WO2018105413A1 - 粘着シート及びその製造方法 - Google Patents
粘着シート及びその製造方法 Download PDFInfo
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- WO2018105413A1 WO2018105413A1 PCT/JP2017/042202 JP2017042202W WO2018105413A1 WO 2018105413 A1 WO2018105413 A1 WO 2018105413A1 JP 2017042202 W JP2017042202 W JP 2017042202W WO 2018105413 A1 WO2018105413 A1 WO 2018105413A1
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- adhesive sheet
- pressure
- sensitive adhesive
- release film
- sheet
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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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
- 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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- 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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- C09J2467/00—Presence of polyester
Definitions
- the present invention can be suitably used for forming 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, and a pen tablet. And a manufacturing method thereof.
- an image display panel such as a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), and the like
- LCD liquid crystal display
- PDP plasma display
- ELD electroluminescence display
- Patent Document 1 Japanese Patent Laid-Open No. 2014-094976 discloses an image in which light having a wavelength of 360 nm or less is irradiated from the side surface side of a laminate in which a pressure-sensitive adhesive layer and a base material layer are laminated.
- a pressure-sensitive adhesive sheet for a display device and a method for producing the same are disclosed.
- Patent Document 2 Japanese Patent No. 4971529
- a pressure-sensitive adhesive sheet that is primarily cross-linked by ultraviolet rays is bonded to an image display device constituent member, and then the adhesive sheet is irradiated with ultraviolet rays through the image display device constituent member to be secondarily cured.
- a method is disclosed.
- the above-described image display device constituent member often has a concavo-convex portion on the adherend surface, such as a print portion formed on the adherend surface, and in order to improve visibility, It is preferable that the concavo-convex portion is also filled with an adhesive. Therefore, in a normal state, that is, in a room temperature state, it can be provided with a peelable adhesiveness (referred to as “tackiness”), and when heated to a temperature capable of hot-melting, has fluidity, A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet have been developed that can be filled to every corner following the unevenness of the bonding surface, and can finally adhere adherends firmly.
- Patent Document 3 Japanese Patent Application Laid-Open No. 2015-105296
- 100 parts by mass of an acrylic copolymer (A) 0.5 to 20 parts by mass of a crosslinking agent (b), and a photopolymerization initiator (C) are disclosed.
- a pressure-sensitive adhesive resin composition containing 0.1 to 5 parts by mass, wherein the acrylic copolymer (A) has a weight average molecular weight of 5.0 ⁇ 10 4 to 5.0 ⁇ 10 5 5.
- An adhesive resin composition is disclosed. Has been.
- This type of pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet laminate obtained by laminating a peelable protective film (also referred to as a “release film”) on the pressure-sensitive adhesive surface from the viewpoint of ensuring handling properties and preventing foreign matter from adhering to the pressure-sensitive adhesive surface. It is common to distribute. Among them, regarding the transparent double-sided pressure-sensitive adhesive sheet used for bonding image display device components such as touch panels, liquid crystal panels, and surface protection panels of touch displays, the transparent pressure-sensitive adhesive sheet itself is used from the viewpoint of ensuring optical properties and flexibility. Since it is preferable to make it thin and flexible, many have been used as a pressure-sensitive adhesive sheet laminate formed by laminating a release film on a pressure-sensitive adhesive sheet.
- Patent Document 4 Japanese Patent Laid-Open No. 2009-102467
- an ABA type triblock copolymer comprising an acrylic ester and a methacrylic ester and a hydroxyl group-containing resin are polymerized.
- a pressure-sensitive adhesive sheet obtained by hot-melt molding a blended acrylic transparent pressure-sensitive adhesive composition between release sheets is disclosed.
- Patent Document 5 Japanese Patent Application Laid-Open No. 2010-185037 discloses an adhesive sheet comprising an adhesive layer on at least one surface of a release film, and the adhesive layer is cross-linked.
- a pressure-sensitive adhesive sheet characterized by having a temperature range of 50,000 Pa to 1 million Pa in any temperature range of 25 ° C. to 120 ° C. when measuring the temperature dispersion behavior of the tensile storage modulus at a frequency of 1 Hz is disclosed. ing.
- JP 2014-094976 A Japanese Patent No. 4971529 Japanese Patent Laying-Open No. 2015-105296 JP 2009-102467 A JP 2010-185037 A
- the pressure-sensitive adhesive sheet having a photo-curable property (referred to as “photo-curable”) has a low gel fraction of the pressure-sensitive adhesive sheet before photo-curing, so that a release film is laminated on both sides of the pressure-sensitive adhesive sheet at room temperature.
- photo-curable When stored in a state, there was a problem that the pressure-sensitive adhesive protruded from the end face of the laminate and dust adhered thereto.
- the adhesive is stored in a state in which the pressure is applied to the adhesive sheet. There was a problem that it was easy to put out.
- the present invention relates to a photocuring pressure-sensitive adhesive sheet, a new pressure-sensitive adhesive sheet capable of effectively suppressing the pressure-sensitive adhesive from protruding from the end face even when stored at room temperature, and its production It is intended to propose a method.
- the present invention is a pressure-sensitive adhesive sheet having a width w [mm] from the sheet edge toward the sheet center (referred to as “edge width area”), and a sheet from the edge width area.
- a pressure-sensitive adhesive sheet is proposed in which a central region (referred to as “central region”) satisfies the following conditions (1) and (2).
- the gel fraction of the adhesive sheet in the edge width region is larger than the gel fraction of the adhesive sheet in the central region.
- the thickness of the pressure-sensitive adhesive sheet is d [mm], 30d ⁇ w ⁇ 100d is satisfied.
- the present invention is also a pressure-sensitive adhesive sheet-wrapped body with a release film obtained by winding a pressure-sensitive adhesive sheet with a release film obtained by laminating a release film on one or both sides of the pressure-sensitive adhesive sheet,
- the pressure-sensitive adhesive sheet has photocurability and has a width w [mm] area from the edge of both lateral sheets toward the center of the sheet (referred to as “edge width area”), and the edge width area.
- a pressure-sensitive adhesive sheet roll with a release film is proposed, characterized in that a region at the center of the sheet (referred to as “central region”) satisfies the following conditions (1) and (2).
- the gel fraction of the adhesive sheet in the edge width region is larger than the gel fraction of the adhesive sheet in the central region.
- the present invention also provides a pressure-sensitive adhesive sheet with a release film prepared by laminating a release film on one side or both sides of a photocurable pressure-sensitive adhesive sheet as a method for producing the pressure-sensitive adhesive sheet.
- a pressure-sensitive adhesive sheet with a release film prepared by laminating a release film on one side or both sides of a photocurable pressure-sensitive adhesive sheet as a method for producing the pressure-sensitive adhesive sheet.
- the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet roll with release film, and the manufacturing method thereof proposed by the present invention it is possible to effectively suppress the pressure-sensitive adhesive from protruding from the end surface even when stored at room temperature. can do. For example, even when the pressure-sensitive adhesive sheet is stored or transported in the state of being rolled up, it is possible to effectively suppress the pressure-sensitive adhesive from protruding from the end face of the roll.
- the pressure-sensitive adhesive sheet according to an example of the embodiment of the present invention is a pressure-sensitive pressure-sensitive adhesive sheet having a width w [mm] from the sheet edge toward the sheet center,
- the gel fraction of the pressure-sensitive adhesive sheet in the region of width w [mm] along the sheet edge on the sheet surface is the region in the center of the sheet from the edge width region (“
- the pressure-sensitive adhesive sheet is characterized by being larger than the gel fraction of the pressure-sensitive adhesive sheet in the “center region”.
- the pressure-sensitive adhesive sheet may be a rectangular pressure-sensitive adhesive sheet, a long pressure-sensitive adhesive sheet, a pressure-sensitive adhesive sheet wound in a roll shape, or other forms. .
- this adhesive sheet may exist in the state by which the release film was laminated
- “long” means that the length dimension is larger than the width dimension. Specifically, the length dimension means 5 m or more, preferably 10 mm or more.
- the upper limit value is not limited. If it prescribes
- a pressure-sensitive adhesive sheet with a release film obtained by winding a pressure-sensitive adhesive sheet with a release film obtained by laminating a release film on one side or both sides of the pressure-sensitive adhesive sheet in a roll shape As an example, a rotator (also referred to as “main body rotator”) can be given. Further, in a normal pressure-sensitive adhesive sheet roll, the pressure-sensitive adhesive sticks out more significantly as the roll width is wider. On the other hand, if it is a main roll, even if it is a wide roll, the protrusion of an adhesive can be suppressed effectively. Accordingly, the roll width of the wound body is preferably 20 mm to 2000 mm, more preferably 50 mm or more or 1500 mm or less.
- the sticking-out behavior of the adhesive has a certain relationship between the width of the edge width region and the thickness of the adhesive sheet. That is, if the width w [mm] of the portion having a high gel fraction is set at a ratio of 30 d ⁇ w with respect to the thickness d [mm] of the pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet can be used in a normal pressure-sensitive adhesive sheet. Even when stored as a roll, it is possible to effectively suppress the pressure-sensitive adhesive from sticking out from the roll end face by appropriately increasing the gel fraction in the edge width region.
- the relationship between the edge width region, that is, the width w [mm] of the portion having a high gel fraction, and the thickness d [mm] of the pressure-sensitive adhesive sheet is preferably 30d ⁇ w, and in particular, 35d ⁇ w, Of these, 40d ⁇ w, and more preferably 45d ⁇ w, is more preferable.
- this pressure-sensitive adhesive sheet when using this pressure-sensitive adhesive sheet as a pressure-sensitive adhesive sheet, it is usually used by cutting out the edge width region, and if the width of the edge width region is too large, the portion not used as a pressure-sensitive adhesive sheet increases. It becomes expensive. From this viewpoint, it is preferable that w ⁇ 100d, especially w ⁇ 80d, more preferably w ⁇ 70d, and even more preferably w ⁇ 60d.
- the width w is preferably 30d ⁇ w ⁇ 100d, 30d ⁇ w ⁇ 80d, 30d ⁇ w ⁇ 70d or 30d ⁇ w ⁇ 60d, and 35d ⁇ w ⁇ 100d, 35d ⁇ More preferably, any of w ⁇ 80d, 35d ⁇ w ⁇ 70d, or 35d ⁇ w ⁇ 60d, and 40d ⁇ w ⁇ 100d, 40d ⁇ w ⁇ 80d, 40d ⁇ w ⁇ 70d, or 40d ⁇ w ⁇ 60d. More preferably, it is either, and it is most preferable that either 45d ⁇ w ⁇ 100d, 45d ⁇ w ⁇ 80d, 45d ⁇ w ⁇ 70d, or 45d ⁇ w ⁇ 60d.
- the width w [mm] of the edge width region is preferably 3 mm to 10 mm, and more preferably 3.5 mm or more. 8.0 mm or less, more preferably 4.0 mm or more or 7.0 mm or less, and particularly preferably 4.5 mm or more or 6.0 mm or less.
- an area having a width w [mm] from the edge of both side sheets toward the center of the sheet may be the edge width area.
- the gel fraction of the pressure-sensitive adhesive sheet in the edge width region is preferably 1% or more larger than the gel fraction of the pressure-sensitive adhesive sheet in the central region, more preferably 5% or more, more preferably 10% or more, and most preferably 15% or more. It is preferable to be larger by less than%.
- the gel fraction of the edge width region is preferably 15% or more and less than 100%, more preferably 20% or more, more preferably 25% or more, and even more preferably 30% or more or 99% or less. Is more preferable.
- the gel fraction of the edge width region is preferably 15% or more and less than 100%, or 15% or more and 99% or less, and is 20% or more and less than 100% or 20% or more and 99% or less. Is more preferably 25% or more and less than 100%, or more preferably 25% or more and 99% or less, and most preferably 30% or more and less than 100%, or 30% or more and 99% or less.
- the standard deviation of the gel fraction is 3% or less, preferably 2.5% or less, and more preferably 2% or less.
- the standard deviation of the gel fraction in the central region is 3% or less, particularly 2.5% or less, and preferably 2% or less.
- that the standard deviation of the gel fraction in the edge width region is 3% or less means that the gel fraction in the edge width region is uniform. Since the gel fraction in the width region is uniformly high, it is possible to more reliably prevent the adhesive from protruding from the end face.
- the lower limit value is preferably 0% or more or 1% or more, for example. However, it is not particularly limited to the lower limit.
- a photocuring product having an edge width region having a gel fraction of 15 to 100% and a central region having a gel fraction smaller than the edge width region.
- the present wound body has photocurability having an edge width region having a gel fraction of 15 to 100% and a central region having a gel fraction of 0% or more and less than 15%.
- This adhesive sheet has photocurability.
- the gel fraction at the time of final curing for example, the gel fraction of the pressure-sensitive adhesive sheet after light irradiation by interposing the present adhesive sheet between the adherends (“the gel fraction at the time of final curing”) 20% to 100%, particularly 25% or more or 95% or less, more preferably 30% or more or 90% or less.
- the “gel fraction at the time of final curing” also means the gel fraction when the pressure-sensitive adhesive sheet is completely cured, and the gel fraction when used without being completely cured. It is also the meaning of rate.
- the pressure-sensitive adhesive sheet used corresponds to this pressure-sensitive adhesive sheet is determined by taking a measurement sample from the edge width region toward the center of the sheet, preferably every 0.1 mm to 1.0 mm width.
- the gel fraction of each measurement sample is measured, (1) whether the gel fraction of the adhesive sheet in the edge width region is larger than the gel fraction of the adhesive sheet in the central region, and (2) the central region It may be determined whether or not the width d [mm] of the edge width region having a larger gel fraction satisfies 30d ⁇ w ⁇ 100d.
- the gel fraction in the central region is preferably 0% or more and less than 15% as described above, and the gel fraction in the edge width region is preferably 15% or more and less than 100%.
- the boundary is defined as a gel fraction of 15%. That is, an area having a gel fraction of 15% or more is defined as an edge width area.
- the value of the gel fraction in the edge width region and the central region is the average value of each region.
- the thickness d of the pressure-sensitive adhesive sheet is preferably 0.05 mm to 1 mm. If it is this range, if it is a thin adhesive sheet like thickness 0.05mm, the adhesive sheet excellent in printing level
- the thickness d of the pressure-sensitive adhesive sheet is preferably 0.05 mm to 1 mm, 0.05 mm to 0.8 mm, or 0.05 mm to 0.5 mm or less, and 0.075 mm to 1 mm. , 0.075 mm to 0.8 mm or 0.075 mm to 0.5 mm or less, more preferably 0.1 mm to 1 mm, 0.1 mm to 0.8 mm or 0.1 mm to 0.5 mm or less. Most preferred is either.
- the thickness d of this adhesive sheet does not include the thickness of the release film.
- This pressure-sensitive adhesive sheet may be a single layer of a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive composition, or may be provided with a plurality of pressure-sensitive adhesive layers such as two layers or three layers.
- the pressure-sensitive adhesive sheet may have a structure in which a base layer (non-sticky layer) is provided as a core layer, and layers made of a pressure-sensitive adhesive are laminated on both sides of the base layer. .
- the base material layer as the core layer preferably has a material and characteristics such that the pressure-sensitive adhesive sheet laminate can be thermoformed.
- the pressure sensitive adhesive sheet is in a state where the contribution of viscosity is larger than elasticity.
- Tan ⁇ of this pressure-sensitive adhesive sheet is preferably more than 1. It is not always necessary to set the upper limit value. If the upper limit value is set intentionally, it is 10 or less.
- the value of Tan ⁇ can be adjusted by adjusting the constituents of the pressure-sensitive adhesive composition.
- it can be adjusted by the molecular weight of the base resin, the crosslinking conditions, etc., in addition to the types and composition ratios of the monomers constituting the base resin, the types and amounts of the crosslinking agent and the initiator.
- Tan ⁇ is determined by using a viscoelasticity measuring device dynamic analyzer (for example, “RDAII” manufactured by Rheometrics) under the following conditions for storage shear modulus (G ′) and loss shear modulus (G ′′). What is necessary is just to obtain
- ⁇ Conditions> ⁇ Jig: ⁇ 20mm parallel plate ⁇ Temperature: ⁇ 50 to 200 ° C. (measured at a heating rate of 3 ° C./min) ⁇ Frequency: 1 Hz ⁇ Strain angle: 0.1%
- the adhesive layer of this adhesive sheet has photocurability, it can be formed from a conventionally well-known adhesive material.
- the photo-curing property preferably has curability that can be cured by light having a wavelength other than an electron beam, specifically, light in a wavelength region of 200 nm to 780 nm.
- the pressure-sensitive adhesive layer of the present pressure-sensitive adhesive sheet is, for example, 1) (meth) acrylic acid ester polymer (hereinafter referred to as “acrylic acid ester (co) polymer”). Used as a pressure-sensitive adhesive composition comprising a crosslinking monomer, a crosslinking initiator or a reaction catalyst, if necessary, 2) A pressure-sensitive adhesive composition in which a butadiene or isoprene-based (co) polymer is used as a base resin, and a crosslinking monomer, a crosslinking initiator or a reaction catalyst, if necessary, is blended therein, 3) A pressure-sensitive adhesive composition comprising a silicone-based polymer as a base resin and a crosslinking monomer, and a crosslinking initiator or a reaction catalyst as necessary, 4) A polyurethane-based pressure-sensitive adhesive composition using a polyurethane-based polymer as a base resin.
- acrylic acid ester (co) polymer Used as a pressure-sensitive adhesive composition compris
- a suitable pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer, a (meth) acrylic (co) polymer (a) as a base resin, a crosslinking agent (b), a photopolymerization initiator ( and c).
- the (meth) acrylic (co) polymer (a) has characteristics such as glass transition temperature (Tg) depending on the type, composition ratio, polymerization conditions, etc. of the acrylic monomer and methacrylic monomer used to polymerize the (meth) acrylic (co) polymer. Can be adjusted as appropriate.
- Tg glass transition temperature
- acrylic ester (co) polymers (meth) acrylic acid alkyl ester (co) polymers are particularly preferable.
- the polymerization form of the acrylic ester copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer.
- Examples of the monomer component constituting the (meth) acrylic acid alkyl ester (co) polymer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl ( (Meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, Cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate
- hydroxyethyl (meth) acrylate hydroxypropyl (hydrophilic group, organic functional group, etc.) Hydroxyl group-containing (meth) acrylates such as (meth) acrylate, hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) Acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid Acid, 2- (meta Car
- a (meth) acrylic copolymer (a1) composed of a graft copolymer having a macromonomer as a branch component can be given.
- the pressure-sensitive adhesive layer is formed using the acrylic copolymer (a1) as a base resin, the pressure-sensitive adhesive layer can exhibit a self-adhesive property while maintaining a sheet shape at room temperature, and when heated in an uncrosslinked state It has a hot melt property that melts or flows, and can be photocured, and after photocuring, it exhibits excellent cohesive force and can be bonded. Therefore, if the acrylic copolymer (a1) is used as the base polymer, it exhibits adhesiveness at room temperature (20 ° C.) even in an uncrosslinked state, and is 50 to 100 ° C., more preferably 60 ° C. or higher. Alternatively, it can have the property of softening or fluidizing when heated to a temperature of 90 ° C. or lower.
- the glass transition temperature of the copolymer component constituting the trunk component of the acrylic copolymer (a1) is the flexibility of the adhesive layer at room temperature, the wettability of the adhesive layer to the adherend,
- the glass transition temperature is preferably ⁇ 70 ° C. to 0 ° C., in particular, ⁇ 65 ° C. in order for the pressure-sensitive adhesive sheet to have appropriate adhesion (tackiness) at room temperature because it affects the adhesion. Above, or ⁇ 5 ° C. or less, particularly preferably ⁇ 60 ° C. or more or ⁇ 10 ° C. or less.
- the viscoelasticity can be adjusted by adjusting the molecular weight. For example, it can be made more flexible by reducing the molecular weight of the copolymer component.
- Examples of the (meth) acrylic acid ester monomer contained in the backbone component of the acrylic copolymer (a1) include various monomer components listed above.
- the acrylic copolymer (a1) preferably contains a macromonomer as a branch component of the graft copolymer and contains a repeating unit derived from the macromonomer.
- the macromonomer is a polymer monomer having a terminal polymerizable functional group and a high molecular weight skeleton component.
- the glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer component constituting the acrylic copolymer (a1). Specifically, since the glass transition temperature (Tg) of the macromonomer affects the heating and melting temperature (hot melt temperature) of the present adhesive sheet, the glass transition temperature (Tg) of the macromonomer is 30 ° C. to 120 ° C. Of these, 40 ° C. or higher or 110 ° C. or lower, and more preferably 50 ° C. or higher or 100 ° C. or lower among these. With such a glass transition temperature (Tg), by adjusting the molecular weight, it is possible to maintain excellent processability and storage stability, and to adjust so as to hot-melt near 80 ° C.
- the glass transition temperature of the macromonomer refers to the glass transition temperature of the macromonomer itself, and can be measured with a differential scanning calorimeter (DSC).
- the branch components are attracted to each other and can maintain a state where they are physically cross-linked as a pressure-sensitive adhesive composition, and the physical cross-linking is released by heating to an appropriate temperature.
- the macromonomer is preferably contained in the acrylic copolymer (a1) in a proportion of 5% by mass to 30% by mass, particularly 6% by mass or 25% by mass, and more preferably 8% by mass. It is preferable that the amount is 20% by mass or more.
- the number average molecular weight of the macromonomer is preferably 500 or more and less than 8000, more preferably 800 or more and less than 7500, and particularly preferably 1000 or more and less than 7000.
- the macromonomer those generally produced (for example, a macromonomer manufactured by Toa Gosei Co., Ltd.) can be appropriately used.
- the high molecular weight skeleton component of the macromonomer is preferably composed of an acrylic polymer or a vinyl polymer.
- Examples of the terminal polymerizable functional group of the macromonomer include a methacryloyl group, an acryloyl group, and a vinyl group.
- Crosslinking agent (b) As the crosslinking agent (b), a crosslinking monomer used when the acrylic ester polymer is crosslinked can be used.
- a crosslinking monomer used when the acrylic ester polymer is crosslinked can be used.
- at least one crosslinkable functional group selected from (meth) acryloyl group, epoxy group, isocyanate group, carboxyl group, hydroxyl group, carbodiimide group, oxazoline group, aziridine group, vinyl group, amino group, imino group, and amide group The crosslinking agent which has can be mentioned, You may use 1 type or in combination of 2 or more types.
- the crosslinkable functional group may be protected with a deprotectable protecting group.
- a polyfunctional organic function having two or more organic functional groups such as a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups, an isocyanate group, an epoxy group, a melamine group, a glycol group, a siloxane group or an amino group.
- An organometallic compound having a metal complex such as a base resin, zinc, aluminum, sodium, zirconium, or calcium can be preferably used.
- the content of the crosslinking agent (b) is a ratio of 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer from the viewpoint of balancing the flexibility and cohesive force of the pressure-sensitive adhesive sheet.
- it is preferably 0.5 parts by mass or more and 15 parts by mass or less, particularly preferably 1 part by mass or more or 13 parts by mass or less.
- Photopolymerization initiator (c) When crosslinking the acrylic ester polymer, a crosslinking initiator (peroxidation initiator, photopolymerization initiator) and reaction catalyst (tertiary amine compound, quaternary ammonium compound, tin laurate compound, etc.) are appropriately used. It is effective when added.
- a crosslinking initiator peroxidation initiator, photopolymerization initiator
- reaction catalyst tertiary amine compound, quaternary ammonium compound, tin laurate compound, etc.
- a photopolymerization initiator (c).
- the photopolymerization initiator (c) is roughly classified into two types depending on the radical generation mechanism.
- the photopolymerization initiator is capable of generating a radical by cleaving the single bond of the photopolymerization initiator itself, and photoexcitation.
- the initiator and the hydrogen donor in the system form an exciplex and can be roughly classified into a hydrogen abstraction type photopolymerization initiator that can transfer hydrogen of the hydrogen donor.
- the cleavage type photopolymerization initiator is decomposed when a radical is generated by light irradiation to be another compound, and once excited, it does not function as a reaction initiator.
- the intramolecular cleavage type is used as a photopolymerization initiator having an absorption wavelength in the visible light region, light-reactive light is obtained after the pressure-sensitive adhesive sheet is cross-linked by light irradiation as compared with the case of using a hydrogen abstraction type.
- a polymerizable initiator is preferable because it remains as an unreacted residue in the pressure-sensitive adhesive composition and is unlikely to cause an unexpected change with time or promotion of crosslinking.
- the coloring specific to the photopolymerizable initiator is also preferable because it becomes a reaction decomposition product, so that absorption in the visible light region is eliminated and a color to be erased can be appropriately selected.
- a hydrogen abstraction type photopolymerization initiator does not generate a decomposition product such as a cleavage type photopolymerization initiator during radical generation reaction by irradiation of active energy rays such as ultraviolet rays, so that it is difficult to become a volatile component after completion of the reaction. Damage to the body can be reduced.
- the content of the photopolymerization initiator (c) is not particularly limited.
- a photoinitiator (c) can be used 1 type or in combination of 2 or more types.
- This adhesive sheet may contain the well-known component mix
- a reaction catalyst A tertiary amine type compound, a quaternary ammonium type compound, a lauric acid tin compound, etc.
- This pressure-sensitive adhesive sheet produces a pressure-sensitive adhesive sheet with a release film obtained by laminating a release film on one or both sides of the pressure-sensitive adhesive sheet, and in the edge width region of the pressure-sensitive adhesive sheet with a release film. It can manufacture by raising the gel fraction of the adhesive sheet in an edge width area
- the adhesive with a release film formed by laminating the long release films 11 and 12 on one side or both sides of the long adhesive sheet 10 having photocurability for example.
- the sheet from the edge of the sheet at both end portions in the sheet width direction (TD direction) of the pressure-sensitive adhesive sheet with release film 1 The edge width regions 1A and 1A having a width w [mm] toward the center are respectively irradiated with light to cure the edge width regions 1A and 1A of the pressure-sensitive adhesive sheet 10, and then with the release film.
- the manufacturing method characterized by winding up the adhesive sheet 1 in roll shape and obtaining the roll-shaped adhesive sheet 2 can be mentioned.
- the pressure-sensitive adhesive sheet with a release film 1 before light irradiation is a long laminated sheet obtained by laminating release films 11 and 12 on both front and back sides of the pressure-sensitive adhesive sheet 10, and the pressure-sensitive adhesive sheet 10 has photocurability.
- the gel fraction is preferably in the range of 0 to 15%, more preferably 12% or less, and most preferably 10% or less. However, it is good also as a structure formed by laminating a release film only on the front and back sides of the pressure-sensitive adhesive sheet 10.
- Examples of the method for producing the pressure-sensitive adhesive sheet 1 with a release film include a method in which a pressure-sensitive adhesive composition is sandwiched between two release films 11 and 12 and a pressure-sensitive adhesive layer is formed using a laminator. Moreover, after apply
- Examples of methods for applying the pressure-sensitive adhesive composition include conventionally known coating methods such as reverse roll coating, gravure coating, bar coating, and doctor blade coating.
- a known release film can be used as appropriate.
- a polyester-based, polypropylene-based, or polyethylene-based cast film or stretched film that has been subjected to a release treatment by applying a silicone resin, or a release paper can be appropriately selected and used.
- blended with an above described adhesive composition can also be similarly mix
- FIG. when the edge width region is cured by a method of irradiating light through a release film, the release film preferably has a property of not absorbing or reflecting the irradiation light. .
- release films 11 and 12 are laminated on both sides of the pressure-sensitive adhesive sheet 10, even if one release film 11 has the same laminate structure or material as the other release film 12, a different laminate structure or material. It may be. Further, the thickness may be the same or different. In addition, release films having different peeling forces and release films having different thicknesses can be laminated on both sides of the pressure-sensitive adhesive sheet 10.
- the thickness of the release films 11 and 12 is preferably 50 to 200 ⁇ m, and more preferably 75 ⁇ m or more or 150 ⁇ m or less. With the thickness in such a range, light irradiation from above the sheet is not hindered, and the gel fraction in the edge width region and the central region can be easily adjusted.
- the edge width region 1 ⁇ / b> A is cured by irradiating light with respect to the upper surface of the pressure-sensitive adhesive sheet 1 with a release film, or from below with respect to the lower surface of the sheet. Or it is preferable to irradiate light from both the upper and lower sides of the upper and lower sides of the sheet.
- region 1A, 1A of the transversal direction (TD direction) both sides in the adhesive sheet 1 with a release film It is preferable to install the light source 3 above and irradiate light vertically upward with respect to the upper surface of the sheet, or obliquely 60 to 90 ° above, particularly 70 to 90 ° above, particularly 80 to 90 ° above. By irradiating at such an angle, the difference (boundary) in the gel fraction between the edge width region and the central region becomes clear, so that the sticking out of the adhesive can be suppressed more efficiently. .
- a light source is installed below the areas 1A and 1A, and light is irradiated from the lower side perpendicular to the lower surface of the sheet, or obliquely from 60 to 90 °, particularly from 70 to 90 °, particularly from 80 to 90 °. preferable.
- FIG. 3 (A) As a method of irradiating light to the sheet width direction (TD direction) both ends of the pressure-sensitive adhesive sheet with release film 1 while conveying the pressure-sensitive adhesive sheet with release film 1 in a certain direction (MD direction), for example, FIG.
- 3 (A) light is irradiated from a perpendicular direction with respect to the sheet
- the light source 3 is installed above the upper surface or below the lower surface, and from above the upper surface of the pressure-sensitive adhesive sheet with release film 1, or from the lower surface thereof, or both surfaces thereof.
- the method of irradiating light from both above and below can be mentioned.
- the light source 3 is installed in the sheet surface extension direction (horizontal direction horizontal side of a figure) of the adhesive sheet 1 with a release film, and the sheet width direction of the adhesive sheet 1 with a release film is shown.
- TD direction A method of irradiating light from both sides in the horizontal direction can be mentioned. When these methods are compared, light is emitted from the extending direction of the sheet surface with respect to the sheet width direction (TD direction) both end surfaces of the pressure-sensitive adhesive sheet with release film 1, that is, from the horizontal side as shown in FIG.
- the standard deviation of the gel fraction in the edge width region can be set to 3% or less as described above.
- the curing in the edge width region can be made uniform, and the adhesive can be effectively prevented from gradually protruding.
- the type and content of the crosslinking agent and crosslinking initiator in the pressure-sensitive adhesive sheet, etc. can do. However, it is not limited to these.
- the light source 3 for irradiating light preferably uses an LED from the viewpoint of high directivity of light.
- the light source 3 which has various emission wavelengths from each manufacturer is disclosed, it is particularly preferable that the light source 3 emits light in a wavelength range absorbed by a generally used initiator. Specifically, it is preferably 200 nm to 450 nm, particularly preferably 220 nm or more or 400 nm or less.
- the light source 3 for irradiating light is preferably a light source having a light diffusion angle of 50 ° or less, particularly 40 ° or less, and more preferably 30 ° or less, from the viewpoint of high directivity of light.
- irradiating light it is preferable to irradiate light having a wavelength of at least 200 nm to 450 nm from the viewpoint of the absorption wavelength of the initiator. Moreover, when irradiating the light, from the viewpoint of sufficient gel fraction can be obtained in suppressing the protrusion of adhesive, 1000mJ / cm 2 ⁇ 10000mJ / cm 2 per unit area, among others 1500 mJ / cm 2 or more, or 9000 mJ / cm 2 or less, the light of 2000 mJ / cm 2 or more, or 8000 mJ / cm 2 or less integrated light dose among them, it is preferable to irradiate on each side of the edge width region.
- the integrated light amount per unit time can be adjusted by the output of the light source, the distance between the light source and the pressure-sensitive adhesive sheet with a release film, the conveyance speed of the pressure-sensitive adhesive sheet with a release film, and the like.
- preferable conditions are listed below.
- the output of the light source 3 contributes viewpoint in compact equipment, but is preferably 0.5W / cm 2 ⁇ 50W / cm 2, among others 1.0 W / cm 2 or more, or 40W / cm 2 or less, among them is also 2.0 W / cm 2 or more, or 30 W / cm 2 or less and even more preferred.
- the length 3L of the light source 3 in the MD direction is preferably 30 mm to 2000 mm from the viewpoint of making the manufacturing equipment compact, and more preferably 50 mm or more or 1000 mm or less. Of these, the thickness is more preferably 100 mm or more or 500 mm or less.
- the conveyance speed when conveying the pressure-sensitive adhesive sheet with a release film 1 in a certain direction is preferably 1 m / min to 30 m / min from the viewpoint of providing an increase in productivity and a sufficient gel fraction. Among these, it is more preferably 3 m / min or more or 25 m / min or less, and more preferably 5 m / min or more or 20 m / min or less.
- an LED having an output of 7 W / cm 2 , an irradiation wavelength of 365 nm, a light diffusion angle of 30 °, and an MD length (light source length in the table) of 44 mm is used as the light source 3, and the distance between the light source 3 and the roll-shaped adhesive sheet 2 (
- the light source distance in the table is 10 mm and UV irradiation is performed for about 3.8 s, the integrated light amount becomes about 3200 mJ.
- the winding tension per 1 m of film width that is, the winding tension is preferably 20 to 200 N / m width.
- a winding tension of 20 to 200 N / m width is preferable because it does not cause winding deviation, bulge, or even wrinkle, and can reduce an increase in retardation due to film orientation due to tension.
- the winding tension is preferably 30 to 150 N / m width, and more preferably 50 N / m width or more and 100 N / m width or less.
- Each material of the pressure-sensitive adhesive sheet with a release film before light irradiation, the laminated structure and the production method may be the same as those of the pressure-sensitive adhesive sheet with a release film 1.
- region should just be the same as that of the said adhesive sheet 1 with a release film.
- the photocuring method is not necessarily performed in the state of the pressure-sensitive adhesive sheet with a release film 1 as described above.
- the edge width region of the pressure-sensitive adhesive sheet can be cured in a state before the release film is attached, and then the release film can be attached.
- the edge width region of the pressure-sensitive adhesive sheet is cured well. be able to.
- the pressure-sensitive adhesive sheet itself has photocurability, and it is not always necessary to cure the edge width region by light irradiation.
- the edge width region may be cured by heat.
- the pressure-sensitive adhesive sheet can be used as a pressure-sensitive adhesive sheet after excising an edge width region having a high gel fraction.
- the release films 11 and 12 are removed. It can be peeled off and used as an adhesive sheet.
- the pressure-sensitive adhesive sheet 10 with two image display device constituent members, for example, light, for example, ultraviolet rays is irradiated from at least one image display device constituent member side, and this adhesive sheet is passed through this member.
- Two image display apparatus constituent members can be bonded together by photocrosslinking the sheet 10 to photocuring.
- the hardening method at the time of using this adhesive sheet 10 is not limited to hardening by light irradiation,
- other hardening methods such as the method of hardening by heating
- an image display apparatus structural member as a to-be-adhered body, a surface protection panel, a touch panel, an image display panel etc. can be mentioned, for example.
- (meth) acryl means acryl and methacryl
- (meth) acryloyl means acryloyl and methacryloyl
- (meth) acrylate means acrylate and methacrylate.
- the boundary between the sheet and the film is not clear, and it is not necessary to distinguish the two in terms of the wording in the present invention. Therefore, in the present invention, even when the term “film” is used, the term “sheet” is included. Even when referring to it, “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.
- the width w [mm] of the photocured edge width region is known.
- About 0.05g is arbitrarily sampled from the area of width w [mm] from the edge toward the center of the sheet, and this is used as a measurement sample of the edge width area, while it is arbitrarily selected from the center area that is not photocured.
- About 0.05 g was sampled and used as a measurement sample in the central region.
- the method for obtaining the standard deviation first, the average value of the gel fraction of 6 points was obtained. Next, the difference from the obtained average value was calculated for each of the six points to determine the deviation. Subsequently, the variance was obtained by calculating the mean square of the obtained deviations. Finally, the positive square root of the dispersion was calculated to determine the standard deviation of the gel fraction in the edge width region.
- Integrated dose The cumulative UV dose irradiated in the examples and comparative examples was measured twice using a UV integrated light meter “UIT-250” (manufactured by USHIO INC.) As an integrated light meter, with a 365 nm wavelength light receiving unit attached. The average value was obtained with two significant digits and used as each integrated dose.
- Example 1 As the (meth) acrylic copolymer (a), 15 parts by mass (18 g) of polymethyl methacrylate macromonomer (Tg: 105 ° C.) having a number average molecular weight of 2400 and 81 parts by mass of butyl acrylate (Tg: ⁇ 55 ° C.) 1 kg of an acrylic copolymer (a-1) (weight average molecular weight 230,000) obtained by random copolymerization of (75 mol%) and 4 parts by mass (7 mol%) of acrylic acid (Tg: 106 ° C.), and a crosslinking agent As (b), 90 g of glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) (b-1) and 2,4,6-trimethylbenzophenone and 4-methylbenzophenone as photopolymerization initiator (c) 15 g of a mixture (manufactured by Lanberti, product name: Ezacure TZT) (c-
- the obtained resin composition was subjected to a release treatment similarly to a release film 11 (Mitsubishi Chemical Corporation, product name: Diafoil MRV-V06, thickness: 100 ⁇ m) made of a polyethylene terephthalate (PET) film subjected to a release treatment.
- a release film 12 made of a PET film (a film formed by laminating a release layer of 2 ⁇ m thickness made of a silicone compound on one side of a 75 ⁇ m thick biaxially stretched isophthalic acid copolymerized PET film).
- the adhesive sheet 10 was shaped into a long sheet so that the thickness of the adhesive sheet 10 was 150 ⁇ m, and a long adhesive sheet 1 with a release film was produced.
- the pressure-sensitive adhesive sheet 1 with a release film is conveyed in a constant direction (MD direction) at a conveyance speed (line speed) of 20 m / min, and the sheet width direction of the pressure-sensitive adhesive sheet 1 with a release film is used.
- the pressure-sensitive adhesive sheet with release film 1 is wound at a winding tension (winding tension) of 70 N / m width per 1 m of the film width. It was wound up in a roll shape to obtain a long roll-shaped pressure-sensitive adhesive sheet 2 having a total length of 100 m and a roll width of 1000 mm.
- the light sources 3 are respectively arranged in the widthwise direction (short direction) on both sides of the release sheet-attached pressure-sensitive adhesive sheet 1 vertically upward, and the sheet of the pressure-sensitive adhesive sheet laminate 1.
- Ultraviolet rays were irradiated from vertically above the upper surface.
- the light source 3 an LED having an output of 7 W / cm 2 , an irradiation wavelength of 365 nm, a light diffusion angle of 30 °, and an MD direction length (light source length in the table) of 44 mm was used.
- surface) of the light source 3 and the roll-shaped adhesive sheet 2 was 10 mm, and it irradiated with light so that the accumulated light amount per unit time might be 1600 mJ.
- Example 2 A roll-shaped pressure-sensitive adhesive sheet 2 was obtained in the same manner as in Example 1 except that the conveyance speed (line speed) and the integrated light amount per unit time were changed as shown in the table.
- Example 3 A roll-shaped adhesive sheet 2 was obtained in the same manner as in Example 2 except that the curing width was changed.
- Example 4 A roll-shaped pressure-sensitive adhesive sheet 2 was obtained in the same manner as in Example 2 except that the thickness of the pressure-sensitive adhesive sheet was changed to 100 ⁇ m and the curing width was changed to 35 d.
- the pressure-sensitive adhesive sheet when the pressure-sensitive adhesive sheet is wound in a roll shape and stored at room temperature, it is effective that the pressure-sensitive adhesive protrudes from the end face of the roll.
- the edge width region In order to suppress, at least the gel fraction of the cured region, that is, the edge width region is larger than the gel fraction of the adhesive sheet in the central region, and the width w [mm] of the edge width region is the thickness of the adhesive sheet. It was found that 30d ⁇ w must be satisfied in relation to the length d [mm].
Abstract
Description
(1)端縁幅領域における粘着シートのゲル分率が、中央領域における粘着シートのゲル分率より大きい。
(2)粘着シートの厚さをd[mm]とした時、30d<w<100dを満たす。
(1)端縁幅領域における粘着シートのゲル分率が、中央領域における粘着シートのゲル分率より大きい。
(2)粘着シートの厚さをd[mm]とした時、30d<w<100dを満たす。
本発明の実施形態の一例に係る粘着シート(「本粘着シート」と称する)は、光硬化性を有する粘着シートであって、シート端縁からシート中央に向かって幅w[mm]の領域、言い換えれば、シート面におけるシート端縁に沿った幅w[mm]の領域(「端縁幅領域」と称する)における粘着シートのゲル分率が、当該端縁幅領域よりシート中央の領域(「中央領域」と称する)における粘着シートのゲル分率より大きいという特徴を有する粘着シートである。
本粘着シートは、矩形状の粘着シートであっても、長尺な粘着シートであっても、ロール状に捲回された粘着シート捲回体であっても、その他の形態であってもよい。
また、本粘着シートは、表裏一側又は両側に離型フィルムが積層された状態で存在してもよい。
この際、「長尺」とは、長さ寸法が幅寸法よりも大きいことを意味する。具体的には、前記長さ寸法が、5m以上、好ましくは10mm以上を意味する。上限値は限定するものではない。あえて規定するならば、当該上限値は500m以下であるのが好ましい。
また、通常の粘着シート捲回体においては、ロール幅が広いほど、粘着剤の食み出しが顕著なる。これに対し、本捲回体であれば、広幅のロールであっても粘着剤の食み出しを効果的に抑制することができる。したがって、本捲回体における前記ロール幅は20mm~2000mmであることが好ましく、中でも50mm以上或いは1500mm以下であることがより好ましい。
本発明者らの検討によれば、ロール端面から粘着剤が食み出す現象は、離型フィルムに挟まれた粘着シートの厚さによって挙動が異なることが見出された。すなわち、本粘着シートにおいて、端縁幅領域すなわちゲル分率が高い部分の幅w[mm]が粘着シートの厚さdに対して小さいと、端縁幅領域のゲル分率を高めたとしても、例えば粘着シートをロール状に巻き取った粘着シート捲回体として保管すると、巻圧によって次第に粘着剤がロール端面から食み出してくることが確認されている。
また、粘着剤の食み出しの挙動は、端縁幅領域の幅と粘着シートの厚さとの間に一定の関係性があることが見出された。すなわち、ゲル分率が高い部分の幅w[mm]を粘着シートの厚さd[mm]に対して、30d<wの比率で設定すれば、通常の粘着シートの場合はもちろん、粘着シート捲回体として保管した場合であっても、端縁幅領域のゲル分率を適宜高めることにより、粘着剤がロール端面から食み出すのを効果的に抑制することができる。
かかる観点から、端縁幅領域すなわちゲル分率が高い部分の幅w[mm]と粘着シートの厚さd[mm]との関係は、30d<wであるのが好ましく、中でも35d<w、その中でも40d<w、その中でも45d<wであるのがさらに好ましい。
かかる観点から、w<100dであるのが好ましく、中でもw<80d、その中でもw<70d、その中でもw<60dであるのがさらに好ましい。
以上を総合すると、端縁幅領域のゲル分率は、15%以上100%未満又は15%以上99%以下であることが好ましく、20%以上100%未満又は20%以上99%以下であることがより好ましく、25%以上100%未満、又は、25%以上99%以下であることがさらに好ましく、30%以上100%未満、又は、30%以上99%以下であることが最も好ましい。
なお、中央領域においても、ゲル分率の標準偏差が3%以下、中でも2.5%以下、その中でも2%以下であるのが好ましい。
上述のように、端縁幅領域におけるゲル分率の標準偏差が3%以下であるということは、端縁幅領域におけるゲル分率が均一であることを意味しており、このように端縁幅領域のゲル分率が均一に高いことにより、粘着剤が端面から食み出すのをより一層確実に防ぐことができる。
なお、上述のように、端縁幅領域におけるゲル分率の標準偏差は小さいほど均一性が良いことから、その下限値は、例えば0%以上又は1%以上であるのが好ましい。但し、当該下限値に特に限定されるものではない。
端縁幅領域及び中央領域から約0.05gの粘着剤を採取し、予め質量(X)を測定したステンレスメッシュ(#200)で袋状に包み、袋の口を折って閉じて、この包みの質量(Y)を測定した後、100mlの酢酸エチルに浸漬させ、23℃で24時間暗所保管する。次に、包みを取り出して、70℃で4.5時間加熱し、付着している酢酸エチルを蒸発させ、乾燥した包みの質量(Z)を測定し、求めた質量を下記式に代入して求めることができる。
ゲル分率[%]=[(Z-X)/(Y-X)]×100
この際、中央領域のゲル分率は上述したように0%以上15%未満であるのが好ましく、端縁幅領域におけるゲル分率は15%以上100%未満であるのが好ましい。
したがって、本粘着シートの厚さdは0.05mm~1mmであるのが好ましく、中でも0.075mm以上或いは0.8mm以下、その中でも0.1mm以上或いは0.5mm以下であるのがさらに好ましい。
なお、本粘着シートの厚さdには、離型フィルムの厚さは含まない。
本粘着シートは、粘着剤組成物からなる粘着材層の単層であってもよいし、二層、三層などの複数層の粘着剤層を備えたものでもよい。
また、本粘着シートは、芯層として基材層(粘着性を有さない層)を有し、該基材層の両側に、粘着材からなる層が積層してなる構成であってもよい。このような構成の場合、芯層としての基材層は粘着シート積層体が加熱成形可能となるような材質や特性を有することが好ましい。
具体的には、周波数1Hz、温度80℃において、本粘着シートの損失正接(Tanδ=損失せん断弾性率G'’/貯蔵せん断弾性率G’)の値が1を超えるような場合、本発明の効果が特に顕著に表れる。すなわち、前記条件下で、粘着シートのTanδが1を超えるということは、弾性よりも粘性の寄与が大きいことを意味し、粘着剤がより流れやすい傾向にある。よって、Tanδが1を超える粘着シートに本発明の技術を用いれば、粘着剤の食み出し防止効果が特に顕著に表れることになる。
以上から、本粘着シートのTanδは1を超えることが好ましい。なお、上限値は必ずしも設定する必要はない。あえて当該上限値を設定するとすれば、10以下である。
<条件>
・治具:Φ20mmパラレルプレート
・温度:-50~200℃(昇温速度3℃/minで測定)
・周波数:1Hz
・歪角:0.1%
本粘着シートの粘着剤層は、光硬化性を有していれば、従来公知の粘着材料から形成することができる。
ここで、上記光硬化性としては、電子線以外の波長、具体的には、波長200nm~780nmの波長領域の光で硬化可能な硬化性を有するのが好ましい。
2)ブタジエン又はイソプレン系(共)重合体をベース樹脂として用い、これに架橋モノマー、必要に応じて架橋開始剤や反応触媒などを配合してなる粘着剤組成物や、
3)シリコーン系重合体をベース樹脂と用い、これに架橋モノマー、必要に応じて架橋開始剤や反応触媒などを配合してなる粘着剤組成物や、
4)ポリウレタン系重合体をベース樹脂として用いたポリウレタン系粘着剤組成物などを挙げることができる。
(メタ)アクリル系(共)重合体(a)は、これを重合するために用いられるアクリルモノマーやメタクリルモノマーの種類、組成比率、さらには重合条件等によって、ガラス転移温度(Tg)等の特性を適宜調整することが可能である。
アクリル酸エステル(共)重合体の中でも、(メタ)アクリル酸アルキルエステル系(共)重合体が特に好ましい。
アクリル酸エステル共重合体の重合形態は、ランダム共重合体、ブロック共重合体、グラフト共重合体のいずれであってもよい。
さらにまた、前記アクリルモノマーやメタクリルモノマーと共重合可能な、スチレン、t-ブチルスチレン、α-メチルスチレン、ビニルトルエン、アクリロニトリル、メタクリロニトニル、酢酸ビニル、プロピオン酸ビニル、アルキルビニルエーテル、ヒドロキシアルキルビニルエーテル、アルキルビニルモノマー等の各種ビニルモノマーも適宜用いることができる。
よって、ベースポリマーとしてアクリル系共重合体(a1)を使用すれば、未架橋状態であっても、室温(20℃)において粘着性を示し、且つ、50~100℃、より好ましくは60℃以上或いは90℃以下の温度に加熱すると軟化乃至流動化する性質を備えることができる。
但し、当該共重合体成分のガラス転移温度が同じ温度であったとしても、分子量を調整することにより粘弾性を調整することができる。例えば共重合体成分の分子量を小さくすることにより、より柔軟化させることができる。
マクロモノマーとは、末端の重合性官能基と高分子量骨格成分とを有する高分子単量体である。
具体的には、マクロモノマーのガラス転移温度(Tg)は、本粘着シートの加熱溶融温度(ホットメルト温度)に影響するため、マクロモノマーのガラス転移温度(Tg)は30℃~120℃であるのが好ましく、中でも40℃以上或いは110℃以下、その中でも50℃以上或いは100℃以下であるのがさらに好ましい。
このようなガラス転移温度(Tg)であれば、分子量を調整することにより、優れた加工性や保管安定性を保持できると共に、80℃付近でホットメルトするように調整することができる。
マクロモノマーのガラス転移温度とは、当該マクロモノマー自体のガラス転移温度をさし、示差走査熱量計(DSC)で測定することができる。
かかる観点から、マクロモノマーは、アクリル系共重合体(a1)中に5質量%~30質量%の割合で含有することが好ましく、中でも6質量%以上或いは25質量%以下、その中でも8質量%以上或いは20質量%以下であるのが好ましい。
また、マクロモノマーの数平均分子量は500以上8000未満であることが好ましく、中でも800以上或いは7500未満、その中でも1000以上或いは7000未満であるのが好ましい。
マクロモノマーは、一般に製造されているもの(例えば東亜合成社製マクロモノマーなど)を適宜使用することができる。
前記マクロモノマーの末端重合性官能基としては、例えばメタクリロイル基、アクリロイル基、ビニル基などを挙げることができる。
架橋剤(b)は、アクリル酸エステル重合体を架橋する際に用いる架橋モノマーを使用することができる。例えば(メタ)アクリロイル基、エポキシ基、イソシアネート基、カルボキシル基、ヒドロキシル基、カルボジイミド基、オキサゾリン基、アジリジン基、ビニル基、アミノ基、イミノ基、アミド基から選ばれる少なくとも1種の架橋性官能基を有する架橋剤を挙げることができ、1種又は2種以上を組み合わせて使用してもよい。
なお、前記架橋性官能基は、脱保護可能な保護基で保護されていてもよい。
アクリル酸エステル重合体を架橋する際には、架橋開始剤(過酸化開始剤、光重合開始剤)や反応触媒(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)を適宜添加すると効果的である。
光重合開始剤(c)は、ラジカル発生機構によって大きく2つに分類され、光重合性開始剤自身の単結合を開裂分解してラジカルを発生させることができる開裂型光重合開始剤と、光励起した開始剤と系中の水素供与体とが励起錯体を形成し、水素供与体の水素を転移させることができる水素引抜型光重合開始剤と、に大別される。
これらのうちの開裂型光重合開始剤は、光照射によってラジカルを発生する際に分解して別の化合物となり、一度励起されると反応開始剤としての機能をもたなくなる。このため、可視光線域に吸収波長をもつ光重合開始剤として該分子内開裂型を用いると、水素引抜型を用いる場合に比べて、光線照射によって粘着シートを架橋した後、光線反応性の光重合性開始剤が本粘着剤組成物中に未反応残渣として残り、粘着シートの予期せぬ経時変化や架橋の促進を招く可能性が低いため好ましい。また、光重合性開始剤特有の着色についても、反応分解物となることで、可視光線域の吸収がなくなり、消色するものを適宜選択することができるため好ましい。
他方、水素引抜型の光重合開始剤は、紫外線などの活性エネルギー線照射によるラジカル発生反応時に、開裂型光重合開始剤のような分解物を生じないので、反応終了後に揮発成分となりにくく、被着体へのダメージを低減させることができる。
光重合開始剤(c)は、1種又は2種以上を組み合わせて使用することができる。
本粘着シートは、上記以外の成分として、通常の粘着組成物に配合されている公知の成分を含有してもよい。例えば粘着付与樹脂や、酸化防止剤、光安定化剤、金属不活性化剤、防錆剤、老化防止剤、吸湿剤、加水分解防止剤、増感剤、帯電防止剤、消泡剤、無機粒子などの各種の添加剤を適宜含有させることが可能である。
また、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、必要に応じて適宜含有してもよい。
本粘着シートは、光硬化性を有する粘着シートの表裏一側又は両側に離型フィルムを積層してなる離型フィルム付粘着シートを作製し、当該離型フィルム付粘着シートの端縁幅領域に光を照射することで、端縁幅領域における粘着シートのゲル分率を高めることにより製造することができる。
なお、この際、当該粘着シートのゲル分率は0~10%であることが好ましく、中でも0~5%、その中でも0~3%であれば、より一層本発明の効果を享受することができる。
次に、本粘着シートの一例としての、長尺な粘着シートをロール状に巻き上げてなる粘着シート捲回体すなわちロール状粘着シートの製造方法について詳述する。
光照射前の離型フィルム付粘着シート1は、粘着シート10の表裏両側に離型フィルム11、12を積層してなる長尺な積層シートであり、その粘着シート10は、光硬化性を有し、且つ、粘着シート10の何れの部分においてもゲル分率が0~15%の範囲内であるのが好ましく、中でも12%以下、その中でも10%以下であるのがさらに好ましい。但し、本粘着シート10の表裏一側にのみ離型フィルムを積層してなる構成としてもよい。
また、離型フィルム11、12には、前記した粘着剤組成物に配合することが可能な成分を、同様に配合することもできる。
なお、端縁幅領域を硬化する方法として、後述する通り、離型フィルム越しに光を照射する方法により行う場合は、離型フィルムは、当該照射光を吸収又は反射しない特性を有することが好ましい。
また、同じ厚さであっても、異なる厚さであってもよい。また、剥離力の異なる離型フィルムや厚さの異なる離型フィルムを本粘着シート10の両側に積層することができる。
端縁幅領域1Aに光を照射して硬化させる方法としては、図1に示すように、離型フィルム付粘着シート1のシート上面に対して上方から、又は、そのシート下面に対して下方から、又は、シート上下両面に対してそれぞれ上下両方から、光を照射するのが好ましい。
中でも、離型フィルム付粘着シート1のシート上面に対して上方から光を照射する際には、離型フィルム付粘着シート1における短手方向(TD方向)両側の端縁幅領域1A、1Aの上方に光源3を設置し、シート上面に対して垂直上方向、又は斜め60~90°上方、中でも70~90°上方、その中でも80~90°上方から光を照射するのが好ましい。このような角度で照射を行うことにより、端縁幅領域と中央領域とのゲル分率の差(境界)が明確となるため、より効率的に粘着剤の食み出しを抑制することができる。
離型フィルム付粘着シート1のシート下面に対して下方から光を照射する際には、上記と同様の理由により、離型フィルム付粘着シート1における短手方向(TD方向)両側の端縁幅領域1A、1Aの下方に光源を設置し、シート下面に対して垂直下方向、又は斜め60~90°下方、中でも70~90°下方、その中でも80~90°下方から光を照射するのが好ましい。
また、図3(B)に示すように、離型フィルム付粘着シート1のシート面延長方向(図の水平方向横側)に光源3を設置し、離型フィルム付粘着シート1のシート幅方向(TD方向)両端面に対して水平方向横から光を照射する方法を挙げることができる。
これらの方法を比較すると、離型フィルム付粘着シート1のシート幅方向(TD方向)両端面に対してシート面の延長方向から、すなわち図3(B)のように水平方向横側から光を照射する方法では、シート幅方向両端面の表面部分しか硬化することができないため、ロール状態で掛かる巻圧によって次第に粘着剤が食み出してくることが判明した。これに対し、離型フィルム付粘着シート1に対して上方向又は下方向又は上下両方向から光を照射する方法によれば、光を照射する幅を調整することにより、ロール状態で掛かる巻圧によって粘着剤が次第に食み出してくるのを効果的に防ぐことができることが確認されている。
本離型フィルム付粘着シート捲回体を製造する手段としては、図3(B)のように水平方向横側から光を照射する方法を排除するものではない。但し、この方法に比べて、図3(A)に示すような垂直方向から光を照射する方法の方が極めて効率的に製造することが可能である。
また、光を照射する光源3は、光の指向性が高いという観点から、光拡散角度が50°以下、中でも40°以下、その中でも30°以下である光源を使用するのが好ましい。このような光拡散角度の光源を使用することにより、端縁幅領域と中央領域とのゲル分率の差(境界)が明確となるため、より効率的に粘着剤の食み出しを抑制することができる。
さらに、光を照射する際、粘着剤の食み出しを抑制するのに十分なゲル分率が得られる観点から、単位面積当たり1000mJ/cm2~10000mJ/cm2、中でも1500mJ/cm2以上或いは9000mJ/cm2以下、その中でも2000mJ/cm2以上或いは8000mJ/cm2以下の積算光線量の光を、端縁幅領域のそれぞれの側に照射するのが好ましい。
なお、単位時間当たりの積算光線量は、光源の出力、光源と離型フィルム付粘着シートとの距離、離型フィルム付粘着シートの搬送速度などにより調整することができる。一例として、好ましい条件を以下に挙げる。
端縁幅領域1A、1Aを光硬化させた離型フィルム付粘着シート1をロール状に巻き取る際、フィルム幅1m当たりの巻き取り張力すなわち巻張力は20~200N/m巾であるのが好ましい。
巻き取り張力が20~200N/m巾であれば、巻きずれ、巻き膨れ、さらには巻きじわを生じさせることがなく、張力に伴うフィルムの配向による位相差増大を低減できるため、好ましい。
かかる観点から、巻張力は30~150N/m巾であるのが好ましく、中でも50N/m巾以上或いは100N/m巾以下であるのがさらに好ましい。
また、端縁幅領域の光硬化方法も、上記離型フィルム付粘着シート1と同様であればよい。
また、本粘着シートは、それ自体が光硬化性を有していれば足り、必ずしも端縁幅領域の硬化を光照射によって施す必要は無い。具体的には、端縁幅領域の硬化を熱によって行ってもよい。
本粘着シートは、ゲル分率の高い端縁幅領域を切除した後、粘着シートとして使用することができる。
ここで、被着体としての画像表示装置構成部材としては、例えば表面保護パネル、タッチパネル、画像表示パネルなどを挙げることができる。
本発明において「(メタ)アクリル」とは、アクリル及びメタクリルを、「(メタ)アクリロイル」とは、アクリロイル及びメタクリロイルを、「(メタ)アクリレート」とはアクリレート及びメタクリレートをそれぞれ包括する意味である。
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。
先ずは、実施例・比較例で得たサンプルの各種物性値の測定方法及び評価方法について説明する。
後述する実施例1~4及び比較例1及び4では、光硬化させた端縁幅領域の幅w[mm]が分かっているため、実施例で得た粘着シートにおいて、短手方向両側シート端縁からシート中央に向かって幅w[mm]の領域の中から任意に約0.05g分採取して、これを端縁幅領域の測定サンプルとする一方、光硬化させていない中央領域から任意に約0.05g分採取して、これを中央領域の測定サンプルとした。
他方、比較例2及び3では、短手方向両側シート端縁からシート中央に向かって幅w[mm]=0.5mm毎に順に切出し、各領域の中から任意に約0.05g分採取して、これを端縁幅領域の測定サンプルとする一方、光硬化させていない中央領域から任意に約0.05g分採取して、これを中央領域の測定サンプルとした。
なお、比較例2及び3については、短手方向両側シート端縁からシート中央に向かって幅w[mm]=1~1.5mmの領域のゲル分率も測定したところ、いずれも0%であったので、前記幅w[mm]=1mmを端縁幅領域とした。
ゲル分率[%]=[(Z-X)/(Y-X)]×100
実施例及び比較例で作製したロール状粘着シートを30℃×90%(RH)の恒温高湿環境下で100時間晒した後、その試験片の端面を顕微鏡で観察した。
端面状態が変化しなかったものを「○(good)」、粘着剤が食み出して端面が変形したものを「×(poor)」と評価した。
実施例及び比較例で照射したUVの積算照射量は、積算光量計として紫外線積算光量計「UIT-250」(ウシオ電機社製)を用い、365nm波長の受光部を取り付け、2回計測してその平均値を有効数字2ケタで求め、それぞれの積算照射量とした。
(メタ)アクリル系共重合体(a)として、数平均分子量2400のポリメタクリル酸メチルマクロモノマー(Tg:105℃)15質量部(18mol%)とブチルアクリレート(Tg:-55℃)81質量部(75mol%)とアクリル酸(Tg:106℃)4質量部(7mol%)とがランダム共重合してなるアクリル系共重合体(a-1)(重量平均分子量23万)1kgと、架橋剤(b)として、グリセリンジメタクリレート(日油社製、製品名:GMR)(b-1)90gと、光重合開始剤(c)として、2,4,6-トリメチルベンゾフェノンと4-メチルベンゾフェノンの混合物(Lanberti社製、製品名:エザキュアTZT)(c-1)15gを均一混合し、粘着材層に用いる樹脂組成物を作製した。得られた樹脂組成物のガラス転移温度は-5℃であった。
離型フィルム付粘着シート1における粘着シート10、すなわち硬化前の粘着シート10のゲル分率は0%であった。
光源3には、出力7W/cm2、照射波長365nm、光拡散角度30°、MD方向長さ(表の光源長)44mmのLEDを使用した。また、光源3とロール状粘着シート2の距離(表の光源距離)を10mmとし、単位時間当たりの積算光線量が1600mJとなるように光照射した。
搬送速度(ラインスピード)及び単位時間当たりの積算光線量を表に示すように変更した以外、実施例1と同様に、ロール状粘着シート2を得た。
硬化幅を変更した以外、実施例2と同様に、ロール状粘着シート2を得た。
硬化幅を変更した以外、実施例2と同様に、ロール状粘着シート2を得た。
光を照射する方向を、図3(B)に示すように、離型フィルム付粘着シート1のシート面延長方向すなわち側面方向に変更し、硬化幅を変更した以外、実施例2と同様に、ロール状粘着シート2を得た。
光を照射する方向を、図3(B)に示すように、離型フィルム付粘着シート1のシート面延長方向すなわち側面方向に変更すると共に、光源の種類を変更し、搬送速度(ラインスピード)、単位時間当たりの積算光線量及びその他の条件を表に示すように変更した以外、実施例2と同様に、ロール状粘着シート2を得た。
粘着シートの厚さを100μmに変更し、硬化幅を35dに変更した以外、実施例2と同様に、ロール状粘着シート2を得た。
硬化幅を25dに変更した以外、実施例4と同様に、ロール状粘着シート2を得た。
Claims (15)
- 粘着シートの表裏一側又は両側に離型フィルムを積層してなる離型フィルム付粘着シートを、ロール状に捲回した離型フィルム付粘着シート捲回体であって、
前記粘着シートは、光硬化性を有し、かつ、短手方向両側シート端縁からシート中央に向かって幅w[mm]の領域(「端縁幅領域」と称する)と、当該端縁幅領域よりシート中央の領域(「中央領域」と称する)とが、以下の条件(1)及び(2)を満たすことを特徴とする、離型フィルム付粘着シート捲回体。
(1)端縁幅領域における粘着シートのゲル分率が、中央領域における粘着シートのゲル分率より大きい。
(2)粘着シートの厚さをd[mm]とした時、30d<w<100dを満たす。 - 前記端縁幅領域のゲル分率が15%以上100%以下であることを特徴とする請求項1に記載の離型フィルム付粘着シート捲回体。
- 前記中央領域のゲル分率が0%以上15%未満であることを特徴とする請求項1又は2に記載の離型フィルム付粘着シート捲回体。
- 前記粘着シートの厚さdが0.05mm~1mmであることを特徴とする請求項1~3の何れかに記載の離型フィルム付粘着シート捲回体。
- 端縁幅領域におけるゲル分率の標準偏差が3%以下である、請求項2~4の何れかに記載の離型フィルム付粘着シート捲回体。
- 請求項1~5の何れかに記載の離型フィルム付粘着シート捲回体の製造方法であって、
光硬化性を有する粘着シートの表裏一側又は両側に離型フィルムを積層してなる離型フィルム付粘着シートの端縁幅領域に光を照射することで、端縁幅領域における粘着シートのゲル分率を、中央領域の粘着シートのゲル分率よりも大きくすることを特徴とする、離型フィルム付粘着シート捲回体の製造方法。 - 光を照射した後、離型フィルム付粘着シートをロール状に巻き取ることを特徴とする、請求項6に記載の離型フィルム付粘着シート捲回体の製造方法。
- 前記離型フィルム付粘着シートのシート上面に対して上方から、又は、そのシート下面に対して下方から、又は、シート上下両面に対してそれぞれ上下両方から、光を照射することを特徴とする、請求項6又は7に記載の離型フィルム付粘着シート捲回体の製造方法。
- 光を照射する光源の光拡散角度が50°以下であることを特徴とする、請求項6~8の何れかに記載の離型フィルム付粘着シート捲回体の製造方法。
- 光を照射する光源としてLEDを使用することを特徴とする、請求項6~9の何れかに記載の離型フィルム付粘着シート捲回体の製造方法。
- 光を照射する際、少なくとも200nm~450nmの波長の光を照射することを特徴とする、請求項6~10の何れかに記載の離型フィルム付粘着シート捲回体の製造方法。
- 単位面積当たり1000mJ/cm2~10000mJ/cm2の積算光線量の光を照射することを特徴とする、請求項6~11の何れかに記載の離型フィルム付粘着シート捲回体の製造方法。
- 光硬化性を有する粘着シートであって、シート端縁からシート中央に向かって幅w[mm]の領域(「端縁幅領域」と称する)と、当該端縁幅領域よりシート中央の領域(「中央領域」と称する)とが、以下の条件(1)及び(2)を満たすことを特徴とする粘着シート。
(1)端縁幅領域における粘着シートのゲル分率が、中央領域における粘着シートのゲル分率より大きい。
(2)粘着シートの厚さをd[mm]とした時、30d<w<100dを満たす。 - 長尺な粘着シートであることを特徴とする請求項13に記載の粘着シート。
- 前記端縁幅領域のゲル分率が15~100%であることを特徴とする請求項14に記載の粘着シート。
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