WO2020162519A1 - Feuille adhésive, feuille adhésive pourvue d'une feuille antiadhésive, produit stratifié et procédé de production pour produit stratifié - Google Patents

Feuille adhésive, feuille adhésive pourvue d'une feuille antiadhésive, produit stratifié et procédé de production pour produit stratifié Download PDF

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Publication number
WO2020162519A1
WO2020162519A1 PCT/JP2020/004467 JP2020004467W WO2020162519A1 WO 2020162519 A1 WO2020162519 A1 WO 2020162519A1 JP 2020004467 W JP2020004467 W JP 2020004467W WO 2020162519 A1 WO2020162519 A1 WO 2020162519A1
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WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive sheet
adhesive layer
relative humidity
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PCT/JP2020/004467
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English (en)
Japanese (ja)
Inventor
貴迪 山口
山本　真之
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王子ホールディングス株式会社
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Publication of WO2020162519A1 publication Critical patent/WO2020162519A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to a pressure-sensitive adhesive sheet, a pressure-sensitive adhesive sheet with a release sheet, a laminate, and a method for manufacturing the laminate.
  • a display device such as a liquid crystal display (LCD) and an input device such as a touch panel used in combination with the display device have been widely used.
  • LCD liquid crystal display
  • an input device such as a touch panel used in combination with the display device.
  • transparent adhesive sheets are used for the purpose of bonding optical members, and transparent adhesive sheets are also used for bonding display devices and input devices. ..
  • the pressure-sensitive adhesive composition that forms the pressure-sensitive adhesive sheet for optical members is manufactured by a known polymerization method.
  • this polymerization method include solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization.
  • a solvent is used for the pressure-sensitive adhesive layer.
  • a pressure-sensitive adhesive sheet using a pressure-sensitive adhesive is widely used.
  • the solvent-type adhesive include those containing acrylic resin as a main component. Such an acrylic resin can be obtained by a polymerization reaction in a solvent in which an acrylic monomer is dissolved by a method called solution polymerization.
  • thermosetting property can be improved. And has active energy ray curability.
  • a monomer (B) a cross-linking agent (C) that reacts with the base polymer (A) by heat, and a polymerization initiator (D that initiates a polymerization reaction of the monomer (B) by irradiation with an active energy ray.
  • a solvent (E) the pressure-sensitive adhesive sheet containing the pressure-sensitive adhesive layer obtained by semi-curing by heating.
  • Patent Document 2 discloses a pressure-sensitive adhesive sheet having at least one UV-curable pressure-sensitive adhesive layer.
  • the storage elastic modulus G′ (1 Hz) at a measurement temperature of 20° C. and a frequency of 1 Hz after ultraviolet curing of the pressure-sensitive adhesive layer is 1 ⁇ 10 4 to 1 ⁇ 10 6 Pa.
  • the base material adhesion and durability may be insufficient, and particularly under high temperature and high humidity conditions, the base material It has been found that the adhesion and durability may not be sufficiently obtained.
  • the workability after curing may be insufficient, and attempts have been made to increase the hardness of the pressure-sensitive adhesive layer after curing in order to improve the processability, but if the hardness is too high, an optical member with a large screen may be attached. There is room for improvement because wrinkles are liable to occur in applications such as bonding, and wrinkles are more likely to occur particularly when one of the optical members to be bonded is a triacetyl cellulose film or the like.
  • the present inventors have developed a large-screen optical adhesive sheet that is capable of exhibiting excellent substrate adhesion and durability even under high temperature and high humidity conditions.
  • a pressure-sensitive adhesive sheet that does not easily generate wrinkles and has excellent workability even in applications such as bonding members (construction applications in a relatively large area)
  • investigations have been advanced.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer in which the pressure-sensitive adhesive composition is in a semi-cured state, wherein the pressure-sensitive adhesive composition contains an acid component It contains a specific crosslinkable acrylic copolymer A, a crosslinker B, a polyfunctional monomer C having two or more reactive double bonds in the molecule, and a photopolymerization initiator D, and has a specific physical property group. It has been found that the above-mentioned object can be achieved by the pressure-sensitive adhesive sheet that satisfies the requirements, and the present invention has been completed.
  • the present invention relates to the following pressure-sensitive adhesive sheet, pressure-sensitive adhesive sheet with a release sheet, a laminate, and a method for producing a laminate.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer in which the pressure-sensitive adhesive composition is in a semi-cured state contains a crosslinkable acrylic copolymer A having an acid component, a crosslinker B, a polyfunctional monomer C having two or more reactive double bonds in the molecule, and a photopolymerization initiator D. Then The glass transition temperature (Tg) of the crosslinkable acrylic copolymer A is ⁇ 40° C.
  • the pressure-sensitive adhesive layer has a post-curing property
  • a pressure-sensitive adhesive sheet that satisfies the following physical properties (1) and (2) when the pressure-sensitive adhesive layer is post-cured by irradiating the pressure-sensitive adhesive layer with active energy rays so that the integrated light amount becomes 3000 mJ/cm 2 .
  • Item 3 The pressure-sensitive adhesive sheet according to Item 2, wherein the content of the monofunctional monomer E is 1 to 20 parts by mass with respect to 100 parts by mass of the crosslinkable acrylic copolymer A. 4. Item 4. The pressure-sensitive adhesive sheet according to any one of Items 1 to 3, wherein the content of the polyfunctional monomer C is 1 to 20 parts by mass with respect to 100 parts by mass of the crosslinkable acrylic copolymer A. 5. Item 5. The pressure-sensitive adhesive sheet according to any one of Items 1 to 4, wherein the acid value of the crosslinkable acrylic copolymer A is 1 mgKOH/g or more. 6. Item 6.
  • a pressure-sensitive adhesive sheet capable of exhibiting excellent substrate adhesion and durability even under high-temperature and high-humidity conditions, and wrinkles are unlikely to occur even in applications such as bonding optical members with a large screen.
  • a pressure-sensitive adhesive sheet having excellent processability can be obtained.
  • the present invention will be described in detail below. The description of the constituent elements described below may be made based on typical embodiments or specific examples, but the present invention is not limited to such embodiments.
  • the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
  • (meth)acrylate means both acrylate and methacrylate, or either
  • (meth)acrylic acid means both acrylic acid and methacrylic acid.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer obtained by semi-curing the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition contains a crosslinkable acrylic copolymer A having an acid component, a crosslinker B, a polyfunctional monomer C having two or more reactive double bonds in the molecule, and a photopolymerization initiator D.
  • the glass transition temperature (Tg) of the crosslinkable acrylic copolymer A is ⁇ 40° C.
  • the pressure-sensitive adhesive layer has a post-curing property
  • the adhesive layer satisfies the following physical properties (1) and (2) when it is post-cured by irradiating the adhesive layer with active energy rays so that the integrated light amount becomes 3000 mJ/cm 2 .
  • the pressure-sensitive adhesive sheet of the present invention having the above structure exhibits excellent substrate adhesion and durability even under high temperature and high humidity conditions, and wrinkles are less likely to occur even in applications such as bonding large-screen optical members. Excellent workability.
  • the effect of the present invention is that the crosslinkable acrylic copolymer A contained in the pressure-sensitive adhesive composition has an acid component, has a glass transition temperature (Tg) of ⁇ 40° C. or higher, and has the above-mentioned physical properties (1). ) And (2) are satisfied.
  • Tg glass transition temperature
  • the crosslinkable acrylic copolymer A having an acid component enhances the uniformity of the crosslinked structure formed in the crosslinkable acrylic copolymer A, and thereby enhances the durability of the pressure-sensitive adhesive sheet.
  • the crosslinkable acrylic copolymer A has an acid component, the adhesiveness between the adhesive sheet and the adherend (adhesiveness to the base material) is increased, which also enhances the durability of the adhesive sheet. Conceivable. Furthermore, by satisfying the above condition (1), the pressure-sensitive adhesive layer after post-curing has an appropriate hardness, and even in the case where triacetyl cellulose is used, it can be used for bonding optical members with a large screen. Wrinkles are less likely to occur and workability is excellent.
  • the durability of the pressure-sensitive adhesive sheet can be evaluated by the following method. First, a triacetyl cellulose film is attached to one surface of the pressure-sensitive adhesive sheet, and a polycarbonate plate is attached to the other surface, and active energy rays are irradiated from the surface on the side of the triacetyl cellulose film so that the accumulated light amount becomes 3000 mJ/cm 2. And the adhesive layer is post-cured. Then, the pressure-sensitive adhesive sheet is allowed to stand for 240 hours under the environment of i) 85° C. and relative humidity of 85%, and ii) environment of 85° C. and relative humidity of less than 10%, respectively.
  • the pressure-sensitive adhesive sheet is observed, and it can be determined that the durability is excellent when floating or peeling from the polycarbonate plate and/or the triacetyl cellulose film is suppressed.
  • the determination of the condition i) indicates high temperature and high humidity durability, and the determination of the condition ii) indicates high temperature durability.
  • the pressure-sensitive adhesive sheet of the present invention post-curing end surface stickiness is suppressed, and for example, adhesion of the pressure-sensitive adhesive to the punching blade during punching and deformation of the pressure-sensitive adhesive layer accompanying it can be prevented. .. Furthermore, the pressure-sensitive adhesive sheet of the present invention does not cause deformation, protrusion, peeling, etc. of the pressure-sensitive adhesive layer when it is subjected to punching to a desired size after post-curing and then cutting for the purpose of aligning the end faces, and also has processability. Are better.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet may be a single-layer pressure-sensitive adhesive sheet composed only of a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet may be a single-sided pressure-sensitive adhesive sheet having a substrate (preferably a transparent substrate) on one side, or a double-sided pressure-sensitive adhesive sheet.
  • a single-layer pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer, a multi-layer pressure-sensitive adhesive sheet in which a plurality of pressure-sensitive adhesive layers are laminated, and a multi-layer pressure-sensitive adhesive sheet in which another pressure-sensitive adhesive layer is laminated between pressure-sensitive adhesive layers ,
  • the double-sided pressure-sensitive adhesive sheet has a support
  • a transparent support As the support, a general film used in the optical field, like the transparent substrate, can be used. Since such a double-sided PSA sheet is excellent in transparency as a whole PSA sheet, it can be suitably used for bonding optical members to each other.
  • the pressure-sensitive adhesive layer 11 may be provided with a transparent substrate 12a on one side.
  • the other surface of the adhesive layer 11 is preferably covered with the release sheet 12b.
  • the release sheet 12b may be peeled off and bonded so that the pressure-sensitive adhesive layer 11 adheres to a desired adherend, and then post-curing may be performed by irradiating with active energy rays. preferable.
  • a general film used in the optical field such as a polyethylene terephthalate film, an acrylic film, a polycarbonate film, a triacetyl cellulose film, a cycloolefin polymer film can be used.
  • an easy adhesion layer may be provided on the adhesive layer side of these transparent substrates.
  • a functional layer such as a hard coat layer, an antireflection layer, an antifouling layer, and an ultraviolet absorbing layer may be provided on the surface of the transparent substrate opposite to the adhesive layer.
  • the present invention may relate to a pressure-sensitive adhesive sheet with a release sheet, which comprises release sheets on both sides of the pressure-sensitive adhesive sheet.
  • a release sheet which comprises release sheets on both sides of the pressure-sensitive adhesive sheet.
  • a peelable laminated sheet having a release sheet base material and a release agent layer provided on one surface of the release sheet base material, or a polyolefin film such as a polyethylene film or a polypropylene film as a low polarity base material.
  • a polyolefin film such as a polyethylene film or a polypropylene film as a low polarity base material.
  • Papers and polymer films are used as the base material for the release sheet in the release laminate sheet.
  • the release agent constituting the release agent layer for example, a general-purpose addition type or condensation type silicone type release agent or a long chain alkyl group-containing compound is used.
  • an addition type silicone release agent having high reactivity is preferably used.
  • the silicone-based release agent examples include BY24-4527 and SD-7220 manufactured by Toray Dow Corning Silicone, and KS-3600, KS-774, X62-2600 manufactured by Shin-Etsu Chemical Co., Ltd.
  • the silicone release agent may contain a silicone resin which is an organic silicon compound having SiO 2 units and (CH 3 ) 3 SiO 1/2 units or CH 2 ⁇ CH(CH 3 ) SiO 1/2 units. preferable.
  • Specific examples of the silicone resin include BY24-843, SD-7292, SHR-1404 manufactured by Toray Dow Corning Silicone Co., Ltd., and KS-3800, X92-183 manufactured by Shin-Etsu Chemical Co., Ltd.
  • a commercially available product may be used as the peelable laminated sheet.
  • a heavy separator film which is a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Films
  • a light separator film which is a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Films
  • the pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet
  • the releasability from one side and the releasability from the other are different, it becomes easier to first release only the release sheet having the higher releasability. In that case, the releasability of the release sheet 12a and the release sheet 12b may be adjusted according to the attaching method and the attaching order.
  • the present invention may also relate to an adhesive sheet with a transparent film, which comprises a transparent film on at least one surface of the adhesive sheet.
  • the transparent film is preferably at least one selected from polyethylene terephthalate film, acrylic film, polycarbonate film, triacetyl cellulose film and cycloolefin polymer film.
  • the transparent film-attached pressure-sensitive adhesive sheet may be a sheet in which a transparent film/pressure-sensitive adhesive sheet/release sheet are laminated in this order.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer obtained by semi-curing the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive layer has post-curability.
  • the pressure-sensitive adhesive layer before irradiation is in a semi-cured state.
  • an optical transparent PET separator is attached to both surfaces of the pressure-sensitive adhesive layer, and the active energy ray (high pressure mercury lamp or metal halide lamp) from one optical transparent PET separator side has an integrated light amount of 3000 mJ/cm 2. Irradiate.
  • the gel fraction in the semi-cured state of the pressure-sensitive adhesive layer is preferably 10% by mass or more and less than 75% by mass, more preferably 12% by mass or more and less than 75% by mass, and 15 to 70% by mass. Is more preferable.
  • the gel fraction of the pressure-sensitive adhesive layer after post-curing is preferably 60 to 100% by mass, more preferably 65 to 100% by mass, and even more preferably 70 to 100% by mass.
  • the difference between the gel fraction in the semi-cured state of the pressure-sensitive adhesive layer and the gel fraction after post-curing is preferably 15% or more, and more preferably 20% or more.
  • the “semi-cured state” is preferably the state after heat curing. Then, after that, it is preferable to perform "post-curing" by irradiating with active energy rays. That is, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention is preferably in a semi-cured state by thermosetting the pressure-sensitive adhesive composition and preferably has active energy ray curability.
  • the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is post-cured by irradiating the pressure-sensitive adhesive layer with active energy rays so that the integrated light amount becomes 3000 mJ/cm 2 , the pressure-sensitive adhesive layer satisfies the following physical properties (1) and (2); Physical properties (1): Breaking elongation is 300% or more in a tensile test measurement at a tensile speed of 10 mm/min; Physical Properties (2): Each constant load peeling distance at i) 85° C., relative humidity 85%, and ii) at 85° C., relative humidity less than 10% is 50 mm or less measured under the following measurement conditions: (Measurement condition) A region having a width of 25 mm and a length of 75 mm on the adhesive surface of the adhesive layer having a width of 25 mm and a length of 100 mm is attached to an adherend and post-cured.
  • Physical properties (1) Breaking elongation is 300% or more in a tensile test measurement at a
  • the physical property (1) may be 300% or more, preferably 320% or more, more preferably 350% or more, still more preferably 500% or more.
  • the upper limit of the elongation at break is not particularly limited and is, for example, about 1000%.
  • the breaking elongation is measured according to JIS K 7161-1. At that time, the tensile speed is 10 mm/min, and the measurement is performed at 23° C. and a relative humidity of 50%.
  • a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m, a width of 60 mm and a length of 200 mm is rounded in the length direction and processed into a columnar shape having a cross-sectional area of 5 mm 2 and a height of 60 mm. This is pulled so that the distance between chucks is 30 mm, and the elongation at which the sample breaks is defined as the breaking elongation.
  • the measuring device for example, Autograph AGS-X manufactured by Shimadzu Corporation can be used.
  • a test piece for measurement is prepared by the following method.
  • a triacetyl cellulose film (Fujitac TD60UL, thickness 60 ⁇ m, manufactured by FUJIFILM Corporation) is attached to one surface of the adhesive layer using a hand roller to prepare a laminated film.
  • This laminated film was cut into a size of width 25 mm and length 100 mm, and then the other side of the pressure-sensitive adhesive layer had a width of 25 mm and a length of 100 mm.
  • Polycarbonate plate with hard coat layer Mitsubishi Gas Chemical Co., Inc., Iupilon MR58 (1 mm thickness) is attached to the hard coat surface side using a 2 kg pressure roller. In this state, it is kept in an autoclave under the conditions of 40° C. and 5 atm for 30 minutes to be brought into close contact with the adherend.
  • ultraviolet rays are irradiated from the side of the triacetyl cellulose film of the test piece for measurement so that the integrated light amount becomes 3000 mJ/cm 2 .
  • the constant load peeling distance at i) 85° C. and 85% relative humidity measured under the above measurement conditions is 50 mm or less, preferably 45 mm or less, more preferably 40 mm or less, and 35 mm or less. It is more preferable that the thickness is 30 mm or less, and particularly preferably 30 mm or less. Further, ii) the constant load peeling distance at 85° C. and a relative humidity of less than 10% is 50 mm or less, preferably 45 mm or less, more preferably 40 mm or less, and further preferably 35 mm or less, It is particularly preferably 30 mm or less.
  • the constant load peeling distance at i) 85° C. and relative humidity of 85% and ii) at 85° C. and relative humidity of less than 10% may be 0 mm.
  • the adhesive layer When the adhesive layer is post-cured by irradiating the adhesive layer with active energy rays so that the integrated light amount becomes 3000 mJ/cm 2 , the adhesive layer has the following physical properties (3) in addition to the above physical properties (1) and (2). It is preferable to satisfy.
  • the probe tack value is 1.0 N/5 mm ⁇ or less.
  • the probe tack value of the pressure-sensitive adhesive layer after the post-curing is more preferably 1.0 N/5 mm ⁇ or less, further preferably 0.5 N/5 mm ⁇ or less.
  • the lower limit of the probe tack value is not particularly limited, and is preferably 0.1 N/5 mm ⁇ or more, more preferably 0.01 N/5 mm ⁇ or more, for example.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately set depending on the application and is not particularly limited, but is preferably 5 to 150 ⁇ m, more preferably 8 to 100 ⁇ m, and particularly preferably 10 to 80 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer can be adjusted within the above range, the pressure-sensitive adhesive can be prevented from sticking out and stickiness, so that the processability can be improved.
  • the double-sided pressure-sensitive adhesive sheet can be easily manufactured.
  • the above-mentioned pressure-sensitive adhesive layer is obtained by semi-curing the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition used in the present invention is a dual-curable pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition is a cross-linkable acrylic copolymer A having an acid component (however, the glass transition temperature (Tg) is ⁇ 40° C. or higher), a cross-linking agent B, and a polyfunctional compound having two or more reactive double bonds in the molecule. It contains a monomer C and a photopolymerization initiator D.
  • the crosslinkable acrylic polymer A is not particularly limited as long as it has an acrylic monomer unit containing an acid component and has a glass transition temperature (Tg) of ⁇ 40° C. or higher. It is preferable that the functional (meth)acrylic acid ester unit (a1) and the acrylic monomer unit (a2) having an acid component and having a crosslinkable functional group are copolymerized.
  • the crosslinkable acrylic polymer A is preferably one having transparency to such an extent that the visibility of the display device is not deteriorated.
  • the “unit” is a repeating unit (monomer unit) constituting a polymer.
  • the non-crosslinkable (meth)acrylic acid ester unit (a1) is a repeating unit derived from a (meth)acrylic acid alkyl ester.
  • alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylate.
  • At least one selected from methyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate is preferred because of its high adhesiveness. preferable.
  • the crosslinkable functional group of the crosslinkable acrylic polymer has an acid component.
  • the crosslinkable functional group serving as an acid component is preferably a carboxyl group or a group derived from a carboxyl group, or a sulfo group or a group derived from a sulfo group, and particularly preferably a carboxy group.
  • the acrylic monomer unit (a2) having a crosslinkable functional group having an acid component is preferably a carboxy group-containing monomer unit.
  • the carboxy group-containing monomer unit include acrylic acid and methacrylic acid.
  • crosslinkable functional group of the crosslinkable acrylic polymer A may have a functional group other than the crosslinkable functional group serving as an acid component.
  • Other functional groups may include hydroxy groups, amino groups, amide groups, glycidyl groups or isocyanate groups.
  • the content of the acrylic monomer unit (a2) having a crosslinkable functional group having an acid component in the crosslinkable acrylic polymer A is preferably 0.01 to 40% by mass, and 0.5 to 35% by mass. More preferably.
  • the content of the acrylic monomer unit (a2) having a crosslinkable functional group having an acid component is at least the lower limit value of the above range, the crosslinkability necessary for maintaining a semi-cured state can be sufficiently exhibited, If it is at most the upper limit value of the above range, it is easy to maintain the required tackiness.
  • the crosslinkable acrylic polymer A may have other monomer units, if necessary. Any other monomer may be used as long as it can be copolymerized with the above-mentioned acrylic monomer, and examples thereof include (meth)acrylonitrile, vinyl acetate, styrene, vinyl chloride, vinylpyrrolidone, and vinylpyridine.
  • the content of the other monomer unit in the crosslinkable acrylic polymer is preferably 20% by mass or less, and more preferably 15% by mass or less.
  • the glass transition temperature (Tg) of the crosslinkable acrylic polymer A may be ⁇ 40° C. or higher, preferably ⁇ 38° C. or higher, and more preferably ⁇ 35° C. or higher.
  • the upper limit of the glass transition temperature (Tg) is not limited, but may be 0° C. or lower, for example.
  • the specific glass transition temperature a literature value may be adopted, or a value obtained by measuring the glass transition temperature of the crosslinkable acrylic polymer A using a DSC (differential scanning calorimeter) may be adopted. ..
  • the weight average molecular weight of the crosslinkable acrylic polymer A is preferably 100,000 to 2,000,000, more preferably 200,000 to 1,500,000. When the weight average molecular weight is within the above range, the semi-cured state of the pressure-sensitive adhesive layer can be easily maintained, the hardness after post-curing can be easily obtained, and the workability is excellent.
  • the weight average molecular weight of the crosslinkable acrylic polymer A is a value before being crosslinked with a crosslinking agent.
  • the weight average molecular weight is a value measured by size exclusion chromatography (SEC) and determined on a polystyrene basis.
  • SEC size exclusion chromatography
  • As the crosslinkable acrylic polymer a commercially available one may be used, or one synthesized by a known method may be used.
  • the acid value of the crosslinkable acrylic polymer A is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more, and further preferably 3 mgKOH/g or more.
  • the acid value of the crosslinkable acrylic polymer A is preferably 200 mgKOH/g or less.
  • the acid value of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is also preferably within the above range.
  • Acid value (mgKOH/g) [cKOH ⁇ (V1-V0) ⁇ 5.611]/S (1)
  • cKOH is the molar concentration of 0.1N potassium hydroxide-2-propanol solution.
  • Mol/L the amount of the 0.1 mol/L potassium hydroxide-2-propanol solution required for the titration of the sample
  • V0 the 0.1 mol/L required for the titration in the blank test.
  • L is the amount of potassium hydroxide-2-propanol solution (mL)
  • S is the amount of sample collected (g).
  • the pressure-sensitive adhesive composition contains a crosslinking agent.
  • the cross-linking agent can be appropriately selected in consideration of the reactivity with the cross-linkable functional group of the cross-linkable acrylic polymer A.
  • it can be selected from known crosslinking agents such as an isocyanate compound, an epoxy compound, an oxazoline compound, an aziridine compound, a metal chelate compound and a butylated melamine compound.
  • Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol di Glycidyl ether, tetraglycidyl xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. Can be mentioned.
  • the content of the cross-linking agent in the pressure-sensitive adhesive composition is appropriately selected according to the desired tackiness and the like, but is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the cross-linkable acrylic polymer, and 0 It is more preferably 0.01 to 3 parts by mass.
  • the content of the cross-linking agent within the above range, the adhesion to the base material can be enhanced and the processability can be further enhanced.
  • the cross-linking agent one kind may be used alone or two or more kinds may be used in combination, and when two kinds or more are used in combination, the total mass is preferably within the above range.
  • the pressure-sensitive adhesive composition contains a polyfunctional monomer C having two or more reactive double bonds in the molecule.
  • polyfunctional monomer C examples include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, and di(meth)acrylic acid 1 ,4-butylene glycol, 1,9-nonanediol di(meth)acrylic acid, 1,6-hexanediol diacrylic acid, polybutylene glycol di(meth)acrylic acid, neopentyl glycol di(meth)acrylic acid, di(meth)acrylic acid (Meth)acrylic acid tetraethylene glycol, di(meth)acrylic acid tripropylene glycol, di(meth)acrylic acid polypropylene glycol, bisphenol A diglycidyl ether diacrylate, tri(meth)acrylic acid trimethylolpropane, tri(meth)acrylic acid Examples thereof include (meth)acrylic acid esters of polyhydric alcohols such as pentaerythr,
  • the polyfunctional monomer C has two or more reactive double bonds, and above all, it is preferable that the polyfunctional monomer has two or more and less than five reactive double bonds. It is more preferable that the number is one or more and less than four.
  • a commercially available product can be used as the polyfunctional monomer C.
  • Examples of commercially available products include trifunctional monomer M310 (trimethylolpropane PO modified triacrylate) manufactured by Toagosei Co., Ltd., trifunctional monomer M321 (trimethylolpropane propylene oxide modified triacrylate), bifunctional monomer M211B manufactured by Toagosei Co., Ltd. ( Bisphenol A EO modified diacrylate) and the like.
  • the polyfunctional monomer C may have a bisphenol skeleton in one molecule.
  • Examples of such a polyfunctional monomer C include bisphenol A diglycidyl ether diacrylate, propoxylated bisphenol A diacrylate, and bisphenol F diglycidyl ether diacrylate.
  • the glass transition temperature (Tg) when the polyfunctional monomer C is a homopolymer is preferably 30° C. or higher, and more preferably 50° C. or higher.
  • the glass transition temperature (Tg) when the polyfunctional monomer is a homopolymer may be, for example, 300° C. or lower.
  • the glass transition temperature in this specification is the glass transition temperature when the polyfunctional monomer C is a homopolymer.
  • a specific glass transition temperature literature values may be adopted, but after the polyfunctional monomer C is made into a homopolymer having a weight average molecular weight of 10,000 or more, the glass transition temperature of the homopolymer is determined by DSC ( A value measured by using a differential scanning calorimeter may be adopted.
  • the content of the polyfunctional monomer C in the pressure-sensitive adhesive composition is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, based on 100 parts by mass of the crosslinkable acrylic polymer A. It is more preferably 1 to 10 parts by mass.
  • the polyfunctional monomer C may be used alone or in combination of two or more kinds. When using two or more kinds in combination, the total mass is preferably within the above range.
  • the pressure-sensitive adhesive composition contains a photopolymerization initiator D.
  • the photopolymerization initiator is preferably one which initiates the polymerization of the crosslinkable acrylic polymer or the polyfunctional monomer by irradiation with active energy rays.
  • the photopolymerization initiator E a known photopolymerization initiator can be used.
  • active energy ray means an electromagnetic wave or charged particle beam having energy quantum, and examples thereof include ultraviolet rays, electron rays, visible rays, X-rays, and ion rays. Among them, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable, from the viewpoint of versatility.
  • photopolymerization initiator D examples include acetophenone-based initiators, benzoin ether-based initiators, benzophenone-based initiators, hydroxyalkylphenone-based initiators, thioxanthone-based initiators, amine-based initiators, acylphosphine oxide-based initiators, and the like. Are listed.
  • acetophenone-based initiator examples include diethoxyacetophenone and benzyl dimethyl ketal.
  • benzoin ether-based initiator examples include benzoin and benzoin methyl ether.
  • benzophenone-based initiator examples include benzophenone and methyl o-benzoylbenzoate.
  • hydroxyalkylphenone initiator examples include 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan Ltd., commercially available as IRGACURE184).
  • thioxanthone initiator examples include 2-isopropylthioxanthone and 2,4-dimethylthioxanthone.
  • amine-based initiator examples include triethanolamine and ethyl 4-dimethylbenzoate.
  • acylphosphine oxide initiator examples include phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by BASF Japan Ltd., commercially available as IRGACURE819).
  • the content of the photopolymerization initiator D in the pressure-sensitive adhesive composition is preferably 0.05 to 10 parts by mass, and 0.1 to 5 parts by mass with respect to 100 parts by mass of the crosslinkable acrylic polymer. Is more preferable.
  • the desired hardness can be adjusted by post-curing, and the molecular weight after post-curing can be adjusted to an appropriate range, so that a pressure-sensitive adhesive sheet having excellent processability can be obtained.
  • the photopolymerization initiator D one type may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the total mass is preferably within the above range.
  • the pressure-sensitive adhesive composition may have, in addition to the above essential components, a monofunctional monomer E having one reactive double bond in the molecule.
  • the monofunctional monomer E examples include isobornyl acrylate, isostearyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, N-acryloyloxyethyl hexahydrophthalimide, acrylamide, N,N-dimethylacrylamide, Examples thereof include N,N-diethylacrylamide, acryloylmorpholine, vinylpyrrolidone and the like.
  • the monofunctional monomer is preferably an alkyl (meth)acrylate, preferably at least one selected from isobornyl acrylate and isostearyl acrylate, and more preferably isobornyl acrylate. preferable.
  • Examples of commercially available monofunctional monomer E include DEAA manufactured by KJ Chemicals, and IBXA manufactured by Osaka Organic Chemical Industry.
  • the glass transition temperature (Tg) when the monofunctional monomer E is a homopolymer is preferably 50°C or higher and lower than 200°C, more preferably 55°C or higher and lower than 180°C.
  • the content of the monofunctional monomer E is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the crosslinkable acrylic polymer A. Is more preferable.
  • the monofunctional monomer E one type may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total mass is preferably within the above range.
  • the adhesive composition may contain a solvent.
  • the solvent is used for improving the coating suitability of the pressure-sensitive adhesive composition.
  • the solvent include hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane and methylcyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, trichloroethylene, tetrachloroethylene and dichloropropane; methanol, ethanol, Alcohols such as propanol, isopropyl alcohol, butanol, isobutyl alcohol, diacetone alcohol; ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, is
  • the content of the solvent in the pressure-sensitive adhesive composition is not particularly limited, but is preferably 25 to 500 parts by mass, and more preferably 30 to 400 parts by mass with respect to 100 parts by mass of the crosslinkable acrylic polymer A.
  • the content of the solvent is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass based on the total mass of the pressure-sensitive adhesive composition.
  • the solvent one type may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total mass is preferably within the above range.
  • the pressure-sensitive adhesive composition may contain components other than the above components as long as the effects of the present invention are not impaired.
  • other components include components known as additives for pressure-sensitive adhesives.
  • a plasticizer, an antioxidant, a metal corrosion inhibitor, a tackifier, a silane coupling agent, an ultraviolet absorber, and a light stabilizer such as a hindered amine compound can be selected as necessary.
  • a dye or a pigment may be added for the purpose of coloring.
  • plasticizer examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, and benzoic acid.
  • carboxylic acid vinyl esters such as vinyl, styrene and the like.
  • antioxidants examples include phenolic antioxidants, amine antioxidants, lactone antioxidants, phosphorus antioxidants, sulfur antioxidants and the like. These antioxidants may be used alone or in combination of two or more.
  • a benzotriazole resin can be mentioned as a preferable example because of the compatibility of the pressure-sensitive adhesive and the high effect.
  • tackifier examples include rosin resin, terpene resin, terpene phenol resin, coumarone indene resin, styrene resin, xylene resin, phenol resin, petroleum resin and the like.
  • silane coupling agent examples include mercaptoalkoxysilane compounds (eg, mercapto group-substituted alkoxy oligomers).
  • ultraviolet absorbers examples include benzotriazole compounds and benzophenone compounds. However, when ultraviolet rays are used as the active energy rays at the time of post-curing, it is preferable to add them in a range that does not hinder the polymerization reaction.
  • the method for producing a pressure-sensitive adhesive sheet of the present invention includes a step of applying the above-mentioned pressure-sensitive adhesive composition on a release sheet to form a coating film, and a step of heating the coating film to a semi-cured cured product. It is preferable.
  • the reaction between the crosslinkable acrylic polymer A and the crosslinking agent B proceeds to form a cured product (adhesive layer) in a semi-cured state. That is, during heating, the polymerization reaction of the monomer by the photopolymerization initiator E does not proceed in the coating film, or even if the polymerization reaction proceeds slightly, it is contained in the adhesive composition in the adhesive layer. At least a part of the monomers C and D and the photopolymerization initiator E is contained in an unreacted state.
  • the pressure-sensitive adhesive sheet of the present invention preferably has post-curability and active energy ray curability.
  • the pressure-sensitive adhesive composition in order to bring the pressure-sensitive adhesive composition into a semi-cured state, it is preferable to carry out an aging treatment in which the pressure-sensitive adhesive sheet is left standing at a constant temperature for a certain period after the solvent is removed after coating.
  • the aging treatment can be carried out, for example, by allowing it to stand at 23° C. for 7 days.
  • the coating of the adhesive composition can be carried out using a known coating device.
  • the coating device include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a microgravure coater, a rod blade coater, a lip coater, a die coater, and a curtain coater.
  • a known heating device such as a heating furnace or an infrared lamp can be used to heat the coating film formed by applying the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive sheet of the present invention it is preferable to bring the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet into contact with the surface of the adherend.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet it is preferable that the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is bonded to the adherend when the pressure-sensitive adhesive layer is in a semi-cured state, and the pressure-sensitive adhesive layer is post-cured by irradiation with active energy rays.
  • the pressure-sensitive adhesive sheet of the present invention is a two-stage curable pressure-sensitive adhesive sheet, has a pressure-sensitive adhesive layer that is semi-cured only by heat before bonding, and after bonding, the pressure-sensitive adhesive layer is post-cured by active energy rays. To be done.
  • the pressure-sensitive adhesive sheet of the present invention is an optical member that requires durability, and is preferably used for bonding optical members that require molding after lamination with the optical member.
  • the pressure-sensitive adhesive sheet of the present invention is excellent in substrate adhesion and durability even when it is attached to an adherend such as a base material and post-cured, and then exposed to a high temperature and high humidity environment. Therefore, it is possible to suppress the occurrence of floating and peeling.
  • the pressure-sensitive adhesive sheet of the present invention is, for example, bonded to a polycarbonate substrate, post-cured, and then prevented from floating or peeling from the polycarbonate substrate even when exposed to a high temperature and high humidity environment. can do.
  • the adhesive sheet of the present invention may be attached to an optical member such as a polarizing plate.
  • the polarizing plate includes a polarizer and a polarizer protective film
  • the pressure-sensitive adhesive sheet of the present invention is preferably attached to the polarizer protective film.
  • the polarizer protective film cycloolefin resin film, cellulose acetate resin film such as triacetyl cellulose and diacetyl cellulose, polyester resin film such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, polycarbonate resin film, acrylic Examples thereof include a resin resin film and a polypropylene resin film.
  • the present invention also relates to a laminate having the above-mentioned pressure-sensitive adhesive sheet and an adherend.
  • the laminate is a pressure-sensitive adhesive layer after post-curing, which is obtained by irradiating the pressure-sensitive adhesive layer of the above-mentioned pressure-sensitive adhesive sheet with active energy rays, and at least one surface side of the pressure-sensitive adhesive layer after post-curing. Equipped with. That is, the laminate of the present invention is a laminate having a pressure-sensitive adhesive sheet and an adherend provided on at least one surface side of the pressure-sensitive adhesive sheet, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is irradiated with active energy rays. By doing so, it is post-cured.
  • the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet
  • a laminate is formed by irradiating the two adherends with a semi-cured pressure-sensitive adhesive sheet and irradiating them with active energy rays and post-curing the pressure-sensitive adhesive layer.
  • the adherend is more preferably a base material and an optical member, and particularly preferably a polycarbonate base material, a polarizing plate, a transparent film, a transparent resin or glass.
  • FIG. 2 is a schematic view showing a cross section of an example of the laminate of the present invention.
  • FIG. 2 is a cross-sectional view showing an example of the configuration of the laminate 20 in which the pressure-sensitive adhesive sheet 21 of the present invention is attached to the base material 22 and the optical member 24.
  • the pressure-sensitive adhesive sheet 21 of the present invention is preferably used for bonding to the base material 22, and is used for bonding the base material 22 and the other optical member 24.
  • the pressure-sensitive adhesive sheet 21 of the present invention may be used for bonding with a polarizing plate.
  • optical member included in the laminated body various constituent members in optical products such as a touch panel and an image display device, and an anti-scattering film attached to the cover lens of the outermost layer can be cited.
  • a component of the touch panel for example, an ITO film provided with an ITO film on a transparent resin film, an ITO glass provided with an ITO film on the surface of a glass plate, a transparent conductive film obtained by coating a conductive polymer on a transparent resin film, A hard coat film, a fingerprint resistant film and the like can be mentioned.
  • constituent members of the image display device include an antireflection film, an alignment film, a polarizing film, a retardation film, and a brightness enhancement film used in a liquid crystal display device.
  • Materials used for these members include glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, cycloolefin polymer, triacetyl cellulose, polyimide, cellulose acylate, and the like.
  • the pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet, it can be used for bonding two adherends.
  • the pressure-sensitive adhesive sheet of the present invention is a laminate of transparent optical films in a touch panel, a transparent optical film and a glass, a transparent optical film of a touch panel and a liquid crystal panel, a cover glass. And a transparent optical film, or a cover glass and a transparent optical film, and is useful when either member is a polycarbonate substrate.
  • the transparent optical film a general film used in the optical field such as a polyethylene terephthalate film, an acrylic film, a polycarbonate film, a triacetyl cellulose film, or a cycloolefin polymer film can be used.
  • a hard coat layer may be provided on the transparent optical film or the polycarbonate substrate.
  • FIG. 3 is a schematic view showing a cross section of another example of the laminate of the present invention.
  • the adherend may have stepped portions (27a, 27b, 27c, 27d).
  • the base material has step portions (27a, 27b), and the optical member has step portions (27c, 27d).
  • the thickness of the step portions (27a, 27b, 27c, 27d) is usually 5 to 60 ⁇ m.
  • the pressure-sensitive adhesive sheet 21 of the present invention can be attached to a member having a step portion, and can follow the unevenness generated from the step portion.
  • the method for producing a laminate includes a step of sticking the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet described above to an adherend in a semi-cured state, and then irradiating an active energy ray to post-cure the pressure-sensitive adhesive layer. That is, the method for producing a laminate of the present invention comprises the step 1 of laminating an adherend on at least one surface side of the pressure-sensitive adhesive sheet, and the pressure-sensitive adhesive by irradiating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet with active energy rays. Step 2 of sequentially post-curing the layers.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet Prior to irradiation with active energy rays, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is in a semi-cured state, so that the initial adhesion to the substrate is good. In this way, after the pressure-sensitive adhesive sheet is attached to the adherend, the adhesive layer is post-cured with active energy rays, whereby the cohesive force of the pressure-sensitive adhesive layer is increased and the adhesiveness to the adherend is improved. In addition, the post-cured pressure-sensitive adhesive layer can prevent the base material from being deformed or distorted.
  • the active energy rays include ultraviolet rays, electron rays, visible rays, X rays, ion rays, etc., and can be appropriately selected according to the photopolymerization initiator contained in the adhesive layer. Among them, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable, from the viewpoint of versatility.
  • the ultraviolet light source for example, a high pressure mercury lamp, a low pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, an electrodeless ultraviolet lamp, etc. can be used.
  • an electron beam emitted from each type of electron beam accelerator such as Cockloft-Walt type, Bande-Craft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. is used. it can.
  • the integrated quantity of light is made to be a 100 ⁇ 10000mJ / cm 2, and more preferably made to be 500 ⁇ 5000mJ / cm 2.
  • the active energy ray is irradiated so that the integrated light amount becomes 3000 mJ/cm 2 .
  • a crosslinkable acrylic polymer A (A-1) having an acid component was prepared by solution polymerization in ethyl acetate.
  • butyl acrylate monomer (BA), methyl acrylate monomer (MA), methyl methacrylate (MMA), acrylic acid (AA) are mixed in a mass ratio of 90:1:4:6 to initiate radical polymerization.
  • AIBN azobisisobutyronitrile
  • the solution viscosity at 23° C. of a 21% by mass solution of the crosslinkable acrylic polymer A (A-1) was 4900 mPa ⁇ s. Further, the glass transition temperature (Tg) determined from the composition of the crosslinkable acrylic polymer A (A-1) using the FOX equation was -21°C.
  • a crosslinkable acrylic polymer A (A-2) having no acid component was prepared by solution polymerization in ethyl acetate. Specifically, 2-methoxyethyl acrylate monomer (MEA), 2-hydroxyethyl acrylate monomer (2HEA), methyl methacrylate (MMA), diethyl acrylamide (DEAA) and butyl acrylate (BA) were used in a mass ratio of 70:10:10. :5:5, and AIBN (azobisisobutyronitrile) was dissolved in the solution as a radical polymerization initiator. The solution was heated to 60° C. and subjected to random copolymerization to obtain a crosslinkable acrylic polymer A (A-2).
  • MEA 2-methoxyethyl acrylate monomer
  • 2HEA 2-hydroxyethyl acrylate monomer
  • MMA methyl methacrylate
  • DEAA diethyl acrylamide
  • BA butyl acrylate
  • AIBN azobisisobut
  • the solution viscosity of the 35 mass% solution of the crosslinkable acrylic polymer A (A-2) at 23° C. was 2000 mPa ⁇ s. Further, the glass transition temperature (Tg) determined from the composition of the crosslinkable acrylic polymer A (A-2) using the FOX formula was -11°C.
  • an epoxy compound Te
  • the above-mentioned pressure-sensitive adhesive composition was applied onto a first release sheet (heavy separator film, Teijin DuPont Films, release-treated polyethylene terephthalate film).
  • the coating was performed using a doctor blade YD type manufactured by Yoshimitsu Seiki Co., Ltd. so that the thickness after drying was 25 ⁇ m. Then, it was dried at 100° C. for 3 minutes with a hot air dryer to remove the solvent and form a pressure-sensitive adhesive sheet having a semi-cured pressure-sensitive adhesive layer.
  • a second release sheet (light separator film, manufactured by Teijin DuPont Films Co., Ltd.), which has been subjected to a release treatment having a higher releasability than the first release sheet, is attached to one surface of this pressure-sensitive adhesive sheet, and the pressure-sensitive adhesive sheet with the release sheet is attached.
  • An adhesive sheet of Example 1 was obtained.
  • Example 2 A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were prepared in the same manner as in Example 1 except that the addition amounts of the polyfunctional monomer C and the monofunctional monomer E were changed to 7 parts by mass. Obtained.
  • Example 3 A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were prepared in the same manner as in Example 1 except that the addition amounts of the polyfunctional monomer C and the monofunctional monomer E were changed to 15 parts by mass. Obtained.
  • Example 4 In the same manner as in Example 1 except that the addition amount of the polyfunctional monomer C was changed to 15 parts by mass and the monofunctional monomer E was not added in Example 1, the pressure-sensitive adhesive composition and the adhesive composition An adhesive sheet with a release sheet was obtained.
  • Example 1 In Example 1, the addition amount of the crosslinking agent B was changed to 0.5 parts by mass, the addition amount of the polyfunctional monomer C was changed to 20 parts by mass, and the addition amount of the monofunctional monomer E was 15 parts by mass.
  • a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 1 except that parts were changed.
  • Acid value (mgKOH/g) [cKOH ⁇ (V1-V0) ⁇ 5.611]/S (1)
  • cKOH is the molar concentration of 0.1N potassium hydroxide-2-propanol solution.
  • Mol/L the amount of the 0.1 mol/L potassium hydroxide-2-propanol solution required for the titration of the sample
  • V0 the 0.1 mol/L required for the titration in the blank test.
  • L is the amount of potassium hydroxide-2-propanol solution (mL)
  • S is the amount of sample collected (g).
  • the pressure-sensitive adhesive layer was cut to have a size of 100 mm ⁇ 60 mm to prepare a semi-cured measurement sample.
  • the pressure-sensitive adhesive layer was cut to have a size of 100 mm ⁇ 60 mm, and ultraviolet rays were irradiated from the side of the first release sheet, which is a heavy separator film, so that the integrated light amount was 3000 mJ/cm 2, and the measurement sample after post-curing was obtained. It was made.
  • the second release sheet which is a light separator film of the pressure-sensitive adhesive sheet, was peeled off and attached to a PET film to prepare a measurement sample in a semi-cured state.
  • the second release sheet which is a light separator film of another pressure-sensitive adhesive sheet, was peeled off and attached to a PET film. Next, ultraviolet rays were radiated from the side of the first release sheet, which is a heavy separator film, so that the integrated light amount was 3000 mJ/cm 2, and a measurement sample after post-curing was prepared.
  • Each measurement sample was cut into 3 cm ⁇ 3 cm, and measured with a probe tack tester under the following conditions.
  • the measurement temperature was 23° C. and the relative humidity was 50%.
  • Probe base material Stainless steel surface finish AA#400 Mirror surface weight by polishing: 19.6 g (made of brass) Probe moving speed: 1.0 cm/sec Duel time: 1 sec
  • the breaking elongation was measured according to JIS K 7161-1. At that time, the tensile speed was 10 mm/min, and the measurement was performed in an environment of 23° C. and a relative humidity of 50%.
  • a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m, a width of 60 mm and a length of 200 mm was rolled in the length direction and processed into a columnar shape having a cross-sectional area of 5 mm 2 and a height of 60 mm. The sample was set and pulled so that the distance between chucks was 30 mm, and the elongation at break of the sample was defined as the elongation at break.
  • an autograph AGS-X manufactured by Shimadzu Corporation was used.
  • the light release separator which is the second release sheet was peeled off, and instead of the peeled off separator, a triacetyl cellulose film (Fuji Film Co., Fujitac TD60UL thickness 60 ⁇ m) was laminated using a hand roller to prepare a laminated film. .. This laminated film was cut into a size having a width of 25 mm and a length of 100 mm, and the first release sheet was peeled off.
  • a triacetyl cellulose film Fujitac TD60UL thickness 60 ⁇ m
  • the exposed area of 25 mm in width and 100 mm in length of the adhesive surface is covered with a region of 25 mm in width and 75 mm in length on the hard coat surface side of the adherend (polycarbonate plate with hard coat layer: Mitsubishi Gas Chemical Co., Inc., Iupilon MR58 thickness 1 mm)
  • the adherend polycarbonate plate with hard coat layer: Mitsubishi Gas Chemical Co., Inc., Iupilon MR58 thickness 1 mm
  • the evaluation criteria are as follows, A and B are acceptable (allowable range), and C is unacceptable.
  • the second release sheet which is a light separator film for the pressure-sensitive adhesive layer, was peeled off and laminated on a triacetylcellulose film (Fujitac TD60UL, thickness 60 ⁇ m, manufactured by Fuji Film Co., Ltd.).
  • the first release sheet which is a heavy separator film
  • a PC plate polycarbonate plate with a hard coat layer: Mitsubishi Gas Chemical Co., Inc., Iupilon MR58 thickness 1 mm.
  • the sample of the composition of triacetyl cellulose film/adhesive layer/PC plate is autoclaved (40° C., 0.5 MPa, 30 min), and then the integrated amount of ultraviolet rays from the side of the triacetyl cellulose film becomes 3000 mJ/cm 2. Then, the test sample having a size of 100 mm ⁇ 200 mm was obtained.
  • test sample was allowed to stand for 240 hours in an environment of i) 85° C. and relative humidity of 85%, and ii) environment of 85° C. and less than 10% of relative humidity.
  • the determination of the condition i) indicates high temperature and high humidity durability, and the determination of the condition ii) indicates high temperature durability.
  • the evaluation criteria are as follows, a is a pass (allowable range), and b is a fail. a: 1.0 mm or more floating and peeling is not observed b: 1.0 mm or more floating and/or peeling is observed
  • the pressure-sensitive adhesive sheets of the examples can exhibit excellent substrate adhesion and durability not only under high temperature conditions but also under high temperature and high humidity conditions.
  • the pressure-sensitive adhesive sheets of the examples were free from wrinkles and had good workability even in applications where an optical member having a large screen was attached without sticking on the end faces (construction applications in a relatively large area).
  • the pressure-sensitive adhesive sheets of Comparative Examples were inferior in substrate adhesion and durability under high-temperature conditions and high-temperature high-humidity conditions, and/or workability in construction applications in a relatively large area (occurrence of wrinkles). Was recognized).
  • Adhesive sheet 11 Adhesive layer 12a Transparent base material or release sheet 12b Release sheet 20 Laminated body 21 Adhesive sheet 22 Base material 24 Optical member 27a, 27b, 27c, 27d Step part 30 Triacetyl cellulose film 32 Adherent 34 Weight L Constant load separation distance

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  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
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  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une feuille adhésive qui peut présenter une adhérence supérieure à un matériau de base et une durabilité supérieure même dans des conditions de température élevée et d'humidité élevée et qui est moins susceptible de se froisser même dans une application dans laquelle des éléments optiques présentant un grand écran sont attachés ensemble (une application dans laquelle la feuille présentant une aire relativement grande est appliquée) et présente ainsi une aptitude au façonnage supérieure. La présente invention concerne en particulier une feuille adhésive présentant une couche d'agent adhésif contenant une composition d'agent adhésif dans un état semi-durci, la composition d'agent adhésif contenant un copolymère acrylique réticulable A présentant un constituant acide, un agent de réticulation B, un monomère polyfonctionnel C présentant deux doubles liaisons réactives ou plus dans la molécule et un initiateur de photopolymérisation D, le copolymère acrylique réticulable A présentant une température de transition vitreuse (Tg) de -40°C ou plus, la couche d'agent adhésif étant postdurcissable et, lorsque la couche d'agent adhésif est irradiée par un rayonnement actinique à une quantité de lumière cumulative de 3000 mJ/cm2 pour un post-durcissement, la couche d'agent adhésif satisfait aux propriétés physiques (1) et (2). Propriété physique (1) : l'allongement à la rupture est de 300 % ou plus, tel que mesuré dans un essai de traction à une vitesse d'allongement de 10 mm/min. Propriété physique (2) : les distances de pelage à charge constante i) à 85°C et à une humidité relative de 85 % et ii) à 85°C et à une humidité relative inférieure à 10 % sont chacune de 50 mm ou moins dans les conditions de mesure suivantes : (conditions de mesure) une région présentant une largeur de 25 mm et une longueur de 75 mm de la surface adhésive de la couche d'agent adhésif mesurant 25 mm de large et 100 mm de long est fixée à une partie adhérée et subit un postdurcissement. La partie adhérée est fixée horizontalement de telle sorte que la région non fixée de la couche d'agent adhésif pend vers le bas dans chacun des environnements : i) 85°C et une humidité relative de 85 % ; et ii) 85°C et une humidité relative inférieure à 10 %. Une charge de 100 g est appliquée à une extrémité dans la direction de la longueur de la région non fixée de la couche d'agent adhésif pendant 5 minutes, pendant lesquelles la distance sur laquelle la région fixée de la couche d'agent adhésif est libérée de la partie adhérée est mesurée en tant que distances de pelage à charge constante respectives à i) 85°C et à une humidité relative de 85 % et ii) à 85°C et à une humidité relative inférieure à 10 %.
PCT/JP2020/004467 2019-02-08 2020-02-06 Feuille adhésive, feuille adhésive pourvue d'une feuille antiadhésive, produit stratifié et procédé de production pour produit stratifié WO2020162519A1 (fr)

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JP2019021747A JP7247622B2 (ja) 2019-02-08 2019-02-08 粘着シート、剥離シート付き粘着シート、積層体及び積層体の製造方法
JP2019-021747 2019-02-08

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WO2013061938A1 (fr) * 2011-10-24 2013-05-02 王子ホールディングス株式会社 Feuille adhésive sensible à la pression, son procédé d'utilisation et stratifié
WO2014175306A1 (fr) * 2013-04-24 2014-10-30 王子ホールディングス株式会社 Feuille adhésive et stratifié, et leur procédé de production
JP2016089066A (ja) * 2014-11-06 2016-05-23 綜研化学株式会社 光硬化型粘着性組成物、粘着シートおよび積層体
WO2017033236A1 (fr) * 2015-08-21 2017-03-02 グンゼ株式会社 Composition adhésive sensible à la pression, feuille adhésive sensible à la pression, et panneau tactile et dispositif d'affichage comprenant tous deux la feuille adhésive sensible à la pression
JP2017066294A (ja) * 2015-09-30 2017-04-06 リンテック株式会社 粘着剤組成物及び粘着シート
JP2020007407A (ja) * 2018-07-04 2020-01-16 王子ホールディングス株式会社 粘着シート、剥離シート付き粘着シート、透明フィルム付き粘着シート、積層体および積層体の製造方法

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JP5967007B2 (ja) * 2013-04-24 2016-08-10 王子ホールディングス株式会社 粘着シート及びその使用方法並びに積層体
JP6307186B2 (ja) * 2017-02-22 2018-04-04 リンテック株式会社 光学用粘着シート

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013061938A1 (fr) * 2011-10-24 2013-05-02 王子ホールディングス株式会社 Feuille adhésive sensible à la pression, son procédé d'utilisation et stratifié
WO2014175306A1 (fr) * 2013-04-24 2014-10-30 王子ホールディングス株式会社 Feuille adhésive et stratifié, et leur procédé de production
JP2016089066A (ja) * 2014-11-06 2016-05-23 綜研化学株式会社 光硬化型粘着性組成物、粘着シートおよび積層体
WO2017033236A1 (fr) * 2015-08-21 2017-03-02 グンゼ株式会社 Composition adhésive sensible à la pression, feuille adhésive sensible à la pression, et panneau tactile et dispositif d'affichage comprenant tous deux la feuille adhésive sensible à la pression
JP2017066294A (ja) * 2015-09-30 2017-04-06 リンテック株式会社 粘着剤組成物及び粘着シート
JP2020007407A (ja) * 2018-07-04 2020-01-16 王子ホールディングス株式会社 粘着シート、剥離シート付き粘着シート、透明フィルム付き粘着シート、積層体および積層体の製造方法

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TWI820300B (zh) 2023-11-01

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