled.
The first binder composition, particularly the first acrylic pressure-sensitive adhesive compositions preferably contain linking agent.By using linking agent, make the contained base polymer of binder layer (for example, forming the acrylic polymers of the first acrylic adhesives layer) crosslinked, can further improve the cohesive force of binder layer.As linking agent, be not particularly limited, can from known or usual linking agent, suitably select.Can for example preferably enumerate: multifunctional melamine compound (melamine class linking agent), multi-functional epoxy compound's (epoxies linking agent), polyfunctional isocyanate's compound (isocyanates linking agent).Wherein, more preferably isocyanates linking agent, epoxies linking agent, further preferred isocyanate class linking agent.In addition, linking agent may be used singly or two or more in combination.
As above-mentioned isocyanates linking agent, for example can enumerate: lower aliphatic polyisocyanates, as ethylene vulcabond, tetramethylene vulcabond, hexamethylene vulcabond etc.; Alicyclic polyisocyanates class, as cyclopentylidene vulcabond, cyclohexylidene vulcabond, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate etc.; Aromatic polyisocyanate class, as 2,4 toluene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, xylylene diisocyanate etc.; Deng.In addition, can enumerate TriMethylolPropane(TMP)/tolylene diisocyanate affixture [Nippon Polyurethane Industry Co., Ltd.'s system, trade(brand)name " コ ロ ネ ー ト L "], TriMethylolPropane(TMP)/1, the commercially available products such as 6-hexylidene diisocyanate affixture [Nippon Polyurethane Industry Co., Ltd.'s system, trade(brand)name " コ ロ ネ ー ト HL "].
As above-mentioned epoxies linking agent, for example can enumerate: N, N, N ', N '-four glycidyl group m-xylene diamine, diglycidylaniline, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, 1, 6-hexylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol bisthioglycolate glycidyl ether, propylene glycol diglycidyl ether, polyoxyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, the many glycidyl ethers of sorbyl alcohol, the many glycidyl ethers of glycerine, the many glycidyl ethers of tetramethylolmethane, the many glycidyl ethers of Polyglycerine, the many glycidyl ethers of anhydrous sorbitol, trimethylolpropane polyglycidyl ether, hexanodioic acid 2-glycidyl ester, o-phthalic acid diglycidyl ester, three (2-hydroxyethyl) triglycidyl isocyanurate, Resorcinol diglycidyl ether, bisphenol-S diglycidyl base ether, and in molecule, there is epoxy resin of more than two epoxy group(ing) etc.In addition, can enumerate the commercially available product such as trade(brand)name " テ ト ラ ッ De C " that Mitsubishi Gas Chemical Co., Ltd manufactures.
In the first binder composition, the content of linking agent is not particularly limited, for example,, the in the situation that of containing isocyanates linking agent in the first acrylic pressure-sensitive adhesive compositions, with respect to acrylic polymers 100 weight parts, be preferably 0～5 weight part, more preferably 1～3 weight part.In addition, the in the situation that of containing epoxies linking agent in the first acrylic pressure-sensitive adhesive compositions, with respect to acrylic polymers 100 weight parts, be preferably 0.01～1.0 weight part, more preferably 0.02～0.07 weight part.
In addition, from improving fusible viewpoint, consider, the first binder composition, particularly the first acrylic pressure-sensitive adhesive compositions preferably contain tackifier (tackifying resin).As above-mentioned tackifier, for example can enumerate: terpenes tackifier, phenols tackifier, rosin based tackifier, petroleum-type tackifier etc.In addition, as tackifier, can enumerate oligopolymer (polymkeric substance that weight-average molecular weight is less than 20,000).As this oligopolymer, can enumerate such as acrylic acid or the like oligopolymer, styrenic oligopolymer etc.Wherein, as tackifier, preferably rosin based tackifier or acrylic acid or the like oligopolymer.In addition, above-mentioned tackifier may be used singly or two or more in combination.
As above-mentioned terpenes tackifier, for example can enumerate: the terpenoid resins such as α-pinene polymkeric substance, beta-pinene polymer, Dipentine (ジ ペ Application テ Application) polymkeric substance and modification terpenoid resin (for example, terpene phenolic resinoid, phenylethene modified terpenoid resin, aromatic series modification terpenoid resin, hydriding terpene resinoid etc.) that these terpenoid resin modifications (phenol modification, aromatic series modification, hydrogenation modification, hydrocarbon modification etc.) are obtained etc.
In addition, as above-mentioned phenols tackifier, for example can enumerate: various phenols (for example, phenol, meta-cresol, 3, 5-xylenol, to alkylphenol, Resorcinol etc.) with the condenses of formaldehyde (for example, induced by alkyl hydroxybenzene resin, dimethylamino benzophenone air aldehyde resin etc.), above-mentioned phenols and formaldehyde carry out the resole that addition reaction obtains under alkaline catalysts, above-mentioned phenols and formaldehyde carry out the phenolic varnish that condensation reaction obtains under acid catalyst, and rosin based (unmodified rosin, modified rosin, various rosin derivatives etc.) under acid catalyst, carry out addition thermopolymerization and the Abietyl modified phenol resins that obtains etc. with phenol.
In addition, as above-mentioned rosin based tackifier, for example can enumerate: the unmodified rosin such as gum resin, wood rosin, starex (pine gum), utilize hydrogenation, disproportionation, polymerization etc. by these unmodified Abietyl modified and the modified rosin (staybelite, nilox resin, polymerized rosin and other rosin through chemically modified etc.) that obtains and various rosin derivatives etc.In addition, as above-mentioned rosin derivative, for example can enumerate: the rosin ester classes such as the carboxylate of the carboxylate of the rosin unmodified rosin esterification being obtained with alcohols, the modified rosin modified rosin esterifications such as staybelite, nilox resin, polymerized rosin being obtained with alcohols; With unsaturated fatty acids by unmodified rosin or modified rosin (staybelite, nilox resin, polymerized rosin etc.) modification and the unsaturated fatty acids modified rosin class obtaining; Unsaturated fatty acids modified rosin ester class rosin esters modification being obtained with unsaturated fatty acids; Carboxyl in unmodified rosin, modified rosin (staybelite, nilox resin, polymerized rosin etc.), unsaturated fatty acids modified rosin class or unsaturated fatty acids modified rosin ester class is reduced and processed and the rosin alcohols that obtains; The metal-salt of the rosin based such as unmodified rosin, modified rosin, various rosin derivatives (particularly rosin ester class) etc.
In addition, as above-mentioned petroleum-type tackifier, for example can enumerate: fragrant same clan petroleum resin, aliphatic category petroleum resin, alicyclic ring same clan petroleum resin (aliphatics ring-type petroleum resin), aliphatic-aromatic class petroleum resin, aliphatics-alicyclic ring same clan petroleum resin, hydrogenated petroleum resin, coumarone resinoid, coumarone indene resinoid etc.As above-mentioned fragrant same clan petroleum resin, for example can enumerate: to use one or more carbonatomss be only 8～10 containing the polymkeric substance of vinylaromatic hydrocarbon (vinylbenzene, adjacent Vinyl toluene, a Vinyl toluene, to Vinyl toluene, alpha-methyl styrene, Beta-methyl vinylbenzene, indenes, methyl indenes etc.) etc.Wherein, the fragrant same clan petroleum resin (so-called " C9 class petroleum resin ") that preferably obtained by the cuts such as Vinyl toluene or indenes (so-called " C9 petroleum fractions ").In addition, as above-mentioned aliphatic category petroleum resin, for example can enumerate: only use the alkene of one or more carbonatomss 4～5 or the diene [alkene such as 1-butylene, iso-butylene, 1-amylene; The diene such as divinyl, m-pentadiene (1,3-pentadiene), isoprene etc.] polymkeric substance etc.Wherein, the aliphatic category petroleum resin (so-called " C4 class petroleum resin " or " C5 class petroleum resin " etc.) that preferably obtained by the cuts such as divinyl, m-pentadiene or isoprene (so-called " C4 petroleum fractions " or " C5 petroleum fractions " etc.).In addition, as above-mentioned alicyclic ring same clan petroleum resin, for example can enumerate: by the alicyclic hydrocarbon resin that carries out polymerization after aliphatic category petroleum resin (so-called " C4 class petroleum resin " or " C5 class petroleum resin " etc.) Cyclodimerization and obtain, cyclic diene compound (cyclopentadiene, dicyclopentadiene, ethylidene norbornene, Dipentine, ethylidene double-heptene, vinyl suberene, tetrahydro-indenes, vinyl cyclohexene, limonene etc.) polymkeric substance or its hydride, alicyclic hydrocarbon resin that the aromatic nucleus hydrogenation of above-mentioned aromatic hydrocarbon resin or following aliphatic-aromatic class petroleum resin is obtained etc.In addition, as aliphatic-aromatic class petroleum resin, can enumerate vinylbenzene-olefinic copolymer etc.As alicyclic-fragrant same clan petroleum resin, can enumerate so-called " C5/C9 Copolymer petroleum resin " etc.
As above-mentioned tackifying resin, also can enumerate commercially available product, for example, can enumerate trade(brand)name " Ha リ エ ス タ ー " (Ha リ マ changes into Co., Ltd. and manufactures), trade(brand)name " エ ス テ Le ガ system ", " ペ Application セ Le " (Arakawa Chemical Industries, Ltd.'s manufacture), trade(brand)name " リ カ タ ッ Network " (manufacture of the physics and chemistry Off ァ イ of Co., Ltd. Application テ Network) etc.
In the first binder composition, the content of tackifying resin is not particularly limited, for example, and the in the situation that of the first acrylic pressure-sensitive adhesive compositions, with respect to preferably 10～50 weight parts of acrylic polymers (100 weight part), more preferably 15～45 weight parts.
In addition, in the first binder composition (particularly the first acrylic pressure-sensitive adhesive compositions), not damaging in the scope of effect of the present invention, can further contain the known additives such as crosslinking accelerator, antiaging agent, tinting material (pigment, dyestuff etc.), UV light absorber, antioxidant, chain-transfer agent, softening agent, tenderizer, tensio-active agent, antistatic agent, silane coupling agent or solvent (operable solvent the etc. during solution polymerization of above-mentioned acrylic polymers).In addition, not damaging in the scope of effect of the present invention, in the first binder composition (particularly the first acrylic pressure-sensitive adhesive compositions), can contain oligopolymer (polymkeric substance that weight-average molecular weight is less than 20,000 does not comprise the oligopolymer as above-mentioned tackifier).
The first binder composition, is not particularly limited, and can make by known method.For example, can be by the mixing such as acrylic polymers (or acrylic polymers solution), linking agent, solvent, tackifier be made to the first acrylic pressure-sensitive adhesive compositions.
As the formation method of the first binder layer, be not particularly limited, for example can enumerate the first binder composition (particularly the first acrylic pressure-sensitive adhesive compositions) coating (coating) is also dried as required and/or curing method on tinsel or partition.
In addition, the coating (coating) in the formation method of the first binder layer can be used known coating method.For example can enumerate use: the method for the coating machines such as gravure roll coating machine, reverse roll coating machine, touch roll coating machine, immersion roll-coater, metering bar coater, knife coater, spraying machine, comma scraper coating machine, direct coating machine.
The gel fraction of the first binder layer is 5～69 % by weight, preferably 20～69 % by weight, more preferably 35～68 % by weight.More than above-mentioned gel fraction is adjusted to 5 % by weight, can prevents that the cohesive force of binder layer from becoming too small, and can prevent that undercapacity and binder layer from becoming soft.In addition, adhesive attachment binder layer distortion and, so-called " adhesive paste outstanding " outstanding from the end of adherend to blade or while pasting on adherend in the time of can preventing the cutting processing of self adhesive tape.In addition, can prevent life-time service or perk or peel off from adherend while using under harsh envrionment conditions.In addition, can obtain good gluing reliability.On the other hand, by above-mentioned gel fraction is adjusted to below 69 % by weight, can prevents that the cohesive force of binder layer from becoming excessive, and can obtain soft binder layer.In addition, binder layer is easily followed discrepancy in elevation part and jog, can obtain good discrepancy in elevation absorptivity and good gluing reliability.In addition, the tracing ability under adhesivity and the low temperature when pasting on adherend is good.In addition, life-time service or while using under harsh envrionment conditions, even if environmental change is also not easy to reduce the electrical conductivity that can play stably with the contact area of adherend.
In addition, the gel fraction of the first binder layer can be by controls such as the kind of polyfunctional monomer or linking agent or content (usage quantity).
The gel fraction (ratio of the insoluble composition of solvent) of the first binder layer can be used as the insoluble component content of ethyl acetate and obtains.Particularly, can be used as the first binder layer is obtained with respect to the weight fraction (unit: % by weight) of the sample (the first binder layer) before flooding at the lower insoluble composition flooding after 7 days of room temperature (23 ℃) in ethyl acetate.More specifically, above-mentioned gel fraction is the value of calculating by following " measuring method of gel fraction ".
(measuring method of gel fraction)
Get about 0.1g the first binder layer, with porous tetrafluoroethylene sheet (trade(brand)name " NTF1122 ", the Nitto Denko Corp manufactures) parcel of mean pore size 0.2 μ m, then with kite string, tighten, measure weight now, using this weight weight before dipping.In addition, before this dipping, weight is the gross weight of the first binder layer, tetrafluoroethylene sheet and kite string.In addition, measure the total weight of tetrafluoroethylene sheet and kite string, using this weight as packing bag weight.
Then, the first binder layer is tightened and the object (being called " sample ") that obtains is put into the 50ml container that is full of ethyl acetate with tetrafluoroethylene sheet parcel and with kite string, and 23 ℃ standing 1 week (7 days).Then, take out from container sample (ethyl acetate process after), transfer in aluminum cup, in drying machine 130 ℃ dry 2 hours and remove after ethyl acetate, gravimetry, using this weight weight after dipping.
And, by following formula calculated for gel mark.
Gel fraction (% by weight)=(A-B)/(C-B) × 100
In above formula, A is the rear weight of dipping, and B is packing bag weight, and C is weight before flooding.
The thickness of the first binder layer is not particularly limited, preferably 10～80 μ m, more preferably 20～60 μ m, further preferred 20～50 μ m.More than thickness being set as to 10 μ m, the stress producing when pasting easily disperses, thereby be not easy to produce, peels off.On the other hand, by thickness being set as below 80 μ m, miniaturization and filming to product are favourable.Particularly, in the case of the following electroconductive pressure-sensitive adhesive tape with through hole (electroconductive pressure-sensitive adhesive tape a), when the thickness of binder layer is blocked up, (the protuberance of offering through hole and form sinks, protuberance subsides to the direction of stopping up through hole), tinsel can not be exposed on the surface of binder layer side (this phenomenon being called to " erosion being caused by binder layer ") thus, has the tendency that is difficult to increase portion of terminal area.By thickness being set as to, below 80 μ m, can suppress the above-mentioned erosion being caused by binder layer, and can effectively increase the area of portion of terminal, the electrical conductivity that therefore can play stably.
The thickness of the electroconductive pressure-sensitive adhesive tape of first method is not particularly limited, preferably 20～180 μ m, more preferably 40～140 μ m, further preferred 50～110 μ m.More than above-mentioned thickness is set as to 20 μ m, there is sufficient belt strength, workability improves.On the other hand, by above-mentioned thickness being set as below 180 μ m, filming and miniaturization to product are favourable.In addition, above-mentioned " thickness of electroconductive pressure-sensitive adhesive tape " refers to metal foil surface (not having the surface of a side of binder layer metal foil surface) from the electroconductive pressure-sensitive adhesive tape thickness to adhesive face.
In addition, in the electroconductive pressure-sensitive adhesive tape of first method, except above-mentioned tinsel, binder layer, not damaging in the scope of effect of the present invention, can there is other layer (for example, middle layer, undercoat etc.).
As the preferred concrete mode of the electroconductive pressure-sensitive adhesive tape of first method, be not particularly limited, can preferably enumerate: the one side side in tinsel has the first binder layer, there is the portion of terminal of exposing on the surface of the first binder layer side, by the every 30mm of the first binder layer (surface of the first binder layer side) 2the total area of the portion of terminal of middle existence controls to 0.15～5mm 2electroconductive pressure-sensitive adhesive tape (following, the electroconductive pressure-sensitive adhesive tape of this concrete mode is called to " electroconductive pressure-sensitive adhesive tape A ").
Above-mentioned " portion of terminal " metal part (also comprising the oxidized situation in surface of metal part) for exposing on the surface of the first binder layer side of electroconductive pressure-sensitive adhesive tape A, and for electroconductive pressure-sensitive adhesive tape A in the part that conducts of tinsel.Particularly, refer to while observing electroconductive pressure-sensitive adhesive tape A from the first adhesive layer surface side the metal part of exposing.
Electroconductive pressure-sensitive adhesive tape A has such portion of terminal, while therefore pasting on adherend described at least a portion of portion of terminal contact with adherend, can guarantee thus conducting between adherend and the tinsel of electroconductive pressure-sensitive adhesive tape A.That is, described portion of terminal plays the effect of the electrical conductivity on performance thickness direction in electroconductive pressure-sensitive adhesive tape A.Wherein, as described portion of terminal, from performance thickness direction, the viewpoint of stable electroconductibility is considered, be preferably the portion of terminal being formed by the part of tinsel that forms electroconductive pressure-sensitive adhesive tape, a part for the tinsel by forming electroconductive pressure-sensitive adhesive tape is exposed the portion of terminal forming on the surface of the first binder layer side.
The every 30mm of the first binder layer in electroconductive pressure-sensitive adhesive tape A 2the total area (the every 30mm in surface of the first binder layer side of the portion of terminal of middle existence 2the total area of the portion of terminal of middle existence) (following, sometimes referred to as " total area of portion of terminal ") be 0.15～5mm 2, preferably 0.3～5mm 2, more preferably 0.4～5mm 2.By the total area of described portion of terminal is adjusted to 0.15mm 2above, the resistance value that can prevent life-time service or use contact area that cause, that follow portion of terminal and adherend (below sometimes referred to as " contact area ") to reduce under severe rugged environment sharply rises, the electrical conductivity that can play stably.On the other hand, by the total area of described portion of terminal is adjusted to 5mm 2below, the binding property of adherend is improved.In addition, " area of portion of terminal " refers to while observing the first binder layer side surperficial of electroconductive pressure-sensitive adhesive tape A from direction perpendicular to the first adhesive layer surface, the area of the metal part (portion of terminal) of exposing.That is, refer to when observing the first binder layer side surperficial perpendicular to the direction of the first adhesive layer surface the shadow area of portion of terminal.
The total area of above-mentioned portion of terminal is not particularly limited, for example, and can be by the every 30mm of the first binder layer 2whole portion of terminal of middle existence are measured area (shadow area) separately, and they are sued for peace to measure.More specifically, can measure by routine method described as follows.
[measuring method of the total area of portion of terminal]
Electroconductive pressure-sensitive adhesive tape is cut into long 6mm × wide 5mm(area: 30mm 2) size, set it as working sample.
(the キ ー エ of Co., Ltd. Application ス manufactures to use digital microscope, model " VHX-600 "), to measure 200 times of multiples (lens use " VH-Z20 "), observe the surface of the binder layer side of said determination sample, and take the image (image on projection plane) of portion of terminal (the metal part of exposing on the surface of binder layer side).Then, under measurement pattern, specify the region of portion of terminal in described image, and measure the area in this region, measure thus the area of portion of terminal.Similarly, measure the area of all portion of terminal that exist in said determination sample, and by they summations, calculate thus the every 30mm of binder layer 2the total area of the portion of terminal of middle existence.
More specifically, can measure by the method for recording in " area of (3) portion of terminal " in aftermentioned (evaluation).
In addition, when the tape width of electroconductive pressure-sensitive adhesive tape is less than 6mm, for example, can use to make the area of binder layer is 30mm 2mode regulate the working sample that cutting obtains after length to measure, also can be by the area that uses binder layer be less than to 30mm 2working sample measure the value obtaining and be scaled the every 30mm of binder layer 2value measure.
In addition, as the measuring method of the total area of above-mentioned portion of terminal, be not limited to above-mentioned measuring method, for example, also can adopt and measure every arbitrary area (for example 100cm 2deng) binder layer in whole portion of terminal of existing area (shadow area) and by they summations, be then scaled the every 30mm of binder layer 2the method of numerical value.
As the method that forms described portion of terminal in electroconductive pressure-sensitive adhesive tape A, be not particularly limited, for example can enumerate: thereby implement embossing processing from tinsel side, a part for tinsel is exposed on the surface of the first binder layer side, and set it as the method for portion of terminal; From tinsel side, offer through hole, on the surface of the first binder layer side, form the protuberance of tinsel, and set it as the method for portion of terminal; Deng.Wherein, preferably from tinsel side, offer through hole, on the surface of the first binder layer side, form the protuberance of tinsel, and set it as the method for portion of terminal, from the viewpoint of the more stable electrical conductivity of performance, consider, preferably from tinsel side, offer through hole, on the surface of the first binder layer side, form the protuberance of tinsel, then this protuberance is folded and set it as the method for portion of terminal.That is, as the portion of terminal in electroconductive pressure-sensitive adhesive tape A, be preferably by offering through hole from tinsel side, on the surface of the first binder layer side, form the protuberance of tinsel, then this protuberance is folded and the portion of terminal of formation.While forming portion of terminal by aforesaid method, easily by the every 30mm of the first binder layer 2the total area of the portion of terminal of middle existence controls in above-mentioned scope, therefore preferred.
Below, to from tinsel side, offer through hole by above-mentioned, on the surface of the first binder layer side, form the protuberance of tinsel, then this protuberance is folded and set it as the electroconductive pressure-sensitive adhesive tape that the method for portion of terminal obtains and be called " electroconductive pressure-sensitive adhesive tape a ".That is, electroconductive pressure-sensitive adhesive tape a is, portion of terminal, for by offer through hole from tinsel side, forms the protuberance of tinsel on the surface of the first binder layer side, then this protuberance is the folding and electroconductive pressure-sensitive adhesive tape of the portion of terminal that forms.Below, electroconductive pressure-sensitive adhesive tape a is elaborated.But the electroconductive pressure-sensitive adhesive tape of first method is not limited to this.In addition, described " protuberance " refers to while offering above-mentioned through hole in the outstanding tinsel in the surface of the first binder layer side, sometimes also referred to as " burr (バ リ) ".In addition, in this specification sheets, " protuberance is folding " refers to and the tinsel that forms protuberance exposed above-mentioned protuberance bending on the surface of binder layer side.
Electroconductive pressure-sensitive adhesive tape a is the one side self adhesive tape with following formation: the one side side in tinsel has the first binder layer, be provided with the hole (through hole) of running through tinsel and the first binder layer, a part for tinsel is exposed to the surface of the first binder layer side by above-mentioned through hole, and sets it as portion of terminal.By thering is such portion of terminal, can guarantee in tinsel and between to the adhesive face of adherend electrical conductivity (electroconductibility on thickness direction).Fig. 1 and Fig. 2 are the schematic diagram that represents an example of the formation of electroconductive pressure-sensitive adhesive tape a.In Fig. 1 (schematic diagram (sectional view of portion of terminal) of electroconductive pressure-sensitive adhesive tape a), electroconductive pressure-sensitive adhesive tape 13 has the first binder layer 12a in the one side side of tinsel 11, on tinsel 11 and the first binder layer 12a, be provided with through hole 15, a part for tinsel 11 is exposed to the surface of the first binder layer side by through hole 15, form thus portion of terminal 14.Visible, in electroconductive pressure-sensitive adhesive tape a, by through hole 15 and portion of terminal 14, form and play the conducting portion 16 that makes the effect of energising between tinsel 11 and portion of terminal 14.
Fig. 2 is the schematic diagram (vertical view) that represents an example of electroconductive pressure-sensitive adhesive tape a.The position pattern of the through hole 15 in Fig. 2 is so-called scatter diagram case, and for example, the row that can to use the configuration space of length direction be x are arranged with interval y and the pattern of half spacing that staggers between adjacent row.As above-mentioned configuration space x, be not particularly limited, for example preferably 1～5mm, more preferably 2～4mm.In addition, as above-mentioned interval y, be not particularly limited, for example preferably 1～4mm, more preferably 2～3mm.
The every 30mm of the first binder layer in electroconductive pressure-sensitive adhesive tape a 2quantity (density) (the every 30mm in surface of binder layer side of the through hole of middle existence 2the quantity of the through hole of middle existence) be not particularly limited, for example, preferably 3～10/30mm 2, more preferably 3～6/30mm 2.By the quantity of above-mentioned through hole is set as to 3/30mm 2above, the portion of terminal of electroconductive pressure-sensitive adhesive tape and the contact site of adherend increase, even if therefore cause portion of terminal contact area separately reduces using due to life-time service or under harsh envrionment conditions, also can, by keeping enough contacts site to guarantee to conduct, thereby can suppress resistance value, sharply rise.On the other hand, by the quantity of above-mentioned through hole is set as to 10/30mm 2below, electroconductive pressure-sensitive adhesive tape can keep sufficient intensity, thereby workability improves.
The quantity (density) of above-mentioned through hole is not particularly limited, for example, and can for example, by estimating or use the every arbitrary area of counting (, the 30mm such as digital microscope 2, 100cm 2deng) binder layer in the quantity of the through hole that exists, and be scaled as required the every 30mm of binder layer 2in quantity measure.
In electroconductive pressure-sensitive adhesive tape a, with respect to average area each through hole, portion of terminal (following, sometimes referred to as " average area of portion of terminal "), be preferably 50,000～500,000 μ m 2, more preferably 100,000～400,000 μ m 2, further preferred 100,000～300,000 μ m 2.By the average area of portion of terminal being adjusted to 50,000 μ m 2above, the contact area of portion of terminal and adherend increases, even if therefore cause contact area reduces using due to life-time service or under harsh envrionment conditions, also can keep the contact area of sufficient to guarantee electrical conductivity, thus the electrical conductivity that can play stably.On the other hand, by the average area of portion of terminal being adjusted to 500,000 μ m 2below, it is excessive that through hole can not become, and therefore electroconductive pressure-sensitive adhesive tape can keep sufficient intensity, thereby workability improves.
The average area of above-mentioned portion of terminal is not particularly limited, and for example, can pass through the every 30mm of binder layer 2whole portion of terminal of middle existence, measure shadow area separately, and use area (the every 30mm of binder layer that its summation is obtained 2the total area of the portion of terminal of middle existence) divided by the every 30mm of binder layer 2the quantity of the through hole of middle existence is obtained.More specifically, can measure by routine method described as follows.
[measuring method of the average area of portion of terminal]
Electroconductive pressure-sensitive adhesive tape is cut into long 6mm × wide 5mm(area: 30mm 2) size, set it as working sample.
(the キ ー エ of Co., Ltd. Application ス manufactures to use digital microscope, model " VHX-600 "), to measure 200 times of multiples (lens use " VH-Z20 "), observe the surface of the binder layer side of said determination sample, and take the image (image on projection plane) of portion of terminal (the metal part of exposing on the surface of binder layer side).Then, under measurement pattern, specify the region of portion of terminal in above-mentioned image, and measure the area in this region, measure thus the area of portion of terminal.Similarly, measure the area of all portion of terminal that exist in said determination sample, and by they summations, calculate thus the every 30mm of binder layer 2the total area of the portion of terminal of middle existence.
With the total area of the portion of terminal of above-mentioned measurement, divided by the quantity of the through hole existing in said determination sample (can by countings such as range estimation or digital microscopes), can obtain thus with respect to average area each through hole, portion of terminal.
In addition, when the tape width of electroconductive pressure-sensitive adhesive tape is less than 6mm, for example, can use to make the area of binder layer is 30mm 2mode regulate the working sample that cutting obtains after length to measure, also can be by the area that uses binder layer be less than to 30mm 2working sample measure the value obtaining and be scaled the every 30mm of binder layer 2value measure.
In addition, more specifically, can measure by the method for recording in " area of (3) portion of terminal " in aftermentioned (evaluation).
In addition, as the measuring method of the average area of above-mentioned portion of terminal, be not limited to above-mentioned measuring method, for example, also can use and measure every arbitrary area (for example 100cm 2deng) binder layer in whole portion of terminal of existing area (shadow area) and by they summations, then, divided by the method for the quantity of the average through hole existing in above-mentioned binder layer (binder layer of arbitrary area).
As the tinsel that forms electroconductive pressure-sensitive adhesive tape a, can preferably use above-mentioned illustrative tinsel.In addition, about the thickness of above-mentioned tinsel, preferably control in above-mentioned scope.In addition, electroconductive pressure-sensitive adhesive tape a " thickness of tinsel " refers to the thickness that does not form the tinsel of the part of portion of terminal in electroconductive pressure-sensitive adhesive tape a.
As the first binder layer that forms electroconductive pressure-sensitive adhesive tape a, can preferably use above-mentioned illustrative binder layer.In addition, about the thickness of the first binder layer, preferably control in above-mentioned scope.In addition, electroconductive pressure-sensitive adhesive tape a " thickness of the first binder layer " refers to the thickness of the first binder layer of the part that does not form portion of terminal in electroconductive pressure-sensitive adhesive tape a.
In electroconductive pressure-sensitive adhesive tape a, the thickness of the first binder layer is preferably 0.1～10 with respect to the ratio [(thickness of the first binder layer)/(thickness of tinsel)] of the thickness of tinsel, and more preferably 0.2～9, further preferably 0.3～8.By the thickness of the first binder layer is adjusted to more than 0.1 with respect to the ratio of the thickness of tinsel, can obtain the sufficient bounding force of rigidity to base material (tinsel).On the other hand, by the thickness of the first binder layer is adjusted to below 10 with respect to the ratio of the thickness of tinsel, can suppress the above-mentioned erosion being caused by binder layer, and can expand the area of portion of terminal.
As the concrete manufacture method of electroconductive pressure-sensitive adhesive tape a, be not particularly limited, for example can enumerate: the one side side that is at least included in tinsel has on the duplexer of the first binder layer offers through hole from tinsel side, on the surface of the first binder layer, form the operation (sometimes this operation being called to " operation 1 ") of the protuberance of tinsel, then by the operation folding described protuberance manufacture method of (sometimes this operation being called to " operation 2 ").After described operation 2, can comprise as required the operation (sometimes this operation being called to " operation 3 ") of implementing press process.Fig. 3 is the schematic diagram that represents an example of the manufacture method of electroconductive pressure-sensitive adhesive tape a.In figure 11 represents tinsel, and 12a represents the first binder layer.In addition, 15 represent through hole, and 17 represent protuberance, and 14 represent portion of terminal.
The duplexer in the one side side of tinsel with the first binder layer is not particularly limited, and for example, can form the first binder layer by the one side side in tinsel and manufacture.In addition, the operation that forms binder layer in the one side side of tinsel can be implemented respectively with the manufacture of electroconductive pressure-sensitive adhesive tape a, also can as a series of operation (that is, in (the イ Application ラ イ Application) mode of connecting), implement with the manufacture of electroconductive pressure-sensitive adhesive tape a.During as the above-mentioned duplexer of manufacture, in the one side side of tinsel, form the method for the first binder layer, can use the formation method of known usual binder layer, be not particularly limited, for example, can use the formation method of the first above-mentioned binder layer.In addition, now, can directly form on the surface of tinsel the first binder layer (direct method), also can on partition, form after the first binder layer, its transfer printing (stickup), on tinsel, is arranged to the first binder layer (transfer printing) thus on the surface of tinsel.
[operation 1]
In operation 1, in the one side side of tinsel, have on the duplexer of the first binder layer, from tinsel side, offer through hole, on the surface of the first binder layer side, form the protuberance of tinsel.As the method for offering described through hole, be not particularly limited, for example, can enumerate known usual method for punching.Wherein, from the viewpoint that forms uniform through hole, consider, preferably use the through hole formation method of the formpiston that is provided with the pin that is used to form through hole on surface.
As the shape of above-mentioned pin, as long as forming the shape for lugs of through hole, be not particularly limited.For example can enumerate: the prisms (polygon prism) such as the pyramids such as circular cone, triprismo, rectangular pyramid (polygonal pyramid), cylinder, triangular prism, quadrangular or with their similar shapes etc.Wherein, as the shape of above-mentioned pin, from the viewpoint that forms uniform through hole, consider, preferably pyramidal shape.
As the configuration of selling described in above-mentioned formpiston, be not particularly limited, the configuration of the through hole that can have according to electroconductive pressure-sensitive adhesive tape a is suitably selected.For example,, as the interval of the pin corresponding with the length direction (MD) of electroconductive pressure-sensitive adhesive tape a, preferably 1～5mm, more preferably 2～4mm.In addition, as the interval of the pin corresponding with the width (TD) of electroconductive pressure-sensitive adhesive tape, preferably 1～4mm, more preferably 2～3mm.About the position pattern of above-mentioned pin, be not particularly limited, for example, can be configured by the scatter diagram case same with the position pattern of through hole in the electroconductive pressure-sensitive adhesive tape a shown in Fig. 2.
More specifically, the formpiston using when above-mentioned through hole is set, for example can use take the position pattern shown in Fig. 6 (by the configuration space of length direction (length direction of electroconductive pressure-sensitive adhesive tape) as the row of i with interval h, arrange and adjacent row between the stagger scatter diagram case of half spacing) dispose the formpiston of the pin of the rhombus rectangular pyramid shape shown in Fig. 4 and Fig. 5.As the size of the bottom shape (rhombus) of such pin, for example, can use the c in Fig. 4 to be preferably 0.5～3mm, more preferably 0.5～2mm, the d in Fig. 4 is preferably 0.5～3mm, more preferably the pin of 0.5～2mm.In addition, as the bottom surface angle e in Fig. 4, for example, and preferably 30～120 °, more preferably 40～100 °.
In addition, as the height of the f(pin in Fig. 5), be for example preferably 0.5～3mm, more preferably 1～2mm.As the g in Fig. 5, for example, be preferably 0.01～0.5mm, more preferably 0.02～0.4mm.
In addition, as the interval i in Fig. 6, for example, be preferably 1～5mm, more preferably 2～4mm.In addition, as the interval h in Fig. 6, for example, be preferably 1～4mm, more preferably 2～3mm.
Although be not particularly limited, to state in the use formpiston and form in the situation of through hole, preferably combination is used the former with recess corresponding to the shape of the pin having with formpiston.By using such former, can form more easily folding protuberance, there is the tendency that can increase portion of terminal area.The shape and size of the recess that above-mentioned former has, are not particularly limited, and the shape and size of the pin that can have according to formpiston are suitably selected.Particularly, can enumerate the cylindrical bore etc. of cross-sectional shape as shown in Figure 7 of example.The size of the cylindrical bore shown in Fig. 7 is not particularly limited, and for example, can use the j(base diameter in Fig. 7) be the k(degree of depth in 0.5～3mm, Fig. 7) be the cylindrical bore of 0.5～3mm.
One example of pin and the configuration of cylindrical bore when Fig. 8 represents to use the former 22 that has the formpiston 21 of the pin shown in Fig. 4, Fig. 5 and have a cylindrical bore shown in Fig. 7 to carry out stamping-out.
Fig. 9 represents formpiston by using the above-mentioned illustrative pin with rhombus rectangular pyramid shape and has stamping-out that the former of cylindrical bore carries out to process the schematic diagram of an example of the shape of the through hole that forms and protuberance.In this example, through hole be shaped as rhombus, in each this through hole, be formed with four protuberances.
As the concrete grammar that forms through hole by the stamping-out that uses the above-mentioned formpiston that is provided with pin to carry out, for example can enumerate: the duplexer that makes to have the first binder layer in the one side side of tinsel is being formed with required roller (being sometimes referred to as " formpiston roller ") that surface is formed with pin and the roller surface of being configured in the method that the mode that contacts with formpiston roller with the tinsel side of described duplexer between the roller (being sometimes referred to as " former roller ") of recess (hole, ditch etc.) is passed through.
[operation 2]
In operation 2, above-mentioned protuberance (protuberance forming in operation 1) is folded and formation portion of terminal.By protuberance is folding, can increase the area of portion of terminal.As by method folding protuberance, be not particularly limited, from the viewpoint that can effectively increase portion of terminal area, consider, preferably use the method for scraper plate.By using scraper plate, can once fold multiple protuberances, and can they are folding neat.Therefore, can increase the area of the tinsel of exposing on the surface of the first binder layer side, i.e. the area of portion of terminal.Particularly, easily increase with respect to average area each through hole, portion of terminal, therefore can effectively increase the every 30mm of the first binder layer 2the total area of middle portion of terminal.
Figure 10 is illustrated in the manufacture method of electroconductive pressure-sensitive adhesive tape a, uses scraper plate that protuberance is folding and form the schematic diagram of the mode of portion of terminal." direct of travel " in Figure 10 represents the direct of travel of the duplexer with through hole and protuberance obtaining by operation 1, and Figure 11 too.As shown in figure 10, the surface mode relative with the front end of scraper plate 31 with the first binder layer 12a of the duplexer with through hole 15 and protuberance 17 that obtains in operation 1 is configured, the first binder layer 12a is moved with respect to scraper plate 31, utilize thus the front end of scraper plate 31 by folding protuberance 17.Now, in protuberance 17, with respect to through hole 15, be positioned at the protuberance 17a of the direct of travel side of above-mentioned duplexer, conventionally to the direction bending of stopping up through hole 15, therefore the tinsel of protuberance 17a can not exposed on the surface of the first binder layer side, does not form portion of terminal.On the other hand, be positioned at the protuberance 17b of the opposition side of the direct of travel of above-mentioned duplexer with respect to through hole 15, to folding with the direction of the opposite direction side of stopping up through hole 15, therefore the tinsel of protuberance 17b is exposed on the surface of the first binder layer side.That is, by protuberance 17b, form portion of terminal 14.Visible, by utilizing scraper plate that protuberance is folding, can effectively increase with respect to area each through hole, portion of terminal.
On the other hand, Figure 11 is the schematic diagram that represents to form in existing electroconductive pressure-sensitive adhesive tape the mode of portion of terminal.Portion of terminal in existing electroconductive pressure-sensitive adhesive tape, for example, by using the pressure roller 18 shown in Figure 11 that protuberance 17 conquassation of the duplexer with through hole 15 and protuberance 17 are formed.Now, the protuberance 17a of direct of travel side that is positioned at above-mentioned duplexer with respect to through hole 15 in protuberance 17 is conventionally to utilize the form of tinsel that binder layer covers protuberance 17a by conquassation, and therefore the tinsel of protuberance 17a is exposed on the surface of binder layer hardly.On the other hand, with respect to through hole 15, be positioned at the protuberance 17b of the direct of travel opposition side of above-mentioned duplexer, the mode bending that utilizes pressure roller to expose on the surface of binder layer side with tinsel, but simultaneously by conquassation, therefore the major part of the tinsel of protuberance 17b is covered by tackiness agent layer, and result only has a small amount of tinsel to expose on the surface of binder layer side.Visible, for existing manufacture method, can not increase with respect to area each through hole, portion of terminal, the electroconductive pressure-sensitive adhesive tape therefore obtaining by the method can not be by every binder layer 30mm 2the total area of the portion of terminal of middle existence controls in above-mentioned scope, the electrical conductivity that can not play stably.
As the material of above-mentioned scraper plate, be not particularly limited, can enumerate known usual material.For example can enumerate: iron, stainless steel etc.Wherein, from the viewpoint of rigidity, consider preferred iron scraper plate.
As the shape of above-mentioned scraper plate, special restriction useless, for example can enumerate: known usual shape.Wherein, the viewpoint consideration of calm foldable protuberance, preferably using the cross section shown in Figure 10 is scraper plate trapezoidal and that front end is sharp-pointed (so-called sword shape scraper plate).
For example, while using above-mentioned sword shape scraper plate as scraper plate, as its toe angle, be not particularly limited, preferably 10～80 °, more preferably 20～60 °.In addition, as the front-end radius (front end R) of above-mentioned scraper plate, preferably 0.1～1, more preferably 0.2～0.8.In addition, above-mentioned " toe angle " refers to the angle of front end in the cross-sectional shape of sword shape scraper plate, for example, refers to 32 angles that represent in Figure 10.
When above-mentioned protuberance is folding, preferably make the front end of scraper plate contact the first adhesive layer surface completely.This is because by the first adhesive layer surface is contacted completely with the front end of scraper plate, can, from root by protuberance bending, can effectively increase the area of portion of terminal.
When above-mentioned protuberance is folding the first adhesive layer surface with scrape front edge of board angulation, be not particularly limited, for example, preferably 30～80 °, more preferably 40～80 °.In addition, the first adhesive layer surface with scrape front edge of board angulation, for example, refer in Figure 10 33 angles that represent.By being more than 30 ° by above-mentioned angular adjustment, can be from root, protuberance is folding, can effectively increase the area of portion of terminal.When above-mentioned angle is less than 30 °, the front end of scraper plate slides in the mode of the front end that dabs protuberance, thereby has the tendency of folding insufficient area that can not increase portion of terminal.On the other hand, by being below 80 ° by above-mentioned angular adjustment, can prevent breaking of the electroconductive pressure-sensitive adhesive tape that produces when folding protuberance.
The speed that when above-mentioned protuberance is folding, binder layer (duplexer) is moved with respect to scraper plate is not particularly limited, for example, and preferably 1～20m/ minute, more preferably 2～10m/ minute.By being more than 1m/ minute by above-mentioned Speed Setting, productivity improves.On the other hand, by being below 20m/ minute by above-mentioned Speed Setting, can utilize scraper plate stably to carry out the folding of protuberance.In addition, when above-mentioned protuberance is folding, can make as mentioned above binder layer (duplexer) move with respect to scraper plate, also can make scraper plate mobile with respect to binder layer (duplexer).About making the scraper plate speed mobile with respect to binder layer (duplexer), preferably meet above-mentioned scope.
[operation 3]
In operation 3, as required the protuberance after folding in described operation 2 is carried out to press process.By via this operation 3, can make portion of terminal and the first binder layer become smoothly, therefore can easily make portion of terminal contact with adherend, and can improve the tackiness of electroconductive pressure-sensitive adhesive tape to adherend.
As the method for above-mentioned press process, be not particularly limited, can enumerate known customary way.For example can enumerate: use roller, thin plate (Unit plate) etc. press working method.Wherein, from the viewpoint of boosting productivity, consider, preferably use the press process of rolling device.In addition, during press process, preferably with partition, protect the first binder layer.
In the manufacture method of above-mentioned electroconductive pressure-sensitive adhesive tape a, as required, after operation 2 or operation 3, can arrange electroconductive pressure-sensitive adhesive tape is cut into the operation of suitable product width, electroconductive pressure-sensitive adhesive tape is wound as to the various operations such as the operation of drum.
For the electroconductive pressure-sensitive adhesive tape of first method, by the every 30mm of the first binder layer 2the total area control of the portion of terminal of middle existence is 0.15～5.0mm 2, and the resistance value multiple of measuring in above-mentioned thermal cycling test is controlled to below 5 times, for life-time service or under severe rugged environment, use and can bring into play more stable electrical conductivity thus.Infer that this is mainly the reason due to following (1), (2).(1) by increasing the area of each portion of terminal, increase the average area with respect to the portion of terminal of each through hole, even the in the situation that while using at life-time service or under severe rugged environment, contact area slightly reducing, the contact area that also can keep sufficient to guarantee to conduct.(2) by increasing the quantity of the portion of terminal existing in the first binder layer of unit surface, even the in the situation that while using at life-time service or under severe rugged environment, contact area reducing, the contact site that also can keep sufficient to guarantee to conduct.Particularly, by use scraper plate in the formation of portion of terminal, can form the portion of terminal of the size (area) that existing manufacture method can not form (, can obtain the effect of above-mentioned (1)), therefore can effectively obtain the total area of portion of terminal to control to the electroconductive pressure-sensitive adhesive tape in above-mentioned scope.
On the other hand, for existing electroconductive pressure-sensitive adhesive tape, the area that can not increase each portion of terminal (particularly, can not be adjusted to the average area of the portion of terminal with respect to each through hole 50,000 μ m 2above), and when wish increases the total area of portion of terminal by increasing the quantity of portion of terminal, very many through holes need to be set, the intensity of electroconductive pressure-sensitive adhesive tape and binding property significantly decline thus, due to the reason such as above-mentioned, and can not be by every binder layer 30mm 2the total area of the portion of terminal of middle existence controls to 0.15～5.0mm 2.Therefore,, when existing electroconductive pressure-sensitive adhesive tape is used at life-time service or under harsh environment, the contact area of adherend and portion of terminal is reduced to the degree that hinders conducting, resistance value rising thus, the electrical conductivity that can not play stably.Reducing of such adherend and the contact area of portion of terminal, supposition is owing to producing (or sneaking into) small bubble in binder layer when the manufacture of electroconductive pressure-sensitive adhesive tape or when pasting on adherend, near the bubble existing portion of terminal according to the variation of envrionment temperature etc. repeatedly expands and shrinks, thus on the contact surface of adherend and portion of terminal stress application and the phenomenon that produces.
In addition, electroconductive pressure-sensitive adhesive tape A or electroconductive pressure-sensitive adhesive tape aat the first binder layer side surface, there is portion of terminal, the gel fraction of the first binder layer is 5～69 % by weight, the first binder layer has sufficient intensity, flexibility is good, and gluing reliability is good, therefore when the manufacture of electroconductive pressure-sensitive adhesive tape or when pasting on adherend, be not easy to sneak into bubble.In addition, even if infer and produce (or sneaking into) small bubble in binder layer, near the bubble existing portion of terminal according to the variation of envrionment temperature etc. repeatedly expands and shrinks, thereby stress application on the contact surface of adherend and portion of terminal, also can suppress the reducing of contact area of adherend and portion of terminal.
[electroconductive pressure-sensitive adhesive tape of second method]
It is 5～69 % by weight and the binder layer that contains electroconductive stuffing that the electroconductive pressure-sensitive adhesive tape of second method has gel fraction in the one side side of tinsel.In this specification sheets, sometimes by the binder layer of the electroconductive pressure-sensitive adhesive tape of second method, gel fraction in specific scope and the binder layer that contains electroconductive stuffing be called " the second binder layer ".
(tinsel)
The tinsel of electroconductive pressure-sensitive adhesive tape that forms second method can be used the tinsel same with the tinsel of electroconductive pressure-sensitive adhesive tape that forms first method.The tinsel that forms the electroconductive pressure-sensitive adhesive tape of second method is not particularly limited, as long as having the tinsel of self-supporting and demonstration electrical conductivity.As above-mentioned tinsel, for example can use: the tinsel of copper, aluminium, nickel, silver, iron, lead and their alloy etc.Wherein, from the viewpoint of electroconductibility, cost, processibility, consider, preferably aluminium foil, Copper Foil, more preferably Copper Foil.
In addition, above-mentioned tinsel can be implemented various surface treatments.For example, can implement the metallic surface plating processing that utilizes such as zinc-plated, silver-plated, gold-plated.Particularly, from the viewpoint that suppresses to corrode the resistance value rising causing, consider, preferably implement zinc-plated.
As above-mentioned tinsel, particularly preferably implement the Copper Foil (zinc-plated Copper Foil) after zinc-plated.
As the thickness of above-mentioned tinsel, be not particularly limited preferably 10 μ m～100 μ m, more preferably 20 μ m～80 μ m, further preferred 30 μ m～60 μ m.More than thickness being set as to 10 μ m, there is sufficient intensity, therefore workability improves.On the other hand, by thickness being set as below 100 μ m, aspect cost, be favourable.In addition, thickness is 100 μ m when following, aspect productivity, is favourable.
(the second binder layer)
As the kind of tackiness agent that forms the second binder layer, be not particularly limited, can enumerate for example as the illustrative tackiness agent of tackiness agent that forms the first binder layer.Above-mentioned tackiness agent can be used separately, or is used in combination.In addition, above-mentioned tackiness agent can be the tackiness agent with any form, for example, can be active energy ray curable tackiness agent, solvent-borne type (solution-type) tackiness agent, Emulsion Adhesive, hot-melt type tackiness agent (Hotmelt Adhesive) etc.
Wherein, as the tackiness agent that forms the second binder layer, from the viewpoint of the easiness of thermotolerance, weathering resistance and polymer design, preferably acrylic adhesives.That is, the second binder layer is preferably acrylic adhesives layer.In addition, in this specification sheets, sometimes the acrylic adhesives layer as the second bonding coat is called on " the second acrylic adhesives layer ".
The second binder layer is formed by binder composition.In addition, in this specification sheets, sometimes the binder composition that forms the second binder layer is called to " the second binder composition ".
Acrylic adhesives layer (the second acrylic adhesives layer) as the second binder layer preferably forms by containing second binder composition (the second acrylic pressure-sensitive adhesive compositions) of acrylic polymers as neccessary composition.The content of the acrylic polymers in the second acrylic adhesives layer is not particularly limited, and is preferably 30 % by weight above (for example, 30～100 % by weight), more preferably 45～99 % by weight, further preferred 55～98 % by weight.
In the second acrylic adhesives layer, to be preferably to have (methyl) alkyl acrylate of straight or branched alkyl be the acrylic polymers that necessary monomer component (monomer component) forms to contained acrylic polymers.In addition, form in the monomer component of aforesaid propylene acids polymkeric substance, can also contain polar functionalities monomer, polyfunctional monomer or other copolymerisable monomer as comonomer composition.By using these comonomer compositions, for example, can improve the adhesive power to adherend, or can improve the cohesive force of binder layer.In addition, the monomer component that forms aforesaid propylene acids polymkeric substance can be only a kind of, can be also two or more.
As above-mentioned (methyl) alkyl acrylate with straight or branched alkyl ((methyl) alkyl acrylate), for example can enumerate: as monomer component illustrative (methyl) alkyl acrylate that forms acrylic polymers contained in the first acrylic adhesives layer.Wherein, (methyl) alkyl acrylate that the carbonatoms of preferred alkyl is 1～12.In addition, above-mentioned (methyl) alkyl acrylate may be used singly or two or more in combination.
Particularly, from considering with the viewpoint of the binding property of substrate surface and the volumetric modulus of elasticity of tackiness agent, as above-mentioned (methyl) alkyl acrylate, (methyl) alkyl acrylate that the carbonatoms of (methyl) alkyl acrylate that is preferably 1～4 by the carbonatoms of alkyl and alkyl is 5～12 is used in combination.That is, the second binder layer is preferably the acrylic adhesives layer of the acrylic polymers that the carbonatoms that contains (methyl) alkyl acrylate using the carbonatoms of alkyl as 1～4 and alkyl forms as necessary monomer component as (methyl) alkyl acrylate of 5～12.Particularly, (methyl) alkyl acrylate that is 1～4 as the carbonatoms of alkyl, preferably n-butyl acrylate.In addition, (methyl) alkyl acrylate that is 5～12 as the carbonatoms of alkyl, preferably 2-EHA, vinylformic acid ester in the different ninth of the ten Heavenly Stems.
As above-mentioned (methyl) alkyl acrylate, when (methyl) alkyl acrylate that the carbonatoms of (methyl) alkyl acrylate that is 1～4 by the carbonatoms of alkyl and alkyl is 5～12 is used in combination, the ratio of (methyl) alkyl acrylate that (methyl) alkyl acrylate that is 1～4 as the carbonatoms of alkyl and the carbonatoms of alkyl are 5～12 [the former: the latter] (weight ratio), be not particularly limited, when but the ratio of (methyl) alkyl acrylate that the carbonatoms of alkyl is 1～4 is too much, sometimes viscosity dies down, thereby binding property declines, on the other hand, the carbonatoms of alkyl is that the ratio of (methyl) alkyl acrylate of 5～12 is when too much, sometimes binder layer is excessively soft, therefore preferred 50:50～90:10, more preferably 60:40～80:20.
Above-mentioned (methyl) alkyl acrylate, with respect to the ratio of the monomer component total amount (100 % by weight) of formation aforesaid propylene acids polymkeric substance, is not particularly limited, and is preferably 50～100 % by weight, more preferably 60～99.9 % by weight.
As above-mentioned polar functionalities monomer, can enumerate for example as the illustrative polar functionalities monomer of monomer component that forms acrylic polymers contained in the first acrylic adhesives layer.Wherein, preferred carboxyl group-containing monomer, hydroxyl monomer, more preferably vinylformic acid, vinylformic acid 4-hydroxyl butyl ester.In addition, above-mentioned polar functionalities monomer may be used singly or two or more in combination.
Above-mentioned polar functionalities monomer is not particularly limited with respect to the ratio of the monomer component total amount (100 % by weight) that forms aforesaid propylene acids polymkeric substance, is preferably 1～30 % by weight, more preferably 3～20 % by weight.More than the ratio of polar functionalities monomer is set as to 1 % by weight, the cohesive force of binder layer improves.On the other hand, by the ratio of polar functionalities monomer is set as below 30 % by weight, the cohesive force of binder layer can be not too high, and binding property improves.
In addition, as above-mentioned polyfunctional monomer, can enumerate for example as the illustrative polyfunctional monomer of monomer component that forms acrylic polymers contained in the first acrylic adhesives layer.In addition, above-mentioned polyfunctional monomer may be used singly or two or more in combination.
Above-mentioned polyfunctional monomer is not particularly limited with respect to the ratio of the monomer component total amount (100 % by weight) that forms aforesaid propylene acids polymkeric substance, is preferably 0.5 % by weight following (for example, 0～0.5 % by weight), more preferably below 0～0.3 % by weight.By the ratio of polyfunctional monomer is set as below 0.5 % by weight, the cohesive force of binder layer can be not too high, and binding property improves.In addition, use in the situation of linking agent, can not use polyfunctional monomer, do not use in the situation of linking agent, the ratio of polyfunctional monomer is preferably 0.001～0.5 % by weight, more preferably 0.002～0.1 % by weight.
In addition, as other copolymerisable monomer beyond polar functionalities monomer and polyfunctional monomer, can enumerate for example as illustrative other copolymerisable monomer of monomer component that forms acrylic polymers contained in the first acrylic adhesives layer.
As the making method of aforesaid propylene acids polymkeric substance, be not particularly limited, can enumerate known or usual polymerization process.For example, aforesaid propylene acids polymkeric substance can be by utilizing known or usual polymerization process that above-mentioned monomer component polymerization is obtained.As above-mentioned polymerization process, for example can enumerate: solution polymerization process, emulsion polymerisation process, bulk polymerization, the polymerization process (active energy beam polymerization process) etc. that utilizes active energy beam to irradiate.Wherein, from viewpoints such as the transparency, water tolerance, costs, consider preferred solution polymerization process, active energy beam polymerization process, more preferably solution polymerization process.
During above-mentioned solution polymerization, can use various common solvents.As such solvent, can enumerate the illustrative solvent of solvent using when for example conduct is made acrylic polymers contained in the first acrylic adhesives layer by solution polymerization.In addition, solvent may be used singly or two or more in combination.
The polymerization starter using during the polymerization of aforesaid propylene acids polymkeric substance is not particularly limited, and can from known or usual polymerization starter, suitably select.For example can enumerate: the illustrative polymerization starter of polymerization starter using during as the polymerization of acrylic polymers contained in the first acrylic adhesives layer.In addition, polymerization starter may be used singly or two or more in combination.In addition, the usage quantity of polymerization starter is not particularly limited, as long as in the past as the operable scope of polymerization starter.
The weight-average molecular weight of aforesaid propylene acids polymkeric substance is not particularly limited, and is preferably 300,000～1,200,000, and more preferably 350,000～1,000,000, further preferably 400,000～900,000.By the weight-average molecular weight of acrylic polymers is adjusted to more than 300,000, binding property improves.On the other hand, by being adjusted to below 1,200,000, coating improves.The controls such as the kind that the weight-average molecular weight of acrylic polymers can be by polymerization starter or temperature when its usage quantity, polymerization or time and monomer concentration, monomer dropping speed.
The second binder layer contains electroconductive stuffing (electroconductive particle).The second binder layer of the electroconductive pressure-sensitive adhesive tape of second method contains electroconductive stuffing, therefore pastes on adherend, easily guarantees conducting between the tinsel of electroconductive pressure-sensitive adhesive tape of adherend and second method.The second binder composition, particularly the second acrylic pressure-sensitive adhesive compositions preferably contain electroconductive stuffing.
As above-mentioned electroconductive stuffing, be not particularly limited, for example can enumerate: the filler (metallic stuffing, metallics) that comprises the metals such as nickel, iron, chromium, cobalt, aluminium, indium, antimony, molybdenum, tin, zinc, titanium, copper, silver, platinum, gold; The alloy that comprises above-mentioned metal or the filler of oxide compound etc.In addition, as above-mentioned electroconductive stuffing, for example can enumerate: the filler (carbon particles) that carbon black, carbon nanotube etc. comprises carbon; The filler (metallic cover filler) obtaining with above-mentioned metallic cover polymeric beads, resin etc. etc.In addition, electroconductive stuffing may be used singly or two or more in combination.
Wherein, above-mentioned electroconductive stuffing, considers preferable alloy filler, metallic cover filler, more preferably silver fillers (silver particles) from the viewpoint of long-term conducting reliability.
As the shape of above-mentioned electroconductive stuffing, be not particularly limited, from viewpoint dispersed binder layer, that have binding property and electrical conductivity concurrently, consider, for example preferred spherical, spike is more preferably spherical.In addition, above-mentioned electroconductive stuffing can only consist of single shape, also can consist of two or more shapes.For example, above-mentioned electroconductive stuffing can only consist of spherical electroconductive stuffing, also can consist of the electroconductive stuffing of spherical electroconductive stuffing and spike.
The length-to-diameter ratio of above-mentioned electroconductive stuffing is not particularly limited, for example, and preferably 1.0～2.0, more preferably 1.0～1.5.In addition, above-mentioned length-to-diameter ratio can be passed through scanning electron microscope (SEM) mensuration.
In addition, electroconductive stuffing can be used commercially available product.For example can enumerate: trade(brand)name " Ag-HWQ-400 " (Fukuda Metal Foil & POwder Co., Ltd. manufactures, silver fillers) etc.
In the second binder composition, the content of electroconductive stuffing is not particularly limited, all solids composition (100 weight part) with respect to the binder composition except electroconductive stuffing is preferably 25～250 weight parts, more preferably 30～150 weight parts, further preferred 35～100 weight parts.More than the content of electroconductive stuffing is set as to 25 weight parts, electrical conductivity improves.On the other hand, by the content of electroconductive stuffing being set as to, below 250 weight parts, can suppress the cohesion of electroconductive stuffing, adhesive face can be too not coarse, therefore can have long-term conducting reliability and bounding force concurrently.In addition, aspect cost, be also favourable.
The second binder composition, particularly the second acrylic pressure-sensitive adhesive compositions preferably contain linking agent.By using linking agent, make the contained base polymer of binder layer (for example forming the acrylic polymers of the second acrylic adhesives layer) crosslinked, can further improve the cohesive force of binder layer.As above-mentioned linking agent, be not particularly limited, for example can enumerate: as the illustrative linking agent of the linking agent containing in the first binder composition.Wherein, above-mentioned linking agent is isocyanates linking agent, epoxies linking agent more preferably, further preferred isocyanate class linking agent.In addition, above-mentioned linking agent may be used singly or two or more in combination.
In the second binder composition, the content of linking agent is not particularly limited, and for example, the in the situation that of the second acrylic pressure-sensitive adhesive compositions, with respect to acrylic polymers 100 weight parts, is preferably 0～5 weight part, more preferably 1～3 weight part.
In addition, the second binder layer composition, particularly the second acrylic pressure-sensitive adhesive compositions preferably contain tackifier.As above-mentioned tackifier, be not particularly limited, for example can enumerate: as the illustrative tackifier of tackifier contained in the first binder composition.In addition, as tackifier, can enumerate oligopolymer (polymkeric substance that weight-average molecular weight is less than 20,000).As this oligopolymer, can enumerate such as acrylic acid or the like oligopolymer, styrenic oligopolymer etc.Wherein, as tackifier, preferably rosin based tackifier or acrylic acid or the like oligopolymer.In addition, above-mentioned tackifier may be used singly or two or more in combination.
In the second binder composition, the content of tackifying resin is not particularly limited, for example, and the in the situation that of the second acrylic pressure-sensitive adhesive compositions, with respect to preferably 10～50 weight parts of acrylic polymers (100 weight part), more preferably 15～45 weight parts.
In addition, in the second binder composition, particularly the second acrylic pressure-sensitive adhesive compositions, not damaging in the scope of effect of the present invention, can contain the known additives such as crosslinking accelerator, antiaging agent, tinting material (pigment, dyestuff etc.), UV light absorber, antioxidant, chain-transfer agent, softening agent, tenderizer, tensio-active agent, antistatic agent, silane coupling agent or solvent (operable solvent the etc. during solution polymerization of above-mentioned acrylic polymers).In addition, not damaging in the scope of effect of the present invention, in the second binder composition (particularly the second acrylic pressure-sensitive adhesive compositions), can contain oligopolymer (polymkeric substance that weight-average molecular weight is less than 20,000 does not comprise the oligopolymer as above-mentioned tackifier).
The second binder composition, is not particularly limited, and can make by known method.For example, can be by the mixing such as acrylic polymers (or acrylic polymers solution), linking agent, solvent, tackifier be made to the second acrylic pressure-sensitive adhesive compositions.
As the formation method of the second binder layer, be not particularly limited, for example can enumerate the second binder composition (particularly the second acrylic pressure-sensitive adhesive compositions) coating (coating) is also dried as required and/or curing method on tinsel or partition.
In addition, the coating (coating) in the formation method of the second binder layer can be used known coating method.For example can enumerate use: the method for the coating machines such as gravure roll coating machine, reverse roll coating machine, touch roll coating machine, immersion roll-coater, metering bar coater, knife coater, spraying machine, comma scraper coating machine, direct coating machine.
The gel fraction of the second binder layer is 5～69 % by weight, preferably 20～69 % by weight, more preferably 35～68 % by weight.More than above-mentioned gel fraction is adjusted to 5 % by weight, can prevents that the cohesive force of binder layer from becoming too small, and can prevent that undercapacity and tackiness agent from becoming soft.In addition, adhesive attachment binder layer distortion and, so-called " adhesive paste outstanding " outstanding from the end of adherend to blade or while pasting on adherend in the time of can preventing the cutting processing of self adhesive tape.In addition, can prevent life-time service or perk or peel off from adherend while using under harsh envrionment conditions.In addition, can obtain good gluing reliability.On the other hand, by above-mentioned gel fraction is adjusted to below 69 % by weight, can prevents that the cohesive force of binder layer from becoming excessive, and can obtain soft binder layer.In addition, binder layer is easily followed discrepancy in elevation part and jog, can obtain good discrepancy in elevation absorptivity and good gluing reliability.In addition, the tracing ability under adhesivity and the low temperature when pasting on adherend is good.In addition, life-time service or while using under harsh envrionment conditions, even if environmental change is also not easy to decline with the contact area of adherend, the electrical conductivity that can play stably.
In addition, the gel fraction of the second binder layer can be by controls such as the kind of polyfunctional monomer or linking agent or content (usage quantity).
The gel fraction (ratio of the insoluble composition of solvent) of the second binder layer is the gel fraction of the part except electroconductive stuffing.Above-mentioned gel fraction can be used as except not containing electroconductive stuffing with the insoluble component content of ethyl acetate of the binder layer of the second binder layer same composition and obtains.Particularly, first, making except not containing electroconductive stuffing with form as the binder composition of binder composition same composition of the second binder layer (binder layer that contains electroconductive stuffing) of object of obtaining gel fraction, by method, the condition identical with the formation method of the second binder layer of object as obtaining above-mentioned gel fraction, make binder layer (evaluation binder layer).Then, as this evaluation is obtained with respect to the weight fraction (unit: % by weight) of the sample (evaluation binder layer) before flooding at the lower insoluble composition flooding after 7 days of room temperature (23 ℃) in ethyl acetate with binder layer.More specifically, above-mentioned gel fraction is the value of calculating by following " measuring method of gel fraction ".
(measuring method of gel fraction)
Making except not containing electroconductive stuffing with form as the binder composition of binder composition same composition of the second binder layer (binder layer that contains electroconductive stuffing) of object of obtaining gel fraction, by method, the condition identical with the formation method of the second binder layer of object as obtaining above-mentioned gel fraction, make binder layer (evaluation binder layer).
Then, get about 0.1g evaluation binder layer, by the porous tetrafluoroethylene sheet (trade(brand)name " NTF1122 " of mean pore size 0.2 μ m, Nitto Denko Corp manufactures) parcel, then with kite string, tighten, measure weight now, using this weight weight before dipping.In addition, before this dipping, weight is the gross weight of evaluating with binder layer, tetrafluoroethylene sheet and kite string.In addition, measure the total weight of tetrafluoroethylene sheet and kite string, using this weight as packing bag weight.
Then, by evaluating, wrap up and tighten and the object (being called " sample ") that obtains is put into the 50ml container that is full of ethyl acetate with kite string with binder layer tetrafluoroethylene sheet, and 23 ℃ standing 1 week (7 days).Then, take out from container sample (ethyl acetate process after), transfer in aluminum cup, in drying machine 130 ℃ dry 2 hours and remove after ethyl acetate, gravimetry, using this weight weight after dipping.
And, by following formula calculated for gel mark.
Gel fraction (% by weight)=(D-E)/(F-E) × 100
In above formula, D is the rear weight of dipping, and E is packing bag weight, and F is weight before flooding.
The thickness of the second binder layer is not particularly limited, preferably 10～100 μ m, more preferably 15～80 μ m, further preferred 20～40 μ m.More than thickness being set as to 10 μ m, the stress producing when pasting easily disperses, thereby be not easy to produce, peels off.On the other hand, by thickness being set as below 100 μ m, even if life-time service or while using under severe condition also can be guaranteed fully long-term conducting reliability.In addition, the miniaturization to product and filming are favourable.
As described later, for the electroconductive pressure-sensitive adhesive tape of second method, preferably rate being exposed in the surface of electroconductive stuffing controls in specified range, particularly, rate is exposed when too small (lower than 2%) in the surface of electroconductive stuffing, sometimes conductive path can not be formed fully, electroconductibility and long-term conducting reliability can not be guaranteed.On the contrary, rate is exposed when excessive (exceeding 5%) in the surface of electroconductive stuffing, and the contact area of binder layer and adherend reduces, and sometimes can not guarantee sufficient binding property.In order to control such surface, expose rate, the relation of controlling the thickness of the second binder layer and the content of electroconductive stuffing is effective, by obtaining their balance, when life-time service or the use under harsh environment, can bring into play more stable electrical conductivity.In addition, even in the situation that electroconductive pressure-sensitive adhesive tape is used with narrow width, also can have sufficient electroconductibility and binding property (tackiness) concurrently.
Therefore, the thickness of the second binder layer is preferably by determining with the balance of the interpolation umber (content) of electroconductive stuffing.While increasing thickness in the poor situation of electroconductive stuffing, sometimes can not form sufficient conductive path, while reducing thickness in the many situation of the content of electroconductive stuffing, sometimes intensity or fusible aspect have problems.For example, when thickness is 30 μ m, by the content of electroconductive stuffing being set as to approximately 35～approximately 100 weight parts, can form sufficient conductive path on the surface of the second binder layer side, can guarantee long-term conducting reliability.In addition, on the surface of the second binder layer side, also there is fully binder layer, therefore also can guarantee binding property, can make and have long-term conducting reliability and fusible electroconductive pressure-sensitive adhesive tape concurrently.In addition, for example, thickness is in the situation of the second binder layer of 50 μ m, when the interpolation umber of electroconductive stuffing is 35 weight part with respect to all solids composition (100 weight part) of the binder composition except electroconductive stuffing, can not guarantee long-term conducting reliability, on the other hand, if add umber, be 200 weight parts, can guarantee long-term conducting reliability.
The thickness of the electroconductive pressure-sensitive adhesive tape of second method is not particularly limited, preferably 25～600 μ m, more preferably 30～200 μ m, further preferred 40～140 μ m.More than above-mentioned thickness is set as to 25 μ m, there is sufficient belt strength, workability improves.On the other hand, by above-mentioned thickness being set as below 600 μ m, filming or miniaturization to product are favourable.In addition, above-mentioned " thickness of electroconductive pressure-sensitive adhesive tape " refers to metal foil surface (not having the surface of a side of binder layer metal foil surface) from the electroconductive pressure-sensitive adhesive tape thickness to adhesive face.
In addition, in the electroconductive pressure-sensitive adhesive tape of second method, except above-mentioned tinsel, binder layer, not damaging in the scope of effect of the present invention, can there is other layer (for example, middle layer, undercoat etc.).
The electroconductive pressure-sensitive adhesive tape of second method can form the second binder layer by the one side side in tinsel and manufacture.For example, the electroconductive pressure-sensitive adhesive tape of second method can directly form on the surface of tinsel the second binder layer (direct method), also can on partition, form after the second binder layer, its transfer printing (stickup), on tinsel, is arranged to the second binder layer (transfer printing) thus on the surface of tinsel.
The surface of the electroconductive stuffing of the second adhesive layer surface of the electroconductive pressure-sensitive adhesive tape of second method is exposed rate (area occupation ratio is exposed on surface) and is not particularly limited, and is preferably 2%～5%, and more preferably 3%～5%, further more preferably 4%～5%.By rate is exposed in above-mentioned surface, be adjusted to more than 2%, can further improve the electrical conductivity while pasting adherend.In addition, though life-time service or while using in harsh environment, also can further suppress resistance value through time rise, can obtain more stable electrical conductivity.Particularly, even the narrow width that is 1.0mm～10mm at the width of the electroconductive pressure-sensitive adhesive tape of second method, life-time service or while using under harsh environment, also can obtain more stable electrical conductivity.On the other hand, by rate is exposed in above-mentioned surface, be adjusted to below 5%, easily guarantee bounding force, and easily guarantee long-term conducting reliability.Particularly, even the narrow width that is 1.0mm～10mm at the width of electroconductive pressure-sensitive adhesive tape, also easily guarantee bounding force, and easily guarantee long-term conducting reliability.
The surface of the electroconductive stuffing of the second adhesive layer surface is exposed rate and can be measured according to following [measuring method of rate is exposed on surface].
[measuring method of rate is exposed on surface]
Use the 0.5 % by weight ruthenic acid aqueous solution, at room temperature by the second adhesive layer surface steam dyeing of the electroconductive pressure-sensitive adhesive tape of second method 30 minutes; Then, use sputter equipment " E-3200 " (Hitachi Ltd.'s system), carry out the Pt-Pd sputter process of adhesive layer surface, make observation sample.
Use scanning electron microscope (FE-SEM) " S-4800 " (Hitachi Ltd.'s system), at acceleration voltage 5kV, measure under the condition of 200 times of multiples, measure the backscattered electron image (range of observation: 450 × 575 μ m of observing by the adhesive layer surface side of the present invention of sample 2(450 μ m × 570 μ m)).
For obtained backscattered electron image, use image processing software " Winroof " (three paddy business Co., Ltd. systems) to carry out binaryzation, calculate the area ratio of the inorganic layer part that belongs to electroconductive stuffing, thereby measure surface, expose rate.
For binary conversion treatment, if can the background (binder layer) beyond electroconductive stuffing and electroconductive stuffing be distinguished by distinct colors, for example, the region of electroconductive stuffing can be set as white (0), also can be set as black (1).
The surface of the electroconductive pressure-sensitive adhesive tape of second method is exposed rate and can be controlled by the thickness of the addition of such as electroconductive stuffing, the second binder layer etc.For example, when the thickness of the second binder layer (adhesive paste thickness) is set as to 30 μ m, by the interpolation umber of electroconductive stuffing is set as to 35 weight part～100 weight parts, can guarantee to consider bounding force and the long-term conducting reliability of workability.When the thickness of the second binder layer is set as to 50 μ m, by the interpolation umber of electroconductive stuffing is set as to 150 weight part～200 weight parts, can guarantee to consider bounding force and the long-term conducting reliability of workability.By the thickness of the second binder layer and the interpolation umber of electroconductive stuffing, can expose rate by control surface, can design thus the adhesive tape of guaranteeing bounding force and long-term conducting reliability.
The surface of the electroconductive stuffing of the second adhesive layer surface of the electroconductive pressure-sensitive adhesive tape of second method expose the quantitative earth's surface of rate show electroconductive stuffing expose area (belong to electroconductive stuffing inorganic layer expose area) with respect to the ratio of the surperficial area of the second binder layer side.For for the electroconductive pressure-sensitive adhesive tape of second method, find the control index of electrical conductivity stable when above-mentioned surface is exposed electrical conductivity and binding property and the life-time service that rate is electroconductive pressure-sensitive adhesive tape or uses under harsh envrionment conditions.In addition, found particularly in the situation that electroconductive pressure-sensitive adhesive tape is narrow width, for the electrical conductivity of bringing into play high electrical conductivity and good binding property and play stably and the scope of rate is exposed on the surface that should control.
On the other hand, for the electroconductive pressure-sensitive adhesive tape that there is the adhesive layer that contains electroconductive particle or binder layer for existing at least one surface in tinsel and this tinsel, particularly in the case of the shape with narrow width is used, owing to guaranteeing that the interpolation umber of belt strength or electroconductive stuffing is few, therefore can not guarantee long-term conducting reliability.For the electroconductive pressure-sensitive adhesive tape of second method of the present invention, be conceived to expose rate (conductive path) as the surface of the essential electroconductive stuffing for guaranteeing conducting reliability, and by its quantification, even can design thus the in the situation that of narrow width, also can guarantee good bounding force and high electrical conductivity, the particularly electroconductive pressure-sensitive adhesive tape of long-term conducting reliability.The electroconductive pressure-sensitive adhesive tape of second method, even using to the various shape of narrow width at the width with leniently, also can bring into play good long-term conducting reliability, therefore versatility is high.
(electroconductive pressure-sensitive adhesive tape of the present invention)
The width of electroconductive pressure-sensitive adhesive tape of the present invention is not particularly limited, and when the electronics for further miniaturization, thin space etc., preferable width is little.The width of electroconductive pressure-sensitive adhesive tape of the present invention for example preferably 1.0～10mm, more preferably 1.5～6mm.
In addition, the adhesive layer surface (the second adhesive layer surface in the first adhesive layer surface in the electroconductive pressure-sensitive adhesive tape of first method or the electroconductive pressure-sensitive adhesive tape of second method) of electroconductive pressure-sensitive adhesive tape of the present invention, measure with the draw speed of 300mm/ minute 180 of aluminium sheet ° of peel adhesion are not particularly limited, from can temporarily pasting, guarantee the viewpoint consideration of long-term conducting reliability, be preferably 0.1～1.0N/2mm, more preferably 0.2～0.9N/2mm, further preferred 0.2～0.8N/2mm.In addition, above-mentioned 180 ° of peel adhesion can be according to JIS Z0237(2000), under 23 ℃, the environment of 50%RH, use tensile testing machine, by 180 ° of stripping tests using aluminium sheet as adherend (draw speed: 300mm/ minute, is crimped onto the condition on adherend: 2kg roller once comes and goes), measure.
The maximum resistance of the 1st circulation of measuring in following thermal cycling test of electroconductive pressure-sensitive adhesive tape of the present invention (electroconductive pressure-sensitive adhesive tape of first method and the electroconductive pressure-sensitive adhesive tape of second method) is not particularly limited, from obtaining the viewpoint consideration as the sufficient electrical conductivity of electroconductive pressure-sensitive adhesive tape, be preferably below 0.1 Ω, more preferably 0.0001～0.5 Ω, further preferred 0.0001～0.05 Ω.In addition, sometimes the maximum resistance of above-mentioned the 1st circulation is called to " initial resistivity value ".
In addition, the maximum resistance of the 200th circulation of measuring in thermal cycling test described later of electroconductive pressure-sensitive adhesive tape of the present invention (electroconductive pressure-sensitive adhesive tape of first method and the electroconductive pressure-sensitive adhesive tape of second method) is not particularly limited, be preferably 5 times following (for example 1～5 times) of the maximum resistance of the 1st circulation, more preferably 1～4 times, further preferably 1～3 times, further more preferably 1～2.5 times.In addition, in this specification sheets, sometimes the maximum resistance of the 200th circulation is called to " resistance value multiple " with respect to the value [(maximum resistance of the 200th circulation)/(maximum resistance of the 1st circulation)] (doubly) of the maximum resistance of the 1st circulation.
In this specification sheets, " resistance value multiple " is while using by electroconductive pressure-sensitive adhesive tape life-time service or under harsh envrionment conditions, and this electroconductive pressure-sensitive adhesive tape can be brought into play the index of electrical conductivity stable in which kind of degree.Think little at resistance value multiple and be below 5 times time, the electrical conductivity that is pasted with the part of electroconductive pressure-sensitive adhesive tape be not easy through time decline, even while using at life-time service or under harsh envrionment conditions, electric current also stably continues to flow, and therefore uses the product of this electroconductive pressure-sensitive adhesive tape can bring into play higher reliability.
Above-mentioned thermal cycling test is following test: for by implementing on the silver-plated conductive pattern obtaining to paste the evaluation substrate with circuit that electroconductive pressure-sensitive adhesive tape forms, when passing into constant current in described circuit, make described evaluation exposure of substrates under the temperature environment condition that periodically becomes low temperature and high temperature, and measure continuously the tinsel of electroconductive pressure-sensitive adhesive tape and implement silver-plated and resistance between the conductive pattern that obtains (that is, electroconductive pressure-sensitive adhesive tape and the contact resistance of fitting part (adhesive portion) of implementing silver-plated and conductive pattern that obtain).
The maximum resistance of the maximum resistance of above-mentioned the 1st circulation and the 200th circulation can be measured as follows.Electroconductive pressure-sensitive adhesive tape is pasted on silvering (implementing conductive pattern silver-plated and that obtain) and makes adhesive portion be of a size of 5mm × 6mm(area: 30mm 2), in the electroconductive pressure-sensitive adhesive tape that comprises adhesive portion and silvering (implementing conductive pattern silver-plated and that obtain), pass into the constant current of 2A.Put it into and in thermostatic bath, carry out cooling and heat, and measure continuously betwixt the resistance value (contact resistance value) of described adhesive portion.Being set as of described thermostatic bath: the design temperature in groove (thermal cycle conditions) is kept 10 minutes at-40 ℃ from 25 ℃ cool to-40 ℃, then, at 85 ℃, keep 10 minutes after being warmed up to 85 ℃, then cool to 25 ℃, using this process as 1 circulation, and repeatedly carry out this circulation.More specifically, can measure according to following [thermal cycling test].
[thermal cycling test]
(evaluating the making with substrate)
Use is formed with implements glass epoxy substrate silver-plated and conductive pattern that obtain, silver-plated in described enforcement and paste electroconductive pressure-sensitive adhesive tape on the conductive pattern that obtains, and silver-plated in described enforcement and connect constant current power supply and potentiometer on the conductive pattern that obtains, form thus circuit, thereby make evaluation substrate.In Figure 12, represent an example of the formation of concrete evaluation substrate.On glass epoxy substrate 48a, form and implement conductive pattern silver-plated and that obtain (below, sometimes referred to as " conductive pattern ") 41a～d, by the roller that makes 5kg once come and go and by electroconductive pressure-sensitive adhesive tape 42(width: 6mm) paste (crimping) to conductive pattern 41a～41d.Now, with the adhesive portion 43 of conductive pattern 41b and electroconductive pressure-sensitive adhesive tape, be of a size of 5mm × 6mm(area: 30mm 2) mode paste.By this adhesive portion 43, can guarantee conduct (the conducting on thickness direction) between conductive pattern 41b and the tinsel of electroconductive pressure-sensitive adhesive tape 42.
In addition, when the width of electroconductive pressure-sensitive adhesive tape is less than 6mm, the mode take total width as 6mm is pasted (for example, when the width of electroconductive pressure-sensitive adhesive tape is 2mm, pasting three), thus can implementation evaluation.
Then, conductive pattern 41b is connected with constant current power supply 44 with 41d, conductive pattern 41a is connected with potentiometer 45 with 41b, thereby form circuit, set it as evaluation substrate.In addition, although be not particularly limited,, for example, described conductive pattern with constant current power supply, potentiometric connection can go between or utilize the common connection means such as welding to implement by use.Figure 13 represents the equivalent circuit of the evaluation shown in Figure 12 with the circuit in substrate.In Figure 13 47 represents the resistance (contact resistance) of the adhesive portion 43 in Figure 12.
(making of sample for resistance evaluation)
In the above-mentioned evaluation use circuit of substrate, by least fitting part of conductive pattern and electroconductive pressure-sensitive adhesive tape (adhesive portion) use vinyl-vinyl acetate copolymer (EVA) sealing between glass epoxy substrate and sheet glass, make resistance evaluation sample.In Figure 14, represent the schematic diagram (sectional view of the adhesive portion 43 of Figure 12) of resistance evaluation sample.Resistance evaluation has fitting part (adhesive portion) 43 that at least conductive pattern 41b and electroconductive pressure-sensitive adhesive tape 42 the form cured article with EVA(EVA between glass epoxy substrate 48a and sheet glass 48b with sample) formations of 49 sealings.In addition, shown in Figure 12 with the cured article of EVA(EVA) example in the region (sealing area) 46 of sealing.Above-mentionedly be not particularly limited with EVA sealing, for example, can implement by the following method.In the evaluation shown in Figure 12, use on the sealing area 46 of substrate, the film (eva film) of mounting thermoset ethylene-vinyl acetate copolymer (for example, the thermoset eva film of vinyl acetate content 28%), overlapping sheet glass thereon again, thus the duplexer that " evaluating with substrate/eva film/sheet glass " forms there is.Use vacuum press, first described duplexer is vacuumized to 40 seconds under the state of 150 ℃ in the situation that not suppressing, then, under the state vacuumizing, under 150 ℃, the pressure of 0.1MPa, suppress 400 seconds (vacuumize from starting to vacuumize at 400 seconds time finish), afterwards, from vacuum press, take out described duplexer, in the baking oven of 150 ℃, heat 40 minutes, make EVA thermofixation.
By like this with EVA by least the fitting part of conductive pattern and electroconductive pressure-sensitive adhesive tape (adhesive portion) sealing, adhesive portion is fixed, therefore can obtain the measurement result that error is little, stable.
(envrionment temperature in chamber (thermostatic bath) is set)
Design temperature (thermal cycle conditions) in chamber is as described below.In addition, although be not particularly limited, during the envrionment temperature by following setting changing chamber, the humidity (relative humidity) that can not carry out in chamber is controlled.
Take following setting: starting temperature is set as to 25 ℃, since 25 ℃ of speed with 100 ℃/h, cools to-40 ℃, and keep 10 minutes at-40 ℃.Then, from-40 ℃ of beginnings, with the speed of 100 ℃/h, be warmed up to 85 ℃, and keep 10 minutes at 85 ℃.Afterwards, again with the speed of 100 ℃/h, lower the temperature, and reach 25 ℃, using above process as a circulation, and it is at least repeated 200 times.In addition, a required time of circulation is 170 minutes.Design temperature (thermal cycle conditions) in the sky of above-mentioned chamber shown in Figure 15, till the temperature curve of the 2nd circulation.In addition, the IEC61215(of this design temperature (thermal cycle conditions) based on IEC standard the 2nd edition), IEC61646(the 2nd edition).
As above-mentioned chamber (thermostatic bath), can enumerate known usual chamber, be not particularly limited, for example can enumerate: the commercially available products such as trade(brand)name " PL-3KP " (manufacture of エ ス ペ ッ Network Co., Ltd.), trade(brand)name " PWL-3KP " (manufacture of エ ス ペ ッ Network Co., Ltd.).Figure 16 is illustrated in chamber (the エ ス ペ ッ Network Co., Ltd. manufacture to use in above-mentioned setup control aftermentioned (evaluation) " (2) resistance value (thermal cycling test) ", trade(brand)name " PL-3KP ") in the situation of temperature under, temperature in the groove of chamber (thermostatic bath) (envrionment temperature in groove) and evaluate an example of the surface temperature curve of the electroconductive pressure-sensitive adhesive tape of using substrate.In the groove of chamber, temperature changes according to imposing a condition, top temperature and approximately 85 ℃ of the basic identical demonstrations of setting, and minimum temperature is than setting approximately-30 ℃ of slightly high demonstrations.In addition, the surface temperature of electroconductive pressure-sensitive adhesive tape shows the substantially same variation of temperature in the groove stopping up with chamber.
(mensuration of resistance value)
To the circuit in sample for above-mentioned resistance evaluation, utilize constant current that constant current power supply (constant current power supply 44 in Figure 12) passes into 2A (, in adhesive portion 43 in Figure 12, pass into the constant current of 2A), and resistance evaluation is put into the chamber that groove envrionment temperature is set as 25 ℃ with sample.Then, by above-mentioned design temperature (thermal cycle conditions), repeat the cooling and heating of resistance evaluation sample, therebetween, utilize potentiometer 45 to measure continuously voltage (for example, the sample period: 5～10 times/10 minutes), obtain continuously thus the resistance value of adhesive portion 43.Thus, measure the maximum resistance (initial resistivity value) of the 1st circulation, the maximum resistance of the 200th circulation, and calculate above-mentioned resistance value multiple.
In the past, it is that electroconductive pressure-sensitive adhesive tape is pasted on conductor (electrical conductors) that electroconductive pressure-sensitive adhesive tape is brought into play the electrical conductivity which kind of degree is stable, guaranteeing under the state conducting between the tinsel of described electroconductive pressure-sensitive adhesive tape and described conductor, be exposed under the ambient temperature conditions of repetition high temperature and low temperature, by which kind of the degree ground of electrical conductivity (that is, resistance (contact resistance)) of the adhesive portion of electroconductive pressure-sensitive adhesive tape before and after exposure, change and evaluate.But, the variation of the electrical conductivity under described ambient temperature conditions before and after exposure is that the electrical conductivity of therefore whether always playing stably in the middle of being exposed under high temperature or cold condition is indefinite by the resistance value of measuring at normal temperatures after the resistance value of measuring at normal temperatures before exposing and exposure is compared and evaluated.Therefore, the inventor adopts the above-mentioned thermal cycling test of the resistance (contact resistance) of also measuring continuously the adhesive portion of electroconductive pressure-sensitive adhesive tape during being exposed to high temperature or cold condition, and the electrical conductivity of electroconductive pressure-sensitive adhesive tape is evaluated.Found that, for existing electroconductive pressure-sensitive adhesive tape, although the resistance value of measuring under normal temperature environment through time rise littlely, particularly the resistance value under hot environment slowly increases, thus electrical conductivity through time decline.On the other hand, for electroconductive pressure-sensitive adhesive tape, the resistance value multiple of measuring in above-mentioned thermal cycling test is below 5 times time, the rising of the resistance value that can suppress to measure under hot environment, also can bring into play more stable electrical conductivity for life-time service or the use under harsh envrionment conditions.
In addition, partition (release liner) can be set on the adhesive face of electroconductive pressure-sensitive adhesive tape of the present invention.As above-mentioned partition, can use usual interleaving paper etc., be not particularly limited, for example can enumerate: low tackiness base material that there is the base material of lift-off processing layer, the low tackiness base material that comprises fluoropolymer, comprises non-polar polymer etc.As the above-mentioned base material with lift-off processing layer, for example can enumerate: utilize the stripping treatment agents such as polysiloxane-based, chain alkyl class, fluorine-containing type, moly-sulfide to carry out plastics film after surface treatment or paper etc.As above-mentioned fluoropolymer, for example can enumerate: tetrafluoroethylene, polychlorotrifluoroethylene, fluorinated ethylene propylene, poly(vinylidene fluoride), tetrafluoraoethylene-hexafluoropropylene copolymer, chlorine vinyl fluoride-vinylidene fluoride copolymer etc.In addition, as above-mentioned non-polar polymer, for example can enumerate: olefine kind resin (for example, polyethylene, polypropylene etc.) etc.Wherein, from the viewpoint that suppresses partition perk (the partition phenomenon that part is peeled off from adhesive face), consider, preferably comprise polyethylene or polyacrylic partition.In addition, partition can form by known customary way.In addition, thickness of partition etc. is also not particularly limited.
The electromagnetic wave shielding purposes of purposes, electric/electronic device or the cable conducting between two positions that electroconductive pressure-sensitive adhesive tape of the present invention can be suitable for making to isolate etc.Particularly, purposes that can the electrical conductivity that resistance value does not rise, can play stably when requiring use under various environment or life-time service, particularly, the ground connection of the ground connection of such as printed wiring board, the outer packaging shielding case of electronics, ground connection, supply unit or the electronics etc. that anti-electrostatic is used (for example, liquid crystal indicator, organic EL(electroluminescent) display unit, PDP(plasma display), display unit, the solar cell etc. such as Electronic Paper) internal wiring etc.
Embodiment
Below, based on embodiment, illustrate in greater detail the present invention, still, the present invention is not limited to the examples.
(embodiment 1)
The Production Example of acrylic polymers
Using as n-butyl acrylate (BA) 70 weight parts of monomer component, 2-EHA (2EHA) 30 weight parts, vinylformic acid (AA) 3 weight parts, vinylformic acid 4-hydroxyl butyl ester (HBA) 0.05 weight part, as 2 of polymerization starter, 2 '-Diisopropyl azodicarboxylate, 0.2 weight part and putting in detachable flask as toluene 27 weight parts of polymer solvent stirs 1 hour when introducing nitrogen.After like this oxygen in polymerization system being removed, be warmed up to 63 ℃ of reactions 10 hours, then add toluene adjusting concentration, obtain the acrylic polymers solution of solid component concentration 30 % by weight.
In addition, the weight-average molecular weight of the aforesaid propylene acids polymkeric substance in acrylic polymers solution is 440,000.
The preparation example of binder composition solution
In aforesaid propylene acids polymers soln, with respect to 100 weight part aforesaid propylene acids polymkeric substance (solids component), with solids component, convert and add the isocyanates linking agent (trade(brand)name " コ ロ ネ ー ト L " of 3 weight parts, Nippon Polyurethane Industry Co., Ltd. manufactures) (C/L), and convert and add the tackifier (trade(brand)name " ペ Application セ Le D-125 " of 30 weight parts with solids component with respect to 100 weight part aforesaid propylene acids polymkeric substance (solids component), Arakawa Chemical Industries, Ltd. manufactures), and by its mixing, prepare thus binder composition solution.
The Production Example of adhesive tape for electroconductive pressure-sensitive adhesive tape (タ ッ ク テ ー プ)
On the interleaving paper that is coated with polysiloxane, being coated with above-mentioned binder composition solution, to make dried thickness be 45 μ m, and it is obtained to binder layer at 130 ℃ after dry 3 minutes in baking oven.
Then, the adhesive layer surface obtaining fit zinc-plated Copper Foil (implement the Copper Foil after zinc-plated, thickness: 35 μ m), then, gains are wound as to drum, are there is thus the drum coiling body of the electroconductive pressure-sensitive adhesive tape adhesive tape of the formation of " zinc-plated Copper Foil/binder layer/interleaving paper ".
The Production Example of electroconductive pressure-sensitive adhesive tape
From drum coiling body obtained above, electroconductive pressure-sensitive adhesive tape is laid out with adhesive tape, use is with the pattern (h=2.598mm shown in Fig. 6, i=1.5mm) in surface configuration, there is the pin (c=1.0427mm of shape shown in Fig. 4 and Fig. 5, d=1.8061mm, e=60 °, f=1.2mm, g=0.1mm) formpiston roller and be formed with the former roller of the cylindrical bore of the diameter 1.6mm φ × degree of depth 1.4mm shown in Fig. 7 on surface, the mode contacting with formpiston roller by the tinsel side of adhesive tape with above-mentioned electroconductive pressure-sensitive adhesive tape is by carrying out stamping-out between above-mentioned roller (formpiston roller and former roller), thereby on the surface of through hole and binder layer side, form the protuberance (burr) of tinsel.
Then, interleaving paper is peeled off, as shown in figure 10, make scraper plate (material: iron (FK4), toe angle: 45 °, front end R(front-end radius): 0.5) take the front end angulation (angle 33 in Figure 10) of adhesive layer surface and described scraper plate as the mode of 20 ° and in the mode of the front end in contact of adhesive layer surface and described scraper plate, be configured (, scraping front edge of board is crimped on binder layer side surface), and make binder layer move (scraping) with the speed of 1m/ minute, thus that described protuberance is folding.
In addition, partition is fitted to adhesive layer surface, then make it pass through between pressure roller, in the lamination that carries out partition, implement thus press process protuberance and binder layer after folding are become smoothly, thereby obtain having on the surface of binder layer side the electroconductive pressure-sensitive adhesive tape (thering is the electroconductive pressure-sensitive adhesive tape of through hole) of portion of terminal (the metal part of exposing).
(embodiment 2)
The preparation example of binder composition solution
Obtain similarly to Example 1 acrylic polymers solution.
Then, in this acrylic polymers solution, with respect to acrylic polymers (solids component) 100 weight parts, with solids component, convert and add 3 weight part isocyanates linking agents (trade(brand)name " コ ロ ネ ー ト L ", Nippon Polyurethane Industry Co., Ltd. manufactures) (C/L), and convert and add the tackifier (trade(brand)name " ペ Application セ Le D-125 " of 30 weight parts with solids component with respect to 100 weight part aforesaid propylene acids polymkeric substance (solids component), Arakawa Chemical Industries, Ltd. manufactures) (ペ Application セ Le D125), and by its mixing, obtain thus solution A.
Then, in above-mentioned solution A, with respect to solids component 100 weight parts that form mixed solution A, coordinate 35 weight part silver fillers (trade(brand)name " Ag-HWQ-400 ", Fukuda Metal Foil & POwder Co., Ltd. manufactures, filler diameter d 50:13.2 μ m, filler diameter d 95:43.0 μ m, spherical), with stirrer mixing 10 minutes, thereby obtain binder composition solution.That is, the content of silver fillers is 35 weight parts with respect to all solids composition (100 weight part) of the binder composition solution except silver fillers.
The Production Example of electroconductive pressure-sensitive adhesive tape
On the interleaving paper that is coated with polysiloxane, being coated with above-mentioned binder composition solution, to make dried thickness be 30 μ m, and it is obtained to binder layer at 130 ℃ after dry 3 minutes in baking oven.
Then, at the adhesive layer surface the obtaining zinc-plated Copper Foil of fitting, (implement the Copper Foil after zinc-plated, thickness: 35 μ m), obtain having the electroconductive pressure-sensitive adhesive tape of the tackiness agent that contains silver fillers.
(embodiment 3)
Monomer component is set as to n-butyl acrylate (BA) 95 weight parts, vinylformic acid (AA) 5 weight parts, obtains similarly to Example 1 acrylic polymers solution.In addition, the weight-average molecular weight of the aforesaid propylene acids polymkeric substance in acrylic polymers solution is 600,000.
Then, using as cyclohexyl methacrylate [second-order transition temperature of homopolymer (polycyclohexyl methacrylate): 66 ℃] 95 weight parts of monomer component, vinylformic acid 5 weight parts, as α-methylstyrenedimer 10 weight parts of chain-transfer agent, as 2 of polymerization starter, 2 '-Diisopropyl azodicarboxylate, 10 weight parts and putting in detachable flask as toluene 120 weight parts of polymer solvent stir 1 hour when introducing nitrogen.Remove thus after the oxygen in polymerization system, be warmed up to 85 ℃, react 5 hours, thereby obtain the acrylic acid or the like oligomer solution of solid component concentration 50 % by weight.
In addition, the weight-average molecular weight of the aforesaid propylene acids oligopolymer in acrylic acid or the like oligomer solution is 4300.
Then, in aforesaid propylene acids polymers soln, with respect to acrylic polymers (solids component) 100 weight parts, with solids component, convert and add 0.15 weight part silane coupling agent (trade(brand)name " KBM403 ", Shin-Etsu Chemial Co., Ltd manufactures) (KBM403), with respect to acrylic polymers (solids component) 100 weight parts, with solids component, convert and add 0.075 weight part linking agent (trade(brand)name " TERAD-C ", Mitsubishi Gas Chemical Co., Ltd manufactures) (T/C), and adding aforesaid propylene acids oligomer solution makes with respect to acrylic polymers (solids component) 100 weight parts, take the amount of solids component conversion acrylic acid or the like oligopolymer as 25 weight parts, by its mixing, prepared thus binder composition solution.
And, use above-mentioned binder composition solution, obtained similarly to Example 1 having on the surface of binder layer side the electroconductive pressure-sensitive adhesive tape of portion of terminal.
(embodiment 4)
Obtain similarly to Example 1 acrylic polymers solution.
Then, in this acrylic polymers solution, with respect to acrylic polymers (solids component) 100 weight parts, with solids component, convert and add 3 weight part isocyanates linking agents (trade(brand)name " コ ロ ネ ー ト L ", Nippon Polyurethane Industry Co., Ltd. manufactures) (C/L), and mixed, prepare thus binder composition solution.
And, use above-mentioned binder composition solution, obtained similarly to Example 1 having on the surface of binder layer side the electroconductive pressure-sensitive adhesive tape of portion of terminal.
(comparative example 1)
Obtain similarly to Example 1 acrylic polymers solution.
Then, in this acrylic polymers solution, with respect to acrylic polymers (solids component) 100 weight parts, with solids component, convert and add 0.2 weight part linking agent (trade(brand)name " TETRAD-C ", society of gas chemistry strain trade union of Mitsubishi manufactures) (T/C), and with respect to acrylic polymers (solids component) 100 weight parts, with solids component, convert and add 30 weight part tackifier (trade(brand)name " ペ Application セ Le D-125 ", Arakawa Chemical Industries, Ltd. manufactures) (ペ Application セ Le D125), and by its mixing, prepare thus binder composition solution.
And, use above-mentioned binder composition solution, obtained similarly to Example 1 having on the surface of binder layer side the electroconductive pressure-sensitive adhesive tape of portion of terminal.
(comparative example 2)
Monomer component is set as to vinylformic acid 2-methoxyl group ethyl ester (2MEA) 66 weight parts, ethyl propenoate (EA) 23 weight parts, methyl methacrylate (MMA) 10 weight parts, vinylformic acid 4-hydroxyl butyl ester (HBA) 1 weight part, obtains similarly to Example 1 acrylic polymers solution.
In addition, the weight-average molecular weight of the aforesaid propylene acids polymkeric substance in acrylic polymers solution is 900,000.
Then, in this acrylic polymers solution, with respect to acrylic polymers (solids component) 100 weight parts, with solids component, convert and add 0.3 weight part polyisocyanates (trade(brand)name " デ ュ ラ ネ ー ト MEA-75X ", the ケ ミ カ of Asahi Chemical Industry Le ズ Co., Ltd. manufactures) (デ ュ ラ ネ ー ト), and with respect to acrylic polymers (solids component) 100 weight parts, add 0.2 weight part methyl ethyl diketone, and mixed, obtain thus binder composition solution.
And, use above-mentioned binder composition solution, obtained similarly to Example 1 having on the surface of binder layer side the electroconductive pressure-sensitive adhesive tape of portion of terminal.
[evaluation]
Electroconductive pressure-sensitive adhesive tape for embodiment and comparative example carries out following mensuration or evaluation.Its result is as shown in table 1.
(1) gel fraction
The gel fraction of embodiment 1, embodiment 3, embodiment 4, comparative example 1 and comparative example 2 is obtained according to the measuring method of the gel fraction of above-mentioned the first binder layer.In addition, the gel fraction of embodiment 2 is obtained according to the measuring method of the gel fraction of the second above-mentioned binder layer.
(2) resistance value (thermal cycling test)
(evaluating the making with substrate) (with reference to Figure 17)
The electroconductive pressure-sensitive adhesive tape obtaining in embodiment and comparative example is cut into the size of wide 6mm × long 60mm, and partition is peeled off, thereby obtain electroconductive pressure-sensitive adhesive tape sheet.
Use is formed with and implements the silver-plated and conductive pattern that obtains (the μ m/Au0.03 μ m/Ag5 μ m) glass epoxy substrate of 51a～h (thickness: 1.6mm) in Cu18 μ m/Ni3～7 is of a size of 5mm × 6mm(area: 30mm with the adhesive portion 53a～d of electroconductive pressure-sensitive adhesive tape and described conductive pattern with the configuration shown in Figure 17 2) mode, by the roller that makes 5kg, once come and go and paste (crimping) electroconductive pressure-sensitive adhesive tape sheet (52a, 52b).Then, use lead-in wire by welding constant current power supply (54a, 54b) and potentiometer (55a～d) be connected with described conductive pattern 51a～h.
In addition, the evaluation shown in Figure 17 is equivalent to the circuit of the evaluation of two Figure 12 in substrate to form side by side with the circuit in substrate.
[making of resistance sample for evaluation]
In the evaluation shown in Figure 17, use on the region 56 of substrate, the heat curing-type eva film (thickness: 0.6mm) of overlapping vinyl acetate content 28%, again from overlapping sheet glass (thickness: 3.2mm) above, thereby there is the duplexer of the formation of " evaluating with substrate/eva film/sheet glass ".Use vacuum press, first described duplexer is vacuumized to 40 seconds under the state of 150 ℃ in the situation that not suppressing, then, under the state vacuumizing, under 150 ℃, the pressure of 0.1MPa, suppress 400 seconds (vacuumize from starting to vacuumize at 400 seconds time finish), afterwards, from vacuum press, take out described duplexer, in the baking oven of 150 ℃, heat 40 minutes, make EVA thermofixation, obtain thus resistance sample for evaluation.
[envrionment temperature in chamber is set]
Commodity in use name " PL-3K " (manufacture of エ ス ペ ッ Network Co., Ltd.) is as chamber, the as described below setting of design temperature (thermal cycle conditions) in chamber.In addition, under the following conditions Repeat-heating and cooling during, the humidity in chamber (relative humidity) is not controlled especially, relative humidity during beginning in chamber is 50%RH.
Take following setting: starting temperature is set as to 25 ℃, since 25 ℃ of speed with 100 ℃/h, cools to-40 ℃, and keep 10 minutes at-40 ℃.Then, from-40 ℃ of beginnings, with the speed of 100 ℃/h, be warmed up to 85 ℃, and keep 10 minutes at 85 ℃.Afterwards, again with the speed of 100 ℃/h, lower the temperature, and reach 25 ℃, using above process as a circulation, and repeated 200 times.
When Figure 16 is illustrated in the indoor temperature of control chamber under described design temperature (thermal cycle conditions), an example of the surface temperature distribution of temperature (envrionment temperature) and electroconductive pressure-sensitive adhesive tape in the groove of chamber (thermostatic bath).
[mensuration of resistance value]
By above-mentioned resistance sample for evaluation utilize constant current power supply (54a, 54b) pass into 2A constant current state (, in adhesive portion 53a～d in Figure 17, pass into the state of the constant current of 2A) under, put into the above-mentioned chamber that the envrionment temperature of groove is adjusted to 25 ℃, and under above-mentioned thermal cycle conditions, repeat cooling and heating.(55a～d) measure continuously voltage (sample period: 1 time/1 minute), obtains the resistance value (contact resistance value) of adhesive portion 53a～d continuously to utilize potentiometer therebetween.Thus, measure the maximum resistance (initial resistivity value) of the 1st circulation and the maximum resistance of the 200th circulation, and calculated resistance value multiple.The mean value (N=4) of the initial resistivity value of shown in table 1, adhesive portion 53a～d being measured respectively and resistance value multiple.
(3) area of portion of terminal (total area of portion of terminal, the average area of portion of terminal)
The electroconductive pressure-sensitive adhesive tape of embodiment 1, embodiment 3, embodiment 4, comparative example 1 and comparative example 2 is cut into the size (area: 30mm of wide 5mm × long 6mm 2), partition is peeled off, set it as working sample.
Use digital microscope (the キ ー エ of Co., Ltd. Application ス manufactures, model " VHX-600 "), to measure 200 times of multiples (lens: VH-Z20), observe the image (image on projection plane) of the portion of terminal of the binder layer side surface of described working sample.Then, under measurement pattern, specify the region of portion of terminal in described image, measure the area in this region, thus the area of measurement terminal portion.Similarly, measure the area of all portion of terminal that exist in described sample, and by they summations, calculate thus the every 30mm of binder layer 2the total area of the portion of terminal of middle existence.
In addition, the quantity of the through hole existing in described working sample is counted the every 30mm of binder layer going out by previous calculations 2the total area of the portion of terminal of middle existence, divided by the quantity of described through hole, calculates thus with respect to average area each through hole, portion of terminal.
(4) rate is exposed on surface
Use the 0.5 % by weight ruthenic acid aqueous solution, at room temperature by the adhesive layer surface steam dyeing of the electroconductive pressure-sensitive adhesive tape of embodiment 2 30 minutes.Then, use sputter equipment " E-3200 " (Hitachi Ltd.'s system), adhesive layer surface of the present invention is carried out to Pt-Pd sputter process, make observation sample.
Use scanning electron microscope (FE-SEM) " S-4800 " (Hitachi Ltd.'s system), at acceleration voltage 5kV, measure under the condition of 200 times of multiples, measure the backscattered electron image (range of observation: 450 × 575 μ m of observing by the adhesive layer surface side of the present invention of sample 2).
For obtained backscattered electron image, use image processing software " Winroof " (three paddy business Co., Ltd. systems) to carry out binaryzation, calculating belongs to the area of inorganic layer part of electroconductive stuffing with respect to the ratio of the surperficial area of binder layer side of the present invention, thereby measure surface, exposes rate.
Table 1
Figure BDA0000471180410000601
In addition, the amount of the silver fillers of " composition of binder composition " of table 1 is the amount with respect to all solids composition 100 weight parts of the binder composition beyond desilver.
" electrically conducting manner " of table 1 refers to " for improving the mode of electrical conductivity of binder layer ", " through hole mode " refer to " from tinsel side, offer through hole; on the surface of binder layer side, form the protuberance of tinsel; and set it as the mode of portion of terminal ", " containing conducting particles mode " refers to " make contain electroconductive particle in binder layer mode ".
In addition, embodiment 1,3 and 4 is equivalent to the electroconductive pressure-sensitive adhesive tape of first method, and embodiment 2 is equivalent to the electroconductive pressure-sensitive adhesive tape of second method.
Industrial applicability
Electroconductive pressure-sensitive adhesive tape of the present invention, can be for making between two positions of isolation the purposes that conducts etc.
Reference numeral
11 tinsels
12 binder layers
12a the first binder layer
13 electroconductive pressure-sensitive adhesive tapes
14 portion of terminal
15 through holes
16 conducting portions
17 protuberances (burr)
17a is positioned at the protuberance of the direct of travel side of binder layer with respect to through hole 15
17b is positioned at and the protuberance of the direct of travel opposition side of binder layer with respect to through hole 15
18 pressure rollers
21 formpistons
22 formers
31 scraper plates (sword shape scraper plate)
32 toe angles
33 adhesive layer surface with scrape front edge of board angulation
41a～d implements conductive pattern (conductive pattern) silver-plated and that obtain
42 electroconductive pressure-sensitive adhesive tapes
43 adhesive portion
44 constant current power supplies
45 potentiometers
46 regions (sealing area) by vinyl-vinyl acetate copolymer (EVA) sealing
The resistance (contact resistance) of 47 adhesive portion
48a glass epoxy substrate
48b sheet glass
The cured article of 49 vinyl-vinyl acetate copolymers (EVA)
51a～h implements conductive pattern (conductive pattern) silver-plated and that obtain
52a, 52b electroconductive pressure-sensitive adhesive tape (electroconductive pressure-sensitive adhesive tape sheet)
53a～d adhesive portion (fitting part of electroconductive pressure-sensitive adhesive tape and conductive pattern)
54a, 54b constant current power supply
55a～d potentiometer
56 regions (sealing area) by vinyl-vinyl acetate copolymer (EVA) sealing

Claims (11)

1. an electroconductive pressure-sensitive adhesive tape, is characterized in that,
One side side in tinsel has binder layer,
Described binder layer has the gel fraction of 5～69 % by weight and does not contain electroconductive stuffing.
2. electroconductive pressure-sensitive adhesive tape as claimed in claim 1, wherein,
The maximum resistance of the 1st circulation of measuring in following thermal cycling test is below 1 Ω and the maximum resistance of the 200th circulation is below 5 times of maximum resistance of the 1st circulation,
Thermal cycling test:
Electroconductive pressure-sensitive adhesive tape is pasted on silvering and makes adhesive portion be of a size of 5mm × 6mm(area 30mm 2), in the electroconductive pressure-sensitive adhesive tape that comprises adhesive portion and silvering, pass into the constant current of 2A, put it into repeat to carry out cooling and heating in thermostatic bath that the mode of following circulation sets, measure continuously the resistance value of described adhesive portion therebetween,
Described circulation is:
Design temperature in groove is cooled to-40 ℃ from 25 ℃, at-40 ℃, keep 10 minutes, then, at 85 ℃, keep 10 minutes after being warmed up to 85 ℃, and cooling reaches 25 ℃ again, using this process as a circulation.
3. electroconductive pressure-sensitive adhesive tape as claimed in claim 1 or 2, wherein,
There is the portion of terminal of exposing on the surface of described binder layer side, the every 30mm of described binder layer 2the total area of the portion of terminal of middle existence is 0.15～5mm 2.
4. electroconductive pressure-sensitive adhesive tape as claimed in claim 3, wherein,
Described portion of terminal is, by offering through hole from described tinsel side, at the protuberance of the surface of described binder layer side formation tinsel, then this protuberance to be folded and the portion of terminal of formation.
5. electroconductive pressure-sensitive adhesive tape as claimed in claim 4, wherein,
With respect to average area through hole described in each, portion of terminal, be 50,000～500,000 μ m 2.
6. an electroconductive pressure-sensitive adhesive tape, is characterized in that,
One side side in tinsel has binder layer,
Described binder layer has the gel fraction of 5～69 % by weight and contains electroconductive stuffing.
7. electroconductive pressure-sensitive adhesive tape as claimed in claim 6, wherein,
The maximum resistance of the 1st circulation of measuring in following thermal cycling test is below 1 Ω and the maximum resistance of the 200th circulation is below 5 times of maximum resistance of the 1st circulation,
Thermal cycling test:
Electroconductive pressure-sensitive adhesive tape is pasted on silvering and makes adhesive portion be of a size of 5mm × 6mm(area 30mm 2), in the electroconductive pressure-sensitive adhesive tape that comprises adhesive portion and silvering, pass into the constant current of 2A, put it into repeat to carry out cooling and heating in thermostatic bath that the mode of following circulation sets, measure continuously the resistance value of described adhesive portion therebetween,
Described circulation is:
Design temperature in groove is cooled to-40 ℃ from 25 ℃, at-40 ℃, keep 10 minutes, then, at 85 ℃, keep 10 minutes after being warmed up to 85 ℃, and cooling reaches 25 ℃ again, using this process as a circulation.
8. the electroconductive pressure-sensitive adhesive tape as described in claim 6 or 7, wherein,
It is 2%～5% that rate is exposed on the surface of electroconductive stuffing described in the described adhesive layer surface of measuring by following method,
Rate measuring method is exposed on surface:
Use the 0.5 % by weight ruthenic acid aqueous solution, at room temperature by the described adhesive layer surface steam dyeing of electroconductive pressure-sensitive adhesive tape 30 minutes; Then, use sputter equipment " E-3200 " (Hitachi Ltd.'s system), carry out the Pt-Pd sputter process of described adhesive layer surface, make observation sample;
Use scanning electron microscope (FE-SEM) " S-4800 " (Hitachi Ltd.'s system), at acceleration voltage 5kV, measure under the condition of 200 times of multiplying powers, measure the backscattered electron image (range of observation: 450 × 575 μ m of observing by the described adhesive layer surface side of sample 2);
For obtained backscattered electron image, use image processing software " Winroof " (three paddy business Co., Ltd. systems) to carry out binaryzation, calculate the area ratio of the inorganic layer part that belongs to electroconductive stuffing, thereby measure surface, expose rate.
9. the electroconductive pressure-sensitive adhesive tape as described in any one in claim 6～8, wherein,
The thickness of described binder layer is 10～100 μ m.
10. the electroconductive pressure-sensitive adhesive tape as described in any one in claim 6～9, wherein,
With respect to all solids composition (100 weight part) of the binder layer except electroconductive stuffing, the content of described electroconductive stuffing is 25～250 weight parts.
11. electroconductive pressure-sensitive adhesive tapes as described in any one in claim 1～10, wherein,
Described binder layer is served as reasons and is contained the binder layer that acrylic polymers forms as the binder composition of base polymer.
CN201280042413.5A 2011-08-30 2012-08-08 Conductive adhesive tape Pending CN103764780A (en)

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JP2011187683A JP2013049764A (en) 2011-08-30 2011-08-30 Conductive adhesive tape
JP2011-187683 2011-08-30
JP2011-187682 2011-08-30
JP2011187682A JP2013049763A (en) 2011-08-30 2011-08-30 Conductive adhesive tape
PCT/JP2012/070184 WO2013031500A1 (en) 2011-08-30 2012-08-08 Conductive adhesive tape

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