CN109423228A - The manufacturing method of adhesive sheet, display body and display body - Google Patents

The manufacturing method of adhesive sheet, display body and display body Download PDF

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Publication number
CN109423228A
CN109423228A CN201810868558.XA CN201810868558A CN109423228A CN 109423228 A CN109423228 A CN 109423228A CN 201810868558 A CN201810868558 A CN 201810868558A CN 109423228 A CN109423228 A CN 109423228A
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CN
China
Prior art keywords
display body
agent layer
adhering agent
methyl
formation
Prior art date
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Pending
Application number
CN201810868558.XA
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Chinese (zh)
Inventor
小鲭翔
高桥洋
高桥洋一
渡边旭平
荒井隆行
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Lintec Corp
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Lintec Corp
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Publication date
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Publication of CN109423228A publication Critical patent/CN109423228A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Abstract

Project of the invention is the manufacturing method for providing a kind of xanthochromia for being able to suppress adhering agent layer, and having the adhesive sheet of excellent resistance to foaming, display body and display body simultaneously.The present invention provides a kind of adhesive sheet (1), it has the adhering agent layer (11) for being bonded a display body member of formation (21) Yu another display body member of formation (22), the ultraviolet-shielding type component that the light transmittance that at least one of one display body member of formation (21) and another display body member of formation (22) are wavelength 340nm is 5% or less and the light transmittance of wavelength 390nm is 10% or more, the Photoepolymerizationinitiater initiater that adhering agent layer (11) is 0.3 or more by the absorbance containing the wavelength 390nm in the acetonitrile solution of 0.1 mass % of concentration, the sticker of active energy ray-curable is constituted.

Description

The manufacturing method of adhesive sheet, display body and display body
Technical field
The present invention relates to a kind of adhesive sheet for being suitable for display body (display), use display body obtained from the adhesive sheet And the manufacturing method of display body.
Background technique
In recent years, the case where automobile carrying auto-navigation system, gradually increases.In the display body (display of auto-navigation system Device) in, the surface side of display module is provided with protection panels.Usual protection panels are via adhering agent layer thus and display body The bonding such as module.
It is main mostly using plastic plate from the angle of safety as the protection panels of auto-navigation system, and Without using glass plate.However, plastic plate is different from glass plate, generated under the conditions of high temperature and humidity (damp and hot) degassing (outgas) or Through vapor.The blistering for generating bubble between plastic plate and adhering agent layer sometimes as a result, floating, peel off etc..Therefore, It is required that above-mentioned adhering agent layer has resistance to foaming.
As the adhesive sheet of touch panel, patent document 1 discloses a kind of ultraviolet-crosslinkable adhesive sheet comprising monomer (methyl) acrylic copolymer, the monomer include with ultraviolet-crosslinkable position (benzophenone structural) (methyl) third Olefin(e) acid ester, and define the storage modulus before and after ultraviolet-crosslinkable.The ultraviolet-crosslinkable adhesive sheet is bonded with adherend Afterwards, ultraviolet light irradiation is carried out, carries out cross-linking reaction thus to improve cohesiveness.By improving the solidifying of sticker in the above described manner Poly- power has a possibility that capable of assigning resistance to foaming.
However, when being auto-navigation system used in car inside, since the case where being exposed under ultraviolet light, is more, Therefore ultraviolet light easily propagates through protection panels and reaches adhering agent layer.When constituting adhering agent layer by common sticker, because of irradiation Ultraviolet light and there is a situation where xanthochromia is more, at this point, the appearance of display and visual reducing.
As used in optical association product, using yellowing resistance as the sticker of project, patent document 2 discloses one Kind sticker.The sticker is obtained by the ultraviolet hardening sticker contained the following substances with resin combination: making polyalcohol (a), carbamate (first obtained from polyisocyanate (b) and (methyl) acyclic compound (c) with hydroxyl react Base) acrylate (A)；(methyl) acrylic monomers (B)；And Photoepolymerizationinitiater initiater (C)；And further with mass ratio 95/5~5/95 range and the light stabilizer (D) that contains and antioxidant (E).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2011-184582 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2014-015573 bulletin
Summary of the invention
The technical problem to be solved in the present invention
In order to inhibit the xanthochromia of adhering agent layer, it is contemplated that not by improving the yellowing resistance of sticker itself, but with purple The mode that outside line does not reach adhering agent layer makes protection panels have the function of ultraviolet light (UV) barrier property.
But the ultraviolet-crosslinkable adhesive sheet of such as patent document 1 is used in UV barrier property protection panels, and penetrating should When protection panels irradiate ultraviolet light to adhering agent layer, ultraviolet light is obstructed that adhering agent layer will not be reached by protection panels, causes The ultra-violet solidified insufficient solidification of sticker.Such not sufficiently cured adhering agent layer of sticker is easy to produce blistering.
The present invention carried out in view of above-mentioned actual conditions, and its purpose is to provide a kind of adhering agent layers that is able to suppress Xanthochromia, while there is the manufacturing method of the adhesive sheet of excellent resistance to foaming, display body and display body.
Solve the technological means of technical problem
To achieve the goals above, first, the present invention provides a kind of adhesive sheet, has for being bonded a display body structure At the adhering agent layer of component and another display body member of formation, which is characterized in that one display body member of formation and institute Stating the light transmittance that at least one of another display body member of formation is wavelength 340nm is the saturating of 5% or less and wavelength 390nm The ultraviolet-shielding type component that light rate is 10% or more, the adhering agent layer is by containing the acetonitrile solution in 0.1 mass % of concentration In wavelength 390nm absorbance be 0.3 or more Photoepolymerizationinitiater initiater active energy ray-curable sticker constitute (invention 1).
In foregoing invention (invention 1), adhering agent layer is made of the sticker containing above-mentioned Photoepolymerizationinitiater initiater.As a result, Even if irradiating active energy beam to the adhering agent layer through ultraviolet-shielding type component, sufficiently solidify due to the adhering agent layer and For adhering agent layer after the solidification with required coherency, thus after the solidification adhering agent layer resistance to foaming it is excellent.Further, since It is easy adhering agent layer after making to solidify the ultraviolet light of xanthochromia occurs to be shielded by ultraviolet-shielding type component, therefore after being able to suppress solidification The xanthochromia of adhering agent layer.
In foregoing invention (invention 1), the preferably described sticker is sticker below: by containing (methyl) acrylate The adherence group of polymer (A), crosslinking agent (B), active energy ray-curable ingredient (C) and the Photoepolymerizationinitiater initiater (D) It closes obtained from object and containing described (methyl) acrylate polymer (A) each other via made of the crosslinking agent (B) crosslinking Cross-linked structure, the unreacted active energy ray-curable ingredient (C) and the Photoepolymerizationinitiater initiater (D), active energy Measure the sticker (invention 2) of ray-curable.
In foregoing invention (invention 1,2), preferably described (methyl) acrylate polymer (A) contains 5 mass % or more The 60 mass % monomer with hydroxyl in the molecule below is as the monomer (invention 3) for constituting the polymer.
In foregoing invention (invention 1~3), preferably with respect to 100 mass of (methyl) acrylate polymer (A) Part, the content of the crosslinking agent (B) in the adherence composition is 0.01 mass parts or more 3 below the mass (invention 4).
In foregoing invention (invention 1~4), the gel fraction of the sticker of the preferably described active energy ray-curable is 30% or more 70% or less (invention 5).
In foregoing invention (invention 1~5), the preferably described ultraviolet-shielding type component is plastic plate (invention 6).
In foregoing invention (invention 1~6), it is preferably provided with 2 stripping films and with the release surface with 2 stripping films The adhering agent layer (invention 7) that the mode of contact is clamped by the stripping film.
Second, the present invention provides a kind of display body, has a display body member of formation, another display body constitutes structure Sticker after part and the solidification that one display body member of formation and another described display body member of formation mutually fit Layer, which is characterized in that at least one of one display body member of formation and another display body member of formation by The ultraviolet-shielding type component structure that the light transmittance of wavelength 340nm is 5% or less and the light transmittance of wavelength 390nm is 10% or more At adhering agent layer is to make the adhering agent layer of the adhesive sheet (invention 1~7) carry out active energy beam to consolidate after the solidification Adhering agent layer (invention 8) after solidifying made of change.
In foregoing invention (invention 8), the gel fraction for preferably comprising the sticker of adhering agent layer after the solidification is 40% or more 95% or less (invention 9).
Third, the present invention provide a kind of manufacturing method of display body, which is characterized in that at least one is the purple by production A display body member of formation and another display body member of formation for outside line shielding component is via the adhesive sheet (invention 1 ~7) laminated body made of adhering agent layer fitting, and through the ultraviolet-shielding type component to the described viscous of the laminated body Oxidant layer irradiate active energy beam, make adhering agent layer solidification to become adhering agent layer (invention 10) after solidification.
Invention effect
Adhesive sheet and display body of the invention is able to suppress the xanthochromia of adhering agent layer, while having excellent resistance to foaming. In addition, the manufacturing method of display body according to the present invention, can manufacture the xanthochromia for being able to suppress adhering agent layer, while resistance to foaming is excellent Different display body.
Detailed description of the invention
Fig. 1 is the sectional view of the adhesive sheet of an embodiment of the invention.
Fig. 2 is the sectional view of the display body of an embodiment of the invention.
Description of symbols
1: adhesive sheet；11: adhering agent layer；12a, 12b: stripping film；2: display body；11 ': adhering agent layer after solidification；21: the One display body member of formation (ultraviolet-shielding type component)；22: the second display body member of formation；3: printing layer.
Specific embodiment
Hereinafter, embodiments of the present invention will be described.
[adhesive sheet]
The adhesive sheet of present embodiment, which has, constitutes structure for being bonded a display body member of formation and another display body The adhering agent layer of part.At least one of said one display body member of formation and another display body member of formation are wavelength The ultraviolet-shielding type component that the light transmittance of 340nm is 5% or less and the light transmittance of wavelength 390nm is 10% or more.About aobvious Show body and display body member of formation, is illustrated below.It is preferred that passing through the single side that stripping film is layered in the adhering agent layer Or the two-sided upper adhesive sheet into present embodiment.
Specific composition as the adhesive sheet of present embodiment example is shown in Fig. 1.
As shown in Figure 1, the adhesive sheet 1 of an embodiment is made of 2 stripping films 12a, 12b and adhering agent layer 11, In, adhering agent layer 11 is in a manner of with the removing face contact of above-mentioned 2 stripping films 12a, 12b by 2 stripping film 12a, 12b folders It holds.In addition, the release surface of the stripping film in this specification refers to the face with fissility in stripping film, comprising being implemented with removing It the face of processing and lift-off processing is not carried out also shows any one of face of fissility.
1. each component
1-1. adhering agent layer
Above-mentioned adhering agent layer 11 is by the absorbance containing wavelength 390nm in the acetonitrile solution of 0.1 mass % of concentration The sticker of the active energy ray-curable of 0.3 or more Photoepolymerizationinitiater initiater is constituted.
Additionally, it is preferred that the active energy beam of present embodiment has essence in wavelength region of the wavelength greater than 365nm Property intensity shine.As the wavelength region, preferably 380~450nm, more preferably 390~410nm.In addition, by 365nm When maximum emission intensity (usually having maximum peak intensity near 365nm) below is set as 100%, preferably in above-mentioned wavelength zone At least part in domain has the active energy beam of 20% or more intensity.
Using present embodiment adhesive sheet 1 when, using the adhering agent layer 11 of adhesive sheet 1 by a display body member of formation After being bonded with another display body member of formation, through a display body member of formation or another display body member of formation, excellent Choosing penetrate the ultraviolet-shielding type component, to adhering agent layer 11 irradiate active energy beam, make adhering agent layer 11 solidification to As adhering agent layer after solidification (being adhering agent layer 11 ' after solidification in aftermentioned Fig. 2).
In addition, referring to " after solidification " for adhering agent layer is glued based on what active energy beam irradiated after the solidification of present embodiment The gel fraction of agent rising less than 5 percentage points state.
Here, by previous Photoepolymerizationinitiater initiater, for example 1- hydroxycyclohexylphenylketone is used for sticker when, transmission is ultraviolet When line shielding component irradiates active energy beam to adhering agent layer, the light transmittance of the wavelength 340nm of ultraviolet-shielding type component It is 5% or less.Therefore, for keeping the active energy beam of the wavelength (near 340nm) of above-mentioned Photoepolymerizationinitiater initiater cracking purple The shielding of outside line shielding component, causes the cracking of Photoepolymerizationinitiater initiater to be hindered.As a result, active energy ray-curable at Divide and do not carry out curing reaction well, the solidification of adhering agent layer is insufficient.As if it does, if resistance to foaming reduce, and showing Body member of formation with solidify after adhering agent layer interface on the blistering that is easy to produce bubble, floats, peel off etc..
In this regard, the adhering agent layer 11 of the adhesive sheet 1 of present embodiment contains in the acetonitrile solution of 0.1 mass % of concentration The Photoepolymerizationinitiater initiater that the absorbance of wavelength 390nm is 0.3 or more.Even if at this point, through above-mentioned ultraviolet-shielding type component pair Adhering agent layer 11 irradiates active energy beam, since the light transmittance of the wavelength 390nm of ultraviolet-shielding type component is 10% or more, The active energy beam for being accordingly used in the wavelength (near 390nm) for cracking Photoepolymerizationinitiater initiater will not be by ultraviolet-shielding type Component shielding, Photoepolymerizationinitiater initiater without problem crack.As a result, the sticker of active energy ray-curable is good Ground carries out curing reaction, and adhering agent layer 11 sufficiently solidifies, and the cohesiveness of adhering agent layer gets a promotion after obtained solidification.By This, even if will be provided with display body member of formation (ultraviolet-shielding type component), another display body member of formation and incite somebody to action The laminated body of adhering agent layer, particularly by a display body member of formation (ultraviolet-shielding type structure after the solidification that they are bonded Part) it is the laminated body for generating degassing or the plastic plate through vapor under the condition of high temperature and high humidity, in stringent high temperature and humidity item Under part, such as 85 DEG C, placed under the conditions of 85%RH 1000 it is small in the case of, be also able to suppress in display member of formation and solid The blistering for generating bubble on the interface of adhering agent layer after change, floating, peel off etc..
In addition, by above-mentioned ultraviolet-shielding type component and in adhering agent layer is laminated after solidifying laminated body, it can benefit Inhibit the transmission of the ultraviolet light near wavelength 340nm with the ultraviolet-shielding type component.Although the ultraviolet light of the wavelength region holds Easily make sticker (the especially ingredients such as crosslinking agent, active energy ray-curable ingredient) that xanthochromia occurs, but by utilizing purple Outside line shielding component inhibits the transmission of the ultraviolet light near wavelength 340nm, which is not easy from ultraviolet-shielding type Component side reaches adhering agent layer after solidification.Thus, it is possible to inhibit the xanthochromia of adhering agent layer after solidifying.
Constitute above-mentioned adhering agent layer 11 sticker be preferably acrylic compounds active energy ray-curable sticker, It is particularly preferably obtained by the adherence composition (hereinafter sometimes referred to " adherence composition P ") containing following substances: (methyl) Acrylate polymer (A)；Crosslinking agent (B)；Active energy ray-curable ingredient (C)；And the acetonitrile in 0.1 mass % of concentration The Photoepolymerizationinitiater initiater (D) that the absorbance of wavelength 390nm in solution is 0.3 or more.Also, above-mentioned sticker preferably contains (methyl) acrylate polymer (A) is penetrated via cross-linked structure made of crosslinking agent (B) crosslinking, unreacted active-energy each other The sticker of the active energy ray-curable of line curability composition (C) and Photoepolymerizationinitiater initiater (D).Above-mentioned active energy beam Curability sticker is obtained and adherence composition P is crosslinked (heat cross-linking), due to penetrating containing unreacted active-energy Line curability composition (C) and Photoepolymerizationinitiater initiater (D), therefore active energy ray-curable.When using adhesive sheet 1 (after fitting adherend), active energy ray-curable ingredient (C) gathers when irradiating active energy beam to adhering agent layer 11 Merge solidification.In addition, in the present specification, (methyl) acrylic acid refers to both acrylic acid and methacrylic acid.It is other similar Term is also identical.In addition, " polymer " also includes the concept of " copolymer ".
Since adherence composition P is crosslinked above-mentioned active energy ray-curable sticker made of (heat cross-linking), Stage before curing based on active energy beam irradiation is relatively soft, therefore adhesive sheet 1 is attached to the display body with segment difference When on member of formation, adhering agent layer 11 is easy to follow segment difference, is able to suppress near segment difference and generates gap, floats.That is, adhesion The initial stage segment difference tracing ability of oxidant layer 11 is excellent.Further, since the sticker for constituting adhering agent layer 11 carries out heat cross-linking, there is certain The crosslink density of degree and there is defined cohesiveness, therefore 11 film intensity of adhering agent layer is higher.Thus, for example to adhesion Whens piece carries out severing processing etc., be able to suppress sticker be attached on blade or be able to suppress in keeping etc. sticker from Adhering agent layer 11 oozes out.
Adhering agent layer 11 is as being crosslinked active energy ray-curable sticker made of (heat cross-linking) for adherence composition P When composition, when irradiating active energy beam to adhering agent layer 11 through above-mentioned ultraviolet-shielding type component, for drawing photopolymerization The active energy beam of the wavelength (near 390nm) of hair agent (D) cracking is not shielded by ultraviolet-shielding type component, therefore photopolymerization Initiator (D) without problem cracks.As a result, active energy ray-curable ingredient (C) carries out solidifying instead well It answers, adhering agent layer 11 sufficiently solidifies, and the cohesiveness of adhering agent layer is promoted after obtained solidification.It adheres after solidifying as a result, The resistance to foaming of oxidant layer becomes excellent.
(1) constituent
(1-1) (methyl) acrylate polymer (A)
(methyl) acrylate polymer (A), which preferably comprises, contains reactive functional with reactive functional groups in the molecule Single group body is as the monomer for constituting the polymer.By containing (methyl) acrylate polymer (A) containing reactive functional groups Monomer passes through the reactive official from the monomer containing reactive functional groups as the monomeric unit for constituting the polymer under heating It can roll into a ball and be reacted with crosslinking agent (B).Thereby, it is possible to form cross-linked structure (tridimensional network), can obtain having required The sticker of cohesiveness.
Contain reaction as the monomeric unit for constituting the polymer as contained by (methyl) acrylate polymer (A) Property monomer, preferably enumerate the monomer with hydroxyl (hydroxyl monomer) in the molecule, in the molecule with carboxyl Monomer (carboxyl group-containing monomer), in the molecule monomer (emulsion stability) with amino etc..These monomers containing reactive functional groups It can be used alone a kind, also can be used simultaneously two or more.
Among above-mentioned monomer containing reactive functional groups, preferably hydroxyl monomer and carboxyl group-containing monomer, from the angle of resistance to foaming Degree sets out, particularly preferred hydroxyl monomer.In hydroxyl monomer, glass transition temperature (Tg) higher substance is more, passes through Using the hydroxyl monomer as structures alone (especially with more amount), obtained (methyl) acrylate polymer (A) Glass transition temperature (Tg) it is high.The storage modulus for being formed by adhering agent layer 11 as a result, is got higher, and resistance to foaming is more excellent.
As hydroxyl monomer, such as (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxyl can be enumerated Propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 3- hydroxybutyl, (first Base) acrylic acid 4- hydroxybutyl etc. (methyl) hydroxyalkyl acrylates etc..Wherein, excellent from the angle of resistance to foaming Select (methyl) acrylic acid 2- hydroxy methacrylate and (methyl) acrylic acid 4- hydroxybutyl.They can be used alone, and also can be used in combination 2 Kind or more.
As carboxyl group-containing monomer, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, Yi Kang acid, lemon can be enumerated The ethylenically unsaturated carboxylic acids of health acid etc..Wherein, from the carboxyl and crosslinking agent in obtained (methyl) acrylate polymer (A) (B) it reactivity and sets out with the copolymerizable this point of other monomers, preferably acrylic acid.They can be used alone, and can also combine Use two or more.
(methyl) acrylate polymer (A) preferably comprises 5 mass % or more, further preferably 10 matter in terms of lower limit value Measure % or more, particularly preferably containing 20 mass % or more, further preferably 30 mass % or more contain reactive functional groups Monomer is as the monomeric unit for constituting the polymer.Particularly preferably (methyl) acrylate polymer (A) is contained with above-mentioned amount Carboxylic monomer is as the monomeric unit for constituting the polymer.The resistance to foaming of adhesive sheet 1 is more excellent as a result, at the same with active energy The compatibility for measuring ray-curable ingredient (C) is also good, and the transparency of adhering agent layer is also promoted after obtained solidification.
In addition, (methyl) acrylate polymer (A) in terms of upper limit value, preferably comprise 60 mass % or less, particularly preferably Contain 50 mass % or less, further preferably 40 mass % monomer containing reactive functional groups below as the composition polymerization The monomeric unit of object.It is obtained viscous thereby, it is possible to substantially ensure the content of the monomer in addition to monomer containing reactive functional groups Agent adherence it is more excellent.
Further preferably (methyl) acrylate polymer (A) is without containing carboxyl group-containing monomer as the monomer list for constituting the polymer Member.Since carboxyl is sour component, by not containing carboxyl group-containing monomer, even if existing on the attaching object of sticker because of acid And whens generating the substance of unfavorable condition, transparent conductive film or metal film, metallic mesh etc. such as tin indium oxide (ITO), Also it is able to suppress because acid causes their unfavorable condition (burn into resistance change etc.).
Here, " not containing carboxyl group-containing monomer ", which refers to, is practically free of carboxyl group-containing monomer, in addition to being entirely free of containing carboxyl Other than monomer, also allow not generate the degree of the corrosion of the transparent conductive film as caused by carboxyl or metal line etc. and contain containing carboxylic Base monomer.Specifically, in (methyl) acrylate polymer (A), allow with 0.1 mass % amount below, preferably with 0.01 mass % amount below further preferably using 0.001 mass % amount below contains carboxyl group-containing monomer as monomeric unit.
It is preferred that (methyl) acrylate polymer (A) contains (methyl) alkyl acrylate as the list for constituting the polymer Body unit.Thereby, it is possible to show good adherence.Alkyl can be straight-chain or branched.
From the angle of adherence, as (methyl) alkyl acrylate, the carbon atom number of optimizing alkyl is 1~20 (methyl) alkyl acrylate.Carbon atom number as alkyl is 1~20 (methyl) alkyl acrylate, such as can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) Acrylic acid n-pentyl ester, (methyl) the just own ester of acrylic acid, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (first Base) the positive last of the ten Heavenly stems ester of acrylic acid, positive ten diester of (methyl) acrylic acid, (methyl) myristyl ester, (methyl) acrylic acid palm ester, (methyl) octadecyl acrylate etc..They can be used alone, and also can be used in combination two or more.
Among above-mentioned, from effectively imparting adhesion strength, simultaneously from the angle of resistance to foaming, the carbon of more preferable alkyl is former (methyl) alkyl acrylate that subnumber is 2~12, the alkyl acrylate that the carbon atom number of particularly preferred alkyl is 4~10. Specifically, it is different preferably to enumerate (methyl) butyl acrylate, (methyl) 2-EHA and (methyl) acrylic acid Monooctyl ester, it may be more preferable to enumerate butyl acrylate, 2-EHA and Isooctyl acrylate monomer.They can be used alone, Also it can be used in combination two or more.
(methyl) acrylate polymer (A) preferably comprises 20 mass % or more, further preferably 25 in terms of lower limit value Quality % or more, particularly preferably (methyl) acrylic acid containing 30 mass % or more, further preferably 40 mass % or more Arrcostab is as the monomeric unit for constituting the polymer.If the lower limit value of (methyl) acrylic acid alkyl ester content is above-mentioned, (first Base) acrylate polymer (A) can play suitable adherence.In addition, (methyl) acrylate polymer (A), with the upper limit Value meter, preferably comprise 99 mass % or less, further preferably 90 mass % or less, particularly preferably containing 80 mass % or less, into One step preferably comprises 60 mass % (methyl) alkyl acrylate below as the monomeric unit for constituting the polymer.If (first Base) acrylic acid alkyl ester content upper limit value be it is above-mentioned, then can be by the other monomers ingredient of monomer containing reactive functional groups etc. It is imported in (methyl) acrylate polymer (A) with suitable amount.
Furthermore it is preferred that (methyl) acrylate polymer (A) contains the monomer (structure containing ester ring type with ester ring type structure Monomer) as the monomeric unit for constituting the polymer.Presumption is since the volume of the structures alone containing ester ring type is larger, by depositing it It is in polymer, the interval between polymer can be expanded, the flexibility of obtained sticker can be made excellent.It glues as a result, The segment difference tracing ability of agent become excellent.
The carbocyclic ring of ester ring type structure can be saturated structures, can also have unsaturated bond.In addition, ester ring type structure can be monocycle Ester ring type structure, can also be the polycyclic ester ring type structure such as two rings, tricyclic.The carbon atom number of ester ring type structure is preferably 5~ 20, particularly preferably 6~15, further preferably 7~12.
As ester ring type structure, for example, be preferably listed containing cyclohexyl skeleton, bicyclopentadiene skeleton, adamantane framework, Isobornyl skeleton, cycloalkanes skeleton (cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, ring hendecane bone Frame, cyclododecane skeleton etc.), cyclenes skeleton (cycloheptene skeleton, cyclo-octene skeleton etc.), enb skeleton, norbornadiene The rouge of skeleton, polycycle skeleton (cubane skeleton, basket alkane skeleton, room alkane skeleton etc.), spiral shell skeleton (spiro skeleton) etc. Ring structures.Wherein, from the superior angle of resistance to foaming is made, adamantane framework and isobornyl skeleton are preferably comprised.
As above-mentioned structures alone containing ester ring type, (methyl) acrylate monomer of above-mentioned skeleton is preferably comprised, specifically For, (methyl) cyclohexyl acrylate, (methyl) dicyclopentanyl acrylate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (first can be enumerated Base) isobornyl acrylate, (methyl) acrylic acid dicyclopentenyl base ester, (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester etc., In, preferably (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) isobornyl acrylate.They can be used alone a kind, and can also combine makes Use two or more.
It is preferred that (methyl) acrylate polymer (A) containing 3 mass % or more, further preferably 6 mass % or more, Particularly preferably contain the structures alone containing ester ring type of 9 mass % or more as the monomeric unit for constituting the polymer.In addition, from true The angle for protecting the blended amount of other compositions is set out, preferably by the list of structure containing ester ring type in (methyl) acrylate polymer (A) The content of body is set as 30 mass % hereinafter, being further preferably set as 20 mass % hereinafter, being particularly preferably set as 15 mass % or less. If the ratio of the structures alone containing ester ring type is above range, the segment difference tracing ability of obtained sticker is more excellent, simultaneously More excellent is also become to the adhesion strength of plastics.
In addition it is also preferred that above-mentioned (methyl) acrylate polymer (A) contains nitrogen atom monomer as the composition polymerization The monomeric unit of object.By making in polymer there are nitrogen atom monomers as structural unit, sticker can be assigned and be provided Polarity, even if sticker is made to as glass to there is polar adherend to a certain degree also to have excellent compatibility. As above-mentioned nitrogen atom monomer, from the rigid angle for making (methyl) acrylate polymer (A) that there is appropriateness, preferably With nitrogen-containing heterocycle monomer.
As with nitrogenous heterocyclic monomer, such as N- (methyl) acryloyl morpholine, N- vinyl -2- pyrroles can be enumerated Alkanone, N- (methyl) acryloyl group pyrrolidones, N- (methyl) acryloylpiperidine, N- (methyl) acryloyl group pyrrolidines, N- (methyl) acryloyl group aziridine, (methyl) acrylic acid aziridine base ethyl ester, 2- vinylpyridine, 4- vinylpyridine Pyridine, 2- vinylpyrazine, 1- vinyl imidazole, N- vinyl carbazole, N- vinyl phthalimide etc., wherein preferably Play N- (methyl) acryloyl morpholine of superior adhesion strength, particularly preferred N- acryloyl morpholine.They can be used alone 1 Kind, it also can be used in combination two or more.
When (methyl) acrylate polymer (A) contains nitrogen atom monomer as the monomeric unit for constituting the polymer, Preferably comprise 0.5 mass % or more, this particularly preferably containing 1 mass % or more, further preferably 3 mass % or more contains Nitrogen-atoms monomer.Furthermore it is preferred that (methyl) acrylate polymer (A) contains 20 mass % or less, particularly preferably contains 15 matter % or less, further preferably 10 mass % nitrogen atom monomer below is measured as the monomer list for constituting the polymer Member.If the content of nitrogen atom monomer is within the above range, obtained sticker can be given full play to the excellent of glass Adhesion strength.
Furthermore it is preferred that (methyl) acrylate polymer (A) is the solution polymer obtained using solution polymerization process.Due to By making its solution polymer, be easy to get the polymer of high molecular weight and it can be expected that obtained sticker cohesiveness Promotion, therefore resistance to foaming becomes more excellent.
The polymeric species of (methyl) acrylate polymer (A) can be random copolymer, can also be block copolymer.
The lower limit value of the weight average molecular weight of (methyl) acrylate polymer (A) is preferably 200,000 or more, particularly preferably 300000 or more, further preferably 400,000 or more.If the lower limit value of the weight average molecular weight of (methyl) acrylate polymer (A) is More than above-mentioned, then the resistance to foaming of obtained sticker is more excellent.
In addition, the upper limit value of the weight average molecular weight of (methyl) acrylate polymer (A) is preferably 2,000,000 hereinafter, especially Preferably 1,500,000 hereinafter, further preferably 1,000,000 or less.The weight average molecular weight of (if methyl) acrylate polymer (A) Upper limit value is above-mentioned hereinafter, then the segment difference tracing ability of obtained sticker is more excellent.In addition, dividing equally in this specification again Son amount be using gel permeation chromatography (GPC) method and measure standard polystyren conversion value.
In addition, (methyl) acrylate polymer (A) can be used alone a kind in adherence composition P, can also combine Use two or more.
The lower limit value of the content of (methyl) acrylate polymer (A) in the adherence composition P of present embodiment is excellent It is selected as 50 mass % or more, particularly preferably 60 mass % or more, further preferably 70 mass % or more.By making (methyl) The lower limit value of the content of acrylate polymer (A) be it is above-mentioned, the adhesion strength of obtained sticker becomes more good.This Outside, the upper limit value of the content of (methyl) acrylate polymer (A) is preferably 99 mass % hereinafter, particularly preferably 97 mass % Hereinafter, further preferably 95 mass % or less.In the upper limit value of content by making (methyl) acrylate polymer (A) State, it can be ensured that crosslinking agent (B), active energy ray-curable ingredient (C) and Photoepolymerizationinitiater initiater (D) other compositions contain Amount, and resistance to foaming becomes more excellent.
(1-2) crosslinking agent (B)
(methyl) acrylate polymer (A) can be crosslinked by crosslinking agent (B) by the heating of adherence composition P, and Tridimensional network is formed well.The cohesiveness of obtained sticker further gets a promotion as a result, and resistance to foaming becomes It is more excellent.
As above-mentioned crosslinking agent (B), if with reactive functional groups possessed by (methyl) acrylate polymer (A) into Row reaction, such as isocyanates crosslinking agent, epoxies crosslinking agent, amine cross-linking agent, melamine class can be enumerated and handed over Join agent, oxirane class crosslinking agent, hydrazine crosslinking agent, aldehyde crosslinking agent, oxazoline class crosslinking agent, the crosslinking of metal alkoxide class Agent, metal-chelating species crosslinking agent, metallic salt crosslinking agent, ammonium salt class crosslinking agent etc..Here, (methyl) acrylate polymer (A), it is preferable to use having the excellent reactive isocyanic acid with hydroxyl when containing hydroxyl monomer as structures alone unit Esters crosslinking agent is as crosslinking agent (B).In addition, (methyl) acrylate polymer (A) contains carboxyl group-containing monomer as structure list When body unit, it is preferable to use with the excellent reactive epoxies crosslinking agent with carboxyl as crosslinking agent (B).In addition, handing over Connection agent (B) can be used alone a kind or two or more is applied in combination.
Isocyanates crosslinking agent at least contains polyisocyanate compounds.As polyisocyanate compounds, such as can The fragrant adoption for enumerating toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, benzene dimethylene diisocyanate etc. is different Cyanate, the aliphatic polymeric isocyanate of hexamethylene diisocyanate etc., isophorone diisocyanate, hydrogenated diphenyl first Ester ring type polyisocyanate of alkane diisocyanate etc. etc. and their biuret body, isocyanuric acid ester body so as with The reactant of the low molecules active hydrogen-contg compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil adds At object etc..Wherein, from the reactive angle with hydroxyl, the preferably modified aromatic series polyisocyanate of trimethylolpropane The modified phenylenedimethylidyne diisocyanate of ester, particularly preferred trimethylolpropane modified toluene diisocyanate and trimethylolpropane Ester.
As epoxies crosslinking agent, such as 1,3- bis- (N, N- 2-glycidyl aminomethyl) hexamethylenes, N, N can be enumerated, N ', N '-four glycidyl group-m-xylene diamine, ethylene glycol diglycidylether, 1,6 hexanediol diglycidylether, three Hydroxymethyl-propane diglycidyl ether, diglycidylaniline, 2-glycidyl amine etc..Wherein, from the reactivity with carboxyl Angle set out, bis- (N, the N- 2-glycidyl aminomethyl) hexamethylenes of preferably 1,3-.
Relative to 100 mass parts of (methyl) acrylate polymer (A), crosslinking agent (B's) in adherence composition P contains Amount is preferably 0.01 mass parts or more, more than special standby preferably 0.05 mass parts, more than further preferably 0.1 mass parts.This Outside, which is preferably that 3 below the mass, more preferably 1 below the mass, and particularly preferably 0.5 below the mass, further Preferably 0.3 below the mass.By making the content of crosslinking agent (B), crosslinking degree becomes suitably, acquired within the above range The resistance to foaming of sticker become more excellent.In addition, among crosslinking agent (B), though especially isocyanates crosslinking agent is It is easy to happen the ingredient of xanthochromia, but the content by making crosslinking agent (B) is within the above range, is glued after solidification can be further suppressed The xanthochromia of oxidant layer.It, can be by crosslinking agent (B) by making (methyl) acrylate polymer (A) that there is above-mentioned preferred composition Content be suppressed to less amount as described above.
(1-3) active energy ray-curable ingredient (C)
By making adherence composition P contain active energy ray-curable ingredient (C), adherence composition P is crosslinked Sticker obtained from (heat cross-linking) becomes the sticker of active energy ray-curable.The sticker is estimated to be glued by attaching Active energy beam after object irradiates and solidifies, and thus active energy ray-curable ingredient (C) is aggregated with one another, after the polymerization Active energy ray-curable ingredient (C) is wrapped in cross-linked structure (the three-dimensional netted knot of (methyl) acrylate polymer (A) Structure) on.Since the cohesiveness of the sticker with higher-dimension structure is higher and the high film intensity of display, resistance to foaming become It is more excellent.
Active energy ray-curable ingredient (C) as long as solidified by the irradiation of active energy beam and available The ingredient of said effect, is just not particularly limited, and can be any one of monomer, oligomer or polymer, can also be them Mixture.Wherein, the multifunctional acrylic acid excellent in compatibility with (methyl) acrylate polymer (A) etc. is preferably enumerated Esters monomer.
As multifunctional acrylates monomer, such as 1,4-butanediol two (methyl) acrylate, 1,6- can be enumerated Hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, new penta Glycol adipic acid two (methyl) acrylate, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, two (first of bicyclopentyl Base) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) propylene Acid esters, two (acryloyl-oxyethyl) isocyanuric acid esters, allylation cyclohexyl two (methyl) acrylate, Ethoxylated bisphenol The bifunctional type of bis- [4- (2- acryloyloxyethoxy) phenyl] fluorenes of A diacrylate, 9,9- etc.；Trimethylolpropane tris Modified dipentaerythritol three (methyl) acrylate of (methyl) acrylate, dipentaerythritol three (methyl) acrylate, propionic acid, Pentaerythrite three (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, three (acryloyl-oxies Base ethyl) isocyanuric acid ester, modified three-(2- (methyl) acryloyl-oxyethyl) isocyanuric acid esters of 6-caprolactone etc. trifunctional Type；The tetrafunctional type of diglycerol four (methyl) acrylate, pentaerythrite four (methyl) acrylate etc.；Propionic acid was modified for two seasons penta Five functional-types of tetrol five (methyl) acrylate etc.；Dipentaerythritol six (methyl) acrylate, two season penta of caprolactone modification Six functional-types etc. of tetrol six (methyl) acrylate etc..Among above-mentioned, from the resistance to foaming and high temperature of obtained sticker The angle of segment difference tracing ability under super-humid conditions is set out, preferably two (acryloyl-oxyethyl) isocyanuric acid esters, three (acryloyl-oxies Base ethyl) isocyanuric acid ester, modified three-(2- (methyl) acryloyl-oxyethyl) isocyanuric acid esters of 6-caprolactone etc. are in the molecule Multifunctional acrylates monomer containing isocyanurate structure contains isocyanide urea more than more preferable trifunctional and in the molecule The multifunctional acrylates monomer of acrylate structure, modified three-(2- (methyl) the acryloxy second of particularly preferred 6-caprolactone Base) isocyanuric acid ester.They can be used alone a kind, also can be used in combination two or more.In addition, from poly- with (methyl) acrylate The angle for closing the compatibility of object (A) is set out, and preferably the molecular weight of multifunctional acrylates monomer is less than 1000.
As active energy ray-curable ingredient (C), it is also able to use the acrylate of active energy ray curable Quasi-oligomer.As the example of such acrylate quasi-oligomer, polyester acrylates, epoxy acrylate can be enumerated Class, urethane acrylate class, polyoxyalkylene acrylate esters, polybutadiene acrylic acid esters, silicone acrylates class Deng.
The weight average molecular weight of above-mentioned acrylate quasi-oligomer is preferably 50,000 hereinafter, particularly preferably 1, and 000~50, 000, further preferably 3,000~40,000.These acrylate quasi-oligomers can be used alone a kind, also can be used in combination 2 Kind or more.
In addition, being also able to use to be imported in side chain has (methyl) third as active energy ray-curable ingredient (C) The addition acrylic polymer of the group of enoyl-.Such addition acrylic polymer, is able to use (methyl) The copolymer of acrylate and the monomer in the molecule with cross-linking functional group, can be by making to have and (methyl) acryloyl group And the compound of the group of cross-linking functional group's reaction is reacted with a part of the cross-linking functional group of the copolymer and is obtained It arrives.
The weight average molecular weight of above-mentioned addition acrylic polymer is preferably 50,000~900,000 or so, particularly preferably 10 Ten thousand~500,000 or so.
Active energy ray-curable ingredient (C), can be from above-mentioned multifunctional acrylates monomer, esters of acrylic acid In oligomer and addition acrylic polymer select a kind use, two or more can be also applied in combination, also can with remove Active energy ray-curable ingredient other than the above is applied in combination.
From the angle for making the cohesiveness of obtained sticker be promoted, keep resistance to foaming excellent, relative to (methyl) 100 mass parts of acrylate polymer (A), the content of the active energy ray-curable ingredient (C) in adherence composition P Lower limit value is preferably 1 mass parts or more, more than more preferably 3 mass parts, more than particularly preferably 5 mass parts.On the other hand, from It prevents from active energy ray-curable ingredient (C) from generating the angle mutually separated with (methyl) acrylate polymer (A) to set out, on The upper limit value for stating content is preferably that 50 below the mass, more preferably 20 below the mass, if it is further contemplated that the section at initial stage Poor tracing ability is better, then particularly preferably 10 below the mass.
(1-4) Photoepolymerizationinitiater initiater (D)
The suction of wavelength 390nm of the Photoepolymerizationinitiater initiater (D) of present embodiment in the acetonitrile solution of 0.1 mass % of concentration Luminosity is 0.3 or more.By making the sticker for constituting adhering agent layer 11 contain the Photoepolymerizationinitiater initiater (D), even if through purple When outside line shielding component irradiates active energy beam to adhering agent layer 11, Photoepolymerizationinitiater initiater (D) is also without problem Cracking, adhering agent layer 11 (active energy ray-curable ingredient (C)) solidify well.It adheres after being formed by solidification as a result, The cohesiveness of oxidant layer is high, and resistance to foaming is excellent.
From above-mentioned angle, the absorbance of the wavelength 390nm of Photoepolymerizationinitiater initiater (D) is preferably 0.5 or more, especially Preferably 1.0 or more.The upper limit value of the absorbance is not particularly limited, but preferably generally 2.5 hereinafter, particularly preferably 2.0 Below.If absorbance is greater than 2.5, when being formed or keeping adhesive sheet, can exist causes because of the ambient light of fluorescent lamp etc. The curing reaction of active energy ray-curable ingredient (C) based on Photoepolymerizationinitiater initiater (D) occurs, segment difference when subsequent use The case where tracing ability reduces.Here, shown in the measuring method of the absorbance of Photoepolymerizationinitiater initiater (D) test example as be described hereinafter.
In addition, the extinction of wavelength 200~500nm of the Photoepolymerizationinitiater initiater (D) in the acetonitrile solution of 0.1 mass % of concentration The very big wavelength of the absorption of degree is preferably 350nm or more, particularly preferably 370nm or more, further preferably 380nm or more.Separately Outside, when wavelength very big there are the absorption of the absorbance of multiple 200~500nm of wavelength, at least one absorbs very big wavelength above-mentioned In range.As a result, when irradiating active energy beam to adhering agent layer 11 through ultraviolet-shielding type component, adhering agent layer The curability of 11 (active energy ray-curable ingredient (C)) further gets a promotion, and cohesiveness increases, and resistance to foaming becomes more Add excellent.On the other hand, the upper limit value of the very big wavelength of above-mentioned absorption is not particularly limited, viscous from preventing from taking care of in ambient light Oxidant layer 11 when carry out curing reaction angle set out, preferably 450nm hereinafter, particularly preferably 410nm hereinafter, further it is excellent It is selected as 405nm or less.
As such Photoepolymerizationinitiater initiater (D), such as 2 can be enumerated, 4,6- trimethylbenzoy-diphenies-oxygen Change phosphine, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides etc..They can be used alone, also can be used in combination 2 kinds with On.
Relative to 100 mass parts of active energy ray-curable ingredient (C), the photopolymerization in adherence composition P causes The lower limit value of the content of agent (D) is preferably 2 mass parts or more, and it is more than particularly preferably 4 mass parts, further preferably 5 mass Part or more.In addition, the upper limit value of the content of Photoepolymerizationinitiater initiater (D) is preferably that 15 below the mass, spy is than being preferably 12 mass Part hereinafter, further preferably 10 below the mass.
(1-5) silane coupling agent (E)
It is preferred that adherence composition P further contains silane coupling agent (E).Even if adherend is plastic plate or is as a result, Glass component also gets a promotion with the adherence of the adherend, and resistance to foaming becomes more excellent.
As silane coupling agent (E), preferably at least there is 1 alkoxysilyl (alkoxysilyl) in the molecule Organo-silicon compound, it is good with the compatibility of (methyl) acrylate polymer (A) and there is translucency.
As the silane coupling agent (E), such as vinyltrimethoxysilane, vinyl triethoxyl silicon can be enumerated The silicon compound containing polymerism unsaturated group such as alkane, methacryloxypropyl trimethoxy silane；The third oxygen of 3- epoxy Propyl trimethoxy silicane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane etc. have the silicon compound of epoxy construction； 3-mercaptopropyi trimethoxy silane, 3- Mercaptopropyltriethoxysilane, 3- mercaptopropyi dimethoxymethylsilane etc. contain There is the silicon compound of sulfydryl；3- TSL 8330, N- (2- amino-ethyl) -3- aminopropyl trimethoxy silicon The silicon compounds containing amino such as alkane, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane；3- chloropropyl front three Oxysilane, 3- isocyanate group propyl-triethoxysilicane or at least one kind of and methyltriethoxysilane, second in them The condensation product etc. of the silicon compounds containing alkyl such as ethyl triethoxy silicane alkane, methyltrimethoxysilane, ethyl trimethoxy silane.It Can be used alone a kind, also can be used in combination two or more.
Silane coupling agent (E) relative to 100 mass parts of (methyl) acrylate polymer (A), in adherence composition P Content be preferably 0.01 mass parts or more, it is more than particularly preferably 0.05 mass parts, further preferably 0.1 mass parts with On.In addition, the content is preferably that 1 below the mass, particularly preferably 0.5 below the mass, further preferably 0.3 mass parts Below.
(1-6) various additives
According to required, the various additives being typically used in acrylic compounds sticker can be added in adherence composition P, Such as ultraviolet absorbing agent, antistatic agent, tackifier, antioxidant, light stabilizer, softening agent, filler, adjustable refractive index Agent, antirust agent etc..In addition, aftermentioned polymer solvent and retarder thinner are not included in the additive for constituting adherence composition P.
But adherence composition P does not preferably contain ultraviolet absorbing agent.Ultraviolet absorbing agent exist from sticker (Gu Adhering agent layer after change) exudation a possibility that, obtained display body can be polluted.In the present embodiment, due to a display body At least one of member of formation and another display body member of formation be ultraviolet-shielding type component, therefore solidify after sticker Necessity of the layer containing ultraviolet absorbing agent is lower.
(2) manufacture of adherence composition
Adherence composition P can be prepared by following manner: preparation (methyl) acrylate polymer (A), will be acquired (methyl) acrylate polymer (A), crosslinking agent (B), active energy ray-curable ingredient (C) and Photoepolymerizationinitiater initiater (D) it mixes, while according to required, addition silane coupling agent (E) and additive.
The mixture polymerization that the monomer of polymer can will be constituted by using common radical polymerization, to prepare (methyl) acrylate polymer (A).Polymerization initiator can be used according to required, and (first is carried out by solution polymerization process etc. Base) acrylate polymer (A) polymerization.As polymer solvent, such as ethyl acetate, n-butyl acetate, acetic acid can be enumerated Isobutyl ester, toluene, acetone, hexane, methyl ethyl ketone etc., also can be used simultaneously two or more.
As polymerization initiator, azo compound, organic peroxide etc. can be enumerated, also can be used simultaneously 2 kinds with On.As azo compound, such as 2,2 '-azodiisobutyronitriles, 2,2 '-azos bis- (2- methylbutyronitriles), 1 can be enumerated, 1 '-azo bis- (hexamethylene 1- formonitrile HCNs), 2,2 '-azos bis- (2,4- methyl pentane nitriles), the bis- (2,4- dimethyl -4- of 2,2 '-azos Methoxyl-valeronitrile), dimethyl 2,2 '-azo bis- (2 Methylpropionic acid esters), 4,4 '-azos bis- (4- cyanopentanoic acids), 2,2 '-azos Bis- (2- hydroxymethylpropionitriles), 2,2 '-azos bis- [2- (2- imidazoline -2- base) propane] etc..
As organic peroxide, such as benzoyl peroxide, t-butyl perbenzoate, hydrogen peroxide isopropyl can be enumerated Benzene, di-isopropyl peroxydicarbonate, peroxy dicarbonate di-n-propyl ester, dicetyl peroxydicarbonate two (2- ethoxyethyl group) ester, New peroxide tert-butyl caprate, tert-Butyl peroxypivalate, peroxidating (3,5,5- trimethyl acetyl), dipropyonyl peroxide, Diacetyl peroxide etc..
In addition, by blending the chain-transferring agent of 2 mercapto ethanol etc., can be adjusted obtained in above-mentioned polymerization process The weight average molecular weight of polymer.
After obtaining (methyl) acrylate polymer (A), the solution in (methyl) acrylate polymer (A) can be passed through Middle addition crosslinking agent (B), active energy ray-curable ingredient (C), Photoepolymerizationinitiater initiater (D) and the silicon added according to required Alkane coupling agent (E), additive, and be sufficiently mixed, to obtain through the diluted adherence composition P of solvent (coating solution). In addition, using solid-like above-mentioned each ingredient it is any when or generated when being mixed with other compositions with undiluted state In the case where precipitation, after can also individually dissolving in advance by the ingredient or be diluted in retarder thinner, then mix with other compositions.
As above-mentioned retarder thinner, such as the aliphatic hydrocarbon for being able to use hexane, heptane, hexamethylene etc.；Toluene, dimethylbenzene Deng aromatic hydrocarbon；The halogenated hydrocarbons of methylene chloride, dichloroethanes etc.；Methanol, ethyl alcohol, propyl alcohol, butanol, 1- methoxy-2-propanol Deng alcohol；The ketone of acetone, methyl ethyl ketone, 2 pentanone, isophorone, cyclohexanone etc.；The ester of ethyl acetate, butyl acetate etc.； The cellosolve type solvents etc. of ethyl cellosolve etc..
As the concentration viscosity of the coating solution so prepared, as long as not limited especially for the range that can be coated with System, can according to circumstances and suitably select.For example, in a manner of making the concentration of adherence composition P become 10~60 mass % It is diluted.In addition, the addition of retarder thinner etc. is not necessary condition, as long as adherence composition P when obtaining coating solution For the viscosity etc. that can be coated with, then retarder thinner can not also be added.At this point, adherence composition P becomes (methyl) acrylate Coating solution of the polymer solvent of polymer (A) directly as retarder thinner.
(3) formation of adhering agent layer
Adhering agent layer 11 is preferably by constituting sticker made of adherence composition P heat cross-linking.That is, adherence composition The crosslinking of P is carried out by heat treatment.In addition, also can be by the drying process after the coating of adherence composition P as being The heat treatment.
The heating temperature of heat treatment is preferably 50~150 DEG C, and particularly preferably 70~120 DEG C.In addition, heating time is excellent It is selected as 10 seconds~10 minutes, particularly preferably 50 seconds~2 minutes.Further, particularly preferably after a heating treatment, it is arranged in room temperature The maturation period in or so 1~2 week under (such as 23 DEG C, 50%RH).
By above-mentioned heat treatment (and curing), (methyl) acrylate polymer (A) is good via crosslinking agent (B) Ground crosslinking.
(4) thickness of adhering agent layer
The lower limit value of the thickness (value measured according to JIS K7130) of adhering agent layer 11 is preferably 20 μm or more, more excellent It is selected as 25 μm or more, particularly preferably 30 μm or more, further preferably 50 μm or more.In addition, the thickness of adhering agent layer 11 Upper limit value be preferably 500 μm hereinafter, more preferably 400 μm hereinafter, particularly preferably 300 μm or less.If the thickness of adhering agent layer 11 Within the above range, then resistance to foaming becomes more excellent to degree.
1-2. stripping film
Stripping film 12a, 12b protect adhering agent layer 11 until using adhesive sheet 1, are using 1 (sticker of adhesive sheet Layer 11) when be stripped.In the adhesive sheet 1 of present embodiment, one or both of stripping film 12a, 12b may not be required.
As stripping film 12a, 12b, for example, be able to use polyethylene film, polypropylene screen, polybutene film, polybutadiene film, Polymethylpentene film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate Film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene-(methyl) third Olefin(e) acid co-polymer membrane, ethylene-(methyl) acrylate copolymer film, polystyrene film, polycarbonate membrane, polyimide film, fluorine Resin film etc..Furthermore, it is possible to use their cross linking membrane.It further, can also be their stacked film.
It is preferred that the release surface (face especially contacted with adhering agent layer 11) of above-mentioned stripping film 12a, 12b are implemented at removing Reason.As the remover used in lift-off processing, for example, can enumerate alcohol acids, silicone, fluorine class, unsaturated polyester (UP) class, The remover of polyolefins, wax class.In addition, a stripping film is preferably set as the big stripping again of peeling force in stripping film 12a, 12b Another stripping film is set as the small light exfoliated stripping film of peeling force by release stripping film.
The thickness of stripping film 12a, 12b are not particularly limited, but usually 20~150 μm or so.
2. the manufacture of adhesive sheet
As a Production Example of adhesive sheet 1, by the coating solution coating of above-mentioned adherence composition P in a stripping film In the release surface of 12a (or 12b), heat treatment is carried out to which adherence composition P is crosslinked (heat cross-linking), forms coating layer Afterwards, the release surface of another stripping film 12b (or 12a) is superimposed on the coating layer.It needs to cure when the maturation period by setting Phase, above-mentioned coating layer is directly becoming adhering agent layer 11 when not needing the maturation period.Thereby, it is possible to obtain above-mentioned adhesive sheet 1.At heating Reason and the condition of curing are as described above.
As other Production Examples of adhesive sheet 1, by the coating solution coating of above-mentioned adherence composition P in a stripping film In the release surface of 12a, heat treatment is carried out to which adherence composition P is crosslinked (heat cross-linking), forms coating layer to obtain The stripping film 12a of attached coating layer.In addition, by the coating solution coating of above-mentioned adherence composition P another stripping film 12b's In release surface, heat treatment is carried out to which adherence composition P is crosslinked (heat cross-linking), forms coating layer to obtain attached coating The stripping film 12b of layer.Then, the stripping film 12a of attached coating layer is mutually connected with the stripping film 12b of attached coating layer with two coating layers The mode of touching is bonded.It needs to pass through the setting maturation period when maturation period, the above-mentioned coating layer being laminated is straight when not needing the maturation period It is connected into as adhering agent layer 11.Thereby, it is possible to obtain above-mentioned adhesive sheet 1.According to the Production Example, even if thicker in adhering agent layer 11 In the case of, also can steadily it be manufactured.
As the method for the coating solution for being coated with above-mentioned adherence composition P, such as stick rubbing method can be utilized, scrape cutter painting Cloth method, rolling method, scraping blade rubbing method, die coating methods, gravure coating process etc..
3. the physical property of adhesive sheet
(1) gel fraction
Gel fraction before the irradiation of (1-2) active energy beam
Constitute the gel point of the active energy ray-curable sticker (before active energy beam irradiation) of adhering agent layer 11 The lower limit value of rate is preferably 30% or more, and more preferably 40% or more, particularly preferably 45% or more.If active energy beam is solid Change property sticker gel fraction lower limit value be it is above-mentioned, then the cohesiveness of adhering agent layer 11 gets a promotion, and can effectively press down System sticker when carrying out severing processing etc. to adhesive sheet 1 be attached on blade or in keeping etc. stickers from adhering agent layer The case where 11 exudation.In addition, the upper limit value of the gel fraction of active energy ray-curable sticker is preferably 70% hereinafter, special It You Xuanwei not be 65% hereinafter, further preferably 61% or less.If the gel fraction of active energy ray-curable sticker Upper limit value be it is above-mentioned, then sticker will not become really up to the mark, and the segment difference tracing ability at initial stage becomes more excellent.The active energy beam Shown in the measuring method of the gel fraction of curability sticker (before active energy beam irradiation) test example as be described hereinafter.
Gel fraction after the irradiation of (1-2) active energy beam
Constitute the sticker (active-energy to adhering agent layer after solidifying made of the irradiation active energy beam of adhering agent layer 11 After radiation exposure) the lower limit value of gel fraction be preferably 40% or more, more preferably 50% or more, particularly preferably 60% with On, further preferably 66% or more.If the lower limit value of above-mentioned gel fraction be it is above-mentioned, constitute gluing for adhering agent layer after solidify The cohesiveness of agent become sufficiently, superior resistance to foaming can be played.In addition, constitute solidify after adhering agent layer sticker The upper limit value of gel fraction be preferably 95% hereinafter, particularly preferably 90% hereinafter, further preferably 80% or less.On if The upper limit value for stating gel fraction is above-mentioned, the then adhesion strength of adhering agent layer after capable of ensuring to solidify, and can be obtained adequately durable Property.Constitute the measuring method of the gel fraction of the sticker (active energy beam irradiation after) of adhering agent layer after solidify as be described hereinafter Shown in test example.
The variable quantity of (1-3) gel fraction
Constitute adhering agent layer 11 active energy ray-curable sticker, along with based on active energy beam irradiate Gel fraction variable quantity (by constitute solidify after the gel fraction of sticker of adhering agent layer subtract active energy ray-curable Value obtained from the gel fraction of property sticker) it is preferably 5 percentage points or more, more than particularly preferably 10 percentage points, further It is more than preferably 15 percentage points.By rising gel fraction so, the resistance to foaming of adhering agent layer after obtained solidification Become more excellent.In addition, the upper limit of the rising of the gel fraction, is not particularly limited, but the adhering agent layer after preventing solidification The angle for becoming too hard is set out, and the rising of gel fraction is preferably 40 percentage points hereinafter, more preferably 30 percentage points are hereinafter, especially Below preferably 25 percentage points.
(2) adhesion strength
Irradiating active energy beam by the adhering agent layer 11 of the adhesive sheet 1 to present embodiment makes its solidification to become After solidification when adhering agent layer, which is preferably 20N/25mm or more to the lower limit value of the adhesion strength of soda-lime glass, more preferably For 25N/25mm or more, particularly preferably 30N/25mm or more, further preferably 35N/25mm or more.The adhesion of adhesive sheet 1 When the lower limit value of power is above-mentioned, resistance to foaming is more excellent.On the other hand, the upper limit value of above-mentioned adhesion strength is not particularly limited, but Preferably generally 100N/25mm hereinafter, more preferably 90N/25mm hereinafter, particularly preferably 80N/25mm or less.In addition, above-mentioned Adhesion strength refers to the adhesion strength substantially measured using the 180 degree stripping method according to JIS Z0237:2009, specific to test Shown in method test example as be described hereinafter.
[display body]
The adhesive sheet 1 of present embodiment is able to use in the manufacture of display body 2 as illustrated in Figure 2.As shown in Fig. 2, The display body 2 of present embodiment has following composition: the first display body at least on by the face of fitting side with segment difference is constituted Component 21 (a display body member of formation)；Second display body member of formation 22 (another display body member of formation)；And it is located at Sticker after solidifications between them, that the first display body member of formation 21 and the second display body member of formation 22 mutually fit Layer 11 '.In the display body 2 of present embodiment, the first display body member of formation 21 after hardening the face of 11 ' side of adhering agent layer or There is segment difference on the face of 11 side of adhering agent layer, specifically, having the segment difference formed by printing layer 3, but be not limited by it.
Here, when a display body member of formation (such as first display body member of formation 21) is ultraviolet screener component When, preferably another display body member of formation (such as second display body member of formation 22) is that performance is deteriorated because ultraviolet light irradiates Component or for can not from another display body member of formation side to adhering agent layer 11 irradiate active energy beam knot The component of structure.Even if the component having the limitation that is used as display body member of formation, as long as using above-mentioned embodiment Optics adhesive sheet 1, can be by irradiating active energy beam from ultraviolet-shielding type component side to making adhering agent layer 11 Sufficiently solidification becomes adhering agent layer 11 ' after solidification, can obtain the excellent display body 2 of resistance to foaming.
Adhering agent layer 11 ' is to make above-mentioned adhesive sheet 1 by irradiation energy ray after solidification possessed by above-mentioned display body 2 Adhering agent layer 11 solidify made of layer.Constitute adhering agent layer 11 sticker by adherence composition P crosslinking (heat cross-linking) and Cheng Shi, the sticker for constituting adhering agent layer 11 ' after the solidification have by (methyl) acrylate polymer (A) and crosslinking agent (B) The cross-linked structure of composition, simultaneously contain energy ray-curable ingredient (C) solidfied material (polymer), and according to it is required can be into one Step contains Photoepolymerizationinitiater initiater (D) and additive.At this point, active energy ray-curable ingredient (C) winding after presumption polymerization In the cross-linked structure being made of (methyl) acrylate polymer (A) and crosslinking agent (B), higher-dimension structure is formed.
In addition, constituting the Photoepolymerizationinitiater initiater (D) after above-mentioned solidification contained by the sticker of adhering agent layer 11 ' is adherence Photoepolymerizationinitiater initiater (D) contained by composition P does not also crack and remaining photopolymerization even by active energy beam irradiation Initiator.Therefore, content is few, is 0.00001 mass % or more, 0.1 mass % usually in sticker hereinafter, preferably 0.0001 mass % or more, 0.01 mass % or less.
The haze value of adhering agent layer 11 ' is preferably 5% hereinafter, more preferably 3% hereinafter, particularly preferably 1% after solidification Hereinafter, further preferably 0.5% or less.When the haze value of adhering agent layer 11 ' is 5% or less after solidification, the transparency is very high, Suitable for optical applications (display body use).Haze value in this specification is set as measuring according to JIS K7136:2000 Value.
In the display body 2 of present embodiment, in the first display body member of formation 21 and the second display body member of formation 22 At least one is the ultraviolet-shielding type component with ultraviolet-shielding type.As mentioned above, it is necessary, the wave of the ultraviolet-shielding type component The light transmittance of long 340nm is 5% hereinafter, the light transmittance of wavelength 390nm is 10% or more.In addition, the light transmittance in this specification Measuring method test example as be described hereinafter shown in.
When the light transmittance of the wavelength 390nm of ultraviolet-shielding type component is 10% or more, through the ultraviolet-shielding type structure When part irradiates active energy beam to adhering agent layer 11, Photoepolymerizationinitiater initiater without problem is cracked.As a result, active energy The curing reaction for measuring the sticker of ray-curable carries out well, and adhering agent layer 11 sufficiently solidifies, and is capable of forming resistance to foaming Adhering agent layer 11 ' after excellent solidification.Under the angle, the light transmittance of the wavelength 390nm of ultraviolet-shielding type component Limit value is 10% or more, preferably 30% or more, particularly preferably 50% or more, further preferably 60% or more.Ultraviolet light The upper limit value of the light transmittance of the wavelength 390nm of shielding component is not particularly limited, but preferably generally 98% hereinafter, especially excellent It is selected as 85% or less.
On the other hand, it when the light transmittance of the wavelength 340nm of ultraviolet-shielding type component is 5% or less, is easy after making solidification The active energy beam that xanthochromia occurs for adhering agent layer 11 ' is shielded by ultraviolet-shielding type component, so that it is solid to be not easily accessible to it Adhering agent layer 11 ' after change.Thereby, it is possible to inhibit adhering agent layer 11 ' after solidification that xanthochromia occurs.From the angle, ultraviolet screen The upper limit value of the light transmittance of the wavelength 340mm of covering property component is for 5% hereinafter, preferably 3% hereinafter, particularly preferably 1% or less. The lower limit value of the light transmittance of the wavelength 340nm of ultraviolet-shielding type component is not particularly limited, but preferably generally 0.01% with On, particularly preferably 0.1% or more.
Here, after solidifying adhering agent layer 11 ' xanthochromia degree, can pass through according to CIE1976L*a*b*As defined in color specification system Transmit form and aspect b*Variable quantity and judge.Specifically, in the environment of 43 DEG C, 50%RH, to having for ultraviolet-shielding type Adhering agent layer after one display body member of formation of component, another display body member of formation and the solidification that is bonded them The illumination that laminated body irradiate from ultraviolet-shielding type component side 1000 hours is 350mW/cm2Active energy beam it is resistance to Phototesting, by the b after the Light Resistance Test*1B before subtracting Light Resistance Test*0Obtained value Δ b*Preferably 0.3 hereinafter, particularly preferably For 0.2 hereinafter, further preferably 0.1 or less.By making Δ b*Be it is above-mentioned, be able to suppress the Huang of adhering agent layer 11 ' after solidifying Become.
Whether before Light Resistance Test or after Light Resistance Test, the b of adhering agent layer 11 ' after solidification*Both preferably -1.0~ 1.0, particularly preferably -0.7~0.7, further preferably -0.5~0.5.By the b for making adhering agent layer 11 ' after solidifying*Upper It states in range, is able to suppress the xanthochromia of adhering agent layer 11 ' after solidifying, the appearance and visuality of display are good.In addition, b*Survey Determine shown in method test example as be described hereinafter.
Above-mentioned ultraviolet-shielding type component is preferably made of plastic plate, particularly preferably by the plastics containing ultraviolet absorbing agent Plate is constituted.Here, when under conditions of plastic plate placement under the high temperature conditions, being for example usually placed on 85 DEG C, internal low boiling Point ingredient gasification, exist plastic plate with solidify after adhering agent layer 11 ' interface on generation bubble, the blistering that floats, peel off etc. A possibility that.But even if the display body 2 of present embodiment has such plastic plate, by making adhering agent layer 11 ' after solidifying Adhesive sheet 1 from present embodiment can also inhibit the generation of blistering well.
It as plastic plate, is not particularly limited, such as polycarbonate resin (PC) plate, poly-methyl methacrylate can be enumerated The acrylic resin board of ester resin (PMMA) plate etc.；Plexiglass layer etc. is laminated on polycarbonate resin plate Acrylate resin layer made of plastic plate etc..In addition, above-mentioned polycarbonate resin plate can also containing except polycarbonate resin with Outer resin is as constituent material, in addition, above-mentioned acrylic resin board contains the resin conduct in addition to acrylic resin Constituent material.
The thickness of plastic plate is not particularly limited, but usually 0.2~5mm, preferably 0.4~3mm, particularly preferably 0.6~2.5mm, further preferably 1~2.1mm.
First display body member of formation 21 is preferably protection panels (the covering material being made of above-mentioned ultraviolet-shielding type component Material).Various functional layers (transparent conductive film, metal layer, two can be set on the single or double of the ultraviolet-shielding type component Silicon oxide layer, hard conating, antiglare layer etc.), optical component can also be laminated with.In addition, transparent conductive film and metal layer can also be through scheming Case.
Second display body member of formation 22 can be glass plate, can also be that should be attached on the first display body member of formation 21 Optical component, (such as liquid crystal (LCD) module, light emitting diode (LED) module, organic electroluminescent are (organic for display module EL) module etc.), as display module a part optical component or comprising show module laminated body.These optics Component, display module, laminated body etc. can also have glass plate.
It as above-mentioned glass plate, is not particularly limited, such as chemically reinforced glass, alkali-free glass, quartzy glass can be enumerated Glass, soda-lime glass, containing barium strontium glass, aluminum silicate glass, lead glass, pyrex, barium pyrex etc..Glass plate Thickness is not particularly limited, usually 0.1~10mm, preferably 0.2~5mm, more preferably 0.8~2mm.
Various functional layers can be set on the single or double of glass plate for constituting the second display body member of formation 22 (thoroughly Bright conductive film, metal layer, silicon dioxide layer, hard conating, antiglare layer etc.), optical component can also be laminated with.In addition, electrically conducting transparent Film and metal layer can also be patterned.
As above-mentioned optical component, such as anti-disperse film, polarization plates (polarizing coating), polarizer, phase difference board can be enumerated (phase difference film), compensation film for angular field of view, luminance raising film, contrast promote film, liquid crystalline polymer film, diffusion barrier, semi-penetration Film, transparent and electrically conductive film etc..As the anti-film that disperses, it can exemplify and be applied firmly made of hard conating is formed on the single side of base material film Film etc..Above-mentioned optical component can also contain ultraviolet absorbing agent.
Furthermore it is preferred that component that the second display body member of formation 22 is performance to be deteriorated by ultraviolet light irradiation or be with Active-energy can not be irradiated from adhering agent layer 11 of 22 side of the second display body member of formation to active energy ray-curable to penetrate The component of the structure of line.Specifically, it is preferable that the second display body member of formation 22 is to show module or comprising showing module Laminated body.
When first display body member of formation 21 is protection panels, printing layer 3 is usually in the first display body member of formation 21 11 ' side of adhering agent layer is formed as frame-shaped after solidification.
The material for constituting printing layer 3 is not particularly limited, and is able to use the well known materials of printing.The thickness of printing layer 3, That is the height of segment difference is usually 3~50 μm or so.If adhering agent layer 11 ' after the solidification, even if then to such printing layer 3 Can show sufficient tracing ability, and can not with bubble etc. is generated on the interface of printing layer 3.
As display body 2, such as liquid crystal (LCD) display, light emitting diode (LED) display, Organic Electricity can be enumerated Photoluminescence (organic EL) display, Electronic Paper etc. can also be touch panel.In addition, display body 2 can also be one for constituting them The component divided.
In order to manufacture above-mentioned display body 2, as an example, a stripping film 12a of adhesive sheet 1 is removed, will be adhered The presence that the adhering agent layer 11 that piece 1 exposes is fitted in the first display body member of formation 21 has on the face of side of printing layer 3.This When, since adhering agent layer 11 has excellent initial stage segment difference tracing ability, it is able to suppress attached in segment difference as caused by printing layer 3 Nearly the case where generating gap and floating.
Then, another stripping film 12b is removed from the adhering agent layer 11 of adhesive sheet 1, the adhesion that adhesive sheet 1 is exposed Oxidant layer 11 is bonded to obtain laminated body with the second display body member of formation 22.Furthermore, as another example it is sub, also change first The coating squence of display body member of formation 21 and the second display body member of formation 22.
After obtaining above-mentioned laminated body, through for ultraviolet-shielding type component display body member of formation, preferably penetrate first Display body member of formation 21 irradiates active energy beam to the adhering agent layer 11 in the laminated body.As noted previously, as making The active energy beam of the cured wavelength of adhering agent layer 11 penetrates the ultraviolet-shielding type component, therefore by irradiating the activity energy Ray is measured, the sufficiently solidification of adhering agent layer 11 is to become adhering agent layer 11 ' after solidification.It is excellent thereby, it is possible to obtain resistance to foaming Display body 2.
As described above, active energy beam used in present embodiment has in wavelength region of the wavelength greater than 365nm There is shining for substantive intensity.As the radiation source of such active energy beam, for example, preferably enumerate high-pressure sodium lamp, Metal halid lamp, xenon lamp etc..The exposure of the active energy beam, illumination are preferably 50~1000mW/cm2Left and right.In addition, Light quantity is preferably 50~10000mJ/cm2, more preferably 80~5000mJ/cm2, particularly preferably 200~2000mJ/cm2。
In above-mentioned display body 2, it is ultraviolet for being easy the active energy beam for the wavelength region for making sticker that xanthochromia occur The display body member of formation (the first display body member of formation 21) of line shielding component shields, therefore glues after being not easily accessible to solidification Oxidant layer 11 '.Thereby, it is possible to inhibit the xanthochromia of adhering agent layer 11 ' after solidifying.
In addition, the present invention also provides the composition body for constituting a part of above-mentioned display body (display body 2).This composition body has Following composition: a display body member of formation, another display body member of formation, by a display body member of formation and another Adhering agent layer after the solidification that display body member of formation mutually fits.Said one display body member of formation is with ultraviolet screener The ultraviolet-shielding type component of property.Another above-mentioned display body member of formation can penetrate for the ultraviolet light with ultraviolet light permeability Property component.
Adhering agent layer is solidified by the adhering agent layer of active energy ray-curable after above-mentioned solidification.It is preferred that the activity energy The adhering agent layer of ray-curable is measured as the adhering agent layer 11 of the adhesive sheet 1 of above embodiment, preferably penetrating is ultraviolet light The display body member of formation of shielding component irradiates active energy beam to the adhering agent layer 11, so that adhering agent layer 11 be made to become Adhering agent layer after the solidification of state is fully cured.
As an above-mentioned display body member of formation, such as preferably enumerates and have the modeling containing ultraviolet absorbing agent The protection panels of flitch.In addition, as another above-mentioned display body member of formation, such as glass plate or above-mentioned can be enumerated Various optical components etc..
The implementation described above be for easy understanding the present invention and record, rather than in order to limit the present invention And it records.Therefore, disclosed each element is also comprising belonging to the whole of technical scope of the invention in the above-described embodiment The objective of design alteration and equipollent.
For example, any one of stripping film 12a, 12b of adhesive sheet 1 can be omitted.In addition, the first display body member of formation 21 There can also be the segment difference in addition to printing layer 3, can also not have segment difference.Moreover, it is not only the first display body member of formation 21, the Two display body member of formation 22 can also have segment difference in 11 ' side of adhering agent layer after hardening.
Embodiment
Hereinafter, more specific description is carried out to the present invention by embodiment etc., but the scope of the present invention is not by these realities Apply the restriction of example etc..
[embodiment 1]
The preparation of (1. methyl) acrylate polymer (A)
By solution polymerization process, make 60 mass parts of 2-EHA, 5 mass parts of N- acryloyl morpholine, acrylic acid 15 mass parts of isobornyl thiocyanoacetate and the copolymerization of 20 mass parts of acrylic acid 2- hydroxy methacrylate, are prepared for (methyl) acrylate polymer (A).The molecular weight of (methyl) acrylate polymer (A) is determined using aftermentioned method, as a result, weight average molecular weight (Mw) It is 500,000.
2. the preparation of adherence composition
100 mass parts (the solid component scaled value of (methyl) acrylate polymer (A) obtained in above-mentioned operation 1； It is same as below), as crosslinking agent (B) trimethylolpropane modified toluene diisocyanate (TOYOCHEM CO., LTD manufacture, Name of product " BHS8515 ") 0.2 mass parts, the modified three-(2- of 6-caprolactone as active energy ray-curable ingredient (C) Acryloyl-oxyethyl) isocyanuric acid ester (SHIN-NAKAMURA CHEMICAL CO., LTD manufacture, name of product " A-9300- 1CL ") 7 mass parts, bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides (D1) 0.7 as Photoepolymerizationinitiater initiater (D) Mass parts, 3- glycidoxy-propyltrimethoxy silane (Shin-Etsu Chemical Co., Ltd. as silane coupling agent Manufacture, name of product " KBM-403 ") 0.28 mass parts are mixed and are sufficiently stirred, is diluted using methyl ethyl ketone, by This has obtained the coating solution of adherence composition.
Here, adherence when (methyl) acrylate polymer (A) to be set as to 100 mass parts (solid component scaled value) Each proportion (solid component scaled value) of composition is shown in table 1.In addition, the detailed following institute of ellipsis recorded in table 1 etc. Show.
[(methyl) acrylate polymer (A)]
2EHA: 2-EHA
BA: n-butyl acrylate
ACMO:N- acryloyl morpholine
IBXA: isobornyl acrylate
HEA: acrylic acid 2- hydroxy methacrylate
4HBA: acrylic acid 4- hydroxybutyl
AA: acrylic acid
[crosslinking agent (B)]
TDI: trimethylolpropane modified toluene diisocyanate (TOYOCHEM CO., LTD manufacture, name of product “BHS8515”)
Epoxies: bis- (N, N- 2-glycidyl aminomethyl) hexamethylene (the MITSUBISHI GAS CHEMICAL of 1,3- COMPANY, INC. manufacture, name of product " TC-5 ")
[Photoepolymerizationinitiater initiater (D)]
D1: bis- (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides
D2:2,4,6- trimethylbenzoy-dipheny-phosphine oxide
D3:1- hydroxycyclohexylphenylketone
3. the manufacture of adhesive sheet
Using knife type coater, the coating solution coating of the adherence composition obtained in above-mentioned operation 2 is being used Silicone remover re-releases type stripping film (Lintec to what the single side of polyethylene terephthalate film had carried out lift-off processing Corporation manufacture, name of product " SP-PET752150 ") lift-off processing face on after, is carried out at 90 DEG C 1 minute add Heat treatment, so as to form coating layer (thickness: 50 μm).By the coating layer for re-releasing type stripping film of obtained attached coating layer The face of side has carried out the light exfoliated of lift-off processing with using single side of the silicone remover to polyethylene terephthalate film The lift-off processing face paste of stripping film (Lintec Corporation manufacture, name of product " SP-PET381130 ") is closed, by 23 DEG C, cure 7 days under conditions of 50%RH, manufactured with re-releasing the adhesion of type stripping film/active energy ray-curable The adhesive sheet of oxidant layer (thickness: 50 μm)/light exfoliated stripping film composition.
In addition, the thickness of above-mentioned adhering agent layer is that (Teclock is public according to JIS K7130 and using level pressure thickness tester Department's manufacture, name of product " PG-02 ") and the value of measurement.
4. the manufacture of the adhesive sheet with covering material
Light exfoliated stripping film is removed from the adhesive sheet obtained in above-mentioned operation 3, the active-energy of exposing is penetrated The adhering agent layer of line curability be fitted in it is as covering material, by acrylate resin layers such as plexiglass layers The polycarbonate resin of plastic plate A made of being layered on polycarbonate resin plate (thickness: 0.7mm, containing ultraviolet absorbing agent) On the face of rouge plate side, the adhesive sheet with covering material has been obtained.Similarly, in addition, above-mentioned covering material is equivalent to ultraviolet light Shielding component.
[embodiment 2]
In addition to by Photoepolymerizationinitiater initiater (D) be changed to 2,4,6- trimethylbenzoy-dipheny-phosphine oxide (D2) with Outside, it is prepared for the coating solution of adherence composition in the same manner as example 1, using knife type coater by the adherence The coating solution coating of composition is removed using single side of the silicone remover to polyethylene terephthalate film The lift-off processing for re-releasing type stripping film (Lintec Corporation manufacture, name of product " SP-PET752150 ") of processing After on face, is heated 1 minute with 90 DEG C, so as to form coating layer (thickness: 50 μm), manufactured the stripping again with coating layer Release stripping film.
On the other hand, in addition to Photoepolymerizationinitiater initiater (D) is changed to 2,4,6- trimethylbenzoy-diphenies-oxidation Other than phosphine (D2), it is prepared for the coating solution of adherence composition in the same manner as example 1, it will using knife type coater The coating solution coating of the adherence composition using silicone remover to the single side of polyethylene terephthalate film into The light exfoliated stripping film (Lintec Corporation manufacture, name of product " SP-PET381130 ") of lift-off processing is gone After on lift-off processing face, is heated 1 minute with 90 DEG C, so as to form coating layer (thickness: 50 μm), manufactured 3 and had The light exfoliated stripping film of coating layer.
By the face of the coating surface side for re-releasing type stripping film with coating layer obtained in the above described manner and with above-mentioned side The face paste of the coating layer side for the stripping film in the light exfoliated stripping film with coating layer that formula obtains is closed, and is used It re-releases type stripping film and light exfoliated stripping film clamping thickness adds up to first layer stack made of 100 μm of coating layer.
Then, light exfoliated stripping film will be removed from above-mentioned first layer stack and the exposed surface of coating layer exposed with The face paste of the coating layer side for the stripping film in the light exfoliated stripping film with coating layer that aforesaid way obtains is closed, and is obtained Using re-releasing type stripping film and light exfoliated stripping film clamping thickness adds up to the second stacking made of 150 μm of coating layer Body.
Then, light exfoliated stripping film will be removed from above-mentioned second laminated body and the exposed surface of coating layer exposed with The face paste of the coating layer side for the stripping film in the light exfoliated stripping film with coating layer that aforesaid way obtains is closed, and is obtained Using re-releasing type stripping film and light exfoliated stripping film clamping thickness adds up to third made of 200 μm of coating layer and is laminated Body.
By curing 7 days above-mentioned third laminated body under conditions of 23 DEG C, 50%RH, having manufactured, there is the type that re-releases to shell Adhesive sheet from piece/active energy ray-curable adhering agent layer (thickness: 200 μm)/light exfoliated stripping film composition.
Light exfoliated stripping film is removed from above-mentioned obtained adhesive sheet, by the active energy ray-curable of exposing Adhering agent layer be fitted in it is as covering material, the acrylate resin layers such as plexiglass layer are layered in it is poly- The polycarbonate resin plate side of plastic plate A made of on carbonate resin plate (thickness: 0.7mm, containing ultraviolet absorbing agent) On face, the adhesive sheet with covering material has been obtained.In addition, above-mentioned covering material is equivalent to ultraviolet-shielding type component.
[embodiment 3~9]
In addition to the type of each monomer of (methyl) acrylate polymer (A) and the type of ratio, crosslinking agent (B) will be constituted And other than the type and blended amount of blended amount and Photoepolymerizationinitiater initiater (D) are changed to shown in table 1, with same as Example 1 Mode has manufactured adhesive sheet and the adhesive sheet with covering material.
[embodiment 10]
In addition to being changed to covering material by plexiglass layer stackup on polycarbonate resin plate and At plastic plate B (thickness: 2mm, containing ultraviolet absorbing agent) other than, manufactured adhesive sheet in the same manner as example 1 And the adhesive sheet with covering material.
[embodiment 11]
In addition to being changed to covering material by plexiglass layer stackup on polycarbonate resin plate and At plastic plate B (thickness: 2mm, containing ultraviolet absorbing agent) other than, manufactured adhesive sheet in the same way as in example 2 And the adhesive sheet with covering material.
[embodiment 12~16]
In addition to being changed to covering material by plexiglass layer stackup on polycarbonate resin plate and At plastic plate B (thickness: 2mm, containing ultraviolet absorbing agent) and will constitute (methyl) acrylate polymer (A) each list The type and ratio of body, the type of crosslinking agent (B) and blended amount and the change of the type and blended amount of Photoepolymerizationinitiater initiater (D) Other than shown in table 1, adhesive sheet and the adhesive sheet with covering material have been manufactured in the same manner as example 1.
[comparative example 1]
Other than Photoepolymerizationinitiater initiater (D) is changed to 1- hydroxycyclohexylphenylketone (D3), with same as Example 2 Mode manufactured adhesive sheet.
Light exfoliated stripping film is removed from obtained adhesive sheet, by the viscous of the active energy ray-curable of exposing Oxidant layer be fitted in soda-lime glass plate (KAWAMURA KYUZO SHOTEN Co., Ltd manufacture, ProductName as covering material : 1.1mm is claimed " soda-lime glass ", thickness not contain ultraviolet absorbing agent) on, obtain the adhesive sheet with covering material.Separately Outside, above-mentioned covering material is not equivalent to ultraviolet-shielding type component.
[comparative example 2~5]
In addition to the type of each monomer of (methyl) acrylate polymer (A) and the type of ratio, crosslinking agent (B) will be constituted And other than the type and blended amount of blended amount and Photoepolymerizationinitiater initiater (D) are changed to shown in table 1, with same as Example 1 Mode has manufactured adhesive sheet and the adhesive sheet with covering material.
[comparative example 6~9]
In addition to the type of each monomer of (methyl) acrylate polymer (A) and the type of ratio, crosslinking agent (B) will be constituted And other than the type of blended amount, the type of Photoepolymerizationinitiater initiater (D) and blended amount and covering material is changed to shown in table 1, with Mode same as Example 1 has manufactured adhesive sheet and the adhesive sheet with covering material.
Here, above-mentioned weight average molecular weight (Mw) is using gel permeation chromatography (GPC), under the following conditions measures The weight average molecular weight of the polystyrene conversion of (GPC measurement).
<determination condition>
GPC measurement device: TOSOH CORPORATION manufacture, HLC-8020
■ GPC chromatographic column (passes through) according to sequence below: TOSOH CORPORATION manufacture
TSK guard column HXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
■ measures solvent: tetrahydrofuran
■ measuring temperature: 40 DEG C
[test example 1] (measurement of light transmittance)
It uses haze meter (NIPPON DENSHOKU INDUSTRIES Co., LTD manufacture, name of product " NDH5000 ") And the light transmittance (%) of covering material used in Examples and Comparative Examples is determined according to JIS K7361-1:1997.By wavelength The measurement result of the light transmittance of the light transmittance and wavelength 390nm of 340nm is shown in table 1.
[test example 2] (measurement of absorbance)
The acetonitrile solution for preparing the 0.1 mass % of concentration of the Photoepolymerizationinitiater initiater used in Examples and Comparative Examples, makes With UV, visible light near-infrared (UV-Vis-NIR) spectrophotometer, (Shimadzu Corporation is manufactured, name of product " UV- 3600 ") absorbance of the range of 200~500nm of wavelength in the solution, is determined.Wavelength is derived based on its result The very big wavelength of absorption (nm) in the absorbance of 200~500nm of absorbance and wavelength of 390nm.Show the result in table 1.
[test example 3] (measurement of gel fraction)
Polyester net will be utilized in size of the adhesive sheet severing obtained in Examples and Comparative Examples as 80mm × 80mm Shape object (mesh size 200) wraps up the adhering agent layer of the active energy ray-curable, weighs its quality using precision balance, and The individual quality of above-mentioned mesh is subtracted by it, has thus calculated the quality of sticker itself.Quality at this time is denoted as M1.
Then, by the sticker wrapped up by above-mentioned polyester mesh at room temperature (23 DEG C), impregnate in ethyl acetate 72 hours.Then sticker is taken out and is air-dried 24 hours in the environment of 23 DEG C of temperature, relative humidity 50%, is further existed It has been dried in 80 DEG C of baking oven 12 hours.After drying, its quality is weighed using precision balance, it is independent to subtract above-mentioned mesh by it Quality, thus calculated the quality of sticker itself.Quality at this time is denoted as M2.Gel is indicated with (M2/M1) × 100 Divide rate (%).It is derived gel fraction (the active energy beam photograph of sticker (active energy ray-curable sticker) as a result, Before penetrating).Show the result in table 2.
On the other hand, to the adhesive sheet for having covering material obtained in Examples and Comparative Examples, simultaneously through covering material Active energy beam is irradiated with following conditions, the adhering agent layer of active energy ray-curable is made to solidify to glue after becoming solidification Oxidant layer.It is derived the gel point of the sticker (sticker after solidification) of adhering agent layer after the solidification in the same manner as described above Rate (after active energy beam irradiation).In addition, having calculated the gel fraction after being irradiated by active energy beam subtracts active energy Value (variable quantity obtained from gel fraction before measuring radiation exposure；Percentage point).Show the result in table 2.
<active energy beam irradiation condition>
■ uses high-pressure sodium lamp
■ illumination 200mW/cm2, light quantity 1000mJ/cm2
■ illumination quantometer is using EYE GRAPHICS CO., " UVPF-A1 " of LTD. manufacture
[test example 4] (measurement of haze value)
With active energy beam irradiation condition identical with test example 2, through covering material in Examples and Comparative Examples The obtained adhesive sheet irradiation active energy beam with covering material, makes adhering agent layer solidification to become sticker after solidification Layer.Haze meter (NIPPON DENSHOKU is used according to JIS K7136:2000 to adhering agent layer after the solidification INDUSTRIES Co., LTD manufacture, name of product " NDH-2000 ") determine haze value (%).Show the result in table 2.
[test example 5] (measurement of adhesion strength)
Light exfoliated stripping film is removed on the adhesive sheet obtained in the Examples and Comparative Examples, by the adhering agent layer of exposing It is fitted in polyethylene terephthalate (PET) film (TOYOBO CO., LTD. manufacture, name of product with easy adhesive layer " PET A4300 ", thickness: 100 μm) easy adhesive layer on, obtained re-releasing type stripping film/active energy ray-curable Adhering agent layer/PET film laminated body.Obtained laminated body severing is become into 25mm wide, 100mm long.
In the environment of 23 DEG C, 50%RH, type stripping film will be re-released and removed from above-mentioned laminated body, by the adhesion of exposing Oxidant layer is fitted in soda-lime glass (Nippon Sheet Glass Co Ltd's manufacture), the pressure manufactured using KURIHARA CORPORATION Hot device has pressurizeed 20 minutes at 0.5MPa, 50 DEG C.Then, make PET film facing towards upside, by as covering material, will gather Plastic plate A made of the acrylate resin layers such as polymethyl methacrylate resin layer are layered on polycarbonate resin plate (thickness: 0.7mm, containing ultraviolet absorbing agent) mounting is on a pet film.Then, item is irradiated with active energy beam identical with test example 2 Part irradiates active energy beam to active energy ray-curable adhering agent layer through the covering material and PET film, makes sticker Layer solidification is to become adhering agent layer after solidification.After being placed 24 hours under conditions of 23 DEG C, 50%RH, covering material is removed And to the sample with adhering agent layer after the solidification, using cupping machine (ORIENTEC Co., LTD manufacture, TENSILON), With peeling rate 300mm/min, the condition of peel angle 180 degree, adhesion strength (N/25mm) is determined.In addition to being recorded in this item Condition other than part is determined according to JIS Z0237:2009.Show the result in table 2.
[test example 6] (transmission form and aspect b*Measurement)
Type stripping film will be re-released to remove on the adhesive sheet obtained in the Examples and Comparative Examples with covering material, it will The adhering agent layer of the active energy ray-curable of exposing is fitted in soda-lime glass (manufacture of Japanese plate glass company, thickness On 1.1mm).Then, autoclave processing in 20 minutes is carried out under conditions of 50 DEG C, 0.5MPa and in normal pressure, 23 DEG C, 50%RH Under placed 24 hours.
Then, with active energy beam irradiation condition identical with test example 2, through covering material to active energy beam The adhering agent layer of curability irradiates active energy beam, makes adhering agent layer solidification to become adhering agent layer after solidification.It is solid to this Adhering agent layer after change, using survey simultaneously light beam splitting type colorimeter (NIPPON DENSHOKU INDUSTRIES Co., LTD manufacture, Name of product " SQ2000 "), it determines according to CIE1976L*a*b*Form and aspect b is transmitted as defined in color specification system*0(initial stage).Result is shown In table 2.
Then, the adhering agent layer of active energy ray-curable is had become adhering agent layer after solidifying with covering material Adhesive sheet investment light fastness test machine (Suga Test Instruments Co., Ltd. manufacture, " ultraviolet light takes off name of product Color tester (fade-meter) U48 ", light source: carbon arc lamp) in, 1000 hours active-energies have been irradiated from covering material side Ray (illumination: 350mW/cm2) (Light Resistance Test).Then, it to adhering agent layer after solidification, determines in the same manner as described above Transmit form and aspect b*1(after Light Resistance Test).Further, the b that initial stage is subtracted by the b*1 after Light Resistance Test has been calculated*0Obtained from It is worth Δ b*(variable quantity).Show the result in table 2.
[test example 7] (evaluation of resistance to foaming)
Type stripping film will be re-released to remove on the adhesive sheet obtained in the Examples and Comparative Examples with covering material, it will The adhering agent layer of the active energy ray-curable of exposing is attached to soda-lime glass (manufacture of Japanese plate glass company, thickness On 1.1mm).Then, autoclave processing in 20 minutes is carried out under conditions of 50 DEG C, 0.5MPa and in normal pressure, 23 DEG C, 50%RH Under placed 24 hours.
Then, with active energy beam irradiation condition identical with test example 2, through covering material to active energy beam The adhering agent layer of curability irradiates active energy beam, makes adhering agent layer solidification to become adhering agent layer after solidification.Then, will Obtained laminated body has been taken care of 1000 hours under the conditions of 85 DEG C, the high temperature and humidity of 85%RH.Then, confirmation is solid by visual observation The state at the interface of adhering agent layer and adherend after change, according to benchmark evaluation below resistance to foaming.Show the result in table 2.
◎ ... bubble-free floats peeling.
Zero ... generates 2 or bubble of 1 diameter less than 1mm, but nothing floats peeling.
△ ... generates the bubble that 3 or more 9 or less diameters are less than 1mm, but nothing floats peeling
× ... it produces bubble, float peeling.
[table 2]
As shown in Table 2, Huang is less likely to occur adhering agent layer after the solidification formed using adhesive sheet obtained in embodiment Become, and resistance to foaming is also excellent.
Industrial applicibility
Adhesive sheet of the invention is applicable to protection panels and display body structure in the display body of such as auto-navigation system At the fitting of component, the protection panels are made of the plastic plate containing ultraviolet absorbing agent.

Claims (10)

1. a kind of adhesive sheet has the adhesion for being bonded a display body member of formation and another display body member of formation Oxidant layer, which is characterized in that
At least one of one display body member of formation and another display body member of formation are wavelength 340nm's The ultraviolet-shielding type component that light transmittance is 5% or less and the light transmittance of wavelength 390nm is 10% or more,
The adhering agent layer is 0.3 or more by the absorbance containing the wavelength 390nm in the acetonitrile solution of 0.1 mass % of concentration Photoepolymerizationinitiater initiater active energy ray-curable sticker constitute.
2. adhesive sheet according to claim 1, which is characterized in that the sticker is by containing (methyl) acrylic ester polymerization Object (A), crosslinking agent (B), active energy ray-curable ingredient (C) and the Photoepolymerizationinitiater initiater (D) adherence composition And it obtains, and to be crosslinked each other via made of the crosslinking agent (B) crosslinking containing (methyl) acrylate polymer (A) The active energy beam of structure, the unreacted active energy ray-curable ingredient (C) and the Photoepolymerizationinitiater initiater (D) The sticker of curability.
3. adhesive sheet according to claim 1, which is characterized in that (methyl) acrylate polymer (A) contains 5 matter 60 mass % of % or more the monomer with hydroxyl in the molecule below is measured as the monomer for constituting the polymer.
4. adhesive sheet according to claim 1, which is characterized in that relative to (methyl) acrylate polymer (A) 100 mass parts, the content of the crosslinking agent (B) in the adherence composition be 0.01 mass parts or more 3 below the mass.
5. adhesive sheet according to claim 1, which is characterized in that the sticker of the active energy ray-curable coagulates Glue divides rate to be 30% or more 70% or less.
6. adhesive sheet according to claim 1, which is characterized in that the ultraviolet-shielding type component is plastic plate.
7. adhesive sheet according to claim 1, which is characterized in that have 2 stripping films and with 2 stripping films Removing face contact the adhering agent layer that is clamped by the stripping film of mode.
8. a kind of display body has a display body member of formation, another display body member of formation and one will show Adhering agent layer after showing body member of formation and solidification that another described display body member of formation mutually fits, which is characterized in that
At least one of one display body member of formation and another display body member of formation are by wavelength 340nm's The ultraviolet-shielding type component that light transmittance is 5% or less and the light transmittance of wavelength 390nm is 10% or more is constituted,
Adhering agent layer is to carry out the adhering agent layer of adhesive sheet described in any one of claims 1 to 7 after the solidification Adhering agent layer after solidifying made of active energy ray-curable.
9. display body according to claim 8, which is characterized in that constitute the solidifying of the sticker of adhering agent layer after the solidification Glue divides rate to be 40% or more 95% or less.
10. a kind of manufacturing method of display body, which is characterized in that
At least one is that the light transmittance of wavelength 340nm is 5% or less and the light transmittance of wavelength 390nm is 10% or more by manufacture A display body member of formation and another display body member of formation for ultraviolet-shielding type component is via in claim 1 to 7 Laminated body made of the adhering agent layer fitting of described in any item adhesive sheets,
Active energy beam is irradiated through the adhering agent layer of the ultraviolet-shielding type component to the laminated body, is made described Adhering agent layer solidification, thus adhering agent layer after being solidified.
CN201810868558.XA 2017-08-30 2018-08-02 The manufacturing method of adhesive sheet, display body and display body Pending CN109423228A (en)

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