WO2021181767A1 - 粘着シート、構成体および構成体の製造方法 - Google Patents

粘着シート、構成体および構成体の製造方法 Download PDF

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Publication number
WO2021181767A1
WO2021181767A1 PCT/JP2020/044897 JP2020044897W WO2021181767A1 WO 2021181767 A1 WO2021181767 A1 WO 2021181767A1 JP 2020044897 W JP2020044897 W JP 2020044897W WO 2021181767 A1 WO2021181767 A1 WO 2021181767A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive layer
meth
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/044897
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English (en)
French (fr)
Japanese (ja)
Inventor
高橋　洋一
翔 小鯖
結加 藤井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lintec Corp
Original Assignee
Lintec Corp
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 Lintec Corp filed Critical Lintec Corp
Priority to CN202080056135.3A priority Critical patent/CN114207066A/zh
Priority to JP2021518824A priority patent/JP6987306B1/ja
Priority to US17/910,119 priority patent/US12552970B2/en
Priority to KR1020217038939A priority patent/KR20220147495A/ko
Priority to CN202411800440.5A priority patent/CN119391307A/zh
Publication of WO2021181767A1 publication Critical patent/WO2021181767A1/ja
Priority to JP2021193942A priority patent/JP7369757B2/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/10—Registration, licensing, or like devices
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J7/10—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
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/354—Applications of adhesives in processes or use of adhesives in the form of films or foils for automotive applications
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • 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 an adhesive sheet suitable for use in a structure such as an electronic license plate, a structure obtained by using the adhesive sheet, and a method for manufacturing the structure.
  • the display surface side of the electronic license plate is usually covered with an adhesive layer for the purpose of protecting the above-mentioned display device.
  • the materials are laminated.
  • the electronic license plates are used with the above-mentioned display device in the cover material for the purpose of imparting light resistance, which is a property that can prevent discoloration and deterioration of the display device due to the ultraviolet rays. May be provided with a coat layer containing an ultraviolet absorber on the opposite surface side.
  • the electronic license plate since the electronic license plate is left outdoors for a long period of time while being attached to the exterior of the vehicle, it is often exposed to high temperature and high humidity conditions. Under such high temperature and high humidity conditions, outgas is generated from the resin member constituting the cover material and the display device, and the outgas is generated at the interface between the cover material and the pressure-sensitive adhesive layer and between the pressure-sensitive adhesive layer and the display device. It may accumulate at the interface and cause blister such as air bubbles, floating, and peeling.
  • the present invention has been made in view of the above-mentioned actual conditions, and is an adhesive sheet capable of achieving both light resistance and blister resistance satisfactorily, and a structure having satisfactorily achieving light resistance and blister resistance. And it is an object of the present invention to provide the manufacturing method of the said structure.
  • the present invention is a pressure-sensitive adhesive sheet including at least a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive having active energy ray curability and ultraviolet absorption, and the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer is cured by irradiating one side of the surface with ultraviolet rays having a light amount of 2000 mJ / cm 2 , the irradiated surface and the irradiated surface, which are the surfaces of the cured pressure-sensitive adhesive layer irradiated with ultraviolet rays, are When the infrared absorption spectrum of each of the non-irradiated surfaces, which is the opposite surface, is measured by the total reflection measurement method, the infrared absorption spectrum of the non-irradiated surface is subtracted from the infrared absorption spectrum of the irradiated surface.
  • the maximum value of the absolute value of the absorbance in the range of 700 to 1000 cm -1 is 0.0001 or more and 0.012 or less, and ultraviolet rays having a light amount of 2000 mJ / cm 2 are applied to the pressure-sensitive adhesive layer.
  • the difference in the gel fraction of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer before and after the irradiation is 5 points or more and 50 points or less.
  • An adhesive sheet is provided (Invention 1).
  • the pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive having ultraviolet absorption, it is not necessary to separately provide a coat layer, and good light resistance can be realized. Further, since the pressure-sensitive adhesive layer has active energy ray curability and is composed of a pressure-sensitive adhesive that satisfies the above-mentioned conditions relating to the difference spectrum, the pressure-sensitive adhesive has ultraviolet absorption. By irradiating the active energy rays after the constituent members are bonded to each other, the pressure-sensitive adhesive layer can be satisfactorily cured to exhibit suitable cohesiveness, and the surface of the pressure-sensitive adhesive layer is not exposed to the active energy rays.
  • All of the irradiated surfaces exhibit suitable adhesion.
  • the adhesiveness is further improved. As a result, excellent blister resistance can be realized.
  • the thickness of the pressure-sensitive adhesive layer is preferably 20 ⁇ m or more and 1000 ⁇ m or less (Invention 2).
  • the pressure-sensitive adhesive layer when the pressure-sensitive adhesive layer is irradiated with ultraviolet rays having a light amount of 2000 mJ / cm 2 to cure the pressure-sensitive adhesive layer, the pressure-sensitive adhesive constituting the cured pressure-sensitive adhesive layer is formed.
  • the gel content of the agent is preferably 40% or more and 95% or less (Invention 3).
  • the pressure-sensitive adhesive layer after curing is at 23 ° C.
  • the storage elastic modulus is preferably 0.03 MPa or more and 2.00 MPa or less (Invention 4).
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer has a cross-linked structure composed of the (meth) acrylic acid ester polymer and a cross-linking agent, and has an active energy ray-curable property. It preferably contains an ingredient and an ultraviolet absorber (Invention 5).
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains a photopolymerization initiator (Invention 6).
  • the present invention includes a first constituent member, a second constituent member, and a post-curing adhesive layer for bonding the first constituent member and the second constituent member to each other.
  • a body wherein the cured pressure-sensitive adhesive layer is obtained by curing the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheets (Inventions 1 to 7) (Invention 8).
  • the surface of at least one of the first constituent member and the second constituent member in contact with the cured pressure-sensitive adhesive layer is made of a resin material (Invention 9).
  • the first constituent member is a cover material
  • the second constituent member is a display device
  • the constituent body is a display body attached to the exterior of a moving body.
  • the moving body is preferably a vehicle (Invention 11).
  • the present invention is a method for manufacturing the constituents (inventions 8 to 11), wherein the first constituent member and the second constituent member are attached to the pressure-sensitive adhesive sheet (invention 1 to 7).
  • the bonding step of bonding to each other by the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer after bonding are irradiated with active energy rays via at least one of the first component and the second component.
  • the present invention provides a method for producing a constituent body, which comprises an irradiation step of curing the pressure-sensitive adhesive layer to obtain the pressure-sensitive adhesive layer after curing (Invention 12).
  • the adhesive sheet according to the present invention can satisfactorily realize both light resistance and blister resistance, and the structure according to the present invention can satisfactorily realize both light resistance and blister resistance.
  • the pressure-sensitive adhesive sheet according to the present embodiment is a pressure-sensitive adhesive sheet including at least a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive having active energy ray curability and ultraviolet-absorbing property, and preferably one side or both sides of the pressure-sensitive adhesive layer. It is an adhesive sheet obtained by laminating a release sheet on the surface.
  • FIG. 1 shows a specific configuration as an example of the pressure-sensitive adhesive sheet according to the present embodiment.
  • the adhesive sheet 1 according to the embodiment is in contact with the two release sheets 12a and 12b and the release surfaces of the two release sheets 12a and 12b. , 12b and the pressure-sensitive adhesive layer 11 sandwiched between the two.
  • the peeling surface of the release sheet in the present specification means a surface of the release sheet that has peelability, and includes both a surface that has been peeled and a surface that exhibits peelability without peeling. ..
  • the adhesive sheet 1 according to the present embodiment can be used for manufacturing the structure 2 as illustrated in FIG.
  • the pressure-sensitive adhesive layer 11 is irradiated with active energy rays.
  • the pressure-sensitive adhesive layer 11 is cured to become the cured pressure-sensitive adhesive layer 11', and the first component 21, the cured pressure-sensitive adhesive layer 11', and the second component 22 are laminated in this order. 2 is obtained.
  • the gel fraction is increased by curing, the cohesive force is increased, and the active energy ray-irradiated surface and the non-irradiated surface of the cured adhesive layer 11'are both in good adhesion. Demonstrate. Therefore, even when the obtained structure 2 is left for 72 hours under low temperature conditions of ⁇ 40 ° C., high temperature conditions of 95 ° C., high temperature and high humidity conditions such as 85 ° C. and 85% RH, etc., after curing. Bubbles, floating, peeling, etc. are suppressed at the interface between the pressure-sensitive adhesive layer 11'and the constituent members, and excellent blister resistance is exhibited.
  • the wave frequency is in the range of 700 to 1000 cm -1 in the difference spectrum obtained by subtracting the infrared absorption spectrum of the non-irradiated surface from the infrared absorption spectrum of the irradiated surface.
  • the maximum value of the absolute value of the absorbance in the above is 0.0001 or more and 0.012 or less.
  • the pressure-sensitive adhesive layer 11 in the present embodiment is composed of a pressure-sensitive adhesive having active energy ray curability, and the pressure-sensitive adhesive layer 11 is cured by irradiating the pressure-sensitive adhesive layer 11 with active energy rays.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 11 has ultraviolet-absorbing property, and such a pressure-sensitive adhesive absorbs active energy rays (particularly ultraviolet rays) irradiated to the pressure-sensitive adhesive, resulting in adhesion. It is difficult to sufficiently cure the adhesive because the agent layer is not cured at all or the degree of curing on the active energy ray irradiated surface and the non-irradiated surface is different, resulting in excellent blister resistance and light resistance.
  • the present inventors pay attention to the above-mentioned difference spectrum, and by using an adhesive that satisfies the above-mentioned conditions regarding the difference spectrum, excessive active energy rays are generated even though they have ultraviolet absorption. It has been found that the pressure-sensitive adhesive layer can be sufficiently cured without irradiation to exhibit excellent blister resistance and light resistance.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 11 has ultraviolet absorption, it is adhered by irradiation with active energy rays.
  • the agent layer 11 is well cured with an even degree of curing in the thickness direction, and excellent cohesiveness can be exhibited. Further, both the irradiated surface and the non-irradiated surface of the active energy ray of the pressure-sensitive adhesive layer exhibit suitable adhesion. These make it possible to exhibit excellent blister resistance.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 11 has ultraviolet-absorbing property, the pressure-sensitive adhesive layer does not require a separate coat layer for blocking ultraviolet rays on the manufactured structure 2. Good light resistance can be realized by the cured pressure-sensitive adhesive layer 11'formed by curing 11. As described above, in the pressure-sensitive adhesive sheet 1 of the present embodiment, both excellent blister resistance and excellent light resistance can be satisfactorily achieved.
  • the maximum value of the absolute value of the absorbance in the above-mentioned difference spectrum is preferably 0.010 or less, and particularly preferably 0.008 or less.
  • the lower limit of the maximum value is not particularly limited, and may be, for example, 0.0005 or more, and particularly 0.0010 or more.
  • the above-mentioned maximum value regarding the difference spectrum measured in the same manner as in the case of the light amount of 2000 mJ / cm 2 is 0, except that the light amount of the ultraviolet rays to be irradiated is changed to 200 mJ / cm 2. It is preferably .0001 or more, more preferably 0.0005 or more, particularly preferably 0.001 or more, and further preferably 0.005 or more.
  • the maximum value is preferably 0.100 or less, more preferably 0.080 or less, particularly preferably 0.050 or less, and further preferably 0.040 or less. ..
  • the maximum value in the case of a light amount of 200 mJ / cm 2 is within such a range, it becomes easy to satisfy the condition regarding the difference spectrum in the case of a light amount of 2000 mJ / cm 2.
  • the pressure-sensitive adhesive sheet 1 except for changing the light quantity of ultraviolet light irradiating the 1000 mJ / cm 2, the maximum value mentioned above regarding the difference spectra measured as in the case of the light amount 2000 mJ / cm 2 is 0 It is preferably .0001 or more, particularly preferably 0.0005 or more, and further preferably 0.001 or more.
  • the maximum value is preferably 0.050 or less, more preferably 0.030 or less, particularly preferably 0.020 or less, and further preferably 0.010 or less. ..
  • the maximum value in the case of a light amount of 1000 mJ / cm 2 is within such a range, it becomes easy to satisfy the condition regarding the difference spectrum in the case of a light amount of 2000 mJ / cm 2.
  • the difference in gel fraction is preferably 8 points or more, particularly preferably 10 points or more, and further preferably 12 points or more.
  • the upper limit of the gel fraction is preferably 50 points or less, more preferably 40 points or less, and particularly preferably 40 points or less, from the viewpoint that the adhesive force and the storage elastic modulus described later are likely to be within a predetermined range. It is preferably 30 points or less, and more preferably 20 points or less.
  • the above-mentioned difference in gel fraction can generally be used as an index of the active energy ray curability of the pressure-sensitive adhesive layer. That is, those having a predetermined difference in the gel fraction described above are judged to have active energy ray curability, and those having no predetermined difference are judged to have no active energy ray curability. Can be done.
  • the pressure-sensitive adhesive layer 11 in the present embodiment can be said to have active energy ray curability when, for example, the difference in gel fractions described above is 5 points or more.
  • the gel fraction of the pressure-sensitive adhesive (the pressure-sensitive adhesive before being cured by irradiation with active energy rays) constituting the pressure-sensitive adhesive layer 11 is preferably 20% or more, and particularly 30%. % Or more, and more preferably 38% or more.
  • the gel fraction is preferably 90% or less, more preferably 80% or less, particularly preferably 70% or less, further preferably 60% or less, and 53%. Most preferably: When the gel fraction is in these ranges, it becomes easy to satisfy the conditions regarding the difference spectrum when the light intensity is 2000 mJ / cm 2 and the above-mentioned difference in gel fraction.
  • the adhesiveness to the adherend (followability at the time of adhering, etc.) is improved, and the adhesion to the adherend is easily improved. This makes it easy to exhibit excellent blister resistance.
  • the pressure-sensitive adhesive layer 11 when the pressure-sensitive adhesive layer 11 is cured by irradiating the pressure-sensitive adhesive layer 11 with ultraviolet rays having a light amount of 200 mJ / cm 2, the pressure-sensitive adhesive layer 11 is obtained.
  • the gel fraction of the pressure-sensitive adhesive constituting ′ is preferably 30% or more, particularly preferably 35% or more, and further preferably 40% or more.
  • the gel fraction is preferably 95% or less, more preferably 85% or less, particularly preferably 75% or less, and further preferably 65% or less.
  • the obtained cured pressure-sensitive adhesive layer 11' is likely to exhibit suitable cohesiveness, and is likely to exhibit blister resistance.
  • the pressure-sensitive adhesive layer 11 when the pressure-sensitive adhesive layer 11 is cured by irradiating the pressure-sensitive adhesive layer 11 with ultraviolet rays having a light amount of 1000 mJ / cm 2, the pressure-sensitive adhesive layer 11 is obtained.
  • the gel fraction of the pressure-sensitive adhesive constituting ‘’ is preferably 40% or more, more preferably 45% or more, particularly preferably 50% or more, and further preferably 55% or more. preferable.
  • the gel fraction is preferably 95% or less, more preferably 90% or less, particularly preferably 85% or less, and further preferably 75% or less.
  • the obtained cured pressure-sensitive adhesive layer 11' is likely to exhibit suitable cohesiveness, and is likely to exhibit blister resistance.
  • the pressure-sensitive adhesive layer 11 when the pressure-sensitive adhesive layer 11 is cured by irradiating the pressure-sensitive adhesive layer 11 with ultraviolet rays having a light amount of 2000 mJ / cm 2, the pressure-sensitive adhesive layer 11 is obtained.
  • the gel fraction of the pressure-sensitive adhesive constituting ‘’ is preferably 40% or more, more preferably 45% or more, particularly preferably 50% or more, and further preferably 55% or more. It is preferably 58% or more, and most preferably 58% or more.
  • the gel fraction is preferably 95% or less, particularly 90% or less, and further preferably 85% or less.
  • the obtained cured pressure-sensitive adhesive layer 11'easily exhibits suitable cohesiveness, so that blister resistance is easily exhibited.
  • the storage elastic modulus of the pressure-sensitive adhesive (the pressure-sensitive adhesive before being cured by irradiation with active energy rays) constituting the pressure-sensitive adhesive layer 11 at 23 ° C. is 0. It is preferably 01 MPa or more, more preferably 0.03 MPa or more, particularly preferably 0.05 MPa or more, further preferably 0.07 MPa or more, and particularly 0 from the viewpoint of blister resistance. It is preferably .08 MPa or more.
  • the storage elastic modulus at 23 ° C. is preferably 1.00 MPa or less, more preferably 0.50 MPa or less, particularly preferably 0.20 MPa or less, and further preferably 0.10 MPa or less. Is preferable.
  • the storage elastic modulus of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 11 at 23 ° C. is within these ranges, it becomes easy to satisfy the condition regarding the difference spectrum when the light intensity is 2000 mJ / cm 2.
  • the adhesiveness to the adherend (followability at the time of adhering, etc.) is improved, and the adhesion to the adherend is easily improved. This makes it easy to exhibit excellent blister resistance.
  • the pressure-sensitive adhesive sheet 1 when the pressure-sensitive adhesive layer 11 is irradiated with ultraviolet rays having a light amount of 2000 mJ / cm 2 to cure the pressure-sensitive adhesive layer 11, the cured pressure-sensitive adhesive layer 11 is obtained.
  • the storage elastic modulus of the pressure-sensitive adhesive constituting ′ at 23 ° C. is preferably 0.03 MPa or more, particularly preferably 0.05 MPa or more, and further preferably 0.08 MPa or more, and the adhesive strength. From the viewpoint of improvement, it is preferably 0.12 MPa or more, more preferably 0.15 MPa or more, particularly preferably 0.20 MPa or more, further preferably 0.25 MPa or more, and tolerate.
  • the storage elastic modulus at 23 ° C. is preferably 2.00 MPa or less, particularly preferably 1.00 MPa or less, and further preferably 0.50 MPa or less.
  • the storage elastic modulus at 23 ° C. in the case of a light amount of 2000 mJ / cm 2 is within these ranges, it becomes easy to satisfy the condition regarding the difference spectrum in the case of a light amount of 2000 mJ / cm 2.
  • the transmittance of the light beam having a wavelength of 360 nm in the pressure-sensitive adhesive layer 11 in the present embodiment is preferably 20% or less, particularly preferably 10% or less, and further 5% or less. It is preferably 1% or less, and most preferably 1% or less.
  • the pressure-sensitive adhesive layer 11 in the present embodiment is likely to exhibit excellent ultraviolet absorption, and is manufactured by using the pressure-sensitive adhesive sheet 1 according to the present embodiment.
  • the structure 2 has better light resistance.
  • the lower limit of the transmittance of light rays having a wavelength of 360 nm is not particularly limited, and may be, for example, 0% or more, 0.01% or more, and particularly 0.10% or more. Further, it may be 0.50% or more.
  • the transmittance of light having a wavelength of 380 nm is preferably 50% or less, preferably 30% or less, particularly preferably 20% or less, and 10 % Or less, and most preferably 1% or less.
  • the transmittance of the light beam having a wavelength of 380 nm is in the above range, the pressure-sensitive adhesive layer 11 in the present embodiment is likely to exhibit excellent ultraviolet absorption, and is manufactured by using the pressure-sensitive adhesive sheet 1 according to the present embodiment.
  • the structure 2 has better light resistance.
  • the lower limit of the transmittance of light rays having a wavelength of 380 nm is not particularly limited, and may be, for example, 0% or more, 0.01% or more, and particularly 0.1% or more. Further, it may be 0.50% or more.
  • the pressure-sensitive adhesive layer 11 in the present embodiment preferably has a transmittance of light rays having a wavelength of 400 nm of 70% or less, more preferably 50% or less, and particularly preferably 30% or less. Further, it is preferably 21% or less.
  • the transmittance of the light beam having a wavelength of 400 nm is in the above range, the pressure-sensitive adhesive layer 11 in the present embodiment is likely to exhibit excellent ultraviolet absorption, and is manufactured by using the pressure-sensitive adhesive sheet 1 according to the present embodiment.
  • the structure 2 has better light resistance.
  • the lower limit of the transmittance of light rays having a wavelength of 400 nm is not particularly limited, and may be, for example, 0% or more, 1% or more, particularly 5% or more, and further 10%. That may be the above.
  • the adhesive strength with respect to soda lime glass is preferably 1N / 25 mm or more. It is more preferably 5N / 25mm or more, particularly preferably 10N / 25mm or more, further preferably 20N / 25mm or more, and most preferably 28N / 25mm or more.
  • the adhesive strength is 1N / 25 mm or more, the adhesiveness to the adherend is good, excellent adhesion is easily exhibited, and more excellent blister resistance is easily exhibited.
  • the upper limit of the adhesive strength is not particularly limited, and may be, for example, 100 N / 25 mm or less, 80 N / 25 mm or less, particularly 60 N / 25 mm or less, and further 50 N / 25 mm or less. It may be.
  • the adhesive strength against soda lime glass is 5 N /. It is preferably 25 mm or more, more preferably 10 N / 25 mm or more, particularly preferably 20 N / 25 mm or more, preferably 35 N / 25 mm or more, and most preferably 42 N / 25 mm or more. .. When the adhesive strength is 5 N / 25 mm or more, it becomes easy to exhibit more excellent blister resistance.
  • the upper limit of the adhesive strength is not particularly limited, and may be, for example, 100 N / 25 mm or less, 80 N / 25 mm or less, 60 N / 25 mm or less, and further 50 N / 25 mm. It may be:
  • the above adhesive strength basically refers to the adhesive strength measured by the 180-degree peeling method according to JIS Z0237: 2009, and the specific test method is as shown in the test example described later.
  • Adhesive Layer 11 is composed of an adhesive having active energy ray curability and ultraviolet absorption, and the adhesive satisfies the above-mentioned conditions regarding the difference spectrum. If so, there is no particular limitation.
  • the pressure-sensitive adhesive layer 11 has a cross-linked structure composed of a (meth) acrylic acid ester polymer (A) and a cross-linking agent (B), and also has an active energy ray-curable component (C) and an ultraviolet absorber. It is preferable to contain (E).
  • Such a pressure-sensitive adhesive layer 11 contains, for example, a (meth) acrylic acid ester polymer (A), a cross-linking agent (B), an active energy ray-curable component (C), and an ultraviolet absorber (E). It can be composed of a pressure-sensitive adhesive obtained by cross-linking (thermally cross-linking) a composition (hereinafter, may be referred to as "adhesive composition P").
  • the adhesive composition P preferably further contains a photopolymerization initiator (D), if desired.
  • (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms. Furthermore, the concept of "polymer” shall also be included in "polymer”.
  • the pressure-sensitive adhesive layer 11 obtained by cross-linking (thermally cross-linking) the above-mentioned pressure-sensitive adhesive composition P is still cured by active energy rays at the stage of the pressure-sensitive adhesive sheet 1, that is, the stage before being attached to the adherend. Since the storage elastic modulus is relatively low, the stress generated when the adherend is attached to the adherend can be relaxed. As a result, even when the pressure-sensitive adhesive layer 11 is attached to a surface having irregularities on the adherend, the pressure-sensitive adhesive layer 11 easily follows the irregularities, and gaps, floats, etc. may occur in the vicinity of the irregularities. It is suppressed and exhibits excellent adhesion to the adherend.
  • the uncured component since the gel fraction is relatively low before being attached to the adherend, the uncured component easily wets and spreads on the surface of the adherend due to the plastic action of the uncured component when the gel is attached to the adherend. Demonstrates excellent adhesion. Combined with the above-mentioned adhesion and adhesion to the adherend, the blister resistance is excellent.
  • the (meth) acrylic acid ester polymer (A) is a (meth) acrylic acid alkyl ester and a monomer having a reactive functional group in the molecule (reactive functional group-containing monomer) as a monomer unit constituting the polymer. And are preferably contained.
  • the (meth) acrylic acid ester polymer (A) can exhibit preferable adhesiveness by containing the (meth) acrylic acid alkyl ester as the monomer unit constituting the polymer.
  • the (meth) acrylic acid alkyl ester a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms is preferable.
  • the alkyl group may be linear or branched chain, or may have a cyclic structure.
  • Examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, and n- (meth) acrylic acid.
  • the (meth) acrylic acid alkyl ester a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 20 carbon atoms is preferable from the viewpoint of blister resistance.
  • the (meth) acrylic acid alkyl ester having an alkyl group having 4 to 20 carbon atoms include n-butyl (meth) acrylic acid, 2-ethylhexyl (meth) acrylic acid, isooctyl (meth) acrylic acid, and (meth) acrylic acid.
  • Isobornyl and the like are preferable, and in particular, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and isobornyl (meth) acrylate, which provide excellent adhesiveness and blister resistance, are preferable, and n-butyl acrylate is preferable. , 2-Ethylhexyl acrylate and isobornyl acrylate are particularly preferred.
  • the (meth) acrylic acid ester polymer (A) preferably contains 40% by mass or more of the (meth) acrylic acid alkyl ester as a monomer unit constituting the polymer, and more preferably 50% by mass or more. It is preferable to contain 60% by mass or more, and more preferably 70% by mass or more. When the (meth) acrylic acid alkyl ester is contained in an amount of 40% by mass or more, the (meth) acrylic acid ester polymer (A) can exhibit suitable adhesiveness. Further, the (meth) acrylic acid ester polymer (A) preferably contains 99% by mass or less of the (meth) acrylic acid alkyl ester as a monomer unit constituting the polymer, and particularly contains 95% by mass or less.
  • the content is 90% by mass or less.
  • the (meth) acrylic acid ester polymer (A) contains a hydroxyl group-containing monomer as a monomer constituting the polymer
  • the (meth) acrylic acid ester polymer (A) is a monomer constituting the polymer.
  • the (meth) acrylic acid alkyl ester as a unit is preferably contained in an amount of 85% by mass or less, particularly preferably 80% by mass or less, and further preferably 75% by mass or less. By adjusting the amount of the (meth) acrylic acid alkyl ester to 99% by mass or less, a suitable amount of other monomer components can be introduced into the (meth) acrylic acid ester polymer (A).
  • the (meth) acrylic acid ester polymer (A) contains a reactive functional group-containing monomer as a monomer unit constituting the polymer, and thus via a reactive functional group derived from the reactive functional group-containing monomer. , Reacts with the cross-linking agent (B) described later, thereby forming a cross-linked structure (three-dimensional network structure), and a pressure-sensitive adhesive having a desired cohesive force can be obtained.
  • the reactive functional group-containing monomer contained in the (meth) acrylic acid ester polymer (A) as a monomer unit constituting the polymer includes a monomer having a hydroxyl group in the molecule (hydroxyl-containing monomer) and carboxy in the molecule.
  • Preferred examples include a monomer having a group (carboxy group-containing monomer), a monomer having an amino group in the molecule (amino group-containing monomer), and the like. These reactive functional group-containing monomers may be used alone or in combination of two or more.
  • a hydroxyl group-containing monomer or a carboxy group-containing monomer is preferable from the viewpoint of easily adjusting the crosslink density and easily obtaining a pressure-sensitive adhesive having a desired cohesive force, and from the viewpoint of adhesive force, a hydroxyl group-containing monomer is preferable.
  • Monomers are preferred.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and (meth).
  • Hydroxyalkyl esters of (meth) acrylic acid such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylic acid can be mentioned.
  • a (meth) acrylic acid hydroxyalkyl ester having a hydroxyalkyl group having 1 to 4 carbon atoms is preferable.
  • 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like are preferable, and 2-hydroxyethyl acrylate or 4-hydroxybutyl acrylate are particularly preferable. Be done. These may be used alone or in combination of two or more.
  • carboxy group-containing monomer examples include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.
  • carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid.
  • acrylic acid is preferable from the viewpoint of the cohesive force of the obtained (meth) acrylic acid ester polymer (A). These may be used alone or in combination of two or more.
  • the (meth) acrylic acid ester polymer (A) preferably contains 1% by mass or more of a reactive functional group-containing monomer, and particularly 3% by mass or more, as a monomer unit constituting the polymer. It is preferable, and it is preferable that the content is 5% by mass or more.
  • the reactive functional group-containing monomer is a hydroxyl group-containing monomer, it is preferably contained in an amount of 10% by mass or more, particularly preferably 18% by mass or more, and further preferably 24% by mass or more.
  • the (meth) acrylic acid ester polymer (A) preferably contains a reactive functional group-containing monomer in an amount of 50% by mass or less, particularly 40% by mass or less, as a monomer unit constituting the polymer.
  • the reactive functional group-containing monomer is a carboxy group-containing monomer, it is preferably contained in an amount of 20% by mass or less, particularly preferably 15% by mass or less, and further preferably 10% by mass or less. ..
  • the (meth) acrylic acid ester polymer (A) contains a nitrogen atom-containing monomer as a monomer unit constituting the polymer.
  • a nitrogen atom-containing monomer By allowing a nitrogen atom-containing monomer to be present in the polymer as a constituent unit, a predetermined polarity is imparted to the pressure-sensitive adhesive, and the adhesive has excellent affinity for an adherend having a certain degree of polarity such as glass. Can be.
  • the nitrogen atom-containing monomer include a monomer having an amide group, a monomer having a nitrogen-containing heterocycle, and the like, in addition to the amino group-containing monomer as the reactive functional group-containing monomer described above, and among them, (meth) acrylic. From the viewpoint of imparting appropriate rigidity to the acid ester polymer (A), a monomer having a nitrogen-containing heterocycle is preferable.
  • Examples of the monomer having a nitrogen-containing heterocycle include N- (meth) acryloylmorpholin, N-vinyl-2-pyrrolidone, N- (meth) acryloylpyrrolidone, N- (meth) acryloylpiperidin, and N- (meth) acryloyl.
  • N- (meth) acryloylmorpholin which exhibits more excellent adhesive strength, is preferable, and N-acryloylmorpholin is particularly preferable.
  • N-vinylcarboxylic acid amide for example, N-vinylcarboxylic acid amide, (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-tert-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-ethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-phenyl (meth) acrylamide, dimethylaminopropyl ( Meta) Acrylamide, N-vinylcaprolactam and the like can also be used.
  • N-vinylcarboxylic acid amide for example, N-vinylcarboxylic acid amide, (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-tert
  • the above nitrogen atom-containing monomers may be used alone or in combination of two or more.
  • the nitrogen atom-containing monomer is preferably contained in an amount of 0.5% by mass or more, particularly. It is preferably contained in an amount of 1% by mass or more, and more preferably 3% by mass or more. Further, the (meth) acrylic acid ester polymer (A) preferably contains the nitrogen atom-containing monomer in an amount of 20% by mass or less, and particularly preferably 15% by mass or less, as a monomer unit constituting the polymer. It is preferable, and it is preferable that the content is 8% by mass or less. When the content of the nitrogen atom-containing monomer is within the above range, the obtained pressure-sensitive adhesive can effectively exhibit excellent adhesiveness to an adherend such as glass. In addition, the gel fraction and storage elastic modulus described above can be easily adjusted to suitable values.
  • the (meth) acrylic acid ester polymer (A) may contain other monomers as the monomer unit constituting the polymer, if desired.
  • examples of other monomers include (meth) acrylic acid alkoxyalkyl esters such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate, vinyl acetate, and styrene. These may be used alone or in combination of two or more.
  • the (meth) acrylic acid ester polymer (A) is preferably a linear polymer. Since it is a linear polymer, entanglement of molecular chains is likely to occur, and improvement in cohesive force can be expected, so that a pressure-sensitive adhesive having better blister resistance can be obtained.
  • the (meth) acrylic acid ester polymer (A) is preferably a solution polymer obtained by a solution polymerization method. Since it is a solution polymer, a high molecular weight polymer can be easily obtained, and an improvement in cohesive force can be expected, so that a pressure-sensitive adhesive having better blister resistance can be obtained.
  • the polymerization mode of the (meth) acrylic acid ester polymer (A) may be a random copolymer or a block copolymer.
  • the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is preferably 200,000 or more as a lower limit value, particularly preferably 300,000 or more, and further preferably 400,000 or more.
  • the lower limit of the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is equal to or higher than the above, it becomes easy to adjust the gel fraction and storage elastic modulus described above to suitable values, and the resistance of the obtained pressure-sensitive adhesive. The blister property becomes better.
  • the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is preferably 2 million or less, more preferably 1.5 million or less, and particularly preferably 1 million or less, as an upper limit value. Further, it is preferably 800,000 or less.
  • the upper limit of the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is not more than the above, the adhesiveness and adhesion of the obtained pressure-sensitive adhesive to the adherend are more excellent.
  • the gel fraction and storage elastic modulus described above can be easily adjusted to suitable values.
  • the weight average molecular weight in the present specification is a standard polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method.
  • the (meth) acrylic acid ester polymer (A) may be used alone or in combination of two or more.
  • cross-linking agent (B) can cross-link the (meth) acrylic acid ester polymer (A) by heating the adhesive composition P, and can satisfactorily form a three-dimensional network structure. As a result, the cohesive force of the obtained adhesive is further improved, and the blister resistance is further improved.
  • the cross-linking agent (B) may be any one that reacts with the reactive functional group of the (meth) acrylic acid ester polymer (A), and is, for example, an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, or an amine-based cross-linking agent.
  • the reactive group of the (meth) acrylic acid ester polymer (A) is a hydroxyl group
  • the reactive group of the polymer (A) is a carboxy group
  • the cross-linking agent (B) may be used alone or in combination of two or more.
  • the isocyanate-based cross-linking agent contains at least a polyisocyanate compound.
  • the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanates, and alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate.
  • biurets, isocyanurates, and adducts which are reactants with low molecular weight active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.
  • active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil.
  • epoxy-based cross-linking agent examples include 1,3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N, N, N', N'-tetraglycidyl-m-xylylene diamine, and ethylene glycol diglycidyl ether. , 1,6-Hexanediol diglycidyl ether, trimethylpropan diglycidyl ether, diglycidyl aniline, diglycidyl amine and the like. Of these, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane is preferable from the viewpoint of reactivity with a carboxy group.
  • the content of the cross-linking agent (B) in the adhesive composition P is preferably 0.01 part by mass or more with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A), and in particular, 0. It is preferably 05 parts by mass or more, and more preferably 0.1 parts by mass or more.
  • the content is preferably 3 parts by mass or less, particularly preferably 2 parts by mass or less, and further preferably 1 part by mass or less.
  • Active energy ray-curable component (C) The pressure-sensitive adhesive obtained by cross-linking (thermally cross-linking) the pressure-sensitive adhesive composition P by containing the active energy ray-curable component (C) in the pressure-sensitive adhesive composition P becomes an active energy ray-curable pressure-sensitive adhesive. ..
  • the active energy ray-curable components (C) are polymerized with each other by curing by irradiation with active energy rays after the adherend is attached, and the polymerized active energy ray-curable components (C) are (meth) acrylics. It is presumed that it is entwined with the crosslinked structure (three-dimensional network structure) of the acid ester polymer (A).
  • the pressure-sensitive adhesive having such a high-order structure has high cohesive force and exhibits high film strength, and thus has excellent blister resistance.
  • the active energy ray-curable component (C) is not particularly limited as long as it is a component that is cured by irradiation with active energy rays and obtains the above effects, and may be any of monomers, oligomers, and polymers, and they may be used. May be a mixture of. Among them, a polyfunctional acrylate-based monomer having excellent compatibility with the (meth) acrylic acid ester polymer (A) and the like can be preferably mentioned.
  • polyfunctional acrylate-based monomer examples include tricyclodecanedimethanol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di ().
  • Meta) acrylate polyethylene glycol di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, dicyclopentanyldi (meth) acrylate, caprolactone-modified dicyclopentenyldi (Meta) acrylate, ethylene oxide modified di (meth) acrylate, di (acryloxyethyl) isocyanurate, allylated cyclohexyl di (meth) acrylate, ethoxylated bisphenol A diacrylate, 9,9-bis [4- (2) -Acryloyloxyethoxy) phenyl] fluorene and other bifunctional types; trimethylpropantri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acryl
  • the polyfunctional acrylate-based monomer preferably has a molecular weight of less than 1000.
  • the content of the active energy ray-curable component (C) in the adhesive composition P is a (meth) acrylic acid from the viewpoint of facilitating the above-mentioned gel fraction and storage elasticity of the obtained adhesive to be set to desired values.
  • the lower limit is preferably 1 part by mass or more with respect to 100 parts by mass of the ester polymer (A), and from the viewpoint of facilitating the above-mentioned conditions regarding the difference spectrum and the above-mentioned difference in gel fraction, 2 parts by mass.
  • the amount is preferably 3 parts or more, more preferably 3 parts by mass or more, particularly preferably 5 parts by mass or more, and further preferably 8 parts by mass or more.
  • the above-mentioned content is desired from the viewpoint of preventing the active energy ray-curable component (C) from phase-separating from the (meth) acrylic acid ester polymer (A) and the above-mentioned gel fraction and storage elastic modulus.
  • the upper limit value is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, particularly preferably 20 parts by mass or less, and further preferably 15 parts by mass or less. Is preferable.
  • the pressure-sensitive adhesive composition P preferably further contains a photopolymerization initiator (D).
  • a photopolymerization initiator (D) By containing the photopolymerization initiator (D) in this way, the active energy ray-curable component (C) can be efficiently polymerized, and the polymerization curing time and the irradiation amount of the active energy rays can be reduced. can.
  • the peak region of the light absorption wavelength of the photopolymerization initiator (D) is different from the peak region of the light absorption wavelength of the ultraviolet absorber (E) described later.
  • the photopolymerization initiator (D) is cleaved without any problem without being hindered by the ultraviolet absorber (E). ..
  • the curing reaction of the active energy ray-curable component (C) proceeds satisfactorily, and the above-mentioned conditions regarding the difference spectrum and the above-mentioned difference in gel fraction are easily satisfied.
  • the "peak region of the light absorption wavelength" in the present specification means a wavelength region having an absorbance of 20% or more of the maximum absorbance.
  • the active energy ray in the present embodiment has a substantial intensity of light emission in a wavelength region exceeding 365 nm.
  • the wavelength region is preferably 380 to 450 nm, more preferably 390 to 410 nm. Further, when the maximum emission intensity at 365 nm or less (usually having the maximum peak intensity near 365 nm) is 100%, at least a part of the wavelength region has an intensity of 20% or more. Is preferable.
  • the photopolymerization initiator (D) preferably has a maximum absorption wavelength of absorption at a wavelength of 200 to 500 nm in an acetonitrile solution having a concentration of 0.1% by mass of 350 nm or more, particularly preferably 370 nm or more, and further preferably 380 nm. It is preferable that the above is present. When there are a plurality of maximum absorption wavelengths having an absorbance of 200 to 500 nm, at least one maximum absorption wavelength may be in the above range.
  • the photopolymerization initiator (D) is cleaved without any problem without being hindered by the ultraviolet absorber (E) described later, and the active energy ray-curable component (C). ) Is further improved, and the obtained pressure-sensitive adhesive has a high cohesive force, which makes it easier to satisfy the above-mentioned storage elastic modulus and gel fraction.
  • the upper limit of the maximum absorption wavelength is not particularly limited, but is preferably 450 nm or less from the viewpoint of preventing the progress of the curing reaction when the pressure-sensitive adhesive layer 11 is stored in ambient light such as a fluorescent lamp. In particular, it is preferably 410 nm or less, and more preferably 405 nm or less.
  • the absorbance at a wavelength of 380 nm in an acetonitrile solution having a concentration of the photopolymerization initiator (D) of 0.1% by mass is preferably 0.3 or more, more preferably 0.5 or more, and particularly 1. It is preferably 0 or more.
  • the upper limit of the absorbance is not particularly limited, but is usually preferably 2.5 or less, and particularly preferably 2.0 or less.
  • the curing reaction of the active energy ray-curable component (C) by the photopolymerization initiator (D) proceeds due to ambient light such as a fluorescent lamp during the formation or storage of the pressure-sensitive adhesive sheet, and then the curing reaction of the active energy ray-curable component (C) proceeds. Durability during use may decrease.
  • the method for measuring the absorbance of the photopolymerization initiator (D) is as shown in a test example described later.
  • Examples of such a photopolymerization initiator (D) include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like. .. These may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator (D) in the adhesive composition P is preferably 0.1 part by mass or more as a lower limit value with respect to 100 parts by mass of the active energy ray-curable component (C). In particular, it is preferably 1 part by mass or more, and more preferably 5 parts by mass or more.
  • the upper limit is preferably 30 parts by mass or less, particularly preferably 15 parts by mass or less, and preferably 10 parts by mass or less.
  • the curability of the component (C) is further improved, and it becomes easier to satisfy the above-mentioned conditions regarding the difference spectrum and the above-mentioned difference in gel fraction.
  • the above-mentioned storage elastic modulus and gel fraction can be easily satisfied.
  • UV absorber (E) As the ultraviolet absorber (E), one in which the pressure-sensitive adhesive layer 11 can achieve ultraviolet absorption can be used, and an ultraviolet absorber (E) in which the pressure-sensitive adhesive layer 11 can satisfy the above-mentioned optical physical characteristics is used. It is preferable to do so. Further, it is preferable that the peak region of the light absorption wavelength of the ultraviolet absorber (E) is different from the peak region of the light absorption wavelength of the photopolymerization initiator (D) described above.
  • the ultraviolet absorber (E) preferably has an absorption maximum wavelength of 400 nm or less, particularly preferably 390 nm or less, and further 380 nm or less, in an acetonitrile solution having a concentration of 0.1% by mass and having an absorbance of 200 to 500 nm. It is preferable to be in. When there are a plurality of absorption maximum wavelengths having an absorbance of 200 to 500 nm, at least one absorption maximum wavelength may be in the above range.
  • the photopolymerization initiator (D) is cleaved without any problem without being hindered by the ultraviolet absorber (E), and the active energy ray-curable component (C)
  • the curability of the adhesive is further improved, and the obtained pressure-sensitive adhesive has a high cohesive force, so that the above-mentioned storage elastic modulus and gel fraction can be easily satisfied.
  • the lower limit of the absorption maximum wavelength is preferably 200 nm or more, particularly preferably 250 nm or more, and further preferably 280 nm or more from the viewpoint of protecting various members from ultraviolet rays.
  • Examples of the ultraviolet absorber (E) include compounds such as benzophenone-based, benzotriazole-based, benzoate-based, benzoxazineone-based, triazine-based, phenylsalicylate-based, cyanoacrylate-based, and nickel complex salt-based compounds. It may be used alone or in combination of two or more.
  • UV absorbers (E) it is preferable to use a benzophenone compound or a benzotriazole compound, and it is preferable to use a benzophenone compound.
  • These compounds tend to have excellent compatibility with the above-mentioned (meth) acrylic acid ester polymer (A), the active energy ray-curable component (C), and the like, and the obtained pressure-sensitive adhesive satisfies the above-mentioned optical physical characteristics. It will be easy.
  • benzophenone compound examples include 2,2-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate. , 2-Hydroxy-4-n-octyloxybenzophenone and the like are preferably mentioned.
  • benzotriazole compound examples include 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole and octyl-3- [3-t-butyl-4-hydroxy-5- (5-chloro).
  • the content of the ultraviolet absorber (E) in the adhesive composition P is preferably an amount that satisfies the following conditions. That is, when the content of the ultraviolet absorber (E) in the pressure-sensitive adhesive layer 11 is X% by mass and the thickness of the pressure-sensitive adhesive layer 11 is Y ⁇ m, the following formula (I) is satisfied. preferable. 90 ⁇ X x Y ⁇ 1000 ... (I) When the content of the ultraviolet absorber (E) is an amount satisfying the above conditions, the optical physical properties of the pressure-sensitive adhesive layer 11 described above can be more effectively satisfied.
  • the lower limit of X ⁇ Y in the above formula (I) is preferably 90 or more, more preferably 120 or more, particularly preferably 180 or more, and further preferably 230 or more. It is preferable to have. Further, the upper limit of X ⁇ Y in the above formula (I) is preferably 1000 or less, more preferably 600 or less, particularly preferably 400 or less, and further preferably 300 or less. preferable.
  • the lower limit of the content of the ultraviolet absorber (E) in the adhesive composition P is preferably 0.01 part by mass or more with respect to 100 parts by mass of the active energy ray-curable component (C), and is 0. It is more preferably 10 parts by mass or more, particularly preferably 0.50 parts by mass or more, and preferably 1.0 part by mass or more.
  • the upper limit of the content of the ultraviolet absorber (E) is preferably 30 parts by mass or less and 20 parts by mass or less with respect to 100 parts by mass of the active energy ray-curable component (C).
  • the ultraviolet absorber (E) is more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and most preferably 2 parts by mass or less.
  • the upper limit of the content of the ultraviolet absorber (E) is in the above range, it becomes easy to satisfy the above-mentioned conditions regarding the difference spectrum, and it becomes easy to achieve both light resistance and blister resistance at a high level.
  • the above-mentioned storage elastic modulus and gel fraction can be easily satisfied.
  • the tacky composition P contains various additives usually used for acrylic pressure-sensitive adhesives, such as silane coupling agents, antistatic agents, tackifiers, and antioxidants, if desired. , Light stabilizers, softeners, fillers, refractive index adjusters and the like can be added. The polymerization solvent and the dilution solvent described later are not included in the additives constituting the adhesive composition P.
  • the adhesive composition P contains a silane coupling agent
  • the obtained adhesive has improved adhesion to a glass member or a plastic plate.
  • the obtained pressure-sensitive adhesive becomes more excellent in blister resistance.
  • the silane coupling agent is an organosilicon compound having at least one alkoxysilyl group in the molecule, which has good compatibility with the (meth) acrylic acid ester polymer (A) and has light transmittance. preferable.
  • silane coupling agent examples include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacrypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 2-(. 3,4-Epoxycyclohexyl) Silicon compounds having an epoxy structure such as ethyltrimethoxysilane, mercapto group-containing silicon compounds such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane.
  • polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacrypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 2-(. 3,4-Epoxycyclohexyl) Silicon compounds
  • Amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-Chloropropyltrimethoxysilane, 3-isocyanuspropyltriethoxysilane, or at least one of these, and alkyl group-containing silicon compounds such as methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, and ethyltrimethoxysilane. Examples thereof include a condensate of. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content thereof is preferably 0.01 part by mass or more with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A). In particular, it is preferably 0.05 parts by mass or more, and further preferably 0.1 parts by mass or more.
  • the content is preferably 2 parts by mass or less, particularly preferably 1 part by mass or less, and further preferably 0.5 parts by mass or less.
  • the adhesive composition P produced a (meth) acrylic acid ester polymer (A) and crosslinked with the obtained (meth) acrylic acid ester polymer (A). It can be produced by mixing an agent (B), an active energy ray-curable component (C), an ultraviolet absorber (E), a photopolymerization initiator (D), and an additive, if desired. ..
  • the (meth) acrylic acid ester polymer (A) can be produced by polymerizing a mixture of monomers constituting the polymer by an ordinary radical polymerization method.
  • the polymerization of the (meth) acrylic acid ester polymer (A) is preferably carried out by a solution polymerization method using a polymerization initiator, if desired.
  • the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone and the like, and two or more kinds may be used in combination.
  • Examples of the polymerization initiator include azo compounds and organic peroxides, and two or more types may be used in combination.
  • Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane1-carbonitrile), and 2, , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2- (2-imidazolin-2-yl)) Propane] and the like.
  • organic peroxide examples include benzoyl peroxide, t-butylperbenzoate, cumenehydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, and di (2-ethoxyethyl) peroxy.
  • examples thereof include dicarbonate, t-butylperoxyneodecanoate, t-butylperoxyvivarate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.
  • the weight average molecular weight of the obtained polymer can be adjusted by adding a chain transfer agent such as 2-mercaptoethanol.
  • a cross-linking agent (B), an active energy ray-curable component (C), and an ultraviolet absorber are added to the solution of the (meth) acrylic acid ester polymer (A).
  • a photopolymerization initiator (D), an additive, and a diluting solvent can be added and mixed thoroughly to obtain a solvent-diluted adhesive composition P (coating solution).
  • a solvent-diluted adhesive composition P coating solution
  • diluting solvent examples include aliphatic hydrocarbons such as hexane, heptane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol and butanol.
  • Alcohols such as 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolve solvents such as ethyl cellosolve are used.
  • the concentration and viscosity of the coating solution prepared in this manner may be any range as long as it can be coated, and is not particularly limited and can be appropriately selected depending on the situation.
  • the adhesive composition P is diluted so as to have a concentration of 10 to 60% by mass. It should be noted that the addition of a diluting solvent or the like is not a necessary condition when obtaining the coating solution, and the diluting solvent may not be added as long as the adhesive composition P has a coatable viscosity or the like. In this case, the adhesive composition P becomes a coating solution using the polymerization solvent of the (meth) acrylic acid ester polymer (A) as it is as a diluting solvent.
  • the thickness of the pressure-sensitive adhesive layer 11 in the pressure-sensitive adhesive sheet 1 according to the present embodiment is preferably 20 ⁇ m or more, more preferably 50 ⁇ m or more, and particularly 100 ⁇ m or more. It is preferably 150 ⁇ m or more, and most preferably 180 ⁇ m or more.
  • the thickness of the pressure-sensitive adhesive layer 11 is preferably 1000 ⁇ m or less, more preferably 800 ⁇ m or less, particularly preferably 500 ⁇ m or less, further preferably 400 ⁇ m or less, and more preferably 300 ⁇ m or less. Most preferably. When the thickness of the pressure-sensitive adhesive layer 11 is within the above range, it becomes easy to exert a desired adhesive force and also easily exerts excellent blister resistance.
  • peeling sheets 12a and 12b protect the pressure-sensitive adhesive layer 11 until the time when the pressure-sensitive adhesive sheet 1 is used, and are peeled off when the pressure-sensitive adhesive sheet 1 (the pressure-sensitive adhesive layer 11) is used.
  • the release sheets 12a and 12b are not always necessary.
  • release sheets 12a and 12b examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, and polybutylene. Telephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluorine A resin film or the like is used. In addition, these crosslinked films are also used. Further, these laminated films may be used.
  • the peeling surfaces (particularly the surfaces in contact with the pressure-sensitive adhesive layer 11) of the peeling sheets 12a and 12b are subjected to a peeling treatment.
  • the release agent used in the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents.
  • the release sheets 12a and 12b it is preferable that one release sheet is a heavy release type release sheet having a large release force and the other release sheet is a light release type release sheet having a small release force.
  • the thickness of the release sheets 12a and 12b is not particularly limited, but is usually about 20 to 150 ⁇ m.
  • the coating solution of the adhesive composition P is applied to the peeling surface of one of the release sheets 12a (or 12b) and heat-treated to perform the adhesive composition. After P is thermally crosslinked to form a coating layer, the peeling surface of the other release sheet 12b (or 12a) is superposed on the coating layer. When the curing period is required, the curing period is set, and when the curing period is not required, the coating layer becomes the adhesive layer 11 as it is. As a result, the adhesive sheet 1 is obtained.
  • the heating temperature of the above heat treatment is preferably 50 to 150 ° C, particularly preferably 70 to 120 ° C.
  • the heating time is preferably 10 seconds to 10 minutes, and particularly preferably 50 seconds to 2 minutes.
  • the heat treatment can also be used as a drying treatment for volatilizing the diluting solvent or the like from the coating film of the adhesive composition P applied to the desired object.
  • a curing period of about 1 to 2 weeks may be provided at room temperature (for example, 23 ° C., 50% RH).
  • room temperature for example, 23 ° C., 50% RH.
  • the coating solution of the pressure-sensitive adhesive composition P is applied to the peel-off surface of one of the release sheets 12a, and heat treatment is performed to thermally crosslink the pressure-sensitive adhesive composition P and apply the pressure-sensitive adhesive composition P.
  • a layer is formed to obtain a release sheet 12a with a coating layer.
  • the coating solution of the adhesive composition P is applied to the peeling surface of the other release sheet 12b, heat treatment is performed to thermally crosslink the adhesive composition P to form a coating layer, and the coating layer is attached.
  • the release sheet 12b of Then, the release sheet 12a with the coating layer and the release sheet 12b with the coating layer are bonded so that both coating layers are in contact with each other.
  • the curing period is required, the curing period is set, and when the curing period is not required, the laminated coating layer becomes the pressure-sensitive adhesive layer 11. As a result, the adhesive sheet 1 is obtained. According to this production example, stable production is possible even when the pressure-sensitive adhesive layer 11 is thick.
  • a method for applying the coating solution of the adhesive composition P for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method and the like can be used.
  • the component 2 As shown in FIG. 2, the component 2 according to the present embodiment is located between the first component 21 (one component) and the second component 22 (other components).
  • the cured adhesive layer 11' that attaches the first constituent member 21 and the second constituent member 22 to each other is provided.
  • the cured pressure-sensitive adhesive layer 11' is a product obtained by curing the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1 described above by irradiation with active energy rays.
  • the post-curing pressure-sensitive adhesive layer 11' means that the pressure-sensitive adhesive layer 11 is completely cured, and in particular, when the post-curing pressure-sensitive adhesive layer 11'is further irradiated with active energy rays.
  • the gel fraction of the adhesive layer 11'after curing has an increase rate of 10% or less, and in particular, an increase rate of 5% or less.
  • the pressure-sensitive adhesive constituting the cured pressure-sensitive adhesive layer 11' has a cross-linked structure composed of a (meth) acrylic acid ester polymer (A) and a cross-linking agent (B), and has an energy ray-curable component (C).
  • a photopolymerization initiator (D) and an additive are further contained.
  • the polymerized energy ray-curable component (C) is entangled with the crosslinked structure composed of the (meth) acrylic acid ester polymer (A) and the thermal crosslinking agent (B) to form a higher-order structure. It is presumed that there is.
  • the adhesive layer 11'after curing is formed by curing the adhesive layer 11 of the adhesive sheet 1 described above, excellent blister resistance can be exhibited. Therefore, in the structure 2 according to the present embodiment, it is preferable that the surface of at least one of the first component 21 and the second component 22 that comes into contact with the cured pressure-sensitive adhesive layer 11'is made of a resin material. be. That is, even when outgas is generated from such a resin material, the post-curing pressure-sensitive adhesive layer 11'in the present embodiment can exhibit excellent blister resistance.
  • At least one of the first constituent member 21 and the second constituent member 22 may be a resin plate.
  • the resin plate is not particularly limited, and examples thereof include a polycarbonate resin plate, an acrylic resin plate, a PET resin plate, a polystyrene resin plate, a polypropylene resin plate, and a hybrid resin plate thereof.
  • at least one of the first constituent member 21 and the second constituent member 22 may be a glass plate.
  • the glass plate is not particularly limited, and for example, chemically strengthened glass, non-alkali glass, quartz glass, soda lime glass, barium / strontium-containing glass, aluminosilicate glass, lead glass, borosilicate glass, barium borosilicate. Examples include glass.
  • at least one of the first constituent member 21 and the second constituent member 22 may be a laminated body including a resin plate, a glass plate, and the like.
  • the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1 described above is made of a pressure-sensitive adhesive having an ultraviolet-absorbing property, and the cured pressure-sensitive adhesive layer 11'of the component 2 also has a UV-absorbing property. It is possible to exhibit excellent light resistance (particularly, member protection which is a performance of protecting the members constituting the component 2 from ultraviolet rays). Therefore, it is preferable that the configuration 2 according to the present embodiment is one that may be irradiated with ultraviolet rays for a long period of time, and above all, a display body that is attached to the exterior of the moving body is preferable. ..
  • the moving body is a concept including a vehicle moving on the ground, a flying body flying in the air, a ship moving on the water, and the like, and these movements are not limited to either outdoors or indoors.
  • the structure 2 according to the present embodiment is particularly preferably a display body attached to the exterior of an outdoor mobile body.
  • the configuration body 2 according to the present embodiment is preferably a display body attached to the exterior of the vehicle or a flying object, and more preferably a display body attached to the exterior of the vehicle.
  • An electronic license plate is preferable.
  • the component 2 according to the present embodiment is the display body described above, it is preferable that the first component 21 is a cover material and the second component 22 is a display device.
  • the first constituent member 21 When the first constituent member 21 is a cover material, the first constituent member 21 may be a resin plate, a glass plate, or a laminate of a resin plate and a glass plate as described above.
  • the thickness of the first constituent member 21 is preferably 0.3 mm or more, particularly preferably 0.5 mm or more, and further 1.0 mm. The above is preferable. The thickness is preferably 30 mm or less, particularly preferably 20 mm or less, and further preferably 10 mm or less.
  • the second component 22 is a display body
  • the display body examples include a liquid crystal (LCD) panel, a light emitting diode (LED) panel, an organic electroluminescence (organic EL) panel, and the like.
  • Examples of the method for manufacturing the structure 2 include a bonding step in which the first component 21 and the second component 22 are bonded to each other by the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1 described above.
  • the adhesive layer 11 after the bonding is irradiated with active energy rays through at least one of the first component 21 and the second component 22, and the adhesive layer 11 is cured to cure the adhesive layer after curing.
  • Examples thereof include a method including an irradiation step of obtaining 11'.
  • one of the release sheets 12a of the pressure-sensitive adhesive sheet 1 is peeled off, and the exposed pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1 is bonded to one side of the first constituent member 21.
  • the other release sheet 12b is peeled from the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1, and the exposed pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1 and the second constituent member 22 are bonded together to obtain a laminate.
  • the bonding order of the first constituent member 21 and the second constituent member 22 may be changed.
  • the active energy ray irradiated in the above irradiation step means an electromagnetic wave or a charged particle beam having an energy quantum, and specific examples thereof include ultraviolet rays and electron beams.
  • ultraviolet rays which are easy to handle, are particularly preferable.
  • the amount of ultraviolet light is preferably 500 mJ / cm 2 or more, particularly preferably 1000 mJ / cm 2 or more, and further preferably 2000 mJ / cm 2 or more. Since the cured pressure-sensitive adhesive layer 11'in the structure 2 according to the present embodiment is obtained by curing the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1 described above, even a light amount of about 500 mJ / cm 2 is sufficient. After curing, the adhesive layer 11'can be obtained.
  • the upper limit of the amount of the ultraviolet, in terms of not too excessively irradiated with ultraviolet rays is preferably 10000 mJ / cm 2 or less, particularly preferably 8000 mJ / cm 2 or less, still more preferably not more than 5000 mJ / cm 2, 3000 mJ It is preferably / cm 2 or less.
  • the illuminance of ultraviolet rays can be, for example, about 50 to 1000 mW / cm 2. Further, the irradiation of ultraviolet rays can be carried out by using a high-pressure mercury lamp, a fusion H lamp, a xenon lamp or the like.
  • the irradiation amount of the electron beam is preferably about 10 to 1000 grad.
  • either one of the release sheets 12a and 12b in the adhesive sheet 1 may be omitted.
  • Example 1 1. Preparation of (meth) acrylic acid ester polymer (A) 30 parts by mass of 2-ethylhexyl acrylate, 25 parts by mass of n-butyl acrylate, 5 parts by mass of 4-acryloyl morpholine, 15 parts by mass of isobornyl acrylate, and 2 parts by mass of acrylic acid. -Hydroxyethyl 25 parts by mass was copolymerized by a solution polymerization method to prepare a (meth) acrylic acid ester polymer (A). When the molecular weight of this (meth) acrylic acid ester polymer (A) was measured by the method described later, it was found to have a weight average molecular weight (Mw) of 600,000.
  • Adhesive Composition 100 parts by mass (solid content conversion value; the same applies hereinafter) of the (meth) acrylic acid ester polymer (A) obtained in the above step 1 and trimethylolpropane-modified bird as a cross-linking agent (B). 0.2 parts by mass of range isocyanate, 8.0 parts by mass of ⁇ -caprolactone-modified tris- (2-acryloxyethyl) isocyanurate as an active energy ray-curable component (C), and as a photopolymerization initiator (D).
  • 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide 0.8 parts by mass and a benzophenone-based ultraviolet absorber as an ultraviolet absorber (E) (manufactured by CYTEC INDUSTRIES, "Siasorb UV-24”).
  • the adhesive composition is prepared by mixing 1.3 parts by mass and 0.2 parts by mass of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent, stirring well, and diluting with methyl ethyl ketone. A coating solution was obtained.
  • Adhesive Sheet A heavy release type release sheet (manufactured by Lintec Corporation, product name "SP-PET752150”) in which one side of a polyethylene terephthalate film is peeled off with a silicone-based release agent from the coating solution of the adhesive composition obtained in step 2 above. A coating layer (thickness: 200 ⁇ m) was formed on the peeled surface to be coated with a knife coater and then heat-treated at 90 ° C. for 1 minute.
  • a light release type release sheet (manufactured by Lintec Corporation, product name "SP-PET381130") in which the surface on the coating layer side of the obtained heavy release type release sheet with a coating layer and one side of the polyethylene terephthalate film are peeled with a silicone-based release agent. ”) Peeling treatment Surface bonding and curing under the conditions of 23 ° C. and 50% RH for 7 days to form a heavy peeling type peeling sheet / adhesive layer (thickness: 200 ⁇ m) / light peeling type peeling sheet. An adhesive sheet made of was prepared.
  • the thickness of the adhesive layer is a value measured using a constant pressure thickness measuring device (manufactured by Teclock Co., Ltd., product name "PG-02") in accordance with JIS K7130.
  • the above-mentioned weight average molecular weight (Mw) is a polystyrene-equivalent weight average molecular weight measured under the following conditions (GPC measurement) using gel permeation chromatography (GPC).
  • GPC measurement gel permeation chromatography
  • -GPC measuring device HLC-8320 manufactured by Tosoh Corporation -GPC column (passed in the following order): TSK gel superH-H manufactured by Tosoh Corporation TSK gel superHM-H TSK gel superH2000 -Measurement solvent: tetrahydrofuran-Measurement temperature: 40 ° C
  • Examples 2 to 8, Comparative Examples 1 to 5 Composition of each monomer constituting the (meth) acrylic acid ester polymer (A), weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A), type and blending amount of the cross-linking agent (B), activity.
  • Table 1 shows the type and amount of the energy ray-curable component (C), the type and amount of the photopolymerization initiator (D), the amount of the ultraviolet absorber (E), and the amount of the silane coupling agent.
  • An adhesive sheet was produced in the same manner as in Example 1 except that the adhesive sheet was changed to.
  • the surface (irradiation surface) of the cured pressure-sensitive adhesive layer irradiated with ultraviolet rays and the surface opposite to the irradiated surface.
  • a total internal reflection measurement method using diamond, measurement range: 400
  • a Fourier transform infrared spectrophotometer manufactured by PerkinElmer, product name "Spectrum One"
  • the infrared absorption spectrum was measured by ⁇ 4000 cm -1).
  • the difference spectrum was obtained by subtracting the infrared absorption spectrum for the non-irradiated surface from the infrared absorption spectrum for the irradiated surface. Furthermore, for the difference spectrum, the maximum value of the absolute value of the absorbance in the wave number range of 700 to 1000 cm -1 was specified. The maximum value is shown in Table 2 as the maximum value regarding the difference spectrum for the light intensity “2000 mJ / cm 2”.
  • the maximum value was specified for the pressure-sensitive adhesive layer which was not irradiated with ultraviolet rays and was not cured by irradiation with ultraviolet rays, as described above.
  • the maximum value is shown in Table 1 as the maximum value for the difference spectrum for "unirradiated”.
  • the maximum values of the pressure-sensitive adhesive layers in which the amount of light under the ultraviolet irradiation conditions was changed to 200 mJ / cm 2 and 1000 mJ / cm 2 were specified in the same manner as described above. These maximum values are shown in Table 2 as the maximum value related to the difference spectra for each "200 mJ / cm 2" and "1000 mJ / cm 2".
  • the adhesive wrapped in the polyester mesh was immersed in ethyl acetate at room temperature (23 ° C.) for 24 hours. Then, the adhesive was taken out, air-dried for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and further dried in an oven at 80 ° C. for 12 hours. After drying, the mass was weighed with a precision balance, and the mass of the adhesive alone was calculated by subtracting the mass of the mesh alone. The mass at this time is M2.
  • the gel fraction (%) is represented by (M2 / M1) ⁇ 100. As a result, the gel fraction of the pressure-sensitive adhesive was derived. The results are shown in Table 2 as the "unirradiated" gel fraction.
  • UV illuminance / photometer uses "UVPF-A1" manufactured by iGraphics.
  • the gel fraction (%) was derived in the same manner as described above.
  • the results are shown in Table 2 as a gel fraction of "2000 mJ / cm 2".
  • the heavy-release type release sheet was peeled off from the above-mentioned laminated body after cutting, and the exposed adhesive layer was attached to soda lime glass (manufactured by Nippon Sheet Glass Co., Ltd.).
  • a sample for measurement was obtained by pressurizing with an autoclave manufactured by Kurihara Seisakusho Co., Ltd. at 0.5 MPa and 50 ° C. for 20 minutes.
  • the measurement sample was left to stand for 24 hours under the conditions of 23 ° C. and 50% RH, and then adhered using a tensile tester (Tencilon manufactured by Orientec Co., Ltd.) under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 degrees.
  • the force (N / 25 mm) was measured.
  • Conditions other than those described here were measured in accordance with JIS Z0237: 2009. The results are shown in Table 2 as "unirradiated" adhesive strength.
  • the pressure-sensitive adhesive layer of the measurement sample prepared in the same manner as described above was cured by irradiating the PET film with ultraviolet rays under the following conditions.
  • the adhesive strength (N / 25 mm) of the cured sample was also measured in the same manner as described above. The results are shown in Table 2 as the adhesive strength of "2000 mJ / cm 2".
  • ⁇ Ultraviolet irradiation conditions> ⁇ Uses high-pressure mercury lamp ⁇ Illuminance 200mW / cm 2 , light intensity 2000mJ / cm 2 ⁇ UV illuminance / photometer uses "UVPF-A1" manufactured by iGraphics.
  • the pressure-sensitive adhesive layer was irradiated with ultraviolet rays through the plastic plate under the following conditions to cure the pressure-sensitive adhesive layer to obtain a cured pressure-sensitive adhesive layer.
  • the obtained laminate of the non-alkali glass plate / cured adhesive layer / plastic plate was used as a measurement sample.
  • a test of storing for 72 hours and a test of irradiating a light beam having a wavelength of 300 to 400 nm at an illuminance of 60 W / m 2 for 500 hours using a xenon weatherometer (XeWOM) were carried out.
  • the pressure-sensitive adhesive layer was irradiated with ultraviolet rays under the following conditions through the non-alkali glass plate to cure the pressure-sensitive adhesive layer to obtain a cured pressure-sensitive adhesive layer.
  • the obtained laminate of the hard coat layer / base material layer / adhesive layer / cured adhesive layer / non-alkali glass plate was used as a sample for light resistance evaluation.
  • ⁇ Ultraviolet irradiation conditions> ⁇ Uses high-pressure mercury lamp ⁇ Illuminance 200mW / cm 2 , light intensity 2000mJ / cm 2 ⁇ UV illuminance / photometer uses "UVPF-A1" manufactured by iGraphics.
  • the light resistance evaluation sample was irradiated with a light beam having a wavelength of 300 to 400 nm from the non-alkali glass plate side at an illuminance of 60 W / m 2 for 500 hours using a xenon weather ometer (XeWOM).
  • XeWOM xenon weather ometer
  • Table 1 shows each formulation (solid content conversion value) of the adhesive composition when the (meth) acrylic acid ester polymer (A) is 100 parts by mass (solid content conversion value). Details of the abbreviations and the like shown in Table 1 are as follows. [(Meta) acrylic acid ester polymer (A)] 2EHA: 2-ethylhexyl acrylate BA: n-butyl acrylate ACMO: 4-acryloyl morpholine IBXA: isobornyl acrylate HEA: 2-hydroxyethyl acrylate AA: acrylic acid [crosslinking agent (B)] B1: Trimethylolpropane-modified tolylene diisocyanate B2: Trimethylolpropane-modified xylylene diisocyanate B3: 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane [active energy ray-curable component (C)] C1: ⁇ -caprolactone-modified tris
  • the cured pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive sheet obtained in the examples was excellent in both blister resistance and light resistance.
  • the adhesive sheet of the present invention can be suitably used for manufacturing electronic license plates.
  • Adhesive sheet 11 Adhesive sheet 11 . Adhesive layer 12a, 12b ... Release sheet 2 . Component 11'... Adhesive layer after curing 21 ... First component 22 ... Second component

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  • Chemical Kinetics & Catalysis (AREA)
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  • Mechanical Engineering (AREA)
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  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
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