WO2016194957A1 - Feuille adhésive photodurcissable, feuille adhésive et dispositif d'affichage d'image - Google Patents

Feuille adhésive photodurcissable, feuille adhésive et dispositif d'affichage d'image Download PDF

Info

Publication number
WO2016194957A1
WO2016194957A1 PCT/JP2016/066215 JP2016066215W WO2016194957A1 WO 2016194957 A1 WO2016194957 A1 WO 2016194957A1 JP 2016066215 W JP2016066215 W JP 2016066215W WO 2016194957 A1 WO2016194957 A1 WO 2016194957A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
pressure
acrylate
sensitive adhesive
adhesive sheet
Prior art date
Application number
PCT/JP2016/066215
Other languages
English (en)
Japanese (ja)
Inventor
かほる 新美
亮太 山本
内田　貴久
誠 稲永
Original Assignee
三菱樹脂株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 三菱樹脂株式会社 filed Critical 三菱樹脂株式会社
Priority to CN201680032296.2A priority Critical patent/CN107709493B/zh
Priority to KR1020187000091A priority patent/KR102080224B1/ko
Priority to KR1020207004561A priority patent/KR20200019792A/ko
Publication of WO2016194957A1 publication Critical patent/WO2016194957A1/fr

Links

Images

Classifications

    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • the present invention relates to a photocurable pressure-sensitive adhesive sheet before photocuring and a pressure-sensitive adhesive sheet obtained by photocuring the same.
  • the present invention relates to an image display device such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, a pen tablet, and the like, and an adhesive sheet that can be suitably used as a constituent member thereof.
  • an image display panel such as a liquid crystal display (LCD), a plasma display (PDP) or an electroluminescence display (ELD), and a protection disposed on the front side (viewing side) thereof.
  • LCD liquid crystal display
  • PDP plasma display
  • ELD electroluminescence display
  • a space between the panel and the touch panel member is filled with an adhesive sheet, a liquid adhesive, or the like to suppress reflection of incident light or outgoing light from a display image at the air layer interface.
  • Patent Document 1 As a method of filling the gap between the constituent members for an image display device with an adhesive, a method of filling the gap with a liquid adhesive resin composition containing an ultraviolet curable resin and then curing it by irradiating with ultraviolet rays. Is known (Patent Document 1).
  • Patent Document 2 discloses an image of a pressure-sensitive adhesive sheet that has been primarily cross-linked with ultraviolet rays as a method for producing a laminate for constituting an image display device having a structure in which image display device constituent members are laminated on at least one side of the pressure-sensitive adhesive sheet.
  • a method is disclosed in which, after bonding to a display device constituent member, the pressure-sensitive adhesive sheet is irradiated with ultraviolet rays through the image display device constituent member and subjected to secondary curing.
  • Patent Document 3 discloses a sheet using a hot melt type adhesive composition having a loss tangent at 25 ° C. of less than 1 based on urethane (meth) acrylate having a weight average molecular weight of 20,000 to 100,000. Is disclosed.
  • Patent Document 4 discloses a touch panel comprising a (meth) acrylic polymer obtained by copolymerizing a monomer containing a (meth) acrylic monomer having a crosslinkable functional group and a specific macromer, and a crosslinking agent.
  • a pressure-sensitive adhesive layer suitable for pasting is disclosed.
  • a black concealment portion is generally printed in a frame shape on the peripheral edge portion of the surface protection panel. Therefore, the pressure-sensitive adhesive sheet for bonding the constituent members having such a printing unit is required to have a printing level followability that can be filled to every corner following the printing level difference.
  • image display devices such as touch panels have come to be used in a wide range, and accordingly, pressure-sensitive adhesive sheets used for image display device configuration laminates are exposed to light such as illumination and sunlight for a long time.
  • adhesion reliability that does not degrade the performance.
  • the first object of the present invention is to follow the stepped portion of the bonding surface in a state before photocuring and to fill every corner, and in the state after photocuring, even if light irradiation is applied for a long time, it is reliable in adhesion.
  • the present invention is to provide a new pressure-sensitive adhesive sheet that does not deteriorate in properties and that can be easily bonded.
  • the second object of the present invention is to provide a stepped portion or the like even when a component member for an image display device having a light impermeable portion such as a printing portion and a light transmissive portion in the bonding surface is bonded.
  • a component member for an image display device having a light impermeable portion such as a printing portion and a light transmissive portion in the bonding surface is bonded.
  • followability and surface flatness can be obtained, distortion and deformation do not occur even in light-impermeable portions, adherends can be firmly bonded with high cohesion, and high temperature and high humidity
  • An object of the present invention is to provide a new pressure-sensitive adhesive sheet that can prevent the exposed pressure-sensitive adhesive surface from sticking even under harsh environments such as underneath.
  • the third object of the present invention is a pressure-crosslinkable pressure-sensitive adhesive sheet, which has pressure-sensitive adhesive properties even before photocrosslinking, and the pressure-sensitive adhesive material flows too much at the time of bonding, and the pressure-sensitive adhesive resin composition protrudes.
  • An object of the present invention is to provide a pressure-sensitive adhesive sheet that does not crush and can obtain sufficient hardness after photocrosslinking.
  • the present invention is formed from a resin composition containing the (meth) acrylic copolymer (A), a crosslinking agent (B), and a photopolymerization initiator (C).
  • a pressure-sensitive adhesive sheet before photocuring which has photocurability and has the following characteristics (1) and (2), is proposed.
  • (1) The shape can be maintained at 0 to 40 ° C. and exhibits self-adhesiveness.
  • the viscosity is 100 to 3000 Pa ⁇ s at 70 to 100 ° C.
  • the pressure-sensitive adhesive sheet proposed by the present invention to achieve the first object can maintain the sheet shape at room temperature of 0 to 40 ° C., that is, in a normal state, and can exhibit self-adhesion. In addition to being easy to handle, for example, positioning at the time of sticking is easy to perform, so that the bonding work can be performed efficiently. Further, when the temperature is 70 to 100 ° C., the viscosity becomes 100 to 3000 Pa ⁇ s and exhibits hot melt properties, and therefore, for example, the pressure-sensitive adhesive can be filled following uneven portions such as printing steps.
  • the photocurable pressure-sensitive adhesive sheet proposed by the present invention is suitably used as a constituent member of an image display device such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, and a pen tablet. can do.
  • an image display device such as a personal computer, a mobile terminal (PDA), a game machine, a television (TV), a car navigation system, a touch panel, and a pen tablet. can do.
  • the present invention is a pressure-sensitive adhesive sheet containing a (meth) acrylic copolymer (A) and having a gel fraction of less than 1%,
  • the pressure-sensitive adhesive sheet is characterized by having a sheet portion having a gel fraction of 40% or more.
  • the pressure-sensitive adhesive sheet proposed in order to achieve the second object of the present invention is capable of obtaining followability to a stepped portion or the like and surface flatness by a sheet portion having a gel fraction of less than 1%. While the sheet portion having a gel fraction of 40% or more can relieve the distortion and deformation of the adhesive, it can not only make the adhesive surface sticky, but also adheres adherends firmly with high cohesive strength. You can also. Therefore, for example, even when a structural member for an image display device having a light opaque portion and a light transmissive portion such as a printing portion in the bonding surface is bonded, the entire pressure-sensitive adhesive sheet follows the printing step portion.
  • the present invention provides 100 parts by weight of a (meth) acrylic copolymer (A), 0.5 to 20 parts by weight of a crosslinking agent (B), a photopolymerization initiator (C)
  • a pressure-sensitive adhesive sheet comprising a resin composition containing 0.1 to 5 parts by mass, wherein a ratio (X1 / X2) between a tensile elastic modulus (X1) before photocrosslinking and a tensile elastic modulus (X2) after photocrosslinking ) Is 3 or more, and a pressure-sensitive adhesive sheet is proposed.
  • the pressure-sensitive adhesive sheet proposed by the present invention to achieve the third object has a feature that the difference in tensile elastic modulus (X1) before and after photocrosslinking is remarkably large. It has adhesiveness, and the adhesive material does not flow excessively at the time of bonding, so that the adhesive resin composition does not protrude or be crushed, and sufficient hardness can be obtained after photocrosslinking.
  • X1 tensile elastic modulus
  • An adhesive sheet according to an example of an embodiment of the present invention includes a (meth) acrylic copolymer (1-A), a crosslinking agent (1-B), and photopolymerization initiation.
  • a pressure-sensitive adhesive sheet formed from a resin composition containing the agent (1-C) (referred to as “the present pressure-sensitive adhesive composition 1”), having photo-curability, and A pressure-sensitive adhesive sheet having the characteristics (1) and (2).
  • the shape can be maintained at 0 to 40 ° C. and exhibits self-adhesiveness.
  • the viscosity is 100 to 3000 Pa ⁇ s at 70 to 100 ° C.
  • the "pressure-sensitive adhesive sheet before photocuring" is sufficient if it is a pressure-sensitive adhesive sheet, and does not mean only a pressure-sensitive adhesive sheet that has not undergone any photocuring process. That is, for example, any pressure-sensitive adhesive sheet that has undergone a photo-curing process, that can be further photo-cured, and that exhibits the effects of the present invention is included in the present invention.
  • this pressure-sensitive adhesive sheet 1 Since this pressure-sensitive adhesive sheet 1 has the above-mentioned properties (1) and (2) before being photocured, it can maintain a sheet shape in a room temperature state of 0 to 40 ° C., in other words, in a normal state. Moreover, it has the property of exhibiting self-adhesiveness, that is, the adhesive strength as it is. Furthermore, it exhibits a hot melt property that melts or flows when heated, exhibits an excellent cohesive force after photocuring, and can exhibit foam resistance after, for example, light irradiation for a long time.
  • the pressure-sensitive adhesive sheet 1 has the characteristics that (1) the sheet shape can be maintained at a room temperature of 0 to 40 ° C. in a state before photocuring and exhibits self-adhesion. Thus, if it can hold
  • the present pressure-sensitive adhesive sheet 1 may be produced from the pressure-sensitive adhesive composition (1-I) or (1-II) described later. However, the present invention is not limited to this.
  • the pressure-sensitive adhesive sheet 1 can have the following feature (6). That is, (6) 180 ° to the glass when the pressure-sensitive adhesive sheet 1 is peeled off from the soda-lime glass at 23 ° C. and 40% RH at a peeling angle of 180 ° and a peeling speed of 60 mm / min. °
  • the peeling force can be 3 N / cm or more.
  • a 180 ° peeling force at 23 ° C. of 3 N / cm or more is preferable because it has appropriate adhesion to an adherend at room temperature and is excellent in bonding workability. From such a viewpoint, the 180 ° peeling force at 23 ° C.
  • the present adhesive sheet 1 is produced from the adhesive composition (1-I) or (1-II) described later. Furthermore, what is necessary is just to adjust the kind and composition ratio of a crosslinking agent and a photoinitiator, and to adjust the heating and pressurization conditions at the time of bonding, and the light irradiation conditions after bonding. However, it is not limited to such a method.
  • the pressure-sensitive adhesive sheet 1 is characterized in that (2) when heated to 70 to 100 ° C. before photocuring, the viscosity becomes 100 to 3000 Pa ⁇ s and exhibits fluidity. If the pressure-sensitive adhesive sheet 1 has such a hot melt property, it can be filled with the pressure-sensitive adhesive by following heating and softening or fluidizing to follow uneven portions such as a printing step, and so on. It can be filled without producing. In order to obtain such characteristics, for example, the present pressure-sensitive adhesive sheet 1 may be produced from the pressure-sensitive adhesive composition (1-I) or (1-II) described later. However, the present invention is not limited to this.
  • the pressure-sensitive adhesive sheet 1 has a viscosity of 100 to 3000 Pa ⁇ s when heated to 70 to 100 ° C., preferably 150 Pa ⁇ s or more or 2700 Pa ⁇ s or less, and more preferably 200 Pa ⁇ s or more or 2500 Pa ⁇ s or less. .
  • the pressure-sensitive adhesive sheet 1 can have the following feature (7). That is, (7) when the pressure-sensitive adhesive sheet 1 is peeled off from the soda lime glass at 80 ° C. and 10% RH at a peeling angle of 180 ° and a peeling speed of 60 mm / min. It is a cohesive failure, and the 180 ° peeling force for glass can be 1 N / cm or less. A 180 ° peeling force at 80 ° C. of 1 N / cm or less is preferable because high wettability to the adherend can be obtained. From this viewpoint, the 180 ° peeling force at 80 ° C.
  • the present adhesive sheet 1 is produced from the adhesive composition (1-I) or (1-II) described later. Furthermore, what is necessary is just to adjust the kind and composition ratio of a crosslinking agent and a photoinitiator, and to adjust the heating and pressurization conditions at the time of bonding, and the light irradiation conditions after bonding. However, it is not limited to such a method.
  • This pressure-sensitive adhesive sheet 1 can be photocured, and (3) after photocuring, has a characteristic that the viscosity at 70 to 100 ° C. is 3000 to 50000 Pa ⁇ s.
  • the pressure-sensitive adhesive sheet 1 preferably has a viscosity at 70 to 100 ° C. of 3000 to 50000 Pa ⁇ s after photocuring from the viewpoint of obtaining a high cohesive force, particularly 3500 Pa ⁇ s or more or 48000 Pa ⁇ s or less, and more preferably 4000 Pa. More preferably, it is s or more or 45000 Pa ⁇ s or less.
  • the pressure-sensitive adhesive sheet 1 can have the following feature (4) after photocuring. That is, (4) a pressure-sensitive adhesive sheet that has been pressure-bonded to soda-lime glass and cured by light irradiation at 23 ° C. and 40% RH at a peeling angle of 180 ° and a peeling speed of 60 mm / min.
  • the 180 ° peeling force to the glass when the adhesive sheet is peeled off from the glass can be 3 N / cm or more. If the 180 ° peeling force at 23 ° C. after photocuring is 3 N / cm or more, it is preferable because adherends can be firmly bonded to each other.
  • the 180 ° peeling force at 23 ° C. after photocuring of the pressure-sensitive adhesive sheet 1 is preferably 3 N / cm or more, more preferably 4 N / cm or more, particularly 5 N / cm or more, or 30 N / cm. It is particularly preferred that
  • the pressure-sensitive adhesive sheet 1 can have the following feature (5) after photocuring. That is, (5) a pressure-sensitive adhesive sheet that has been pressure-bonded to soda-lime glass and cured by irradiation with light at 80 ° C. and 10% RH at a peeling angle of 180 ° and a peeling speed of 60 mm / min.
  • the 180 ° peeling force with respect to the glass can be 3 N / cm or more. If the 180 ° peel strength at 80 ° C. after photocuring is 3 N / cm or more, it is preferable because the foam resistance in a high temperature environment is excellent.
  • the 180 ° peeling force at 80 ° C. after photocuring of the pressure-sensitive adhesive sheet 1 is preferably 3 N / cm or more, especially 4 N / cm or more, and especially 5 N / cm or more or 20 N / cm. It is particularly preferred that
  • this pressure-sensitive adhesive sheet 1 In order to adjust the 180 ° peel strength at 23 ° C. or 80 ° C. after photocuring in the present pressure-sensitive adhesive sheet 1, for example, from the pressure-sensitive adhesive composition (1-I) or (1-II) described later, this pressure-sensitive adhesive sheet 1 And the kind and composition ratio of the crosslinking agent and the photopolymerization initiator may be adjusted, or the heating / pressurizing conditions during bonding and the light irradiation conditions after bonding may be adjusted. However, it is not limited to such a method.
  • This pressure-sensitive adhesive sheet 1 after photocuring has an outgas generation amount of 40,000 ppm or more in terms of hexadecane after being irradiated for 24 hours with a xenon arc lamp type light resistance tester specified in JIS K7350-2 (ISO 4892-2). Is preferred. If the outgas generation amount is 40000 ppm or more in terms of hexadecane, the tackiness of the pressure-sensitive adhesive sheet and the wettability to the adherend are improved, which is preferable.
  • the outgas generation amount in the pressure-sensitive adhesive sheet 1 is preferably 40000 ppm or more in terms of hexadecane, more preferably 45000 ppm or more, and particularly preferably 50000 ppm or more.
  • the pressure-sensitive adhesive sheet 1 may be produced from, for example, a pressure-sensitive adhesive composition (1-I) or (1-II) described later.
  • the present invention is not limited to this.
  • this pressure-sensitive adhesive sheet 1 after photocuring exhibits foam resistance such that the diameter of the bubbles is 5 mm or less in the following foam resistance test.
  • Foam resistance test A laminate was prepared by sandwiching an adhesive sheet between two glass plates having a diagonal length of 5 inches or more and a thickness of 1 mm or less, in accordance with JIS K7350-2 (ISO 4822-2). When the light is irradiated for 24 hours with a xenon arc lamp light resistance tester, the diameter of bubbles generated in the pressure-sensitive adhesive sheet is measured.
  • the pressure-sensitive adhesive sheet 1 Since the pressure-sensitive adhesive sheet 1 has a feature that the viscosity at 70 to 100 ° C. after photocuring is 3000 to 50000 Pa ⁇ s, it can exhibit such foam resistance after photocuring. Therefore, it exhibits the property that the reliability does not decrease even if it is irradiated for a long time. Obtainable.
  • the present pressure-sensitive adhesive sheet 1 may be produced from the pressure-sensitive adhesive composition (1-I) or (1-II) described later. However, the present invention is not limited to this.
  • This pressure-sensitive adhesive composition 1 As a preferred example of the present pressure-sensitive adhesive composition 1 used for the production of the present pressure-sensitive adhesive sheet 1, an acrylic copolymer (1-A1) comprising a graft copolymer having a macromonomer as a branch component, and a crosslinking agent (1 An adhesive composition (1-I) containing -B1) and a photopolymerization initiator (1-C1) can be mentioned.
  • this pressure-sensitive adhesive sheet 1 is produced from the pressure-sensitive adhesive composition (1-I) or (1-II) prepared by a known method, it can exhibit self-adhesion while maintaining the sheet shape at room temperature, It has a hot melt property that melts or flows when heated in an uncrosslinked state, can be photocured, and exhibits excellent cohesive strength after photocuring.
  • the acrylic copolymer (1-A1) as the base polymer may be a graft copolymer having a macromonomer as a branch component.
  • the trunk component of the acrylic copolymer (1-A1) is preferably composed of a copolymer component containing a repeating unit derived from (meth) acrylic acid ester.
  • the glass transition temperature of the copolymer constituting the trunk component of the acrylic copolymer (1-A1) is preferably ⁇ 70 to 0 ° C.
  • the glass transition temperature of the copolymer component constituting the trunk component is the glass transition temperature of the polymer obtained by copolymerizing only the monomer component constituting the trunk component of the acrylic copolymer (1-A1).
  • Point. Specifically, it means a value calculated by the Fox formula from the glass transition temperature and the composition ratio of the polymer obtained from the homopolymer of each component of the copolymer.
  • the calculation formula of Fox is a calculation value calculated
  • the glass transition temperature of the copolymer component constituting the backbone component of the acrylic copolymer (1-A1) is determined depending on the flexibility of the pressure-sensitive adhesive composition (1-I) at room temperature, Since the wettability of the pressure-sensitive adhesive composition (1-I), that is, the adhesiveness is affected, in order for the pressure-sensitive adhesive composition (1-I) to obtain appropriate adhesiveness (tackiness) at room temperature, the glass
  • the transition temperature is preferably ⁇ 80 ° C. to 0 ° C., more preferably ⁇ 75 ° C. or higher or ⁇ 5 ° C. or lower, and particularly preferably ⁇ 70 ° C. or higher or ⁇ 10 ° C. or lower.
  • the viscoelasticity can be adjusted by adjusting the molecular weight. For example, it can be made more flexible by reducing the molecular weight of the copolymer component.
  • Examples of the (meth) acrylic acid ester monomer contained in the main component of the acrylic copolymer (1-A1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth).
  • n-butyl (meth) acrylate isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl ( Acrylate), t-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lau
  • hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate having a hydrophilic group or an organic functional group
  • ) Acrylic acid 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalate Acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- (me
  • Monomers containing amide groups, vinylpyrrolidone, vinylpyridine, heterocyclic basic monomers such as vinyl carbazole, etc. can also be used.
  • styrene, t-butylstyrene, ⁇ -methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, alkyl vinyl ether, hydroxyalkyl vinyl ether, alkyl which can be copolymerized with the above acrylic monomers and methacrylic monomers.
  • Various vinyl monomers such as vinyl monomers can also be used as appropriate.
  • the trunk component of the acrylic copolymer (1-A1) preferably contains a hydrophobic (meth) acrylate monomer and a hydrophilic (meth) acrylate monomer as constituent units.
  • the trunk component of the acrylic copolymer (1-A1) is composed only of a hydrophobic monomer, there is a tendency to wet-heat whitening. Is preferred.
  • the hydrophobic (meth) acrylate monomer is preferably an alkyl ester having no polar group (excluding methyl acrylate), such as n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) Acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, de
  • hydrophilic (meth) acrylate monomer methyl acrylate or an ester having a polar group is preferable.
  • the acrylic copolymer (1-A1) preferably contains a macromonomer-derived repeating unit as a branch component of the graft copolymer.
  • the macromonomer is a polymer monomer having a terminal polymerizable functional group and a high molecular weight skeleton component.
  • the glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer component constituting the acrylic copolymer (1-A1). Specifically, since the glass transition temperature (Tg) of the macromonomer affects the heating and melting temperature (hot melt temperature) of the pressure-sensitive adhesive composition (1-I), the glass transition temperature (Tg) of the macromonomer is 30.
  • the temperature is preferably from 120 ° C. to 120 ° C., more preferably from 40 ° C. to 110 ° C., and particularly preferably from 50 ° C. to 100 ° C.
  • the glass transition temperature of a macromonomer refers to the glass transition temperature of the macromonomer itself, and can be measured with a differential scanning calorimeter (DSC) (heating rate: 5 ° C./min, inflection of baseline shift) Tg is measured from the point).
  • DSC differential scanning calorimeter
  • the branch components are attracted to each other and can maintain a state where they are physically cross-linked as a pressure-sensitive adhesive composition, and the physical cross-linking is released by heating to an appropriate temperature.
  • the macromonomer is preferably contained in the acrylic copolymer (1-A1) in a proportion of 5% by mass to 30% by mass, particularly 6% by mass or more and 25% by mass or less. It is preferably at least 20% by mass or less than 20% by mass.
  • the number average molecular weight of the macromonomer is preferably 500 or more and less than 8000, more preferably 800 or more and less than 7500, and particularly preferably 1000 or more and less than 7000.
  • a generally produced one for example, a macromonomer manufactured by Toa Gosei Co., Ltd.
  • the high molecular weight skeleton component of the macromonomer is preferably composed of an acrylic polymer or a vinyl polymer.
  • the high molecular weight skeleton component of the macromonomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) Acrylate, 2-ethylhexyl acrylate, n-octyl
  • Examples of the terminal polymerizable functional group of the macromonomer include a methacryloyl group, an acryloyl group, and a vinyl group.
  • Crosslinking agent (1-B1) for example, a crosslinking agent having two or more crosslinking groups such as an epoxy group, an isocyanate group, an oxetane group, a silanol group, and a (meth) acryloyl group can be appropriately selected.
  • a crosslinking agent having two or more crosslinking groups such as an epoxy group, an isocyanate group, an oxetane group, a silanol group, and a (meth) acryloyl group
  • the cross-linking agent (1-B1) is cross-linked in the adhesive material, so that the sheet has a high cohesive force in a high temperature environment instead of losing hot melt properties. It can be expressed and excellent foaming reliability can be obtained.
  • Examples of such (meth) acrylate include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin glycidyl ether di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polyalkoxydi (meth) acrylate , Bisphenol F polyalkoxy di (meth) acrylate, polyalkylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, ⁇ -caprolactone modified tris 2-hydroxyethyl) isocyanurate tri (meth)
  • a polyfunctional monomer or oligomer containing a polar functional group such as a hydroxyl group is preferable from the viewpoint of improving the adhesion to the adherend and the effect of suppressing the heat and whitening.
  • a polyfunctional (meth) acrylic acid ester having a hydroxyl group or a carboxyl group it is preferable to use a polyfunctional (meth) acrylic acid ester having a hydroxyl group or a carboxyl group. Therefore, from the viewpoint of preventing wet heat whitening, the acrylic copolymer (1-A1), that is, the graft copolymer, contains a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as a trunk component. Furthermore, it is preferable to use a polyfunctional (meth) acrylic acid ester having a hydroxyl group as the crosslinking agent (1-B).
  • the content of the crosslinking agent (1-B1) is not particularly limited. As a guideline, 0.5 to 20 parts by mass with respect to 100 parts by mass of the acrylic copolymer (1-A1), especially 1 to 15 parts by mass, and more than 2 to 10 parts by mass. It is preferable that the ratio is By containing the cross-linking agent (1-B1) in the above range, both the shape stability of the present pressure-sensitive adhesive sheet 1 in an uncrosslinked state and the anti-foaming reliability of the pressure-sensitive adhesive material after crosslinking can be achieved. However, this range may be exceeded in balance with other elements.
  • the photopolymerization initiator (1-C1) functions as a reaction initiation assistant in the crosslinking reaction of the crosslinking agent (1-B1) described above.
  • the photopolymerization initiator those currently known can be used as appropriate.
  • a photopolymerization initiator that is sensitive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of easy control of the crosslinking reaction.
  • a photopolymerization initiator that is sensitive to light having a wavelength longer than 380 nm is preferable in that the sensitive light can easily reach the deep part of the pressure-sensitive adhesive sheet 1.
  • Photopolymerization initiators are roughly classified into two types depending on the radical generation mechanism, a cleavage type photopolymerization initiator that can cleave and decompose a single bond of the photopolymerization initiator itself, and a photoexcited initiator. And a hydrogen donor in the system form an exciplex and can be roughly classified into a hydrogen abstraction type photopolymerization initiator that can transfer hydrogen of the hydrogen donor.
  • the cleavage type photopolymerization initiator is decomposed when a radical is generated by light irradiation to be another compound, and once excited, it does not function as a reaction initiator. For this reason, it does not remain as an active species in the pressure-sensitive adhesive after the crosslinking reaction is completed, and it is not likely to cause unexpected light degradation or the like in the pressure-sensitive adhesive, which is preferable.
  • a hydrogen abstraction type photopolymerization initiator does not generate a decomposition product such as a cleavage type photopolymerization initiator during radical generation reaction by irradiation of active energy rays such as ultraviolet rays, so that it is difficult to become a volatile component after completion of the reaction. This is useful in that damage to the body can be reduced.
  • cleavage type photoinitiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- ON, 1- (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- ⁇ 4- (2-hydroxy-2 -Methyl-propionyl) benzyl ⁇ phenyl] -2-methyl-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), phenylglyoxylic Methyl acid, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- ON, 2- (dimethylamino
  • Examples of the hydrogen abstraction type photoinitiator include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4- (meth) Acryloyloxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate, bis (2-phenyl-2-oxoacetic acid) oxybisethylene, 4- (1,3-acryloyl-1,4,7,10,13- Pentaoxotridecyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2,4-dimethylthioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone and their derivatives And so on.
  • the photopolymerization initiator is not limited to the substances listed above. Any one of the above-mentioned cleavage type photopolymerization initiator and hydrogen abstraction type photopolymerization initiator may be used, or two or more kinds may be used in combination.
  • the content of the photopolymerization initiator (1-C1) is not particularly limited. As a guideline, 0.1 to 10 parts by weight, especially 0.5 parts by weight or more and 5 parts by weight or less, and more preferably 1 part by weight or more or 3 parts by weight with respect to 100 parts by weight of the acrylic copolymer (1-A1). It is preferable to contain it in the ratio below the part.
  • the pressure-sensitive adhesive composition (1-I) may contain known components blended in a normal pressure-sensitive adhesive composition as components other than those described above. For example, if necessary, tackifier resin, antioxidant, light stabilizer, metal deactivator, anti-aging agent, hygroscopic agent, polymerization inhibitor, ultraviolet absorber, rust inhibitor, silane coupling agent Various additives such as inorganic particles can be appropriately contained. Moreover, you may contain reaction catalyst (A tertiary amine type compound, a quaternary ammonium type compound, a lauric acid tin compound, etc.) suitably as needed.
  • reaction catalyst A tertiary amine type compound, a quaternary ammonium type compound, a lauric acid tin compound, etc.
  • An agent composition can be mentioned.
  • the (meth) acrylic copolymer (1-A2) as the base polymer is preferably a (meth) acrylic acid ester copolymer or a vinyl copolymer.
  • the (meth) acrylic acid ester copolymer or vinyl copolymer preferably has a weight average molecular weight of 50,000 to 500,000, particularly 60000 from the viewpoint of achieving both shape retention at room temperature and hot melt properties. It is more preferably 450,000 or less, more preferably 70000 or more and 400000 or less.
  • Acrylic acid ester-based copolymers have physical properties such as glass transition temperature (Tg) and molecular weight by appropriately selecting the types, composition ratios, and polymerization conditions of acrylic monomers and methacrylic monomers used to adjust them. Can be adjusted as appropriate.
  • examples of the acrylic monomer constituting the acrylic ester copolymer include 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, n-butyl acrylate, ethyl acrylate, and the like as main raw materials.
  • a (meth) acrylic monomer having various functional groups may be copolymerized with the acrylic monomer according to the purpose of imparting cohesive force or imparting polarity.
  • the (meth) acrylic monomer having a functional group include methyl methacrylate, methyl acrylate, hydroxyethyl acrylate, acrylic acid, glycidyl acrylate, N-substituted acrylamide, acrylonitrile, methacrylonitrile, fluorine-containing alkyl acrylate, and organosiloxy group An acrylate etc. can be mentioned.
  • examples of the vinyl copolymer include vinyl copolymers obtained by appropriately polymerizing vinyl acetate copolymerizable with the above acrylic monomer and methacrylic monomer, and various vinyl monomers such as alkyl vinyl ether and hydroxyalkyl vinyl ether. .
  • the (meth) acrylic copolymer (1-A2) of the pressure-sensitive adhesive sheet 1 includes a monomer a1 having a glass transition temperature (Tg) of less than 0 ° C. and a glass transition temperature (Tg) of from 0 ° C. to less than 80 ° C.
  • the glass transition temperatures (Tg) of the monomers a1, a2, and a3 are the meanings of the glass transition temperatures (Tg) when a polymer is produced from the monomer (homogenization).
  • the monomer a1 is preferably a (meth) acrylic acid ester monomer having an alkyl group structure having a side chain having 4 or more carbon atoms, for example.
  • the side chain having 4 or more carbon atoms may be a straight chain or a branched carbon chain.
  • the monomer a1 is a (meth) acrylate monomer having a linear alkyl group structure having 4 to 10 carbon atoms, or a branched alkyl group structure having 6 to 18 carbon atoms ( It is preferably a (meth) acrylic acid ester monomer.
  • (meth) acrylic acid ester monomer having a linear alkyl group structure having 4 to 10 carbon atoms includes n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n- A decyl acrylate etc. can be mentioned.
  • examples of the “(meth) acrylic acid ester monomer having a branched alkyl group structure having 6 to 18 carbon atoms” include 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-methylhexyl acrylate, isooctyl acrylate, isononyl acrylate, Examples include isodecyl acrylate and isodecyl methacrylate.
  • the monomer a2 has a (meth) acrylic acid ester monomer having 4 or less carbon atoms, a (meth) acrylic acid ester monomer having a cyclic skeleton in the side chain, a vinyl monomer having 4 or less carbon atoms, or a cyclic skeleton in the side chain.
  • a vinyl monomer is preferred.
  • the monomer a2 is particularly preferably a vinyl monomer having 4 or less carbon atoms in the side chain.
  • the “(meth) acrylic acid ester monomer having 4 or less carbon atoms” includes methyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl methacrylate, t- Examples thereof include butyl acrylate, isobutyl acrylate, and isobutyl methacrylate.
  • “(Meth) acrylic acid ester monomer having a cyclic skeleton in the side chain” includes isobornyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, tetrahydrofurfuryl methacrylate, benzyl acrylate, benzyl methacrylate , Phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, cyclic trimethylolpropane formal acrylate, 4-ethoxylated cumylphenol acrylate, dicyclopentenyl Oxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl acrylate - it can be mentioned, such as theft.
  • Examples of the “vinyl monomer having 4 or less carbon atoms” include vinyl acetate, vinyl propionate, vinyl butyrate, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and the like.
  • Examples of the “vinyl monomer having a cyclic skeleton in the side chain” include styrene, cyclohexyl vinyl ether, norbornyl vinyl ether, norbornenyl vinyl ether and the like. Among these, a vinyl monomer having 4 or less carbon atoms in the side chain or an acrylate monomer having 4 or less carbon atoms in the side chain is particularly suitable.
  • the monomer a3 is preferably a (meth) acrylic acid ester monomer having a side chain having 1 or less carbon atoms or a (meth) acrylic acid ester monomer having a cyclic skeleton in the side chain.
  • examples of the “(meth) acrylic acid ester monomer having a side chain having 1 or less carbon atoms” include methyl methacrylate, acrylic acid, and methacrylic acid.
  • Examples of the (meth) acrylate monomer having a cyclic skeleton in the side chain include isobornyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, And cyclopentenyl methacrylate.
  • the monomer a1, the monomer a2, and the monomer a3 in the (meth) acrylic ester copolymer or vinyl copolymer constituting the (meth) acrylic copolymer (1-A2) Is preferably a2>a1> a3.
  • Crosslinking agent (1-B2) By crosslinking the crosslinking agent (1-B2) in the pressure-sensitive adhesive sheet 1, the pressure-sensitive adhesive sheet 1 exhibits a high cohesive force in a high-temperature environment and can obtain excellent foaming reliability.
  • a crosslinking agent (1-B2) for example, a crosslinking agent having two or more crosslinking groups such as an epoxy group, an isocyanate group, an oxetane group, a silanol group, and a (meth) acryloyl group can be appropriately selected.
  • a crosslinking agent having two or more crosslinking groups such as an epoxy group, an isocyanate group, an oxetane group, a silanol group, and a (meth) acryloyl group
  • Examples of such (meth) acrylates include 1,4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di ( (Meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, tri Methylolpropane trioxyethyl (meth) acrylate, ⁇ -caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate Propoxylated pentaerythritol tri (me
  • the content of the crosslinking agent (1-B2) is not particularly limited. As a standard, 0.5 to 20 parts by mass, especially 1 part by mass or more and 15 parts by mass or less, especially 2 parts by mass or more or 10 parts per 100 parts by mass of the (meth) acrylic copolymer (1-A2).
  • the ratio is preferably less than or equal to parts by mass.
  • the photopolymerization initiator (1-C2) serves as a reaction initiation assistant in the crosslinking reaction of the above-described crosslinking agent (1-B2).
  • the photopolymerization initiator (1-C2) Those described can be used as appropriate.
  • the content of the photopolymerization initiator (1-C2) is not particularly limited. As a guideline, 0.1 to 10 parts by weight, especially 0.5 parts by weight or more and 5 parts by weight or less, and more preferably 1 part by weight or more with respect to 100 parts by weight of the (meth) acrylic copolymer (1-A2) Or it is preferable to contain in the ratio of 3 mass parts or less.
  • the pressure-sensitive adhesive composition (1-II) may contain known components blended in a normal pressure-sensitive adhesive composition as components other than those described above.
  • tackifier resin antioxidant, light stabilizer, metal deactivator, anti-aging agent, hygroscopic agent, polymerization inhibitor, ultraviolet absorber, rust inhibitor, silane coupling agent
  • reaction catalyst A tertiary amine type compound, a quaternary ammonium type compound, a lauric acid tin compound, etc.
  • the pressure-sensitive adhesive sheet 1 may be a single-layer sheet or a multilayer sheet in which two or more layers are laminated.
  • the pressure-sensitive adhesive sheet 1 is a multi-layer pressure-sensitive adhesive sheet, it is only necessary to have a pressure-sensitive adhesive layer (referred to as “the present pressure-sensitive adhesive layer 1”) formed from the pressure-sensitive adhesive composition 1, for example, an intermediate layer and an outermost layer.
  • the outermost layer is preferably formed from the present pressure-sensitive adhesive composition 1, and among them, the pressure-sensitive adhesive composition (1-I) (1-II). .
  • this adhesive sheet 1 may be provided with the structure formed by forming this adhesive layer 1 formed from this adhesive composition 1 on a release film, and, for example, an adherend, for example
  • the structure which forms the said this adhesion layer 1 in the structural member for image displays as mentioned later may be provided.
  • it may be a pressure-sensitive adhesive sheet with a base material having a configuration in which the main pressure-sensitive adhesive layer 1 is formed on a base material, or a base-less pressure-sensitive adhesive sheet having no base material.
  • the double-sided pressure-sensitive adhesive sheet having the main pressure-sensitive adhesive layer 1 on both upper and lower sides may be used, or the single-sided pressure-sensitive adhesive sheet having the main pressure-sensitive adhesive layer 1 only on the upper and lower single-sided sides.
  • the thickness of the maximum thickness portion is preferably 250 ⁇ m or less.
  • the pressure-sensitive adhesive sheet 1 may be a sheet having a uniform thickness or a non-uniform sheet having a partially different thickness.
  • the thickness of the thick part is preferably 250 ⁇ m or less.
  • the thickness of the maximum thickness portion is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 15 ⁇ m or more.
  • the pressure-sensitive adhesive sheet 1 can be used as it is, but can also be used as follows. However, the usage method of this adhesive sheet 1 is not limited.
  • the present adhesive sheet 1 can be provided, for example, as an adhesive sheet laminate having a configuration in which a release film is laminated on one or both surfaces of the present adhesive sheet 1.
  • an image display device configuration laminate having a configuration in which two image display device components are laminated via the pressure-sensitive adhesive sheet 1 (hereinafter referred to as “the image display device configuration laminate 1”). .) Can be made and provided.
  • the image display device constituting laminate 1 is formed by, for example, laminating an image display device constituting member and another image display device constituting member via the present adhesive sheet 1, and the former image display device constituting member. It can be produced by irradiating the pressure-sensitive adhesive sheet 1 via a light and photocuring the pressure-sensitive adhesive sheet.
  • the laminate 1 for constituting the present image display device in addition to the laminate comprising the configuration of the protective panel / the present adhesive sheet 1 / polarizing film, for example, the image display panel / the present adhesive sheet 1 / touch panel, the image display panel / the present adhesive.
  • a configuration example of a protective panel can be given.
  • the protection panel and the image display panel may include a touch panel sensor incorporated in the protection panel or the image display panel itself.
  • the pressure-sensitive adhesive sheet 1 is heated and hot-melted, and the image display device component and another image display device component are laminated via the pressure-sensitive adhesive sheet 1.
  • the present pressure-sensitive adhesive sheet 1 is moderately soft, it can sufficiently follow the steps while maintaining storage stability.
  • light such as ultraviolet rays is irradiated from the outside of the constituent member for an image display device.
  • the crosslinking reaction proceeds and can be photocured, and excellent peel resistance and foam resistance can be realized.
  • the two image display device components include, for example, personal computers, mobile terminals (PDAs), game machines, televisions (TVs), car navigation systems, touch panels, pen tablets, and other image display devices such as LCDs, PDPs, and ELs.
  • PDAs mobile terminals
  • TVs televisions
  • car navigation systems touch panels
  • pen tablets and other image display devices
  • LCDs LCDs
  • PDPs PDPs
  • ELs electrostatic display devices
  • any one of a group consisting of a touch panel, an image display panel, a surface protection panel, and a polarizing film, or a laminate composed of a combination of two or more types can be given.
  • An adhesive sheet according to an example of another embodiment of the present invention contains a (meth) acrylic copolymer (A) as a base polymer and is partially photocured.
  • a sheet part having a gel fraction of less than 1% referred to as “soft part” and a sheet part having a gel fraction of 40% or more (“hard part”).
  • the pressure-sensitive adhesive sheet contains a (meth) acrylic copolymer (A) as a base polymer and is partially photocured.
  • Examples of the method for measuring the gel fraction include extraction with a solvent. Specifically, when the polymer constituting the pressure-sensitive adhesive sheet is not crosslinked, a solvent (good solvent) that dissolves the polymer is selected, and then the pressure-sensitive adhesive sheet is extracted using the solvent.
  • the solvent for extraction include ethyl acetate, acetone, toluene, xylene, lower alcohol, tetrahydrofuran and the like. What is necessary is just to set arbitrarily the temperature and time at the time of extraction. After performing the extraction operation, the component that does not dissolve in the solvent (swelling component) is collected and dried, and then the weight fraction may be measured. Specific examples of the extraction method include Soxhlet extraction and methods described in Examples described later. In addition, when a gel fraction is high, you may crush an adhesive sheet suitably and use for extraction.
  • a display screen of a mobile phone employs a configuration in which a polarizing film or the like is laminated on a liquid crystal panel display (LCD), and a plastic protective panel is laminated thereon via an adhesive or sheet.
  • a light-impermeable portion such as a printing portion is attached to the peripheral portion of the back surface of the protective panel.
  • the pressure-sensitive adhesive sheet is not smooth, the pressure-sensitive adhesive sheet is distorted or deformed when the image display constituent member is bonded, and this causes a decrease in visibility due to display unevenness. Is required. In addition, there is a problem that distortion and deformation easily occur in the pressure-sensitive adhesive sheet due to a printing step or the like. On the other hand, the exposed adhesive surface is required not to be sticky even under harsh environments such as high temperature and high humidity. In addition, the adhesive sheet after the image display device constituent member is bonded via the adhesive sheet is also required to have high cohesive force that does not cause peeling or foaming.
  • the present invention is capable of following a stepped portion or the like even when, for example, a component for an image display device having a light impermeable portion such as a printing portion and a light transmissive portion on the bonding surface is bonded. And surface flatness can be obtained without causing distortion or deformation even in the light-impermeable portion, and the adherends can be firmly bonded with high cohesive force.
  • the present invention is intended to provide a new pressure-sensitive adhesive sheet 2 that can prevent the exposed pressure-sensitive adhesive surface from becoming sticky even under severe conditions.
  • the “base polymer” means a resin constituting the main component of the pressure-sensitive adhesive composition forming each layer.
  • the specific content of the base polymer is not specified, but as a guideline, it is 50% by mass or more of the resin contained in the pressure-sensitive adhesive composition forming each layer, particularly 80% by mass or more, of which 90% by mass or more. (Including 100% by mass).
  • the total amount thereof corresponds to the content.
  • the gel fraction of the soft part is preferably less than 1% from the viewpoint that the followability to the step part, surface flatness, and further distortion and deformation in the sheet can be relaxed, and in particular 0.8 It is particularly preferably less than 0.5%, and more preferably less than 0.5%.
  • the gel fraction of the hard part is 40% or more from the viewpoint of exhibiting a high cohesive force to improve the adhesiveness, and the adhesive surface does not become sticky even under severe environments such as high temperature and high humidity. Among them, 45% or more is preferable, and 50% or more is particularly preferable.
  • the glass transition temperature (Tg [S]) of the soft part measured using a differential scanning calorimeter (DSC) is ⁇ 70 to ⁇ 10 ° C.
  • the Tg of the soft part is preferably ⁇ 70 to ⁇ 10 ° C., more preferably ⁇ 65 ° C. or higher or ⁇ 15 ° C. or lower, and particularly preferably ⁇ 60 ° C. or higher or ⁇ 20 ° C. or lower.
  • the glass transition temperature (Tg [H]) of the hard part measured using a differential scanning calorimeter (DSC) is ⁇ 60 to + 10 ° C., a high cohesive force can be obtained.
  • Tg is preferably ⁇ 60 to + 20 ° C., more preferably ⁇ 55 ° C. or more and + 15 ° C. or less, and particularly preferably ⁇ 50 ° C. or more and + 10 ° C. or less. Further, if the difference (Tg [H] ⁇ Tg [S]) between the glass transition temperature (Tg [S]) of the soft part and the glass transition temperature (Tg [H]) of the hard part is 3 ° C. or more, the flexibility As a result of satisfying the contradiction quality of the cohesive force at a higher level, it is possible to satisfy both the followability to the adherend surface at the time of bonding and the excellent anti-foaming reliability after forming the laminate.
  • the difference (Tg [H] ⁇ Tg [S]) in the glass transition temperature (Tg [H]) of the hard part is preferably 3 ° C. or more, especially 5 ° C. or more, and more preferably 7 ° C. or more. Is particularly preferred.
  • the Asker hardness (c) of the soft part in the pressure-sensitive adhesive sheet 2 is 10 or more, it is preferable because appropriate hardness related to cutting workability and ease of handling can be obtained. Further, it is preferable that the Asker hardness (c) is less than 60 because moderate flexibility and adhesion to an adherend can be obtained. From this viewpoint, the Asker hardness (c) of the soft part in the pressure-sensitive adhesive sheet 2 is preferably 10 or more and less than 60, more preferably 15 or more and 55 or less, and particularly preferably 20 or more and 50 or less.
  • the Asker hardness (d) of the hard part in the pressure-sensitive adhesive sheet 2 is 40 or more, a high cohesive force can be obtained, and a laminate having excellent shape stability and foam resistance can be obtained. Moreover, when the Asker hardness (d) is less than 90, it is preferable because a laminate having excellent impact resistance can be obtained without becoming too brittle. From this viewpoint, the Asker hardness (d) of the hard part in the pressure-sensitive adhesive sheet 2 is preferably 40 or more and less than 90, particularly 43 or 88 or less, and particularly preferably 45 or 85 or less.
  • the difference ((d)-(c)) between the Asker hardness (c) of the soft part and the Asker hardness (d) of the hard part is preferably 20 or more. It is particularly preferably 80 or less, more preferably 25 or more and 75 or less.
  • the composition ratio of the crosslinking agent and the photopolymerization initiator is adjusted in the composition and the production method, What is necessary is just to adjust the light irradiation amount to an agent composition.
  • it is not limited to such a method.
  • the 180 ° peeling force of the soft part in the pressure-sensitive adhesive sheet 2 is 3 N / cm or more, it has an appropriate adhesion to the adherend at normal temperature and is excellent in the bonding workability, which is preferable.
  • the 180 ° peeling force of the soft part in the present adhesive sheet 2 is preferably 3 N / cm or more, particularly 20 N / cm or less, particularly 4 N / cm or more or 15 N / cm or less. preferable.
  • the 180 ° peeling force of the hard part in this pressure-sensitive adhesive sheet 2 is 5 N / cm or more, excellent foaming resistance and peelability are obtained, which is preferable. From this point of view, the 180 ° peeling force of the hard part in the pressure-sensitive adhesive sheet 2 is preferably 5 N / cm or more, more preferably 25 N / cm or less, and particularly preferably 6 N / cm or more or 20 N / cm or less. .
  • this pressure-sensitive adhesive sheet 2 in order to adjust the 180 ° peeling force of the soft part and the hard part, in the composition and the production method, the kind and composition ratio of the crosslinking agent and the photopolymerization initiator are adjusted, What is necessary is just to adjust pressurization conditions and the light irradiation conditions after bonding. However, it is not limited to such a method.
  • the holding force at a temperature of 40 ° C. of the soft part in the pressure-sensitive adhesive sheet 2 is less than 10 mm, the excellent processability and storage stability can be obtained. From such a viewpoint, the holding force at a temperature of 40 ° C. of the soft part of the pressure-sensitive adhesive sheet 2 is preferably less than 10 mm, more preferably less than 8 mm, and most preferably less than 5 mm.
  • the sticking surface shifts and the weight falls in less than 10 minutes with respect to the holding force at a temperature of 70 ° C. of the soft part in the pressure-sensitive adhesive sheet 2, excellent adhesion to the adherend at the time of bonding. And unevenness absorbability are obtained.
  • the holding force at a temperature of 70 ° C. of the soft part in the pressure-sensitive adhesive sheet 2 that the sticking surface shifts in less than 10 minutes and the weight falls, and in particular, the sticking surface shifts in less than 8 minutes. It is more preferable that the weight is dropped, and it is further more preferable that the sticking surface is shifted and the weight is dropped within 6 minutes.
  • the holding force at 40 ° C. and 70 ° C. of the hard part of the pressure-sensitive adhesive sheet 2 is preferably such that the deviation length is less than 1 mm, more preferably less than 0.7 mm, and less than 0.5 mm. Is more preferable.
  • the holding power at 40 ° C. and 70 ° C. of the hard part in the pressure-sensitive adhesive sheet 2 is in the above range, high cohesive force can be obtained, and shape stability and foaming reliability can be obtained in a humid heat environment. .
  • This adhesive sheet 2 can be produced as follows.
  • a light-impermeable member that is, a light-impermeable member used for photocuring
  • the portion covered with can be made a soft portion, and the portion not covered with the light-impermeable member, that is, the portion irradiated with light can be photocured to be a hard portion.
  • the end surface portion of the pressure-sensitive adhesive sheet is made a hard portion and the other portion is made a soft portion.
  • light may be irradiated from the vertical direction, horizontal direction, or diagonally up and down direction (assuming that the front and back sides of the sheet are arranged vertically and vertically) to the end surface portion of the adhesive sheet.
  • a light-impervious sheet used for photocuring may be laminated on the side or both sides, and light may be irradiated from the vertical direction, the horizontal direction, or the diagonally up and down direction.
  • a release sheet having polyethylene terephthalate as a base polymer, a polyethylene terephthalate film or a polyolefin film is kneaded with an ultraviolet absorber, or the surface absorbs ultraviolet rays. It is particularly preferable to use a release sheet that does not transmit light used for photocuring, such as a release sheet using a film coated with an agent.
  • an end surface part and its peripheral part may become a hard part.
  • a soft part and a hard part can be formed in an adhesive sheet even if it prepares the adhesive sheet which each has a desired gel fraction separately, and makes both integrate.
  • the pressure-sensitive adhesive sheet X has a gel fraction (a) before photocuring of less than 1%, particularly less than 0.8%, and more preferably less than 0.5% from the viewpoint that it can exhibit hot melt properties before photocuring. It is particularly preferred that it is less than%.
  • the pressure-sensitive adhesive sheet X can obtain a high cohesive force after photocuring, and the gel fraction (b) after photocuring is 40% or more from the viewpoint of obtaining foaming reliability in a wet heat environment. Of these, 45% or more or 95% or less is preferable, and 50% or more or 90% or less is particularly preferable.
  • the composition ratio of the crosslinking agent and photopolymerization initiator can be adjusted in the composition and production method.
  • the temperature during processing and the amount of light irradiation may be adjusted. However, it is not limited to such a method.
  • the present pressure-sensitive adhesive composition 2 A resin composition (hereinafter referred to as “the present pressure-sensitive adhesive composition 2”) that can be suitably used to form the pressure-sensitive adhesive sheet X will be described. However, this is only an example, and the present invention is not limited to this.
  • the pressure-sensitive adhesive composition 2 is preferably a photocurable pressure-sensitive adhesive composition.
  • a resin composition containing a (meth) acrylic copolymer (2-A), a crosslinking agent (2-B), and a photopolymerization initiator (2-C) is preferable.
  • the composition of the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive sheet 2 is limited as long as the gel fraction after sticking can be varied depending on the site in the pressure-sensitive adhesive sheet. It is not a thing.
  • the pressure-sensitive adhesive sheet 2 can normally maintain a sheet shape, has a hot melt property that melts or flows when heated in an uncrosslinked state, and can be photocured. It is particularly preferable that the PSA sheet has If the sheet shape can be maintained in a normal state, it is easy to handle as compared with the liquid adhesive, and the work of filling the liquid can be omitted, so that the productivity is particularly excellent. In addition, if it has a normal stickiness, that is, a property of adhering to an adherend with a light force in a short time (called “tackiness”) in the normal state, that is, near room temperature, positioning is performed when sticking.
  • tackiness a property of adhering to an adherend with a light force in a short time
  • tackiness in the normal state that is, near room temperature
  • it has a hot melt property that melts or flows when heated it can be softened or fluidized by heating so that it can be filled with the adhesive following the uneven portions such as a printing step. It can be filled without causing such as.
  • it has photocurability it can adhere
  • a pressure-sensitive adhesive sheet that can normally maintain a sheet shape, has a hot melt property that melts or flows when heated in an uncrosslinked state, and can be photocured.
  • a single-layer pressure-sensitive adhesive sheet may be prepared from the pressure-sensitive adhesive composition (2-I) or (2-II) described below.
  • a multilayer pressure-sensitive adhesive sheet for example, two types 2 in which a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive composition (2-I) or (2-II) and a pressure-sensitive adhesive layer made of another pressure-sensitive adhesive composition are laminated.
  • Layer structure two-type three-layer structure in which an adhesive layer made of an adhesive composition (2-I) or (2-II) is arranged on the front and back via an intermediate resin layer, or an adhesive composition (2-I ) Or (2-II), an intermediate layer composed of an intermediate resin composition, and an adhesive layer composed of another pressure-sensitive adhesive composition are laminated in this order.
  • the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive sheet 2 is not limited to the pressure-sensitive adhesive composition (2-I) or (2-II).
  • the acrylic copolymer (2-A1) as the base polymer may be a graft copolymer having a macromonomer as a branch component.
  • the trunk component of the acrylic copolymer (2-A1) is preferably composed of a copolymer component containing a repeating unit derived from (meth) acrylic acid ester.
  • the glass transition temperature of the copolymer constituting the main component of the acrylic copolymer (2-A1) is preferably ⁇ 70 to 0 ° C.
  • the glass transition temperature of the copolymer component constituting the trunk component is the glass transition temperature of the polymer obtained by copolymerizing only the monomer component constituting the trunk component of the acrylic copolymer (2-A1).
  • Point. Specifically, it means a value calculated by the Fox formula from the glass transition temperature and the composition ratio of the polymer obtained from the homopolymer of each component of the copolymer.
  • the calculation formula of Fox is a calculation value calculated
  • the glass transition temperature of the copolymer component constituting the backbone component of the acrylic copolymer (2-A1) is determined depending on the flexibility of the pressure-sensitive adhesive composition (2-I) at room temperature, Since the wettability of the pressure-sensitive adhesive composition (2-I), that is, the adhesiveness is affected, in order for the pressure-sensitive adhesive composition (2-I) to obtain appropriate adhesiveness (tackiness) at room temperature, the glass
  • the transition temperature is preferably ⁇ 70 ° C. to 0 ° C., more preferably ⁇ 65 ° C. or higher or ⁇ 5 ° C. or lower, and particularly preferably ⁇ 60 ° C. or higher or ⁇ 10 ° C. or lower.
  • the viscoelasticity can be adjusted by adjusting the molecular weight. For example, it can be made more flexible by reducing the molecular weight of the copolymer component.
  • Examples of the (meth) acrylic acid ester monomer contained in the main component of the acrylic copolymer (2-A1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth).
  • n-butyl (meth) acrylate isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl ( Acrylate), t-butylcyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, lau
  • hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glycerol (meth) acrylate having a hydrophilic group or an organic functional group
  • ) Acrylic acid 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalate Acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- (me
  • Monomers containing amide group, vinyl pyrrolidone, vinyl pyridine can also be used heterocyclic basic monomers such as vinyl carbazole.
  • styrene, t-butylstyrene, ⁇ -methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, alkyl vinyl ether, hydroxyalkyl vinyl ether, alkyl which can be copolymerized with the above acrylic monomers and methacrylic monomers.
  • Various vinyl monomers such as vinyl monomers can also be used as appropriate.
  • the trunk component of the acrylic copolymer (2-A1) preferably contains a hydrophobic (meth) acrylate monomer and a hydrophilic (meth) acrylate monomer as constituent units. If the trunk component of the acrylic copolymer (2-A1) is composed only of a hydrophobic monomer, there is a tendency to wet-heat whitening. Therefore, hydrophilic monomers are also introduced into the trunk component to prevent wet-heat whitening. Is preferred.
  • a hydrophobic (meth) acrylate monomer a hydrophilic (meth) acrylate monomer, and a polymerizable functional group at the terminal of the macromonomer
  • a copolymer component formed by random copolymerization a hydrophobic (meth) acrylate monomer, a hydrophilic (meth) acrylate monomer, and a polymerizable functional group at the terminal of the macromonomer
  • a copolymer component formed by random copolymerization a copolymer component formed by random copolymerization.
  • the hydrophobic (meth) acrylate monomer is preferably an alkyl ester having no polar group (excluding methyl acrylate), such as n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) Acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, de
  • hydrophilic (meth) acrylate monomer methyl acrylate or an ester having a polar group is preferable.
  • the acrylic copolymer (2-A1) preferably contains a macromonomer as a branch component of the graft copolymer and contains a repeating unit derived from the macromonomer.
  • the macromonomer is a polymer monomer having a terminal polymerizable functional group and a high molecular weight skeleton component.
  • the glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer component constituting the acrylic copolymer (2-A1). Specifically, since the glass transition temperature (Tg) of the macromonomer affects the heating and melting temperature (hot melt temperature) of the pressure-sensitive adhesive composition (2-I), the glass transition temperature (Tg) of the macromonomer is 30.
  • the temperature is preferably from 120 ° C. to 120 ° C., more preferably from 40 ° C. to 110 ° C., and particularly preferably from 50 ° C. to 100 ° C.
  • the glass transition temperature of the macromonomer refers to the glass transition temperature of the macromonomer itself, and can be measured with a differential scanning calorimeter (DSC). (Temperature increase rate: 5 ° C / min, Tg measured from inflection point of baseline shift)
  • the branch components are attracted to each other and can maintain a state where they are physically cross-linked as a pressure-sensitive adhesive composition, and the physical cross-linking is released by heating to an appropriate temperature.
  • the macromonomer is preferably contained in the acrylic copolymer (2-A1) at a ratio of 5% by mass to 30% by mass, especially 6% by mass or more and 25% by mass or less. It is preferably at least 20% by mass or less than 20% by mass.
  • the number average molecular weight of the macromonomer is preferably 500 or more and less than 8000, more preferably 800 or more and less than 7500, and particularly preferably 1000 or more and less than 7000.
  • a generally produced one for example, a macromonomer manufactured by Toa Gosei Co., Ltd.
  • the high molecular weight skeleton component of the macromonomer is preferably composed of an acrylic polymer or a vinyl polymer.
  • the high molecular weight skeleton component of the macromonomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) Acrylate, 2-ethylhexyl acrylate, n-octyl
  • Examples of the terminal polymerizable functional group of the macromonomer include a methacryloyl group, an acryloyl group, and a vinyl group.
  • Crosslinking agent (2-B1) for example, a crosslinking agent having two or more crosslinking groups such as an epoxy group, an isocyanate group, an oxetane group, a silanol group, and a (meth) acryloyl group can be appropriately selected. Among them, from the viewpoint of reactivity and the strength of the cured product to be obtained, it has a polyfunctional (meth) acrylate having 2 or more (meth) acryloyl groups, especially 3 or more, an epoxy group, an isocyanate group, or a silanol group (meta ) Acrylate is preferred.
  • the cross-linking agent (2-B1) is cross-linked in the adhesive material, so that the sheet has a high cohesive force in a high temperature environment instead of losing hot melt properties. It can be expressed and excellent foaming reliability can be obtained.
  • Examples of such (meth) acrylate include 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin glycidyl ether di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polyalkoxydi (meth) acrylate , Bisphenol F polyalkoxy di (meth) acrylate, polyalkylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, ⁇ -caprolactone modified tris 2-hydroxyethyl) isocyanurate tri (meth)
  • a polyfunctional monomer or oligomer containing a polar functional group such as a hydroxyl group is preferable from the viewpoint of improving the adhesion to the adherend and the effect of suppressing the heat and whitening.
  • a polyfunctional (meth) acrylic acid ester having a hydroxyl group or a carboxyl group it is preferable to use a polyfunctional (meth) acrylic acid ester having a hydroxyl group or a carboxyl group. Therefore, from the viewpoint of preventing wet heat whitening, the acrylic copolymer (2-A1), that is, the graft copolymer, contains a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as a trunk component. Furthermore, it is preferable to use a polyfunctional (meth) acrylic acid ester having a hydroxyl group as the crosslinking agent (2-B).
  • the content of the crosslinking agent (2-B1) is not particularly limited.
  • a guideline 0.5 to 20 parts by weight with respect to 100 parts by weight of the acrylic copolymer (2-A1), in particular 1 part to 15 parts by weight, and 2 parts to 10 parts by weight. It is preferable that the ratio is
  • the crosslinking agent (2-B1) in the above range both the shape stability of the pressure-sensitive adhesive sheet 2 in an uncrosslinked state and the anti-foaming reliability in the pressure-sensitive adhesive material after crosslinking can be achieved. However, this range may be exceeded in balance with other elements.
  • the photopolymerization initiator (2-C1) functions as a reaction initiation assistant in the crosslinking reaction of the aforementioned crosslinking agent (2-B1).
  • the photopolymerization initiator those currently known can be used as appropriate.
  • a photopolymerization initiator that is sensitive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of easy control of the crosslinking reaction.
  • a photopolymerization initiator that is sensitive to light having a wavelength longer than 380 nm is preferable in that the sensitive light easily reaches the deep part of the pressure-sensitive adhesive sheet 2.
  • Photopolymerization initiators are roughly classified into two types depending on the radical generation mechanism, a cleavage type photopolymerization initiator that can cleave and decompose a single bond of the photopolymerization initiator itself, and a photoexcited initiator. And a hydrogen donor in the system form an exciplex and can be roughly classified into a hydrogen abstraction type photopolymerization initiator that can transfer hydrogen of the hydrogen donor.
  • the cleavage type photopolymerization initiator is decomposed when a radical is generated by light irradiation to be another compound, and once excited, it does not function as a reaction initiator. For this reason, it does not remain as an active species in the pressure-sensitive adhesive after the crosslinking reaction is completed, and it is not likely to cause unexpected light degradation or the like in the pressure-sensitive adhesive, which is preferable.
  • a hydrogen abstraction type photopolymerization initiator does not generate a decomposition product such as a cleavage type photopolymerization initiator during radical generation reaction by irradiation of active energy rays such as ultraviolet rays, so that it is difficult to become a volatile component after completion of the reaction. This is useful in that damage to the body can be reduced.
  • cleavage type photoinitiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- ON, 1- (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- ⁇ 4- (2-hydroxy-2 -Methyl-propionyl) benzyl ⁇ phenyl] -2-methyl-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), phenylglyoxylic Methyl acid, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- ON, 2- (dimethylamino
  • Examples of the hydrogen abstraction type photoinitiator include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4- (meth) Acryloyloxybenzophenone, methyl 2-benzoylbenzoate, methyl benzoylformate, bis (2-phenyl-2-oxoacetic acid) oxybisethylene, 4- (1,3-acryloyl-1,4,7,10,13- Pentaoxotridecyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2,4-dimethylthioxanthone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone and their derivatives And so on.
  • the photopolymerization initiator is not limited to the substances listed above. Any one of the above-mentioned cleavage type photopolymerization initiator and hydrogen abstraction type photopolymerization initiator may be used, or two or more kinds may be used in combination.
  • the content of the photopolymerization initiator (2-C1) is not particularly limited. As a guideline, 0.1 to 10 parts by weight, particularly 0.5 parts by weight or more and 5 parts by weight or less, and more preferably 1 part by weight or more or 3 parts by weight, per 100 parts by weight of the acrylic copolymer (2-A1). It is preferable to contain it in the ratio below the part.
  • the pressure-sensitive adhesive composition (2-I) may contain known components blended in a normal pressure-sensitive adhesive composition as components other than those described above.
  • tackifier resin antioxidant, light stabilizer, metal deactivator, anti-aging agent, hygroscopic agent, polymerization inhibitor, ultraviolet absorber, rust inhibitor, silane coupling agent
  • reaction catalyst A tertiary amine type compound, a quaternary ammonium type compound, a lauric acid tin compound, etc.
  • the (meth) acrylic copolymer (2-A2) as the base polymer is preferably a (meth) acrylic acid ester copolymer or a vinyl copolymer.
  • the above (meth) acrylic acid ester copolymer or vinyl copolymer preferably has a weight average molecular weight of 50,000 to 400,000 from the viewpoint of achieving both shape retention at room temperature and hot melt properties. It is more preferably 350,000 or less, more preferably 70000 or more or 300000 or less.
  • Acrylic acid ester-based copolymers have physical properties such as glass transition temperature (Tg) and molecular weight by appropriately selecting the types, composition ratios, and polymerization conditions of acrylic monomers and methacrylic monomers used to adjust them. Can be adjusted as appropriate.
  • examples of the acrylic monomer constituting the acrylic ester copolymer include 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, n-butyl acrylate, ethyl acrylate, and the like as main raw materials.
  • a (meth) acrylic monomer having various functional groups may be copolymerized with the acrylic monomer according to the purpose of imparting cohesive force or imparting polarity.
  • the (meth) acrylic monomer having a functional group include methyl methacrylate, methyl acrylate, hydroxyethyl acrylate, acrylic acid, glycidyl acrylate, N-substituted acrylamide, acrylonitrile, methacrylonitrile, fluorine-containing alkyl acrylate, and organosiloxy group An acrylate etc. can be mentioned.
  • examples of the vinyl copolymer include vinyl copolymers obtained by appropriately polymerizing vinyl acetate copolymerizable with the above acrylic monomer and methacrylic monomer, and various vinyl monomers such as alkyl vinyl ether and hydroxyalkyl vinyl ether. .
  • the (meth) acrylic copolymer (2-A2) of the pressure-sensitive adhesive sheet 2 includes a monomer a having a glass transition temperature (Tg) of less than 0 ° C. and a glass transition temperature (Tg) of from 0 ° C. to less than 80 ° C.
  • the glass transition temperatures (Tg) of the monomers a, b and c are the meanings of the glass transition temperatures (Tg) when a polymer is produced from the monomers (homopolymerization).
  • the monomer a is preferably a (meth) acrylic acid ester monomer having an alkyl group structure having a side chain having 4 or more carbon atoms, for example.
  • the side chain having 4 or more carbon atoms may be a straight chain or a branched carbon chain.
  • the monomer a is a (meth) acrylic acid ester monomer having a linear alkyl group structure having 4 to 10 carbon atoms, or a branched alkyl group structure having 6 to 18 carbon atoms ( It is preferably a (meth) acrylic acid ester monomer.
  • (meth) acrylic acid ester monomer having a linear alkyl group structure having 4 to 10 carbon atoms includes n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n- A decyl acrylate etc. can be mentioned.
  • examples of the “(meth) acrylic acid ester monomer having a branched alkyl group structure having 6 to 18 carbon atoms” include 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-methylhexyl acrylate, isooctyl acrylate, isononyl acrylate, Examples include isodecyl acrylate and isodecyl methacrylate.
  • the monomer b has a (meth) acrylic acid ester monomer having 4 or less carbon atoms, a (meth) acrylic acid ester monomer having a cyclic skeleton in the side chain, a vinyl monomer having 4 or less carbon atoms, or a cyclic skeleton in the side chain.
  • a vinyl monomer is preferred.
  • the monomer b is particularly preferably a vinyl monomer having 4 or less carbon atoms in the side chain.
  • the “(meth) acrylic acid ester monomer having 4 or less carbon atoms” includes methyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl methacrylate, t- Examples thereof include butyl acrylate, isobutyl acrylate, and isobutyl methacrylate.
  • “(Meth) acrylic acid ester monomer having a cyclic skeleton in the side chain” includes isobornyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 1,4-cyclohexanedimethanol monoacrylate, tetrahydrofurfuryl methacrylate, benzyl acrylate, benzyl methacrylate , Phenoxyethyl acrylate, phenoxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, cyclic trimethylolpropane formal acrylate, 4-ethoxylated cumylphenol acrylate, dicyclopentenyl Oxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl acrylate - it can be mentioned, such as theft.
  • Examples of the “vinyl monomer having 4 or less carbon atoms” include vinyl acetate, vinyl propionate, vinyl butyrate, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and the like.
  • Examples of the “vinyl monomer having a cyclic skeleton in the side chain” include styrene, cyclohexyl vinyl ether, norbornyl vinyl ether, norbornenyl vinyl ether and the like. Among these, a vinyl monomer having 4 or less carbon atoms in the side chain or an acrylate monomer having 4 or less carbon atoms in the side chain is particularly suitable.
  • the monomer c is preferably a (meth) acrylic acid ester monomer having a side chain having 1 or less carbon atoms, or a (meth) acrylic acid ester monomer having a cyclic skeleton in the side chain.
  • examples of the “(meth) acrylic acid ester monomer having a side chain having 1 or less carbon atoms” include methyl methacrylate, acrylic acid, and methacrylic acid.
  • Examples of the (meth) acrylate monomer having a cyclic skeleton in the side chain include isobornyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, And cyclopentenyl methacrylate.
  • the molar ratio is preferably b>a> c.
  • Crosslinking agent (2-B2) By cross-linking the crosslinking agent (2-B2) in the pressure-sensitive adhesive sheet 2, the pressure-sensitive adhesive sheet 2 exhibits a high cohesive force in a high-temperature environment and can obtain excellent foaming reliability.
  • a crosslinking agent (2-B2) for example, a crosslinking agent having two or more crosslinking groups such as an epoxy group, an isocyanate group, an oxetane group, a silanol group, and a (meth) acryloyl group can be appropriately selected.
  • a polyfunctional (meth) acrylate having 2 or more (meth) acryloyl groups, especially 3 or more, an epoxy group, an isocyanate group, or a silanol group (meta ) Acrylate is preferred.
  • Examples of such (meth) acrylates include 1,4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di ( (Meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, tri Methylolpropane trioxyethyl (meth) acrylate, ⁇ -caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate Propoxylated pentaerythritol tri (me
  • a polyfunctional monomer or oligomer containing a polar functional group is preferable from the viewpoint of improving adhesion to the adherend, heat resistance, and wet heat whitening suppression effect.
  • polyfunctional (meth) acrylic acid ester having an isocyanuric ring skeleton is preferable to use.
  • the content of the crosslinking agent (2-B2) is not particularly limited. As a standard, 0.5 to 20 parts by mass, especially 1 part by mass or more and 15 parts by mass or less, especially 2 parts by mass or more or 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer (2-A2).
  • the ratio is preferably less than or equal to parts by mass.
  • the photopolymerization initiator (2-C2) serves as a reaction initiation assistant in the crosslinking reaction of the above-mentioned crosslinking agent (2-B2).
  • the photopolymerization initiator (2-C2) Those described can be used as appropriate.
  • the content of the photopolymerization initiator (2-C2) is not particularly limited. As a guideline, 0.1 to 10 parts by weight with respect to 100 parts by weight of (meth) acrylic copolymer (2-A2). Or it is preferable to contain in the ratio of 3 mass parts or less. By setting the content of the photopolymerization initiator (2-C2) within the above range, an appropriate reaction sensitivity to active energy rays can be obtained.
  • the pressure-sensitive adhesive composition (2-II) may contain known components blended in a normal pressure-sensitive adhesive composition as components other than those described above.
  • tackifier resin antioxidant, light stabilizer, metal deactivator, anti-aging agent, hygroscopic agent, polymerization inhibitor, ultraviolet absorber, rust inhibitor, silane coupling agent
  • reaction catalyst A tertiary amine type compound, a quaternary ammonium type compound, a lauric acid tin compound, etc.
  • the pressure-sensitive adhesive sheet X is prepared by a solution coating method in which the pressure-sensitive adhesive compositions (2-I) and (2-II) prepared by a known method are dissolved in a solvent, or the pressure-sensitive adhesive composition Examples include a hot melt coating method in which coating is performed by heating and melting.
  • the target pressure-sensitive adhesive sheet it is not particularly limited and can be prepared by a known method.
  • the pressure-sensitive adhesive compositions (2-I) and (2-II) when a thin film product having a thickness of 50 ⁇ m or less is molded, it is preferable to employ a solution coating method from the viewpoint of easy thickness control.
  • a hot melt coating method in view of environmental pollution and ease of thick film molding.
  • the pressure-sensitive adhesive sheet 2 may be a single-layer sheet or a multilayer sheet in which two or more layers are laminated.
  • this adhesive sheet 2 is used as a multilayer transparent double-sided adhesive material, as a laminated structure, specifically, a two-type two-layer structure in which the present adhesive composition 2 and another adhesive resin composition are laminated,
  • a two-kind three-layer configuration in which the present pressure-sensitive adhesive composition 2 is arranged on the front and back via the intermediate resin layer, the present pressure-sensitive adhesive composition 2, the intermediate resin composition, and the other pressure-sensitive adhesive resin composition in this order.
  • a three-layer three-layer structure formed by laminating can be exemplified.
  • the outermost layer is preferably formed from the present pressure-sensitive adhesive composition 2, for example, the above-mentioned pressure-sensitive adhesive composition (2-I) (2-II).
  • the present pressure-sensitive adhesive composition 2 and another pressure-sensitive adhesive resin composition are each formed into a sheet shape on different release films or image display device constituent members, and both pressure-sensitive adhesive surfaces are laminated to form the present pressure-sensitive adhesive sheet 2.
  • the present pressure-sensitive adhesive composition 2, the intermediate resin composition, and the pressure-sensitive adhesive resin composition are coextruded in this order to obtain a two-kind three-layered pressure-sensitive adhesive sheet 2.
  • the pressure-sensitive adhesive sheet 2 may be obtained by laminating the pressure-sensitive adhesive composition 2 or another pressure-sensitive adhesive resin composition on the front and back surfaces of the intermediate resin layer.
  • a pressure-sensitive adhesive sheet with a base material provided with a pressure-sensitive adhesive layer (referred to as “the present pressure-sensitive adhesive layer 2”) formed from the pressure-sensitive adhesive composition 2 is a group having no base material.
  • a material-less pressure-sensitive adhesive sheet may be used.
  • it may be a double-sided pressure-sensitive adhesive sheet having the main pressure-sensitive adhesive layer 2 on both upper and lower sides, or may be a single-sided pressure-sensitive adhesive sheet having the main pressure-sensitive adhesive layer 2 only on the upper and lower sides.
  • the thickness of the maximum thickness portion is preferably 250 ⁇ m or less.
  • the pressure-sensitive adhesive sheet 2 may be a sheet having a uniform thickness or a non-uniform sheet having a partially different thickness.
  • the thickness of the thick part is preferably 250 ⁇ m or less.
  • the thickness of the maximum thickness portion is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 15 ⁇ m or more.
  • the present adhesive sheet 2 can be used as it is, but can also be used as follows. However, the usage method of this adhesive sheet 2 is not limited.
  • This adhesive sheet 2 can be provided as the adhesive sheet laminated body 2 provided with the structure which laminates
  • the present pressure-sensitive adhesive sheet 2 may have a form having the soft portion and the hard portion in the sheet surface.
  • At least one end surface portion of the pressure-sensitive adhesive sheet may have the hard portion.
  • the entire end surface portion may be the hard portion, or a part of the end surface portion may be the hard portion.
  • FIGS. 4 (A) and 4 (B) if the end surface portion of the pressure-sensitive adhesive sheet 2 is a hard portion, the exposed end surface portion becomes sticky even under a severe environment such as high temperature and high humidity. Therefore, it can be suitably stored.
  • this adhesive sheet 2 has the said soft part and the said hard part in a sheet
  • An image display device constituting laminate (hereinafter, referred to as “image display device constituting laminate 2”) can be produced and provided.
  • the laminated body 2 for constituting an image display device includes, for example, an image display device constituting member having a light non-transmissive portion and a light transmissive portion on a bonding surface, and another image display device constituting member, the pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive sheet X can be produced by laminating via X, irradiating the pressure-sensitive adhesive sheet X with light through the former image display device constituting member, and partially curing the pressure-sensitive adhesive sheet.
  • the laminate 2 for constituting the present image display device in addition to the laminate comprising the configuration of the protective panel / the present adhesive sheet 2 / the polarizing film, for example, the image display panel / the present adhesive sheet 2 / touch panel, the image display panel / the present adhesive.
  • the protection panel and the image display panel may include a touch panel sensor incorporated in the protection panel or the image display panel itself.
  • An image display device (hereinafter referred to as “the present image display device 2”) can also be configured using the pressure-sensitive adhesive sheet 2 or the laminate for constituting the image display device.
  • the image display device 2 includes at least two image display device components facing each other, and at least one of the image display device components includes an image non-transmission portion and a light transmission portion on the bonding surface.
  • an image display apparatus having a configuration in which a space between the two structural members for an image display apparatus is filled with an adhesive sheet, wherein the gel fraction at a position in contact with the light transmission portion of the adhesive sheet is 40. %, And the gel fraction at the position in contact with the light-impermeable portion is less than 1%.
  • a portion that does not transmit light having a wavelength necessary for photocuring such as a print portion around the screen (referred to as a “light-opaque portion” in the present invention).
  • a component for an image display device having a portion that transmits light having a wavelength necessary for photocuring (referred to as a “light transmission portion” in the present invention) on the bonding surface, and another component for an image display device Is bonded to the light non-transparent part with a gel fraction of less than 1%, and the gel fraction of the position in contact with the light transmissive part is set to 40% or more by the light non-transparent part.
  • the stress received by being pressed can be relaxed, the strain generated in this portion can be reduced, and the adherends can be firmly bonded to each other with high cohesive force.
  • the gel fraction at the position in contact with the light-impermeable portion is particularly preferably less than 1%, and more preferably less than 0.8%.
  • the gel fraction at the position in contact with the light transmission part is particularly preferably 40% or more, and more preferably 45% or more.
  • the pressure-sensitive adhesive sheet X is heated and melted, and the constituent member 1 for an image display device having the printing unit (1) and the constituent member 3 for an image display device are stacked via the pressure-sensitive adhesive sheet X.
  • the pressure-sensitive adhesive sheet X is moderately soft, it can sufficiently follow the steps while maintaining storage stability.
  • light such as ultraviolet rays is irradiated from the outside of the image display device component 1.
  • the printing unit (1) shields the light, the light does not reach the portion in contact with the printing unit (1) or the reaching light is significantly limited, while the light without the printing unit (1). Light sufficiently reaches the part in contact with the transmission part (3), the crosslinking reaction of this part proceeds and can be photocured, and excellent peel resistance and foam resistance can be realized.
  • the two image display device components include, for example, personal computers, mobile terminals (PDAs), game machines, televisions (TVs), car navigation systems, touch panels, pen tablets, and other image display devices such as LCDs, PDPs, and ELs.
  • PDAs mobile terminals
  • TVs televisions
  • car navigation systems touch panels
  • pen tablets and other image display devices
  • LCDs LCDs
  • PDPs PDPs
  • ELs electrostatic display devices
  • any one of a group consisting of a touch panel, an image display panel, a surface protection panel, and a polarizing film, or a laminate composed of a combination of two or more types can be given.
  • the pressure-sensitive adhesive sheet 2 may be wound in a roll shape.
  • the pressure-sensitive adhesive sheet X may be produced by irradiating only the end face with light and photocuring, or the pressure-sensitive adhesive sheet 2 obtained by photocuring only the end face is wound into a roll shape. Also good.
  • the end surface of the pressure-sensitive adhesive sheet wound in the form of a roll is a photocured portion, the exposed end surface of the roll does not become sticky even under harsh environments such as high temperature and high humidity. Therefore, it can be suitably stored.
  • a double-sided pressure-sensitive adhesive sheet (hereinafter referred to as “the pressure-sensitive adhesive sheet 3”) according to another example of the embodiment of the present invention includes 100 parts by weight of a (meth) acrylic copolymer (3-A) and a crosslinking agent (3- B) An adhesive resin composition containing 0.5 to 20 parts by mass and 0.1 to 5 parts by mass of a photopolymerization initiator (3-C) (hereinafter referred to as “the present adhesive resin composition 3”) )), And the tensile modulus is a ratio (X 1 / X 2 ) between the tensile modulus (X 1 ) before photocrosslinking and the tensile modulus (X 2 ) after photocrosslinking.
  • the pressure-sensitive adhesive sheet is 3 or more.
  • a black concealment portion is generally printed in a frame shape on the peripheral edge portion of the surface protection panel. Therefore, the pressure-sensitive adhesive sheet for bonding the constituent members having such a printing unit is required to have a printing level followability that can be filled to every corner following the printing level difference.
  • the present invention is a photocrosslinkable pressure-sensitive adhesive sheet, which has adhesiveness even before photocrosslinking, and the pressure-sensitive adhesive resin composition protrudes or is crushed because the pressure-sensitive adhesive material flows too much at the time of bonding.
  • the present pressure-sensitive adhesive sheet 3 that can obtain sufficient hardness after photocrosslinking is provided.
  • the present pressure-sensitive adhesive sheet 3 has a feature that the difference in tensile elastic modulus (X 1 ) before and after photocrosslinking is remarkably large, and has adhesiveness even before photocrosslinking, and the adhesive material is bonded at the time of bonding.
  • the pressure-sensitive adhesive resin composition does not overflow and does not collapse due to excessive flow, and sufficient hardness can be obtained after photocrosslinking.
  • the adhesive resin composition 3 contains the (meth) acrylic copolymer (3-A), the crosslinking agent (3-B), and the photopolymerization initiator (3-C) as described above. It is a resin composition.
  • the (meth) acrylic copolymer (3-A) as the base polymer is preferably a graft copolymer (3-A1) having a macromonomer as a branch component.
  • base polymer means a resin that forms the main component of the present adhesive resin composition 3.
  • the specific content of the base polymer is not specified, but as a guideline, it is 50% by mass or more of the resin contained in the present adhesive resin composition 3, particularly 80% by mass or more, of which 90% by mass or more ( (Including 100% by mass).
  • the total amount thereof corresponds to the content.
  • the trunk component of the graft copolymer (3-A1) is preferably composed of a copolymer component containing a repeating unit derived from (meth) acrylic acid ester.
  • the glass transition temperature of the copolymer constituting the trunk component of the graft copolymer (3-A1) is preferably ⁇ 70 to 0 ° C.
  • the glass transition temperature of the copolymer component constituting the trunk component is the glass transition temperature of the polymer obtained by copolymerizing only the monomer component constituting the trunk component of the graft copolymer (3-A1).
  • it means a value calculated by the Fox formula from the glass transition temperature and the composition ratio of the polymer obtained from the homopolymer of each component of the copolymer.
  • the calculation formula of Fox is a calculation value calculated
  • the glass transition temperature of the copolymer component constituting the trunk component of the graft copolymer (3-A1) is such that the flexibility of the pressure-sensitive adhesive resin composition 3 at room temperature and the pressure-sensitive adhesive on the adherend Since the wettability of the resin composition 3, that is, the adhesiveness is affected, in order for the pressure-sensitive adhesive resin composition 3 to obtain appropriate adhesiveness (tackiness) at room temperature, the glass transition temperature is ⁇ 70 ° C. It is preferably ⁇ 0 ° C., more preferably ⁇ 65 ° C. or more and ⁇ 5 ° C. or less, particularly preferably ⁇ 60 ° C. or more or ⁇ 10 ° C. or less.
  • the viscoelasticity can be adjusted by adjusting the molecular weight. For example, it can be made more flexible by reducing the molecular weight of the copolymer component.
  • Examples of the (meth) acrylic acid ester monomer contained in the trunk component of the graft copolymer (3-A1) include 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, n-butyl acrylate, ethyl acrylate, methyl Examples include methacrylate and methyl acrylate.
  • Various vinyl monomers such as vinyl acetate, alkyl vinyl ether, and hydroxyalkyl vinyl ether that can be copolymerized with the acrylic monomer or methacryl monomer can also be used as appropriate.
  • the trunk component of the graft copolymer (3-A1) preferably contains a hydrophobic (meth) acrylate monomer and a hydrophilic (meth) acrylate monomer as constituent units. If the trunk component of the graft copolymer (3-A1) is composed only of a hydrophobic monomer, a tendency to wet-heat whitening is observed. Therefore, a hydrophilic monomer is also introduced into the trunk component to prevent wet-heat whitening. preferable.
  • a hydrophobic (meth) acrylate monomer a hydrophilic (meth) acrylate monomer, a polymerizable functional group at the terminal of the macromonomer, and Can be a copolymer component formed by random copolymerization.
  • the hydrophobic (meth) acrylate monomer is preferably an alkyl ester having no polar group (excluding methyl acrylate), such as n-butyl (meth) acrylate, n-hexyl (meth).
  • hydrophilic (meth) acrylate monomer methyl acrylate or an ester having a polar group is preferable.
  • the macromonomer is a polymer monomer having a terminal polymerizable functional group and a high molecular weight skeleton component.
  • the glass transition temperature (Tg) of the macromonomer is preferably higher than the glass transition temperature of the copolymer component constituting the graft copolymer (3-A1). Specifically, since the glass transition temperature (Tg) of the macromonomer affects the heating and melting temperature (hot melt temperature) of the present adhesive resin composition 3, the glass transition temperature (Tg) of the macromonomer is 30 ° C. to It is preferably 120 ° C., more preferably 40 ° C. or more and 110 ° C. or less, and particularly preferably 50 ° C. or more or 100 ° C. or less.
  • the glass transition temperature of the macromonomer refers to the glass transition temperature of the macromonomer itself, and can be measured with a differential scanning calorimeter (DSC). (Temperature increase rate: 5 ° C / min, Tg measured from inflection point of baseline shift)
  • the branch components are attracted to each other and can maintain a state where the present pressure-sensitive adhesive resin composition 3 is physically cross-linked, and further, the physical cross-linking can be achieved by heating to an appropriate temperature. It is also preferable to adjust the molecular weight and content of the macromonomer so that the fluidity can be obtained by solving the problem.
  • the macromonomer is preferably contained in the graft copolymer (3-A1) in a proportion of 5% by mass to 30% by mass, particularly 6% by mass or more and 25% by mass or less, of which 8% by mass. % Or more or 20% by mass or less is preferable.
  • the number average molecular weight of the macromonomer is preferably 500 or more and less than 8000, more preferably 800 or more and less than 7500, and particularly preferably 1000 or more and less than 7000.
  • a generally produced one for example, a macromonomer manufactured by Toa Gosei Co., Ltd.
  • the high molecular weight skeleton component of the macromonomer is preferably composed of an acrylic polymer or a vinyl polymer.
  • examples of the high molecular weight skeleton component of the macromonomer include polystyrene, a copolymer of styrene and acrylonitrile, poly (t-butylstyrene), poly ( ⁇ -methylstyrene), polyvinyltoluene, and polymethylmethacrylate. it can.
  • Examples of the terminal polymerizable functional group of the macromonomer include a methacryloyl group, an acryloyl group, and a vinyl group.
  • the (meth) acrylic copolymer (3-A) preferably has a complex viscosity of 100 to 800 Pa ⁇ s at a temperature of 130 ° C. and a frequency of 0.02 Hz, more preferably 150 to 700 Pa ⁇ s, and more preferably 170 to 600 Pa ⁇ s is more preferable.
  • the complex viscosity at a temperature of 130 ° C. of the (meth) acrylic copolymer (3-A) affects the fluidity of the pressure-sensitive adhesive resin composition when the transparent double-sided pressure-sensitive adhesive material is hot-melted. When the complex viscosity is 100 to 800 Pa ⁇ s, excellent hot melt suitability can be obtained.
  • the method of adjusting can be mentioned. However, it is not limited to this method.
  • crosslinking agent (3-B) for example, a crosslinking agent having two or more crosslinking groups such as an epoxy group, an isocyanate group, an oxetane group, a silanol group, and a (meth) acryloyl group can be appropriately selected. Among them, from the viewpoint of reactivity and the strength of the cured product to be obtained, it has a polyfunctional (meth) acrylate having 2 or more (meth) acryloyl groups, especially 3 or more, an epoxy group, an isocyanate group, or a silanol group (meta ) Acrylate is preferred.
  • polyfunctional (meth) acrylates examples include 1,4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, glycerin glycidyl ether di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
  • a polyfunctional monomer or oligomer containing a polar functional group such as a hydroxyl group is preferable from the viewpoint of improving the adhesion to the adherend and the effect of suppressing the heat and whitening.
  • polyfunctional (meth) acrylic acid ester having a hydroxyl group it is preferable to use polyfunctional (meth) acrylic acid ester having a hydroxyl group. Therefore, from the viewpoint of preventing wet heat whitening, it is preferable to contain a hydrophobic acrylate monomer and a hydrophilic acrylate monomer as the trunk component of the graft copolymer (3-A1).
  • the agent (3-B) it is preferable to use a polyfunctional (meth) acrylic acid ester having a hydroxyl group.
  • the content of the crosslinking agent (3-B) is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer (3-A). More preferably, it is a ratio of not less than 15 parts by mass and more preferably not less than 2 parts by mass and not more than 10 parts by mass.
  • the photopolymerization initiator (3-C) functions as a reaction initiation assistant in the crosslinking reaction of the aforementioned crosslinking agent (3-B).
  • the photopolymerization initiator those currently known can be used as appropriate.
  • a photopolymerization initiator that is sensitive to ultraviolet rays having a wavelength of 380 nm or less is preferable from the viewpoint of easy control of the crosslinking reaction.
  • a photopolymerization initiator that is sensitive to light having a wavelength longer than 380 nm is preferable in that the sensitive light easily reaches the deep part of the pressure-sensitive adhesive sheet 3.
  • Photopolymerization initiators are roughly classified into two types depending on the radical generation mechanism, a cleavage type photopolymerization initiator that can cleave and decompose a single bond of the photopolymerization initiator itself, and a photoexcited initiator. And a hydrogen donor in the system form an exciplex and can be roughly classified into a hydrogen abstraction type photopolymerization initiator that can transfer hydrogen of the hydrogen donor.
  • the cleavage type photopolymerization initiator is decomposed when a radical is generated by light irradiation to be another compound, and once excited, it does not function as a reaction initiator. For this reason, it does not remain as an active species in the pressure-sensitive adhesive after the crosslinking reaction is completed, and it is not likely to cause unexpected light degradation or the like in the pressure-sensitive adhesive, which is preferable.
  • a hydrogen abstraction type photopolymerization initiator does not generate a decomposition product such as a cleavage type photopolymerization initiator during radical generation reaction by irradiation of active energy rays such as ultraviolet rays, so that it is difficult to become a volatile component after completion of the reaction. This is useful in that damage to the body can be reduced.
  • cleavage type photoinitiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1- ON, 1- (4- (2-hydroxyethoxy) phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- ⁇ 4- (2-hydroxy-2 -Methyl-propionyl) benzyl ⁇ phenyl] -2-methyl-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), phenylglyoxylic Methyl acid, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- ON, 2- (dimethylamino
  • the photopolymerization initiator is not limited to the substances listed above. Any one of the above-mentioned cleavage type photopolymerization initiator and hydrogen abstraction type photopolymerization initiator may be used, or two or more kinds may be used in combination.
  • the content of the photopolymerization initiator (3-C) is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic copolymer (3-A). More preferably, it is contained in an amount of 0.5 parts by mass or more or 3 parts by mass or less, and more preferably 1 part by mass or more.
  • This adhesive resin composition 3 may contain the well-known component mix
  • reaction catalyst A tertiary amine type compound, a quaternary ammonium type compound, a lauric acid tin compound, etc.
  • This pressure-sensitive adhesive sheet 3 can normally maintain a sheet shape, has a hot-melt property that melts or flows when heated in an uncrosslinked state, and has a photo-curing property that can be photo-cured. It can be a sheet. If the sheet shape can be maintained in a normal state, it is easy to handle as compared with the liquid adhesive, and the work of filling the liquid can be omitted, so that the productivity is particularly excellent.
  • a single-layer pressure-sensitive adhesive sheet may be prepared from the pressure-sensitive adhesive resin composition 3 described above.
  • a multilayer adhesive sheet for example, a two-layer two-layer configuration in which an adhesive layer made of the present adhesive resin composition 3 and an adhesive layer made of another adhesive resin composition are laminated, or an intermediate resin layer A two-layer three-layer configuration in which an adhesive layer made of the present adhesive resin composition 3 is arranged on the front and back, an adhesive layer made of the present adhesive resin composition 3, an intermediate layer made of an intermediate resin composition, Examples thereof include a three-layer three-layer structure in which an adhesive layer made of another adhesive resin composition is laminated in this order.
  • the pressure-sensitive adhesive resin composition for forming the pressure-sensitive adhesive sheet 3 is not limited to the pressure-sensitive adhesive resin composition 3.
  • a branch component The graft copolymer (A1) provided with a macromonomer may be used, and the composition ratio of the crosslinking agent and the photopolymerization initiator may be adjusted, or the processing temperature and light irradiation amount may be adjusted.
  • a branch component The graft copolymer (A1) provided with a macromonomer may be used, and the composition ratio of the crosslinking agent and the photopolymerization initiator may be adjusted, or the processing temperature and light irradiation amount may be adjusted.
  • the ratio (X 1 / X 2 ) between the tensile elastic modulus (X 1 ) before photocrosslinking and the tensile elastic modulus (X 2 ) after photocrosslinking of the present pressure-sensitive adhesive sheet 3 is 3 or more, good step absorption And foaming reliability can be obtained.
  • the ratio (X 1 / X 2 ) between the tensile elastic modulus (X 1 ) before photocrosslinking and the tensile elastic modulus (X 2 ) after photocrosslinking is preferably 3 or more. 30 or less, more preferably 10 or more and 27 or less.
  • the tensile elastic modulus (X 1 ) before photocrosslinking is preferably 0.01 MPa or more and 0.2 MPa or less, and more preferably 0.05 MPa or more or 0.1 MPa or less.
  • the tensile elastic modulus (X 2 ) after photocrosslinking is preferably 0.8 MPa or more and 2.0 MPa or less, and more preferably 1.0 MPa or more or 1.8 MPa or less.
  • the pressure-sensitive adhesive sheet 3 has a ratio (Y 1 / Y 2 ) between the maximum tensile stress (Y 1 ) before photocrosslinking and the maximum tensile stress (Y 2 ) after photocrosslinking of 5 or more and 20 or less. Of these, 8 or more and 15 or less are more preferable.
  • the maximum tensile stress (Y 1 ) before photocrosslinking is preferably 0.5 N or more and 5 N or less, and particularly preferably 0.8 N or more or 2 N or less.
  • the tensile maximum stress (Y 2 ) after photocrosslinking is preferably 7N or more and 15N or less, and particularly preferably 9N or more and 12N or less.
  • the pressure-sensitive adhesive sheet 3 has a ratio (Z 1 / Z 2 ) between the tensile breaking stress (Z 1 ) before photocrosslinking and the tensile breaking stress (Z 2 ) after photocrosslinking of 10 or more and 50 or less. Of these, it is particularly preferably 15 or more or 40 or less.
  • the tensile breaking stress (Z 1 ) before photocrosslinking is preferably 0.1 N or more and 2 N or less, particularly preferably 0.2 N or more or 0.6 N or less.
  • the tensile breaking stress (Z 2 ) after photocrosslinking is preferably 7N or more and 16N or less, and particularly preferably 9N or more and 12N or less.
  • this pressure-sensitive adhesive sheet 3 in order to adjust the tensile elastic modulus, the maximum tensile stress and the tensile breaking stress within the above ranges, for example, a (meth) acrylic copolymer (3-A) and a macromonomer as a branch component are used.
  • the provided graft copolymer (3-A1) may be used and the type and number of parts of the macromonomer may be adjusted. However, it is not limited to this method.
  • the graft copolymer (3-A1) having a macromonomer as a branch component is used as the (meth) acrylic copolymer (3-A)
  • the sheet shape can be maintained even in a normal state, and heating is performed. By doing so, the fluidity can be exhibited and the step following ability can be satisfied, and the curing reaction can be promoted by UV crosslinking so that excellent adhesion reliability can be obtained.
  • the pressure-sensitive adhesive sheet 3 may be a single layer sheet or a multilayer sheet in which two or more layers are laminated.
  • the pressure-sensitive adhesive sheet 3 is a multi-layer transparent double-sided pressure-sensitive adhesive material
  • the outermost layer has both uneven followability and foam resistance reliability as in the case of the single layer. It is preferable to mold using the pressure-sensitive adhesive resin composition 3.
  • the intermediate layer does not contribute to adhesion with the image display device constituent member, it does not impair the transparency, and has a light transmittance that does not hinder the secondary curing reaction of the outermost layer, and has a cutting property. In addition, it preferably has a property of improving handling properties.
  • middle layer is transparent resin, it will not specifically limit.
  • the base polymer forming the intermediate layer may be the same resin as the base polymer of the outermost layer or a different resin. Among these, it is preferable to use the same acrylic resin as the base polymer of the outermost layer from the viewpoints of ensuring transparency and ease of production, and preventing light refraction at the lamination boundary surface.
  • the intermediate layer and other resin layers may or may not have active energy ray curability.
  • it may be formed so as to be cured by ultraviolet crosslinking or may be formed so as to be cured by heat. Further, it may be formed so as not to be post-cured.
  • it is preferably formed so as to be post-cured, and particularly preferably formed so as to be UV-crosslinked. In that case, since light transmittance will fall, if content of a crosslinking initiator increases, it is preferable to contain a ultraviolet-ray crosslinking agent by the content rate lower than the content rate in the outer layer of the crosslinking initiator in an intermediate
  • this pressure-sensitive adhesive sheet 3 is a multilayer transparent double-sided pressure-sensitive adhesive material
  • the laminated structure is specifically a two-type two-layer structure in which the present pressure-sensitive adhesive resin composition 3 and another pressure-sensitive adhesive resin composition are laminated.
  • a two-layer three-layer configuration in which the present adhesive resin composition 3 is arranged on the front and back through an intermediate resin layer, the present adhesive resin composition 3, an intermediate resin composition, and other adhesive resin compositions Can be listed as a three-layer three-layer structure in which are stacked in this order.
  • the pressure-sensitive adhesive resin composition 3 and another pressure-sensitive adhesive resin composition are formed into a sheet shape on different release films or image display device constituent members, and the pressure-sensitive adhesive sheet 3 is formed by laminating both pressure-sensitive adhesive surfaces.
  • the pressure-sensitive adhesive resin composition 3, the intermediate resin composition, and the pressure-sensitive adhesive resin composition are coextruded in this order to obtain a two-kind three-layer pressure-sensitive adhesive sheet 3.
  • the pressure-sensitive adhesive sheet 3 may be obtained by laminating the pressure-sensitive adhesive resin composition 3 or another pressure-sensitive adhesive resin composition on the front and back surfaces of the intermediate resin layer.
  • the pressure-sensitive adhesive sheet with a base material having a configuration in which the main pressure-sensitive adhesive layer 3 is formed on a base material or a base-less pressure-sensitive adhesive sheet having no base material may be used.
  • the double-sided pressure-sensitive adhesive sheet having the main pressure-sensitive adhesive layer 3 on both upper and lower sides may be used, or the single-sided pressure-sensitive adhesive sheet having the main pressure-sensitive adhesive layer 3 only on the upper and lower sides.
  • the printing thickness of the peripheral concealing layer in the conventional image display device is higher, specifically, from the viewpoint of filling up to a step of about 80 ⁇ m, the total thickness of the pressure-sensitive adhesive sheet 3 is more preferably 75 ⁇ m or more, In particular, the thickness is more preferably 100 ⁇ m or more. On the other hand, from the viewpoint of meeting the demand for thinning, it is preferably 500 ⁇ m or less, more preferably 350 ⁇ m or less. Further, from the viewpoint of not hindering the adhesion strength and impact absorption with the adherend, the thickness of the maximum thickness portion is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 15 ⁇ m or more.
  • the ratio of the thickness of each outermost layer to the thickness of the intermediate layer is preferably 1: 1 to 1:20, and more preferably 1: 2 to 1:10. If the thickness of the intermediate layer is within the above range, the contribution of the thickness of the pressure-sensitive adhesive layer in the laminate is not too large, and it is preferable that the workability relating to cutting and handling is not deteriorated because it is too flexible. In addition, if the outermost layer is in the above range, it is preferable because the adhesion to the adherend and the wettability can be maintained without being inferior in conformity to unevenness and a bent surface.
  • the thickness of the maximum thickness part of this adhesive sheet 3 is 250 micrometers or less.
  • the pressure-sensitive adhesive sheet 3 may be a sheet having a uniform thickness or a non-uniform sheet having a partially different thickness.
  • the thickness of the thick part is preferably 250 ⁇ m or less.
  • the pressure-sensitive adhesive sheet 3 can be provided as a pressure-sensitive adhesive sheet laminate having a configuration in which a release film is laminated on one surface or both surfaces of the pressure-sensitive adhesive sheet 3, for example.
  • laminated body 3 for configuring the present image display device As an example of the application of the pressure-sensitive adhesive sheet 3, a laminated body for image display device configuration (hereinafter referred to as “the present image display device” having a configuration in which two structural members for the image display device are laminated via the pressure-sensitive adhesive sheet 3. This will be referred to as “Structural Laminate 3”).
  • the image display device configuration laminate 3 includes, for example, at least two image display device components facing each other, and at least one of the image display device configuration members has a light impermeable portion and a light transmissive portion on the bonding surface.
  • examples of the constituent member for the image display device include a laminate composed of any one of a group consisting of a touch panel, an image display panel, a surface protection panel, and a polarizing film, or a combination of two or more kinds.
  • the laminate 3 for constituting the image display device in addition to the laminate comprising the configuration of the protective panel / the present adhesive sheet 3 / the polarizing film, for example, the image display panel / the present adhesive sheet 3 / touch panel, the image display panel / the present adhesive.
  • the protection panel and the image display panel may include a touch panel sensor incorporated in the protection panel or the image display panel itself.
  • the laminate 3 for constituting an image display device can be manufactured, for example, through the following steps (1) to (3).
  • the manufacturing method of the image display device constituting laminate 3 may include at least the following steps (1) to (3), other steps may be added or other steps may be performed between the steps. It is possible to insert a process.
  • a pressure-sensitive adhesive resin composition containing a (meth) acrylic copolymer (3-A), a crosslinking agent (B), and a photopolymerization initiator (C) is prepared, and the pressure-sensitive adhesive resin composition The process which forms this adhesive sheet 3 by shape
  • this pressure-sensitive adhesive resin composition 3 is prepared by a known method, and is formed into a single-layer or multi-layer uncrosslinked sheet having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive resin composition.
  • the present adhesive sheet 3 is prepared.
  • a method for forming the pressure-sensitive adhesive resin composition 3 into a sheet shape a currently known method can be arbitrarily adopted.
  • the pressure-sensitive adhesive resin composition 3 is formed into a single-layer or multilayer sheet on the release film to produce a single-layer or multilayer transparent double-sided pressure-sensitive adhesive material having an adhesive layer. Also good.
  • the pressure-sensitive adhesive resin composition 3 is formed into a single-layer or multi-layer sheet on the image display device constituent member, and the single-layer or multi-layer provided with the adhesive layer on the image display device constituent member. You may make it produce a transparent double-sided adhesive material.
  • step (2) two image display device constituent members can be adhered and laminated via the pressure-sensitive adhesive sheet 3.
  • the graft copolymer (A1) is used as a base polymer of the pressure-sensitive adhesive sheet 3
  • the macromonomer aggregates to form a physical cross-linked structure in a normal state, that is, a room temperature state. 3 can be provided with excellent storage stability and cutting processability.
  • the (meth) acrylic copolymer (3-A) has a complex viscosity of 100 to 800 Pa ⁇ s at a temperature of 130 ° C. and a frequency of 0.02 Hz, it is excellent when used as a hot melt sheet at the time of bonding. Workability can be enjoyed.
  • step (2) two image display device constituent members can be adhered and laminated via the present adhesive sheet 3. If it does in this way, since adhesiveness of the level which can be easily stuck only by pressing this adhesive sheet 3 to a to-be-adhered body can be obtained, it is easy to position to stick an adhesive material, and it is very convenient on operation. . Further, since the present pressure-sensitive adhesive sheet 3 is excellent in shape retention and can be processed into an arbitrary shape in advance, an image display device for laminating the present pressure-sensitive adhesive sheet 3 formed on a release film It can also be cut in advance according to the dimensions of the constituent members.
  • the cutting method at this time is generally punched with a Thomson blade, cut with a super cutter or laser, and half-cuts leaving either the front or back release film in a frame shape so that the release film can be easily peeled off. Is more preferable.
  • the pressure-sensitive adhesive sheet 3, that is, the transparent double-sided pressure-sensitive adhesive material is in an uncrosslinked state.
  • step (3) active energy rays are applied to the adhesive layer of the adhesive sheet 3 from the outside of at least one of the image display apparatus constituent members to crosslink the adhesive layer, and the two image display apparatus constituent members are
  • the laminate 3 for constituting the image display device can be manufactured by bonding.
  • this pressure-sensitive adhesive sheet 3 contains a crosslinking agent (B) and a photopolymerization initiator (C), the adhesive layer of this pressure-sensitive adhesive sheet 3 is irradiated with active energy rays, and the pressure-sensitive adhesive layer is crosslinked and cured.
  • the two image display device constituent members can be firmly attached.
  • an energy ray that sensitizes the polymerization initiator such as a heat ray, an X-ray, an electron beam, an ultraviolet ray, or a visible ray, may be irradiated.
  • ultraviolet rays particularly ultraviolet rays having a wavelength of 380 nm or less
  • the UV irradiation conditions there are no particular restrictions on the UV irradiation conditions.
  • the type of energy rays to which the adhesive material is sensitive in accordance with the interposed member is the type of polymerization initiator. It is preferable to adjust as appropriate.
  • a step of heating and melting the pressure-sensitive adhesive layer of the transparent double-sided pressure-sensitive adhesive material by heating the laminate obtained in the step (2) may be inserted. That is, the laminate stuck in the step (2) may be heated so that the adhesive layer of the present adhesive sheet 3 is heated and melted (hot melt).
  • the adhesive sheet 3 When the pressure-sensitive adhesive sheet 3 is heated, the aggregation of the macromonomers is released, the physical cross-linked structure is eliminated, and high fluidity can be exhibited. Therefore, when there are irregularities such as printing steps on the landing surface, the adhesive sheet 3 is heated to flow (hot melt) when the two image display device constituent members are laminated, thereby producing irregularities on the adhesive material. The followability and wettability to the adherend are increased, and the members can be more firmly integrated without leaving any distortion. At this time, it is preferably heated to 60 to 100 ° C. and hot melted. If it is 60 degreeC or more, the fluidity
  • the hot melt temperature is preferably 60 to 100 ° C., more preferably 62 ° C. or more and 95 ° C. or less, and particularly preferably 65 ° C. or more and 90 ° C. or less.
  • An image display device (hereinafter referred to as “the present image display device 3”) can also be configured using the pressure-sensitive adhesive sheet 3 or the laminate for constituting the image display device.
  • the image display device 3 includes at least two image display device components facing each other, and at least one of the image display device components includes an image non-transmission portion and a light transmission portion on the bonding surface.
  • the apparatus include an image display apparatus having a configuration in which a space between the two structural members for the image display apparatus is filled with an adhesive sheet. Under the present circumstances, the gel fraction of the position which touches the said light transmissive part of the said adhesive sheet is 50% or more, and the gel fraction of the position which contact
  • a portion that does not transmit light having a wavelength necessary for photocuring such as a printed portion around the screen (referred to as a “light-impermeable portion” in the present invention).
  • a component for an image display device having a portion that transmits light having a wavelength necessary for photocuring (referred to as a “light transmission portion” in the present invention) on the bonding surface, and another component for an image display device Is bonded to the light non-transparent part with a gel fraction of less than 1%, and the gel fraction of the position in contact with the light transmissive part is set to 40% or more by the light non-transparent part.
  • the stress received by being pressed can be relaxed, the strain generated in this portion can be reduced, and the adherends can be firmly bonded to each other with high cohesive force.
  • the pressure-sensitive adhesive sheet 3 is heated and hot-melted, and the image display device constituent member having a printing portion, that is, a light opaque portion, and the image display device constituent member are laminated via the pressure sensitive adhesive sheet 3. .
  • the pressure-sensitive adhesive sheet 3 is moderately soft, it can sufficiently follow the steps while maintaining storage stability.
  • light such as ultraviolet rays is irradiated from the outside of the constituent member for an image display device.
  • the printing unit shields the light, the light does not reach the portion in contact with the printing unit, or the reaching light is remarkably limited, while the light contacts the light transmitting unit without the printing unit. It can be sufficiently reached, the cross-linking reaction of this part proceeds and can be photocured, and excellent peel resistance and foam resistance can be realized.
  • the two image display device components include, for example, personal computers, mobile terminals (PDAs), game machines, televisions (TVs), car navigation systems, touch panels, pen tablets, and other image display devices such as LCDs, PDPs, and ELs.
  • PDAs mobile terminals
  • TVs televisions
  • car navigation systems touch panels
  • pen tablets and other image display devices
  • LCDs LCDs
  • PDPs PDPs
  • ELs electrostatic display devices
  • any one of a group consisting of a touch panel, an image display panel, a surface protection panel, and a polarizing film, or a laminate composed of a combination of two or more types can be given.
  • “Sheet” generally refers to a product that is thin by definition in JIS and has a thickness that is small and flat for the length and width.
  • “film” is thicker than the length and width.
  • JISK6900 Japanese Industrial Standard
  • the term “sheet” is included and the term “sheet” is used.
  • “film” is included.
  • the expression “panel” such as an image display panel and a protection panel includes a plate, a sheet and a film, or a laminate thereof.
  • X to Y (X and Y are arbitrary numbers) is described, it means “preferably greater than X” or “preferably,” with the meaning of “X to Y” unless otherwise specified. The meaning of “smaller than Y” is also included. Further, when described as “X or more” (X is an arbitrary number), it means “preferably larger than X” unless otherwise specified, and described as “Y or less” (Y is an arbitrary number). In the case of a case, it means “preferably smaller than Y” unless otherwise specified.
  • Example 1-1 As the (meth) acrylic copolymer (1-A), 15 parts by mass (18 mol%) of a polymethyl methacrylate macromonomer (Tg: 105 ° C.) having a number average molecular weight of 2400 and 81 of butyl acrylate (Tg: ⁇ 55 ° C.) Acrylic copolymer (1-A-1) obtained by random copolymerization of 4 parts by mass (7 mol%) with 75 parts by mass (75 mol%) and acrylic acid (Tg: 106 ° C.) (weight average molecular weight: 230,000) 1 kg, 75 g of glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) (1-B-1) as a crosslinking agent (1-B), and 2,4 as a photopolymerization initiator (1-C) , 6-Trimethylbenzophenone and 4-methylbenzophenone mixture (manufactured by Lanberti, product name: Ezacure TZT
  • composition 1-1 was divided into two release films, ie two peeled polyethylene terephthalate films (“Diafoil MRV-V06” manufactured by Mitsubishi Plastics, Inc., thickness 100 ⁇ m / “Diafoil MRQ manufactured by Mitsubishi Plastics, Inc.). ”, Having a thickness of 75 ⁇ m), and shaped into a sheet shape with a laminator to a thickness of 150 ⁇ m, to produce an adhesive sheet 1-1 (thickness 150 ⁇ m).
  • An attached glass plate was prepared.
  • One release film of the pressure-sensitive adhesive sheet 1-1 was peeled off and roll-bonded to soda lime glass having a thickness of 150 mm ⁇ 200 mm and a thickness of 1 mm.
  • the remaining release film is peeled off, and after press-bonding to the printing surface of the glass plate with printing steps using a vacuum press so that the four sides of the adhesive surface are on the printing steps (absolute pressure 5 kPa, temperature 80 ° C., A press pressure of 0.04 MPa) and an autoclave treatment (80 ° C., gauge pressure of 0.2 MPa, 20 minutes) were applied and finished.
  • the pressure-sensitive adhesive sheet 1-1 is cured by irradiating ultraviolet light with a high-pressure mercury lamp so that ultraviolet light having a wavelength of 365 nm reaches 2000 mJ / cm 2 from the printed glass side. 1 was produced.
  • Example 1-2 As the (meth) acrylic copolymer (1-A), 2-ethylhexyl acrylate (Tg: ⁇ 70 ° C.) 55 parts by mass (36 mol%) and vinyl acetate (Tg: 32 ° C.) 40 parts by mass (56 mol%) And 1 kg of an acrylic copolymer (1-A-2) (weight average molecular weight: 170,000) obtained by random copolymerization of 5 parts by mass (8 mol%) of acrylic acid (Tg: 106 ° C.) As a crosslinking agent (1-B), ⁇ -caprolactone-modified isocyanuric acid triacrylate (1-B-2) (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A9300-1CL), and a photopolymerization initiator (1-C) Then, Ezacure KTO46 (1-C-2) (manufactured by Lanberti) was uniformly mixed to prepare an adhesive composition 1-2.
  • the composition 1-2
  • Example 1-3 As the (meth) acrylic copolymer (1-A), 10 parts by mass (17 mol%) of a polymethyl methacrylate macromonomer having a number average molecular weight of 1400 (Tg: 105 ° C.) and 2-ethylhexyl acrylate (Tg: ⁇ 70 ° C.) ) 90% by mass (83 mol%) of an acrylic copolymer (1-A-3) (weight average molecular weight: 230,000) obtained by random copolymerization and propoxylation as a crosslinking agent (1-B) 50 g of pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: ATM-4PL) (1-B-3) and 4-methylbenzophenone (1-C-3) as a photopolymerization initiator (1-C) 15 g of the mixture was uniformly mixed to prepare an adhesive composition 1-3.
  • the composition 1-3 was shaped into a sheet in the same manner as
  • Example 1-4 As the (meth) acrylic copolymer (1-A), 12 parts by mass (19 mol%) of a polymethyl methacrylate macromonomer having a number average molecular weight of 2400 (Tg: 105 ° C.) and 2-ethylhexyl acrylate (Tg: ⁇ 70 ° C.) ) Acrylic copolymer (1-A-4) obtained by random copolymerization of 85 parts by mass (74 mol%) and 3 parts by mass (7 mol%) of acrylic acid (Tg: 106 ° C.) (weight average molecular weight: 8) 1 kg, glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) (1-B-1) 90 g as a crosslinking agent (1-B), and Ezacure KTO46 as a photopolymerization initiator (1-C) 5 g of (1-C-2) (manufactured by Lanberti) was uniformly mixed to prepare an adhesive composition
  • the laminated body 5 was produced as follows so that it might correspond to the Example of international publication 2012/032995 gazette.
  • the (meth) acrylic copolymer (1-A) 2-ethylhexyl acrylate (Tg: ⁇ 70 ° C.) 75 parts by mass (57 mol%) and vinyl acetate (Tg: 32 ° C.) 20 parts by mass (33 mol%)
  • Trimethylolpropane as a crosslinking agent (1-B) is added to 1 kg of an acrylic copolymer (1-A-5) obtained by random copolymerization with 5 parts by mass (10 mol%) of acrylic acid (Tg: 106 ° C.).
  • a resin composition for an intermediate layer was prepared by mixing and adding 200 g of triacrylate (1-B-4) and 10 g of 4-methylbenzophenone (1-C-3) as a photopolymerization initiator (1-C).
  • the intermediate layer resin composition is sandwiched between two exfoliated polyethylene terephthalate films (manufactured by Panac, NP75Z01, thickness 75 ⁇ m / manufactured by Toyobo, E7006, thickness 38 ⁇ m) so that the sheet has a thickness of 80 ⁇ m.
  • the intermediate layer sheet ( ⁇ ) was produced.
  • the adhesive layer resin composition was divided into two release films, that is, two peeled polyethylene terephthalate films (“Diafoil MRA” manufactured by Mitsubishi Plastics Co., Ltd., thickness 75 ⁇ m / “E7006” manufactured by Toyobo Co., Ltd.) 38 ⁇ m) and shaped into a sheet shape to a thickness of 35 ⁇ m to produce a resin sheet ( ⁇ ) for an adhesive layer.
  • two peeled polyethylene terephthalate films (“Diafoil MRA” manufactured by Mitsubishi Plastics Co., Ltd., thickness 75 ⁇ m / “E7006” manufactured by Toyobo Co., Ltd.) 38 ⁇ m
  • the adhesive layer resin composition was sandwiched between two exfoliated polyethylene terephthalate films (Mitsubishi Resin, Diafoil MRF, thickness 75 ⁇ m / Toyobo, E7006, thickness 38 ⁇ m). In this way, it was shaped into a sheet to produce an adhesive layer resin sheet ( ⁇ ′).
  • the PET film on both sides of the intermediate layer sheet ( ⁇ ) is sequentially peeled and removed, and the PET film on one side of the adhesive layer resin sheets ( ⁇ ) and ( ⁇ ′) is peeled off, and the exposed adhesive surface is used for the intermediate layer.
  • a three-layer pressure-sensitive adhesive sheet composed of ( ⁇ ) / ( ⁇ ) / ( ⁇ ′) was prepared by sequentially pasting on both surfaces of the sheet ( ⁇ ).
  • the composition 1-6 was applied to a release surface of a release film having a thickness of 50 ⁇ m, that is, a release-treated polyethylene terephthalate film (“MRF75” manufactured by Mitsubishi Plastics Co., Ltd .: 75 ⁇ m), and the thickness after drying was 75 ⁇ m. Then, the solvent was dried by heating to prepare an adhesive sheet having a thickness of 75 ⁇ m. Further, the composition 1-6 was applied to the release surface of a release film, that is, a release-treated polyethylene terephthalate film ("Diafoil MRV-V06" manufactured by Mitsubishi Plastics, thickness 100 ⁇ m), and the thickness after drying was 75 ⁇ m. Then, the solvent was dried by heating to produce an adhesive sheet having a thickness of 75 ⁇ m. Adhesive sheets 1-6 (thickness 150 ⁇ m) were prepared by sticking the respective adhesive surfaces to the two prepared adhesive sheets and curing them for one week.
  • An attached glass plate was prepared.
  • One release film of the pressure-sensitive adhesive sheet 1-6 was peeled off and roll-bonded to soda lime glass having a thickness of 150 mm ⁇ 200 mm and a thickness of 1 mm.
  • the remaining release film is peeled off, and after press-bonding to the printing surface of the glass plate with printing steps using a vacuum press so that the four sides of the adhesive surface are on the printing steps (absolute pressure 5 kPa, temperature 80 ° C., A press pressure of 0.04 MPa) and an autoclave treatment (80 ° C., gauge pressure of 0.2 MPa, 20 minutes) were applied and finished and a laminate 1-6 was produced.
  • Laminate 1-7 was produced as follows so as to correspond to the example of WO2010038366.
  • a crosslinking agent (1-B ) 1 kg of polyurethane acrylate having a carbonate skeleton (1-B-4) manufactured by Negami Kogyo Co., Ltd., UN5500, weight average molecular weight 67,000
  • 1-cyclohexyl as a photopolymerization initiator (1-C)
  • a pressure-sensitive adhesive composition 1-7 was prepared by uniformly mixing 43 g of phenyl ketone (1-C-4) (Irgacure 184, manufactured by BASF). The composition 1-7 was shaped into a sheet in the same manner as in Example 1-1 to produce an adhesive sheet 1-7 (thickness 150 ⁇ m
  • An attached glass plate was prepared.
  • One release film of the pressure-sensitive adhesive sheet 1-7 was peeled off, and roll-laminated to 150 mm ⁇ 200 mm 1 mm thick soda lime glass while heating at 80 ° C.
  • a laminated body 1-7 is produced by irradiating UV light with a high-pressure mercury lamp from the printed glass side so that ultraviolet light having a wavelength of 365 nm reaches 2000 mJ / cm 2 to the adhesive sheet, and curing the adhesive sheet 1-7. did.
  • the pressure-sensitive adhesive sheet is irradiated with ultraviolet rays through a polyethylene terephthalate film so that the integrated light amount at 365 nm is 2000 mJ / cm 2 .
  • the adhesive sheet was cured.
  • the cured adhesive sheet was laminated so as to have a thickness of 1 mm to 2 mm, and punched into a circle having a diameter of 20 mm.
  • adhesive jig ⁇ 25 mm parallel plate, strain: 0.5%, frequency: 1 Hz, heating rate: 3 ° C./min, 70 ° C. to 120 ° C.
  • the complex viscosity of the pressure-sensitive adhesive sheet after photocuring was measured.
  • Adhesive strength after curing Remove one release film of adhesive sheets 1-1 to 1-7 produced in Examples and Comparative Examples, and bond 50 ⁇ m PET film (Made by Mitsubishi Plastics, Diafoil T100, thickness 50 ⁇ m) as backing film Then, a laminated product was prepared. After the laminated product was cut into a length of 150 mm and a width of 10 mm, the adhesive layer exposed by peeling off the remaining release film was roll-bonded to soda lime glass by reciprocating a 2 kg roll. After the autoclave treatment (80 ° C, gauge pressure 0.2MPa, 20 minutes) is applied to the bonded product, the adhesive sheet is cured by irradiating with ultraviolet light so that the integrated light quantity at 365nm is 2000mJ / cm 2.
  • the outgas after light irradiation according to the present invention is detected by the following analysis method.
  • the pressure-sensitive adhesive sheets 1-1 to 1-5 and 1-7 produced in the examples and comparative examples were pressure-bonded through a polyethylene terephthalate film using a high-pressure mercury lamp so that the integrated light amount at 365 nm was 2000 mJ / cm 2.
  • the sheet was irradiated with ultraviolet rays, and a corresponding pressure-sensitive adhesive sheet was prepared after photocuring.
  • the photocured adhesive sheet was cut into 1 cm ⁇ 3 cm and sealed in a 20 ml vial.
  • This vial was placed in a xenon UV irradiation apparatus (Suntest CPS: manufactured by Toyo Seiki Co., Ltd.) and subjected to UV irradiation treatment at an illuminance of 765 W / m 2 and a temperature of 60 ° C. for 24 hours.
  • the pressure-sensitive adhesive sheet 1-6 of Comparative Example 1-2 was cut into 1 cm ⁇ 3 cm and sealed in a 20 ml vial.
  • This vial was placed in a xenon UV irradiation apparatus (Suntest CPS: manufactured by Toyo Seiki Co., Ltd.) and subjected to UV irradiation treatment at an illuminance of 765 W / m 2 and a temperature of 60 ° C. for 24 hours.
  • the generated gas from the UV-treated resin composition as described above can be measured by a gas chromatography analysis method (HS-GC) equipped with a headspace sampler.
  • HS-GC gas chromatography analysis method
  • the laminates 1-1 to 1-7 prepared in Examples and Comparative Examples were put into a xenon UV irradiation apparatus (Suntest CPS: manufactured by Toyo Seiki Co., Ltd.), and irradiated with UV at an illuminance of 765 W / m 2 and a temperature of 60 ° C. for 24 hours. The appearance after applying was observed. “ ⁇ (poor)” indicates that bubbles with a diameter of 5 mm or more are generated on the adhesive sheet, “ ⁇ (usual)” indicates bubbles with a diameter of 5 mm or less, and “ ⁇ (poor)” indicates that there is no foaming and no change in appearance. (Good) ”.
  • the pressure-sensitive adhesive sheets prepared in Examples 1-1 to 1-4 have excellent wettability on the adherend surface, as shown by the fact that the peeling mode at a high temperature before photocuring is cohesive failure. In addition to excellent followability, the adhesive strength after photocuring was high. Therefore, using the pressure-sensitive adhesive sheets prepared in Examples 1-1 to 1-4, it does not cause peeling, foaming or deformation even under severe environmental tests such as long-term ultraviolet irradiation at high temperatures, and has high reliability. A laminate with good properties could be obtained. In addition, the pressure-sensitive adhesive sheets produced in Examples 1-1 to 1-4 were able to maintain the shape at 0 to 40 ° C. and exhibited self-adhesiveness.
  • the pressure-sensitive adhesive resin composition was partially cross-linked by ultraviolet irradiation, that is, when laminated with glass with a printed step because of the state after photocuring, Unevenness due to residual strain was observed, and the bonded appearance was inferior. Moreover, after photocuring this again, since adhesive force was low and it was inferior to cohesive force, foaming was seen by the ultraviolet irradiation test, and it was also inferior to bonding reliability. In Comparative Example 1-2, since the crosslinking reaction of the pressure-sensitive adhesive resin composition was already completed at the stage before being bonded to the member, changes in the viscosity and adhesive force appeared even when irradiated with ultraviolet rays.
  • Comparative Example 1-3 is a hot-melt adhesive sheet using an adhesive resin composition that does not use a (meth) acrylic copolymer as a main component and has a certain degree of rigidity in a room temperature range. .
  • the sheet of Comparative Example 1-3 has a very low tack property near room temperature as compared with the pressure-sensitive adhesive sheet of the Example, at 0 to 40 ° C. Self-adhesiveness was insufficient.
  • the pressure-sensitive adhesive sheet of Comparative Example 1-3 had to be preheated from the positioning stage when bonding, and there was a problem that the work was complicated compared to a pressure-sensitive adhesive sheet that could be stuck at room temperature only by pressure bonding .
  • Example 2-1 As the (meth) acrylic copolymer (2-A), 15 parts by mass (18 mol%) of a macromonomer having a number average molecular weight of 2900 consisting of polymethyl methacrylate (Tg: 105 ° C.) and butyl acrylate (Tg: ⁇ 55) ° C.) acrylic graft copolymer (2-A-1) (weight average) obtained by random copolymerization of 81 parts by mass (75 mol%) and 4 parts by mass (7 mol%) of acrylic acid (Tg: 106 ° C.) 1 kg of molecular weight: 230,000), 90 g of glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) (2-B-1) as a crosslinking agent (2-B), and a photopolymerization initiator (2-C) A mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (product name: Ezacure TZT) (2-C
  • a release-treated polyethylene terephthalate film Y (Mitsubishi Resin, Diafoil MRV-V06, thickness 100 ⁇ m, referred to as “release film Y”) and a release-treated polyethylene terephthalate film Z (Mitsubishi Resin, Dia. Foil MRQ, thickness 75 ⁇ m, referred to as “release film Z”), sandwiched the composition 2-1, and shaped into a sheet shape with a laminator to a thickness of 150 ⁇ m, and adhesive sheet X1 (thickness) 150 ⁇ m).
  • a black sheet (LSL-8 manufactured by Inoac Co., Ltd., light transmittance 0%), which is a double-sided tape and cut into 50 mm ⁇ 100 mm. Bonding was performed to form a light-impermeable portion, and a pressure-sensitive adhesive sheet laminate having a light-transmitting portion and a light-impermeable portion in the sheet surface was produced.
  • Example 2-2 As the (meth) acrylic copolymer (2-A), 55 parts by mass (36 mol%) of 2-ethylhexyl acrylate (Tg: ⁇ 70 ° C.) and 40 parts by mass (56 mol%) of vinyl acetate (Tg: 32 ° C.) And 1 kg of an acrylic copolymer (2-A-2) (weight average molecular weight: 170,000) obtained by random copolymerization of 5 parts by mass (8 mol%) of acrylic acid (Tg: 106 ° C.)
  • a cross-linking agent (2-B) 70 g of a mixture of isocyanuric acid EO-modified diacrylate and isocyanuric acid EO-modified triacrylate (2-B-2) (product name: Aronix M313, manufactured by Toagosei Co., Ltd.), photopolymerization started As an agent (2-C), 5 g of Ezacure KTO46 (2-C-2) (manufactured by Lanberti
  • the composition 2-2 was sandwiched between the release films Y and Z, and formed into a sheet shape having a thickness of 150 ⁇ m using a laminator to prepare an adhesive sheet X2 (thickness 150 ⁇ m).
  • a pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 2-1, except that the pressure-sensitive adhesive sheet X2 was used. Further, a pressure-sensitive adhesive sheet 2-2 having a soft part and a hard part was produced in the same manner as in Example 2-1. .
  • Example 2-3 As the (meth) acrylic copolymer (2-A), 10 parts by mass (17 mol%) of a polymethyl methacrylate macromonomer (Tg: 105 ° C.) having a number average molecular weight of 1400 and 2-ethylhexyl acrylate (Tg: ⁇ 70 ° C.) ) 1 kg of an acrylic graft copolymer (2-A-3) (weight average molecular weight: 230,000) obtained by random copolymerization with 90 parts by mass (83 mol%), and triglyceride as a crosslinking agent (2-B).
  • a polymethyl methacrylate macromonomer Tg: 105 ° C.
  • 2-ethylhexyl acrylate Tg: ⁇ 70 ° C.
  • a pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 2-1, except that the pressure-sensitive adhesive sheet X3 was used. Further, in the same manner as in Example 2-1, a pressure-sensitive adhesive sheet 2-3 having a soft part and a hard part was produced. did.
  • Example 2-4 As the (meth) acrylic copolymer (2-A), 12 parts by mass (19 mol%) of a polymethyl methacrylate macromonomer (Tg: 105 ° C.) having a number average molecular weight of 2400 and 2-ethylhexyl acrylate (Tg: ⁇ 70 ° C.) )
  • Acrylic graft copolymer (2-A-4) obtained by random copolymerization of 85 parts by mass (74 mol%) and 3 parts by mass (7 mol%) of acrylic acid (Tg: 106 ° C.) (weight average molecular weight: 1 kg of 80,000), 90 g of glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) (2-B-1) as a crosslinking agent (2-B), and a photopolymerization initiator (2-C) A mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (manufactured by Lanberti, product name
  • the composition 2-4 was sandwiched between the release films Y and Z, and formed into a sheet shape having a thickness of 150 ⁇ m using a laminator to prepare an adhesive sheet X4 (thickness 150 ⁇ m).
  • a pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 2-1, except that the pressure-sensitive adhesive sheet X4 was used. Further, in the same manner as in Example 2-1, a pressure-sensitive adhesive sheet 2-4 having a soft part and a hard part was produced. did.
  • Example 2-5 1 kg of the acrylic copolymer (2-A-1) (weight average molecular weight: 230,000) used in Example 2-1 and trimethylolpropane triacrylate (2-B—) as a crosslinking agent (2-B) 4) 70 g and a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone as photopolymerization initiator (2-C) (manufactured by Lanberti, product name: Ezacure TZT) (2-C-1) 8 g Were uniformly mixed to prepare an adhesive resin composition 2-5.
  • a pressure-sensitive adhesive sheet laminate was produced in the same manner as in Example 2-1, except that the pressure-sensitive adhesive sheet X5 was used. Further, in the same manner as in Example 2-1, a pressure-sensitive adhesive sheet 2-5 having a soft part and a hard part was produced. did.
  • the intermediate layer resin composition is sandwiched between two exfoliated polyethylene terephthalate films (manufactured by Panac, NP75Z01, thickness 75 ⁇ m / manufactured by Toyobo, E7006, thickness 38 ⁇ m) so that the sheet has a thickness of 80 ⁇ m.
  • the intermediate layer sheet ( ⁇ ) was prepared.
  • the adhesive layer resin composition is sandwiched between two exfoliated polyethylene terephthalate films (Mitsubishi Resin, Diafoil MRF, thickness 75 ⁇ m / Toyobo, E7006, thickness 38 ⁇ m), thickness 35 ⁇ m Then, it was shaped into a sheet shape so that an adhesive layer resin sheet ( ⁇ ′) was produced.
  • exfoliated polyethylene terephthalate films Mitsubishi Resin, Diafoil MRF, thickness 75 ⁇ m / Toyobo, E7006, thickness 38 ⁇ m
  • the PET film on both sides of the intermediate layer sheet ( ⁇ ) is sequentially peeled and removed, and the PET film on one side of the adhesive layer resin sheets ( ⁇ ) and ( ⁇ ′) is peeled off, and the exposed adhesive surface is used for the intermediate layer.
  • a three-layer pressure-sensitive adhesive sheet composed of ( ⁇ ) / ( ⁇ ) / ( ⁇ ′) was prepared by sequentially pasting on both surfaces of the sheet ( ⁇ ).
  • the pressure-sensitive adhesive sheet laminate was formed by bonding to the surface of Diafoil MRF) to form light-opaque, and having a light-transmitting part and a light-impermeable part in the sheet surface.
  • a high-pressure mercury lamp is used to irradiate ultraviolet rays so that the integrated light quantity at a wavelength of 365 nm is 2000 mJ / cm 2.
  • Light was further irradiated to the adhesive material in contact with the transmission part to produce an adhesive sheet 2-6.
  • composition 2-7 was sandwiched between two stripped polyethylene terephthalate films (Mitsubishi Resin, Diafoil MLV-V06, thickness 100 ⁇ m / Mitsubishi Resin, Diafoil MRQ, thickness 75 ⁇ m), and a laminator was formed into a sheet shape so as to have a thickness of 150 ⁇ m, and an adhesive sheet X7 (thickness 150 ⁇ m) was produced.
  • two stripped polyethylene terephthalate films Mitsubishi Resin, Diafoil MLV-V06, thickness 100 ⁇ m / Mitsubishi Resin, Diafoil MRQ, thickness 75 ⁇ m
  • a laminator was formed into a sheet shape so as to have a thickness of 150 ⁇ m, and an adhesive sheet X7 (thickness 150 ⁇ m) was produced.
  • a polyethylene terephthalate film obtained by applying a double-sided tape on one side of a black sheet (LSL-8, manufactured by Inoac Co., Ltd.) and cutting it to 50 mm ⁇ 100 mm, which is one of the adhesive sheets X7 is peeled off.
  • the pressure-sensitive adhesive sheet laminate was formed by bonding to the surface of Diafoil MRQ) to form light impermeability and having a light transmission part and a light impermeability part in the sheet surface.
  • the solvent was dried by heating to produce an adhesive sheet having a thickness of 75 ⁇ m. Further, the composition 2-6 was applied to the release surface of a peeled polyethylene terephthalate film (Mitsubishi Resin, Diafoil MRV-V06, thickness 100 ⁇ m) so that the thickness after drying was 75 ⁇ m. Then, the solvent was dried by heating to produce a pressure-sensitive adhesive sheet having a thickness of 75 ⁇ m. With respect to the two prepared adhesive sheets, the respective adhesive surfaces were stuck and cured for 1 week to react with the curing agent, thereby preparing an adhesive sheet 2-8 (thickness 150 ⁇ m).
  • a peeled polyethylene terephthalate film Mitsubishi Resin, Diafoil MRV-V06, thickness 100 ⁇ m
  • Glass transition temperature (Tg) Glass transition temperature (Tg)
  • DSC-8500 differential scanning calorimeter
  • ISO 3146 JIS K-7121
  • the portions that are in contact with the light-impermeable portion, that is, the soft portions are peeled off from the release film of the sheet, and the exposed adhesive surfaces are sequentially overlapped to obtain a plurality of sheets.
  • the pressure-sensitive adhesive sheet was laminated so that the total thickness was in the range of 5 mm to 7 mm. Thereby, the influence of the hardness of the stage on which the measurement sample is placed can be reduced, and the indentation hardness peculiar to the material can be compared and measured.
  • the tip terminal of the Asker C2L hardness meter was pressed vertically downward at a speed of 3 mm / min against the exposed adhesive surface of the laminated adhesive sheet, and the C2 Asker hardness (c) of the soft part was measured.
  • the adhesive sheet is laminated so as to be within the range of 5 mm to 7 mm for the portions in contact with the light transmitting portions of the adhesive sheets 2-1 to 2-7 produced in the examples and comparative examples, that is, the hard portions.
  • the C2 Asker hardness (d) of the hard part was measured. With respect to the pressure-sensitive adhesive sheet 2-8 produced in Comparative Example 2-3, the same measurement was performed at an arbitrary position.
  • the portions in contact with the light-impermeable portions that is, the soft portions were cut out, and then one of the release films was peeled off, and a 50 ⁇ m PET film ( A laminated product was prepared by bonding Mitsubishi Plastics, Diafoil T100, thickness 50 ⁇ m). After the laminated product was cut into a length of 150 mm and a width of 10 mm, the adhesive sheet exposed by peeling off the remaining release film was reciprocated with a 2 kg roll on soda lime glass, and the pressure-sensitive adhesive sheet was roll-bonded. When this adhesive strength measurement sample was peeled off at 23 ° C.
  • the adhesive sheet After the autoclave treatment (80 ° C., gauge pressure 0.2 MPa, 20 minutes) is applied to the pasted product, the adhesive sheet is cured by irradiating ultraviolet rays with an integrated light amount of 365 nm of 2000 mJ / cm 2. , And cured for 15 hours to obtain a peel force measurement sample.
  • the peeling force (N / cm) to the glass was measured and light transmission was performed. It was set as the 180 degree peeling force of the location which contact
  • the pressure-sensitive adhesive sheet 2-8 prepared in Comparative Example 2-3 the pressure-sensitive adhesive sheet was cut out at an arbitrary position, and then measured in the same manner as the procedure for 180 ° C. peeling force of the soft part.
  • the adhesive sheet 2-1 to 2-7 produced in the examples and comparative examples were cut at 50 mm ⁇ 100 mm at the part in contact with the light-opaque part, that is, the soft part, and then the release film on one side was peeled off.
  • One surface was stuck with a hand roller so as to overlap a polyethylene terephthalate film (38 ⁇ m thick) for backing, and this was cut into a strip of 25 mm width ⁇ 100 mm length to obtain a test piece.
  • the remaining release film was peeled off, and a test piece was attached to the SUS plate (thickness 120 mm, 5 mm ⁇ 1.5 mm) erected vertically by a hand roller so as to overlap the length of 20 mm. .
  • the sticking area of the transparent double-sided PSA sheet and the SUS plate is 25 mm ⁇ 20 mm.
  • a 4.9 N weight was attached to the test piece in the vertical direction and left to stand for 30 minutes. The length (mm) by which the sticking position was shifted downward was measured. For the case where the sticking surface was displaced and the weight was dropped, the time required for the weight to drop was measured. Since the pressure-sensitive adhesive sheet 2-7 of Comparative Example 2-2 does not have self-adhesive properties, the test piece laminated on the SUS plate is preheated at 80 ° C. for 5 minutes, and is held in close contact with the adherend. Measurements were made.
  • the part of the adhesive sheet 2-1 to 2-7 produced in the example and the comparative example is in contact with the light transmission part, that is, one of the release films is peeled off from the hard part, and the exposed adhesive surface is covered with two soda lime glasses ( 82 mm ⁇ 53 mm ⁇ 0.5 mm thickness) was roll-bonded, and then autoclaved (80 ° C., gauge pressure 0.2 MPa, 20 minutes) and finished and bonded to prepare a laminate for optical evaluation.
  • the pressure-sensitive adhesive sheet 2-8 prepared in Comparative Example 2-3 samples were prepared in the same manner at arbitrary locations.
  • the haze value according to JISK7136 and the total light transmittance (%) according to JISK7361-1 were calculated
  • a ZEONOR film manufactured by Nippon Zeon Co., Ltd., 100 ⁇ m thickness
  • autoclave treatment 80 ° C., gauge pressure 0.2 MPa, 20 minutes
  • ultraviolet rays with a wavelength of 365 nm are irradiated with ultraviolet rays with a high-pressure mercury lamp so that the sheet X reaches 2000 mJ / cm 2 , and the unprinted opening, that is, the light transmitting portion is irradiated.
  • the sheet at the place of contact was cured to prepare evaluation laminates 2-1 to 2-6.
  • an evaluation laminate 2-7 was similarly prepared using a printed soda lime glass having a printing thickness of 15 ⁇ m.
  • soda-lime glass and ZEONOR film manufactured by Nippon Zeon Co., Ltd., 100 ⁇ m thickness
  • an autoclave treatment 80 ° C., gauge pressure 0.2 MPa, 20 minutes
  • a laminate 2-8 for evaluation was obtained.
  • the evaluation laminates 2-1 to 2-8 prepared by the unevenness absorption evaluation were placed in a constant temperature and humidity chamber at 85 ° C. and 85% RH, and the appearance after curing for 100 hours was observed. The case where bubbles were generated in the pressure-sensitive adhesive sheet was determined as “ ⁇ ”, and the case where the appearance did not change was determined as “ ⁇ ”.
  • the pressure-sensitive adhesive sheets produced in Examples 2-1 to 2-5 exhibit high fluidity by heating because the gel fraction of the soft part is less than 1%. Therefore, by heating and melting at the time of bonding, not only the followability to the uneven surface is excellent, but even if one of the adherends is a low rigidity material such as a film, it does not bend near the step and is smooth. A layered product could be obtained. Furthermore, since the gel fraction of the hard part is 40% or more, it exhibits high cohesive force even under severe environmental tests such as high temperature and high humidity, and does not cause peeling, foaming or deformation, and has high reliability. It was possible to obtain a laminate having
  • Comparative Example 2-1 is a hot-melt type pressure-sensitive adhesive sheet that does not use a (meth) acrylic copolymer and uses a pressure-sensitive resin composition having a certain degree of rigidity in a room temperature range.
  • the sheet of Comparative Example 2-2 had a very low tack property near room temperature as compared with the adhesive sheet of the example.
  • the fluidity during heating is low, so the unevenness due to the printed step is slightly transferred to the sheet side, and the smoothness of the laminate is inferior compared to the adhesive sheet of the example.
  • the sheet has high rigidity and does not have self-adhesion during the bonding operation.
  • the body has to be preheated, and there is also a problem that the operation is complicated as compared with a pressure-sensitive adhesive sheet that can be attached at room temperature only by pressure bonding.
  • the gel fraction of the soft part in an adhesive sheet surface is less than 1%, and it is preferable that the gel fraction of a hard part is 40% or more.
  • the glass transition temperature (measured Tg) of the soft part in the surface of the adhesive sheet is preferably ⁇ 70 to ⁇ 10 ° C., and the glass transition temperature (measured Tg) of the hard part is ⁇ 60 to + 20 ° C.
  • the difference between the glass transition temperature (Tg [H]) of the part and the glass transition temperature (Tg [S]) of the soft part (Tg [H] ⁇ Tg [S]) is preferably 3 ° C. or more. it can.
  • Example 2-6 About the pressure-sensitive adhesive sheet X1 produced in Example 2-1, a long laminated sheet having a width of 150 mm and a length of 100 m was wound around a plastic core having a diameter of 6 inches with an initial winding tension of 70 N and a taper ratio of 20%. An adhesive sheet roll was prepared. A pressure-sensitive adhesive sheet roll having a hard part on the end face part by irradiating the end face part of the manufactured sheet roll with light using a high-pressure mercury lamp so that the integrated light quantity with a wavelength of 365 nm reaches 500 mJ / cm 2. It was.
  • Example 2-4 A pressure-sensitive adhesive sheet roll was produced in the same manner as Example 2-6 except that no light irradiation was performed.
  • Example 3-1 As the (meth) acrylic copolymer (3-A), polymethyl methacrylate macromonomer (Tg: 105 ° C., number average molecular weight is 2400) 15 parts by mass (18 mol%) and butyl acrylate (Tg: ⁇ 55 ° C.) A graft copolymer (3-A1) obtained by random copolymerization of 81 parts by mass (75 mol%) and 4 parts by mass (7 mol%) of acrylic acid (Tg: 106 ° C.) was used.
  • the glass transition temperature of the copolymer constituting the trunk component is ⁇ 60 ° C.
  • the content of the macromonomer in the graft copolymer (3-A1) is 15% by mass.
  • the complex viscosity at a temperature of 130 ° C. and a frequency of 0.02 Hz was 260 Pa ⁇ s.
  • this graft copolymer (3-A1) 1 kg of this graft copolymer (3-A1), 90 g of glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) as a crosslinking agent (3-B), and as a photopolymerization initiator (3-C) 15 g of a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (manufactured by Lanberti, product name: Ezacure TZT) was uniformly mixed to prepare an adhesive resin composition 3-1.
  • GMR glycerin dimethacrylate
  • 3-C photopolymerization initiator
  • the pressure-sensitive adhesive resin composition 3-1 was prepared by using two release films, that is, two peeled polyethylene terephthalate films (“Diafoil MRV-V06” manufactured by Mitsubishi Plastics, Inc., thickness 100 ⁇ m / manufactured by Mitsubishi Plastics “ Diafoil MRQ ”(thickness 75 ⁇ m) and sandwiched into a sheet shape with a laminator to a thickness of 150 ⁇ m to produce an adhesive sheet 3-1 (thickness 150 ⁇ m).
  • two release films that is, two peeled polyethylene terephthalate films (“Diafoil MRV-V06” manufactured by Mitsubishi Plastics, Inc., thickness 100 ⁇ m / manufactured by Mitsubishi Plastics “ Diafoil MRQ ”(thickness 75 ⁇ m) and sandwiched into a sheet shape with a laminator to a thickness of 150 ⁇ m to produce an adhesive sheet 3-1 (thickness 150 ⁇ m).
  • Example 3-2 Adhesive as in Example 3-1, except that 90 g of glycerin dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: NK ester 701) (3-B-1) was used as the crosslinking agent (3-B). Resin composition 3-2 was produced. Using the pressure-sensitive adhesive resin composition 3-2, a pressure-sensitive adhesive sheet 3-2 (thickness 150 ⁇ m) was prepared in the same manner as in Example 3-1.
  • Example 3-3 1 kg of the same graft copolymer (3-A1) as in Example 3-1, 90 g of glycerin dimethacrylate (manufactured by NOF Corporation, product name: GMR) as a crosslinking agent (3-B), a photopolymerization initiator ( 3-C) as a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone (manufactured by Lanberti, product name: Ezacure TZT) and UV stabilizer (product name: TIN123) 50 g was uniformly mixed to prepare an adhesive resin composition 3-3. Then, using this adhesive resin composition 3-3, an adhesive sheet 3-3 (thickness 150 ⁇ m) was prepared in the same manner as in Example 3-1.
  • glycerin dimethacrylate manufactured by NOF Corporation, product name: GMR
  • 3-C photopolymerization initiator
  • 3-C photopolymerization initiator
  • UV stabilizer product name: TIN123
  • Example 3-4 As the (meth) acrylic copolymer (3-A), polymethyl methacrylate macromonomer (Tg: 105 ° C., number average molecular weight is 2500) 10 parts by mass (12 mol%) and butyl acrylate (Tg: ⁇ 55 ° C.) A graft copolymer (3-A2) obtained by random copolymerization of 88 parts by mass (84 mol%) and 2 parts by mass (7 mol%) of acrylic acid (Tg: 106 ° C.) was used.
  • Tg polymethyl methacrylate macromonomer
  • Tg number average molecular weight is 2500
  • butyl acrylate Tg: ⁇ 55 ° C.
  • a graft copolymer (3-A2) obtained by random copolymerization of 88 parts by mass (84 mol%) and 2 parts by mass (7 mol%) of acrylic acid (Tg: 106 ° C.) was used.
  • the glass transition temperature of the copolymer constituting the trunk component is ⁇ 60 ° C.
  • the content of the macromonomer in the graft copolymer (3-A2) is 10% by mass.
  • the complex viscosity at a temperature of 130 ° C. and a frequency of 0.02 Hz was 240 Pa ⁇ s.
  • Example 3-5 As the (meth) acrylic copolymer (3-A), polymethyl methacrylate macromonomer (Tg: 105 ° C., number average molecular weight 2500) 8 parts by mass (10 mol%) and butyl acrylate (Tg: ⁇ 55 ° C.) A graft copolymer (3-A3) obtained by random copolymerization of 89 parts by mass (85 mol%) and 3 parts by mass (5 mol%) of acrylic acid (Tg: 106 ° C.) was used.
  • the glass transition temperature of the copolymer constituting the trunk component is ⁇ 40 ° C.
  • the content of the macromonomer in the graft copolymer (3-A3) is 8% by mass.
  • the complex viscosity at a temperature of 130 ° C. and a frequency of 0.02 Hz was 220 Pa ⁇ s.
  • a resin composition for an intermediate layer was prepared by mixing and adding 200 g of methylolpropane triacrylate (3-B-4) and 10 g of 4-methylbenzophenone (3-C-3) as a photopolymerization initiator (3-C). .
  • the intermediate layer resin composition is sandwiched between two exfoliated polyethylene terephthalate films (Panac, NP75Z01, thickness 75 ⁇ m / Toyobo, E7006, thickness 38 ⁇ m), so that the sheet has a thickness of 80 ⁇ m.
  • the intermediate layer sheet ( ⁇ ) was prepared.
  • the adhesive layer resin composition was divided into two release films, that is, two peeled polyethylene terephthalate films (“Diafoil MRA” manufactured by Mitsubishi Plastics Co., Ltd., thickness 75 ⁇ m / “E7006” manufactured by Toyobo Co., Ltd.) 38 ⁇ m) and shaped into a sheet shape so as to have a thickness of 35 ⁇ m to produce a resin sheet ( ⁇ ) for an adhesive layer.
  • two peeled polyethylene terephthalate films (“Diafoil MRA” manufactured by Mitsubishi Plastics Co., Ltd., thickness 75 ⁇ m / “E7006” manufactured by Toyobo Co., Ltd.) 38 ⁇ m
  • the adhesive layer resin composition was sandwiched between two exfoliated polyethylene terephthalate films (Mitsubishi Resin, Diafoil MRF, thickness 75 ⁇ m / Toyobo, E7006, thickness 38 ⁇ m). In this way, it was shaped into a sheet shape to prepare a resin sheet for adhesive layer ( ⁇ ′).
  • exfoliated polyethylene terephthalate films Mitsubishi Resin, Diafoil MRF, thickness 75 ⁇ m / Toyobo, E7006, thickness 38 ⁇ m.
  • the PET film on both sides of the intermediate layer sheet ( ⁇ ) is sequentially peeled and removed, and the PET film on one side of the adhesive layer resin sheets ( ⁇ ) and ( ⁇ ′) is peeled off, and the exposed adhesive surface is used for the intermediate layer.
  • a three-layer pressure-sensitive adhesive sheet composed of ( ⁇ ) / ( ⁇ ) / ( ⁇ ′) was prepared by sequentially pasting on both surfaces of the sheet ( ⁇ ).
  • a pressure-sensitive adhesive sheet was produced according to Example 6 of WO2010 / 038366. That is, as an alternative to the (meth) acrylic copolymer (3-A), 650 g of phenoxy resin (InChem, PKHH, weight average molecular weight 52,000) and the crosslinking agent (3-B), 1 kg of polyurethane acrylate having carbonate skeleton (Negami Kogyo Co., Ltd., UN5500, weight average molecular weight 67,000), 43 g of 1-cyclohexyl phenyl ketone (Irgacure 184, BASF) as a photopolymerization initiator (3-C)
  • a pressure-sensitive adhesive resin composition 3-7 was prepared by mixing. For the composition 3-7, an adhesive sheet 3-7 (thickness: 150 ⁇ m) was prepared in the same manner as in Example 3-1.
  • the pressure-sensitive adhesive sheets 3-1 to 3-7 were cut into a width of 20 mm, and used as tensile test measurement samples before photocrosslinking. After the adhesive sheets 3-1 to 3-7 are cut to a width of 20 mm, the adhesive sheet is irradiated with ultraviolet rays from a release PET side using a high-pressure mercury lamp so that the integrated light quantity at 365 nm is 2000 mJ / cm 2. Cured and cured at 23 ° C. and 50% RH for 15 hours to obtain a tensile test measurement sample after photocrosslinking.
  • the tensile test measurement sample was measured for tensile modulus, tensile strength at break, and tensile elongation at tension at a test speed of 300 mm / min in an environment of 23 ° C. and 50% RH.
  • the measurement conditions for the tensile modulus were a displacement of 30 to 50 mm.
  • Adhesive sheets 3-1 to 3-7 cut to 50 mm ⁇ 50 mm square were sandwiched between two glass plates having a thickness of 100 mm ⁇ 100 mm and a thickness of 2 mm to produce a laminate.
  • a weight of 500 g was placed on the laminate, and after standing for 24 hours in an environment at 60 ° C., visual observation was performed to determine whether the adhesive protruded from the laminate. Visual observation of the prepared laminate, "X" indicates that the adhesive protruded as a whole, “ ⁇ ” indicates that the adhesive protruded only at the corner, and “ ⁇ ” indicates that the adhesive did not protrude Judged.
  • Step absorbency The pressure-sensitive adhesive sheets 3-1 to 3-6 prepared in Examples 3-1 to 3-5 and Comparative Example 3-1 were cut into 50 mm ⁇ 80 mm, and one release film was peeled off. The exposed adhesive surface is vacuumed so that the four sides of the adhesive material cover the printing step on the printing surface of soda lime glass (82 mm x 53 mm x 0.5 mm thickness) printed with a thickness of 80 ⁇ m on the periphery 3 mm. A press was used for press-bonding (absolute pressure 5 kPa, temperature 80 ° C., press pressure 0.04 MPa).
  • a ZEONOR film manufactured by Nippon Zeon Co., Ltd., 100 ⁇ m thickness
  • autoclaving 80 ° C., gauge pressure 0.2 MPa, 20 minutes
  • ultraviolet rays with a wavelength of 365 nm are irradiated with ultraviolet rays with a high-pressure mercury lamp so that the sheet X reaches 2000 mJ / cm 2 , and an unprinted opening, that is, light
  • the sheet at the portion in contact with the transmission portion was cured to prepare evaluation laminates 3-1 to 3-6.
  • the pressure-sensitive adhesive sheets produced in Examples 3-1 to 3-5 had greatly changed tensile properties before and after photocuring. Because of these characteristics, the pressure-sensitive adhesive sheets prepared in Examples 3-1 to 3-5 have excellent step absorbability before photocuring, and excellent foam resistance after photocuring. It was confirmed that it could have. On the other hand, in the comparative example, since the change in tensile properties was insufficient before and after photocuring, in Comparative Example 3-1, the change after photocrosslinking was insufficient, so that the sheet was inferior in reliability. In -2, the sheet was inferior in workability (storage property) before photocrosslinking.

Landscapes

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

Abstract

La présente invention concerne une feuille adhésive qui peut remplir complètement une surface de fixation le long de parties à gradin de celle-ci pour permettre que la tâche de fixation soit aisément conduite sans dégradation de fiabilité d'adhérence même lorsqu'elle est irradiée avec de la lumière pendant une longue durée. À cet effet, selon la présente invention, il est décrit une feuille adhésive destinée à être photodurcie qui est formée à partir d'une composition de résine contenant un copolymère (méth)acrylique (A), un agent de réticulation (B) et un initiateur de photopolymérisation (C), la feuille adhésive étant caractérisée en ce qu'elle est photodurcissable et présente les caractéristiques suivantes (1) et (2) : (1) présente une rétention de forme et une auto-adhérence à 0 à 40 °C ; et (2) ayant une viscosité de 100 à 3000 Pa.S à 70-100 °C.
PCT/JP2016/066215 2015-06-02 2016-06-01 Feuille adhésive photodurcissable, feuille adhésive et dispositif d'affichage d'image WO2016194957A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201680032296.2A CN107709493B (zh) 2015-06-02 2016-06-01 光固化型粘合片、粘合片及图像显示装置
KR1020187000091A KR102080224B1 (ko) 2015-06-02 2016-06-01 광경화형 점착 시트, 점착 시트 및 화상 표시 장치
KR1020207004561A KR20200019792A (ko) 2015-06-02 2016-06-01 광경화형 점착 시트, 점착 시트 및 화상 표시 장치

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2015111939 2015-06-02
JP2015-111941 2015-06-02
JP2015-111940 2015-06-02
JP2015-111939 2015-06-02
JP2015111941 2015-06-02
JP2015111940 2015-06-02

Publications (1)

Publication Number Publication Date
WO2016194957A1 true WO2016194957A1 (fr) 2016-12-08

Family

ID=57440473

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/066215 WO2016194957A1 (fr) 2015-06-02 2016-06-01 Feuille adhésive photodurcissable, feuille adhésive et dispositif d'affichage d'image

Country Status (4)

Country Link
KR (2) KR20200019792A (fr)
CN (3) CN107709493B (fr)
TW (5) TW202024273A (fr)
WO (1) WO2016194957A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019031426A1 (fr) * 2017-08-08 2019-02-14 三菱ケミカル株式会社 Feuille adhésive autocollante photodurcissable, stratifié de feuille adhésive autocollante photodurcissable, procédé de production pour stratifié de feuille adhésive autocollante photodurcissable, et procédé de production pour stratifié de panneau d'affichage d'image
CN109988512A (zh) * 2018-01-03 2019-07-09 泰柏斯科技有限公司 紫外线可固化光学粘合剂及其制备方法与用于其的组合物
JP2019210445A (ja) * 2017-08-08 2019-12-12 三菱ケミカル株式会社 光硬化性粘着シート
JP2019210446A (ja) * 2017-08-08 2019-12-12 三菱ケミカル株式会社 光硬化性粘着シート積層体、光硬化性粘着シート積層体の製造方法及び画像表示パネル積層体の製造方法
CN110945581A (zh) * 2017-06-28 2020-03-31 迪睿合株式会社 图像显示装置的制造方法、光固化性树脂组合物和透光性固化树脂层
CN111511857A (zh) * 2017-12-18 2020-08-07 王子控股株式会社 粘合片及层叠体的制造方法
JPWO2022210894A1 (fr) * 2021-03-31 2022-10-06

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108641620A (zh) * 2018-03-28 2018-10-12 广州慧谷工程材料有限公司 一种用于图像光学构件、接触面板、显示装置的压敏胶及其应用方法
TWI828735B (zh) * 2018-08-06 2024-01-11 日商三菱化學股份有限公司 光硬化性黏著片材、黏著片材積層體、圖像顯示裝置用積層體及圖像顯示裝置
KR102024081B1 (ko) * 2018-11-27 2019-09-24 주식회사 테이팩스 광 경화형 광학용 점착제 조성물, 상기 조성물로부터 제조된 점착제, 및 상기 점착제의 제조 방법
KR102352953B1 (ko) * 2018-12-14 2022-01-18 삼성에스디아이 주식회사 점착 필름, 이를 포함하는 광학 부재 및 이를 포함하는 광학표시장치
KR102473023B1 (ko) * 2019-11-01 2022-12-01 코제노벨머티얼리스코리아 주식회사 점착 필름
WO2021100635A1 (fr) * 2019-11-22 2021-05-27 三菱ケミカル株式会社 Feuille adhésive, feuille en tranches, éléments de dispositif d'affichage d'image souple, et dispositif d'affichage d'image souple
CN111518480B (zh) * 2020-04-28 2021-07-16 常州百佳年代薄膜科技股份有限公司 复合胶膜及制备方法、设备、热熔胶、胶黏剂、光伏组件
CN114149388B (zh) * 2021-11-10 2023-05-02 广东红墙新材料股份有限公司 一种预聚体及其衍生物以及它们的制备方法与应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001049200A (ja) * 1999-08-11 2001-02-20 Soken Chem & Eng Co Ltd アクリル系粘着剤組成物、該組成物を用いた粘着テープの製造方法および粘着テープ
JP2014088549A (ja) * 2012-10-05 2014-05-15 Toagosei Co Ltd 粘着剤組成物およびその用途

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1318181B1 (fr) * 2001-12-07 2008-07-09 3M Innovative Properties Company Adhesif acrylique thermofusible autocollant et son utilisation
JP4493643B2 (ja) * 2006-12-06 2010-06-30 日東電工株式会社 再剥離型粘着剤組成物、及び粘着テープ又はシート
JP4524320B2 (ja) * 2008-08-11 2010-08-18 日東電工株式会社 粘着剤組成物、粘着剤層、および粘着剤シート
TWI485214B (zh) 2008-09-05 2015-05-21 Kyoritsu Chemical Co Ltd And a photohardenable resin composition for bonding an optical functional material
JP5716881B2 (ja) 2008-10-04 2015-05-13 スリーボンドファインケミカル株式会社 光硬化性接着剤組成物
JP5586497B2 (ja) * 2010-04-21 2014-09-10 日東電工株式会社 光学部材用の粘接着剤組成物、粘接着剤層、粘接着剤層が設けられた光学部材、光学部材付画像表示装置、および画像表示装置の製造方法
JP2012007047A (ja) 2010-06-23 2012-01-12 Nitto Denko Corp 再剥離粘着テープおよびその製造方法
JP4971529B2 (ja) 2010-09-06 2012-07-11 三菱樹脂株式会社 画像表示装置構成用積層体の製造方法、及びこの積層体を用いてなる画像表示装置
JP5757809B2 (ja) 2011-07-13 2015-08-05 綜研化学株式会社 積層体および該積層体を有するタッチパネル
JP5971498B2 (ja) * 2011-08-19 2016-08-17 エルジー・ケム・リミテッド 偏光板
KR20220038770A (ko) * 2012-01-18 2022-03-29 미쯔비시 케미컬 주식회사 화상 표시 장치용 투명 양면 점착 시트 및 이를 사용한 화상 표시 장치
US9834708B2 (en) * 2013-07-08 2017-12-05 Samsung Sdi Co., Ltd. Adhesive composition for polarizing plate, adhesive film for polarizing plate comprising the same, polarizing plate comprising the same and display device comprising the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001049200A (ja) * 1999-08-11 2001-02-20 Soken Chem & Eng Co Ltd アクリル系粘着剤組成物、該組成物を用いた粘着テープの製造方法および粘着テープ
JP2014088549A (ja) * 2012-10-05 2014-05-15 Toagosei Co Ltd 粘着剤組成物およびその用途

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110945581A (zh) * 2017-06-28 2020-03-31 迪睿合株式会社 图像显示装置的制造方法、光固化性树脂组合物和透光性固化树脂层
CN110945581B (zh) * 2017-06-28 2022-01-14 迪睿合株式会社 图像显示装置的制造方法、光固化性树脂组合物和透光性固化树脂层
CN111876091A (zh) * 2017-08-08 2020-11-03 三菱化学株式会社 带脱模薄膜的光固化性粘合片
JP2019210446A (ja) * 2017-08-08 2019-12-12 三菱ケミカル株式会社 光硬化性粘着シート積層体、光硬化性粘着シート積層体の製造方法及び画像表示パネル積層体の製造方法
JP2019210445A (ja) * 2017-08-08 2019-12-12 三菱ケミカル株式会社 光硬化性粘着シート
WO2019031426A1 (fr) * 2017-08-08 2019-02-14 三菱ケミカル株式会社 Feuille adhésive autocollante photodurcissable, stratifié de feuille adhésive autocollante photodurcissable, procédé de production pour stratifié de feuille adhésive autocollante photodurcissable, et procédé de production pour stratifié de panneau d'affichage d'image
JP2021004373A (ja) * 2017-08-08 2021-01-14 三菱ケミカル株式会社 光硬化性粘着シート積層体、光硬化性粘着シート積層体の製造方法及び画像表示パネル積層体の製造方法
CN111876091B (zh) * 2017-08-08 2023-04-14 三菱化学株式会社 带脱模薄膜的光固化性粘合片
CN111511857A (zh) * 2017-12-18 2020-08-07 王子控股株式会社 粘合片及层叠体的制造方法
CN111511857B (zh) * 2017-12-18 2022-08-16 王子控股株式会社 粘合片及层叠体的制造方法
CN109988512A (zh) * 2018-01-03 2019-07-09 泰柏斯科技有限公司 紫外线可固化光学粘合剂及其制备方法与用于其的组合物
CN109988512B (zh) * 2018-01-03 2022-07-26 泰柏斯科技有限公司 紫外线可固化光学粘合剂及其制备方法与用于其的组合物
JPWO2022210894A1 (fr) * 2021-03-31 2022-10-06
WO2022210894A1 (fr) * 2021-03-31 2022-10-06 大日本印刷株式会社 Film de transfert, film de revêtement dur, article moulé à revêtement dur et son procédé de production
JP7276730B2 (ja) 2021-03-31 2023-05-18 大日本印刷株式会社 転写フィルム、ハードコートフィルム、ならびにハードコート成形体およびその製造方法

Also Published As

Publication number Publication date
CN107709493B (zh) 2022-08-09
TWI792369B (zh) 2023-02-11
KR20180015716A (ko) 2018-02-13
TW201716536A (zh) 2017-05-16
CN111732904A (zh) 2020-10-02
KR20200019792A (ko) 2020-02-24
TW202024272A (zh) 2020-07-01
CN107709493A (zh) 2018-02-16
TW202024273A (zh) 2020-07-01
TWI726883B (zh) 2021-05-11
CN108977113A (zh) 2018-12-11
KR102080224B1 (ko) 2020-02-21
TW202136462A (zh) 2021-10-01
CN108977113B (zh) 2020-03-10
TWI792195B (zh) 2023-02-11
TWI728711B (zh) 2021-05-21
TW202126775A (zh) 2021-07-16

Similar Documents

Publication Publication Date Title
WO2016194957A1 (fr) Feuille adhésive photodurcissable, feuille adhésive et dispositif d'affichage d'image
JP6977761B2 (ja) 粘着シート及びこれを用いた画像表示装置
JP6388023B2 (ja) 画像表示装置構成用積層体の製造方法
JP6904448B2 (ja) 光硬化型粘着シート、粘着シート及び画像表示装置
JP6361734B2 (ja) 透明粘着シート
JP6252626B2 (ja) 粘着シート
JP7415366B2 (ja) 光硬化性粘着シート、粘着シート積層体、画像表示装置用積層体及び画像表示装置
WO2020032134A1 (fr) Feuille adhésive photodurcissable, stratifié pour dispositif d'affichage d'image, et dispositif d'affichage d'image
JP6256664B6 (ja) 画像表示装置用積層体の製造方法
JPWO2016194958A6 (ja) 画像表示装置用積層体の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16803391

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20187000091

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 16803391

Country of ref document: EP

Kind code of ref document: A1