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WO2020009181A1 - Feuille adhésive, feuille adhésive dotée d'une feuille antiadhésive, feuille adhésive dotée d'un film transparent, stratifié et procédé de production d'un stratifié - Google Patents

Feuille adhésive, feuille adhésive dotée d'une feuille antiadhésive, feuille adhésive dotée d'un film transparent, stratifié et procédé de production d'un stratifié Download PDF

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Publication number
WO2020009181A1
WO2020009181A1 PCT/JP2019/026601 JP2019026601W WO2020009181A1 WO 2020009181 A1 WO2020009181 A1 WO 2020009181A1 JP 2019026601 W JP2019026601 W JP 2019026601W WO 2020009181 A1 WO2020009181 A1 WO 2020009181A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive sheet
adhesive layer
post
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/026601
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English (en)
Japanese (ja)
Inventor
山本　真之
貴迪 山口
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oji Holdings Corp
Original Assignee
Oji Holdings Corp
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Filing date
Publication date
Priority claimed from JP2018127338A external-priority patent/JP6769460B2/ja
Priority claimed from JP2018134386A external-priority patent/JP6724946B2/ja
Application filed by Oji Holdings Corp filed Critical Oji Holdings Corp
Publication of WO2020009181A1 publication Critical patent/WO2020009181A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—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 pressure-sensitive adhesive sheet with a transparent film, a laminate, and a method for producing a laminate.
  • an input device used in combination with a display device such as a liquid crystal display (LCD) or a display device such as a touch panel has been widely used.
  • a transparent adhesive sheet is used for bonding optical members, and a transparent adhesive sheet is also used for bonding the display device and the input device.
  • polymerization methods as described below as a method for polymerizing a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive sheet. Specifically, a two-stage process in which (1) polymerization by heat, (2) polymerization by active energy rays, (3) polymerization by heat (or active energy rays), and then polymerization by active energy rays (or heat). There are methods such as polymerization and (4) two-stage polymerization in which polymerization by active energy rays is performed after polymerization by active energy rays.
  • a pressure-sensitive adhesive sheet used for the above-mentioned applications, (3) a two-stage polymerization in which polymerization is performed by heat (or active energy rays) followed by polymerization by active energy rays (or heat).
  • a curing method may be used. Since such a pressure-sensitive adhesive sheet is formed from, for example, a pressure-sensitive adhesive composition having both thermosetting properties and active energy ray-curing properties (hereinafter, sometimes referred to as “dual-curable pressure-sensitive adhesive composition”), It has thermosetting properties and active energy ray curability.
  • temporary bonding can be performed by, for example, performing only thermal curing, and thereafter, the substrate is further cured with an active energy ray (referred to as post-curing or after-curing). Can be firmly adhered to the body.
  • Patent Literature 1 discloses a base polymer (A) containing a non-crosslinkable (meth) acrylate unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group, and lauryl acrylate (b1).
  • B containing a monomer, a cross-linking agent (C) that reacts with the base polymer (A) by heat, and a polymerization initiator (D ) And a solvent (E).
  • the pressure-sensitive adhesive sheet includes a pressure-sensitive adhesive layer obtained by semi-curing a pressure-sensitive adhesive composition containing heat.
  • Patent Literature 2 discloses a method in which a glass material is bonded as a plate material with an adhesive sheet having at least two glass plates, a glass plate and a synthetic resin plate or at least two synthetic resin plates, and at least one ultraviolet-curable adhesive layer. A method for producing a transparent laminate in which the pressure-sensitive adhesive layer is cured by ultraviolet irradiation from the side is described.
  • liquid crystal displays are also used for in-vehicle applications such as a car navigation system CID (center information display). Since the inside of a vehicle is often in a high-temperature environment, a liquid crystal display for in-vehicle use is required to have higher strict high-temperature durability than use for a smartphone or a personal computer. Therefore, the present inventors have studied to improve the high-temperature durability of a pressure-sensitive adhesive sheet having post-curability in order to solve such problems of the related art.
  • CID center information display
  • the present inventors have determined that in a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer in a semi-cured state, the post-cured pressure-sensitive adhesive layer satisfies predetermined physical properties. As a result, it has been found that the pressure-sensitive adhesive layer after post-curing can exhibit excellent high-temperature durability.
  • the present invention has the following configuration.
  • An adhesive sheet having an adhesive layer in which the adhesive composition is in a semi-cured state A pressure-sensitive adhesive sheet that satisfies the following physical properties (101) when it 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 ;
  • Probe base material stainless steel surface finish AA # 400 Polished mirror surface weight: 19.6 ⁇ 0.2 g (made of brass)
  • a load of 300 g is applied to the longitudinal end of the non-bonded area of the adhesive sheet for 30 minutes, and a distance at which the bonded area of the adhesive sheet has separated from the adherend is measured as a constant load peeling distance at 23 ° C .; (Measurement conditions (b)) A region having a width of 25 mm and a length of 75 mm among the pressure-sensitive adhesive surfaces of the pressure-sensitive adhesive sheet having a width of 25 mm and a length of 100 mm is bonded to an adherend and post-cured. In an environment of 85 ° C., the adherend is fixed horizontally so that the non-bonded area of the pressure-sensitive adhesive sheet hangs downward.
  • a load of 100 g is applied to the longitudinal end portion of the non-bonded area of the pressure-sensitive adhesive sheet for 10 minutes, and a distance at which the bonded area of the pressure-sensitive adhesive sheet is separated from the adherend is measured as a constant load peeling distance at 85 ° C.
  • the pressure-sensitive adhesive composition is a crosslinkable acrylic polymer, a crosslinker, a polyfunctional monomer having two or more reactive double bonds in a molecule, a monofunctional having one reactive double bond in a molecule.
  • a monomer and a polymerization initiator The pressure-sensitive adhesive sheet according to any one of [1] to [3], wherein the polyfunctional monomer has a bisphenol skeleton in one molecule.
  • the gel fraction of the pressure-sensitive adhesive layer in a semi-cured state is 10% by mass or more and less than 70% by mass, and The pressure-sensitive adhesive sheet according to any one of [1] to [5], wherein when the pressure-sensitive adhesive layer is post-cured, the gel fraction after post-curing is 10% by mass or more higher than the gel fraction in a semi-cured state.
  • Adhesive sheet [9] The pressure-sensitive adhesive sheet according to any one of [4] to [8], wherein the content of the polyfunctional monomer is 5 to 30 parts by mass based on 100 parts by mass of the crosslinkable acrylic polymer. [10] The pressure-sensitive adhesive sheet according to any one of [4] to [9], wherein the monofunctional monomer is an alkyl (meth) acrylate. [11] The pressure-sensitive adhesive sheet according to any one of [4] to [10], wherein the polymerization initiator initiates polymerization of the polyfunctional monomer and / or the monofunctional monomer by irradiation with active energy rays.
  • An adhesive sheet having an adhesive layer in which the adhesive composition is in a semi-cured state
  • the pressure-sensitive adhesive composition contains a crosslinkable acrylic polymer, a crosslinker, a polyfunctional monomer having two or more reactive double bonds in the molecule, and a photopolymerization initiator,
  • the acid value of the pressure-sensitive adhesive composition is 1 mgKOH / g or more
  • the adhesive according to [1] which satisfies the following physical properties (1 ′′) and (2 ′′) when the adhesive layer is post-cured by irradiating the adhesive layer with an active energy ray so that the integrated light amount becomes 3000 mJ / cm 2.
  • the gel fraction of the pressure-sensitive adhesive layer in a semi-cured state is 10% by mass or more and less than 75% by mass, and The pressure-sensitive adhesive sheet according to any one of [12] to [18], wherein when the pressure-sensitive adhesive layer is post-cured, the gel fraction after post-curing is 10% by mass or more higher than the gel fraction in a semi-cured state.
  • a pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet according to any one of [1] to [20] which is post-cured by irradiating the pressure-sensitive adhesive layer with active energy rays and post-cured, and a post-cured pressure-sensitive adhesive layer.
  • a laminate comprising an adherend on at least one surface side of the laminate.
  • a method for producing a laminate including a step of curing.
  • the high-temperature durability of the post-curing pressure-sensitive adhesive sheet can be improved.
  • FIG. 1 is a schematic diagram illustrating a cross section of a release sheet or a pressure-sensitive adhesive sheet having a substrate.
  • FIG. 2 is a diagram illustrating a method of measuring a constant load peeling distance.
  • FIG. 3 is a schematic diagram illustrating a cross section of an example of the laminate of the present invention.
  • FIG. 4 is a schematic diagram illustrating a cross section of another example of the laminate of the present invention.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
  • (meth) acrylate represents both or either acrylate and methacrylate
  • (meth) acrylic acid represents both or either acrylic acid or methacrylic acid.
  • “monomer” and “monomer” have the same meaning
  • “polymer” and “polymer” have the same meaning.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer in which the pressure-sensitive adhesive composition is in a semi-cured state.
  • the pressure-sensitive adhesive layer has a post-curing property.
  • the pressure-sensitive adhesive layer is post-cured by irradiating the pressure-sensitive adhesive layer with an active energy ray so that the integrated light amount becomes 3000 mJ / cm 2 , the following physical properties (101) are obtained. Fulfill. Physical properties (101): Probe tack value measured at 23 ° C., relative humidity 50% and the following measurement conditions is 1.0 N / 5 mm ⁇ or less.
  • the post-curing pressure-sensitive adhesive sheet can have high-temperature durability.
  • the hardness of the pressure-sensitive adhesive layer after post-curing can be increased by satisfying the condition of the physical property (101). Further, in the present invention, by satisfying the condition of the physical property (101), the high-temperature durability of the pressure-sensitive adhesive layer after post-curing can be increased.
  • the pressure-sensitive adhesive sheet according to the first aspect of the present invention satisfies the following physical properties (1) to (3) 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.
  • it is Physical properties (1): Tensile storage modulus E ′ measured at 23 ° C. and frequency 1 Hz is 5.0 ⁇ 10 6 Pa or more, and tensile storage modulus E ′ measured at 85 ° C. and frequency 1 Hz is 3. 0 ⁇ 10 5 Pa or more.
  • Physical property (2) The probe tack value measured at 23 ° C. and the following measurement conditions is 1.0 N / 5 mm ⁇ or less.
  • the high-temperature durability of the pressure-sensitive adhesive sheet having post-curability and workability can be improved.
  • the hardness of the pressure-sensitive adhesive layer after post-curing can be increased by satisfying the conditions of the above physical properties (1) and (2). Thereby, the stickiness (tackiness) of the end face of the pressure-sensitive adhesive layer after the post-curing can be suppressed low, and the workability of the pressure-sensitive adhesive layer can be improved.
  • the high-temperature durability of the pressure-sensitive adhesive layer after post-curing can be increased.
  • the triacetyl cellulose film on one side of the pressure-sensitive adhesive sheet, a polycarbonate plate is laminated on the other side, and after post-curing at 105 ° C. under a dry environment for 240 hours. Also, when the pressure-sensitive adhesive sheet is prevented from floating or peeling off from the polycarbonate plate, it can be determined that the high-temperature durability is excellent.
  • the stickiness of the end face after post-curing is suppressed, and for example, it is possible to prevent the pressure-sensitive adhesive layer from being attached to the punching blade at the time of punching and the pressure-sensitive adhesive layer from being deformed.
  • the pressure-sensitive adhesive sheet of the present invention is subjected to a punching process to a desired size after post-curing and then cut for the purpose of trimming the end surface, deformation and protrusion of the pressure-sensitive adhesive layer, peeling and the like do not occur, and the workability is also improved. Are better.
  • a pressure-sensitive adhesive composition is prepared by adding a crosslinkable acrylic polymer, a crosslinker, It is preferable to comprise a polyfunctional monomer having two or more heavy bonds, a monofunctional monomer having one reactive double bond in the molecule, and a polymerization initiator. Further, the polyfunctional monomer more preferably has a bisphenol skeleton in one molecule. When the pressure-sensitive adhesive composition contains a polyfunctional monomer having a bisphenol skeleton in one molecule, the hardness of the pressure-sensitive adhesive layer after post-curing can be increased.
  • the stickiness (tackiness) of the end face of the pressure-sensitive adhesive layer after the post-curing can be suppressed low, and the workability of the pressure-sensitive adhesive layer can be improved.
  • the pressure-sensitive adhesive layer after post-curing satisfies the above physical properties (1) to (3), the pressure-sensitive adhesive layer in a semi-cured state can be kept low in tackiness (tackiness).
  • the wettability to the substrate can be increased. That is, the pressure-sensitive adhesive sheet of the present invention has a property that the adhesiveness to the base material is enhanced in the semi-cured state and the hardness becomes high after the post-curing, so that the end face can be easily processed.
  • the elongation at break of the pressure-sensitive adhesive layer after post-curing in a tensile test at a tensile speed of 10 mm / min is preferably less than 800%, more preferably less than 600%.
  • the breaking elongation is measured according to JIS K 7161-1.
  • the tensile speed is set to 10 mm / min, and the measurement is performed at 23 ° C. and a relative humidity of 50%.
  • a pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) having a thickness of 25 ⁇ m, a width of 60 mm, and a length of 200 mm, which 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, is used. This is pulled so that the distance between the chucks becomes 30 mm, and the elongation at break of the sample is defined as the elongation at break.
  • a measuring instrument for example, an autograph AGS-X manufactured by Shimadzu Corporation can be used.
  • the pressure-sensitive adhesive sheet according to the second aspect of the present invention is 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 a crosslinkable acrylic polymer, a crosslinker, It contains a polyfunctional monomer having two or more reactive double bonds and a photopolymerization initiator.
  • the acid value of the pressure-sensitive adhesive composition is 1 mgKOH / g or more. Is an adhesive sheet that satisfies the following physical properties (1 ′′) and (2 ′′) when it is post-cured by irradiating so as to give 3000 mJ / cm 2 .
  • Measurement condition of probe tack value Measuring equipment: NS probe tack tester (Nichiban Co., Ltd.) Probe diameter: 5mm ⁇ Probe base material: stainless steel surface finish AA # 400 Polished mirror surface weight: 19.6 ⁇ 0.2 g (made of brass) Probe moving speed: 1.0 cm / sec Duel time: 1 second Physical property (2 ′′): The constant load peel distance at 85 ° C. and 85% relative humidity measured under the following measurement conditions is 100 mm or less.
  • a region having a width of 25 mm and a length of 75 mm among the pressure-sensitive adhesive surfaces of the pressure-sensitive adhesive sheet having a width of 25 mm and a length of 100 mm is bonded to an adherend and post-cured.
  • the adherend In an environment of 85 ° C. and a relative humidity of 85%, the adherend is fixed horizontally so that the non-bonding area of the pressure-sensitive adhesive sheet hangs downward.
  • a load of 100 g was applied to the lengthwise end of the non-bonded area of the pressure-sensitive adhesive sheet for 5 minutes.
  • the distance at which the bonded area of the pressure-sensitive adhesive sheet was separated from the adherend was 85 ° C. and a constant load peeling at 85% relative humidity. Measure as distance.
  • the high temperature and high humidity durability can be improved.
  • Such effects of the present invention can be obtained by setting the acid value of the pressure-sensitive adhesive composition used to 1 mgKOH / g or more and satisfying the conditions of the above physical properties (1 '') and (2 ''). It is considered that by setting the acid value of the pressure-sensitive adhesive composition in the above range, the uniformity of the crosslinked structure formed in the acrylic polymer is increased, and the durability of the pressure-sensitive adhesive sheet is thereby increased. Further, it is considered that by setting the acid value of the pressure-sensitive adhesive composition in the above range, the adhesiveness between the pressure-sensitive adhesive sheet and the adherend is increased, whereby the durability of the pressure-sensitive adhesive sheet is increased.
  • the high-temperature high-humidity durability can be evaluated by the following method. First, a triacetyl cellulose film is bonded to one surface of the adhesive sheet and a polycarbonate plate is bonded to the other surface, and the active energy ray is irradiated from the surface on the triacetyl cellulose film side so that the integrated light amount becomes 3000 mJ / cm 2. Then, the pressure-sensitive adhesive layer is post-cured. Thereafter, the pressure-sensitive adhesive sheet is allowed to stand for 240 hours in an environment of 85 ° C. and a relative humidity of 85%.
  • the pressure-sensitive adhesive sheet is observed, and when it is suppressed from floating or peeling off from the polycarbonate plate and / or the triacetyl cellulose film, it can be determined that the high-temperature and high-humidity durability is excellent.
  • the stickiness of the end face after post-curing is suppressed, and for example, it is possible to prevent the pressure-sensitive adhesive layer from being attached to the punching blade at the time of punching and the pressure-sensitive adhesive layer from being deformed.
  • the pressure-sensitive adhesive sheet of the present invention is subjected to a punching process to a desired size after post-curing and then cut for the purpose of trimming the end surface, deformation and protrusion of the pressure-sensitive adhesive layer, peeling and the like do not occur, and the workability is also improved. 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 of only 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 double-sided pressure-sensitive adhesive sheet a single-layer pressure-sensitive adhesive sheet composed of a pressure-sensitive adhesive layer, a multilayer pressure-sensitive adhesive sheet in which a plurality of pressure-sensitive adhesive layers are laminated, a multilayer pressure-sensitive adhesive in which another pressure-sensitive adhesive layer is laminated between the pressure-sensitive adhesive layers Sheet, a multi-layer pressure-sensitive adhesive sheet in which a support is laminated between pressure-sensitive adhesive layers, a multi-layer pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is laminated on one side of the support and another pressure-sensitive adhesive layer is laminated on the other side Is mentioned.
  • a transparent support is preferably used as the support.
  • a general film used in the optical field as well as the transparent substrate can be used.
  • Such a double-sided pressure-sensitive adhesive sheet has excellent transparency as a whole pressure-sensitive adhesive sheet, and thus can be suitably used for bonding optical members.
  • the pressure-sensitive adhesive layer 11 may be provided with a transparent substrate 12a on one side thereof. In this case, it is preferable that the other surface of the pressure-sensitive adhesive layer 11 is covered with the release sheet 12b.
  • the release sheet 12b may be peeled off and bonded so that the adhesive layer 11 adheres to a desired adherend, and then post-cured by irradiating active energy rays or the like. 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, and the like can be used.
  • an easy-adhesion layer may be provided on the pressure-sensitive 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 opposite side of the transparent substrate from the adhesive layer.
  • the present invention may relate to a pressure-sensitive adhesive sheet with a release sheet provided with release sheets on both surfaces of the pressure-sensitive adhesive sheet.
  • release sheets are provided on both surfaces of the pressure-sensitive adhesive sheet of the present invention, it is preferable to have release sheets 12a and 12b on both surfaces of the pressure-sensitive adhesive layer 11, as shown in FIG.
  • a release laminate sheet having a release sheet substrate and a release agent layer provided on one surface of the release sheet substrate, or a polyolefin film such as a polyethylene film or a polypropylene film as a low-polar substrate Is mentioned. Papers and polymer films are used as the release sheet substrate in the release laminate sheet.
  • a release agent constituting the release agent layer for example, a general-purpose addition-type or condensation-type silicone release agent or a compound having a long-chain alkyl group is used. In particular, an addition type silicone release agent having high reactivity is preferably used.
  • the silicone release agent examples include BY24-4527 and SD-7220 manufactured by Dow Corning Toray Silicone Co., Ltd., and KS-3600, KS-774, X62-2600 manufactured by Shin-Etsu Chemical Co., Ltd. Is mentioned.
  • the silicone-based release agent may contain a silicone resin that is an organosilicon compound having SiO 2 units and (CH 3 ) 3 SiO 1/2 units or CH 2 CHCH (CH 3 ) SiO 1/2 units. preferable.
  • Specific examples of the silicone resin include BY24-843, SD-7292 and SHR-1404 manufactured by Dow Corning Toray Silicone Co., Ltd., and KS-3800 and 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 that is a release-treated polyethylene terephthalate film manufactured by Teijin Dupont Film Co., Ltd. and a light separator film that is a release-treated polyethylene terephthalate film manufactured by Teijin Dupont Film Co., Ltd. may be mentioned. it can.
  • the pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet
  • the releasability from one side is different from the releasability from the other side, it becomes easy to peel off only the release sheet having higher releasability first.
  • the releasability of the release sheet 12a and the release sheet 12b may be adjusted according to the bonding method and the bonding order.
  • the present invention may also relate to an adhesive sheet with a transparent film provided with a transparent film on at least one surface of the adhesive sheet.
  • the transparent film is preferably at least one selected from a polyethylene terephthalate film, an acrylic film, a polycarbonate film, a triacetyl cellulose film, and a cycloolefin polymer film.
  • the pressure-sensitive adhesive sheet with a transparent film may be a sheet in which a transparent film / pressure-sensitive adhesive sheet / release sheet is laminated in this order.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer in which the pressure-sensitive adhesive composition is in a semi-cured state, and the pressure-sensitive adhesive layer has post-curability.
  • the pressure-sensitive adhesive layer before irradiation or heating is reduced by half. Let it be in the 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) is applied from the optical transparent PET separator side. Or a metal halide lamp) so that the integrated light amount becomes 3000 mJ / cm 2 .
  • the gel fraction in the semi-cured state of the pressure-sensitive adhesive layer is preferably from 10% by mass to less than 75% by mass, more preferably from 10% by mass to less than 70% by mass, and more preferably from 12% by mass to 70% by mass. It is more preferably less than 15% by mass, more preferably 15 to 70% by mass, and particularly preferably 15 to 65% by mass.
  • the gel fraction of the pressure-sensitive adhesive layer after post-curing is preferably from 60 to 100% by mass, more preferably from 65 to 100% by mass, further preferably from 70 to 100% by mass.
  • the “semi-cured state” is preferably a state after thermal curing. Then, it is preferable to perform “post-curing” by irradiating with active energy rays thereafter. That is, the “semi-cured state” is a state after thermal curing, and is preferably a soft pressure-sensitive adhesive layer before irradiation with active energy rays.
  • the “post-curing” is preferably a step of completely curing the pressure-sensitive adhesive layer by heat or active energy rays, and more preferably a step of completely curing the pressure-sensitive adhesive layer by 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 heat-curing 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, the pressure-sensitive adhesive layer satisfies the following physical properties (1) to (3). That is, the pressure-sensitive adhesive layer having a gel fraction of 65 to 100% by mass when irradiated with active energy rays satisfies the following physical properties (1) to (3).
  • the tensile storage modulus E ′ measured at 23 ° C. and a frequency of 1 Hz is preferably 1.0 ⁇ 10 7 Pa or more, and is 1.5 ⁇ 10 7 Pa or more. Is more preferable.
  • the upper limit of the tensile storage modulus E ′ measured at 23 ° C. and a frequency of 1 Hz is not particularly limited, and can be, for example, 1.0 ⁇ 10 9 Pa or less.
  • the upper limit of the tensile storage modulus E ′ measured at 85 ° C. and a frequency of 1 Hz is not particularly limited, and can be, for example, 1.0 ⁇ 10 8 Pa or less.
  • Physical property (2) The probe tack value measured at 23 ° C. and the following measurement conditions is 1.0 N / 5 mm ⁇ or less. (Measurement condition of probe tack value) Measuring equipment: NS probe tack tester (Nichiban Co., Ltd.) Probe diameter: 5mm ⁇ Probe base material: stainless steel surface finish AA # 400 Polished mirror surface weight: 19.6 ⁇ 0.2 g (made of brass) Probe moving speed: 1.0 cm / sec Duel time: 1 sec
  • the probe tack value of the pressure-sensitive adhesive sheet measured at 23 ° C. and the above measurement conditions is more preferably 0.8 N / 5 mm ⁇ or less, and further preferably 0.5 N / 5 mm ⁇ or less.
  • the lower limit of the probe tack value of the pressure-sensitive adhesive sheet measured at 23 ° C. and the above measurement conditions is not particularly limited, but may be, for example, 0.01 N / 5 mm ⁇ or more.
  • the pressure-sensitive adhesive sheet satisfies the following physical properties (3).
  • Physical property (3) The constant load peel distance at 23 ° C. measured under the following measurement conditions (a) is 20 mm or less, and the constant load peel distance at 85 ° C. measured under the following measurement conditions (b) is 100 mm or less. . (Measurement conditions (a)) A region having a width of 25 mm and a length of 75 mm among the pressure-sensitive adhesive surfaces of the pressure-sensitive adhesive sheet having a width of 25 mm and a length of 100 mm is bonded to an adherend and post-cured.
  • the adherend In an environment of 23 ° C., the adherend is fixed in the horizontal direction such that the non-bonded area of the adhesive sheet hangs downward.
  • a load of 300 g is applied to the lengthwise end of the non-bonding area of the pressure-sensitive adhesive sheet for 30 minutes, and the distance at which the bonding area of the pressure-sensitive adhesive sheet peeled from the adherend is measured as a constant load peeling distance at 23 ° C. (Measurement conditions (b))
  • a region having a width of 25 mm and a length of 75 mm among the pressure-sensitive adhesive surfaces of the pressure-sensitive adhesive sheet having a width of 25 mm and a length of 100 mm is bonded to an adherend and post-cured.
  • the adherend In an environment of 85 ° C., the adherend is fixed horizontally so that the non-bonded area of the pressure-sensitive adhesive sheet hangs downward. A load of 100 g is applied to the longitudinal end portion of the non-bonded area of the pressure-sensitive adhesive sheet for 10 minutes, and a distance at which the bonded area of the pressure-sensitive adhesive sheet is separated from the adherend is measured as a constant load peeling distance at 85 ° C.
  • a test piece for measurement is prepared by the following method.
  • a triacetylcellulose film (Fujitack TD60UL, thickness 60 ⁇ m, manufactured by FUJIFILM Corporation) is attached to one surface of the pressure-sensitive adhesive sheet using a hand roller to prepare a laminated film.
  • This laminated film is cut into a size of 25 mm in width and 100 mm in length. Then, the 25 mm wide and 75 mm long area of the other 25 mm wide and 100 mm long adhesive surface of the pressure-sensitive adhesive sheet is adhered (hardware).
  • a polycarbonate plate with a coat layer Attached to the hard coat surface side of Mitsubishi Gas Chemical Company, Iupilon MR58 1 mm thick) using a 2 kg pressure roller.
  • the substrate is kept in an autoclave under conditions of 40 ° C. and 5 atm for 30 minutes to adhere to the adherend.
  • Two such test pieces are prepared.
  • ultraviolet rays are irradiated from the triacetyl cellulose film side of the test specimen for measurement so that the integrated light amount becomes 3000 mJ / cm 2, and the temperature is 23 ° C. and the relative humidity is 50%. For 24 hours in the environment described above.
  • one set of test pieces was placed in a 23 ° C. environment, as shown in FIG. A 300 g weight 34 is hung on the part, and a load of 300 g is applied in a direction at 90 ° to the plane of the adherend 32, and left in this state for 30 minutes. During that time, the length L (constant load peeling distance) of the portion where the laminated film was peeled off is measured (constant load peeling distance under measurement condition (a)). The other set of test pieces was left for 30 minutes in an environment of 85 ° C., and then, in an environment of 85 ° C., in the length direction of the non-bonded area (width 25 mm, length 25 mm) of the laminated film as shown in FIG.
  • a 100 g weight 34 is hung on the end, a load of 100 g is applied in a direction at 90 ° to the plane of the adherend 32, and the load is left for 10 minutes. During that time, the length L (constant load peeling distance) of the portion where the laminated film was peeled off is measured (constant load peeling distance under measurement condition (b)).
  • the constant load peeling distance at 23 ° C. measured under the measurement condition (a) is preferably 10 mm or less, more preferably 5 mm or less.
  • the constant load peeling distance at 23 ° C. measured under the measurement condition (a) may be 0 mm.
  • the constant load peeling distance at 85 ° C. measured under the measurement condition (b) is preferably 80 mm or less, and more preferably 70 mm or less.
  • the constant load peeling distance at 85 ° C. measured under the measurement condition (b) may be 0 mm.
  • the pressure-sensitive adhesive sheet In a state before the pressure-sensitive adhesive layer is post-cured, that is, when the pressure-sensitive adhesive layer is in a semi-cured state, the pressure-sensitive adhesive sheet preferably satisfies the following physical properties (4).
  • the shear storage modulus G ′ measured at 23 ° C. and a frequency of 1 Hz is more preferably 6.5 ⁇ 10 5 Pa or less.
  • the lower limit of the shear storage modulus G ′ measured at 23 ° C. and a frequency of 1 Hz is not particularly limited, and can be, for example, 1.0 ⁇ 10 3 Pa or more.
  • the shear storage modulus G ′ measured at 85 ° C. and a frequency of 1 Hz is more preferably 8.0 ⁇ 10 4 Pa or less.
  • the lower limit of the shear storage modulus G ′ measured at 85 ° C. and a frequency of 1 Hz is not particularly limited, and may be, for example, 1.0 ⁇ 10 3 Pa or more.
  • the probe tack value measured at 23 ° C. and the above measurement conditions is more preferably 0.8 N / 5 mm ⁇ or more, and more preferably 1.0 N / 5 mm ⁇ or more. preferable.
  • the probe tack value measured at 23 ° C. and the above measurement conditions is preferably 20.0 N / 5 mm ⁇ or less, more preferably 15.0 N / 5 mm ⁇ or less. preferable.
  • the pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive layer satisfies the following physical properties (1 ′′) and (2 ′′). That is, the pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer post-cured by irradiating with an active energy ray so that the integrated light amount becomes 3000 mJ / cm 2 satisfies the following physical properties (1 ′′) and (2 ′′).
  • the probe tack value of the pressure-sensitive adhesive sheet measured at 23 ° C. and the above measurement conditions is more preferably 0.8 N / 5 mm ⁇ or less, and further preferably 0.5 N / 5 mm ⁇ or less.
  • the lower limit of the probe tack value of the pressure-sensitive adhesive sheet measured at 23 ° C. and the above measurement conditions is not particularly limited, but may be, for example, 0.01 N / 5 mm ⁇ or more.
  • the pressure-sensitive adhesive sheet When the pressure-sensitive adhesive layer is post-cured, the pressure-sensitive adhesive sheet satisfies the following physical properties (2 ′′).
  • the constant load peel distance at 85 ° C. and 85% relative humidity measured under the following measurement conditions is 100 mm or less: (Measurement condition) A region having a width of 25 mm and a length of 75 mm among the pressure-sensitive adhesive surfaces of the pressure-sensitive adhesive sheet having a width of 25 mm and a length of 100 mm is bonded to an adherend and post-cured. In an environment of 85 ° C. and a relative humidity of 85%, the adherend is fixed horizontally so that the non-bonding area of the pressure-sensitive adhesive sheet hangs downward.
  • a load of 100 g was applied to the lengthwise end of the non-bonded area of the pressure-sensitive adhesive sheet for 5 minutes. During this time, the distance at which the bonded area of the pressure-sensitive adhesive sheet was separated from the adherend was 85 ° C. and a constant load peeling at 85% relative humidity. Measure as distance.
  • a test piece for measurement is prepared by the following method.
  • a triacetylcellulose film (Fujitack TD60UL, thickness 60 ⁇ m, manufactured by FUJIFILM Corporation) is attached to one surface of the pressure-sensitive adhesive sheet using a hand roller to prepare a laminated film.
  • This laminated film is cut into a size of 25 mm in width and 100 mm in length. Then, the 25 mm wide and 75 mm long area of the other 25 mm wide and 100 mm long adhesive surface of the pressure-sensitive adhesive sheet is adhered (hardware).
  • a polycarbonate plate with a coat layer Attached to the hard coat surface side of Mitsubishi Gas Chemical Company, Iupilon MR58 1 mm thick) using a 2 kg pressure roller.
  • the substrate is kept in an autoclave under conditions of 40 ° C. and 5 atm for 30 minutes to adhere to the adherend.
  • ultraviolet rays are irradiated from the triacetyl cellulose film side of the test piece for measurement so that the integrated light amount becomes 3000 mJ / cm 2 .
  • a non-bonding area of the laminated film (width 25 mm, length 25 mm) as shown in FIG. 2 under an environment of 85 ° C. and a relative humidity of 85%.
  • a weight 34 of 100 g is hung at the end in the longitudinal direction, a load of 100 g is applied in a direction at 90 ° to the plane of the adherend 32, and the load is left for 5 minutes in that state.
  • the length L constant load peeling distance
  • the constant load peel distance at 85 ° C. and a relative humidity of 85% measured under the above measurement conditions may be 100 mm or less, preferably 80 mm or less, more preferably 70 mm or less, and more preferably 50 mm or less. Is more preferable, and particularly preferably 30 mm or less.
  • the constant load peeling distance at 85 ° C. and a relative humidity of 85% measured under the above measurement conditions may be 0 mm.
  • the elongation at break in a tensile test measurement at a tensile speed of 10 mm / min of the post-cured adhesive layer is as follows: It is preferably less than 600%, more preferably less than 500%, and even more preferably less than 480%.
  • the breaking elongation is measured according to JIS K 7161-1.
  • the tensile speed is set to 10 mm / min, and the measurement is performed at 23 ° C. and a relative humidity of 50%.
  • a pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) having a thickness of 25 ⁇ m, a width of 60 mm, and a length of 200 mm, which 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, is used. This is pulled so that the distance between the chucks becomes 30 mm, and the elongation at break of the sample is defined as the elongation at break.
  • a measuring instrument for example, an autograph AGS-X manufactured by Shimadzu Corporation can be used.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately set according to 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 is within the above range, the pressure-sensitive adhesive can be prevented from sticking out and sticking, so that workability can be improved. Further, by setting the thickness of the pressure-sensitive adhesive layer within the above range, the production of the double-sided pressure-sensitive adhesive sheet becomes easy.
  • the above-mentioned pressure-sensitive adhesive layer is a pressure-sensitive adhesive composition in a semi-cured state.
  • the pressure-sensitive adhesive composition used in the present invention is a dual-curable pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition comprises a crosslinkable acrylic polymer, a crosslinker, a polyfunctional monomer having two or more reactive double bonds in the molecule, and one reactive double bond in the molecule. It is preferable to include a monofunctional monomer having one and a polymerization initiator. In the first embodiment, the polyfunctional monomer preferably has a bisphenol skeleton in one molecule.
  • the pressure-sensitive adhesive composition contains a crosslinkable acrylic polymer, a crosslinker, a polyfunctional monomer having two or more reactive double bonds in the molecule, and a photopolymerization initiator.
  • the acid value of the pressure-sensitive adhesive composition may be 1 mgKOH / g or more, preferably 2 mgKOH / g or more, and more preferably 3 mgKOH / g or more.
  • the acid value of the pressure-sensitive adhesive composition is preferably 200 mgKOH / g or less.
  • the crosslinkable acrylic polymer contains an acidic component.
  • the acidic component of the crosslinkable acrylic polymer refers to a carboxyl group or a component derived from a carboxyl group, or a sulfo group or a component derived from a sulfo group.
  • the acidic component is preferably a carboxyl group or a component derived from the carboxyl group.
  • the acid value of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is preferably within the above range.
  • the crosslinkable acrylic polymer is not particularly limited as long as it has an acrylic monomer unit.
  • the crosslinkable acrylic polymer preferably has transparency to such an extent that the visibility of the display device is not reduced.
  • the "unit” is a repeating unit (monomer unit) constituting the polymer.
  • the non-crosslinkable (meth) acrylate unit (a1) is a repeating unit derived from an alkyl (meth) acrylate.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylate.
  • Isobutyl acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate, (meth) N-dodecyl acrylate, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, ) Ethoxyethyl acrylate, cyclohexyl (meth) acrylate include benzyl (me
  • alkyl (meth) acrylates at least one selected from methyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate is preferred because of its increased tackiness. preferable.
  • the crosslinkable functional group of the crosslinkable acrylic polymer is preferably one or more selected from carboxy, hydroxy, amino, amide, glycidyl and isocyanate groups, It is more preferable that one or more kinds selected from a carboxy group, a hydroxy group, an amino group and a glycidyl group are used.
  • the acrylic monomer unit (a2) having a crosslinkable functional group is preferably a carboxy group-containing monomer unit, a hydroxy group-containing monomer unit, an amino group-containing monomer unit, or a glycidyl group-containing monomer unit.
  • the carboxy group-containing monomer unit include acrylic acid and methacrylic acid.
  • the hydroxy group-containing monomer unit is a repeating unit derived from the hydroxy group-containing monomer.
  • the hydroxy group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; (Meth) acrylic acid [(mono, di or poly) alkylene glycol] such as (meth) acrylic acid mono (diethylene glycol), and (meth) acrylic acid lactone such as (meth) acrylic acid monocaprolactone.
  • amino group-containing monomer unit examples include a repeating unit derived from an amino group-containing monomer such as (meth) acrylamide and allylamine.
  • glycidyl group-containing monomer unit examples include a repeating unit derived from a glycidyl group-containing monomer such as glycidyl (meth) acrylate.
  • the content of the acrylic monomer unit (a2) having a crosslinkable functional group in the crosslinkable acrylic polymer is preferably from 0.01 to 40% by mass, more preferably from 0.5 to 35% by mass.
  • the content of the acrylic monomer unit (a2) having a crosslinkable functional group is at least the lower limit of the above range, the polymer has sufficient crosslinkability required to maintain a semi-cured state, If it is less than or equal to the upper limit of, the necessary tackiness is easily maintained.
  • the content of the carboxy group-containing monomer unit in the crosslinkable acrylic polymer is preferably 1% by mass or less based on the total mass of the crosslinkable acrylic polymer. It may be 0% by mass.
  • the carboxy group-containing monomer unit include acrylic acid and methacrylic acid.
  • the crosslinkable functional group of the crosslinkable acrylic polymer can be an acid component.
  • the crosslinkable functional group of the crosslinkable acrylic polymer is preferably a carboxyl group or a group derived from a carboxyl group, or a group derived from a sulfo group or a sulfo group, and particularly preferably a carboxy group.
  • the acrylic monomer unit (a2) having a crosslinkable functional group is preferably a carboxy group-containing monomer unit.
  • the carboxy group-containing monomer unit include acrylic acid and methacrylic acid.
  • the crosslinkable functional group of the crosslinkable acrylic polymer may have a functional group other than the carboxy group.
  • Other functional groups include a hydroxy group, an amino group, an amide group, a glycidyl group or an isocyanate group.
  • the crosslinkable acrylic polymer contains units derived from an alkoxyalkyl group-containing (meth) acrylate, units derived from a hydroxy group-containing (meth) acrylate, and units derived from methyl (meth) acrylate. You may.
  • alkoxyalkyl (meth) acrylate is alkoxyalkyl (meth) acrylate.
  • the alkoxyalkyl (meth) acrylate for example, an alkoxyalkyl (meth) acrylate in which the alkoxy group has 1 to 12 carbon atoms and the alkylene group bonded to the alkoxy group has 1 to 18 carbon atoms is preferable.
  • the alkoxy group preferably has 1 to 8 carbon atoms, more preferably has 1 to 4 carbon atoms, and particularly preferably has 1 or 2 carbon atoms.
  • the alkylene group bonded to the alkoxy group preferably has 1 to 12 carbon atoms, more preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 to 3. preferable.
  • alkoxyalkyl (meth) acrylates examples include 2-methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxymethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, Examples thereof include 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
  • 2-methoxyethyl (meth) acrylate is particularly preferred.
  • the content of the unit derived from the alkoxyalkyl group-containing (meth) acrylate is based on the total mass of the crosslinkable acrylic polymer. On the other hand, it is preferably at least 50% by mass, more preferably at least 55% by mass, even more preferably at least 60% by mass.
  • the content of the unit derived from the alkoxyalkyl group-containing (meth) acrylate is preferably 90% by mass or less based on the total mass of the crosslinkable acrylic polymer.
  • the pressure-sensitive adhesive layer in a semi-cured state can easily adhere to the base material, while the post-cured pressure-sensitive adhesive
  • the agent layer has a high hardness, and the high-temperature durability and workability can be further improved.
  • Examples of the hydroxy group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth).
  • Examples include acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, and polyalkylene glycol mono (meth) acrylate.
  • at least one selected from 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate is preferably used.
  • the content of the unit derived from the hydroxy group-containing (meth) acrylate is based on the total mass of the crosslinkable acrylic polymer. , Preferably at least 5% by mass, more preferably at least 7% by mass.
  • the content of the unit derived from the hydroxy group-containing (meth) acrylate is preferably 35% by mass or less, more preferably 30% by mass or less, based on the total mass of the crosslinkable acrylic polymer. .
  • the crosslinkable acrylic polymer may contain a unit derived from methyl (meth) acrylate.
  • the content of the unit derived from methyl (meth) acrylate is preferably at least 5% by mass, more preferably at least 7% by mass, based on the total mass of the crosslinkable acrylic polymer.
  • the content of the unit derived from methyl (meth) acrylate is preferably 35% by mass or less, more preferably 30% by mass or less, based on the total mass of the crosslinkable acrylic polymer.
  • the crosslinkable acrylic polymer may further include a unit derived from a nitrogen-containing monomer.
  • the nitrogen-containing monomer is a monomer containing a nitrogen element in one molecule.
  • Examples of the nitrogen-containing monomer include dimethylacrylamide, diethylacrylamide, acryloylmorpholine, hydroxyethylacrylamide, methylolacrylamide, methoxymethylacrylamide, ethoxymethylacrylamide, dimethylaminoethylacrylamide, N-vinylcaprolactam, and N-vinyl-2- Examples thereof include pyrrolidone, dimethylaminoethyl (meth) acrylate, and N-vinylformamide.
  • the nitrogen-containing monomer is preferably at least one selected from an acrylamide derivative, an amino group-containing monomer, and a nitrogen-containing heterocycle-containing monomer, and more preferably an acrylamide derivative.
  • the acrylamide derivative is more preferably at least one selected from dimethylacrylamide, diethylacrylamide and acryloylmorpholine, and particularly preferably dimethylacrylamide.
  • the crosslinkable acrylic polymer by including the unit derived from the nitrogen-containing monomer as described above, the semi-cured pressure-sensitive adhesive layer, while easily adhere to the substrate, after post-curing
  • the pressure-sensitive adhesive layer has high hardness, and can further improve high-temperature durability and workability.
  • the content of the unit derived from the nitrogen-containing monomer is 1% by mass or more based on the total mass of the crosslinkable acrylic polymer. Preferably, it is 3% by mass or more.
  • the content of the unit derived from the nitrogen-containing monomer is preferably 20% by mass or less based on the total mass of the crosslinkable acrylic polymer.
  • the crosslinkable acrylic polymer may have another monomer unit, if necessary.
  • the other monomer may be any copolymerizable with the above-mentioned acrylic monomer, and examples thereof include (meth) acrylonitrile, vinyl acetate, styrene, vinyl chloride, vinyl pyrrolidone, and vinyl pyridine.
  • the content of the other monomer units in the crosslinkable acrylic polymer is preferably 20% by mass or less, more preferably 15% by mass or less.
  • the weight average molecular weight of the crosslinkable acrylic polymer is preferably from 100,000 to 2,000,000, more preferably from 200,000 to 1.5,000,000. When the weight average molecular weight is within the above range, the semi-cured state of the pressure-sensitive adhesive sheet is easily maintained, the hardness after post-curing is easily obtained, and the workability is excellent.
  • the weight average molecular weight of the crosslinkable acrylic polymer is a value before crosslinking with a crosslinking agent.
  • the weight average molecular weight is a value measured by size exclusion chromatography (SEC) and determined based on polystyrene.
  • SEC size exclusion chromatography
  • As the crosslinkable acrylic polymer a commercially available product may be used, or a product synthesized by a known method may be used.
  • the pressure-sensitive adhesive composition contains a crosslinking agent.
  • the crosslinking agent can be appropriately selected in consideration of the reactivity with the crosslinking functional group of the crosslinking acrylic polymer.
  • it can be selected from known crosslinking agents such as isocyanate compounds, epoxy compounds, oxazoline compounds, aziridine compounds, metal chelate compounds, and butylated melamine compounds.
  • it is preferable to use an isocyanate compound or an epoxy compound because the hydroxy group-containing (meth) acrylate can be easily crosslinked.
  • the crosslinking agent is preferably at least one selected from a bifunctional or higher functional epoxy compound and a bifunctional or higher functional isocyanate compound, and more preferably a bifunctional or higher functional isocyanate compound.
  • the crosslinking agent is preferably a bifunctional or higher epoxy compound.
  • Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
  • Examples of commercially available products include tolylene diisocyanate compounds (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) and xylylene diisocyanate compounds (manufactured by Mitsui Chemicals, Inc., Takenate D-110N).
  • 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, and 1,6-hexanediol diglycidyl ether.
  • Glycidyl ether tetraglycidyl xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. No.
  • the content of the cross-linking agent in the pressure-sensitive adhesive composition is appropriately selected depending on 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. 0.01 to 3 parts by mass, more preferably 0.1 to 3 parts by mass.
  • the content of the cross-linking agent within the above range, the adhesion to the base material can be improved, and the processability can be further improved.
  • the crosslinking agent 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 in the above range.
  • the pressure-sensitive adhesive composition contains a polyfunctional monomer having two or more reactive double bonds in a molecule, and the polyfunctional monomer has a bisphenol skeleton in one molecule.
  • the polyfunctional monomer has a bisphenol skeleton in one molecule.
  • the hardness of the pressure-sensitive adhesive layer after post-curing can be more effectively increased, and the processability of the pressure-sensitive adhesive sheet can be improved.
  • Such polyfunctional monomers include, for example, dialactate of bisphenol A diglycidyl ether, diacrylate of propoxylated bisphenol A, and dialactate of bisphenol F diglycidyl ether.
  • the polyfunctional monomer has two or more reactive double bonds, and among them, the polyfunctional monomer preferably has two or more reactive double bonds and less than five. It is more preferable to have at least four.
  • polyfunctional monomer examples include Toagosei Co., Ltd., bifunctional monomer M211B (bisphenol A @ ethylene oxide modified diacrylate), Toagosei Co., Ltd., bifunctional monomer M08 (bisphenol F @ ethyleneoxide modified diacrylate), Shinnakamura Chemical Co., Ltd. And a bifunctional monomer A-BPP-3 (propoxylated bisphenol A diacrylate).
  • the content of the polyfunctional monomer is preferably 5 to 30 parts by mass, more preferably 10 to 30 parts by mass, based on 100 parts by mass of the crosslinkable acrylic polymer.
  • One of the above polyfunctional monomers may be used alone, or two or more may be used in combination. When two or more are used in combination, the total mass is preferably within the above range.
  • the pressure-sensitive adhesive composition contains a polyfunctional monomer having two or more reactive double bonds in a molecule.
  • polyfunctional monomer examples include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 1,3-butylene glycol (meth) acrylate.
  • the polyfunctional monomer has two or more reactive double bonds, and among them, the polyfunctional monomer preferably has two or more reactive double bonds and less than five. It is more preferable to have at least four.
  • polyfunctional monomer examples include trifunctional monomers M310 (trimethylolpropane PO modified triacrylate) and trifunctional monomers M321 (trimethylolpropane propylene oxide modified triacrylate, bifunctional monomers M211B manufactured by Toagosei Co., Ltd.) Bisphenol A (EO-modified diacrylate) and the like.
  • the polyfunctional monomer may have a bisphenol skeleton in one molecule.
  • a polyfunctional monomer having a bisphenol skeleton in one molecule the hardness of the pressure-sensitive adhesive layer after post-curing can be more effectively increased, and the processability of the pressure-sensitive adhesive sheet is easily improved.
  • Such polyfunctional monomers include, for example, dialactate of bisphenol A diglycidyl ether, diacrylate of propoxylated bisphenol A, and dialactate of bisphenol F diglycidyl ether.
  • the glass transition temperature (Tg) when the polyfunctional monomer is a homopolymer is preferably 30 ° C. or higher, 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 less.
  • the glass transition temperature in this specification is a glass transition temperature when a polyfunctional monomer is a homopolymer.
  • a specific glass transition temperature a literature value may be adopted. A value measured using a scanning calorimeter) may be employed.
  • the content of the polyfunctional monomer in the pressure-sensitive adhesive composition is preferably 5 to 40 parts by mass, more preferably 8 to 30 parts by mass with respect to 100 parts by mass of the crosslinkable acrylic polymer.
  • One of the above polyfunctional monomers may be used alone, or two or more may be used in combination. When two or more are used in combination, the total mass is preferably within the above range.
  • the pressure-sensitive adhesive composition contains a monofunctional monomer having one reactive double bond in the molecule. Also in the second embodiment, the pressure-sensitive adhesive composition may contain a monofunctional monomer having one reactive double bond in the molecule.
  • the monofunctional monomer examples include isobornyl acrylate, isostearyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, N-acryloyloxyethyl hexahydrophthalimide, acrylamide, N, N-dimethylacrylamide, N , N-diethylacrylamide, acryloylmorpholine, vinylpyrrolidone, and the like.
  • the monofunctional monomer is preferably an alkyl (meth) acrylate, and is preferably at least one selected from isobornyl acrylate and isostearyl acrylate.
  • Examples of commercially available monofunctional monomers include IBXA manufactured by Osaka Organic Chemical Industry, ISTA manufactured by Osaka Organic Chemical Industry, and DEAA manufactured by KJ Chemicals.
  • the glass transition temperature (Tg) of the homopolymer when a monofunctional monomer is polymerized is preferably -20 ° C or higher, more preferably 0 ° C or higher, and 50 ° C or higher. More preferably, the temperature is more preferably 55 ° C or higher, and particularly preferably 60 ° C or higher. Further, the glass transition temperature (Tg) of the homopolymer when the monofunctional monomer is polymerized is preferably 180 ° C. or lower, more preferably 150 ° C. or lower.
  • the glass transition temperature (Tg) when the monofunctional monomer is a homopolymer is preferably 50 ° C. or more and less than 200 ° C., and more preferably 55 ° C. or more and less than 180 ° C.
  • the content of the monofunctional monomer is preferably 1 to 30 parts by mass, more preferably 2 to 30 parts by mass, based on 100 parts by mass of the crosslinkable acrylic polymer.
  • One of the above monofunctional monomers may be used alone, or two or more may be used in combination. When two or more are used in combination, the total mass is preferably within the above range.
  • the total content of the monofunctional monomer and the polyfunctional monomer is preferably 6 to 50 parts by mass, and more preferably 10 to 45 parts by mass based on 100 parts by mass of the crosslinkable acrylic polymer. Is more preferable, and more preferably 15 to 40 parts by mass.
  • the content of the monofunctional monomer is preferably from 0 to 30 parts by mass, more preferably from 2 to 30 parts by mass, based on 100 parts by mass of the crosslinkable acrylic polymer. More preferably, it is 20 parts by mass.
  • One of the above monofunctional monomers may be used alone, or two or more may be used in combination. When two or more are used in combination, the total mass is preferably within the above range.
  • the pressure-sensitive adhesive composition contains a polymerization initiator.
  • the polymerization initiator is preferably one that initiates the polymerization of the polyfunctional monomer and / or the monofunctional monomer by irradiation with active energy rays. More preferably, it is one that initiates polymerization of the product.
  • the polymerization initiator for example, a known one such as a photopolymerization initiator can be used.
  • the “active energy ray” means an electromagnetic wave or a charged particle beam having an energy quantum, and includes ultraviolet rays, electron beams, visible rays, X-rays, and ion beams. Above all, from the viewpoint of versatility, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable.
  • the polymerization initiator examples include an acetophenone-based initiator, a benzoin ether-based initiator, a benzophenone-based initiator, a hydroxyalkylphenone-based initiator, a thioxanthone-based initiator, an amine-based initiator, an acylphosphine oxide-based initiator, and the like.
  • Can be Specific examples of the acetophenone-based initiator include diethoxyacetophenone and benzyldimethyl ketal.
  • Specific examples of the benzoin ether-based initiator include benzoin and benzoin methyl ether.
  • Specific examples of the benzophenone-based initiator include benzophenone and methyl o-benzoylbenzoate.
  • hydroxyalkylphenone-based initiator examples include 1-hydroxy-cyclohexyl-phenyl-ketone (available as IRGACURE 184, manufactured by BASF Japan K.K.).
  • thioxanthone initiator examples include 2-isopropylthioxanthone and 2,4-dimethylthioxanthone.
  • amine initiator examples include triethanolamine and ethyl 4-dimethylbenzoate.
  • acylphosphine oxide-based initiator examples include phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (manufactured by BASF Japan Ltd., commercially available as IRGACURE819).
  • the content of the polymerization initiator in the pressure-sensitive adhesive composition is appropriately selected depending on the content of the monomer, the irradiation amount of the active energy ray at the time of post-curing, and the like. Specifically, the amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5.0 parts by mass, based on 100 parts by mass of the crosslinkable acrylic polymer. When the content is equal to or more than the above lower limit, the desired hardness can be adjusted by post-curing, and the molecular weight after post-curing can be adjusted to an appropriate range.
  • the polymerization initiator 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 include 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 and diacetone alcohol; ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl
  • the content of the solvent in the pressure-sensitive adhesive composition is not particularly limited, but is preferably 25 to 500 parts by mass, more preferably 30 to 400 parts by mass, based on 100 parts by mass of the crosslinkable acrylic polymer. Further, the content of the solvent is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, based on the total mass of the pressure-sensitive adhesive composition.
  • One type of the solvent 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 in the above range.
  • the pressure-sensitive adhesive composition may further contain a plasticizer as long as the effects of the present invention are not impaired.
  • the pressure-sensitive adhesive composition contains a plasticizer, the pressure-sensitive adhesive sheet can fill the steps formed on the adherend, and the step followability is improved.
  • the plasticizer is a non-functional acrylic polymer.
  • the non-functional acrylic polymer a polymer composed of only an acrylic monomer unit having no functional group other than the acrylate group, or having no functional group with an acrylic monomer unit having no functional group other than the acrylate group Examples of the polymer include a non-acrylic monomer unit. Since the non-functional group acrylic polymer does not crosslink, the step followability can be enhanced without affecting the adhesiveness.
  • acrylic monomer unit having no functional group other than the acrylate group examples include a non-crosslinkable alkyl (meth) acrylate.
  • non-acrylic monomer unit having no functional group examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, and stearin
  • vinyl carboxylate such as vinyl acrylate, vinyl cyclohexanecarboxylate, and vinyl benzoate, and styrene.
  • the pressure-sensitive adhesive composition may contain other components other than the above as long as the effects of the present invention are not impaired.
  • components known as additives for pressure-sensitive adhesives can be exemplified.
  • an antioxidant, a metal corrosion inhibitor, a tackifier, a silane coupling agent, an ultraviolet absorber, a light stabilizer such as a hindered amine compound, or the like can be selected as necessary.
  • a dye or a pigment may be added for the purpose of coloring.
  • the antioxidant include phenolic antioxidants, amine antioxidants, lactone antioxidants, phosphorus antioxidants, and sulfur antioxidants. One of these antioxidants may be used alone, or two or more thereof may be used in combination.
  • a benzotriazole-based resin can be mentioned as a preferred example in view of the compatibility and the high effect of the pressure-sensitive adhesive.
  • the tackifier include a rosin resin, a terpene resin, a terpene phenol resin, a coumarone indene resin, a styrene resin, a xylene resin, a phenol resin, and a petroleum resin.
  • the silane coupling agent include a mercaptoalkoxysilane compound (for example, a mercapto group-substituted alkoxy oligomer or the like).
  • Examples of the ultraviolet absorber include a benzotriazole-based compound and a benzophenone-based compound.
  • ultraviolet rays when ultraviolet rays are used as the active energy rays at the time of post-curing, it is preferable to add them within a range that does not inhibit the polymerization reaction.
  • the method for producing a pressure-sensitive adhesive sheet of the present invention includes a step of applying the above-described pressure-sensitive adhesive composition on a release sheet to form a coating film, and a step of heating the coating film to form a semi-cured cured product. Is preferred. By the heating of the coating film, the reaction between the crosslinkable acrylic polymer and the crosslinking agent proceeds, and a cured product (pressure-sensitive adhesive layer) in a semi-cured state is formed.
  • the pressure-sensitive adhesive sheet of the present invention preferably has post-curability and has active energy ray-curability.
  • an aging treatment in which the pressure-sensitive adhesive sheet is allowed to stand at a certain temperature for a certain period of time after the solvent is removed after coating.
  • the aging treatment can be performed, for example, by allowing to stand at 23 ° C. for 7 days.
  • the semi-cured pressure-sensitive adhesive layer can be post-cured by irradiating it with an active energy ray after bonding to an adherend such as a substrate.
  • the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet of a two-stage curing type, has a pressure-sensitive adhesive layer which is semi-cured only by heat before bonding, and is post-cured by an active energy ray after bonding. Is done.
  • the application of the pressure-sensitive adhesive composition can be performed 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, a curtain coater, and the like.
  • a known heating device such as a heating furnace or an infrared lamp can be used for heating the coating film formed by applying the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is brought into contact with the surface of the adherend.
  • the pressure-sensitive adhesive sheet it is preferable that when the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is in a semi-cured state, the pressure-sensitive adhesive sheet is bonded to an adherend and irradiated with active energy rays to post-cur the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet of a two-step curing type, has a pressure-sensitive adhesive layer that has been semi-cured only by heat before lamination, and has a post-curing pressure-sensitive adhesive layer after activation by active energy rays. Is done.
  • the pressure-sensitive adhesive sheet of the present invention is preferably used for an optical member requiring durability, particularly for an application having a complicated shape and requiring punching after forming a laminate.
  • the pressure-sensitive adhesive sheet of the present invention is bonded to an adherend such as a base material, and after post-curing, even when exposed to a high-humidity heat environment, the occurrence of floating and peeling and the generation of bubbles are suppressed. it can.
  • the pressure-sensitive adhesive sheet of the present invention is preferably a pressure-sensitive adhesive sheet used for bonding to a substrate, and more preferably a pressure-sensitive adhesive sheet used for bonding to a polycarbonate substrate.
  • the polycarbonate substrate examples include PC-1151 manufactured by Teijin Chemicals Limited.
  • the pressure-sensitive adhesive sheet of the present invention is, for example, bonded to a polycarbonate substrate, post-cured, and even when exposed to a high-temperature and high-humidity environment, suppresses floating or peeling from the polycarbonate substrate. can do.
  • the pressure-sensitive adhesive sheet of the present invention is preferably a pressure-sensitive adhesive sheet used for application directly to a substrate, but may be used for application indirectly to a substrate.
  • a multilayer substrate including a polycarbonate substrate.
  • Such a multilayer substrate is preferably a substrate having a polycarbonate layer and a hard coat layer.
  • the composition of the hard coat layer is preferably selected from acrylic, urethane, silicone, melamine, and epoxy, and more preferably acrylic and silicone.
  • the composition of the hard coat layer is more preferably an acrylic resin in terms of processability and hardness.
  • MR-58 or IMR05 manufactured by Mitsubishi Gas Chemical Co., Ltd. can be used as a multilayer substrate including a polycarbonate substrate.
  • the configuration of MR-58 is HC (hard coat) / PMMA (polymethyl methacrylate) / PC (polycarbonate) / HC (hard coat).
  • the overall thickness of MR-58 is preferably 0.3 mm to 1.2 mm, and the thickness of one hard coat layer is preferably 0.0005 mm to 0.02 mm.
  • the configuration of the IMR05 is HC (hard coat) / PC (polycarbonate).
  • the pressure-sensitive adhesive sheet of the present invention is bonded to an optical member such as a polarizing plate, and after post-curing, even when exposed to a high humidity and heat environment, bubbles and peeling can be suppressed.
  • the polarizing plate includes a polarizer and a polarizer protective film
  • the pressure-sensitive adhesive sheet of the present invention is preferably bonded to the polarizer protective film.
  • the polarizer protective film include cycloolefin resin films, cellulose acetate resin films such as triacetyl cellulose and diacetyl cellulose, polyester resin films such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, polycarbonate resin films, and acrylic resins.
  • the polarizer protective film is a cellulose acetate resin film
  • the use of the pressure-sensitive adhesive sheet of the present invention exerts an effect of suppressing the generation of bubbles.
  • the generation of air bubbles on the adherend of the pressure-sensitive adhesive sheet can be suppressed, when the pressure-sensitive adhesive sheet is incorporated in a display device or the like, deterioration in visibility can be prevented.
  • 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 by irradiating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet with an active energy ray, and an adherend on at least one surface side of the post-curing pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet is a double-sided pressure-sensitive adhesive sheet
  • the laminate is formed by post-curing by irradiating active energy rays in a state where the two adherends are bonded together with a semi-cured pressure-sensitive adhesive sheet.
  • the adherend is more preferably a substrate and an optical member, and particularly preferably a polycarbonate substrate, a polarizing plate, a transparent film, a transparent resin or glass.
  • FIG. 3 is a schematic view showing a cross section of an example of the laminate of the present invention.
  • FIG. 3 is a cross-sectional view illustrating an example of the configuration of a laminate 20 in which the pressure-sensitive adhesive sheet 21 of the present invention is bonded to a base material 22 and an optical member 24.
  • the pressure-sensitive adhesive sheet 21 of the present invention is preferably used for bonding to a substrate 22, and used for bonding the substrate 22 to another optical member 24.
  • the pressure-sensitive adhesive sheet 21 of the present invention may be used for bonding with a polarizing plate.
  • Examples of the optical member included in the laminate include various components in an optical product such as a touch panel and an image display device, a scattering prevention film stuck to the outermost cover lens, and the like.
  • the constituent members of the touch panel include, for example, an ITO film in which an ITO film is provided on a transparent resin film, an ITO glass in which an ITO film is provided on the surface of a glass plate, a transparent conductive film in which a transparent resin film is coated with a conductive polymer, Hard coat films, fingerprint resistant films and the like can be mentioned.
  • the constituent members of the image display device include, for example, an antireflection film, an alignment film, a polarizing film, a retardation film, and a brightness enhancement film used for a liquid crystal display device.
  • materials used for these members include glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, cycloolefin polymers, triacetyl cellulose, polyimide, and cellulose acylate.
  • 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 used for bonding the transparent optical films inside the touch panel, bonding the transparent optical film and the glass, bonding the transparent optical film of the touch panel to the liquid crystal panel, and covering the cover glass. It is used for laminating a transparent optical film with a cover glass and a transparent optical film, and is useful when any member is a polycarbonate substrate.
  • the transparent optical film general films used in the optical field such as a polyethylene terephthalate film, an acrylic film, a polycarbonate film, a triacetyl cellulose film, and a cycloolefin polymer film can be used. Further, a hard coat layer may be provided on the transparent optical film or the polycarbonate substrate.
  • FIG. 4 is a schematic view showing a cross section of another example of the laminate of the present invention.
  • the adherend may have step portions (27a, 27b, 27c, 27d).
  • the substrate has a step (27a, 27b), and the optical member has a step (27c, 27d).
  • the thickness of the steps (27a, 27b, 27c, 27d) is usually 5 to 60 ⁇ m.
  • the pressure-sensitive adhesive sheet 21 of the present invention can be bonded to a member having a step, and can follow irregularities generated from the step.
  • the method for producing a laminate includes a step of laminating the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet to the adherend in a semi-cured state, and then irradiating active energy rays to post-cure the pressure-sensitive adhesive layer. Before the irradiation with the active energy ray, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is in a semi-cured state, so that the initial adhesiveness to the substrate is improved. As described above, after the pressure-sensitive adhesive sheet is bonded to the adherend, the pressure-sensitive adhesive layer is post-cured with active energy rays, whereby the cohesive force of the pressure-sensitive adhesive layer is increased, and the adhesion to the adherend is improved. The post-cured pressure-sensitive adhesive layer can prevent the substrate from being deformed or distorted.
  • the active energy ray examples include an ultraviolet ray, an electron beam, a visible ray, an X-ray, and an ion beam, and can be appropriately selected according to the polymerization initiator contained in the pressure-sensitive adhesive layer. Above all, from the viewpoint of versatility, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable.
  • 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, and an electrodeless ultraviolet lamp can be used.
  • the electron beam for example, electron beams emitted from various types of electron beam accelerators, such as Cockloft-Wald type, Bande-Crafts type, Resonant transformer type, Insulated core transformer type, Linear type, Dynamitron type, High frequency type, etc. are used. it can.
  • Radiation output of the UV light it is preferable that 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 can be irradiated from the substrate side or the optical member side, but is preferably irradiated from the substrate side.
  • the above-mentioned pressure-sensitive adhesive composition was applied onto a first release sheet (a heavy separator film, a polyethylene terephthalate film subjected to a release treatment, manufactured by Teijin Dupont Film Co., Ltd.).
  • 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.
  • the resultant was dried at 100 ° C. for 3 minutes using a hot air drier to remove the solvent, thereby forming an adhesive sheet having an adhesive layer in a semi-cured state.
  • a second release sheet (light separator film, manufactured by Teijin Dupont Film Co., Ltd.), which has been subjected to a release treatment that is more releasable than the first release sheet, is attached to one side of this adhesive sheet, and the adhesive with the release sheet is attached.
  • An adhesive sheet of Example 1 as a sheet was obtained.
  • Example 2 In ⁇ Synthesis of Crosslinkable Acrylic Polymer> in Example 1, 2-hydroxyethyl acrylate was changed to 4-hydroxybutyl acrylate (4HBA) to obtain a crosslinkable acrylic polymer B.
  • Example 3 In ⁇ Synthesis of crosslinkable acrylic polymer> in Example 1, 2-methoxyethyl acrylate monomer (MEA), 2-hydroxyethyl acrylate monomer (2HEA), methyl methacrylate (MMA), dimethylacrylamide (DMAA) and butyl acrylate ( The crosslinkable acrylic polymer C was obtained by changing the mass ratio of BA) from 70: 10: 10: 5: 5 to 80: 7: 7: 5: 1. The solution viscosity of this 35% by mass solution of the crosslinkable acrylic polymer C at 23 ° C. was 2100 mPa ⁇ s. 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 the addition amount of the cross-linking agent to 100 parts by weight of the crosslinkable acrylic polymer C was 1.0 part by weight.
  • MEA 2-methoxyethyl acrylate monomer
  • 2HEA 2-hydroxyethyl acrylate monomer
  • MMA
  • Example 4 In ⁇ Synthesis of Crosslinkable Acrylic Polymer> of Example 3, 2-hydroxyethyl acrylate was changed to 4-hydroxybutyl acrylate (4HBA) to obtain a crosslinkable acrylic polymer D.
  • the solution viscosity of this 35% by mass solution of the crosslinkable acrylic polymer D at 23 ° C. was 2,400 mPa ⁇ s.
  • the amount of the cross-linking agent added to 100 parts by mass of the cross-linkable acrylic polymer D was 0.2 parts by mass, the amount of the polyfunctional monomer was 20 parts by mass, the amount of the monofunctional monomer was 20 parts by mass, and the polymerization was started.
  • a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 3, except that the amount of the agent was changed to 0.5 part by mass.
  • Example 5 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 the monofunctional monomer of Example 1 was changed from IBXA to ISTA manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • Crosslinkable acrylic polymers were made by solution polymerization in ethyl acetate.
  • a 2-hydroxyethyl acrylate monomer (2HEA), dimethylacrylamide (DMAA) and butyl acrylate (BA) are blended in a mass ratio of 5:20:75, and AIBN (azobisisobutyronitrile) is used as a radical polymerization initiator. )
  • AIBN azobisisobutyronitrile
  • crosslinkable acrylic polymer E With respect to 100 parts by mass of the crosslinkable acrylic polymer E, 0.2 parts by mass of a xylylene diisocyanate compound (manufactured by Mitsui Chemicals, Inc., Takenate D-110N) as a crosslinking agent, and trimethylolpropanepropylene as a polyfunctional monomer.
  • a xylylene diisocyanate compound manufactured by Mitsui Chemicals, Inc., Takenate D-110N
  • trimethylolpropanepropylene As a polyfunctional monomer.
  • Comparative Example 2 A pressure-sensitive adhesive composition of Comparative Example 2 and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 1 except that the polyfunctional monomer, the monofunctional monomer, and the polymerization initiator were not used.
  • Example 4 The polyfunctional monomer of Example 1 was changed from bisphenol A ethylene oxide-modified diacrylate (manufactured by Toagosei Co., Ltd., Aronix M211B) to trimethylolpropane propylene oxide-modified triacrylate (manufactured by Toagosei Co., Ltd., M321). Except for the above, an adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 1.
  • the tensile storage elastic modulus E ′ is in the solid tensile mode, and the shear storage elastic modulus G ′.
  • Measured the tensile storage modulus E ′ and the shear storage modulus G ′ of the pressure-sensitive adhesive layer in the temperature range from 0 ° C. to 150 ° C. under the conditions of a frequency of 1 Hz and a strain of 0.1% using a solid shear mode. .
  • the second release sheet which is a light separator film of the 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 was a light separator film of another pressure-sensitive adhesive sheet, was peeled off and adhered to a PET film.
  • ultraviolet rays were irradiated from the side of the first release sheet, which is a heavy separator film, so that the integrated light amount became 3000 mJ / cm 2 , to prepare a post-curing measurement sample.
  • Each measurement sample was cut into a size of 3 cm ⁇ 3 cm, and measured with a probe tack tester under the following conditions.
  • the measurement temperature was 23 ° C.
  • NS probe tack tester (Nichiban Co., Ltd.) Probe diameter: 5mm ⁇ Probe base material: Stainless steel surface finish AA # 400 Polished mirror surface weight: 19.6 g (made of brass) Probe moving speed: 1.0 cm / sec Duel time: 1 sec
  • the 25 mm wide and 75 mm long region of the exposed adhesive surface having a width of 25 mm and a length of 100 mm was coated on the hard coat side of the adherend (polycarbonate plate with hard coat layer: Mitsubishi Gas Chemical Company, Iupilon MR58 1 mm thick).
  • the adherend (polycarbonate plate with hard coat layer: Mitsubishi Gas Chemical Company, Iupilon MR58 1 mm thick).
  • the adherend was attached using a 2 kg pressure roller.
  • ultraviolet rays are irradiated from the triacetyl cellulose film side so that the integrated light amount becomes 3000 mJ / cm 2 , It was left for 24 hours in an environment of 23 ° C. and 50% relative humidity to prepare a test piece. Two test pieces were prepared.
  • the length of the non-bonded area (width 25 mm, length 25 mm) of the laminated film composed of the adhesive sheet 1 and the triacetyl cellulose film 30 is shown in FIG.
  • a 300 g weight 34 was hung at the end in the direction, a load of 300 g was applied in a direction at 90 ° to the plane of the adherend 32, and the load was allowed to stand for 30 minutes. During that time, the length L (constant load peeling distance) of the portion where the laminated film was peeled was measured.
  • the other test piece was left in an environment of 85 ° C.
  • the pressure-sensitive adhesive layer was cut so as to have a size of 100 mm ⁇ 60 mm, and a measurement sample in a semi-cured state was prepared.
  • the pressure-sensitive adhesive layer is cut so as to have a size of 100 mm ⁇ 60 mm, and ultraviolet rays are irradiated from the first release sheet side, which is a heavy separator film, so that the integrated light amount becomes 3000 mJ / cm 2.
  • About 0.1 g of the pressure-sensitive adhesive sheet of each measurement sample was collected in a sample bottle, and 30 ml of ethyl acetate was added thereto and shaken for 24 hours.
  • the second release sheet which was a light separator film of the pressure-sensitive adhesive layer, was peeled off and bonded to a PET film having a thickness of 25 ⁇ m.
  • the first release sheet which was a heavy separator film, was peeled off and attached to a PC board.
  • the sample having the structure of PET / adhesive layer / PC was subjected to an autoclave treatment (40 ° C., 0.5 MPa, 30 min), and then irradiated with ultraviolet light from the PET film side so that the integrated light amount became 3000 mJ / cm 2.
  • Peeling distance is less than 0.05mm ... ⁇ Peeling distance is 0.05 mm or more and less than 0.1 mm ... ⁇ Peeling distance is 0.1 mm or more ... ⁇
  • the second release sheet which was a light separator film of the pressure-sensitive adhesive layer, was peeled off and bonded to a triacetyl cellulose film (Fujitack TD60UL, thickness 60 ⁇ m, manufactured by FUJIFILM Corporation).
  • the first release sheet which was a heavy separator film, was peeled off and attached to a PC board.
  • the sample having the structure of triacetylcellulose film / adhesive layer / PC was subjected to an autoclave treatment (40 ° C., 0.5 MPa, 30 min), and then irradiated with ultraviolet rays from the PET film side so that the integrated light amount became 3000 mJ / cm 2.
  • test sample having a size of 100 mm ⁇ 200 mm was obtained.
  • the test sample was placed in a dry environment at 105 ° C., and after 240 hours, the presence or absence of floating and peeling was observed. No lifting or peeling is observed ... ⁇ Floating and / or peeling of 1.0 mm or more is observed ... ⁇
  • MEA 2-methoxyethyl acrylate 2HEA: 2-hydroxyethyl acrylate 4HBA: 4-hydroxybutyl acrylate MMA: methyl methacrylate DMAA: dimethylacrylamide BA: butyl acrylate M211B: bisphenol A ethylene oxide-modified diacrylate M321: trimethylolpropane propylene oxide-modified Triacrylate IBXA: Isobornyl acrylate ISTA: Isostearyl acrylate
  • the pressure-sensitive adhesive sheets of Comparative Examples 1 and 4 had a tensile storage elastic modulus E ′ at 23 ° C. after post-curing of less than 5.0 ⁇ 10 6 Pa, and a constant load peeling distance of 100 mm under the measurement condition (b). Therefore, the high temperature durability was inferior. Also in Comparative Example 2, the value of the tensile storage elastic modulus E ′ and the constant load peel distance did not satisfy the predetermined conditions, so that the high-temperature durability was poor, the end face was sticky, and the workability was poor. Also, Comparative Example 3 was inferior in high temperature durability because the tensile storage modulus E ′ did not satisfy the predetermined condition.
  • Crosslinkable acrylic polymer A was made by solution polymerization in ethyl acetate.
  • a butyl acrylate monomer (BA), a methyl acrylate monomer (MA), a methyl methacrylate (MMA), and an acrylic acid (AA) are blended at a mass ratio of 90: 1: 4: 6, and AIBN ( Azobisisobutyronitrile) was dissolved in the solution.
  • AIBN Azobisisobutyronitrile
  • the solution was heated to 60 ° C. for random copolymerization to obtain a crosslinkable acrylic polymer A.
  • the solution viscosity at 23 ° C. of the 21% by mass solution of the crosslinkable acrylic polymer A was 4900 mPa ⁇ s.
  • Crosslinkable acrylic polymer B was made by solution polymerization in ethyl acetate. Butyl acrylate monomer (BA), 2-hydroxyethyl acrylate monomer (2-HEA), methyl methacrylate (MMA), acrylic acid (AA) are blended in a mass ratio of 90: 3: 4: 3 to perform radical polymerization. AIBN (azobisisobutyronitrile) was dissolved in the solution as an initiator. The solution was heated to 60 ° C. for random copolymerization to obtain a crosslinkable acrylic polymer B. The solution viscosity of this 30% by mass solution of the crosslinkable acrylic polymer B at 23 ° C. was 5,400 mPa ⁇ s.
  • Crosslinkable acrylic polymer C was made by solution polymerization in ethyl acetate.
  • AIBN azobisisobutyronitrile
  • the solution was heated to 60 ° C. for random copolymerization to obtain a crosslinkable acrylic polymer C.
  • the solution viscosity of this 35% by mass solution of the crosslinkable acrylic polymer C at 23 ° C. was 2000 mPa ⁇ s.
  • 0.7 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184, manufactured by BASF Japan K.K.) was added as a photopolymerization initiator, and ethyl acetate was used as a solvent so that the solid content concentration became 40% by mass. This was added to obtain an epoxy compound (
  • the above-mentioned pressure-sensitive adhesive composition was applied onto a first release sheet (a heavy separator film, a polyethylene terephthalate film subjected to a release treatment, manufactured by Teijin Dupont Film Co., Ltd.).
  • 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.
  • the resultant was dried at 100 ° C. for 3 minutes using a hot air drier to remove the solvent, thereby forming an adhesive sheet having an adhesive layer in a semi-cured state.
  • a second release sheet (light separator film, manufactured by Teijin Dupont Film Co., Ltd.), which has been subjected to a release treatment that is more releasable than the first release sheet, is attached to one side of the adhesive sheet, and the adhesive with the release sheet is attached.
  • An adhesive sheet of Example 101 which was a sheet was obtained.
  • Example 103 A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 102 except that the monofunctional monomer was not used.
  • a pressure-sensitive adhesive composition Based on 100
  • Acid value (mgKOH / g) [cKOH ⁇ (V1-V0) ⁇ 5.611] / S (1)
  • cKOH is the molar concentration (mol / L) of a 0.1 N potassium hydroxide-2-propanol solution
  • V1 is 0.1 mol / L potassium hydroxide-2 required for titration of the sample.
  • the amount of propanol solution (mL) is the amount (mL) of 0.1 mol / L potassium hydroxide-2-propanol solution required for titration in blank test
  • S is the amount of sample (g ).
  • the second release sheet which is a light separator film of the 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 was a light separator film of another pressure-sensitive adhesive sheet, was peeled off and adhered to a PET film.
  • ultraviolet rays were irradiated from the side of the first release sheet, which is a heavy separator film, so that the integrated light amount became 3000 mJ / cm 2 , to prepare a post-curing measurement sample.
  • Each measurement sample was cut into a size of 3 cm ⁇ 3 cm, and measured with a probe tack tester under the following conditions.
  • the measurement temperature was 23 ° C.
  • the elongation at break 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%.
  • the measurement sample used was a pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) having a thickness of 25 ⁇ m, a width of 60 mm, and a length of 200 mm, which was 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. .
  • the sample was set and pulled so that the distance between the 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 25 mm wide and 75 mm long region of the exposed adhesive surface having a width of 25 mm and a length of 100 mm was coated on the hard coat side of the adherend (polycarbonate plate with hard coat layer: Mitsubishi Gas Chemical Company, Iupilon MR58 1 mm thick).
  • the adherend polycarbonate plate with hard coat layer: Mitsubishi Gas Chemical Company, Iupilon MR58 1 mm thick.
  • the adherend was attached using a 2 kg pressure roller.
  • ultraviolet rays are irradiated from the triacetyl cellulose film side so that the integrated light amount becomes 3000 mJ / cm 2 .
  • Test pieces were prepared. This test piece was left for 24 hours in an environment of 85 ° C.
  • the second release sheet which is a light separator film of the pressure-sensitive adhesive layer, was peeled off and bonded to a triacetyl cellulose film (Fujitack TD60UL, thickness 60 ⁇ m, manufactured by FUJIFILM Corporation).
  • the first release sheet which is a heavy separator film, was peeled off and adhered to a PC plate (polycarbonate plate with hard coat layer: Iupilon MR58, thickness 1 mm, manufactured by Mitsubishi Gas Chemical Company, Inc.).
  • the sample having the constitution of triacetylcellulose film / adhesive layer / PC was subjected to an autoclave treatment (40 ° C., 0.5 MPa, 30 min), and then the ultraviolet light was applied from the triacetylcellulose film side so that the integrated light amount became 3000 mJ / cm 2. Irradiated to obtain a test sample having a size of 100 mm x 200 mm. Next, the test sample was placed in an environment of 85 ° C. and a relative humidity of 85%, and after 240 hours, the presence or absence of floating and peeling was observed. :: No lifting and / or peeling of 1.0 mm or more is observed. ⁇ : Floating and / or peeling of 1.0 mm or more is observed.
  • M321 trimethylolpropane propylene oxide modified triacrylate
  • M211B bisphenol A ethylene oxide modified diacrylate
  • IBXA isobornyl acrylate
  • DEAA diethylacrylamide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention vise à augmenter la durabilité à température élevée d'une feuille adhésive qui offre une aptitude au post-durcissement et une aptitude au traitement. La présente invention concerne une feuille adhésive selon la revendication 1, qui est une feuille adhésive qui possède une couche adhésive d'une composition adhésive qui a été amenée dans un état semi-durci, et qui satisfait à la propriété (101) lorsqu'elle est post-durcie par l'irradiation de la couche adhésive avec un rayonnement d'énergie active à une quantité cumulée de lumière de 3 000 mJ/cm2. Propriété (101) : la valeur d'adhérence à une sonde, mesurée à 23 °C et à une humidité relative de 50 % en utilisant les conditions de mesure suivantes, n'est pas supérieure à 1,0 N/5 mmφ (conditions de mesure de valeur d'adhérence à une sonde). Instrument de mesure : testeur d'adhérence à une sonde NS (Nichiban Co, Ltd) ; diamètre de sonde : 5 mmφ ; substrat de sonde : surface en acier inoxydable finie à un fini de miroir avec un poids abrasif AA#400 : 19,6 ± 0,2 g (laiton) ; vitesse de déplacement de sonde : 1,0 cm/sec ; et temps de séjour : 1 seconde.
PCT/JP2019/026601 2018-07-04 2019-07-04 Feuille adhésive, feuille adhésive dotée d'une feuille antiadhésive, feuille adhésive dotée d'un film transparent, stratifié et procédé de production d'un stratifié Ceased WO2020009181A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018127338A JP6769460B2 (ja) 2018-07-04 2018-07-04 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
JP2018-127338 2018-07-04
JP2018-134386 2018-07-17
JP2018134386A JP6724946B2 (ja) 2018-07-17 2018-07-17 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

Publications (1)

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WO2020009181A1 true WO2020009181A1 (fr) 2020-01-09

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PCT/JP2019/026601 Ceased WO2020009181A1 (fr) 2018-07-04 2019-07-04 Feuille adhésive, feuille adhésive dotée d'une feuille antiadhésive, feuille adhésive dotée d'un film transparent, stratifié et procédé de production d'un stratifié

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WO (1) WO2020009181A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012072382A (ja) * 2010-08-31 2012-04-12 Sekisui Chem Co Ltd 異方性導電材料、ｂステージ状硬化物及び接続構造体の製造方法
JP2017179029A (ja) * 2016-03-29 2017-10-05 リンテック株式会社 ガラスダイシング用粘着シートおよびその製造方法
JP2019089948A (ja) * 2017-11-15 2019-06-13 王子ホールディングス株式会社 粘着シート、積層体の製造方法および積層体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012072382A (ja) * 2010-08-31 2012-04-12 Sekisui Chem Co Ltd 異方性導電材料、ｂステージ状硬化物及び接続構造体の製造方法
JP2017179029A (ja) * 2016-03-29 2017-10-05 リンテック株式会社 ガラスダイシング用粘着シートおよびその製造方法
JP2019089948A (ja) * 2017-11-15 2019-06-13 王子ホールディングス株式会社 粘着シート、積層体の製造方法および積層体

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