WO2012032995A1 - 画像表示装置構成用積層体の製造方法、及びこの積層体を用いてなる画像表示装置 - Google Patents
画像表示装置構成用積層体の製造方法、及びこの積層体を用いてなる画像表示装置 Download PDFInfo
- Publication number
- WO2012032995A1 WO2012032995A1 PCT/JP2011/069880 JP2011069880W WO2012032995A1 WO 2012032995 A1 WO2012032995 A1 WO 2012032995A1 JP 2011069880 W JP2011069880 W JP 2011069880W WO 2012032995 A1 WO2012032995 A1 WO 2012032995A1
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- WIPO (PCT)
- Prior art keywords
- image display
- display device
- sensitive adhesive
- pressure
- laminate
- Prior art date
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Classifications
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- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
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- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B2037/1253—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
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- 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
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
- B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
- B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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- 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
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to a laminate for constituting an image display device that can be used as a constituent member of an image display device such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, a pen tablet and the like. It relates to a manufacturing method.
- a gap between an image display panel such as an LCD, PDP, or EL and a protective panel or touch panel member disposed on the front side (viewing side) is used as an adhesive sheet. Filling with an adhesive or the like suppresses irregular reflection that occurs when filling is not performed, that is, irregular reflection at the air layer interface of incident light or outgoing light from a display image.
- Patent Document 1 discloses a display in which a transparent resin (adhesive) is filled in a gap between an LCD (liquid crystal panel display) and a touch panel to reduce light reflection between the touch panel and the liquid crystal display panel.
- An apparatus is disclosed.
- Patent Documents 2 and 3 after an adhesive composition is previously photocured (or thermally cured) to prepare a partially crosslinked adhesive composition, optical properties are then passed through the adhesive composition.
- a method of manufacturing an optical functional member integrated display device is proposed, in which a functional member and a display portion are bonded together, and then the adhesive composition is thermally cured (or photocured) by heat treatment (or light irradiation). ing.
- Patent Document 4 discloses a technique for increasing cohesive force by containing a high molecular weight acrylic polymer in an adhesive composition and suppressing foaming resistance and peeling.
- the present applicant can attach without any bubbles remaining even if there are irregularities of about 5 ⁇ m to 20 ⁇ m on the adherend surface, and the adherend is an outgas such as plastic.
- a new transparent pressure-sensitive adhesive sheet that can be attached so as not to be foamed in a high-temperature environment of, for example, about 80 ° C. has been proposed.
- Patent Documents 2 and 3 a material having both photocuring property and thermosetting property is used, and the added organic peroxide causes gelation of the composition during processing. Because it may cause problems such as foaming due to reaction products of organic peroxide and oxidative corrosion of adherends, it is necessary to make the adhesive sheet used for this type of application have both photo- and thermosetting properties. Should be avoided.
- the foaming reliability is sufficient, but it is harder. Therefore, if there are irregularities on the surface of the adherend, or if foreign matter or the like is present on the adhesive interface, the irregularities cannot be sufficiently followed.
- an object of the present invention is to provide a method for manufacturing a laminate for constituting an image display device capable of simultaneously realizing unevenness followability and foaming reliability.
- the present invention is a method for producing a laminate for constituting an image display device comprising a constitution in which image display device constituting members are laminated via a transparent double-sided pressure-sensitive adhesive sheet, and includes at least the following (1) and (2)
- the manufacturing method of the laminated body for image display apparatus structures characterized by having a process is proposed.
- (1) A step of forming a transparent double-sided pressure-sensitive adhesive sheet before secondary curing by forming the pressure-sensitive adhesive composition into a single-layer or multi-layered sheet, UV-crosslinking this and performing primary curing.
- ultraviolet rays are irradiated from at least one image display device constituent member side, and the secondary material is passed through this member.
- the transparent double-sided pressure-sensitive adhesive sheet before secondary curing obtained in the step (1) leaves room for further curing, in other words, leaves room for further UV-crosslinking and is flexible so much. Even if there are irregularities on the surface of the body or there are foreign substances or the like at the adhesive interface, these irregularities can be sufficiently followed and adapted. Therefore, in the step (2), if two image display device constituent members are laminated via such a pre-secondary-curing transparent double-sided pressure-sensitive adhesive sheet, the image display device constituent members can be suitably adhered. In the step (2), the transparent double-sided pressure-sensitive adhesive sheet before secondary curing is obtained by irradiating ultraviolet rays from at least one image display device constituting member side, and performing ultraviolet curing through this member and secondary curing.
- the method for producing a laminate for constituting an image display device according to the present embodiment uses a transparent double-sided adhesive sheet (hereinafter referred to as “the present adhesive sheet”) as an image display device constituent member.
- the present adhesive sheet a transparent double-sided adhesive sheet
- a laminate for an image display device comprising a laminate of the image display device, comprising at least the following steps (1) and (2): Hereinafter, it is referred to as “the present laminate”).
- (1) A step of forming a transparent double-sided pressure-sensitive adhesive sheet before secondary curing by forming the pressure-sensitive adhesive composition into a single-layer or multi-layered sheet, UV-crosslinking this and performing primary curing.
- the adhesive material having both photo-curing property and thermosetting property is used to perform primary curing and secondary curing with different crosslinking means.
- it is added for thermal curing.
- Organic peroxides, isocyanate compounds, epoxy compounds, amine compounds, and other thermosetting agents cause gelation of the composition during processing, and cause problems such as foaming due to reaction decomposition products and oxidative corrosion of the adherend. There is a fear.
- both primary curing and secondary curing are performed by ultraviolet crosslinking, the concern regarding such a thermosetting process can be eliminated.
- the transparent double-sided pressure-sensitive adhesive sheet before secondary curing obtained in the step (1) leaves room for further UV-crosslinking and is flexible as much as that, it is applied to the surface of the adherend. Even if there are irregularities or foreign substances are present at the adhesive interface, they can follow the irregularities sufficiently and become familiar and wet and adhere well. And in the said process (2), it can bridge
- the pressure-sensitive adhesive composition (hereinafter referred to as “the pressure-sensitive adhesive composition”) that can be suitably used to form a single-layer transparent double-sided pressure-sensitive adhesive sheet in this production method will be described.
- the pressure-sensitive adhesive composition that can be suitably used to form a single-layer transparent double-sided pressure-sensitive adhesive sheet in this production method.
- the present invention is not limited to this.
- the pressure-sensitive adhesive composition is subjected to ultraviolet crosslinking so as to have a latent ultraviolet reactivity upon the first ultraviolet irradiation, in other words, to leave the ultraviolet reactivity.
- it is a solventless system which does not contain a solvent, and it is preferable to form a film of the pressure-sensitive adhesive composition by hot melt.
- a means for UV-crosslinking the pressure-sensitive adhesive composition so as to be hot-melt moldable and leave UV reactivity for example, a base polymer having a molecular weight in a predetermined range is used, and crosslinking is performed.
- the means include using an intermolecular hydrogen abstraction type photopolymerization initiator as the initiator and reducing the amount of the crosslinking agent. However, it is not limited to such means.
- the pressure-sensitive adhesive composition is a (meth) acrylic acid ester-based polymer (including a copolymer, hereinafter referred to as “acrylic acid ester-based (co) polymer”) from the viewpoints of adhesiveness, transparency, weather resistance, and the like. Is preferably used as the base resin.
- the acrylate ester-based (co) polymer has a glass transition temperature (by appropriately selecting the type and composition ratio of the acrylic monomer and methacrylic monomer used for the polymerization, and further the polymerization conditions. It can be prepared by appropriately adjusting physical properties such as Tg) and molecular weight.
- acrylic monomers and methacrylic monomers used for polymerizing acrylic ester (co) polymers include 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, n-butyl acrylate, ethyl acrylate, methyl methacrylate, methyl acrylate. Etc. Vinyl acetate, hydroxyethyl acrylate, acrylic acid, glycidyl acrylate, acrylamide, acrylonitrile, methacrylonitrile, fluorine acrylate, silicone acrylate, etc. having a hydrophilic group or an organic functional group can also be used.
- polymerization treatment using these monomers known polymerization methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like can be employed.
- a thermal polymerization initiator or photopolymerization is used according to the polymerization method.
- An acrylic ester copolymer can be obtained by using a polymerization initiator such as an initiator.
- This pressure-sensitive adhesive composition is non-solvent, that is, does not contain a solvent, can be hot-melt molded, has an appropriate adhesive strength at the stage of primary curing, and has irregularities and foreign matter on the surface of the adherend. It is preferable that it has the flexibility which can follow. If the molecular weight of the base polymer is too large or too small, it cannot be formed by hot melt. On the other hand, if the molecular weight of the base polymer is too small, there is a possibility that even if it is first cured, the adhesive force may not be exhibited, or it may be too soft and inferior in handling properties. There is a possibility that it becomes hard at the stage of the next curing and cannot follow the unevenness or foreign matter on the surface of the adherend.
- an acrylic acid ester-based (co) polymer having a mass average molecular weight of the base polymer of 100,000 to 700,000, particularly 200,000 or more, or 600,000 or less, particularly 250,000 or more or 500,000 or less. It is preferable to use it.
- an acrylate (co) polymer having a mass average molecular weight (MW) / number average molecular weight (MN) of 5 to 10, especially 6 or 9 or less.
- MW mass average molecular weight
- MN number average molecular weight
- a large mass average molecular weight / number average molecular weight means that the molecular weight distribution is wide. If this value is as large as about 5 to 10, each of the low molecular weight component and the high molecular weight component has fluidity and wettability.
- the workability and the adhesive performance tend to be better than those having a narrow (uniform) molecular weight distribution.
- the glass transition temperature (Tg) of each monomer component constituting the random copolymer that is, acrylate random copolymer
- the difference in glass transition temperature (Tg) between the two types of monomer components is preferably 25 to 300 ° C., particularly 40 ° C. or more and 200 ° C. or less, especially 60 ° C. or more or 180 ° C.
- the temperature is not lower than 180 ° C or not higher than 180 ° C.
- the glass transition temperature (Tg) of one monomer component is ⁇ 100 to 0 ° C., particularly ⁇ 80 to ⁇ 20 ° C.
- the glass transition temperature (Tg) of the other monomer component is 0 to 250 ° C.
- the temperature is preferably 20 to 180 ° C.
- a monomer component having a lower glass transition temperature (Tg) for example, a monomer component having a Tg of ⁇ 100 to 0 ° C., it is preferable to use an acrylate ester having 2 or more, particularly 4 or more carbon atoms in the side chain.
- monomer components having a high glass transition temperature (Tg) include hydrocarbons having 2 or less carbon atoms in the side chain, alicyclic structures, heterocycles, aromatics. It is preferable to use a vinyl monomer or a (meth) acryl monomer having a ring structure such as carbosyl group, a hydroxyl group, an amino group, an amide group, a glycidyl group, an acetyl group or an isocyanate group.
- a monomer component having a high Tg that is, a monomer having a high glass transition temperature when the monomer is polymerized alone
- a monomer component having a low Tg that is, the monomer
- the indentation hardness of the transparent double-sided PSA sheet can be adjusted by adjusting the ratio to the monomer having a low glass transition temperature when polymerized alone. For example, in order to increase the indentation hardness, the content of the monomer component having a high Tg may be increased. Conversely, in order to make it flexible, the content of the monomer component having a low Tg may be increased. Moreover, it can be softened with a plasticizer to lower the hardness, or the hardness can be appropriately adjusted with an additive such as an oligomer.
- Crosslinking agent As the crosslinking monomer (crosslinking agent) used for crosslinking the acrylic ester (co) polymer, for example, a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups is preferable.
- the amount of the crosslinking agent if the amount of the crosslinking agent is large, the reaction proceeds rapidly and it becomes difficult to control the reaction. Therefore, it is preferable to adjust the amount of the crosslinking agent so that the crosslinking can be stopped midway.
- the amount of the crosslinking agent is preferably 0 to 30 parts by mass, particularly 20 parts by mass or less, especially 10 parts by mass or less, and particularly preferably 5 parts by mass or less with respect to 100 parts by mass of the base polymer. Note that the amount of the crosslinking agent can be reduced in this way because an intermolecular hydrogen abstraction type photopolymerizable initiator is used as the crosslinking initiator.
- Crosslinking initiator It is important to employ an intermolecular hydrogen abstraction type photopolymerizable initiator (also referred to as “hydrogen abstraction type photoinitiator”) as the crosslinking initiator used in the present adhesive composition.
- an intermolecular hydrogen abstraction type photopolymerizable initiator also referred to as “hydrogen abstraction type photoinitiator”
- Photopolymerization initiators generate radicals by light irradiation and become the starting point of polymerization reaction in the system, but the reactive radical generation mechanism of (meth) acryloyl group and vinyl group is roughly classified into two, There are an intramolecular cleavage type in which a bond is cleaved and decomposed to generate a radical, and a hydrogen abstraction type in which hydrogen is excited from a hydroxyl group or the like in the system to generate a radical.
- the intramolecular cleavage type decomposes into another compound when a radical is generated by light irradiation, so once it reacts, it no longer functions as a reaction initiator. It can be used as a reaction initiator repeatedly by irradiation with light. Therefore, it is important to use a hydrogen abstraction type photopolymerization initiator in order to impart latent photocurability.
- the hydrogen abstraction type photoinitiator for example, a benzophenone, Michler's ketone, dibenzosuberone, 2-ethylanthraquinone, thioxanthone, benzyl, etc., or a derivative thereof, or a mixed component composed of a combination of two or more of these is used. Can do.
- the hydrogen abstraction type photoinitiator is not limited to the substances listed above.
- an intramolecular cleavage type photopolymerization initiator may be used in various proportions.
- the addition amount of the photopolymerization initiator is not particularly limited, and is generally 0.1 to 10 parts by weight, particularly 0.2 parts by weight or more or 5 parts by weight or less, based on 100 parts by weight of the base resin. In particular, it is preferable to adjust at a ratio of 0.5 parts by mass or more or 3 parts by mass or less. However, this range may be exceeded in balance with other elements.
- reaction catalyst a tertiary amine compound, a quaternary ammonium compound, a tin laurate compound, etc.
- a reaction catalyst a tertiary amine compound, a quaternary ammonium compound, a tin laurate compound, etc.
- the present adhesive sheet is a multilayer transparent double-sided pressure-sensitive adhesive sheet, that is, when a transparent double-sided pressure-sensitive adhesive sheet having a laminated structure including an intermediate layer and an outermost layer is formed, the outermost layer is formed of the above-described main adhesive. What is necessary is just to form from an agent composition.
- the outermost layer has both uneven tracking and anti-foaming reliability as in the case of the single layer. Since it is preferable, it is preferable to form using the present pressure-sensitive adhesive composition.
- the intermediate layer does not contribute to adhesion with the image display device constituent member, it does not impair the transparency, and has a light transmittance that does not hinder the secondary curing reaction of the outermost layer, and has a cutting property. In addition, it preferably has a property of improving handling properties.
- the type of the base polymer forming the intermediate layer is not particularly limited as long as it is a transparent resin, but it is preferable to use the same acrylate (co) polymer as described above. At this time, it is preferable to use the same resin as the base polymer of the outermost layer from the viewpoint of ensuring transparency and ease of manufacture.
- the intermediate layer may be formed so as to be cured by ultraviolet crosslinking or may be formed so as to be cured by heat. Further, it may be formed so as not to be post-cured. However, in consideration of adhesion to the outermost layer, etc., it is preferably formed so as to be post-cured, and particularly preferably formed so as to be UV-crosslinked. In that case, since light transmittance will fall, if content of a crosslinking initiator increases, it is preferable to contain a ultraviolet-ray crosslinking agent by the content rate lower than the content rate in the outer layer of the crosslinking initiator in an intermediate
- the thickness of the pressure-sensitive adhesive sheet is preferably 50 ⁇ m to 1 mm, particularly preferably 100 ⁇ m or more or 500 ⁇ m or less, from the viewpoint of unevenness followability and thinning required for the application member.
- the ratio of the thickness of each outermost layer to the thickness of the intermediate layer is preferably 1: 1 to 1:20, and more preferably 1: 2 to 1:10. Is more preferable. If the thickness of the intermediate layer is within the above range, the contribution of the thickness of the pressure-sensitive adhesive layer in the laminate is not too large, and it is preferable that the workability relating to cutting and handling is not deteriorated because it is too flexible.
- the outermost layer is in the above range, it is preferable because it can maintain the adhesion and wettability to the adherend without being inferior in conformity to unevenness and a bent surface.
- step (1) it is important that the transparent double-sided PSA sheet is UV-cured and primarily cured so as to have a latent UV reactivity, in other words, to leave the UV reactivity.
- the pressure-sensitive adhesive composition is heated and melted (hot melt), applied onto a transparent release resin sheet and formed into a single-layer or multilayer sheet, and then the transparent release resin. What is necessary is just to irradiate an ultraviolet-ray through a sheet
- the transparent release sheet for example, a polyester-type, polypropylene-type, polyethylene-type cast film or stretched film, which has been subjected to a release treatment by applying a silicone resin, or a release paper is appropriately selected.
- release films having different peeling forces and release films having different thicknesses can be used.
- the indentation hardness (C2 Asker hardness) (a) of the transparent double-sided pressure-sensitive adhesive sheet before secondary curing obtained in the step (1) is preferably in the range of 10 ⁇ (a) ⁇ 50.
- the C2 Asker hardness (a) is a value that can be measured with an Asker hardness meter (Asker C2L) in which a transparent double-sided PSA sheet is sequentially laminated so that the total thickness is within a range of 5 mm to 7 mm. is there.
- the transparent double-sided pressure-sensitive adhesive sheet before sticking to a member requires appropriate stiffness to roll it up or cut, and also requires adhesive strength and wettability to stick to the member. is there.
- the C2 Asker hardness (a) is 10 or more, there is no fear that the workability related to handling is lacking due to being too flexible, and if the C2 Asker hardness (a) is less than 50, the surface of the adherend is uneven. Even if there is a foreign substance or the like at the adhesive interface, it is possible to follow these irregularities sufficiently, get wet, and adhere well. Therefore, by making C2 Asker hardness (a) into the said range, workability
- the thickness of the transparent double-sided PSA sheet, the irradiation amount of ultraviolet rays, the irradiation wavelength, the irradiation device, etc. may be adjusted as appropriate.
- step (2) two image display device constituent members are laminated via the transparent double-sided adhesive sheet before secondary curing obtained in step (1), and then irradiated with ultraviolet rays from at least one image display device constituent member side. Then, it is important that the transparent double-sided pressure-sensitive adhesive sheet before secondary curing is subjected to ultraviolet curing via this member and secondarily cured.
- examples of the image display device constituent member include a touch panel, an image display panel, a surface protection panel, a polarizing film, and the like, and any one of these or a laminate composed of a combination of two or more types. There may be.
- the photoinitiator in the transparent double-sided pressure-sensitive adhesive sheet is excited and a sufficient amount of light having an effective wavelength is generated to generate radicals. It is preferable that the ultraviolet transmittance of one of the image display device constituent members is equal to or higher than a certain level because it is necessary to reach the image display device.
- the ultraviolet transmittance of the glass plate is also protected, for example, the glass plate and the adhesive
- the ultraviolet ray transmittance of the laminate of the glass plate, the pressure-sensitive adhesive and the protective sheet is not less than a certain level. Therefore, the ultraviolet transmittance of the constituent members of the image display device laminated on the ultraviolet irradiation side of the transparent double-sided pressure-sensitive adhesive sheet before secondary curing, that is, the light transmittance in the wavelength range of 315 nm to 400 nm of the UV-A wave is 20% or more. It is particularly preferably 30% or more, and particularly preferably 40% or more.
- the member having such light transmittance examples include those composed of polycarbonate resin, acrylic resin, polyvinyl chloride resin, polyester resin, cellulose resin such as triacetyl cellulose and diacetyl cellulose, and styrene resin. be able to.
- polycarbonate resin, acrylic resin, triacetyl cellulose resin, etc. have high hygroscopicity, and moisture absorbed in the resin during storage tends to be released as outgas from the resin when used at high temperatures.
- the polycarbonate resin, the acrylic resin, and the resin member constituting the laminate can be used. It is possible to use a resin member composed of a triacetyl cellulose resin or the like.
- the indentation hardness (C2 Asker hardness) (b) of the post-secondary-curing transparent double-sided PSA sheet obtained in the step (2) is preferably in the range of 33 ⁇ (b) ⁇ 80.
- the C2 Asker hardness (b) is a value that can be measured with an Asker hardness meter (Asker C2L) in which transparent double-sided PSA sheets are sequentially laminated so that the total thickness is within a range of 5 mm to 7 mm.
- the C2 Asker hardness (b) when the C2 Asker hardness (b) is set to 80 or less, the function as pressure-sensitive adhesion is impaired, the adhesion is inferior, and concerns such as peeling and floating can be eliminated.
- the C2 Asker hardness (b) of the transparent double-sided pressure-sensitive adhesive sheet after secondary curing is more preferably 35 or more and 60 or less, and even more preferably 38 or more and 50 or less.
- Examples of the laminate for constituting an image display device that can be produced by this production method include, for example, images such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, a pen tablet, an LCD, a PDP, or an EL.
- images such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, a pen tablet, an LCD, a PDP, or an EL.
- a polarizing film or the like is laminated on a liquid crystal panel display (LCD), and a plastic protective panel is laminated thereon via an adhesive or a sheet.
- LCD liquid crystal panel display
- PVA polyvinyl alcohol
- triacetyl cellulose resin may be used as a constituent material of the polarizing film, and it has been found that these easily release outgas. Therefore, when this laminate is used as a laminate comprising a protective panel / adhesive sheet / polarizing film, foaming due to outgas emitted from the protective panel and the polarizing film is effective when used at high temperatures. Can be suppressed.
- liquid crystal panel / adhesive sheet / touch panel liquid crystal panel / adhesive sheet / protective panel
- liquid crystal panel / adhesive sheet / touch panel / adhesive sheet / protective panel liquid crystal panel / adhesive sheet / touch panel / adhesive sheet / protective panel
- polarizing film / adhesive sheet / touch panel polarizing film / adhesive sheet / touch panel
- a configuration such as a pressure-sensitive adhesive sheet / protective panel can be given as a configuration example of the present laminate.
- sheet refers to a product that is thin by definition in JIS, and whose thickness is small and flat for the length and width.
- film is compared to the length and width.
- a thin flat product whose thickness is extremely small and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japanese Industrial Standard JISK6900).
- the term “sheet” is included and the term “sheet” is used.
- film is included.
- the expression “panel” such as an image display panel and a protection panel includes a plate, a sheet, and a film.
- X to Y (X and Y are arbitrary numbers) is described, it means “preferably greater than X” or “preferably,” with the meaning of “X to Y” unless otherwise specified. The meaning of “smaller than Y” is also included. Further, when described as “X or more” (X is an arbitrary number), it means “preferably larger than X” unless otherwise specified, and described as “Y or less” (Y is an arbitrary number). In the case, unless otherwise specified, the meaning of “preferably smaller than Y” is also included.
- an acrylate copolymer A 100 g of UV-cured resin propoxylated pentaerythritol triacrylate (“ATM-4PL” manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent, and 15 g of 4-methylbenzophenone as a photopolymerization initiator, Were mixed to prepare an intermediate resin layer composition (A-1).
- the intermediate resin layer composition (A-1) is heated and melted in a release-treated polyethylene terephthalate film (“NP75Z01” manufactured by Panac Co., Ltd., thickness 75 ⁇ m) as a coating substrate so that the thickness becomes 110 ⁇ m.
- NP75Z01 polyethylene terephthalate film
- An intermediate resin layer was formed in the same manner as the above laminated sheet 1 for forming an intermediate resin layer, except that 200 g of trimethylolpropane triacrylate was blended as a crosslinking agent and 50 g of 1-hydroxy-cyclohexyl phenyl ketone was blended as a photopolymerization initiator.
- a composition for use (A-2) was prepared.
- the intermediate resin layer composition (A-2) is heated and melted in a release-treated polyethylene terephthalate film (“NP75Z01” manufactured by Panac Co., Ltd., thickness 75 ⁇ m) as a coating substrate so that the thickness becomes 130 ⁇ m.
- a polyethylene terephthalate film (Toyobo E7006, thickness 38 ⁇ m) that has been peeled off is coated, and an intermediate resin composed of PET film / UV crosslinkable intermediate resin layer (A-2, thickness 130 ⁇ m) / PET film A layer forming laminated sheet 2 was produced.
- a pressure sensitive adhesive composition (B-1) was prepared by adding and mixing 20 g of 4-methylbenzophenone as a photopolymerization initiator to 1 kg of the acrylate copolymer A.
- This pressure-sensitive adhesive composition (B-1) was melted by heating, and on a polyethylene terephthalate film ("MRA75" manufactured by Mitsubishi Plastics Co., Ltd., thickness 75 ⁇ m) subjected to release treatment as a coating substrate, the thickness was 35 ⁇ m.
- the PET film / ultraviolet crosslinkable feeling is the same as the laminated sheet 1 for pressure-sensitive adhesive layer formation, except that the coated substrate is changed to a peeled polyethylene terephthalate film (Mitsubishi Resin “MRF50” thickness 50 ⁇ m).
- MRF50 peeled polyethylene terephthalate film
- a laminated sheet 1 ′ for forming a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive layer (B-1 ′, thickness 35 ⁇ m) / PET film was produced.
- the pressure-sensitive adhesive layer-forming laminated sheet 1 was the same as the pressure-sensitive pressure-sensitive adhesive layer-formed laminated sheet 1 except that the pressure-sensitive adhesive layer (B-1) was coated and molded so as to have a thickness of 65 ⁇ m. Then, a laminated sheet 2 for forming a pressure sensitive adhesive layer composed of PET film / ultraviolet crosslinkable pressure sensitive adhesive layer (B-1, thickness 65 ⁇ m) / PET film was prepared.
- Example 1 Production of pressure-sensitive adhesive sheet 1>
- the PET films on both sides of the intermediate resin layer (A-1) in the intermediate resin layer forming laminated sheet 1 are sequentially peeled and removed, and the pressure sensitive adhesive layer (B in the pressure sensitive adhesive layer forming laminated sheets 1 and 1 ′) is removed.
- -1) and (B-1 ′) are peeled off and the exposed adhesive surfaces are sequentially bonded to both surfaces of (A-1) with a laminator, and (B-1) / (A -1) / (B-1 ′) was produced.
- Example 2 Production of pressure-sensitive adhesive sheet 2> An intermediate resin layer composition (A-2) and a pressure sensitive adhesive composition (B-1) are applied to a release-treated polyethylene terephthalate film (Mitsubishi Resin “MRA75”, thickness 75 ⁇ m).
- One side of the polyethylene terephthalate film is irradiated with UV light with an integrated light quantity of 1000 mJ with a high-pressure mercury lamp, and (B-1), (A-2), and (B-1) are UV-crosslinked to be transparent before secondary curing.
- a double-sided pressure-sensitive adhesive sheet 2 (total thickness 180 ⁇ m) was produced.
- a pressure sensitive adhesive composition (B-2) is prepared by mixing and adding 50 g of nonanediol diacrylate as a crosslinking agent and 10 g of 4-methylbenzophenone as a photopolymerization initiator to 1 kg of the acrylate copolymer A. did.
- This pressure-sensitive adhesive composition was heated and melted and applied to a polyethylene terephthalate film (Mitsubishi Resin “MRF75”, 75 ⁇ m thick) with a applicator to form a film and peeled.
- the treated polyethylene terephthalate film (Mitsubishi Resin “MRA50”, thickness 50 ⁇ m) was coated to form a sheet of PET film / pressure-sensitive adhesive layer (B-2) / PET film.
- One side of the polyethylene terephthalate film was irradiated with UV light with an integrated light quantity of 1000 mJ with a high-pressure mercury lamp, and (B-2) was UV-crosslinked to prepare a transparent double-sided pressure-sensitive adhesive sheet 3 (total thickness 170 ⁇ m) before secondary curing. .
- Example 4 Production of pressure-sensitive adhesive sheet 4> Example 1 was used except that the intermediate resin layer-forming laminated sheet 2 (A-2) was used as the intermediate resin layer, and the pressure-sensitive adhesive layer-forming laminated sheets 2 and 2 ′ were used as the pressure-sensitive adhesive layer. Thus, a transparent double-sided pressure-sensitive adhesive sheet 1 (total thickness 260 ⁇ m) before secondary curing comprising the layer constitution (B-1) / (A-2) / (B-1 ′) was produced.
- An adduct type hexamethylene diisocyanate (Duranate P301-75E manufactured by Asahi Kasei) as a cross-linking agent was added to 1 kg of this acrylate copolymer to add 0.2 parts by mass in terms of solid content to prepare an adhesive composition.
- the adhesive composition is coated on a release-treated polyethylene terephthalate film (Mitsubishi resin “MRA75” thickness 75 ⁇ m), and then coated with a release-treated polyethylene terephthalate film (Mitsubishi resin “MRF50” thickness 50 ⁇ m). Then, it was cured for one week under conditions of temperature of 25 ° C. and humidity of 50%, followed by thermal crosslinking to produce a transparent double-sided pressure-sensitive adhesive sheet 5 (total thickness 150 ⁇ m).
- one side is peeled off while confirming the integrated light quantity with a light meter (UNIMETER UIIT150 TYPE UIT-150A manufactured by USHIO INC.) So that ultraviolet light with a wavelength of 365 nm reaches 2000 mJ / cm 2 to the adhesive sheet.
- the pressure-sensitive adhesive sheet corresponding to the transparent double-sided pressure-sensitive adhesive sheet after secondary curing was produced by irradiating with ultraviolet rays from the film side.
- the laminate was laminated so that the total thickness was in the range of 5 mm to 7 mm, and the tip terminal of the Asker C2L hardness tester was 3 mm / min vertically below the exposed adhesive surface with a load of 1 kg.
- C2 Asker hardness (b) was measured by pressing at a speed.
- a polarizing plate (NWF-KDSEGHC-ST22 manufactured by Nitto Denko) was previously bonded to one side of a glass plate (53 ⁇ 83 mm ⁇ t 0.5 mm) with the same dimensions as the test adherend, and the polarization 0.03 mg (about 200 grains) of glass beads having a center particle size of 50 ⁇ m were dispersed as pseudo foaming starting points on the plate surface to obtain a foam resistance test substrate.
- one of the release films of the adhesive sheets 1 to 6 cut by the processability evaluation was peeled off, and the exposed adhesive surface was attached with a hand roller.
- soda lime glass 53 ⁇ 83 mm ⁇ t 0.5 mm
- soda lime glass 53 ⁇ 83 mm ⁇ t 0.5 mm
- autoclave treatment 50 ° C., 0.2 MPa 20
- ⁇ indicates that the glass bead surface scattered on the substrate is wet with the adhesive sheet, and the periphery of the bead is buried in the adhesive layer without a gap, and the glass bead is floating around the glass bead. It was determined as “x”.
- the laminate (sample) produced by the above unevenness followability test was used as a sample for the foam resistance test.
- the adhesive sheets 1 to 4 the laminate (sample) prepared in the above-described unevenness followability test was irradiated with ultraviolet rays through a high pressure mercury lamp through soda lime glass, and the adhesive sheets 1 to 4 were irradiated with ultraviolet rays of 365 nm. Was irradiated with ultraviolet rays so as to reach 2000 mJ / cm 2 to prepare a sample for a foam resistance test.
- the pressure-sensitive adhesive composition was formed into a single-layer or multi-layer sheet, and this was subjected to ultraviolet curing and primary curing, before the secondary curing in a state in which ultraviolet reactivity remained. It is a transparent double-sided pressure-sensitive adhesive sheet.
- Two image display device constituent members are laminated via the transparent double-sided pressure-sensitive adhesive sheet before secondary curing, and ultraviolet rays are irradiated from the image display device constituent member side, and the transparent pre-secondary-curing side surfaces are passed through this member. It was found that when the pressure-sensitive adhesive sheet was subjected to ultraviolet crosslinking and secondarily cured, it could be firmly crosslinked and a transparent double-sided pressure-sensitive adhesive sheet after secondary curing having high indentation hardness could be obtained.
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Abstract
Description
例えば特許文献2及び3には、接着剤組成物を予め光硬化(または熱硬化)させて部分的に架橋状態の接着剤組成物を作製した後、次いで、この接着剤組成物を介して光学機能部材と表示部とを貼り合わせ、その後、加熱処理(または光照射)により接着組成物を熱硬化(または光硬化)させることを特徴とする光学機能部材一体型表示装置の製造方法が提案されている。
(1) 粘着剤組成物を単層又は多層のシート状に形成し、これを紫外線架橋して1次硬化させることにより2次硬化前透明両面粘着シートを形成する工程。
(2) 2次硬化前透明両面粘着シートを介して2つの画像表示装置構成部材を積層した後、少なくとも一方の画像表示装置構成部材側から紫外線を照射し、この部材を介して、前記2次硬化前透明両面粘着シートを紫外線架橋して2次硬化させる工程。
そして、前記工程(2)において、少なくとも一方の画像表示装置構成部材側から紫外線を照射し、この部材を介して、紫外線架橋させて2次硬化させることにより、前記2次硬化前透明両面粘着シートをしっかりと架橋させることができ、例えば保護パネル等から発生するアウトガスのガス圧に対して十分に対抗できるだけの粘着力と凝集力を持たせることができる。
このように、本発明の画像表示装置構成用積層体の製造方法によれば、一般的にはトレードオフの関係にある凹凸追随性と、耐発泡信頼性とを同時に実現することができる。
本実施形態に係る画像表示装置構成用積層体の製造方法(以下「本製造方法」と称する)は、透明両面粘着シート(以下、「本粘着シート」と称する)を介して画像表示装置構成部材が積層されてなる構成を備えた画像表示装置構成用積層体の製造方法であって、少なくとも次の(1)及び(2)の工程を有することを特徴とする画像表示装置構成用積層体(以下、「本積層体」と称する)の製造方法である。
(1) 粘着剤組成物を単層又は多層のシート状に形成し、これを紫外線架橋して1次硬化させることにより2次硬化前透明両面粘着シートを形成する工程。
(2) 2次硬化前透明両面粘着シートを介して2つの画像表示装置構成部材を積層した後、少なくとも一方の画像表示装置構成部材側から紫外線を照射し、この部材を介して、前記2次硬化前透明両面粘着シートを紫外線架橋させて2次硬化させる工程。
また、本製造方法によれば、前記工程(1)で得られる2次硬化前透明両面粘着シートは、さらに紫外線架橋される余地を残しており、それだけ柔軟であるから、被着体の表面に凹凸があったり、粘着界面に異物等が存在したりしても、これらの凹凸に十分に追従して馴染んで濡れて好適に密着することができる。そして、前記工程(2)において、2次硬化させることにより、しっかりと架橋させることができ、例えば保護パネル等から発生するアウトガスのガス圧に対して十分に対抗できるだけの粘着力と凝集力を持たせることができる。
先ず、本製造方法において、単層の透明両面粘着シートを形成するのに好適に用いることができる粘着剤組成物の一例(以下、「本粘着剤組成物」と称する)について説明する。但し、あくまでも一例であって、これに限定されるものではない。
また、溶剤を含まない無溶剤系であって、粘着剤組成物をホットメルトによって製膜することが好ましい。
本粘着剤組成物は、粘着性、透明性及び耐候性などの観点から、(メタ)アクリル酸エステル系重合体(共重合体を含む意で、以下「アクリル酸エステル系(共)重合体」と称する。)をベース樹脂として用いるのが好ましい。
これらのモノマーを用いた重合処理としては、溶液重合、乳化重合、塊状重合、懸濁重合などの公知の重合方法が採用可能であり、その際に重合方法に応じて熱重合開始剤や光重合開始剤などの重合開始剤を用いることによりアクリル酸エステル共重合体を得ることができる。
よって、かかる観点から、ベースポリマーの質量平均分子量は10万~70万、特に20万以上、或いは60万以下、中でも特に25万以上或いは50万以下であるアクリル酸エステル系(共)重合体を用いるのが好ましい。
この際、2種類のモノマー成分のガラス転移温度(Tg)の差は25~300℃であるのが好ましく、特に40℃以上或いは200℃以下、中でも特に60℃以上或いは180℃以下、さらには100℃以上或いは180℃以下であるのがより一層好ましい。
具体的には、一方のモノマー成分のガラス転移温度(Tg)が-100~0℃、特に-80~-20℃であり、他方のモノマー成分のガラス転移温度(Tg)が0~250℃、特に20~180℃であるのが好ましい。
ガラス転移温度(Tg)が低い方のモノマー成分、例えばTgが-100~0℃であるモノマー成分としては、側鎖の炭素数が2以上、特に4以上のアクリル酸エステルを用いるのが好ましい。
他方、ガラス転移温度(Tg)が高いモノマー成分、例えばTgが0~250℃であるモノマー成分としては、側鎖に炭素数が2以下の炭化水素の他、脂環構造、ヘテロ環、芳香族等の環構造や、カルボシル基、水酸基、アミノ基、アミド基、グリシジル基、アセチル基、イソシアネート基などの官能基を有するビニルモノマーもしくは(メタ)アクリルモノマーなどを用いるのが好ましい。
また、可塑剤によって柔軟にして硬度を下げたり、オリゴマー等の添加剤をもって硬度を適宜調整したりすることもできる。
アクリル酸エステル系(共)重合体を架橋する際に用いる架橋モノマー(架橋剤)としては、例えば(メタ)アクリロイル基を2個以上有する多官能(メタ)アクリレートが好ましい。
かかる観点から、架橋剤の量は、ベースポリマー100質量部に対して0~30質量部、特に20質量部以下、中でも10質量部以下、その中でも特に5質量部以下とするのが好ましい。
なお、架橋剤の量をこのように減らすことができるのは、架橋開始剤として分子間水素引抜型光重合性開始剤を使用しているからでもある。
本粘着剤組成物に用いる架橋開始剤としては、分子間水素引抜型光重合性開始剤(「水素引抜型光開始剤」とも称する)を採用することが重要である。
分子内開裂型は、光照射によってラジカルを発生する際、分解して別の化合物となるため、一度反応すると反応開始剤としての機能をもたなくなるが、水素引抜型は、失活後にもとの化合物に戻り、光照射によって繰り返し反応開始剤として用いることができる。したがって、潜在的な光硬化性を付与するためには、水素引抜型の光重合開始剤を用いることが重要である。
アクリル酸エステル系(共)重合体を架橋する際には、必要に応じて反応触媒(三級アミン系化合物、四級アンモニウム系化合物、ラウリル酸スズ化合物など)を適宜添加してもよい。
本粘着シートを多層の透明両面粘着シートとする場合には、すなわち、中間層と最外層とを備えた積層構成の透明両面粘着シートを形成する場合には、その最外層を、上述した本粘着剤組成物から形成すればよい。
その際、架橋開始剤の含有量が多くなると光透過率が低下するため、中間層における架橋開始剤の外層における含有率よりも低い含有率で紫外線架橋剤を含むのが好ましい。
本粘着シートの厚さは、凹凸追随性及び、用途部材に求められる薄肉化の観点から、50μm~1mmであるのが好ましく、特に100μm以上或いは500μm以下であるのが好ましい。
また、多層構成のシートとする場合には、各最外層の厚さと中間層の厚さの比率は1:1~1:20であるのが好ましく、中でも1:2~1:10であるのがさらに好ましい。
中間層の厚みが、上記範囲であれば、積層体における粘着材層の厚みの寄与が大きくなりすぎず、柔軟すぎて裁断や取回しに係る作業性が劣るようになることがなく好ましい。
また、最外層が上記範囲であれば、凹凸や屈曲した面への追随性に劣ることがなく、被着体への接着力や濡れ性を維持する事が出来、好ましい。
工程(1)では、潜在的な紫外線反応性を有するように、言い換えれば紫外線反応性を残すように、透明両面粘着シートを紫外線架橋して1次硬化させることが重要である。
なお、このC2アスカー硬度(a)は、透明両面粘着シートを、全厚みが5mm~7mmの範囲内となるように順次積層してしたものについて、アスカー硬度計(AskerC2L)で測定し得る値である。
部材への貼着前の透明両面粘着シートは、ロール状にして巻き上げたり、裁断したりするために適度なコシが必要であり、かつ部材に貼着するための粘着力や濡れ性が必要である。そのため、C2アスカー硬度(a)が10以上であれば、柔軟すぎて取り回しに係る作業性に欠けるおそれがなく、C2アスカー硬度(a)が50未満であれば、被着体の表面に凹凸があったり、粘着界面に異物等が存在したりしても、これらの凹凸に十分に追従して馴染んで濡れて好適に密着することができる。よって、C2アスカー硬度(a)を上記範囲とすることで、作業性と粘着物性を両立させるができ、また印刷部などによる段差への追随性も確保することが可能となる。
このような点から、C2アスカー硬度(a)は、15以上或いは45以下であるのがより一層好ましく、中でも20以上或いは33未満であるのがさらに好ましい。
工程(2)では、工程(1)で得られた2次硬化前透明両面粘着シートを介して2つの画像表示装置構成部材を積層した後、少なくとも一方の画像表示装置構成部材側から紫外線を照射し、この部材を介して、前記2次硬化前透明両面粘着シートを紫外線架橋させて2次硬化させることが重要である。
具体的に言えば、例えば2次硬化前透明両面粘着シートの紫外線を照射する側に、ガラス板を積層する場合には当該ガラス板の紫外線透過率が、また、例えばガラス板と粘着剤と保護シートを積層する場合にはこれらガラス板、粘着剤及び保護シートの積層体の紫外線透過率が一定以上であることが好ましい。
よって、2次硬化前透明両面粘着シートの紫外線照射側に積層する画像表示装置構成部材の紫外線透過率、すなわちUV-A波の波長範囲315nm~400nmにおける光線透過率が20%以上であることが好ましく、特に30%以上、中でも特に40%以上であるのがより一層好ましい。
なお、このC2アスカー硬度(b)は、透明両面粘着シートを全厚みが5mm~7mmの範囲内となるように順次積層したものについて、アスカー硬度計(AskerC2L)で測定し得る値である。
2次硬化後透明両面粘着シートのC2アスカー硬度(b)を33以上とすることで、十分な粘着力と凝集力を有することになり、例えば保護パネル等から発生するアウトガスのガス圧に対して十分に対抗することができる。他方、C2アスカー硬度(b)を80以下とすることで、硬すぎて感圧接着としての機能が損なわれて密着力に劣り、剥離や浮きが発生するなどの懸念を無くすことができる。
このように、2次硬化後透明両面粘着シートのC2アスカー硬度(b)を上記範囲に調整することで、貼着後に、長期保管や高温高湿環境下にて徐々に貼着界面に凝集するガス圧に耐えられる粘着層の凝集力と、剥離しない程度の適度な密着力を付与させることができる。
このような観点から、2次硬化後透明両面粘着シートのC2アスカー硬度(b)は、35以上或いは60以下であるのがさらに好ましく、中でも38以上或いは50以下であるのがより一層好ましい。
本製造方法で製造し得る画像表示装置構成用積層体としては、例えばパソコン、モバイル端末(PDA)、ゲーム機、テレビ(TV)、カーナビ、タッチパネル、ペンタブレットなど、LCD、PDP又はELなどの画像表示装置の構成部材を挙げることができる。
そこで、保護パネル/粘着シート/偏光フィルムの構成から成る積層体として、本積層体を用いれば、高温下で使用された場合に、保護パネルや偏光フィルムから放出されるアウトガスによる発泡を効果的に抑制することができる。
そのほか、例えば液晶パネル/粘着シート/タッチパネル、液晶パネル/粘着シート/保護パネル、液晶パネル/粘着シート/タッチパネル/粘着シート/保護パネル、偏光フィルム/粘着シート/タッチパネル、偏光フィルム/粘着シート/タッチパネル/粘着シート/保護パネルなどの構成を本積層体の構成例として挙げることができる。
なお、一般的に「シート」とは、JISにおける定義上、薄く、その厚さが長さと幅のわりには小さく平らな製品をいい、一般的に「フィルム」とは、長さ及び幅に比べて厚さが極めて小さく、最大厚さが任意に限定されている薄い平らな製品で、通常、ロールの形で供給されるものをいう(日本工業規格JISK6900)。しかし、シートとフィルムの境界は定かでなく、本発明において文言上両者を区別する必要がないので、本発明においては、「フィルム」と称する場合でも「シート」を含むものとし、「シート」と称する場合でも「フィルム」を含むものとする。
また、画像表示パネル、保護パネル等のように「パネル」と表現する場合、板体、シートおよびフィルムを包含するものである。
また、「X以上」(Xは任意の数字)と記載した場合、特にことわらない限り「好ましくはXより大きい」の意を包含し、「Y以下」(Yは任意の数字)と記載した場合、特にことわらない限り「好ましくはYより小さい」の意も包含するものである。
2-エチルヘキシルアクリレート(ホモポリマーTg-70℃)75質量部と、酢酸ビニル(ホモポリマーTg+32℃)20質量部と、アクリル酸(ホモポリマーTg+106℃)5質量部とをランダム共重合してなるアクリル酸エステル共重合体A(Mw=440000 Mn=62000 Mw/Mn=8 理論Tg-50℃)を用意した。
このアクリル酸エステル共重合体A1kgに、架橋剤としての紫外線硬化樹脂プロポキシ化ペンタエリスリトールトリアクリレート(新中村化学社製「ATM-4PL」)100gと、光重合開始剤としての4-メチルベンゾフェノン15gとを混合して中間樹脂層用組成物(A-1)を調製した。
塗工基材としての剥離処理したポリエチレンテレフタレートフィルム(パナック社製「NP75Z01」、厚み75μm)に、前記中間樹脂層用組成物(A-1)を加熱溶融して、厚み110μmとなるようアプリケータにて塗工した後、剥離処理したポリエチレンテレフタレートフィルム(東洋紡績製「E7006」、厚み38μm)を被覆し、PETフィルム/紫外線架橋性中間樹脂層(A-1、厚さ110μm)/PETフィルムからなる中間樹脂層形成用積層シート1を作製した。
架橋剤として、トリメチロールプロパントリアクリレート200gを配合し、光重合開始剤として、1-ヒドロキシ-シクロヘキシルフェニルケトン50gを配合した以外は、上記中間樹脂層形成用積層シート1と同様にして中間樹脂層用組成物(A-2)を調製した。
塗工基材としての剥離処理したポリエチレンテレフタレートフィルム(パナック社製「NP75Z01」、厚み75μm)に、前記中間樹脂層用組成物(A-2)を加熱溶融して、厚み130μmとなるようアプリケータにて塗工した後、剥離処理したポリエチレンテレフタレートフィルム(東洋紡績製 E7006 厚み38μm)を被覆し、PETフィルム/紫外線架橋性中間樹脂層(A-2、厚さ130μm)/PETフィルムからなる中間樹脂層形成用積層シート2を作製した。
前記アクリル酸エステル共重合体A1kgに、光重合開始剤としての4-メチルベンゾフェノン20gを添加混合して、感圧粘着剤用組成物(B-1)を調製した。
この感圧粘着剤用組成物(B-1)を加熱溶融して、塗工基材としての剥離処理したポリエチレンテレフタレートフィルム(三菱樹脂株式会社製「MRA75」、厚み75μm)上に、厚みが35μmとなるようにシート状に塗工して成形し、剥離処理を施したポリエチレンテレフタレートフィルム(東洋紡績製「E7006」、厚み38μm)を被覆し、PETフィルム/紫外線架橋性感圧粘着剤層(B-1、厚さ35μm)/PETフィルムからなる感圧粘着剤層形成用積層シート1を作製した。
塗工基材を、剥離処理したポリエチレンテレフタレートフィルム(三菱樹脂製「MRF50」厚み50μm)に変えた以外は、上記感圧粘着剤層形成用積層シート1と同様にして、PETフィルム/紫外線架橋性感圧粘着剤層(B-1’、厚さ35μm)/PETフィルムからなる感圧粘着剤層形成用積層シート1’を作製した。
感圧粘着材層形成用積層シート1において、感圧接着層(B-1)の厚みが65μmとなるように塗工成形した以外は、感圧粘着材層形成用積層シート1と同様にして、PETフィルム/紫外線架橋性感圧粘着剤層(B-1、厚さ65μm)/PETフィルムからなる感圧粘着剤層形成用積層シート2を作製した。
塗工基材を、剥離処理したポリエチレンテレフタレートフィルム(三菱樹脂製「MRF50」厚み50μm)に変えた以外は、上記感圧粘着剤層形成用積層シート2と同様にして、PETフィルム/熱架橋性感圧粘着剤層(B-1’、厚さ65μm)/PETフィルムからなる感圧粘着剤層形成用積層シート2’を作製した。
中間樹脂層形成用積層シート1における中間樹脂層(A-1)の両側のPETフィルムを順次剥離除去すると共に、感圧粘着剤層形成用積層シート1及び1’における感圧粘着剤層(B-1)及び(B-1’)の一側のPETフィルムを剥がして、露出した粘着面を(A-1)の両表面にラミネータにて順次貼合し、(B-1)/(A-1)/(B-1’)からなる多層粘着シートを作製した。
(B-1)及び(B-1’)の表面に残るポリエチレンテレフタレートフィルムを介して、365nmの積算光量が1000mJとなるよう高圧水銀ランプにて紫外線を照射し、(B-1)、(A-1)及び(B-1’)を紫外線架橋させて、2次硬化前透明両面粘着シート1(総厚み180μm)を作製した。
剥離処理したポリエチレンテレフタレートフィルム(三菱樹脂性「MRA75」、厚み75μm)上に、中間樹脂層用組成物(A-2)及び感圧粘着剤用組成物(B-1)を、感圧粘着剤層(B-1)/中間樹脂層(A-2)/感圧粘着剤層(B-1)となるように共押出しして、感圧粘着剤層(B-1)/中間樹脂層(A-2)/感圧粘着剤層(B-1)=40/100/40μmとなるように塗工形成し、剥離処理したポリエチレンテレフタレートフィルム(三菱樹脂製「MRA50」、厚み50μm)を被覆して、PETフィルム/(B-1)/(A-2)/(B-1)/PETフィルムからなる多層シートを形成した。
一方のポリエチレンテレフタレートフィルム側から、高圧水銀ランプにて積算光量1000mJの紫外線を照射し、(B-1)、(A-2)及び(B-1)を紫外線架橋させて、2次硬化前透明両面粘着シート2(総厚み180μm)を作製した。
前記アクリル酸エステル共重合体A1kgに、架橋剤としてのノナンジオールジアクリレート50g及び光重合開始剤としての4-メチルベンゾフェノン10gを混合添加して感圧粘着剤用組成物(B-2)を調製した。
この粘着剤組成物を加熱溶融し、剥離処理したポリエチレンテレフタレートフィルム(三菱樹脂製「MRF75」、厚さ75μm)上に、厚さ170μmとなるようアプリケータにて塗工して製膜し、剥離処理したポリエチレンテレフタレートフィルム(三菱樹脂製「MRA50」、厚さ50μm)を被覆し、PETフィルム/感圧粘着剤層(B-2)/PETフィルムからなるシートを形成した。
一方のポリエチレンテレフタレートフィルム側から、高圧水銀ランプにて積算光量1000mJの紫外線を照射し、(B-2)を紫外線架橋させて、2次硬化前透明両面粘着シート3(総厚み170μm)を作製した。
中間樹脂層として中間樹脂層形成用積層シート2(A-2)を用い、感圧接着剤層として感圧粘着剤層形成用積層シート2及び2’を用いる以外は、実施例1と同様にして、層構成(B-1)/(A-2)/(B-1’)からなる2次硬化前透明両面粘着シート1(総厚み260μm)を作製した。
2-エチルヘキシルアクリレート48質量部、2-メトキシエチルアクリレート(ホモポリマーTg-50℃)50質量部及び4-ヒドロキシブチルアクリレート(ホモポリマーTg-80℃)2質量部をランダム共重合してなるアクリル酸エステル共重合体(Mw=100万 理論Tg-61℃)を調製した。
このアクリル酸エステル共重合体1kgに対し、架橋剤としてのアダクト型ヘキサメチレンジイソシアネート(旭化成製デュラネート P301-75E)を、固形分換算0.2質量部添加して粘着材組成物を作製した。
該粘着組成物を、剥離処理したポリエチレンテレフタレートフィルム(三菱樹脂性「MRA75」厚み75μm)上に塗工形成・乾燥の後、剥離処理したポリエチレンテレフタレートフィルム(三菱樹脂性「MRF50」厚み50μm)を被覆し、温度25℃湿度50%条件下にて一週間養生して熱架橋し、透明両面粘着シート5(総厚み150μm)を作製した。
2次硬化前透明両面粘着シート1(総厚み180μm)に、更に高圧水銀ランプにて波長365nmの紫外線が粘着層に1000mJ到達するよう追加照射して、(B-1)、(A-1)及び(B-1’)を2次硬化させた2次硬化後透明両面粘着シート6(総厚み180μm)を作製した。
上記粘着シート1~6について、次のような評価を行った。
上記粘着シート1~6について、剥離フィルムを剥がし、露出した粘着面を順次重ね合せて、複数枚の粘着シートを全厚みが5mm~7mmの範囲内になるように積層した。これにより測定試料を乗せるステージの硬さの影響を低減することができ、材料特有の押込硬度を比較・測定することができる。
そして、積層した粘着シートの露出した粘着面に対してアスカーC2L硬度計の先端端子を荷重1kgにて垂直下方に3mm/分の速度で押し付け、C2アスカー硬度(a)を測定した。
前述と同様の方法にて、全厚みが5mm~7mmの範囲内になるように積層し、露出した粘着面に対してアスカーC2L硬度計の先端端子を荷重1kgにて垂直下方に3mm/分の速度で押し付け、C2アスカー硬度(b)を測定した。
上記粘着シート1~6を、剥離フィルムを積層したままトムソン打抜機を用いて50mm×80mmのトムソン刃で100枚カットし、裁断したシート端部の形状を目視で観察した。
そして、シート端部に糊のはみだしが10枚以上あるものを「×」、10枚未満ものを「○」と判定した。
試験用の被着体として偏光板(日東電工製NWF-KDSEGHC-ST22)を予めガラス板上(53×83mm×t0.5mm)の片面に同寸法にて貼り合わせたものを作製し、前記偏光板面に擬似的な発泡起点として中心粒径50μmのガラスビーズを0.03mg(約200粒)ばら撒いて、耐発泡信頼性試験用基板とした。前記基板上に、加工性評価にて裁断した粘着シート1~6の一方の剥離フィルムを剥がして露出した粘着面をハンドローラにて貼着した。次いで、残る剥離フィルムを剥がし、露出した粘着面にソーダライムガラス(53×83mm×t0.5mm)を、減圧下(絶対圧5kPa)にてプレス貼合した後、オートクレーブ処理(50℃0.2MPa20分)を施して仕上貼着し、積層体(サンプル)を作製した。
作製した積層体を目視観察し、基板上にばら撒いたガラスビーズ表面が粘着シートに濡れ、ビーズ周囲が空隙なく粘着層に埋もれているものを「○」、ガラスビーズ周辺に浮きがあるものを「×」と判定した。
粘着シート5~6については、上記凹凸追随性試験で作製した積層体(サンプル)を耐発泡信頼性試験のサンプルとした。
他方、粘着シート1~4については、上記凹凸追随性試験で作製した積層体(サンプル)に対し、ソーダライムガラス越しに高圧水銀ランプにて紫外線照射し、粘着シート1~4に、365nmの紫外線が2000mJ/cm2到達するよう紫外線照射して耐発泡信頼性試験のサンプルを作製した。
これらの各サンプルを、常態(温度23℃湿度50%)で一日静置した後、温度85℃湿度25%の恒温恒湿機にて6時間養生し、養生後の外観を目視観察した。
ガラスビーズ周辺より新たな浮きが発生しなかったものを「○」、養生により発泡や浮きが発生したものを「×」と判定した。
Claims (8)
- 透明両面粘着シートを介して画像表示装置構成部材が積層されてなる構成を備えた画像表示装置構成用積層体の製造方法であって、少なくとも次の(1)及び(2)の工程を有することを特徴とする画像表示装置構成用積層体の製造方法。
(1) 粘着剤組成物を単層又は多層のシート状に形成し、これを紫外線架橋して1次硬化させることにより2次硬化前透明両面粘着シートを形成する工程。
(2) 2次硬化前透明両面粘着シートを介して2つの画像表示装置構成部材を積層した後、少なくとも一方の画像表示装置構成部材側から紫外線を照射し、この部材を介して、前記2次硬化前透明両面粘着シートを紫外線架橋して2次硬化させる工程。 - 前記工程(1)では、透明離型シート上に、粘着剤組成物をシート状に成形し、前記透明離型シートを介して紫外線を照射して前記粘着剤組成物を紫外線架橋させることを特徴とする、請求項1記載の画像表示装置構成用積層体の製造方法。
- 2次硬化前透明両面粘着シートは、波長315nm~400nmの範囲の何れかにおいて、紫外線架橋反応を開始させる波長吸収域を有することを特徴とする請求項1又は2に記載の画像表示装置構成用積層体の製造方法。
- 前記工程(2)において、2次硬化後の透明両面粘着シートの押し込み硬度(C2アスカー硬度)(b)を33≦(b)≦80とすることを特徴とする請求項1~3の何れかに記載の画像表示装置構成用積層体の製造方法。
- 前記工程(1)の2次硬化前透明両面粘着シートの押し込み硬度(a)と、前記工程(2)における2次硬化後の透明両面粘着シートの押し込み硬度(b)とが、(b)-(a)≧2の関係にあることを特徴とする、請求項1~4の何れかに記載の画像表示装置構成用積層体の製造方法。
- 前記工程(2)において、少なくとも一方の画像表示装置構成部材は、波長315~400nmの範囲における光線透過率が20%以上であることを特徴とする、請求項1~5の何れかに記載の画像表示装置構成用積層体の製造方法。
- 画像表示装置構成部材が、タッチパネル、画像表示パネル、表面保護パネル及び偏光フィルムからなる群のうちの何れか、或いは2種類以上の組み合わせからなる積層体であることを特徴とする請求項1~6の何れかに記載の画像表示装置構成用積層体の製造方法。
- 請求項1~7の何れかに記載の製造方法によって製造された積層体を用いて構成された画像表示装置。
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US14/178,854 Continuation US9481155B2 (en) | 2010-09-06 | 2014-02-12 | Method for producing laminate for configuring image display device, and image display device using the laminate |
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JPWO2012032995A1 (ja) | 2014-01-20 |
JP2017066408A (ja) | 2017-04-06 |
EP2615600B1 (en) | 2018-03-14 |
CN103756600B (zh) | 2017-06-23 |
US20120328890A1 (en) | 2012-12-27 |
TW201301222A (zh) | 2013-01-01 |
JP6848933B2 (ja) | 2021-03-24 |
TWI416445B (zh) | 2013-11-21 |
EP2615600A1 (en) | 2013-07-17 |
JP6328871B2 (ja) | 2018-05-23 |
CN103756600A (zh) | 2014-04-30 |
KR101162558B1 (ko) | 2012-07-05 |
US20140162081A1 (en) | 2014-06-12 |
JP5588081B1 (ja) | 2014-09-10 |
JP2018162465A (ja) | 2018-10-18 |
JP6376203B2 (ja) | 2018-08-22 |
EP2615600A4 (en) | 2015-01-21 |
US9481154B2 (en) | 2016-11-01 |
US9481155B2 (en) | 2016-11-01 |
EP3093832A1 (en) | 2016-11-16 |
JP2012184423A (ja) | 2012-09-27 |
US20140162080A1 (en) | 2014-06-12 |
JP2014209236A (ja) | 2014-11-06 |
EP3093832B1 (en) | 2018-01-31 |
KR20120059638A (ko) | 2012-06-08 |
CN103805076B (zh) | 2016-06-22 |
JP4971529B2 (ja) | 2012-07-11 |
US8715448B2 (en) | 2014-05-06 |
CN103805076A (zh) | 2014-05-21 |
CN102667895A (zh) | 2012-09-12 |
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