WO2016203510A1 - 粘着剤組成物及び粘着テープ - Google Patents
粘着剤組成物及び粘着テープ Download PDFInfo
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- WO2016203510A1 WO2016203510A1 PCT/JP2015/067132 JP2015067132W WO2016203510A1 WO 2016203510 A1 WO2016203510 A1 WO 2016203510A1 JP 2015067132 W JP2015067132 W JP 2015067132W WO 2016203510 A1 WO2016203510 A1 WO 2016203510A1
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- pressure
- sensitive adhesive
- mass
- adhesive composition
- acrylic copolymer
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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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
Definitions
- the present invention relates to a pressure-sensitive adhesive composition excellent in various properties such as resilience resistance, impact resistance, conductivity, and electromagnetic wave shielding properties, and a pressure-sensitive adhesive tape using the same.
- an adhesive tape having conductivity As an adhesive tape for fixing components such as components inside the equipment.
- an adhesive tape is known in which a metal foil is used as a base material and conductive particles are added to an adhesive layer. Due to the conductivity of such an adhesive tape, static electricity can be prevented and electromagnetic waves can be shielded.
- Patent Document 1 describes a conductive pressure-sensitive adhesive sheet having a conductive base material and a conductive pressure-sensitive adhesive layer.
- This conductive pressure-sensitive adhesive layer contains an acrylic copolymer having 1 to 14 carbon atoms (meth) acrylate and a monomer containing a carboxyl group as monomer components and a triazole compound.
- Patent Document 2 describes an adhesive composition containing an adhesive component and a conductive filler.
- the adhesive component various synthetic polymer compounds such as an ethylene-acrylic acid ester copolymer and an ethylene-acrylic acid ester copolymer are described.
- Patent Document 3 describes an adhesive composite material for electromagnetic wave shielding containing a thermoplastic binder and an organic synthetic fiber having a conductive surface film.
- thermoplastic binder various resins such as an acrylate polymer and an ethylene-vinyl acetate copolymer are described.
- Patent Document 1 when the conductive adhesive sheet disclosed in Patent Document 1 is used for the portable electronic devices that have been reduced in size and thickness as described above, they are peeled off due to an internal repulsion force or an external impact due to insufficient adhesive force. There is a fear.
- Patent Document 2 and Patent Document 3 when the compositions of Patent Document 2 and Patent Document 3 are used for the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet, there is a risk that they may be peeled off due to internal repulsion or external impact due to insufficient adhesive force.
- JP 2014-136778 A Japanese Patent Publication No. 01-54392 JP 2004-352926 A
- the present invention has been made to solve the above-described problems of the prior art. That is, the objective of this invention is providing the adhesive composition excellent in various characteristics, such as resilience resistance, impact resistance, electroconductivity, and electromagnetic wave shielding, and an adhesive tape using the same.
- the present invention relates to (meth) acrylic acid alkyl ester (A1) having an alkyl group having 1 to 3 carbon atoms and (meth) acrylic acid having an alkyl group having 4 to 12 carbon atoms.
- Alkyl ester (A2) 50-80% by weight, carboxyl group-containing monomer (A3) 10-15% by weight, hydroxyl group-containing monomer (A4) 0.01-0.5% by weight, and vinyl acetate (A5) 1-5
- Acrylic copolymer having a weight average molecular weight of 950,000 to 2,000,000 and a theoretical Tg of ⁇ 55 ° C. or less.
- It is a pressure-sensitive adhesive composition containing a coalescence (A), a crosslinking agent (B), a silane coupling agent (C), an antioxidant (D), and conductive particles (E).
- this invention is an adhesive tape which has the adhesive layer formed with the adhesive composition of this invention on the single side
- the novel pressure-sensitive adhesive composition [pressure-sensitive adhesive composition containing components (A) to (D)] according to the previous international patent application has a high Tg monomer having an alkyl group having 1 to 3 carbon atoms (meta ) Despite containing a relatively large amount of acrylic acid alkyl ester (A1), it has excellent properties such as resilience and impact resistance. Therefore, even when the conductive particles (E) are added to the adhesive tape and the adhesive tape is excellent in conductivity and electromagnetic wave shielding properties using a strong conductive substrate (metal foil or the like), for example, Various characteristics such as sufficient resilience and impact resistance can be maintained, and for example, peeling due to internal repulsive force or external impact can be prevented.
- the pressure-sensitive adhesive composition of the present invention contains an acrylic copolymer (A), a crosslinking agent (B), a silane coupling agent (C), an antioxidant (D), and conductive particles (E). It is a pressure-sensitive adhesive composition.
- the acrylic copolymer (A) is a (meth) acrylic acid alkyl ester (A1) having an alkyl group having 1 to 3 carbon atoms, and a (meth) acrylic acid having an alkyl group having 4 to 12 carbon atoms.
- (Meth) acrylic acid alkyl ester (A1) is a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 3 carbon atoms, and is a component for improving resilience and impact resistance. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. Of these, methyl (meth) acrylate is preferred.
- the content of the (meth) acrylic acid alkyl ester (A1) is 10 to 20% by mass, preferably 12 to 16% in 100% by mass of the constituent component (monomer unit) of the acrylic copolymer (A). % By mass. The lower limits of these ranges are significant in terms of properties such as resilience resistance and impact resistance. The upper limit is significant in terms of characteristics such as waterproofness.
- (Meth) acrylic acid alkyl ester (A2) is a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms. Specific examples include butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and lauryl (meth) acrylate. It is done. Of these, 2-ethylhexyl (meth) acrylate is preferable.
- the content of the (meth) acrylic acid alkyl ester (A2) is 50 to 80% by mass, preferably 65 to 79% in 100% by mass of the constituent component (monomer unit) of the acrylic copolymer (A). % By mass.
- the carboxyl group-containing monomer (A3) is a component for improving resilience and impact resistance. Specific examples include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 2-carboxy-1-butene, 2-carboxy-1-pentene, 2-carboxy-1-hexene and 2-carboxy. -1-heptene.
- the content of the carboxyl-containing monomer (A3) is 10 to 15% by mass, preferably 10 to 12% by mass, in 100% by mass of the constituent component (monomer unit) of the acrylic copolymer (A). is there. These ranges are significant in terms of characteristics such as resilience resistance and impact resistance.
- the hydroxyl group-containing monomer (A4) is a component for improving resilience and impact resistance. Specific examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- the content of the hydroxyl group-containing monomer (A4) is 0.01 to 0.5% by mass, preferably 0.05, out of 100% by mass of the constituent component (monomer unit) of the acrylic copolymer (A). To 0.15% by mass.
- Vinyl acetate (A5) is a component for improving resilience and impact resistance.
- the content of vinyl acetate (A5) is 1 to 5% by mass, preferably 2 to 4% by mass, in 100% by mass of the constituent component (monomer unit) of the acrylic copolymer (A).
- the lower limits of these ranges are significant in terms of properties such as resilience resistance and impact resistance.
- the acrylic copolymer (A) can be obtained by copolymerizing at least the components (A1) to (A5) described above.
- the polymerization method is not particularly limited, but radical solution polymerization is preferable from the viewpoint of easy polymer design.
- an acrylic syrup composed of the acrylic copolymer (A) and its monomer may be prepared first, and the acrylic syrup may be blended with a crosslinking agent (B) and an additional photopolymerization initiator for polymerization.
- acrylic copolymer (A) monomers other than the components (A1) to (A5) may be copolymerized as long as the effects of the present invention are not impaired.
- the weight average molecular weight of the acrylic copolymer (A) is 950,000 to 2,000,000, preferably 100 to 1,500,000.
- the lower limit of these ranges is significant in terms of characteristics such as resilience resistance and impact resistance.
- the upper limit is significant in terms of properties such as coating properties of the pressure-sensitive adhesive composition.
- This weight average molecular weight is a value measured by the GPC method.
- the theoretical Tg of the acrylic copolymer (A) is ⁇ 55 ° C. or less, preferably ⁇ 55 to ⁇ 75 ° C. This theoretical Tg is a value calculated by the formula of FOX. The upper limit of these ranges is significant in terms of properties such as coating properties of the pressure-sensitive adhesive composition.
- the acrylic copolymer (A) described above is used as a resin component, but other types of additive components may be used in combination as long as the effects of the present invention are not impaired.
- Specific examples include tackifier resins such as rosin tackifiers, terpene resins, petroleum resins, terpene phenol resins, and styrene resins.
- the crosslinking agent (B) used in the present invention is a compound that is blended to react with the acrylic copolymer (A) to form a crosslinked structure.
- a compound capable of reacting with a carboxyl group and / or a hydroxyl group of the acrylic copolymer (A) is preferred.
- an isocyanate type crosslinking agent is preferable from the viewpoint of characteristics such as impact resistance.
- Specific examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and modified prepolymers thereof. Two or more of these may be used in combination.
- the amount of the crosslinking agent (B) is preferably 0.02 to 1 part by mass, more preferably 0.3 to 0.6 part by mass with respect to 100 parts by mass of the acrylic copolymer (A).
- the silane coupling agent (C) is a component for improving the resilience resistance.
- a silane coupling agent containing a glycidyl group is preferable.
- Specific examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane.
- tris- (trimethoxysilylpropyl) isocyanurate Two or more of these may be used in combination.
- the blending amount of the silane coupling agent (C) is preferably 0.01 to 0.5 parts by mass, more preferably 0.02 to 0.5 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). Particularly preferred is 0.03 to 0.3 parts by mass.
- the antioxidant (D) is a component for improving the resilience resistance.
- a hindered phenol antioxidant is preferable.
- the blending amount of the antioxidant (D) is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.5 part by mass with respect to 100 parts by mass of the acrylic copolymer (A).
- the conductive particles (E) are components for imparting conductivity to the pressure-sensitive adhesive composition. If the adhesive composition containing electroconductive particle (E) is used for the adhesive layer of an adhesive tape, for example, the electroconductivity will contribute to the effect which suppresses electrostatic charge and the effect which shields electromagnetic waves. Further, since the pressure-sensitive adhesive composition itself containing components (A) to (D) is excellent in various properties such as resilience and impact resistance, it is sufficiently practical even if conductive particles (E) are added. Various characteristics such as resilience and impact resistance can be maintained. Therefore, for example, when conductive particles (E) in the same amount as the pressure-sensitive adhesive layer of a conventional pressure-sensitive adhesive tape are added, the properties such as resilience and impact resistance are excellent as compared with the conventional pressure-sensitive adhesive tape. It will be. Moreover, it is also possible to increase electroconductivity by increasing the quantity of electroconductive particle (E) rather than the adhesive layer of the conventional adhesive tape.
- the conductive particles (E) include metal particles such as nickel, copper, chromium, gold, silver, alloys thereof or modified products thereof, carbon, graphite, and conductive resin particles in which a metal is coated on the resin surface. It is done. Two or more kinds of conductive particles may be used in combination. Among these, metal particles are preferable, nickel particles and copper particles are more preferable, and nickel particles are most preferable.
- the compounding amount of the conductive particles (E) is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 7 parts by mass, and particularly preferably 0 with respect to 100 parts by mass of the acrylic copolymer (A). 0.05 to 5 parts by mass.
- the pressure-sensitive adhesive composition of the present invention preferably further contains a rust inhibitor (F).
- the rust inhibitor (F) is a component for stabilizing resilience resistance and conductivity.
- imidazole compounds, triazole compounds, tetrazole compounds, and thiadiazole compounds can be suitably used as the rust inhibitor (F).
- triazole compounds are preferred.
- Specific examples of the triazole compound include benzotriazole, 1-aminobenzotriazole, and 5-aminobenzotriazole. In particular, benzotriazole is preferable.
- the blending amount of the rust inhibitor (F) is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and particularly preferably 0 with respect to 100 parts by mass of the acrylic copolymer (A). 0.5-3 parts by mass.
- the pressure-sensitive adhesive composition of the present invention may further contain other additives as necessary. Specifically, various additives (for example, tackifiers, plasticizers, softeners, metal deactivators, pigments, etc.) known to be added to this type of pressure-sensitive adhesive composition can be used.
- additives for example, tackifiers, plasticizers, softeners, metal deactivators, pigments, etc.
- the pressure-sensitive adhesive tape of the present invention has a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of the present invention on one surface or both surfaces of a conductive substrate.
- the conductivity of the substrate contributes to the effect of suppressing electrostatic charging and the effect of shielding electromagnetic waves.
- adhesive tapes are increasingly used at sharp points, and adhesive tapes using strong conductive substrates (metal foil, etc.) It has been demanded that it can be used without problems at sharp points.
- the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition of the present invention is excellent in various properties such as resilience and impact resistance, so even if it is a mode using a strong conductive substrate. Can be used well at sharp corners.
- a metal substrate (particularly metal foil) is preferable.
- the metal constituting the substrate include aluminum, copper, nickel, stainless steel, iron, chromium, and titanium. Of these, copper and aluminum are preferred, and copper is most preferred.
- the thickness of the conductive substrate is preferably 3 to 50 ⁇ m, more preferably 5 to 35 ⁇ m, and particularly preferably 6 to 20 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is preferably 2 to 100 ⁇ m, more preferably 3 to 50 ⁇ m, particularly preferably 5 to 30 ⁇ m, and most preferably 7 to 20 ⁇ m.
- the pressure-sensitive adhesive layer may be formed only on one side of the conductive base material, but it is preferably formed on both sides to form a double-sided pressure-sensitive adhesive tape.
- the pressure-sensitive adhesive layer can be formed by crosslinking reaction of the pressure-sensitive adhesive composition of the present invention.
- the pressure-sensitive adhesive composition can be applied on a conductive substrate and subjected to a crosslinking reaction by heating to form a pressure-sensitive adhesive layer on the conductive substrate.
- the pressure-sensitive adhesive composition can be applied to a release paper or other film and subjected to a crosslinking reaction by heating to form a pressure-sensitive adhesive layer, and this pressure-sensitive adhesive layer can be bonded to one or both sides of a conductive substrate.
- a coating device such as a roll coater, a die coater, or a lip coater can be used.
- the solvent in the pressure-sensitive adhesive composition can be removed together with the crosslinking reaction by heating.
- part means parts by mass
- % means mass%
- Table 1 shows the weight average molecular weight (Mw) and theoretical Tg of each acrylic copolymer.
- This weight average molecular weight (Mw) is a value obtained by measuring the molecular weight of an acrylic copolymer in terms of standard polystyrene by the GPC method using the following measuring apparatus and conditions.
- ⁇ Device LC-2000 series (manufactured by JASCO Corporation) -Column: Shodex KF-806M x 2 and Shodex KF-802 x 1-Eluent: Tetrahydrofuran (THF) ⁇ Flow rate: 1.0 mL / min ⁇ Column temperature: 40 ° C.
- ⁇ Injection volume 100 ⁇ L
- ⁇ Detector Refractometer (RI) Measurement sample: A solution in which an acrylic polymer is dissolved in THF to prepare a solution having an acrylic polymer concentration of 0.5% by mass, and dust is removed by filtration through a filter.
- the theoretical Tg is a value calculated by the FOX equation.
- This pressure-sensitive adhesive composition was applied on a silicone-treated release paper so that the thickness after drying was 10 ⁇ m. Next, the solvent was removed and dried at 110 ° C. and a crosslinking reaction was performed to form an adhesive layer.
- This pressure-sensitive adhesive layer was bonded to both surfaces of a 7 ⁇ m thick conductive substrate (copper foil). And it cured at 40 degreeC for 3 days, and obtained the electroconductive double-sided adhesive tape.
- Example 8> A conductive double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the copper-based conductive particles (E2) were used instead of the nickel-based conductive particles (E1).
- Example 9 Example 1 except that the blending ratio of the nickel-based conductive particles (E1) was increased to 7.0 parts, and the thickness of the pressure-sensitive adhesive layer and the thickness of the base material (copper foil) were increased to 20 ⁇ m and 35 ⁇ m, respectively. In the same manner, a conductive double-sided adhesive tape was obtained.
- Example 10 A conductive double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the tetrazole rust inhibitor (F2) was used instead of the triazole rust inhibitor (F1).
- Example 1 A conductive double-sided pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the acrylic copolymer (A) obtained in Production Example 1 was used instead of the acrylic copolymer (A) obtained in Production Example 1. It was.
- ⁇ Reference Example 1> A conductive non-woven fabric (trade name NW05CN, manufactured by Solueta Co., Ltd.) having a thickness of 30 ⁇ m was used as the conductive substrate instead of copper foil, and the thickness of the pressure-sensitive adhesive layer was increased to 15 ⁇ m. Thus, a conductive double-sided adhesive tape was obtained.
- NW05CN trade name NW05CN, manufactured by Solueta Co., Ltd.
- One release paper of the double-sided pressure-sensitive adhesive tape 1 cut into 2 mm ⁇ 40 mm and 2 mm ⁇ 30 mm is peeled off and attached to four sides of an acrylic plate 4 having a thickness of 2 mm and a thickness of 50 mm ⁇ 40 mm as shown in FIG. Cured for 60 minutes in an atmosphere of% RH. Thereafter, the other release paper of the acrylic plate 4 with the adhesive tape was peeled off, bonded to the adherend 3 (1.5 mm thick SUS plate), and cured for 60 minutes in an atmosphere of 23 ° C. and 50% RH. . Thereafter, as shown in FIG.
- the weight 5 having a constant load (300 g) was dropped while changing the height, the peeling was visually confirmed, and the impact resistance was evaluated according to the following criteria.
- Electromagnetic wave shielding properties were confirmed by the KEC (Kansai Electronics Industry Promotion Center) method.
- the KEC method is a method for evaluating the attenuation when a sample is inserted into the apparatus with a decibel display on the basis of a state where the sample does not exist in the apparatus.
- a commercially available electric field shielding effect evaluation apparatus was used, and the electromagnetic wave shielding property was evaluated as follows, particularly with reference to the attenuation rate at a frequency of 1000 MHz. “ ⁇ ”: Attenuation rate of 60 dB or more at 1000 MHz. “ ⁇ ”: Less than 60 dB attenuation at 1000 MHz.
- the pressure-sensitive adhesive composition of the present invention and the pressure-sensitive adhesive tape using the same are excellent in various properties such as resilience, impact resistance, conductivity, and electromagnetic shielding properties, various uses in fields where such properties are required. Is available. That is, for example, it is suitable for applications that are required to prevent the adverse effects of static electricity and electromagnetic waves in electronic devices and to be prevented from being peeled off by an internal repulsive force or an external impact. Specifically, for example, it can be suitably used for bonding or fixing members in portable electronic devices such as smartphones, tablets, car navigation systems, cameras, audiovisual devices, game machines, and information devices.
- Double-sided adhesive tape 2 Polyimide film 3 Substrate 4 Acrylic plate 5 Weight
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Abstract
Description
本発明の粘着剤組成物は、アクリル系共重合体(A)と、架橋剤(B)と、シランカップリング剤(C)と、酸化防止剤(D)と導電性粒子(E)を含有する粘着剤組成物である。
本発明の粘着テープは、導電性基材の片面又は両面に、本発明の粘着剤組成物により形成された粘着剤層を有する。この基材の導電性は、静電気の帯電を抑制する効果や電磁波を遮蔽する効果に寄与する。例えば近年の製品の小型化、薄型化に伴い粘着テープも鋭角な箇所に使用されることが多くなって来ており、コシの強い導電性基材(金属箔等)を用いた粘着テープも、鋭角な箇所で問題無く使用可能であることが求められて来ている。一方、本発明の粘着剤組成物により形成された粘着剤層は耐反発性、耐衝撃性等の諸特性に優れているので、たとえコシの強い導電性基材を用いた態様であっても鋭角な箇所に良好に使用できる。
攪拌機、温度計、還流冷却器及び窒素ガス導入管を備えた反応装置に、表1に示す量(%)の成分(A1)~(A5)と、酢酸エチル、連鎖移動剤としてn-ドデカンチオール及び過酸化物系ラジカル重合開始剤としてラウリルパーオキサイド0.1部を仕込んだ。反応装置内に窒素ガスを封入し、攪拌しながら窒素ガス気流下で68℃、3時間、その後78℃、3時間で重合反応させた。その後、室温まで冷却し、酢酸エチルを追加した。これにより、固形分濃度30%のアクリル系共重合体(A)を得た。
・装置:LC-2000シリーズ(日本分光株式会社製)
・カラム:Shodex KF-806M×2本、Shodex KF-802×1本
・溶離液:テトラヒドロフラン(THF)
・流速:1.0mL/分
・カラム温度:40℃
・注入量:100μL
・検出器:屈折率計(RI)
・測定サンプル:アクリル系ポリマーをTHFに溶解させ、アクリル系ポリマーの濃度が0.5質量%の溶液を作製し、フィルターによるろ過でゴミを除去したもの。
「MA」:メチルアクリレート
「2-EHA」:2-エチルヘキシルアクリレート
「BA」:n-ブチルアクリレート
「AA」:アクリル酸
「4-HBA」:4-ヒドロキシブチルアクリレート
「Vac」:酢酸ビニル
製造例1~7で得たアクリル系共重合体(A)の固形分100部に対して、架橋剤(B1)、シランカップリング剤(C1)、酸化防止剤(D1)、ニッケル系導電性粒子(E1)、トリアゾール系防錆剤(F1)を表2に示す量(部)加えて混合し、粘着剤組成物を調製した。
ニッケル系導電性粒子(E1)の代わりに銅系導電性粒子(E2)を用いたこと以外は、実施例1と同様にして導電性両面粘着テープを得た。
ニッケル系導電性粒子(E1)の配合割合を7.0部に増やし、粘着剤層の厚さ及び基材(銅箔)の厚さを各々20μm及び35μmと厚くしたこと以外は、実施例1と同様にして導電性両面粘着テープを得た。
トリアゾール系防錆剤(F1)の代わりにテトラゾール系防錆剤(F2)を用いたこと以外は、実施例1と同様にして導電性両面粘着テープを得た。
製造例1で得たアクリル系共重合体(A)の代わりに、製造例8で得たアクリル系共重合体を用いたこと以外は、実施例1と同様にして導電性両面粘着テープを得た。
製造例1で得たアクリル系共重合体(A)の代わりに、製造例9で得たアクリル系共重合体を用いたこと以外は、実施例1と同様にして導電性両面粘着テープを得た。
導電性基材として、銅箔の代わりに厚さ30μmの導電不織布(Solueta社製、商品名NW05CN)を用い、粘着剤層の厚さを15μmと厚くしたこと以外は、実施例1と同様にして導電性両面粘着テープを得た。
「B1」:イソシアネート系架橋剤(東ソー社製、コロネート(登録商標)L-45E)
「C1」:シランカップリング剤(信越化学工業社製、商品名KBM-403)
「D1」:酸化防止剤(BASF社製、イルガノックス(登録商標)1010)
「E1」:ニッケル系導電性粒子(ヴァーレ社製、商品名ニッケルパウダータイプ123)
「E2」:銅系導電性粒子(福田金属箔社製、商品名 電解粉FCC-115)
「F1」:トリアゾール系防錆剤(共同薬品社製、商品名BTZM)
「F2」:テトラゾール系防錆剤(東洋化成社製、商品名M-5T)
実施例及び比較例で得た導電性基材両面テープを以下の方法で評価した。結果を表3に示す。
1mm×20mmに裁断した両面粘着テープ1の一方の離型紙を剥離し、厚さ75μmで20mm×60mmのポリイミドフィルム2の一方に図1に示すように貼り付け、23℃、50%RHの雰囲気下で60分間養生した。その後、ポリイミドフィルム2を図2に示すように折り曲げて粘着テープ1を被着体3(1.5mm厚のSUS板)に貼り合せ、85℃の雰囲気下で72時間放置し、接着部分の剥がれを目視にて確認し、以下の基準で耐反発性を評価した。
「○」:72時間後に接着部分の剥がれ無し。
「×」:72時間後に接着部分の剥がれ有り。
2mm×40mmと2mm×30mmに裁断した両面粘着テープ1の一方の離型紙を剥離し、厚さ2mmで50mm×40mmのアクリル板4の四方に図3に示すように貼り付け、23℃、50%RHの雰囲気下で60分間養生した。その後、粘着テープ付きアクリル板4のもう一方の離離紙を剥離し、被着体3(1.5mm厚のSUS板)に貼り合せ、23℃、50%RHの雰囲気下で60分間養生した。その後、図4に示すように一定の荷重(300g)の錘5を高さを変更しながら落下させ、剥がれを目視で確認し、以下の基準で、耐衝撃性を評価した。
「○」:300mm以上の高さで接着部分の剥がれ無し。
「×」:300mm未満の高さで接着部分の剥がれ有り。
KEC(関西電子工業振興センター)法により電磁波シールド性を確認した。KEC法は、装置内に試料が存在しない状態を基準とし、装置内に試料を挿入した時の減衰量をデシベル表示で評価する方法である。この測定には市販の電界シールド効果評価装置を使用し、特に周波数1000MHzでの減衰率を基準にして、電磁波シールド性を以下のように評価した。
「○」:1000MHzでの減衰率60dB以上。
「×」:1000MHzでの減衰率60dB未満。
25mm×25mmに切断した粘着テープを真ちゅう製(金めっき)の電極に挟みこみ、電極の上部から3.5Nの圧力をかけた状態で、0.1Aの電流が流れるように電圧を調整し、R(抵抗値)=V(電圧)/I(電流)の式から抵抗値(mΩ)を算出した。
2 ポリイミドフィルム
3 被着体
4 アクリル板
5 錘
Claims (11)
- 炭素原子数が1~3のアルキル基を有する(メタ)アクリル酸アルキルエステル(A1)10~20質量%、炭素原子数が4~12のアルキル基を有する(メタ)アクリル酸アルキルエステル(A2)50~80質量%、カルボキシル基含有モノマー(A3)10~15質量%、水酸基含有モノマー(A4)0.01~0.5質量%、及び、酢酸ビニル(A5)1~5質量%をポリマー鎖の構成成分として含み、過酸化物系重合開始剤を用いて得られる共重合体の重量平均分子量が95万~200万、理論Tgが-55℃以下であるアクリル系共重合体(A)と、
架橋剤(B)と、
シランカップリング剤(C)と、
酸化防止剤(D)と、
導電性粒子(E)
を含有する粘着剤組成物。 - シランカップリング剤(C)がグリシジル基を含み、その配合量がアクリル系共重合体(A)100質量部に対して0.01~0.5質量部である請求項1記載の粘着剤組成物。
- 架橋剤(B)が、少なくともイソシアネート系架橋剤を含む請求項1記載の粘着剤組成物。
- 酸化防止剤(D)が、ヒンダードフェノール系酸化防止剤を含む請求項1記載の粘着剤組成物。
- 導電性粒子(E)が、金属粒子を含む請求項1記載の粘着剤組成物。
- 導電性粒子(E)の配合量が、アクリル系共重合体(A)100質量部に対して0.01~10質量部である請求項1記載の粘着剤組成物。
- さらに、防錆剤(F)を含む請求項1記載の粘着剤組成物。
- 防錆剤(F)が、トリアゾール系化合物を含む請求項7記載の粘着剤組成物。
- 導電性基材の片面又は両面に、請求項1記載の粘着剤組成物により形成された粘着剤層を有する粘着テープ。
- 導電性基材が、金属箔である請求項9記載の粘着テープ。
- 粘着剤層の厚さが、2~100μmである請求項9記載の粘着テープ。
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