WO2014069398A1 - 粘着剤組成物及び粘着シート - Google Patents
粘着剤組成物及び粘着シート Download PDFInfo
- Publication number
- WO2014069398A1 WO2014069398A1 PCT/JP2013/079120 JP2013079120W WO2014069398A1 WO 2014069398 A1 WO2014069398 A1 WO 2014069398A1 JP 2013079120 W JP2013079120 W JP 2013079120W WO 2014069398 A1 WO2014069398 A1 WO 2014069398A1
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- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive sheet
- mass
- styrene
- Prior art date
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Images
Classifications
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- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
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- C09J125/00—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 an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
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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
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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
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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
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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
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- H—ELECTRICITY
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- H05B33/00—Electroluminescent light sources
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- H05B33/04—Sealing arrangements, e.g. against humidity
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K85/10—Organic polymers or oligomers
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
-
- 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
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- 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
- C09J2423/00—Presence of polyolefin
-
- 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
- C09J2453/00—Presence of block copolymer
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/842—Containers
- H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet. More specifically, for example, sealing of electronic devices such as display devices such as organic EL elements utilizing electroluminescence of organic materials (hereinafter also abbreviated as “EL”).
- the present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet that are suitably used for the above.
- an organic EL element used in an organic device has an organic layer in which an organic charge transport layer or an organic light emitting layer is laminated between an anode and a cathode, and emits high luminance light by low voltage direct current drive. It attracts attention as a possible light emitting element.
- the organic EL element is also expected as a display that achieves a reduction in thickness, weight, flexibility, and the like by using a plastic film as a substrate.
- Patent Document 1 discloses a method in which an organic EL layer formed on a glass substrate is covered with a photocurable resin having moisture resistance, and a substrate with low water permeability is fixed to the upper part of the photocurable resin layer.
- Patent Document 2 discloses a method of sealing opposing transparent substrates with a sealing material made of frit glass.
- Patent Document 3 discloses a method in which an airtight space is formed by a substrate and a shielding material, and the both are bonded with a cationic curing type ultraviolet curing epoxy resin adhesive.
- Patent Document 4 discloses a method of coating a sealing film formed of a moisture-proof polymer film and an adhesive layer on the outer surface of an organic EL element.
- Patent Document 5 for the purpose of solving the above problem, an adhesive sealing used for sealing an organic EL element containing a hydrogenated cyclic olefin polymer and a polyisobutylene resin having a weight average molecular weight of 500,000 or more.
- a composition for use and an adhesive film using the composition are disclosed.
- the adhesive film using the adhesive sealing composition described in Patent Document 5 is not sufficiently effective in suppressing the intrusion of moisture (water vapor) and the like for sealing applications such as organic EL elements.
- the balance between adhesive strength and holding power is poor.
- the adhesive film is weak under high temperature environment or ultraviolet irradiation, etc., and the organic EL element or device is exposed to high temperature environment or ultraviolet irradiation due to long-time driving or driving environment.
- the resin component in the layer comprised with the said adhesive sealing composition of a film may deteriorate.
- the adhesive film described in Patent Document 5 has a problem in that the performance such as the adhesive force and the moisture intrusion suppressing effect is reduced, and the organic EL element is deteriorated accordingly.
- characteristics, such as transparency, are also requested
- An object of the present invention is to provide a pressure-sensitive adhesive composition that has excellent pressure-sensitive adhesive force, is excellent in moisture penetration suppression effect, and can form a pressure-sensitive adhesive layer of a pressure-sensitive adhesive sheet, and a pressure-sensitive adhesive sheet. To do.
- the present inventors provide a pressure-sensitive adhesive composition containing a polyisobutylene resin having a specific mass average molecular weight, a styrene copolymer having a specific unit, and a tackifier having a specific softening point. We found that the problem could be solved. That is, the present invention provides the following [1] to [15].
- the content of the component (C) is 5 to 60 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B), and any one of the above [1] to [4] The pressure-sensitive adhesive composition described.
- the component (A) includes an isobutylene-isoprene copolymer (A1) having a structural unit (a1) derived from isobutylene and a structural unit (a2) derived from isoprene.
- the adhesive composition in any one.
- the content of the structural unit (a2) in the isobutylene-isoprene copolymer (A1) is 0.1 to 30 mol% with respect to all the structural units of the component (A1). 2.
- the pressure-sensitive adhesive composition according to 1. [8] The pressure-sensitive adhesive composition according to any one of the above [1] to [7], wherein the component (B) has a mass average molecular weight of 10,000 to 400,000. [9] A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition according to any one of [1] to [8]. [10] The pressure-sensitive adhesive sheet according to the above [9], wherein the pressure-sensitive adhesive layer has a configuration sandwiched between two release sheets.
- the pressure-sensitive adhesive sheet according to [9], comprising a base material and the pressure-sensitive adhesive layer.
- the water vapor transmission rate of the pressure-sensitive adhesive layer in an environment of 40 ° C. and a relative humidity of 90% is 10.0 g / m 2 / day or less, according to any one of [9] to [13] above.
- Adhesive sheet [15] The pressure-sensitive adhesive sheet according to any one of [9] to [14], which is used for sealing an organic EL device.
- the pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has an excellent adhesive force, is excellent in the effect of suppressing moisture intrusion, and has good transparency. For this reason, when the pressure-sensitive adhesive sheet is used for sealing an organic EL element or the like, moisture intrusion into the element can be suppressed, and characteristic deterioration of the organic EL element can be suppressed.
- Mw mass average molecular weight
- GPC gel permeation chromatography
- the pressure-sensitive adhesive composition of the present invention comprises a polyisobutylene resin (A) having a mass average molecular weight of 20,000 or more, a styrene-butadiene-styrene triblock copolymer (SBS), and styrene-block- (ethylene-co-butylene).
- A polyisobutylene resin having a mass average molecular weight of 20,000 or more
- SBS styrene-butadiene-styrene triblock copolymer
- styrene-block- (ethylene-co-butylene) ethylene-co-butylene
- SEBS -block-styrene triblock copolymer
- SIB styrene-isobutylene diblock copolymer
- SIBS styrene-isobutylene-styrene triblock copolymer
- the system copolymer (B) and a tackifier (C) having a softening point of 135 ° C. or less are contained.
- the pressure-sensitive adhesive composition of the present invention may contain other additives and other resins other than the components (A) to (C) as long as the effects of the present invention are not impaired.
- the polyisobutylene resin (A) contained in the pressure-sensitive adhesive composition of the present invention is a polyisobutylene resin having a mass average molecular weight of 20,000 or more.
- mass average molecular weight of the component (A) is less than 20,000, the cohesive force of the pressure-sensitive adhesive composition cannot be sufficiently obtained, and the adhesiveness cannot be sufficiently improved.
- the adhesive sheet using an adhesive composition is used for a sealing use, the adhesive force of an adhesive sheet is inadequate and the moisture penetration inhibitory effect of an adhesive sheet is also inadequate. Furthermore, the adherend may be contaminated.
- the weight average molecular weight of the component (A) is 20,000 or more. From the above viewpoint and from the viewpoint of wettability to the adherend and solubility in a solvent, it is preferably 30,000 to 1,000,000, more preferably 50,000 to It is 800,000, more preferably 70,000 to 600,000, and still more preferably 140,000 to 450,000.
- the structure of the polyisobutylene resin (A) is a resin having a polyisobutylene skeleton in the main chain or side chain, specifically, a resin having the following structural unit (a).
- polyisobutylene-based resin examples include polyisobutylene, which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and these copolymers And halogenated butyl rubber obtained by bromination or chlorination.
- polyisobutylene resins may be used alone or in combination of two or more.
- the structural unit derived from isobutylene shall be contained most among all the structural units which comprise the said polyisobutylene resin.
- the content of the structural unit derived from isobutylene is preferably 60 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% with respect to all the structural units of component (A). % Or more, more preferably 95 mol% or more.
- the said polyisobutylene-type resin contained as (A) component is a copolymer
- the said copolymer does not contain the structural unit derived from styrene, and is distinguished from (B) component.
- Examples of the synthesis method of the polyisobutylene resin include a method of polymerizing a monomer component such as isobutylene in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride.
- a Lewis acid catalyst such as aluminum chloride or boron trifluoride.
- commercially available products such as Vistanex (manufactured by Exxon Chemical Co.), Hycar (manufactured by Goodrich), Opanol (manufactured by BASF) and the like can also be used.
- the content of the component (A) with respect to the total amount of the pressure-sensitive adhesive composition of the present invention is preferably 20 to 90% by mass, more preferably 25%, from the viewpoints of improving the adhesive force and improving the moisture penetration inhibiting effect. It is ⁇ 85 mass%, more preferably 30 to 80 mass%, still more preferably 35 to 75 mass%.
- a composition derived from isobutylene from the viewpoint of obtaining a pressure-sensitive adhesive sheet that has a low water vapor permeability value of the pressure-sensitive adhesive layer formed from the resulting pressure-sensitive adhesive composition and is excellent in moisture penetration suppression effect. It is preferable to include an isobutylene-isoprene copolymer (A1) having a unit (a1) and a structural unit (a2) derived from isoprene. From the above viewpoint, the content of the isobutylene-isoprene copolymer (A1) in the component (A) is preferably 50 to 100% by mass, more preferably 65 to 100% by mass, still more preferably 80 to 100% by mass, Even more preferably, it is 90 to 100% by mass.
- the content of the structural unit (a2) derived from isoprene suppresses the value of the water vapor transmission rate of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, and allows water to enter.
- the content of the structural unit (a2) derived from isoprene suppresses the value of the water vapor transmission rate of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, and allows water to enter.
- a pressure-sensitive adhesive sheet excellent in the suppression effect preferably 0.1 to 30.0 mol%, more preferably 0.5 to 20.0 mol%, based on all structural units of the component (A1), More preferably, it is 0.8 to 15.0 mol%, and still more preferably 1.3 to 10.0 mol%.
- the content of the structural unit (a1) derived from isobutylene is preferably 70.0 to 99.9 mol%, more preferably 80.0 to 99.5, based on all structural units of the component (A1). More preferably, it is 85.0 to 99.2, and still more preferably 90.0 to 98.7.
- the mass average molecular weight (Mw) of the component (A1) is 20,000 or more, preferably 30,000 to 1,000,000, more preferably 50,000 to 800,000, more preferably 70,000 to 600,000, and still more preferably 14 It is 10,000 to 450,000, more preferably 180,000 to 350,000.
- a polyisobutylene resin having a high mass average molecular weight, and mass A polyisobutylene resin having a low average molecular weight is preferably used in combination, a polyisobutylene resin ( ⁇ ) having a mass average molecular weight of 270,000 to 600,000 (hereinafter also referred to as “resin ( ⁇ )”), and a mass average molecular weight Is preferably 50,000 to 250,000 polyisobutylene resin ( ⁇ ) (hereinafter also referred to as “resin ( ⁇ )”).
- a resin ( ⁇ ) having a high mass average molecular weight By including a resin ( ⁇ ) having a high mass average molecular weight, it contributes to the improvement of durability, weather resistance and adhesive strength of the pressure-sensitive adhesive layer formed from the obtained pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition is used.
- the adhesive sheet used for sealing When the adhesive sheet used for sealing is used for sealing, it contributes to an improvement in the effect of suppressing moisture intrusion.
- a resin ( ⁇ ) having a low mass average molecular weight it is well compatible with the resin ( ⁇ ), and can appropriately plasticize the resin ( ⁇ ). The wettability with respect to the adherend of the pressure-sensitive adhesive layer to be formed can be improved, and the physical properties of adhesive, flexibility and the like can be improved.
- the mass average molecular weight (Mw) of the resin ( ⁇ ) is preferably 270,000 to 600,000, more preferably 290,000 to 480,000, still more preferably 310,000 to 450,000, and even more preferably 320,000 to 400,000. is there. If the Mw of the resin ( ⁇ ) is 270,000 or more, the cohesive strength of the obtained pressure-sensitive adhesive composition can be sufficiently improved, and the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition and the suppression of water intrusion. The effect can be improved. Moreover, the concern about contamination of the adherend can be solved.
- the Mw of the resin ( ⁇ ) is 600,000 or less, the cohesive force of the resulting pressure-sensitive adhesive composition becomes too high, so that the adverse effects of flexibility and fluidity can be avoided. It is possible to improve the wettability of the pressure-sensitive adhesive layer formed from a product with the adherend. Moreover, when making an adhesive composition into the form of a solution, the solubility with respect to a solvent can be made favorable.
- the mass average molecular weight (Mw) of the resin ( ⁇ ) is preferably 50,000 to 250,000, more preferably 80,000 to 230,000, still more preferably 140,000 to 220,000, and still more preferably 180,000 to 210,000. . If the Mw of the resin ( ⁇ ) is 50,000 or more, in the pressure-sensitive adhesive layer formed from the resulting pressure-sensitive adhesive composition, the resin ( ⁇ ) is separated as a low molecular component and deposited on the surface of the pressure-sensitive adhesive layer. The adverse effect of contaminating the adherend can be prevented. In addition, the influence on physical properties such as an increase in the amount of outgas generated at high temperatures can be avoided. On the other hand, if the Mw of the resin ( ⁇ ) is 250,000 or less, the resin (A1) can be sufficiently plasticized, and the pressure-sensitive adhesive layer formed from the resulting pressure-sensitive adhesive composition is wetted with the adherend. Can be improved.
- the content ratio of the resin ( ⁇ ) to 100 parts by mass of the resin ( ⁇ ) is preferably 5 to 55 parts by mass, more preferably 6 to 40 parts by mass, still more preferably 7 to 30 parts by mass, and still more preferably 8 to 20 parts by mass.
- the content ratio of the resin ( ⁇ ) is 5 parts by mass or more, the resin ( ⁇ ) can be sufficiently plasticized, and the pressure-sensitive adhesive layer formed from the resulting pressure-sensitive adhesive composition is wetted with the adherend. Can be improved, and the adhesive strength can be improved.
- the content ratio of the resin ( ⁇ ) is 55 parts by mass or less, the cohesive force of the obtained pressure-sensitive adhesive composition can be sufficiently improved, so that the pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition is used. Excellent adhesive strength and durability can be imparted.
- the pressure-sensitive adhesive composition of the present invention comprises styrene-butadiene-styrene triblock copolymer (SBS), styrene-block- (ethylene-co-butylene) -block-styrene triblock copolymer (SEBS), styrene-isobutylene. It contains at least one styrenic copolymer (B) selected from the group consisting of a diblock copolymer (SIB) and a styrene-isobutylene-styrene triblock copolymer (SIBS).
- SIB diblock copolymer
- SIBS styrene-isobutylene-styrene triblock copolymer
- component (B) By containing one or more styrene copolymers selected from the above group as component (B) in the pressure-sensitive adhesive composition, suppression of moisture intrusion of the pressure-sensitive adhesive sheet using the resulting pressure-sensitive adhesive composition While making an effect favorable, the adhesive force of the said adhesive sheet can be improved.
- component (B) one or more selected from SBS and SEBS are preferable from the viewpoint of improving the adhesive strength of the pressure-sensitive adhesive sheet using the obtained pressure-sensitive adhesive composition.
- 1 or more types chosen from SIB and SIBS are preferable from a viewpoint of improving the inhibitory effect of the moisture permeation of the said adhesive sheet.
- the weight average molecular weight (Mw) of the component (B) is preferably from the viewpoint of improving the moisture penetration suppression effect of the pressure-sensitive adhesive sheet using the obtained pressure-sensitive adhesive composition and improving the pressure-sensitive adhesive force of the pressure-sensitive adhesive sheet. It is 10,000 to 400,000, more preferably 20,000 to 300,000, still more preferably 25,000 to 200,000, and still more preferably 30,000 to 90,000. If Mw of (B) component is 10,000 or more, the adhesive force of the adhesive sheet using the obtained adhesive composition can be improved. On the other hand, if the Mw of the component (B) is 400,000 or less, the pressure-sensitive adhesive layer formed from the resulting pressure-sensitive adhesive composition while maintaining the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet using the resulting pressure-sensitive adhesive composition is good. The value of the water vapor transmission rate can be reduced, and the effect of suppressing moisture intrusion of the pressure-sensitive adhesive sheet can be improved.
- the softening point of the component (B) is that the pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition is used for sealing applications such as an organic EL device, and the viewpoint of improving the effect of suppressing moisture intrusion of the pressure-sensitive adhesive sheet, and the pressure-sensitive adhesive. From the viewpoint of improving the adhesive strength of the sheet, it is preferably 80 to 200 ° C, more preferably 90 to 160 ° C, still more preferably 100 to 140 ° C, and still more preferably 105 to 135 ° C.
- the ratio of styrene contained in the styrene copolymer of component (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35% by mass.
- the content of component (B) is preferably 5 to 200 parts by weight, more preferably 6 to 140 parts by weight, more preferably 7 to 120 parts by weight, and still more preferably 8 parts per 100 parts by weight of component (A). It is -95 mass parts, More preferably, it is 9-88 mass parts. If the content of the component (B) is 5 parts by mass or more, when a pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition is used for sealing applications such as an organic EL element, moisture intrusion is effectively suppressed and organic It is possible to suppress deterioration of the characteristics of the EL element. Moreover, the adhesive force of the said adhesive sheet can also be improved.
- content of (B) component is 200 mass parts or less, the adhesive force of the adhesive sheet using the obtained adhesive composition can fully be improved, and it is formed from the said adhesive composition.
- the value of the water vapor transmission rate of the pressure-sensitive adhesive layer can be reduced, and the effect of suppressing the water penetration of the pressure-sensitive adhesive sheet can be made favorable.
- the content ratio [(A) / (B)] of the component (A) to the component (B) is preferably 40/60 to 95/5, more preferably 45/55 to 92/8, more preferably 50 / 50 to 90/10, more preferably 55/45 to 88/12, still more preferably 60/40 to 85/15, still more preferably 65/35 to 82/15. If the content ratio is within the above range, the water vapor permeability of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is improved while improving the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet using the obtained pressure-sensitive adhesive composition. A value can be made small and the inhibitory effect of the moisture penetration
- the content of the component (B) relative to the total amount of the pressure-sensitive adhesive composition of the present invention is preferably 2 to 60% by mass, more preferably 4 to 55% by mass, from the viewpoint of improving compatibility and the effect of suppressing moisture intrusion. More preferably, it is 6 to 50% by mass, and still more preferably 8 to 47% by mass.
- the pressure-sensitive adhesive composition of the present invention contains a tackifier (C) having a softening point of 135 ° C. or lower.
- the tackifier can be mixed with the above-mentioned components (A) and (B) and other resin components, and has a function of improving the adhesive performance of these resin components.
- a compound having a molecular weight is meant.
- the number average molecular weight of the tackifier is usually from 100 to 18000, preferably from 100 to 10,000.
- the softening point of the tackifier (C) is 135 ° C. or lower.
- the softening point of the tackifier (C) exceeds 135 ° C., the tackiness of the pressure-sensitive adhesive composition containing the components (A) and (B) is remarkably lowered, which is not preferable.
- zipping may generate
- the softening point of the tackifier (C) is 135 ° C. or less, but from the above viewpoint, it is preferably 132 ° C. or less, more preferably 128 ° C. or less, more preferably 120 ° C.
- the softening point of the tackifier (C) is preferably 60 ° C. or more, more preferably, from the viewpoint of improving the cohesive strength of the obtained pressure-sensitive adhesive composition and obtaining a pressure-sensitive adhesive composition that exhibits excellent tackiness. Is 70 ° C or higher, more preferably 80 ° C or higher, and still more preferably 90 ° C or higher.
- two or more tackifiers (C) having different softening points may be combined. When using several tackifiers, the weighted average of the softening points of these tackifiers should just belong to the said range.
- the weighted average of softening points of a plurality of tackifiers is 135 ° C. or less (if it belongs to the above range)
- a tackifier having a softening point exceeding 135 ° C. in the adhesive composition You may contain in.
- the content of the tackifier having a softening point exceeding 135 ° C is preferably 10% by mass or less, more preferably 4% by mass or less, based on the total amount of the tackifier (C) contained in the adhesive composition. More preferably, it is 1 mass% or less, More preferably, it is 0.01 mass% or less.
- tackifier (C) examples include rosin resins such as aliphatic hydrocarbon resins, rosin resins, rosin phenol resins, and rosin ester resins; hydrogenated rosin resins obtained by hydrogenating these rosin resins; Terpene resins such as resins, terpene phenolic resins, aromatic modified terpene resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; C5 petroleum resins and the C5 petroleum Hydrogenated petroleum resin of resin; C9 petroleum resin obtained by copolymerizing C9 fraction and hydrogenated petroleum resin of this C9 petroleum resin; Things. You may use the said tackifier individually or in combination of 2 or more types.
- C5 fraction means an unsaturated hydrocarbon having 5 carbon atoms, such as pentene, isoprene, piperine, 1.3-pentadiene, which is produced by the thermal decomposition of petroleum naphtha.
- Petroleum resin means a resin obtained by copolymerizing this C5 fraction and containing the C5 fraction as a main component (including at least 20% by mass or more).
- C9 fraction means an unsaturated hydrocarbon having 9 carbon atoms such as indene, vinyltoluene, ⁇ or ⁇ -methylstyrene, which is generated by thermal decomposition of petroleum naphtha.
- Resin means a resin obtained by copolymerizing the C9 fraction and containing the C9 fraction as a main component (including at least 20% by mass or more).
- the above-mentioned “hydrogenated resin” includes not only a completely hydrogenated resin but also a partially hydrogenated resin partially hydrogenated.
- aliphatic hydrocarbons are used from the viewpoint of obtaining a pressure-sensitive adhesive sheet having a small water vapor permeability value of the pressure-sensitive adhesive layer formed from the obtained pressure-sensitive adhesive composition and excellent in moisture penetration suppression effect. Resins are preferred.
- the “aliphatic hydrocarbon resin” is a petroleum-derived resin that does not have an aromatic ring and an alicyclic structure.
- “aliphatic hydrocarbon resins” are clearly distinguished from “aromatic hydrocarbon resins” having aromatic rings and “alicyclic hydrocarbon resins” such as dicyclopentadiene resins. It is.
- the aliphatic hydrocarbon resin is a compound in an oligomer region having a number average molecular weight of 100 to 18000 (preferably 100 to 10,000), and one or more aliphatic hydrocarbons selected from olefins and dienes having 4 or 5 carbon atoms.
- the polymer is preferably.
- the olefin include 1-butene, isobutylene, 1-pentene and the like.
- Examples of the diene include butadiene, 1,3-pentadiene, and isoprene.
- the aliphatic hydrocarbon resin may be a completely hydrogenated resin that is completely hydrogenated or a partially hydrogenated resin that is partially hydrogenated.
- the above aliphatic hydrocarbon resins may be used alone or in combination of two or more.
- aliphatic hydrocarbon resins from the viewpoint of obtaining a pressure-sensitive adhesive sheet having a small water vapor permeability value of the pressure-sensitive adhesive layer formed from the obtained pressure-sensitive adhesive composition and having an excellent effect of suppressing moisture intrusion, Is preferably an aliphatic hydrocarbon resin produced from the main raw material (containing at least 20% by mass or more), more preferably an aliphatic hydrocarbon resin produced from the C5 diene as the main raw material, and 1,3-pentadiene. More preferred are aliphatic hydrocarbon resins produced from the main raw material.
- the content of the aliphatic hydrocarbon resin is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, based on the total amount of the tackifier (C) contained in the adhesive composition of the present invention. More preferably, it is 80 to 100% by mass, and still more preferably 90 to 100% by mass.
- the pressure-sensitive adhesive composition of the present invention from the viewpoint of obtaining a pressure-sensitive adhesive sheet having a small water vapor permeability value of the pressure-sensitive adhesive layer formed from the obtained pressure-sensitive adhesive composition and having an excellent effect of suppressing moisture intrusion. It is preferable not to contain a series hydrocarbon resin or an alicyclic hydrocarbon resin. From the above viewpoint, the content of the aromatic hydrocarbon resin and the alicyclic hydrocarbon resin is preferably 10 mass with respect to the total amount of the tackifier (C) contained in the pressure-sensitive adhesive composition of the present invention. % Or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, and still more preferably 0.01% by mass or less.
- the content of component (C) is preferably 5 to 60 parts by mass, more preferably 8 to 50 parts by mass, and still more preferably 10 to 45 parts per 100 parts by mass of the total of components (A) and (B). Part by mass, more preferably 15 to 42 parts by mass. (C) If content of a component is 5 mass parts or more, about the adhesive layer formed from the obtained adhesive composition, wetting with a to-be-adhered body is fully obtained and adhesive force can be improved. In addition, it is possible to obtain a pressure-sensitive adhesive sheet having a small water vapor permeability value of the pressure-sensitive adhesive layer and having an excellent effect of suppressing moisture intrusion.
- the pressure-sensitive adhesive layer formed from the obtained pressure-sensitive adhesive composition can exhibit an excellent adhesive force regardless of the adherend.
- the occurrence of zipping can be suppressed.
- the value of the water-vapor-permeability of the said adhesive layer is small, and the adhesive sheet excellent in the suppression effect of moisture permeation can be obtained.
- the content of the component (C) with respect to the total amount of the pressure-sensitive adhesive composition of the present invention is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, still more preferably 8 to 35% by mass, and more. More preferably, it is 12 to 30% by mass.
- the pressure-sensitive adhesive composition of the present invention may further contain other additives as long as the effects of the present invention are not impaired.
- other additives include light stabilizers, antioxidants, ultraviolet absorbers, resin stabilizers, fillers, pigments, extenders, softeners, and the like. These additives may be used alone or in combination of two or more.
- the content of each of these other components is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of component (A).
- Examples of the light stabilizer include hindered amine-based, benzophenone-based, and benzotriazole-based light stabilizers.
- Examples of the antioxidant include phosphate ester compounds.
- Examples of the ultraviolet absorber include benzotriazole compounds, oxazolic acid amide compounds, benzophenone compounds, and the like.
- Examples of the resin stabilizer include an imidazole resin stabilizer, a dithiocarbamate resin stabilizer, a phosphorus resin stabilizer, and a sulfur ester resin stabilizer.
- the pressure-sensitive adhesive composition of the present invention may contain other resin components other than the above-mentioned components (A) to (C) as long as the effects of the present invention are not impaired. Preferably not.
- the content of other resin components other than the components (A) to (C) is preferably less than 50% by mass, more preferably 20% by mass or less, still more preferably 5% by mass, based on the total amount of the pressure-sensitive adhesive composition. Hereinafter, it is more preferably 1% by mass or less.
- Examples of other resins other than the components (A) to (C) include styrene copolymers not corresponding to the component (B).
- Examples of the styrene copolymer not corresponding to the component (B) include styrene-butadiene diblock copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene triblock copolymer, and styrene-block-.
- butadiene-co-isoprene -block diblock copolymer
- styrene-block- butadiene-co-isoprene
- block-styrene triblock copolymer styrene-block- (ethylene-co-butylene) -block diblock
- SEB block copolymer
- carboxyl-modified styrene copolymer as described above
- a copolymer of styrene and an aromatic vinyl compound such as ⁇ -methylstyrene.
- the pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as it has a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition of the present invention containing the above-described components.
- the adhesive sheet 1a which has the adhesive layer 12 on the base material 11 is mentioned, for example like Fig.1 (a).
- the adhesive sheet 1b may further have a release sheet on the adhesive layers 12a and 12b. Furthermore, it is good also as the adhesive sheet 1d by which the adhesive layer 12 was clamped by the two peeling sheets 13a and 13b, without using a base material like FIG.1 (d).
- the release sheets 13a and 13b may be of the same type or different types. However, the release sheets 13a and 13b may be used so that the difference in the release force between the release sheet 13a and the release sheet 13b is different. It is preferable to select an appropriate release sheet.
- the shape of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, and examples thereof include a sheet shape and a roll shape.
- a sheet shape when it is used as a member for an electronic device, it is preferably a sheet.
- the pressure-sensitive adhesive sheet of the present invention exhibits an excellent pressure-sensitive adhesive force even when the pressure-sensitive adhesive layer itself is thin, and has a high pressure-sensitive adhesive force regardless of the type of adherend. Specifically, the adhesive strength of an adhesive sheet having an adhesive layer having a thickness of 20 ⁇ m after being left on the adherend for 24 hours in an environment of 23 ° C.
- the body is glass, it is preferably 9.0 N / 25 mm or more, more preferably 10.0 N / 25 mm or more, still more preferably 12.0 N / 25 mm or more, and when the adherend is stainless steel, preferably 9 0.0 N / 25 mm or more, more preferably 10.0 N / 25 mm or more, and still more preferably 12.0 N / 25 mm or more. If the adhesive strength is in the above range, it has sufficient adhesive strength, and even when it generates heat during driving of an organic EL element or when exposed to a high temperature during driving, it is generated by the difference in coefficient of thermal expansion of each component.
- the pressure-sensitive adhesive sheet of the present invention is in the form of a substrate-less pressure-sensitive adhesive sheet such as the pressure-sensitive adhesive sheet 1d in FIG. 1 (d)
- the pressure-sensitive adhesive force when lined with 50 ⁇ m thick polyethylene terephthalate is within the above range. It is preferable to adjust so that it becomes.
- the value of the adhesive force of the said adhesive sheet means the value measured by the method as described in an Example.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention has excellent transparency.
- the pressure-sensitive adhesive sheet of the present invention preferably has a total light transmittance of 90% or more from the viewpoint of application to sealing applications such as organic EL elements.
- the haze of the pressure-sensitive adhesive sheet of the present invention is preferably 1.20 or less, more preferably 1.00 or less, and still more preferably 0.90 or less.
- the total light transmittance value of the pressure-sensitive adhesive sheet is a value measured according to JIS K 7361-1, and the haze value is a value measured according to JIS K 7136. Both show values measured by the method described in the Examples.
- the thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is appropriately selected depending on the application and the like, but is preferably 0.5 to 100 ⁇ m, more preferably 1 to 60 ⁇ m, and still more preferably 3 to 40 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is 0.5 ⁇ m or more, good adhesive force can be obtained for the adherend.
- the thickness of the pressure-sensitive adhesive layer is 100 ⁇ m or less, it is advantageous in terms of productivity and can be an easy-to-handle pressure-sensitive adhesive sheet.
- the water vapor permeability of the pressure-sensitive adhesive layer having a thickness of 60 ⁇ m of the pressure-sensitive adhesive sheet of the present invention in an environment of 40 ° C. and 90% RH (relative humidity) is preferably 10.0 g / m 2 / day or less, more preferably Is 7.0 g / m 2 / day or less, more preferably 5.0 g / m 2 / day or less, and still more preferably 4.0 g / m 2 / day or less.
- the pressure-sensitive adhesive sheet of the present invention is excellent in moisture penetration suppression effect, and even when used for sealing applications such as organic EL elements, Moisture permeation into the organic EL element can be suppressed, and deterioration of the characteristics of the organic EL element can be suppressed.
- the value of the water-vapor-permeation rate of an adhesive layer means the value measured by the method as described in an Example.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention has excellent transparency.
- the total light transmittance of the pressure-sensitive adhesive layer is preferably 90% or more.
- permeability of wavelength 550nm of an adhesive layer is 90% or more. If the total light transmittance or visible light transmittance of the pressure-sensitive adhesive layer is 90% or more, the pressure-sensitive adhesive sheet of the present invention can be suitably used for sealing applications such as organic EL elements.
- the haze of the pressure-sensitive adhesive layer is preferably 1.20 or less, more preferably 1.00 or less, and still more preferably 0.90 or less.
- the total light transmittance value is a value measured according to JIS K 7361-1
- the haze value is a value measured according to JIS K 7136. Specifically, Both mean values measured by the methods described in the Examples. Moreover, the value of said visible light transmittance shows the value measured by the method as described in an Example.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention has a small amount of outgas generation that can be generated from the pressure-sensitive adhesive layer.
- the outgas generation amount is evaluated by comparing n-decane conversion values.
- the amount of outgas generated when the pressure-sensitive adhesive layer having a thickness of 20 ⁇ m is heated at a temperature of 120 ° C. for 30 minutes is preferably less than 1.0 ⁇ g / cm 2 , more preferably 0.5 ⁇ g / cm 2 in terms of n-decane. In the following, it is more preferably 0.1 ⁇ g / cm 2 or less.
- the pressure-sensitive adhesive layer does not corrode the adherend. Therefore, for example, even when the pressure-sensitive adhesive sheet of the present invention is adapted for application to a precision instrument, the possibility of causing a malfunction of the precision electronic member is significantly reduced.
- the value of the outgas generation amount of an adhesive layer shows the value measured by the method as described in an Example.
- the substrate is not particularly limited as long as it is in a sheet shape, and is appropriately selected according to the purpose of use of the pressure-sensitive adhesive sheet of the present invention.
- various types of paper such as high-quality paper, art paper, coated paper, glassine paper, laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials, various synthetic papers, aluminum foil, copper foil and iron Metal foil such as foil, porous material such as nonwoven fabric, polyolefin resin such as polyethylene resin and polypropylene resin, polyester resin such as polybutylene terephthalate resin and polyethylene terephthalate resin, acetate resin, ABS resin, polystyrene resin, vinyl chloride resin, etc.
- a sheet-shaped substrate such as a plastic film or sheet may be unstretched, or may be stretched in a uniaxial direction or a biaxial direction such as longitudinal or lateral.
- the substrate to be used may be colored or not, but when used as a sealing member, it is preferably one that sufficiently transmits ultraviolet rays, and more preferably colorless and transparent in the visible light region.
- the thickness of the substrate is not particularly limited, but is preferably 10 to 250 ⁇ m, more preferably 15 to 200 ⁇ m, and still more preferably 20 to 150 ⁇ m from the viewpoint of ease of handling.
- the base material may further contain an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a slip agent, an antiblocking agent, a colorant and the like.
- the base material is a plastic material
- the oxidation method is not particularly limited, and examples thereof include a corona discharge treatment method, a plasma treatment method, chromic acid oxidation (wet), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment.
- corrugated method For example, a sandblasting method, a solvent processing method, etc. are mentioned.
- These surface treatments are appropriately selected according to the type of the substrate, but the corona discharge treatment method is preferred from the viewpoint of improving the adhesion with the pressure-sensitive adhesive layer and operability.
- primer treatment can also be performed.
- a sealing layer may be provided between the base material and the pressure-sensitive adhesive layer as desired.
- this sealing layer is used to further improve the adhesion between the base material and the pressure-sensitive adhesive layer, or If the paper is too soft, it is provided to give rigidity.
- Such a sealing layer is not particularly limited, but for example, a styrene-butadiene copolymer, an acrylic resin, a polyester resin, a polyurethane resin, a polystyrene resin, or the like as a main component (containing at least 20% by mass or more) And a layer made of a material added with a filler such as clay, silica, calcium carbonate, titanium oxide, and zinc oxide as necessary.
- the thickness of the sealing layer is not particularly limited, but is usually 0.1 to 30 ⁇ m.
- a gas barrier film having a gas barrier base material and a gas barrier layer is preferably used.
- the said gas barrier film should just have a gas barrier layer in the at least one surface side of the base material for gas barrier films.
- the gas barrier layer may be a single layer or a plurality of layers.
- the base material for the gas barrier film is not particularly limited.
- polyolefin such as polyethylene and polypropylene
- polyester such as polyethylene terephthalate and polybutylene terephthalate
- polyimide polyamideimide
- wholly aromatic polyamide nylon 6, nylon 66
- nylon Polyphenylene such as polymer, lubornene polymer, monocyclic olefin polymer, cyclic conjugated diene polymer, vinyl alicyclic hydrocarbon polymer, and cycloolefin polymers such as hydrides thereof, polyphenylene, etc.
- Examples thereof include a sheet made of a resin of ether, polyether ketone, polyether ether ketone, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, or polyarylate.
- polyester, polyamide or cycloolefin polymer is preferable, and polyester or cycloolefin polymer is more preferable from the viewpoint of excellent transparency and versatility.
- the thickness of the gas barrier film substrate is not particularly limited, but is preferably 2 to 200 ⁇ m, more preferably 10 to 150 ⁇ m, and still more preferably 20 to 100 ⁇ m from the viewpoint of ease of handling.
- the material for forming the gas barrier layer is not particularly limited as long as it prevents permeation of oxygen and water vapor, and examples thereof include metals such as aluminum, magnesium, zinc, and tin, silicon nitride, silicon oxide, silicon oxynitride, Silicon compounds such as polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, and tetraorganosilane compounds; aluminum compounds such as aluminum oxide and aluminum oxynitride; inorganics such as magnesium oxide, zinc oxide, indium oxide, and tin oxide Examples thereof include resins such as oxides, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyvinyl chloride, polyvinylidene chloride, and polychlorotrifluoroethylene.
- metals such as aluminum, magnesium, zinc and tin, silicon nitride, silicon oxide, silicon oxynitride, polysilazane compound, polycarbosilane compound, polysilane compound, polyorganosiloxane compound, tetra Silicon compounds such as organosilane compounds, aluminum compounds such as aluminum oxide and aluminum oxynitride, and inorganic oxides such as magnesium oxide, zinc oxide, indium oxide and tin oxide are preferred.
- a polysilazane compound (2) Polycarbosilane compounds, (3) polysilane compounds, (4) polyorganosiloxane compounds, and (5) tetraorganosilane compounds are more preferred. Details of the compounds (1) to (5) will be described below.
- the polysilazane compound is a polymer having a repeating unit containing a (—Si—N—) bond in the molecule, and includes a compound having a repeating unit represented by the following formula (1).
- R 1 , R 2 and R 3 are each independently a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted group.
- R 1 to R 3 any of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and a phenyl group is preferable, and a hydrogen atom is more preferable.
- the polysilazane compound having a repeating unit represented by the formula (1) is an inorganic polysilazane in which R 1 to R 3 are all hydrogen atoms, or R from the viewpoint of easy availability and formation of a layer having excellent gas barrier properties.
- Organic polysilazanes in which at least one of 1 to R 3 is not a hydrogen atom are preferred, inorganic polysilazanes are more preferred, and perhydropolysilazanes are more preferred.
- the number average molecular weight of the polysilazane compound is not particularly limited, but is preferably 100 to 50,000.
- the polycarbosilane compound is a polymer compound having a repeating unit containing a (—Si—C—) bond in the main chain in the molecule, and includes a compound having a repeating unit represented by the following formula (2). .
- R 4 and R 5 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an aralkyl group, an alkenyl group, or a monovalent heterocyclic group.
- R 4 and R 5 may be the same or different from each other.
- R 6 represents an alkylene group, an arylene group or a divalent heterocyclic group.
- R 4 and R 5 are each independently a hydrogen atom, an alkyl group or an aryl group, and R 6 is an alkylene group or an arylene group.
- R 4 and R 5 each independently represents a hydrogen atom or an alkyl group
- R 6 represents an alkylene group
- R 4 and R 5 each independently represent a hydrogen atom.
- an alkyl group having 1 to 4 carbon atoms and R 6 being an alkylene group having 1 to 6 carbon atoms is more preferable.
- the mass average molecular weight of the polycarbosilane compound is usually from 400 to 12,000.
- the polysilane compound is a polymer compound having a repeating unit containing a (—Si—Si—) bond in the molecule.
- this polysilane compound the compound which has a repeating unit represented by following formula (3) is mentioned.
- R 7 and R 8 are each independently a hydrogen atom, hydroxyl group, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, alkoxy group, cycloalkyloxy group, aryl An oxy group, an aralkyloxy group, an amino group optionally having a substituent, a silyl group, or a halogen atom is represented.
- R 7 and R 8 are each independently a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an amino group, or a silyl group. It is preferable that R 7 and R 8 are each independently a hydrogen atom, an alkyl group, or an aryl group, and R 7 and R 8 are each independently a group having 1 to 4 carbon atoms. What is an alkyl group or an aryl group is still more preferable.
- the form of the polysilane compound is not particularly limited, and it may be a non-cyclic polysilane such as linear polysilane, branched polysilane, or network polysilane, or a homopolymer such as cyclic polysilane, random copolymer, block copolymer. It may be a copolymer such as a polymer, an alternating copolymer, or a comb copolymer.
- the terminal group (terminal substituent) of the polysilane compound may be a hydrogen atom, a halogen atom such as a chlorine atom, an alkyl group, a hydroxyl group, an alkoxy group, a silyl group, etc. There may be.
- the mass average molecular weight of the polysilane compound is not particularly limited, but is preferably 300 to 100,000, more preferably 400 to 50,000, and still more preferably 500 to 30,000.
- the compound having a linear main chain structure includes a compound having a repeating unit represented by the following formula (4)
- the compound having a ladder main chain structure includes the following formula (5).
- a compound having a repeating unit represented by the following formula (6) can be given as an example of a compound having a cage-like main chain structure.
- Rx, Ry and Rz are each a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl Represents a non-hydrolyzable group selected from a group and the like.
- Rx, Ry, and Rz in the formula may be the same or different from each other, but both Rx in the formula (4) are not hydrogen atoms.
- Rx, Ry, and Rz each independently, an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms or a phenyl group is preferable, and a methyl group, an ethyl group, a propyl group, 3- A glycidoxypropyl group or a phenyl group is more preferable.
- the tetraorganosilane compound is a compound in which four hydrolyzable groups are bonded to a silicon element.
- the tetraorganosilane compound is a compound represented by the formula (7): SiX 4 .
- X is a group represented by the formula (8): OR (R represents a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group), and the formula (9): OSi (R a ) (R b ) A group represented by (R c ) (R a , R b , R c each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group), a chlorine atom, a bromine atom, etc. And the like.
- tetraorganosilane compound examples include tetra (C1-C10) alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane; trimethoxychlorosilane, triethoxychlorosilane, and tripropoxy Tri (C1 to C10) alkoxyhalogenosilane such as chlorosilane; Di (C1 to C10) dihalogenoalkoxysilane such as dimethoxydicyclosilane, diethoxydichlorosilane, dipropoxydichlorosilane; methoxytrichlorosilane, ethoxytrichlorosilane, propoxytri Mono (C1-C10) alkoxytrihalogenosilanes such as chlorosilane; tetrahalogenosilanes such as
- tetra (C1 to C10) alkoxysilane is preferable from the viewpoint of excellent handleability and improving gas barrier properties.
- These tetraorganosilane compounds are preferably hydrolyzed and dehydrated in a suitable solvent in the presence of water and optionally a catalyst.
- the mass average molecular weight of the hydrolyzate or dehydrated condensate of the tetraorganosilane compound is not particularly limited, but is preferably 200 to 50000, more preferably 200 to 30000, from the viewpoint of forming a gas barrier layer having excellent mechanical strength. More preferably, it is 200 to 10,000. If the mass average molecular weight is 200 or more, it has sufficient film forming ability, and if it is 50000 or less, a film having sufficient mechanical strength is formed.
- the method for forming the gas barrier layer is not particularly limited.
- the coating method is not particularly limited, and examples thereof include known coating methods such as spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
- a method of forming the above-mentioned material on a substrate by vapor deposition, sputtering, ion plating, thermal CVD, plasma CVD, or the like can be given.
- the thickness of the formed gas barrier layer is preferably 20 nm to 100 ⁇ m, more preferably 30 to 500 nm, and still more preferably 40 to 200 nm from the viewpoint of gas barrier performance and handleability.
- a gas barrier layer is nano order, it can be set as the adhesive sheet which has sufficient gas barrier performance.
- the gas barrier layer is obtained by subjecting the surface of the layer containing the polysilazane compound to a conversion treatment from the viewpoint of obtaining a pressure-sensitive adhesive sheet having a small water vapor permeability value and an excellent effect of suppressing moisture intrusion. It is preferable.
- the conversion treatment include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, heat treatment, and the like. Among these, it is preferable to implant ions. By implanting ions, gas barrier performance can be improved while maintaining high transparency.
- the step of implanting ions is not particularly limited, and examples thereof include a method of forming a gas barrier layer on a substrate and then implanting ions into the gas barrier layer.
- implanted ions include rare gases such as argon, helium, neon, krypton, and xenon; ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; gold, silver, copper, and platinum And ions of metals such as nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, and aluminum.
- rare gases such as argon, helium, neon, krypton, and xenon
- ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur
- metals such as nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, and aluminum.
- metals such as nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten,
- the ion implantation method examples include a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions in plasma (plasma ion implantation method), and the like.
- the plasma ion implantation method is preferable from the viewpoint of easily obtaining a pressure-sensitive adhesive sheet having excellent gas barrier properties.
- a plasma is generated in an atmosphere containing a plasma generation gas, and a negative high voltage pulse is applied to the gas barrier layer, so that ions (positive ions) in the plasma are changed to the surface of the gas barrier layer. It can be performed by injecting into the part.
- the thickness of the portion into which ions are implanted can be controlled by implantation conditions such as the type of ion, applied voltage, treatment time, etc., and may be determined according to the thickness of the gas barrier layer, the purpose of use of the adhesive sheet, etc. Usually, it is 10 to 1000 nm, preferably 10 to 200 nm.
- Water vapor permeability of the thus gas barrier film thus obtained is, 40 ° C., at 90% RH (relative humidity), preferably 0.5g / m 2 / day or less, more preferably 0.05g / m 2 / day It is as follows.
- steam, of a gas barrier film can be measured using a well-known gas-permeability measuring apparatus.
- a release sheet that has been subjected to a double-sided release process, a release sheet that has been subjected to a single-sided release process, or the like is used.
- Examples include a release sheet coated on a release sheet substrate.
- the base material for the release sheet include paper base materials such as glassine paper, coated paper, and high-quality paper, laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials, or polyethylene terephthalate resin, polybutylene.
- polyester resin films such as terephthalate resin and polyethylene naphthalate resin
- plastic films such as polyolefin resin films such as polypropylene resin and polyethylene resin.
- the release agent examples include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
- the thickness of the release sheet is not particularly limited, but is preferably 20 to 200 ⁇ m, more preferably 25 to 150 ⁇ m.
- Method for producing pressure-sensitive adhesive sheet of the present invention There is no restriction
- the pressure-sensitive adhesive composition of the present invention may be further mixed with an organic solvent such as toluene, ethyl acetate, or methyl ethyl ketone to form a solution of the pressure-sensitive adhesive composition.
- an organic solvent such as toluene, ethyl acetate, or methyl ethyl ketone
- the concentration of the solid content of the pressure-sensitive adhesive composition solution is preferably 10 to 60% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 30% by mass. If it is 10% by mass or more, the amount of the organic solvent used is sufficient, and if it is 60% by mass or less, the viscosity becomes appropriate and a solution having excellent coating workability can be obtained.
- Examples of the coating method include spin coating, spray coating, bar coating, knife coating, roll coating, roll knife coating, blade coating, die coating, and gravure coating.
- a pressure-sensitive adhesive sheet 1a having a pressure-sensitive adhesive layer on one side of a substrate as shown in FIG. 1A is obtained by, for example, directly applying a solution of the above-mentioned pressure-sensitive adhesive composition on one surface of a base material 11.
- the layer 12 can be formed and formed. Moreover, it can also produce by sticking the adhesive layer which removed both release sheets of the double-sided adhesive sheet 1d like FIG.1 (d) on one surface of the base material 11, and was exposed.
- the pressure-sensitive adhesive sheet 1b having pressure-sensitive adhesive layers on both sides of the substrate as shown in FIG. 1 (b) forms, for example, pressure-sensitive adhesive layers 12a and 12b by directly applying a solution of the pressure-sensitive adhesive composition on both sides of the base material 11.
- the adhesive layer which removed and exposed one peeling sheet of the double-sided adhesive sheet 1d like FIG.1 (d) on one surface of the base material 11 is bonded together, and the other surface of the base material 11 is attached. Further, it can be prepared by directly applying a solution of the pressure-sensitive adhesive composition.
- a pressure-sensitive adhesive sheet 1c having a pressure-sensitive adhesive layer and a release sheet in this order on a substrate as shown in FIG. 1C is, for example, a release sheet 13 on the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet 1a obtained as described above. Can be laminated. Moreover, the adhesive layer 12 and the base material 11 which were formed by directly applying the above-mentioned adhesive composition solution to the release treatment surface of the release sheet 13 can be produced.
- the pressure-sensitive adhesive sheet 1d having a configuration in which the pressure-sensitive adhesive layer 12 is sandwiched between two release sheets without using a substrate as shown in FIG. 1D is, for example, the above-mentioned pressure-sensitive adhesive on the release treatment surface of the release sheet 13a.
- the adhesive layer 12 formed by directly applying the solution of the composition and the release sheet 13b can be bonded to each other.
- the solution of the above-mentioned pressure-sensitive adhesive composition is directly applied to one side of a release sheet that has been subjected to a release treatment on both sides, and wound into a roll to produce a double-sided adhesive tape that does not have a single-layer tape-like substrate. You can also.
- the pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention has excellent adhesive force, is excellent in moisture penetration suppression effect, has good transparency, and suppresses the outgas generation amount. obtain. Therefore, the pressure-sensitive adhesive sheet of the present invention is suitable as a sealing member for organic EL elements and the like, and when the pressure-sensitive adhesive sheet of the present invention is used as a sealing member, it is due to moisture intrusion or heat generation during driving of the organic EL element. Peeling of the pressure-sensitive adhesive sheet can be suppressed, and characteristic deterioration of the organic EL element can be suppressed.
- the pressure-sensitive adhesive sheet of the present invention includes, for example, organic devices such as organic transistors, organic memories, and organic EL elements; liquid crystal displays; electronic paper; thin film transistors; electrochromic devices; It can be used as a sealing member for electronic devices such as thermoelectric conversion devices; piezoelectric conversion devices; Among these, it is preferable that the adhesive sheet of this invention is used as a sealing use of an organic EL element.
- the adhesive sheet of this invention can be used suitably also for the sealing application of not only organic devices, such as an organic EL element, but the above-mentioned various electronic devices.
- a structure 22 is formed on a glass substrate 21.
- the structure 22 is formed by laminating a transparent electrode, a hole transport layer, a light emitting layer, a back electrode, and the like.
- the pressure-sensitive adhesive sheet 1 of the present invention is laminated on the structure 22 and the glass substrate 21, and the gas barrier film 23 is fixed on the pressure-sensitive adhesive sheet 1.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 1 of the present invention is in close contact with and firmly fixed to the structure 22 and the glass substrate 21 to form a sealed organic EL element 20. If the adhesive sheet of this invention is used, processing, such as high temperature heating and ultraviolet irradiation, will not be required, but an organic EL element can be sealed simply.
- FIG. 3 is a diagram showing the relationship between the voltage of the organic EL element sealed with the pressure-sensitive adhesive sheet or glass of the present invention and the light emission luminance.
- heat is generated in the structure of the organic EL element as the voltage increases, and the element is destroyed by the heat, and the emission luminance is reduced.
- the pressure-sensitive adhesive sheet of the present invention can release the heat generated in the structure to the outside, it is possible to suppress a decrease in light emission luminance even when the voltage is increased.
- the mass average molecular weight (Mw) and softening point of the components used in the following Examples and Comparative Examples are values measured by the following methods.
- the adhesive sheet with a base material produced in Examples and Comparative Examples was cut into a size of 25 mm ⁇ 300 mm, and the light release sheet was peeled off in an environment of 23 ° C. and 50% RH (relative humidity) to form the following adherend. Affixed.
- the adhesive sheet is reciprocated once using a 2 kg weight roller, the adherend and the adhesive sheet are temporarily pressure-bonded, and a laminator is used. Lamination was performed at 80 ° C. Thereafter, the sample was allowed to stand for 24 hours after being stuck in an environment of 23 ° C.
- the generated gas amount was calculated as an n-decane conversion amount ( ⁇ g / cm 2 ) from a calibration curve prepared using n-decane by GC Mass (manufactured by PERKIN ELMER, product name “Turbo Mass”).
- FIGS. 4A and 4B are (a) a plan view and (b) a front view (cross-sectional view) of a test laminate used for a moisture penetration test of an adhesive sheet.
- a calcium layer 52 having a length of 32 mm and a width of 40 mm and a thickness of 100 nm was formed on a glass substrate 51 having the size shown in FIG.
- a gas barrier film 23 (trade name “Alpet 7 ⁇ 38”, manufactured by Aya Aluminum Co., Ltd., aluminum layer: 7 ⁇ m, PET film: 38 ⁇ m, which is formed by bonding an aluminum layer 23b onto an polyethylene terephthalate (PET) film 23a with an adhesive. ) was prepared separately.
- the pressure-sensitive adhesive layer 12 released by peeling off the light release sheet of the baseless pressure-sensitive adhesive sheet prepared in Examples and Comparative Examples, and the aluminum layer 23b of the gas barrier film 23 were placed at 23 ° C. and 50% RH (relative Affixed in an environment of humidity. And the adhesive layer 12 which peeled and exposed the heavy release sheet
- the ratio of the calcium layer discolored by moisture intrusion after the produced test laminate 50 was allowed to stand for 24 hours, 72 hours, 100 hours, and 170 hours in an environment of 60 ° C. and 90% RH (relative humidity).
- the rate of penetration) was visually confirmed and evaluated according to the following criteria. In addition, when it became C evaluation in the middle of leaving still for the said time, it complete
- B The area of the calcium layer that has been discolored due to moisture intrusion is 20% or more and less than 60% of the whole.
- C The area of the calcium layer discolored due to moisture intrusion is 60% or more of the whole.
- a test sample was prepared in the following manner using three non-substrate pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples.
- a polyethylene terephthalate (PET) film manufactured by Mitsubishi Plastics, Inc., on the surface of the pressure-sensitive adhesive layer exposed by peeling off the light release sheet of the first substrate-less pressure-sensitive adhesive sheet produced in Examples and Comparative Examples. (Thickness: 6 ⁇ m).
- the pressure-sensitive adhesive layer peeled off and exposed from the first baseless pressure-sensitive adhesive sheet and the second baseless pressure-sensitive adhesive sheet prepared in Examples and Comparative Examples The pressure-sensitive adhesive layer that was peeled and exposed was attached.
- the pressure-sensitive adhesive layer released from the second release sheet of the substrate-less pressure-sensitive adhesive sheet and the light release sheet of the third substrate-less pressure-sensitive adhesive sheet prepared in Examples and Comparative Examples were peeled off.
- the pressure-sensitive adhesive layer thus exposed was bonded to each other, and three pressure-sensitive adhesive layers having a thickness of 20 ⁇ m were superposed.
- the pressure-sensitive adhesive layer peeled off and exposed from the third substrate-free pressure-sensitive adhesive sheet was bonded to a PET film (Mitsubishi Resin, thickness 6 ⁇ m), laminated, and thickened.
- the prepared test sample for measuring the water vapor transmittance in an environment of 40 ° C. and 90% RH (relative speed) is used.
- the water vapor transmission rate was measured.
- the water vapor transmission rate of the two PET films used for lamination was 43 g / m 2 / day. That is, if there is no water vapor barrier property of the pressure-sensitive adhesive layer, the water vapor transmission rate of the test sample to be measured is a value around 43 g / m 2 / day. The lower the value, the better the water vapor barrier property of the pressure-sensitive adhesive layer.
- ⁇ Total light transmittance, haze> The light release sheet of the baseless adhesive sheet prepared in Examples and Comparative Examples was peeled off, and the exposed adhesive layer and a glass plate (manufactured by NS Precision Corporation, product name “Corning Glass Eagle XG”) ”, 150 mm ⁇ 70 mm ⁇ 2 mm). And the heavy release sheet
- the total light transmittance of the pressure-sensitive adhesive sheet with a glass plate was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name “NDH-2000”) according to JIS K 7361-1. Moreover, the haze of the adhesive sheet with a glass plate was measured using said haze meter according to JISK7136.
- Examples 1A to 5A (1) Preparation of solution of pressure-sensitive adhesive composition
- the components (A) to (C) were added, dissolved in toluene, and the solid content concentration was 20% by mass.
- a solution of the pressure-sensitive adhesive composition was prepared.
- the details of the components (A) to (C) shown in Table 1 used in Examples 1A to 5A are as follows. ⁇ (A) component> -"Opanol B50" (trade name, manufactured by BASF): mass average molecular weight 340,000. -"Opanol B30" (trade name, manufactured by BASF): mass average molecular weight 200,000.
- P-907NA trade name, manufactured by Toyo Adre
- the content of component (B) represents the total content (solid content ratio) of SEBS and SEB contained in P-907Y or P-907NA with respect to 100 parts by mass of component (A).
- the solution of the pressure-sensitive adhesive composition prepared above is a base material, a polyethylene terephthalate (PET) film (product name “Cosmo Shine A4100”, thickness 50 ⁇ m, manufactured by Toyobo Co., Ltd.)
- PET polyethylene terephthalate
- a coating film was formed by applying the coating film so that the thickness after drying was 20 ⁇ m, and the coating film was dried at 120 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 20 ⁇ m.
- a release surface of a PET film (product name “SP-PET381130”, thickness 38 ⁇ m, manufactured by Lintec Co., Ltd.), which is a light release sheet and whose surface has been subjected to silicone release treatment, is pasted.
- the adhesive sheet with a base material which has the same structure as the adhesive sheet 1c of FIG.1 (c) was produced.
- a release surface of a PET film (product name “SP-PET381130”, thickness 38 ⁇ m, manufactured by Lintec Co., Ltd.), which is a light release sheet and whose surface has been subjected to silicone release treatment, is pasted.
- the adhesive sheets of Examples 1A to 5A had excellent adhesive strength, high visible light transmittance, and very low outgas generation amount. Moreover, it is thought from the result of a moisture permeation test that the effect of suppressing moisture permeation is high, peeling of the pressure-sensitive adhesive sheet can be suppressed, and characteristic deterioration of the organic EL element and the like can be suppressed. On the other hand, the pressure-sensitive adhesive sheets of Comparative Examples 1A and 2A showed a result that the effect of suppressing water penetration was insufficient compared to the pressure-sensitive adhesive sheets of the examples from the results of the water penetration test.
- Examples 1B to 9B, Comparative Examples 1B to 5B Components (A) to (C) were added in the types and blending amounts (solid content ratio) shown in Table 2, and dissolved in toluene to prepare a pressure-sensitive adhesive composition solution having a solid content concentration of 20% by mass. Then, using the prepared pressure-sensitive adhesive composition solution, a pressure-sensitive adhesive sheet with a substrate and a pressure-sensitive adhesive sheet without a substrate were prepared in the same manner as in Examples 1A to 5A described above.
- ⁇ (B) component> "Kraton G1726" (trade name, manufactured by Kraton Polymer Co., Ltd.): Styrenic copolymer mixture containing SEBS (Mw: 70,000) / SEB (Mw: 35,000) 30/70 (mass ratio) . Styrene content: 30% by mass.
- the pressure-sensitive adhesive sheets of Examples 1B to 9B had excellent adhesive strength, high total light transmittance, and low haze, so that the transparency was good. Further, the pressure-sensitive adhesive sheets of Examples 1B to 9B are excellent in the effect of suppressing moisture intrusion because the water vapor permeability of the pressure-sensitive adhesive layer is kept low, and it is possible to suppress deterioration of characteristics of organic EL elements and the like. Conceivable. On the other hand, the pressure-sensitive adhesive sheet of Comparative Example 1B had a lower water vapor permeability, but the adhesive strength was inferior to the pressure-sensitive adhesive sheets of Examples 1B to 9B.
- the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Comparative Examples 2B to 5B and Comparative Examples 1A to 2A resulted in higher water vapor permeability than the pressure-sensitive adhesive layers of the pressure-sensitive adhesive layers of Examples 1B to 9B. Even if these pressure-sensitive adhesive sheets are used for sealing applications such as organic EL elements, it is considered that it is difficult to suppress deterioration of characteristics of the organic EL elements and the like because the effect of suppressing moisture penetration is insufficient.
- Examples 1C to 26C, Comparative Examples 1C to 11C In the types and blending amounts (solid content ratio) shown in Table 3-1 or Table 3-2, components (A) to (C) and a tackifier are added, dissolved in toluene, and a solid content concentration of 20% by mass. A solution of the pressure-sensitive adhesive composition was prepared. Then, using the prepared pressure-sensitive adhesive composition solution, a pressure-sensitive adhesive sheet with a substrate and a pressure-sensitive adhesive sheet without a substrate were prepared in the same manner as in Examples 1A to 5A described above.
- SIBSTAR 103T (trade name, manufactured by Kaneka Corporation): SIBS, Mw: 100,000, styrene content: 30% by mass.
- SIBSTAR 062M (trade name, manufactured by Kaneka Corporation): SIBS, Mw: 60,000, styrene content: 20 mass%, softening point: 96 ° C.
- ⁇ (C) component "Quinton A-100” (trade name, manufactured by Nippon Zeon): aliphatic hydrocarbon resin, softening point: 100 ° C.
- the pressure-sensitive adhesive sheets of Examples 1C to 26C had excellent adhesive strength, high total light transmittance, and low haze, and therefore had good transparency.
- the pressure-sensitive adhesive sheets of Examples 1C to 26C are excellent in the effect of suppressing moisture intrusion because the water vapor permeability of the pressure-sensitive adhesive layer is kept low, and can suppress deterioration of characteristics of organic EL elements and the like. Conceivable.
- the pressure-sensitive adhesive sheets of Comparative Examples 1C to 3C and 11C had a lower water vapor permeability, but the adhesive strength was inferior to the pressure-sensitive adhesive sheets of Examples 1C to 26C.
- the pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheets of Comparative Examples 4C to 10C resulted in higher water vapor permeability than the pressure-sensitive adhesive layers of the pressure-sensitive adhesive layers of Examples 7C to 26C. Even if an organic EL element or the like is used for sealing applications, it is considered difficult to suppress deterioration of characteristics of the organic EL element or the like because the effect of suppressing moisture infiltration is insufficient. In addition, the pressure-sensitive adhesive sheets of Comparative Examples 4C, 7C, and 10C resulted in not only high water vapor permeability but also insufficient adhesive strength.
- the pressure-sensitive adhesive sheet of the present invention is an organic device such as an organic transistor, an organic memory, or an organic EL; a liquid crystal display; an electronic paper; a thin film transistor; an electrochromic device; It is suitable as a member for sealing an electronic device such as an electricity storage device.
- the pressure-sensitive adhesive sheet of the present invention is a gas barrier film such as a silicon nitride film or a silicon oxide film before performing an etching process, a cleaning process, a heat treatment, an exposure process, an energy beam irradiation process, or the like in an electronic component manufacturing process.
- an electronic material having a conductive film can also be used as a temporary fixing pressure-sensitive adhesive sheet for temporarily fixing a glass plate, a substrate or the like.
- Adhesive sheet 11 Base material 12, 12a, 12b Adhesive layer 13, 13a, 13b Release sheet 20
- Organic EL element 21 Glass substrate 22 Structure 23 Gas barrier film 23a Polyethylene terephthalate (PET) film 23b Aluminum layer 50 Test laminate 51 Glass substrate 52 Calcium layer
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Abstract
Description
例えば、有機デバイスで用いられる有機EL素子は、陽極と陰極との間に、有機電荷輸送層や有機発光層を積層させた有機層を設けたものであり、低電圧直流駆動による高輝度発光が可能な発光素子として注目されている。また、有機EL素子は、プラスチックフィルムを基板として用いることで、薄型化、軽量化、フレキシブル化等を実現するディスプレイとしても期待されている。
また、酸素や水分(水蒸気)の影響や、駆動時の発熱や駆動時に高温下に曝されることで、各構成要素の熱膨張率の違いにより有機EL素子中の構造体の界面で応力が発生し、構造体の界面が剥離する場合もある。このような構造体の機械的劣化も、発光特性の劣化の原因として考えられる。
特許文献1には、ガラス基板上に形成された有機EL層を、耐湿性を有する光硬化性樹脂で覆い、且つ光硬化性樹脂層の上部に透水性の小さい基板を固着させる方法が開示されている。
特許文献2には、対向する透明基板をフリットガラスからなるシール材で封止する方法が開示されている。
特許文献3には、基板とシールド材によって気密空間を形成する際に、両者をカチオン硬化タイプの紫外線硬化型エポキシ樹脂接着剤で接着する方法が開示されている。
特許文献4には、防湿性高分子フィルムと接着層により形成された封止フィルムを有機EL素子の外表面上に被覆する方法が開示されている。
また、有機EL素子等の封止用途の粘着シートには、透明性等の特性も要求される。
すなわち、本発明は、以下の〔1〕~〔15〕を提供する。
〔1〕質量平均分子量が2万以上のポリイソブチレン系樹脂(A)、スチレン-ブタジエン-スチレントリブロック共重合体(SBS)、スチレン-block-(エチレン-co-ブチレン)-block-スチレントリブロック共重合体(SEBS)、スチレン-イソブチレンジブロック共重合体(SIB)、及びスチレン-イソブチレン-スチレントリブロック共重合体(SIBS)からなる群より選ばれる1種以上のスチレン系共重合体(B)、及び軟化点が135℃以下の粘着付与剤(C)を含有する、粘着剤組成物。
〔2〕(C)成分が、脂肪族系炭化水素樹脂を含む、上記〔1〕に記載の粘着剤組成物。
〔3〕(B)成分の軟化点が、80~200℃である、上記〔1〕又は〔2〕に記載の粘着剤組成物。
〔4〕(B)成分の含有量が、(A)成分100質量部に対して、5~200質量部である、上記〔1〕~〔3〕のいずれかに記載の粘着剤組成物。
〔5〕(C)成分の含有量が、(A)成分及び(B)成分の合計100質量部に対して、5~60質量部である、上記〔1〕~〔4〕のいずれかに記載の粘着剤組成物。
〔6〕(A)成分が、イソブチレン由来の構成単位(a1)とイソプレン由来の構成単位(a2)とを有するイソブチレン-イソプレン共重合体(A1)を含む、上記〔1〕~〔5〕のいずれかに記載の粘着剤組成物。
〔7〕イソブチレン-イソプレン共重合体(A1)において、構成単位(a2)の含有量が、(A1)成分の全構成単位に対して、0.1~30モル%である、上記〔6〕に記載の粘着剤組成物。
〔8〕(B)成分の質量平均分子量が1万~40万である、上記〔1〕~〔7〕のいずれかに記載の粘着剤組成物。
〔9〕上記〔1〕~〔8〕のいずれかに記載の粘着剤組成物からなる粘着剤層を有する、粘着シート。
〔10〕前記粘着剤層が2つの剥離シートで挟持した構成を有する、上記〔9〕に記載の粘着シート。
〔11〕基材と前記粘着剤層とを有する、上記〔9〕に記載の粘着シート。
〔12〕前記基材が、ガスバリア用基材とガスバリア層とを有するガスバリアフィルムである、上記〔11〕に記載の粘着シート。
〔13〕全光線透過率が90%以上である、上記〔9〕~〔12〕のいずれかに記載の粘着シート。
〔14〕40℃、相対湿度90%の環境下での前記粘着剤層の水蒸気透過率が10.0g/m2/day以下である、上記〔9〕~〔13〕のいずれかに記載の粘着シート。
〔15〕有機EL素子の封止用途として用いられる、上記〔9〕~〔14〕のいずれかに記載の粘着シート。
また、「軟化点」は、JIS K 2531に準拠して測定した値である。
本発明の粘着剤組成物は、質量平均分子量が2万以上のポリイソブチレン系樹脂(A)、スチレン-ブタジエン-スチレントリブロック共重合体(SBS)、スチレン-block-(エチレン-co-ブチレン)-block-スチレントリブロック共重合体(SEBS)、スチレン-イソブチレンジブロック共重合体(SIB)、及びスチレン-イソブチレン-スチレントリブロック共重合体(SIBS)からなる群より選ばれる1種以上のスチレン系共重合体(B)、及び軟化点が135℃以下の粘着付与剤(C)を含有する。
本発明の粘着剤組成物は、本発明の効果を損なわない範囲において、その他の添加剤や、(A)~(C)成分以外のその他の樹脂を含有してもよい。以下、本発明の粘着剤組成物に含まれる、各成分について詳述する。
本発明の粘着剤組成物中に含まれるポリイソブチレン系樹脂(A)は、質量平均分子量が2万以上のポリイソブチレン系樹脂である。
(A)成分の質量平均分子量が2万未満であると、粘着剤組成物の凝集力が十分に得られず、粘着性を十分に向上させることができない。また、粘着剤組成物を用いた粘着シートを封止用途に用いた際、粘着シートの粘着力が不十分であり、また、粘着シートの水分浸入の抑制効果も不十分である。さらに、被着体を汚染してしまう場合もある。
なお、基本的には、(A)成分の質量平均分子量が高いほど、得られる粘着剤組成物を用いた粘着シートの粘着力を向上させ、当該粘着シートを封止用途に用いた際の水分浸入の抑制効果も向上する傾向にある。
(A)成分の質量平均分子量は、2万以上であるが、上記観点、及び被着体に対する濡れ性や溶媒に対する溶解性の観点から、好ましくは3万~100万、より好ましくは5万~80万、更に好ましくは7万~60万、より更に好ましくは14万~45万である。
これらのポリイソブチレン系樹脂は、単独で又は2種以上を組み合わせて用いてもよい。
イソブチレン由来の構成単位の含有量は、(A)成分の全構成単位に対して、好ましくは60モル%以上、より好ましくは70モル%以上、より好ましくは80モル%以上、更に好ましくは90モル%以上、より更に好ましくは95モル%以上である。
また、(A)成分として含まれる上記ポリイソブチレン系樹脂が共重合体である場合、当該共重合体は、スチレン由来の構成単位を含まないものであり、(B)成分とは区別される。
また、(A)成分としては、Vistanex(Exxon Chemical Co.製)、Hycar(Goodrich社製)、Oppanol(BASF社製)、等の市販品も使用することができる。
(A)成分中のイソブチレン-イソプレン共重合体(A1)の含有量は、上記観点から、好ましくは50~100質量%、より好ましくは65~100質量%、更に好ましくは80~100質量%、より更に好ましくは90~100質量%である。
また、イソブチレン由来の構成単位(a1)の含有量は、(A1)成分の全構成単位に対して、好ましくは70.0~99.9モル%、より好ましくは80.0~99.5、更に好ましくは85.0~99.2、より更に好ましくは90.0~98.7である。
質量平均分子量の高い樹脂(α)を含むことで、得られる粘着剤組成物から形成される粘着剤層の耐久性、耐候性、及び粘着力の向上に寄与し、当該粘着剤組成物を用いた粘着シートを封止用途に用いた際に、水分浸入の抑制効果の向上に寄与する。
また、質量平均分子量の低い樹脂(β)を含むことで、樹脂(α)と良好に相溶して、適度に樹脂(α)を可塑化させることができ、それにより、粘着剤組成物から形成される粘着剤層の被着体に対する濡れ性を高め、粘着物性、柔軟性等を向上させることができる。
樹脂(α)のMwが27万以上であれば、得られる粘着剤組成物の凝集力を十分向上させることができ、当該粘着剤組成物を用いた粘着シートの粘着力、及び水分浸入の抑制効果を向上させることができる。また、被着体への汚染の懸念も解消し得る。
一方、樹脂(α)のMwが60万以下であれば、得られる粘着剤組成物の凝集力が高くなりすぎることにより柔軟性や流動性の低下という弊害を避けることができ、当該粘着剤組成物から形成される粘着剤層の被着体との濡れを良好にすることができる。また、粘着剤組成物を溶液の形態とする際、溶媒に対する溶解性を良好とすることができる。
樹脂(β)のMwが5万以上であれば、得られる粘着剤組成物から形成される粘着剤層において、樹脂(β)が低分子成分として分離して粘着剤層の表面に析出し、被着体が汚染される弊害を防ぐことができる。また、高温下で発生するアウトガス発生量が増加する等の物性に及ぼす影響も回避することができる。
一方、樹脂(β)のMwが25万以下であれば、樹脂(A1)を十分に可塑化させることができ、得られる粘着剤組成物から形成される粘着剤層の被着体との濡れを良好にすることができる。
樹脂(α)100質量部に対する、樹脂(β)の含有割合は、好ましくは5~55質量部、より好ましくは6~40質量部、更に好ましくは7~30質量部、より更に好ましくは8~20質量部である。
樹脂(β)の含有割合が5質量部以上であれば、樹脂(α)を十分に可塑化させることができ、得られる粘着剤組成物から形成される粘着剤層の被着体との濡れを良好とすることができると共に、粘着力を向上させることができる。
一方、樹脂(β)の含有割合が55質量部以下であれば、得られる粘着剤組成物の凝集力を十分に向上させることができるため、当該粘着剤組成物を用いた粘着シートに対して、優れた粘着力、及び耐久性を付与することができる。
本発明の粘着剤組成物は、スチレン-ブタジエン-スチレントリブロック共重合体(SBS)、スチレン-block-(エチレン-co-ブチレン)-block-スチレントリブロック共重合体(SEBS)、スチレン-イソブチレンジブロック共重合体(SIB)、及びスチレン-イソブチレン-スチレントリブロック共重合体(SIBS)からなる群より選ばれる1種以上のスチレン系共重合体(B)を含有する。
粘着剤組成物中に、(B)成分として、上記の群より選ばれる1種以上のスチレン系共重合体を含有することで、得られる粘着剤組成物を用いた粘着シートの水分浸入の抑制効果を良好とすると共に、当該粘着シートの粘着力を向上させることができる。
(B)成分の中でも、得られる粘着剤組成物を用いた粘着シートの粘着力を向上させる観点から、SBS及びSEBSから選ばれる1種以上が好ましい。また、当該粘着シートの水分浸入の抑制効果を向上させる観点から、SIB及びSIBSから選ばれる1種以上が好ましい。
(B)成分のMwが1万以上であれば、得られる粘着剤組成物を用いた粘着シートの粘着力を向上させることができる。一方、(B)成分のMwが40万以下であれば、得られる粘着剤組成物を用いた粘着シートの粘着力を良好に保ちつつ、得られる粘着剤組成物から形成される粘着剤層の水蒸気透過率の値を小さくすることができ、粘着シートの水分浸入の抑制効果を向上させることができる。
(B)成分の含有量が5質量部以上であれば、当該粘着剤組成物を用いた粘着シートを有機EL素子等の封止用途に用いた場合、水分浸入を効果的に抑制し、有機EL素子の特性劣化を抑制することができる。また、当該粘着シートの粘着力を向上させることもできる。
一方、(B)成分の含有量が200質量部以下であれば、得られる粘着剤組成物を用いた粘着シートの粘着力を十分に向上させることができ、当該粘着剤組成物から形成される粘着剤層の水蒸気透過率の値を小さくし、粘着シートの水分浸入の抑制効果を良好とすることができる。
当該含有量比が上記の範囲内であれば、得られる粘着剤組成物を用いた粘着シートの粘着力を向上させつつ、及び当該粘着剤組成物から形成される粘着剤層の水蒸気透過率の値を小さくし、粘着シートの水分浸入の抑制効果を良好とすることができる。
本発明の粘着剤組成物は、軟化点が135℃以下の粘着付与剤(C)を含有する。
本発明において、粘着付与剤とは、上記(A)及び(B)成分やその他の樹脂成分と混合することが可能であり、これらの樹脂成分の粘着性能を向上させる機能を持つ、オリゴマー領域の分子量を有する化合物を意味する。
粘着付与剤の数平均分子量としては、通常100~18000、好ましくは100~10000である。
粘着付与剤(C)の軟化点が135℃を超えると、成分(A)及び(B)を含む粘着剤組成物の粘着性が著しく低下するため好ましくない。また、当該粘着剤組成物を用いた粘着シートの剥離時にジッピングが発生する恐れがある。
粘着付与剤(C)の軟化点は、135℃以下であるが、上記観点から、好ましくは132℃以下、より好ましくは128℃以下、より好ましくは120℃以下、更に好ましくは110℃以下、更に好ましくは105℃以下である。
一方、得られる粘着剤組成物の凝集力を向上させ、優れた粘着性を発現する粘着剤組成物を得る観点から、粘着付与剤(C)の軟化点は、好ましくは60℃以上、より好ましくは70℃以上、更に好ましくは80℃以上、より更に好ましくは90℃以上である。
本発明において、軟化点の異なる粘着付与剤(C)を2種以上組み合わせてもよい。複数の粘着付与剤を用いる場合、これらの粘着付与剤の軟化点の加重平均が上記範囲に属していればよい。そのため、本発明において、複数の粘着付与剤の軟化点の加重平均が135℃以下であれば(上記範囲に属していれば)、軟化点が135℃を超える粘着付与剤を粘着剤組成物中に含有してもよい。
軟化点が135℃を超える粘着付与剤の含有量は、粘着剤組成物中に含まれる粘着付与剤(C)の全量に対して、好ましくは10質量%以下、より好ましくは4質量%以下、更に好ましくは1質量%以下、より更に好ましくは0.01質量%以下である。
上記粘着付与剤は、単独または2種以上を組み合わせて用いてもよい。
ここで、上記の「C5留分」とは、石油ナフサの熱分解で生成する、ペンテン、イソプレン、ピペリン、1.3-ペンタジエン等の炭素数5の不飽和炭化水素を意味し、「C5系石油樹脂」とは、このC5留分を共重合して得られ、C5留分を主成分(少なくとも20質量%以上含む)とする樹脂を意味する。
また、上記の「C9留分」とは、石油ナフサの熱分解で生成する、インデン、ビニルトルエン、α又はβ-メチルスチレン等の炭素数9の不飽和炭化水素を意味し、「C9系石油樹脂」とは、このC9留分を共重合して得られ、C9留分を主成分(少なくとも20質量%以上含む)とする樹脂を意味する。
なお、上記の「水素化した樹脂」は、完全に水素化した完全水素化樹脂だけでなく、一部が水素化された部分水素化樹脂も含まれる。
なお、本発明において、「脂肪族系炭化水素樹脂」は、石油由来の樹脂であって、芳香族環及び脂環構造を有さない石油由来の樹脂である。つまり、「脂肪族系炭化水素樹脂」は芳香族環を有する「芳香族系炭化水素樹脂」や、ジシクロペンタジエン系樹脂等の「脂環族系炭化水素樹脂」とは明確に区別されるものである。
上記オレフィンとしては、例えば、1-ブテン、イソブチレン、1-ペンテン等が挙げられる。
また、上記ジエンとしては、例えば、ブタジエン、1,3-ペンタジエン、イソプレン等が挙げられる。
また、当該脂肪族炭化水素樹脂は、完全に水素化した完全水素化樹脂であってもよく、一部が水素化された部分水素化樹脂であってもよい。
上記の脂肪族系炭化水素樹脂は、単独で又は2種以上を組み合わせて用いてもよい。
芳香族系炭化水素樹脂及び脂環族系炭化水素樹脂の含有量は、上記観点から、本発明の粘着剤組成物中に含まれる粘着付与剤(C)の全量に対して、好ましくは10質量%以下、より好ましくは5質量%以下、更に好ましくは1質量%以下、より更に好ましくは0.01質量%以下である。
(C)成分の含有量が5質量部以上であれば、得られる粘着剤組成物から形成される粘着剤層について、被着体との濡れが十分に得られ、粘着力を向上させることができると共に、当該粘着剤層の水蒸気透過率の値が小さく、水分浸入の抑制効果に優れた粘着シートを得ることができる。
一方、(C)成分の含有量が60質量部以下であれば、得られる粘着剤組成物から形成される粘着剤層について、被着体によらず優れた粘着力を発現させることができ、ジッピングの発生を抑制することができる。また、当該粘着剤層の水蒸気透過率の値が小さく、水分浸入の抑制効果に優れた粘着シートを得ることができる。
本発明の粘着剤組成物は、本発明の効果を損なわない範囲において、さらにその他の添加剤を含有してもよい。
その他の添加剤としては、例えば、光安定剤、酸化防止剤、紫外線吸収剤、樹脂安定剤、充填剤、顔料、増量剤、軟化剤等が挙げられる。これらの添加剤は、単独で又は2種以上を組み合わせて用いてもよい。
これらのその他の成分のそれぞれの含有量は、(A)成分100質量部に対して、好ましくは0.01~5質量部、より好ましくは0.01~2質量部である。
酸化防止剤としては、例えば、リン酸エステル系化合物等が挙げられる。
紫外線吸収剤としては、例えば、ベンゾトリアゾール系化合物、オキサゾリックアシッドアミド化合物、ベンゾフェノン系化合物等が挙げられる。
樹脂安定剤としては、例えば、イミダゾール系樹脂安定剤、ジチオカルバミン酸塩系樹脂安定剤、リン系樹脂安定剤、硫黄エステル系樹脂安定剤等が挙げられる。
なお、本発明の粘着剤組成物には、本発明の効果を損なわない範囲において、上述の(A)~(C)成分以外のその他の樹脂成分を含有してもよいが、実質的に含まないことが好ましい。
(A)~(C)成分以外のその他の樹脂成分の含有量は、粘着剤組成物の全量に対して、好ましくは50質量%未満、より好ましくは20質量%以下、更に好ましくは5質量%以下、より更に好ましくは1質量%以下である。
(B)成分に該当しないスチレン系共重合体としては、例えば、スチレン-ブタジエンジブロック共重合体、スチレン-イソプレンジブロック共重合体、スチレン-イソプレン-スチレントリブロック共重合体、スチレン-block-(ブタジエン-co-イソプレン)-blockジブロック共重合体、スチレン-block-(ブタジエン-co-イソプレン)-block-スチレントリブロック共重合体、スチレン-block-(エチレン-co-ブチレン)-blockジブロック共重合体(SEB)、カルボキシル変性した上記記載のスチレン共重合体、スチレンとα-メチルスチレン等の芳香族系ビニル化合物との共重合体等が挙げられる。
本発明の粘着シートは、上述の成分を含有する本発明の粘着剤組成物からなる粘着剤層を有するものであれば特に限定されない。
本発明の粘着シートの構成としては、例えば、図1(a)のように、基材11上に粘着剤層12を有する粘着シート1aが挙げられる。
他にも、図1(b)のような、基材11の両面に粘着剤層12a、12bを形成した粘着シート1bや、図1(c)のような、基材11上に形成した粘着剤層12上に更に剥離可能な剥離シート13を形成した粘着シート1cとしてもよい。なお、粘着シート1bは、粘着剤層12a、12b上に、更に剥離シートを有していてもよい。
さらに、図1(d)のように、基材を用いずに、粘着剤層12が2つの剥離シート13a、13bで挟持された粘着シート1dとしてもよい。なお、粘着シート1dにおいて、剥離シート13a、13bは、同じ種類のものでもよく、異なる種類のものであってもよいが、剥離シート13aと剥離シート13bとの剥離力差が異なるように、使用する剥離シートを適宜選択することが好ましい。
他にも、表面が剥離処理された剥離シートの片面に粘着剤層を設けたものをロール状に巻いた構成の粘着シートとしてもよい。
具体的には、23℃、50%RH(相対湿度)の環境下で、被着体に貼付後24時間放置した後の、厚み20μmの粘着剤層を有する粘着シートの粘着力について、被着体がガラスである場合、好ましくは9.0N/25mm以上、より好ましくは10.0N/25mm以上、更に好ましくは12.0N/25mm以上であり、被着体がステンレスである場合、好ましくは9.0N/25mm以上、より好ましくは10.0N/25mm以上、更に好ましくは12.0N/25mm以上である。
粘着力が上記範囲であれば、十分な粘着力を有し、有機EL素子の駆動時の発熱や駆動時に高温下に晒された場合でも、各構成要素の熱膨張率の違いにより発生する有機EL素子中の構造体の界面での応力によって、界面が乖離することを抑制することが出来る。
また、本発明の粘着シートが、図1(d)の粘着シート1dのような、基材無し粘着シートの形態である場合、厚み50μmのポリエチレンテレフタレートに裏打ちした際の粘着力が、上記範囲となるように調整することが好ましい。
なお、上記粘着シートの粘着力の値は、実施例に記載の方法により測定された値を意味する。
本発明の粘着シートは、有機EL素子等の封止用途に適用する観点から、全光線透過率が90%以上であることが好ましい。
また、本発明の粘着シートのヘイズは、好ましくは1.20以下、より好ましくは1.00以下、更に好ましくは0.90以下である。
また、上記粘着シートの全光線透過率の値は、JIS K 7361-1に準じて測定された値であり、ヘイズの値は、JIS K 7136に準じて測定された値であって、具体的にはどちらも実施例に記載の方法により測定した値を示す。
<粘着剤層>
粘着シートの粘着剤層の厚さとしては、用途等に応じて適宜選定されるが、好ましくは0.5~100μm、より好ましくは1~60μm、更に好ましくは3~40μmである。
粘着剤層の厚さが0.5μm以上であれば、被着体に対し良好な粘着力が得られる。
一方、粘着剤層の厚さが100μm以下であれば、生産性の面で有利であり、取扱い易い粘着シートとなり得る。
当該粘着剤層の水蒸気透過率が10g/m2/day以下であれば、本発明の粘着シートは水分浸入の抑制効果に優れ、有機EL素子等の封止用途に用いた場合でも、素子内部への水分浸入を抑制することができ、有機EL素子の特性劣化を抑えることができる。
なお、粘着剤層の水蒸気透過率の値は、実施例に記載の方法により測定した値を意味する。
粘着剤層の全光線透過率は、90%以上であることが好ましい。また、粘着剤層の波長550nmの可視光線透過率は、90%以上であることが好ましい。
当該粘着剤層の全光線透過率もしくは可視光線透過率が90%以上であれば、本発明の粘着シートは、有機EL素子等の封止用途として好適に用いることができる。
また、粘着剤層のヘイズは、好ましくは1.20以下、より好ましくは1.00以下、更に好ましくは0.90以下である。
なお、上記の全光線透過率の値は、JIS K 7361-1に準じて測定された値であり、ヘイズの値は、JIS K 7136に準じて測定された値であって、具体的にはどちらも実施例に記載の方法により測定された値を意味する。
また、上記の可視光線透過率の値は、実施例に記載の方法により測定した値を示す。
厚さ20μmの粘着剤層の120℃の温度で30分間加熱した際のアウトガス発生量は、n-デカン換算量で、好ましくは1.0μg/cm2未満、より好ましくは0.5μg/cm2以下、更に好ましくは0.1μg/cm2以下である。
当該アウトガス発生量が1.0μg/cm2未満であれば、粘着剤層が被着体を腐食させることがない。そのため、例えば、本発明の粘着シートを精密機器への貼付用途に適応した場合でも、精密電子部材の誤動作をもたらす可能性が著しく低減する。
なお、粘着剤層のアウトガス発生量の値は、実施例に記載の方法により測定した値を示す。
基材としては、シート形状であれば特に限定されず、本発明の粘着シートの使用目的に応じて適宜選定される。例えば、上質紙、アート紙、コート紙、グラシン紙等や、これらの紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙等の各種紙類、各種合成紙、アルミニウム箔や銅箔や鉄箔等の金属箔、不織布等の多孔質材料、並びにポリエチレン樹脂、ポリプロピレン樹脂等のポリオレフィン樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂等のポリエステル樹脂、アセテート樹脂、ABS樹脂、ポリスチレン樹脂、塩化ビニル樹脂等のプラスチックのフィルム、シート及びこれらの樹脂の混合物又は積層物からなるプラスチックフィルム、シート等が挙げられる。プラスチックフィルム・シート等のシート形状の基材は、未延伸でもよいし、縦又は横等の一軸方向あるいは二軸方向に延伸されていてもよい。
使用する基材は、着色の有無については問わないが、封止用部材として用いる場合は、紫外線を十分に透過するものが好ましく、さらに可視光領域においても無色透明であることがより好ましい。
また、本発明の粘着シートにおいて、上述の材料からなる基材の代わりに、ガスバリア用基材とガスバリア層を有するガスバリアフィルムを基材として用いてもよい。ガスバリアフィルムの詳細は、後述のとおりである。
酸化法としては、特に限定されず、例えば、コロナ放電処理法、プラズマ処理法、クロム酸酸化(湿式)、火炎処理、熱風処理、オゾン・紫外線照射処理等が挙げられる。また、凹凸化法としては、特には限定されず、例えば、サンドブラスト法、溶剤処理法等が挙げられる。
これらの表面処理は、基材の種類に応じて適宜選定されるが、粘着剤層との密着性の向上効果や操作性の観点から、コロナ放電処理法が好ましい。また、プライマー処理を施すこともできる。
このような目止め層としては、特に限定されないが、例えは、スチレン-ブタジエン共重合体、アクリル系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂、ポリスチレン系樹脂等を主成分(少なくとも20質量%以上含有する)として、必要に応じ、クレー、シリカ、炭酸カルシウム、酸化チタン、酸化亜鉛等のフィラーを添加したもの等からなる層が挙げられる。
この目止め層の厚さは、特に制限はないが、通常0.1~30μmである。
本発明の粘着シートの基材としては、ガスバリア用基材とガスバリア層とを有するガスバリアフィルムを用いることが好ましい。当該ガスバリアフィルムは、ガスバリアフィルム用基材の少なくとも一方の面側にガスバリア層を有するものであればよい。なお、ガスバリア層は、単層であっても複数層であってもよい。
ガスバリアフィルム用基材としては、特に制限されず、例えば、ポリエチレン、ポリプロピレン等のポリオレフィン、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル、ポリイミド、ポリアミドイミド、全芳香族ポリアミド、ナイロン6、ナイロン66、ナイロン共重合体等のポリアミド、ルボルネン系重合体、単環の環状オレフィン系重合体、環状共役ジエン系重合体、ビニル脂環式炭化水素重合体、及びこれらの水素化物等のシクロオレフィン系ポリマー等、ポリフェニレンエーテル、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリカーボネート、ポリスルフォン、ポリエーテルスルフォン、ポリフェニレンスルフィド、ポリアリレートの樹脂からなるシート等が挙げられる。
これらの中でも、透明性に優れ、汎用性の観点から、ポリエステル、ポリアミド又はシクロオレフィン系ポリマーが好ましく、ポリエステル又はシクロオレフィン系ポリマーがより好ましい。
ガスバリア層を形成する材料としては、酸素及び水蒸気の透過を阻止するものであれば、特に制約されず、例えば、アルミニウム、マグネシウム、亜鉛、スズ等の金属、窒化珪素、酸化珪素、酸窒化珪素、ポリシラザン化合物、ポリカルボシラン化合物、ポリシラン化合物、ポリオルガノシロキサン化合物、テトラオルガノシラン化合物等の珪素化合物、酸化アルミニウム、酸窒化アルミニウム等のアルミニウム化合物、酸化マグネシウム、酸化亜鉛、酸化インジウム、酸化スズ等の無機酸化物、ポリビニルアルコール、エチレン-ビニルアルコール共重合体、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリクロロトリフロロエチレン等の樹脂等が挙げられる。
これらの中でも、ガスバリア性を向上させる観点から、アルミニウム、マグネシウム、亜鉛、スズ等の金属、窒化珪素、酸化珪素、酸窒化珪素、ポリシラザン化合物、ポリカルボシラン化合物、ポリシラン化合物、ポリオルガノシロキサン化合物、テトラオルガノシラン化合物等の珪素化合物、酸化アルミニウム、酸窒化アルミニウム等のアルミニウム化合物、酸化マグネシウム、酸化亜鉛、酸化インジウム、酸化スズ等の無機酸化物が好ましく、透明性の観点から、(1)ポリシラザン化合物、(2)ポリカルボシラン化合物、(3)ポリシラン化合物、(4)ポリオルガノシロキサン化合物、及び(5)テトラオルガノシラン化合物がより好ましい。
以下、上記の(1)~(5)の化合物の詳細について説明する。
ポリシラザン化合物は、分子内に、(-Si-N-)結合を含む繰り返し単位を有する高分子であり、下記式(1)で表される繰り返し単位を有する化合物が挙げられる。
これらの中でも、R1~R3としては、水素原子、炭素数1~6のアルキル基、及びフェニル基のいずれかが好ましく、水素原子がより好ましい。
式(1)で表される繰り返し単位を有するポリシラザン化合物としては、入手容易性及び優れたガスバリア性を有する層を形成できる観点から、R1~R3が全て水素原子である無機ポリシラザン、又はR1~R3の少なくとも1つが水素原子ではない有機ポリシラザンが好ましく、無機ポリシラザンがより好ましく、ペルヒドロポリシラザンが更に好ましい。
ポリシラザン化合物の数平均分子量は、特に限定されないが、100~50,000であるのが好ましい。
ポリカルボシラン化合物は、分子内の主鎖に、(-Si-C-)結合を含む繰り返し単位を有する高分子化合物であり、下記式(2)で表される繰り返し単位を有する化合物が挙げられる。
また、R6は、アルキレン基、アリーレン基又は2価の複素環基を表す。
ポリカルボシラン化合物の質量平均分子量は、通常400~12000である。
ポリシラン化合物は、分子内に、(-Si-Si-)結合を含む繰り返し単位を有する高分子化合物である。かかるポリシラン化合物としては、下記式(3)で表される繰り返し単位を有する化合物が挙げられる。
ポリシラン化合物が非環状ポリシランである場合は、ポリシラン化合物の末端基(末端置換基)は、水素原子であっても、塩素原子等のハロゲン原子、アルキル基、ヒドロキシル基、アルコキシ基、シリル基等であってもよい。
ポリオルガノシロキサン化合物が有する主鎖構造には制限は無く、直鎖状、ラダー状、籠上のいずれの構造を有する化合物であってもよい。
例えば、直鎖状の主鎖構造を有する化合物としては、下記式(4)で表される繰り返し単位を有する化合物が挙げられ、ラダー状の主鎖構造を有する化合物としては、下記式(5)で表される繰り返し単位を有する化合物が挙げられ、籠状の主鎖構造を有する化合物としては、下記式(6)で表される繰り返し単位を有する化合物が挙げられる。
これらの中でも、Rx、Ry、Rzとしては、それぞれ独立して、無置換若しくは置換基を有する、炭素数1~6のアルキル基又はフェニル基が好ましく、メチル基、エチル基、プロピル基、3-グリシドキシプロピル基、又はフェニル基がより好ましい。
テトラオルガノシラン化合物は、ケイ素元素に4個の加水分解性基が結合した化合物であり、具体的には、式(7):SiX4で表される化合物である。
式(7):SiX4中、Xは加水分解置換基を表し、互いに同一であっても相異なっていてもよい。
Xとしては、式(8):OR(Rは炭素数1~10の炭化水素基、又はアルコキシ基を表す。)で表される基、式(9):OSi(Ra)(Rb)(Rc)で表される基(Ra、Rb、Rcはそれぞれ独立して、水素原子、炭素数1~10のアルキル基、又はフェニル基を表す。)、塩素原子、臭素原子等のハロゲン原子等が挙げられる。
これらのテトラオルガノシラン化合物は、単独で又は2種以上を組み合わせて用いることができる。
また、他の形成方法としては、上記材料を蒸着法、スパッタリング法、イオンプレーティング法、熱CVD法、プラズマCVD法等により基材上に形成する方法が挙げられる。
転化処理としては、イオン注入処理、プラズマ処理、紫外線照射処理、熱処理等が挙げられ、これらの中でも、イオンを注入することが好ましい。イオンを注入することで、高い透明性をもったままガスバリア性能を向上させることができる。イオンを注入する工程としては、特に限定されないが、例えば、基材上にガスバリア層を形成した後、該ガスバリア層にイオンを注入する方法が挙げられる。
これらの中でも、より簡便に注入することができ、特に優れたガスバリア性能と透明性を有する粘着シートを得る観点から、水素、窒素、酸素、アルゴン、ヘリウム、ネオン、キセノン、及びクリプトンからなる群から選ばれる少なくとも一種のイオンが好ましい。
なお、イオンの注入量は、必要なガスバリア性、透明性等の粘着シートの使用目的等を考慮して適宜選択される。
プラズマイオン注入法は、例えば、プラズマ生成ガスを含む雰囲気下でプラズマを発生させ、ガスバリア層に負の高電圧パルスを印加することにより、該プラズマ中のイオン(陽イオン)を、ガスバリア層の表面部に注入して行うことができる。
なお、ガスバリアフィルムの水蒸気等の透過率は、公知のガス透過率測定装置を使用して測定することができる。
剥離シートとしては、両面剥離処理をされた剥離シートや、片面剥離処理された剥離シート等が用いられ、剥離シート用基材上に剥離剤を塗布したもの等が挙げられる。
剥離シート用の基材としては、例えば、グラシン紙、コート紙、上質紙等の紙基材、これらの紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙、又はポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂等のポリエステル樹脂フィルム、ポリプロピレン樹脂、ポリエチレン樹脂等のポリオレフィン樹脂フィルム等のプラスチックフィルム等が挙げられる。
剥離剤としては、例えば、シリコーン系樹脂、オレフィン系樹脂、イソプレン系樹脂、ブタジエン系樹脂等のゴム系エラストマー、長鎖アルキル系樹脂、アルキド系樹脂、フッ素系樹脂等が挙げられる。
剥離シートの厚さは、特に制限ないが、好ましくは20~200μm、より好ましくは25~150μmである。
本発明の粘着シートの製造方法としては、特に制限はなく、公知の方法により製造することができる。例えば、上述の粘着剤組成物に有機溶媒を加えた粘着剤組成物の溶液を公知の塗布方法により製造する方法が挙げられる。
有機溶媒を配合した場合の粘着剤組成物の溶液の固形分濃度は、好ましくは10~60質量%、より好ましくは10~45質量%、更に好ましくは15~30質量%である。10質量%以上であれば、有機溶媒の使用量としては十分であり、60質量%以下であれば、適度な粘度となり、優れた塗布作業性を有する溶液となり得る。
図1(a)のような基材の片面に粘着剤層を有する粘着シート1aは、例えば、基材11の一方の面上に、上述の粘着剤組成物の溶液を直接塗布して粘着剤層12を形成して作製することができる。また、基材11の一方の面上に、図1(d)のような両面粘着シート1dの両方の剥離シートを除去して表出した粘着剤層を貼り合わせて作製することもできる。
本発明の粘着剤組成物から形成された粘着剤層を有する粘着シートは、優れた粘着力を有し、水分浸入の抑制効果に優れており、透明性が良好で、アウトガス発生量を抑制し得る。
そのため、本発明の粘着シートは、有機EL素子等の封止用部材として好適であり、本発明の粘着シートを封止用部材として用いた場合、水分浸入や有機EL素子の駆動時の発熱による粘着シートの剥離を抑制することができ、有機EL素子の特性劣化を抑えることができる。
これらの中でも、本発明の粘着シートは、有機EL素子の封止用途として用いられることが好ましい。
有機EL素子20は、ガラス基板21上に構造体22が形成されている。構造体22は、透明電極、正孔輸送層、発光層及び背面電極等が積層されたものである。そして、この構造体22及びガラス基板21上に、本発明の粘着シート1が積層され、更にこの粘着シート1上にガスバリアフィルム23が固着されている。本発明の粘着シート1の粘着剤層が、構造体22及びガラス基板21と密着し固着されることで、封止された有機EL素子20となる。本発明の粘着シートを用いれば、高温加熱や紫外線照射等の処理を必要とせず、簡便に有機EL素子を封止することができる。
ゲル浸透クロマトグラフ装置(東ソー株式会社製、製品名「HLC-8020」)を用いて、下記の条件下で測定し、標準ポリスチレン換算にて測定した値を用いた。
(測定条件)
・カラム:「TSK guard column HXL-H」「TSK gel GMHXL(×2)」「TSK gel G2000HXL」(いずれも東ソー株式会社製)
・カラム温度:40℃
・展開溶媒:テトラヒドロフラン
・流速:1.0mL/min
JIS K 2531に準拠して測定した値を用いた。
実施例及び比較例で作製した基材付き粘着シートを25mm×300mmの大きさに裁断し、23℃、50%RH(相対湿度)の環境下で、軽剥離シートを剥がし、下記被着体に貼付した。貼付に際しては、被着体に粘着シートを貼着後、当該粘着シート上を重さ2kgのローラーを用いて、1往復させて、被着体と粘着シートを仮圧着し、ラミネーターを用いて、80℃でラミネートした。
その後、23℃、50%RHの環境下で、貼付後24時間静置した後、同環境下で、引張試験機(オリエンテック社製、製品名「テンシロン」)を用いて、剥離速度300mm/分、剥離角度180°の条件で、各被着体に対する粘着力(N/25mm)を測定した。
粘着力の測定に用いた被着体は以下のとおりである(〔 〕は、後述の表中の略称を示す)。
・ソーダライムガラス〔ガラス〕:エヌ・エス・ジー・プレシジョン社製、製品名「コーニングガラス イーグルXG」、150mm×70mm×2mm。
・ステンレス板〔SUS〕:SUS304鋼板、360番研磨。
実施例及び比較例で作製した基材無し粘着シートの軽剥離シートを剥離して、表出した粘着剤層と、ガラス板(エヌ・エス・ジー・プレシジョン社製、製品名「コーニングガラス イーグルXG」、150mm×70mm×2mm)とを貼付した。そして、基材無し粘着シートの重剥離シートを剥離して、粘着剤層が表出したガラス板付き粘着シートを得た。
このガラス板付き粘着シートの粘着剤層の波長550nmの可視光透過率を、可視光透過率測定装置(島津製作所社製、製品名「UV-3101PC」)を用いて、測定した。
実施例及び比較例で作製した基材無し粘着シートを20cm2の大きさに裁断した。
そして、軽剥離シート及び重剥離シートを除去し、両面剥き出しになった粘着シートの粘着剤層をアンプル瓶に封入し、パージ&トラップGC Mass(日本電子工業(株)製、製品名「JHS-100A」)を用いて、当該アンプル瓶を120℃で、30分間加熱して、発生するガスを採取した。
その後、GC Mass(PERKIN ELMER製、製品名「Turbo Mass」)により、n-デカンを用いて作成した検量線より、発生するガス量をn-デカン換算量(μg/cm2)として算出した。
図4は、粘着シートの水分浸入試験に用いる試験用積層体の(a)平面図及び(b)正面図(断面図)である。
まず、図4の(a)に示された大きさのガラス基板51上に、真空蒸着法にて、縦32mm、横40mmで膜厚100nmのカルシウム層52を形成した。
次に、ポリエチレンテレフタレート(PET)フィルム23a上にアルミニウム層23bが接着剤で貼合されたガスバリアフィルム23(アジヤアルミ社製、商品名「アルペット7×38」、アルミニウム層:7μm、PETフィルム:38μm)を別途用意した。
実施例及び比較例で作製した基材無し粘着シートの軽剥離シートを剥離して表出した粘着剤層12と、上記のガスバリアフィルム23のアルミニウム層23bとを、23℃、50%RH(相対湿度)の環境下で貼付した。
そして、基材無し粘着シートの重剥離シートを剥離して表出した粘着剤層12と、ガラス基板51及びカルシウム層52とを、加熱ラミネータ(加熱温度:80℃)を用いて、窒素雰囲気下にて、貼り合わせた。このようにして、カルシウム層52が粘着シートの粘着剤層12により封止された試験用積層体50を作製した(図4の(b)参照)。
作製した試験用積層体50を、60℃、90%RH(相対湿度)の環境下で、24時間、72時間、100時間、170時間静置後、水分浸入によってカルシウム層が変色した割合(水分浸入の割合)を目視で確認し、下記の基準により評価した。
なお、上記時間静置している途中で、C評価になった場合は、その後の評価を行わずに終了した。
・A:水分が浸入して変色しているカルシウム層の面積が全体の20%未満である。
・B:水分が浸入して変色しているカルシウム層の面積が全体の20%以上60%未満である。
・C:水分が浸入して変色しているカルシウム層の面積が全体の60%以上である。
実施例及び比較例で作製した基材無し粘着シートを3枚使用して、以下のようにして、試験サンプルを作製した。
まず、実施例及び比較例で作製した1枚目の基材無し粘着シートの軽剥離シートを剥離して表出した粘着剤層の面上に、ポリエチレンテレフタレート(PET)フィルム(三菱樹脂社製、厚さ:6μm)でラミネートした。
次に、1枚目の基材無し粘着シートの重剥離シートを剥離して表出した粘着剤層と、実施例及び比較例で作製した2枚目の基材無し粘着シートの軽剥離シートを剥離して表出した粘着剤層とを貼り合わせた。
さらに、2枚目の基材無し粘着シートの重剥離シートを剥離して表出した粘着剤層と、実施例及び比較例で作製した3枚目の基材無し粘着シートの軽剥離シートを剥離して表出した粘着剤層とを貼り合わせ、厚み20μmの粘着剤層を3枚重ね合わせた。
最後に、3枚目の基材無し粘着シートの重剥離シートを剥離して表出した粘着剤層と、PETフィルム(三菱樹脂社製、厚さ6μm)とを貼り合わせ、ラミネートし、厚さ60μmの粘着剤層が2枚のPETフィルムにより挟持された、水蒸気透過率測定用の試験サンプルを作製した。
そして、透過率測定器(LYSSY社製、製品名「L89-500」)を用いて、40℃、90%RH(相対速度)の環境下での、作製した水蒸気透過率測定用の試験サンプルの水蒸気透過率を測定した。
なお、ラミネートに用いたPETフィルム2枚の水蒸気透過率は43g/m2/dayであった。つまり、粘着剤層の水蒸気バリア性が全く無ければ、測定される試験サンプルの水蒸気透過率は43g/m2/day前後の値となる。当該値が低いほど、粘着剤層の水蒸気バリア性が優れている。
実施例及び比較例で作製した基材無し粘着シートの軽剥離シートを剥離して、表出した粘着剤層と、ガラス板(エヌ・エス・ジー・プレシジョン社製、製品名「コーニングガラス イーグルXG」、150mm×70mm×2mm)とを貼付した。そして、基材無し粘着シートの重剥離シートを剥離して、粘着剤層が表出したガラス板付き粘着シートを得た。
そして、ガラス板付き粘着シートの全光線透過率を、JIS K 7361-1に準じて、ヘイズメーター(日本電色工業社製、製品名「NDH-2000」)を用いて、測定した。
また、ガラス板付き粘着シートのヘイズは、JIS K 7136に準じて、上記のヘイズメーターを用いて測定した。
(1)粘着剤組成物の溶液の調製
表1に示す種類及び配合量(固形分比)で、(A)~(C)成分を添加し、トルエンで溶解して、固形分濃度20質量%の粘着剤組成物の溶液を調製した。
なお、実施例1A~5Aで使用した、表1に示す(A)~(C)成分の詳細は以下のとおりである。
<(A)成分>
・「Oppanol B50」(商品名、BASF社製):質量平均分子量34万。
・「Oppanol B30」(商品名、BASF社製):質量平均分子量20万。
<(B)成分>
・「P-907Y」(商品名、東洋アドレ社製):SEBS及びSEBを含有する混合樹脂、SEBS及びSEBの含有量=30質量%、軟化点=112℃。
・「P-907NA」(商品名、東洋アドレ社製):SEBS及びSEBを含有する混合樹脂、SEBS及びSEBの含有量=20質量%、軟化点=128℃。
なお、表1中の(B)成分の含有量は、(A)成分100質量部に対する、P-907Y又はP-907NA中に含まれるSEBS及びSEBの合計含有量(固形分比)を表す。
(C)成分
・「アルコンP-125」(商品名、荒川化学工業社製):水素化石油樹脂(脂環族系飽和炭化水素樹脂)、軟化点125℃。
上記の調製した粘着剤組成物の溶液を、基材である、ポリエチレンテレフタレート(PET)フィルム(東洋紡績社製、製品名「コスモシャインA4100」、厚み50μm)上に、乾燥後の厚さが20μmになるように塗布して塗布膜を形成し、当該塗布膜を120℃で2分間乾燥させて、厚さ20μmの粘着剤層を形成した。
次いで、形成した粘着剤層の面上に、軽剥離シートである、表面がシリコーン剥離処理されたPETフィルム(リンテック社製、製品名「SP-PET381130」、厚み38μm)の剥離処理面を貼付して、図1(c)の粘着シート1cと同じ構成を有する、基材付き粘着シートを作製した。
上記の調製した粘着剤組成物の溶液を、重剥離シートである、表面がシリコーン剥離処理されたPETフィルム(リンテック社製、製品名「SP-PET38T103-1」、厚み38μm)の剥離処理された面上に、乾燥後の厚さが20μmになるように塗布して塗布膜を形成し、当該塗布膜を120℃で2分間乾燥させて、厚さ20μmの粘着剤層を形成した。
次いで、形成した粘着剤層の面上に、軽剥離シートである、表面がシリコーン剥離処理されたPETフィルム(リンテック社製、製品名「SP-PET381130」、厚み38μm)の剥離処理面を貼付し、2枚の剥離シートに挟持された、図1(d)の粘着シート1dと同じ構成を有する、基材無しの粘着シートを作製した。
スチレン-イソブチレン-スチレントリブロック共重合体(SIS)(日本ゼオン社製、商品名「Quintac3421」、スチレン含有量:14質量%、Mw:12万)100質量部(固形分)をトルエンに溶解し、固形分濃度20質量%の粘着剤組成物の溶液を調製した。
この調製した粘着剤組成物の溶液を用いて、実施例1A~5Aと同様にして、基材付き粘着シート及び基材無し粘着シートを作製した。
単量体成分として、アクリル酸ブチル90質量部及びアクリル酸10質量部、重合開始剤として、アゾビスイソブチロニトリル0.2質量部を反応器に入れ混合した。そして、4時間窒素ガスで脱気を行い、60℃まで徐々に昇温した後、24時間撹拌しながら重合反応を行ない、アクリル系共重合体(Mw:65万)を含む酢酸エチル溶液(固形分濃度33質量%)を得た。
得られたアクリル系共重合体の酢酸エチル溶液100質量部(固形分)に対し、イソシアネート系架橋剤(日本ポリウレタン社製、製品名「コロネートL」、トリメチロールプロパン変性トリレンジイソシアネートの酢酸エチル溶液、固形分75質量%)を1.5質量部(固形分比)を添加してトルエンに溶解し、固形分濃度20質量%の粘着剤組成物の溶液を調製した。
そして、この調製した粘着剤組成物の溶液を用いて、実施例1A~5Aと同様にして、基材付き粘着シート及び基材無し粘着シートを作製した。
一方、比較例1A及び2Aの粘着シートは、水分浸入試験の結果から、実施例の粘着シートに比べて、水分浸入の抑制効果が不十分である結果となった。
表2に示す種類及び配合量(固形分比)で、(A)~(C)成分を添加し、トルエンで溶解して、固形分濃度20質量%の粘着剤組成物の溶液を調製した。
そして、これらの調製した粘着剤組成物の溶液を用いて、上述の実施例1A~5Aと同様にして、基材付き粘着シート並びに基材無し粘着シートを作製した。
<(A)成分>
・「PIB樹脂混合物」:「Oppanol B50(商品名、BASF社製、Mw:34万のポリイソブチレン系樹脂)」/「Oppanol B30(商品名、BASF社製、Mw:20万のポリイソブチレン系樹脂)」=10/1(質量比)の割合で含有するポリイソブチレン系樹脂混合物。
<(B)成分>
・「KratonG1726」(商品名、クレイトンポリマー社製):SEBS(Mw:7万)/SEB(Mw:3.5万)=30/70(質量比)の割合で含有するスチレン系共重合体混合物。スチレン含有量:30質量%。
<(C)成分>
・「Quinton R-100」(商品名、日本ゼオン社製):脂肪族系炭化水素樹脂(C5留分から抽出された高純度の1,3-ペンタジエンを主原料に製造された石油樹脂)、軟化点:96℃。
一方、比較例1Bの粘着シートは、水蒸気透過率は低く抑えられているものの、本実施例1B~9Bの粘着シートに比べて、粘着力が劣る結果となった。
また、比較例2B~5B及び比較例1A~2Aの粘着シートが有する粘着剤層は、実施例1B~9Bの粘着シートが有する粘着剤層に比べて、水蒸気透過率が高い結果となったため、これらの粘着シートは、有機EL素子等の封止用途に使用しても、水分浸入の抑制効果が不十分であるため、有機EL素子等の特性劣化を抑制することが難しいと考えられる。
表3-1又は表3-2に示す種類及び配合量(固形分比)で、(A)~(C)成分、粘着付与剤を添加し、トルエンで溶解して、固形分濃度20質量%の粘着剤組成物の溶液を調製した。
そして、これらの調製した粘着剤組成物の溶液を用いて、上述の実施例1A~5Aと同様にして、基材付き粘着シート並びに基材無し粘着シートを作製した。
<(A)成分>
・「イソブチレン-イソプレン共重合体」:日本ブチル社製、商品名「Exxon Butyl 268」、Mw:26万、イソブチレン由来の構成単位の含有量:98.3モル%、イソプレン由来の構成単位の含有量:1.7モル%。
<(B)成分>
・「KratonG1726」(商品名、クレイトンポリマー社製):SEBS(Mw:7万)/SEB(Mw:3.5万)=30/70(質量比)の割合で含有するスチレン系共重合体混合物、スチレン含有量:30質量%。
・「SIBSTAR 103T」(商品名、カネカ社製):SIBS、Mw:10万、スチレン含有量:30質量%。
・「SIBSTAR 062M」(商品名、カネカ社製):SIBS、Mw:6万、スチレン含有量:20質量%、軟化点:96℃。
<(C)成分>
・「Quinton A-100」(商品名、日本ゼオン社製):脂肪族系炭化水素樹脂、軟化点:100℃。
<粘着付与剤>
・「アイマープ P-140」(商品名、出光興産社製):ジシクロペンタジエンと芳香族ビニルモノマーとの共重合樹脂、軟化点:140℃。
一方、比較例1C~3C、11Cの粘着シートは、水蒸気透過率は低く抑えられているものの、本実施例1C~26Cの粘着シートに比べて、粘着力が劣る結果となった。
また、比較例4C~10Cの粘着シートが有する粘着剤層は、実施例7C~26Cの粘着シートが有する粘着剤層に比べて、水蒸気透過率が高い結果となったため、これらの粘着シートは、有機EL素子等を封止用途に使用しても、水分浸入の抑制効果が不十分であるため、有機EL素子等の特性劣化を抑制することが難しいと考えられる。加えて、比較例4C、7C、10Cの粘着シートは、水蒸気透過率が高いだけでなく、粘着力も不十分である結果となった。
また、本発明の粘着シートは、電子部品の製造工程において、エッチング処理、洗浄処理、熱処理、露光処理、エネルギー線照射処理等の処理を行う前に、窒化ケイ素膜、酸化ケイ素膜等のガスバリア膜や導電膜を有する電子材料をガラス板や基板等に一時的に固定するための仮固定用粘着シートとしての用途にも適用し得る。
11 基材
12、12a、12b 粘着剤層
13、13a、13b 剥離シート
20 有機EL素子
21 ガラス基板
22 構造体
23 ガスバリアフィルム
23a ポリエチレンテレフタレート(PET)フィルム
23b アルミニウム層
50 試験用積層体
51 ガラス基板
52 カルシウム層
Claims (15)
- 質量平均分子量が2万以上のポリイソブチレン系樹脂(A)、
スチレン-ブタジエン-スチレントリブロック共重合体(SBS)、スチレン-block-(エチレン-co-ブチレン)-block-スチレントリブロック共重合体(SEBS)、スチレン-イソブチレンジブロック共重合体(SIB)、及びスチレン-イソブチレン-スチレントリブロック共重合体(SIBS)からなる群より選ばれる1種以上のスチレン系共重合体(B)、及び
軟化点が135℃以下の粘着付与剤(C)を含有する、粘着剤組成物。 - (C)成分が、脂肪族系炭化水素樹脂を含む、請求項1に記載の粘着剤組成物。
- (B)成分の軟化点が、80~200℃である、請求項1又は2に記載の粘着剤組成物。
- (B)成分の含有量が、(A)成分100質量部に対して、5~200質量部である、請求項1~3のいずれかに記載の粘着剤組成物。
- (C)成分の含有量が、(A)成分及び(B)成分の合計100質量部に対して、5~60質量部である、請求項1~4のいずれかに記載の粘着剤組成物。
- (A)成分が、イソブチレン由来の構成単位(a1)とイソプレン由来の構成単位(a2)とを有するイソブチレン-イソプレン共重合体(A1)を含む、請求項1~5のいずれかに記載の粘着剤組成物。
- イソブチレン-イソプレン共重合体(A1)において、構成単位(a2)の含有量が、(A1)成分の全構成単位に対して、0.1~30モル%である、請求項6に記載の粘着剤組成物。
- (B)成分の質量平均分子量が1万~40万である、請求項1~7のいずれかに記載の粘着剤組成物。
- 請求項1~8のいずれかに記載の粘着剤組成物からなる粘着剤層を有する、粘着シート。
- 前記粘着剤層が2つの剥離シートで挟持した構成を有する、請求項9に記載の粘着シート。
- 基材と前記粘着剤層とを有する、請求項9に記載の粘着シート。
- 前記基材が、ガスバリア用基材とガスバリア層とを有するガスバリアフィルムである、請求項11に記載の粘着シート。
- 全光線透過率が90%以上である、請求項9~12のいずれかに記載の粘着シート。
- 40℃、相対湿度90%の環境下での前記粘着剤層の水蒸気透過率が10.0g/m2/day以下である、請求項9~13のいずれかに記載の粘着シート。
- 有機EL素子の封止用途として用いられる、請求項9~14のいずれかに記載の粘着シート。
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Also Published As
Publication number | Publication date |
---|---|
EP2913372A1 (en) | 2015-09-02 |
TWI591139B (zh) | 2017-07-11 |
TW201431992A (zh) | 2014-08-16 |
JPWO2014069398A1 (ja) | 2016-09-08 |
CN104718263A (zh) | 2015-06-17 |
CN104718263B (zh) | 2017-11-10 |
US20150240133A1 (en) | 2015-08-27 |
KR102128239B1 (ko) | 2020-06-30 |
JP6374793B2 (ja) | 2018-08-15 |
KR20150079567A (ko) | 2015-07-08 |
EP2913372A4 (en) | 2016-06-01 |
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