CN106967380A - No-solvent type adherence composition, sticker, adhesive sheet and display body - Google Patents

No-solvent type adherence composition, sticker, adhesive sheet and display body Download PDF

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Publication number
CN106967380A
CN106967380A CN201610956187.1A CN201610956187A CN106967380A CN 106967380 A CN106967380 A CN 106967380A CN 201610956187 A CN201610956187 A CN 201610956187A CN 106967380 A CN106967380 A CN 106967380A
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China
Prior art keywords
methyl
solvent type
display body
composition
sticker
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CN201610956187.1A
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CN106967380B (en
Inventor
吉延毅朗
小泽祐树
荒井隆行
所司悟
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Lintec Corp
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Lintec Corp
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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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/13338—Input devices, e.g. touch panels
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/0412—Digitisers structurally integrated in a display
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/40—OLEDs integrated with touch screens
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Human Computer Interaction (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)

Abstract

Present invention offer is a kind of can to play no-solvent type adherence composition, sticker, adhesive sheet and the display body of excellent resistance to foaming.The no-solvent type adherence composition that the present invention is provided is characterised by, is contained：Selected from least one of polymerizable vinyl monomer, polymerizable vinyl prepolymer, multifunctional (methyl) acrylate monomer and multifunctional (methyl) acrylate oligomer polymeric composition；And organoalkoxysilane, with straight chain structure, and in its two end there is at least a portion in alkoxysilyl, the polymeric composition to contain active hydrogen-based.

Description

No-solvent type adherence composition, sticker, adhesive sheet and display body
Technical field
No-solvent type adherence composition, the sticker of the display bodies such as touch panel can be used in the present invention relates to a kind of And adhesive sheet and use their display body.
Background technology
In recent years, the various electronic apparatus such as smart mobile phone and flat board computer terminal, possess with liquid crystal cell, light Diode (LED element), organic electroluminescent (organic EL) element etc., use display module display, most cases Under, the display is touch panel.
In display described above, the face side of display module is generally provided with protection panels.Here, in protection Space is provided between panel and display module, in case when protection panels are deformed because of external force, the protection panels of deformation are with showing Show that module is collided.
If however, be air layer in the presence of space as described above, by protection panels and air layer refringence and The reflection loss of air layer and the light caused by the refringence of display module is big, and have that the image quality of display declines asks Topic.It is thus proposed that the space between protection panels and display module is filled up by using adhering agent layer, so as to carry The image quality of high display.
On the other hand, slimming, lightweight with electronic equipment, are investigated above-mentioned protection panels by conventional glass Glass plate is changed to the plastic plates such as acrylic panel or polycarbonate plate.Here, filling up protection panels and display with adhering agent layer In the mode in the space between module, when protection panels are changed into plastic plate, occur under the conditions of hot and humid from plastics Plate produce gas leakage and produce bubble, float, peel off etc. foaming it is new the problem of.Therefore, to filling up display module and protection face Sticker between plate etc., requires resistance to foaming mostly.
As the example of the adhesion agent composition for forming above-mentioned adhering agent layer, contain Patent Document 1 discloses one kind There is the adhesion agent composition for touch panel of epoxies silane coupler.In addition, in patent document 2, as mainly using In the adhesion agent composition of the panel display board such as plasma display and liquid crystal display, disclose one kind and contain The adhesion agent composition of the silane coupler of (methyl) acryloxy.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2013-544931 publications
Patent document 2：Japanese Unexamined Patent Publication 2014-133812 publications
The content of the invention
The technical problem to be solved in the present invention
Here, in the adhesion agent composition containing epoxies silane coupler as disclosed in patent document 1, in order to Coupled action is effectively played, the ring-opening reaction for effectively carrying out epoxy radicals is extremely important.Therefore, it is however generally that, sticker group Compound contains monomer or polymer with acidic groups.But, for the sticker for touch panel, in order to do not become by The nesa coating of viscous thing deteriorates and requires anacidity.Therefore, in the adhesion agent composition as disclosed in patent document 1, nothing Method fully obtains the effect of epoxies coupling agent while meeting anacidity.As a result, resulting sticker is to the close of adherend Raising effect with joint efforts becomes insufficient.Accordingly, it is difficult to obtained as the adhesion agent composition disclosed in patent document 1 anacidity and The sticker of sufficient resistance to foaming can be played.
In addition, in patent document 2, as the specific example of the silane coupler containing (methyl) acryloxy, can enumerate Going out has (methyl) acryloxy an end and has in another end a compound (patent of alkoxysilyl 0038 section of document 2).In adhesion agent composition disclosed in patent document 2 in addition to the coupling agent, also containing (methyl) Acrylic polymer and (methyl) acrylic ester monomer.When solidifying the adhesion agent composition, the coupling agent is inferred (methyl) acryloxy also assist in Raolical polymerizable between these polymer and monomer, as a result, the coupling agent with The state being homogeneously dispersed in sticker is mixed into.Therefore, infer in the adhesion agent composition disclosed in patent document 2, should Silane coupler is present in the near surface of adhering agent layer and can not be improved the effect of closing force.As a result, by patent The sticker that adhesion agent composition disclosed in document 2 is obtained can not play sufficient resistance to foaming.
The present invention is that in view of this kind of actual conditions and complete winner, its purpose a kind of can play excellent resistant blister to provide No-solvent type adherence composition, sticker, adhesive sheet and the display body of property.
Solve the technological means of technical problem
To achieve these goals, first, the present invention provides a kind of no-solvent type adherence composition, it is characterised in that Contain：Selected from polymerizable vinyl monomer, polymerizable vinyl prepolymer, multifunctional (methyl) acrylate monomer and multifunctional At least one of (methyl) acrylate oligomer polymeric composition；And organoalkoxysilane, with straight chain structure, and Its two end has alkoxysilyl, and at least a portion of the polymeric composition contains active hydrogen-based (invention 1).
The no-solvent type adherence composition of deduction foregoing invention (invention 1) is in solidification except polymeric composition is mutual certainly Beyond base polymerisation, the hydrolysis-condensation reaction between polymeric composition and organoalkoxysilane is also produced.It is somebody's turn to do in addition, inferring Hydrolysis-condensation reaction occurs mainly in the near surface of adhering agent layer, so that organoalkoxysilane is present in the table of adhering agent layer Ratio near face increases.Thus, the cohesive force of the adhering agent layer obtained by the adhesion agent composition is excellent, while to adherend Excellent adhesion.As a result, the sticker can play excellent resistance to foaming.
In foregoing invention (invention 1), preferably described active hydrogen-based is hydroxyl (invention 2).
In foregoing invention (invention 1,2), preferably described no-solvent type adherence composition at least contains the polymerism second Alkenyl monomer and multifunctional (methyl) the acrylate oligomer are used as the polymeric composition (invention 3).
In foregoing invention (invention 1~3), preferably described no-solvent type adherence composition also contains Photoepolymerizationinitiater initiater (invention 4).
In foregoing invention (invention 1~4), preferably with respect to the polymeric composition of 100 mass parts, the no-solvent type glues The content of the organoalkoxysilane in the property composition is more than 0.01 mass parts and is (invention below 20 mass parts 5)。
Second, the present invention provides a kind of sticker, and it is by by the no-solvent type adherence composition (invention 1~5) Solidification is formed (invention 6).
In foregoing invention (invention 6), the gel fraction of preferably described sticker is more than 50% and is less than 100% (hair It is bright 7).
3rd, the present invention provides a kind of adhesive sheet, and it has the adhering agent layer formed by the sticker (invention 6,7) (invention 8).
In foregoing invention (invention 8), preferably described adhesive sheet possesses two panels stripping film, and the adhering agent layer is with described two The mode of the release surface contact of piece stripping film is clamped (invention 9) by the stripping film.
3rd, the present invention provides a kind of display body, and it possesses：One display body component parts, at least face in side to be fit With segment difference；Another display body component parts；And adhering agent layer, the display body component parts bonded to each other and described another Display body component parts, the display body is characterised by that the adhering agent layer is the sticker of the adhesive sheet (invention 8,9) Layer.
Invention effect
No-solvent type adherence composition, sticker, adhesive sheet and the display body of the present invention can play excellent resistance to Bubble property.
Brief description of the drawings
Fig. 1 is the sectional view of the adhesive sheet of one embodiment of the present invention.
Fig. 2 is the sectional view of the layered product of one embodiment of the present invention.
Description of reference numerals
1：Adhesive sheet；11：Adhering agent layer；12a、12b：Stripping film；2：Display body；21：First display body component parts； 22：Second display body component parts；3：Printing layer
Embodiment
Hereinafter, embodiments of the present invention are illustrated.
(no-solvent type adherence composition)
The no-solvent type adherence composition of present embodiment (below, is sometimes referred to as " no-solvent type adherence composition P”.) contain：Selected from polymerizable vinyl monomer, polymerizable vinyl prepolymer, multifunctional (methyl) acrylate monomer and many At least one of function (methyl) acrylate oligomer polymeric composition；And organoalkoxysilane, with straight chain structure, And there is alkoxysilyl in its two end.Here, at least a portion in above-mentioned polymeric composition contains active hydrogen-based.Separately Outside, in this specification, (methyl) acrylate refers to both acrylate and methacrylate.Other similar terms also phase Together.
In the no-solvent type adherence composition P for inferring present embodiment, polymeric composition is carried out in solidification mutual certainly By base polymerisation, while the alkoxy first silicon having in the active hydrogen-based that polymeric composition has with organoalkoxysilane Condensation reaction is hydrolyzed between alkyl.The hydrolysis-condensation reaction is more slowly carried out than the Raolical polymerizable, therefore is pushed away After the disconnected Raolical polymerizable is carried out to a certain extent, occurs hydrolysis-condensation reaction.Therefore, the organic alkoxy is inferred The ratio that silane is present in the near surface of adhering agent layer increases.Moreover, the hydrolysis-condensation reaction is being present in organic alkoxy Occur in the alkoxysilyl of two ends of silane, therefore form what organoalkoxysilane was crosslinked between polymeric composition Structure.It is in the mode different from carrying out structure formed by Raolical polymerizable each other by polymeric composition to infer the structure Strengthen sticker, effectively improve cohesive force, therefore resulting sticker has very high cohesive force.Result table above Bright, the cohesive force by the obtained adhering agent layers of the no-solvent type adherence composition P of present embodiment is excellent, while to adherend Excellent adhesion.
Adhered obtained from can be seen that the no-solvent type adherence composition P using present embodiment from above content Agent can play excellent resistance to foaming.For example, showing using obtained from the no-solvent type adherence composition P of present embodiment Show device, though be positioned over it is hot and humid under the conditions of constituted (for example, 85 DEG C, 85%RH) from the display body formed by plastic plate etc. When part produces exhaust, it can also suppress the interface between adhering agent layer and display body component parts and produce bubble, float, peel off Deng foaming.
In addition, above-mentioned reaction or the knot that is formed when solidifying the no-solvent type adherence composition P of present embodiment Structure is to infer, can also occur other reactions or form other structures.For example, the alkane of two ends of organoalkoxysilane Epoxide silicyl need not must with active hydrogen-based key, the alkoxysilyl of an end can also unreacted and it is residual Stay.Alternatively, it is also possible to be organoalkoxysilane occur hydrolysis-condensation reaction each other and formed organoalkoxysilane repeat knot On the basis of structure, the active hydrogen-based bond of the alkoxysilyl and polymeric composition of its two end or an end.And then, it is organic Alkoxy silane not only may reside in the near surface of adhering agent layer, be also present in inside.
(1) polymeric composition
The no-solvent type adherence composition P of present embodiment contains selected from polymerizable vinyl monomer, polymerization sex ethylene At least one of based prepolymers, multifunctional (methyl) acrylate monomer and multifunctional (methyl) acrylate oligomer polymerize Composition.
In the no-solvent type adherence composition P of present embodiment, the active hydrogen of at least a portion in polymeric composition Base.The active hydrogen-based is preferably at least one in hydroxyl and carboxyl, is contracted from Raolical polymerizable as described above with hydrolysis The viewpoint that the speed difference of conjunction reaction becomes the near surface for clearly and easily making organoalkoxysilane be present in adhering agent layer is examined Consider, particularly preferably hydroxyl.In general, if touch panel etc. is positioned under hot and humid environment, moisture immersion is adhered In oxidant layer, when touch panel etc. reverts to normal temperature, adhering agent layer is possible to albefaction and occurs the " damp and hot white of transparency decline Change " the problem of.Here, by making polymeric composition contain above-mentioned active hydrogen-based, so that the group is present in resulting sticker In.Intermiscibility between the group and the moisture of immersion is good, therefore as a result, can suppress the albefaction of adhering agent layer, adheres Agent turns into the excellent sticker of wet-heat resisting albefaction.
In above-mentioned 4 kinds, polymeric composition preferably at least contains polymerizable vinyl monomer and multifunctional (methyl) acrylic acid Ester oligomer.These compounds are contained by polymeric composition, the cohesive force of resulting sticker is improved, and can be obtained resistance to The more excellent sticker of foaming characteristic.
(1-1) polymerizable vinyl monomer
, can be appropriate as long as with the group containing vinyl, being then not particularly limited as polymerizable vinyl monomer Use known polymerizable vinyl monomer.In addition, the polymerizable vinyl monomer in present embodiment refers to, with one The polymerizable vinyl monomer of the individual group containing vinyl, is not repeated with multifunctional (methyl) acrylate monomer described later.
As the specific example of polymerizable vinyl monomer, (methyl) methyl acrylate, (methyl) acrylic acid can be included Ethyl ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (first Base) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid tetradecane base ester, (methyl) aliphatic acrylate, (methyl) third Olefin(e) acid stearyl, (methyl) lauryl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid phenoxy group second Ester, (methyl) benzyl acrylate, polyoxyalkylene-modified (methyl) acrylate etc. do not have in intramolecular removes the base containing vinyl (methyl) acrylate of functional group beyond group.Wherein, 2-EHA or isobornyl acrylate are preferably used.
In addition, polymerizable vinyl monomer can also also have the function in addition to the group containing vinyl in intramolecular The polymerizable vinyl monomer of group.As the example of the functional group, above-mentioned active hydrogen-based, i.e. hydroxyl, carboxyl, mercaptan can be included Base and primary amino radical or secondary amino group etc..As the specific example of the polymerizable vinyl monomer with this kind of functional group, it can include (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) third (methyl) the acrylic acid hydroxyls such as olefin(e) acid 2- hydroxybutyls, (methyl) acrylic acid 3- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls Base Arrcostab；The acrylic amide of the hydroxyls such as N hydroxymethyl acrylamide, N- methylol methacrylamides；Acrylic acid, first Ethene unsaturated carboxylic acid such as base acrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid etc..Wherein, acrylic acid is preferably used 2- hydroxy methacrylates.
In addition, as other polymerizable vinyl monomers, the vinyl acetates such as vinyl acetate, propionate can be included Class；The olefines such as ethene, propylene, isobutene；The halogenated alkenes hydro carbons such as vinyl chloride, vinylidene chloride；Styrene, α-methylstyrene Deng styrene monomer；The diene-based monomers such as butadiene, isoprene, chlorobutadiene；The nitrile list such as acrylonitrile, methacrylonitrile Body；Acrylamide, Methacrylamide, N methacrylamide, N- methyl methacrylamides, N, N- dimethyl (methyl) third Acrylamide, N, the amide-type monomer such as N- diethyl (methyl) acrylamide, NVP；(methyl) acrylic acid N, N- Monomers of tertiary-amino-containing such as lignocaine ethyl ester, N- (methyl) acryloyl morpholine etc..
(1-2) polymerizable vinyl prepolymer
As polymerizable vinyl prepolymer, it is not particularly limited, can suitably uses known polymerism second Alkenyl prepolymer, but preferably use the polymerizable vinyl prepolymer that above-mentioned polymerizable vinyl monomer is polymerized.In addition, In this specification, prepolymer refers to the compound that monomer is polymerized, and refers to constitute by further being polymerize and gathers The compound of compound.
, can be with addition, when by the way that above-mentioned polymerizable vinyl monomer is polymerize when obtaining polymerizable vinyl prepolymer One kind in the monomer is polymerized alone, can also be by a variety of copolymerization.
In addition, polymerizable vinyl prepolymer can be obtained by radical polymerization, can also be by living polymerization Obtain, it is particularly possible to remain reversible addion-fragmentation chain transfer polymerization (RAFT, Reversible Addition- Fragmentation Chain Transfer Polymerization) end polymer.
The weight average molecular weight of polymerizable vinyl prepolymer is preferably 6, more than 000, particularly preferably 7, more than 500, is entered One step is preferably more than 10,000.In addition, the weight average molecular weight is preferably 1, less than 500,000, particularly preferably 1,000,000 Hereinafter, more preferably 100, less than 000.By the weight average molecular weight within the above range, easily solvent-free property is adhered Property composition P viscosity be desired scope.In addition, the weight average molecular weight in this specification is by gel permeation chromatography (GPC) value for being converted into polystyrene standard that method is determined.
(1-3) multifunctional (methyl) acrylate monomer
As multifunctional (methyl) acrylate monomer, it is not particularly limited, can be suitably using known many Function (methyl) acrylate monomer.
Especially, as multifunctional (methyl) acrylate monomer, can preferably include has two in a molecule The monomer of (methyl) acryloyl group above.As the example of this kind of monomer, BDO two (methyl) propylene can be included Acid esters, 1,6-HD two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyethylene glycol two (methyl) propylene Acid esters, neopentyl glycol adipic acid two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) acrylate, two rings penta Base two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, ethylene-oxide-modified di(2-ethylhexyl)phosphate (first Base) acrylate, two (acrylyl oxy-ethyl) isocyanuric acid esters, allylation cyclohexyl two (methyl) acrylate, three hydroxyl first Base propane three (methyl) acrylate, dipentaerythritol three (methyl) acrylate, propionic acid are modified dipentaerythritol three (methyl) Acrylate, pentaerythrite three (methyl) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, three (acrylyl oxy-ethyl) isocyanuric acid ester, double (acrylyl oxy-ethyl) hydroxyethyl isocyanuric acid esters, isocyanuric acid oxirane It is different that the ethylene-oxide-modified triacrylate of modified diacrylate, isocyanuric acid, 6-caprolactone are modified three (acrylyl oxy-ethyls) Cyanurate, two glycerine four (methyl) acrylate, pentaerythrite four (methyl) acrylate, propionic acid are modified dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylic acid Ester etc..
(1-4) multifunctional (methyl) acrylate oligomer
As multifunctional (methyl) acrylate oligomer, it is not particularly limited, can be suitably using known Multifunctional (methyl) acrylate oligomer, but be preferably used in a molecule with more than two (methyl) acryloyl groups Multifunctional (methyl) acrylate oligomer.As the example of this kind of oligomer, urethane acrylate class can be included, gathered Ester esters of acrylic acid, Epoxy Acrylates, polyoxyalkylene acrylate esters, polybutadiene acrylic acid esters, silicon acrylate Deng oligomer.
Urethane acrylate class oligomer for example can be by utilizing (methyl) acrylic acid or (first by polyurethane oligomer Base) acrylic acid derivative is esterified and obtained, wherein the polyurethane oligomer passes through polyalkylene polyol, polyether polyols The compounds such as alcohol, PEPA, the hydrogenated isoprene with C-terminal, hydrogenated butadiene with C-terminal with it is poly- The reaction of isocyanates and obtain.
Here, the example of the polyalkylene polyol used in manufacture as urethane acrylate class oligomer, Polypropylene glycol, polyethylene glycol, polytetramethylene glycol, poly- hexylene glycol etc. can be included, preferred polypropylene glycol is used.In addition, working as gained To the number of functional groups of urethane acrylate class oligomer be set to more than three when, appropriately combined glycerine, trihydroxy methyl third Alkane, triethanolamine, pentaerythrite, ethylenediamine, diethylenetriamine, D-sorbite, sucrose etc..
In addition, as the example of PIC, hexamethylene diisocyanate, the isocyanic acid of trimethylene two can be included The aliphatic diisocyanates such as ester；The aromatic series such as toluene di-isocyanate(TDI), XDI, diphenyl diisocyanate Diisocyanate；Ester ring type diisocyanate such as dicyclohexyl methyl hydride diisocyanate, IPDI etc., its In, aliphatic diisocyanate is preferably used, particularly preferably using hexamethylene diisocyanate.In addition, PIC is simultaneously The PIC of two functions is not limited to, PIC more than trifunctional can also be used.
In addition, as (methyl) acrylic acid derivative, acrylic acid 2- hydroxy methacrylates, acrylic acid 4- hydroxybutyls can be included Deng (methyl) hydroxyalkyl acrylates, 2- isocyanates ethyl acrylate, 2- isocyanatomethyls ethyl acrylate, 1,1- is double (acryloyloxymethyl) ethyl isocyanate etc., particularly preferably uses 2- isocyanates ethyl acrylates.
, can also be by polyalkylene polyol, poly- as another manufacture method of urethane acrylate class oligomer The chemical combination such as ethoxylated polyhydric alcohol, PEPA, the hydrogenated isoprene with C-terminal, hydrogenated butadiene with C-terminal Reaction between the-N=C=O parts that hydroxyl and isocyanates (methyl) alkyl acrylate that thing has has, comes To urethane acrylate class oligomer.In this case, as isocyanates (methyl) alkyl acrylate, it can use Double (acryloyloxymethyl) second of above-mentioned 2- isocyanates ethyl acrylate, 2- isocyanatomethyls ethyl acrylate, 1,1- Based isocyanate etc..
Polyester acrylic esters oligomer for example can be by obtaining as follows：The condensation of polybasic carboxylic acid and polyalcohol will be passed through Obtained from, have in two ends hydroxyl polyester oligomer hydroxyl, be esterified using (methyl) acrylic acid；Or will be The hydroxyl of the end of oligomer obtained from addition alkylene oxide in polybasic carboxylic acid, is esterified using (methyl) acrylic acid.
Epoxy Acrylates oligomer for example can be by making (methyl) acrylic acid and the bisphenol type than lower molecular weight The epoxide ring of epoxy resin or phenol aldehyde type epoxy resin reacts and is esterified and is obtained.Alternatively, it is also possible to use epoxy third Olefin(e) acid esters oligomer using dicarboxylic acid anhydride carry out it is partially modified obtained from carboxy-modified type Epoxy Acrylates oligomerization Body.
Polyoxyalkylene acrylate esters oligomer for example can be by utilizing (methyl) acrylic acid to enter the hydroxyl of PPG Row is esterified and obtained.
The weight average molecular weight of multifunctional (methyl) acrylate oligomer is preferably 10, more than 000, particularly preferably 20, More than 000.In addition, the weight average molecular weight is preferably 350, less than 000, particularly preferably 200, less than 000.
(1-5) adding proportion
When use polymerizable vinyl monomer and multifunctional (methyl) acrylate oligomer both as polymeric composition When, the ratio obtained by the quality of polymerizable vinyl monomer divided by the quality of multifunctional (methyl) acrylate oligomer is preferred For more than 0.18, particularly preferably more than 1, more preferably more than 1.5.In addition, the ratio is preferably less than 999, especially Preferably less than 19, more preferably less than 9.
(2) organoalkoxysilane
The no-solvent type adherence composition P of present embodiment contains organoalkoxysilane, the organoalkoxysilane There is alkoxysilyl with straight chain structure, and in its two end.Here, " straight chain " of " straight chain structure " is substantially Refer to " straight chain ".That is, as long as play well makes the action effect that is crosslinked between polymeric composition using organoalkoxysilane, then Straight chain structure can have side chain, or can contain cyclic structure.In addition, there is alkoxysilyl in two ends, Refer to that there is alkoxysilyl respectively at the both ends of straight chain structure.
Above-mentioned organoalkoxysilane preferably contains multiple alkoxysilyls at least one end.That is, organic alkane TMOS preferably contains two alkoxysilyls or three alkoxysilyls at least one end, particularly preferably Contain three alkoxysilyls.Multiple alkoxy silicanes are contained at least one end by organoalkoxysilane Base, so that being bonded for the active hydrogen-based having with polymeric composition becomes easy, as a result, the cohesive force of obtained sticker becomes Get Geng Gao.
As the example of alkoxysilyl, methoxysilyl, triethoxysilyl, positive third oxygen can be included Base silicyl, isopropoxy silicyl, n-butoxy silicyl, sec-butoxy silicyl, isobutoxy monosilane Base, tert-butoxy silicyl etc..Wherein, from the viewpoint of it can obtain excellent resistance to foaming, preferred methoxy methyl silane Base.
Above-mentioned organoalkoxysilane is in addition to containing alkoxysilyl, preferably without can be with polymeric composition The group of reaction.As the example of the group that can carry out the reaction in addition to alkoxysilyl, it can include (methyl) Acryloxy, ethyleneoxy, allyloxy etc..Do not have this group by above-mentioned organoalkoxysilane, can suppress to have Machine alkoxy silane is equably inhaled into polymeric composition.Thus, organoalkoxysilane is present in resulting adhering agent layer The ratio of near surface become higher, adhering agent layer is further enhanced to the adaptation of adherend.Moreover, by not depositing In the group in addition to alkoxysilyl, alkoxysilyl and the reaction of the active hydrogen-based in polymeric composition are not obstructed Hinder and carry out.Thus, forming organoalkoxysilane well in resulting adhering agent layer makes crosslinking between polymeric composition Structure, the cohesive force on adhering agent layer surface is further enhanced.Result more than, resulting adhering agent layer Resistance to foaming become excellent.
As the example of organoalkoxysilane contained in the no-solvent type adherence composition P of present embodiment, Double (alkoxysilyl) alkane can be included；Double (alkoxysilyl) benzene of 1,4-, the double (alkoxysilyls of 1,4- Alkyl) aromatic compound such as benzene；Double (alkoxysilyl) oxirane of 1,2-, double (alkoxysilyl) rings of 1,3- The olefinated oxygen compounds such as Ethylene Oxide；Double (alkoxysilyl) cyclobutane of 1,3-, 1,3- are double (alkoxysilylalkyl) The ester ring types such as double (alkoxysilyl) hexamethylenes of cyclobutane, 1,4-, double (alkoxysilylalkyl) hexamethylenes of 1,4- Compound etc..Wherein, from molecular volume it is small and easily with from the viewpoint of the active hydrogen-based of sticker formation key, it is particularly preferably double (alkoxysilyl) alkane.
The carbon number of the alkane of double (alkoxysilyl) alkane is more than 1, particularly preferably more than 3, further Preferably more than 5.In addition, the carbon number of the alkane is preferably less than 20, particularly preferably less than 10, more preferably 7 Below.
As the preferred example of double (alkoxysilyl) alkane, the double (trimethyoxysilanes of 1,6- can be included Base) hexane, double (trimethoxysilyl) heptane of 1,7-, double (trimethoxysilyl) octanes of 1,8- etc..Wherein, from energy Obtain from the viewpoint of excellent resistance to foaming, preferably use double (trimethoxysilyl) hexanes of 1,6- or 1,8- double (three Methoxysilyl) octane.
The content of above-mentioned organoalkoxysilane in no-solvent type adherence composition P, relative to 100 mass parts It is more than polymeric composition, preferably 0.01 mass parts, it is more than particularly preferably 0.05 mass parts, more preferably 0.1 mass parts More than.In addition, below polymeric composition of the content relative to 100 mass parts, preferably 20 mass parts, particularly preferably 10 mass Below part, below more preferably 3 mass parts.By making the content within the above range, it can fully obtain being based on above-mentioned The effect above of organoalkoxysilane.
(3) polymerization initiator
The no-solvent type adherence composition P of present embodiment preferably also contains polymerization initiator.By drawing containing polymerization Agent is sent out, solidifies effectively no-solvent type adherence composition P.
As polymerization initiator, it is not particularly limited, known polymerization initiator, but preferably basis can be used No-solvent type adherence composition P curing mode is selected.That is, when making no-solvent type adherence composition P by being used as work Property energy-ray ultraviolet irradiation solidification when, as polymerization initiator, preferably use Photoepolymerizationinitiater initiater.In addition, when logical Cross heating make no-solvent type adherence composition P solidify when, preferably use thermal polymerization.Photopolymerization can also be used simultaneously Initiator and thermal polymerization.
As the example of Photoepolymerizationinitiater initiater, for example, it can include styrax, benzoin methyl ether, benzoin ethyl ether, peace The fragrant isopropyl ether of breath, styrax n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino acetophenone, 2,2- dimethoxy -2- benzene Benzoylformaldoxime, 2,2- diethoxy -2- phenyl acetophenones, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyclohexyl benzene Base ketone, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinyl -1- acetone, 4- (2- hydroxyl-oxethyls) phenyl -2- (hydroxyl - 2- propyl group) ketone, benzophenone, to phenyl benzophenone, 4,4 '-lignocaine benzophenone, dichloro benzophenone, 2- methyl anthracenes Quinone, 2- EAQs, 2- tert-butyl groups anthraquinone, 2- amino anthraquinones, 2- methyl thioxanthones, 2- ethyls thioxanthones, CTX, 2, 4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, benzyl dimethyl ketal, acetophenone dimethyl ketal, to Dimethylaminobenzene Formic acid esters, oligomerization [2- hydroxy-2-methyls -1 [4- (1- methyl ethylenes) phenyl] acetone], 2,4,6- trimethylbenzoyls - Diphenyl-phosphineoxide etc..These may be used alone, can also be used in combination two or more.
As the example of thermal polymerization, the persulfates such as potassium peroxydisulfate, ammonium persulfate can be included；Benzoyl peroxide first The peroxide such as acyl, lauroyl peroxide；Azo-compounds such as azodiisobutyronitrile etc..These can be used alone, can also It is used in combination of two or more.
The content of polymerization initiator in no-solvent type adherence composition P, relative to the polymeric composition of 100 mass parts, More than preferably 0.1 mass parts, more than particularly preferably 0.3 mass parts, more than more preferably 0.5 mass parts.In addition, should Content relative to 100 mass parts polymeric composition, below preferably 10 mass parts, below particularly preferably 5 mass parts, further Below preferably 3 mass parts.By making the content be that more than 0.1 mass parts, can effectively carry out no-solvent type adherence group Compound P solidification.On the other hand, by making the content be that below 10 mass parts, can eliminate or reduce the unreacted in solidification And the polymerization initiator directly remained, and resulting sticker is easily set as to desired physical property.
(4) various additives
, can be according to needing to add various additives, such as silane coupler, ultraviolet in no-solvent type adherence composition P Light absorbers, antistatic additive, tackifier, antioxidant, light stabilizer, softening agent, filler, refractive index adjusters etc..In addition, Polymer solvent described later is set to be not included in the additive for constituting no-solvent type adherence composition P.
If here, no-solvent type adherence composition P contains silane coupler, resulting sticker and glass component Or the adaptation of plastic plate is improved.Thus, the resistance to foaming of resulting sticker becomes more excellent.
As silane coupler, it is in addition to above-mentioned organoalkoxysilane, there is at least one alcoxyl in intramolecular The organo-silicon compound of base silicyl are preferably good and have with the intermiscibility of above-mentioned polymeric composition and organoalkoxysilane The silane coupler of translucency.
As this kind of silane coupler, for example, it can include vinyltrimethoxy silane, vinyl triethoxyl silicon The silicon compound of the unsaturated groups containing polymerism such as alkane, methacryloxypropyl trimethoxy silane；3- glycidol oxygen Base propyl trimethoxy silicane, 2- (3,4- expoxycyclohexyls) ethyl trimethoxy silane etc. have the silication of epoxy based structures Compound；3- mercaptopropyl trimethoxysilanes, 3- mercaptopropyltriethoxysilanes, 3- mercapto dimethylamine epoxide methyl-monosilanes etc. contain mercapto The silicon compound of base；3- aminopropyl trimethoxysilanes, N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, N- (2- ammonia second Base) silicon compound containing amino such as -3- aminopropyltriethoxy dimethoxysilanes；3- r-chloropropyl trimethoxyl silanes, 3- isocyanic acids Ester propyl-triethoxysilicane or they at least one of, with MTES, ethyl triethoxysilane, first Condensation product of the silicon compound containing alkyl such as base trimethoxy silane, ethyl trimethoxy silane etc..These can be used alone One kind, can also be applied in combination two or more.
When no-solvent type adherence composition P contains silane coupler, its content is aggregated into relative to 100 mass parts Point, more than preferably 0.01 mass parts, more than particularly preferably 0.05 mass parts, more than more preferably 0.1 mass parts.Separately Outside, the content relative to 100 mass parts polymeric composition, below preferably 1 mass parts, below particularly preferably 0.5 mass parts, Below more preferably 0.3 mass parts.
(5) manufacture of no-solvent type adherence composition
No-solvent type adherence composition P can be by mixed polymerization composition and organoalkoxysilane, and as needed Additive is added to manufacture.
In addition, the no-solvent type adherence composition P of present embodiment is no-solvent type, therefore mainly pass through polymeric composition And with the viscosity of appropriateness.Therefore, the no-solvent type adherence composition P of present embodiment can be straight without diluent etc. Connect as coating solution.
(sticker)
The sticker of present embodiment is by the way that no-solvent type adherence composition P solidifications are formed.No-solvent type adherence Composition P solidification, the material according to contained by said composition P can be carried out, Huo Zheke by irradiating active energy beam To be carried out by heating.In this way, " solidification " in this specification, unless it is specifically mentioned, otherwise including based on active energy Measure the irradiation of ray solidification and solidification based on heating both.
No-solvent type adherence composition P solidification, is preferably carried out by irradiating active energy beam.Thus, solid Without applying heat during change, can prevent the resin film etc. of coating object as no-solvent type adherence composition P heat deterioration, Thermal contraction etc..Further, since without heating, thus, it is possible to suppress the volatile ingredient in no-solvent type adherence composition P because Heat and disappear.
Active energy beam refers to the active energy beam in electromagnetic wave or charged particle beam with the quantum of energy, it is specific and Speech, can include ultraviolet or electron beam etc..In active energy beam, particularly preferred maneuverable ultraviolet.
Ultraviolet irradiation can be carried out by high-pressure mercury-vapor lamp, fusion H lamps (fusion H lamp), xenon lamp etc., be closed In ultraviolet irradiation amount, illumination is preferably 50mW/cm2Above and for 1000mW/cm2Below.Light quantity is preferably 50mJ/cm2With On, more preferably 80mJ/cm2More than, particularly preferably 200mJ/cm2More than.In addition, light quantity is preferably 10000mJ/cm2With Under, more preferably 5000mJ/cm2Hereinafter, particularly preferably 2000mJ/cm2Below.On the other hand, the irradiation of electron beam can lead to Cross electron-beam accelerator etc. to carry out, the exposure of electron beam is preferably more than 10krad and is below 1000krad.
The heating-up temperature of heating is preferably more than 50 DEG C, particularly preferably more than 70 DEG C.In addition, the heating-up temperature is excellent Elect less than 150 DEG C, particularly preferably less than 120 DEG C as.The heat time of heating is preferably more than 10 seconds, particularly preferably More than 50 seconds.In addition, the heat time is preferably less than 10 minutes, particularly preferably less than 90 seconds.Also can be by being coated with without molten Drying process after formulation adherence composition P doubles as the heating.
In addition, when manufacturing the sticker of present embodiment, active-energy can be carried out after being heated and penetrated Line is irradiated, and two kinds of processing can also be carried out simultaneously.It is also preferable to after heating or after active energy beam irradiation, normal During the maintenance that 1~2 week or so is set under warm (for example, 23 DEG C, 50%RH).
The gel fraction of the sticker of present embodiment is preferably more than 50%, and particularly preferably more than 55%, further Preferably more than 60%.In addition, the gel fraction is preferably less than 100%, particularly preferably less than 80%, more preferably Less than 70%.By the gel fraction of sticker within the above range, the cohesive force of sticker increases, and resistance to foaming becomes more It is excellent.Here, shown in the test example of the assay method of the gel fraction of sticker as be described hereinafter.
The sticker of present embodiment is obtained by the way that above-mentioned no-solvent type adherence composition P is solidified.Therefore, at this During solidification, the mutual polymerisation of polymeric composition is carried out, while the condensation reaction of organoalkoxysilane and active hydrogen-based is with table Face is carried out centered on nearby, therefore firm cross-linked structure is formed in the sticker.As a result, the sticker of present embodiment With very high cohesive force.That is, the sticker of present embodiment, locally improves the cohesive force on the surface contacted with adherend, Simultaneously on the whole rich in flexibility.Thus, the sticker of present embodiment has sufficient segment difference tracing ability, and can play Excellent resistance to foaming.
(adhesive sheet)
The adhesive sheet of present embodiment, which has, is used for fit a display body component parts and another display body component parts Adhering agent layer, the adhering agent layer is formed by the sticker.
Concrete structure as the adhesive sheet of present embodiment example is shown in Fig. 1.As shown in figure 1, one The adhesive sheet 1 of embodiment is made up of following structure：Two panels stripping film 12a, 12b；And with this two panels stripping film 12a, 12b The mode of release surface contact is by the adhering agent layer 11 clamped by the two panels stripping film 12a, 12b.In addition, the stripping in this specification The release surface of piece, refers to there is the face of fissility in stripping film, even if in addition to implementing the face of lift-off processing and being not carried out Lift-off processing displays that both faces of fissility.
(1) adhering agent layer
Adhering agent layer 11 is made up of the sticker, i.e. by the adhesion for solidifying no-solvent type adherence composition P Agent is constituted.
The thickness of adhering agent layer 11 in the adhesive sheet 1 of present embodiment is (according to JIS K7130：1999 values determined) it is excellent Elect more than 10 μm, more preferably more than 25 μm, more preferably particularly preferably more than 50 μm, more than 75 μm as.In addition, should Thickness is preferably less than 1000 μm, more preferably less than 400 μm, particularly preferably less than 300 μm.In addition, adhering agent layer 11 can To be formed by individual layer, it can also be formed multilayer laminated.
If the thickness of adhering agent layer 11 is more than 10 μm, desired adhesion strength is easily played.If in addition, adhering agent layer 11 thickness is less than 1000 μm, then processability is good.
(2) stripping film
Stripping film 12a, 12b, protect adhering agent layer 11 before using adhesive sheet 1, are using (the adhering agent layer of adhesive sheet 1 11) it is stripped when.In the adhesive sheet 1 of present embodiment, one or two in stripping film 12a, 12b it is not absolutely required to.
As stripping film 12a, 12b, can for example use polyethylene film, polypropylene screen, polybutene film, polybutadiene film, Polymethylpentene film, polychloroethylene film, vinyl chloride copolymer film, polyethylene terephthalate film, poly- naphthalenedicarboxylic acid second two Alcohol ester film, polybutylene terephthalate (PBT) film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethene (methyl) acrylic copolymer film, ethene (methyl) acrylate copolymer film, polystyrene film, polycarbonate membrane, polyamides Imines film, fluororesin film etc..Alternatively, it is also possible to use these cross linking membrane.Alternatively, it is also possible to the stacked film for these.
Preferred pair above-mentioned stripping film 12a, 12b release surface (face especially contacted with adhering agent layer 11) are implemented at stripping Reason.As the remover used in lift-off processing, for example, it can include alcohol acids, silicone, fluorine class, unsaturated polyester (UP) Class, TPO, the remover of wax class.In addition, in stripping film 12a, 12b, preferably by a stripping film be set to peeling force compared with Big re-release type stripping film, the less light exfoliated stripping film of peeling force is set to by another stripping film.
For stripping film 12a, 12b thickness, it is not particularly limited, but usually more than 20 μm and for less than 150 μm.
(3) physical property
(3-1) adhesion strength
The adhesive sheet 1 of present embodiment is preferably more than 5N/25mm to the adhesion strength of soda-lime glass, particularly preferably 10N/ More than 25mm, more preferably more than 15N/25mm.In addition, the adhesion strength is preferably below 50N/25mm, particularly preferably Below 40N/25mm, more preferably below 35N/25mm.If the adhesion strength of adhesive sheet 1 is more than 5N/25mm, resistant blister Property becomes more excellent.If in addition, the adhesion strength of adhesive sheet 1 is below 50N/25mm, good re-workability can be obtained, In the case where occurring to fit by mistake, the display body component parts of high price can be recycled.Here, the adhesion strength base in this specification Originally refer to by according to JIS Z0237：Adhesion strength that 2009 180 degree stripping method is determined, specific assay method is as be described hereinafter Shown in test example.
(3-2) haze value
The haze value of the adhering agent layer 11 of the adhesive sheet 1 of present embodiment is preferably less than 5%, particularly preferably 1% with Under, more preferably less than 0.5%.If the haze value of adhering agent layer 11 is less than 5%, the transparency is higher, is suitable for Optical applications (are used for display body).In addition, the haze value in this specification is set to according to JIS K7136：2000 values determined.
(3-3) total light penetration
Total light penetration of the adhering agent layer 11 of the adhesive sheet 1 of present embodiment is preferably more than 90%, particularly preferably For more than 95%, more preferably more than 98%.If total light penetration is more than 98%, the transparency is very high, is adapted to For optical applications.In addition, total light penetration in this specification is set to according to JIS K7361-1：1997 values determined.
(4) manufacture of adhesive sheet
As a Production Example of adhesive sheet 1, above-mentioned nothing is coated with by the release surface in a stripping film 12a (or 12b) Solvent-borne type adherence composition P and form coating layer, and be superimposed on the coating layer another stripping film 12b (or 12a) stripping After face, active energy beam irradiation is carried out to coating layer and/or heats to form adhering agent layer 11.
It is above-mentioned solvent-free in the release surface coating of a stripping film 12a (or 12b) as another Production Example of adhesive sheet 1 Type adherence composition P, and carry out active energy beam irradiation and/or heating and make no-solvent type adherence composition P Solidify to be formed after adhering agent layer 11, another stripping film 12b (or 12a) release surface is superimposed on the adhering agent layer 11.
As the method for the coating fluid for being coated with above-mentioned no-solvent type adherence composition P, for example can using rod coating method, Scraper for coating method, roller rubbing method, scraper plate rubbing method, die coating methods, gravure coating process etc..
In the adhesive sheet 1 of present embodiment manufactured as above, because adhering agent layer 11 is by by above-mentioned no-solvent type adherence The sticker of composition P solidifications is formed, therefore has very high cohesive force as described above.Moreover, inferring in shape Into no-solvent type adherence composition P film when, the organoalkoxysilane with polarity is more to be the film partially Near surface, above-mentioned condensation reaction carries out more near surface.As a result, in the adhesive sheet 1 of present embodiment, deduction is got over Close to the surface of adhering agent layer 11, with higher cohesive force.Thus, according to the adhesive sheet 1 of present embodiment, it can play excellent Resistance to foaming.
(display body)
As shown in Fig. 2 the display body 2 of present embodiment possesses following structure：At least there is section in the face for the side fitted First display body component parts 21 (a display body component parts) of difference；(another display body structure of second display body component parts 22 Into part)；And positioned at bonded to each other between them, by the first display body component parts 21 and the second display body component parts 22 Adhering agent layer 11.In the display body 2 of present embodiment, the first display body component parts 21 has section in the face of the side of adhering agent layer 11 Difference, specifically, with the segment difference formed by printing layer 3.
Adhering agent layer 11 in above-mentioned display body 2 is the adhering agent layer 11 of the adhesive sheet 1.
As display body 2, for example, it can include liquid crystal (LCD) display, light emitting diode (LED) display, organic Electroluminescent (organic EL) display, Electronic Paper etc. or touch panel.In addition, being used as display body 2 or structure Into the part of their part.
First display body component parts 21 is preferably glass plate, plastic plate etc., furthermore it is preferred that for by the stacking including these The protection panels of the compositions such as body.Now, the general side of adhering agent layer 11 in the first display body component parts 21 of printing layer 3 is formed For frame-like.
As above-mentioned glass plate, it is not particularly limited, for example, can includes chemically reinforced glass, alkali-free glass, quartz Glass, soda-lime glass, baric/strontium glass, aluminosilicate glass, lead glass, borosilicate glass, barium borosilicate glass etc..Glass The thickness of plate, is not particularly limited, but usually more than 0.1mm, preferably more than 0.2mm.In addition, the thickness is usually Below 5mm, preferably below 2mm.
As above-mentioned plastic plate, it is not particularly limited, such as can include acrylic panel, polycarbonate plate.Plastics The thickness of plate, is not particularly limited, usually more than 0.2mm, preferably more than 0.4mm.In addition, the thickness is usually 5mm Hereinafter, preferably below 3mm.
In addition, the one or both sides in above-mentioned glass plate or plastic plate can set various functions layers (nesa coating, gold Belong to layer, silicon dioxide layer, hard conating, antiglare layer etc.), can also laminated optical member.In addition, nesa coating and metal level can To be patterned.
Second display body component parts 22 is preferably that should be attached at optical component, the display of the first display body component parts 21 Module (for example, liquid crystal (LCD) module, light emitting diode (LED) module, organic electroluminescent (organic EL) module etc.), work For show module a part optical component or include display module layered product.
As above-mentioned optical component, for example, it can include shatter prevention film, Polarizer (light polarizing film), polarizer, polarizer (phase retardation film), compensation film for angular field of view, brightness enhancement film, contrast improve film, liquid crystalline polymer film, diffusion barrier, Transflective film, thoroughly Bright conductive film etc..As shatter prevention film, it can exemplify in hard coat film of one side formation hard conating of base material film etc..
The material of printing layer 3 is constituted, is not particularly limited, the known material of printing can be used.Printing layer 3 The highly preferred of thickness, i.e. segment difference is more than 3 μm, particularly preferably more than 5 μm, more preferably more than 7 μm, is most preferably More than 10 μm.In addition, it is less than 50 μm that this is highly preferred, particularly preferably less than 35 μm.
When manufacturing above-mentioned display body 2, as an example, a stripping film 12a of adhesive sheet 1 is peeled off, by adhesive sheet 1 The adhering agent layer 11 exposed fit in the first display body component parts 21 presence printing layer 3 side face.Then, from adhesion The adhering agent layer 11 of piece 1 peels off another stripping film 12b, by the display body structure of adhering agent layer 11 and second exposed of adhesive sheet 1 Fitted into part 22.In addition, as another example, the first display body component parts 21 and the second display body can be replaced The coating squence of component parts 22.
In display body 2 more than, infer because adhering agent layer 11 is by above-mentioned no-solvent type adherence composition P is solidified Sticker formed, therefore, as described above with very high cohesive force, especially, closer to adhering agent layer 11 Surface, the cohesive force is higher.Therefore, though by display body 2 be positioned over it is hot and humid under the conditions of and from the first display body constituting portion The display body component parts 22 of part 21 or second produces exhaust, can also suppress to produce bubble, float, peels off etc. and bubbling.
Embodiments described above is recorded to be readily appreciated that the present invention, is not intended to limit the present invention and remember Carry.Therefore, each important document disclosed in above-mentioned embodiment is all designs change for also including belonging to the technical scope of the present invention More with the objective of equivalent.
For example, it is convenient to omit any one in stripping film 12a, 12b in adhesive sheet 1 or two, furthermore it is possible to instead of Stripping film 12a and/or 12b and be laminated desired optical component.Removed in addition, the first display body component parts 21 can also have Segment difference beyond printing layer 3.And then, not only the first display body component parts 21 has segment difference, the second display body component parts 22 There can also be segment difference in the side of adhering agent layer 11.
Embodiment
Hereinafter, the present invention is described in further detail by embodiment etc., but the scope of the present invention and non-limiting In these embodiments etc..
(Production Example 1)
1. the preparation of urethane acrylate class oligomer
(value of solid constituent is converted into by mixing the mass parts of polypropylene glycol 100 that weight average molecular weight is 3000；Following phase Together), the mass parts of hexamethylene diisocyanate 4 and the mass parts of tin dilaurate dioctyl tin 0.02, and stirring 6 is small at 80 DEG C When, and obtain reactant.For resulting reactant, IR spectrum, results verification to isocyanic acid are determined by infrared measure Ester group almost disappears.
Then, by relative to the resulting mass parts of reaction-ure mixture mixing 2- isocyanate ethyls acrylate 1, and Stirred 3 hours at 80 DEG C, and obtain urethane acrylate class oligomer.It is few for resulting urethane acrylate class Aggressiveness, IR spectrum are determined by infrared measure, and results verification to NCO almost disappears.In addition, utilizing side described later Method determines the result of the molecular weight of resulting urethane acrylate class oligomer, and weight average molecular weight (Mw) is 25,000.
2. the preparation of liquefied mixture
By mixing mass parts of 2-EHA 40 as polymerizable vinyl monomer, as polymerization sex ethylene The mass parts of isobornyl acrylate 20 of base monomer, the mass parts of acrylic acid 2- hydroxy methacrylates 10 as polymerizable vinyl monomer And the mass of urethane acrylate class oligomer 30 of the preparation as described above as multifunctional (methyl) acrylate oligomer Part, and carry out Jiao and mix, and obtain liquefied mixture.
Here, the weight average molecular weight (Mw) is to determine (GPC surveys under the following conditions using gel permeation chromatography (GPC) The weight average molecular weight for being converted into polystyrene calmly).
＜ condition determinations ＞
GPC determines device：TOSOH CORPORATION are manufactured, HLC-8020
GPC posts (pass through) in the following order：TOSOH CORPORATION are manufactured
TSK guard column HXL-H
TSK gel GMHXL(×2)
TSK gel G2000HXL
Determine solvent：Tetrahydrofuran
Determine temperature：40℃
(Production Example 2)
By mixing mass parts of 2-EHA 40 as polymerizable vinyl monomer, as polymerization sex ethylene The mass parts of acryloyl morpholine 20 of base monomer, the mass parts of acrylic acid 2- hydroxy methacrylates 10 as polymerizable vinyl monomer and The mass parts of urethane acrylate class oligomer 30 prepared in above-mentioned Production Example 1, and carry out Jiao and mix, and obtain liquid mixing Thing.
(embodiment 1)
1. the preparation of no-solvent type adherence composition
By being blended in, (conversion claims solid constituent to the mass parts of liquefied mixture 100 prepared in above-mentioned Production Example 1 Value；It is same as below), be used as the double mass parts of (trimethoxysilyl) hexane 0.3 of 1,6- and the conduct of organoalkoxysilane The mass parts of 1- hydroxy-cyclohexyl-phenyls -one 0.5 of Photoepolymerizationinitiater initiater, and obtain no-solvent type adherence composition.
2. the manufacture of adhesive sheet
The weight obtained from the one side of polyethylene terephthalate film is carried out into lift-off processing using silicone remover On the lift-off processing face of exfoliated stripping film (LINTEC Corporation are manufactured, name of product " SP-PET752150 "), profit The no-solvent type adherence composition obtained in above-mentioned operation 1 is coated with scraper coating machine.
Then, the coating layer on re-release type stripping film that is obtained in will be above-mentioned, with by polyethylene terephthalate film One side utilize silicone remover to carry out light exfoliated stripping film (LINTEC Corporation systems obtained from lift-off processing Make, name of product " SP-PET382120 "), entered in the way of the lift-off processing face of the light exfoliated stripping film and coating layer Row laminating.
Then, via re-release type stripping film, under the following conditions to coating layer irradiation ultraviolet radiation, and produce by shelling again Release stripping film/adhering agent layer (thickness：100 μm) adhesive sheet that constitutes of the structure of/light exfoliated stripping film.
[ultraviolet irradiation condition]
Light source：High-pressure mercury-vapor lamp
Light quantity：1000mJ/cm2
Illumination：100mW/cm2
(embodiment 2~4, comparative example 1~6)
The species of liquefied mixture and the species of organoalkoxysilane and addition are changed like that as shown in table 1, are removed Beyond this, adhesive sheet is produced similarly to Example 1.In addition, in comparative example 3, the three (front threes as organoalkoxysilane Epoxide silylpropyl) isocyanuric acid ester, using so-called isocyanurate ring as main framing, and relative between the main framing etc. There are three trimethoxy-silylpropyls every bond.Therefore, the organoalkoxysilane, which can not be said to be above-mentioned, has straight chain The organoalkoxysilane of shape structure, not equivalent to the organoalkoxysilane of present embodiment.
(test example 1) (measure of gel fraction)
Adhesive sheet resulting in embodiment and comparative example is cut to 80mm × 80mm size, by its adhering agent layer bag In polyester net (mesh size 200), its quality is weighed by precision balance, the single quality of above-mentioned net is subtracted, thus counts Calculate the quality of only sticker.Quality now is set to M1.
Then, at room temperature (23 DEG C), the sticker wrapped in above-mentioned polyester net is impregnated 3 days in ethyl acetate. Afterwards, sticker is taken out, is dried 3 hours in 100 DEG C of baking oven.After drying, temperature be 23 DEG C, relative humidity be 50% After standing 3 hours under environment, its quality is weighed using precision balance, the single quality of above-mentioned net is subtracted, thus calculated and only glue The quality of agent.Quality now is set to M2.Gel fraction (%) is represented with (M2/M1) × 100.It the results are shown in table 1 In.
(test example 2) (evaluation of optical characteristics)
Adhesive sheet obtained by from embodiment and comparative example peels light exfoliated stripping film off, and the adhering agent layer exposed is pasted Invest after the soda-lime glass (Nippon Sheet Glass Company, Ltd. manufacture) that thickness is 1.1mm, peel re-release off Type stripping film, thus obtains sample for evaluation.
From the incident haze meter in the adhering agent layer side of the evaluation sample (NIPPON DENSHOKU INDUSTRIES CO., LTD. manufacture, name of product " NDH-2000 ") measure light, and determine total light penetration (%) and haze value (%).Respectively 3 measure are carried out, and calculate their average value.It the results are shown in table 1.
(test example 3) (measure of adhesion strength)
Peel off light exfoliated stripping film on adhesive sheet obtained by from embodiment and comparative example, and by exposed sticker Layer fits in polyethylene terephthalate (PET) film (TOYOBO CO., LTD. manufactures, ProductName with adhesive layer Claim " PET A4300 ", thickness：100 μm) adhesive layer, so as to obtain the layered product of stripping film/adhering agent layer/PET film.Will Resulting layered product severing is 25mm width, 150mm length, as sample.
In the environment of 23 DEG C, 50%RH, re-release type stripping film is peeled off from above-mentioned sample, the adhering agent layer exposed is pasted After investing soda-lime glass (Nippon Sheet Glass Company, Ltd. manufacture), by by 2kg roller make a round trip come Crimping.Then, after placing 24 hours under conditions of 23 DEG C, the 50%RH, using cupping machine (ORIENTEC CO., LTD. manufacture, Tensilon), adhesion strength (N/ is determined under conditions of peeling rate 300mm/min, peel angle 180 degree 25mm).Condition in addition to this is recorded in, according to JIS Z0237：2009 are measured.It the results are shown in table 1.
(test example 4) (evaluation of resistance to foaming)
The light exfoliated stripping film of adhesive sheet obtained by peeling off in embodiment and comparative example, the adhering agent layer exposed is pasted Investing polyethylene terephthalate film of the one side provided with nesa coating, (OIKE＆Co., Ltd. are manufactured, name of product " ITO Film ", thickness：125 μm) the face provided with nesa coating, wherein the nesa coating is by tin-doped indium oxide (ITO) shape Into, and it is cut to 60mm × 60mm.Moreover, peeling off re-release type stripping film from adhesive sheet, the adhering agent layer exposed is attached at It is laminated with resin plate (the Mitsubishi Gas Chemical of polymethyl methacrylate (PMMA) and makrolon (PC) Company, Inc. are manufactured, name of product " MR-58 ", thickness：785 μm) polycarbonate side face, thus obtain test film.
By resulting test film under conditions of 50 DEG C, the 0.5MPa after autoclave process 30 minutes, in normal pressure, 23 DEG C, place 24 hours under 50%RH.Then, 85 DEG C, 85%RH it is hot and humid under the conditions of take care of 72 hours.Then, visually Confirm that the interface of adhering agent layer and adherend floats strippings, and the following benchmark evaluation resistance to foaming of utilization.Result is represented In table 1.
○：Bubble can not be confirmed and float stripping.
△：Confirm a small amount of minute bubbles, but it is unconfirmed to floating stripping.
×：Confirm big bubble or float stripping.
(test example 5) (evaluation of wet-heat resisting albefaction)
With polyethylene terephthalate of the two panels one side provided with the nesa coating formed by tin-doped indium oxide (ITO) (OIKE＆Co., Ltd. are manufactured ester film, name of product " ito film ", thickness：125 μm) clamping embodiment or comparative example in obtained by Adhesive sheet adhering agent layer, and obtain layered product.Now, the face provided with nesa coating of the film is attached at sticker Layer.By resulting layered product under conditions of 50 DEG C, the 0.5MPa after autoclave process 30 minutes, normal pressure, 23 DEG C, 50% Placed 24 hours under RH.Then, using haze meter (NIPPON DENSHOKU INDUSTRIES CO., LTD. manufactures, ProductName Claim " NDH2000 "), according to JIS K7136：2000 determine haze value (%).
Then, above-mentioned layered product is taken care of into 120 hours (long duration test) under 85 DEG C, 85%RH wet heat condition.Then, 23 DEG C, 50%RH ambient temperature and moisture are reverted to, and determines haze value (%) again to the layered product.In addition, the haze value, is being incited somebody to action Layered product reverts to being determined within 30 minutes for ambient temperature and moisture.
By the rising value of the haze value (%) before above-mentioned long duration test to the haze value (%) after above-mentioned long duration test, according to Following benchmark evaluation wet-heat resisting albefaction.It the results are shown in table 1.
◎：The rising value of haze value (%) after long duration test is less than 0.90%.
○：The rising value of haze value (%) after long duration test is more than 0.90% and is less than 1.50%.
×：The rising value of haze value (%) after long duration test is more than 1.50%.
(test example 6) (evaluation of segment difference tracing ability)
Glass plate (NSG Precision Co, Ltd. manufacture, name of product " Corning glass Eagle XG ", Vertical 90mm × horizontal 50mm × thickness 0.5mm) surface on, in the way of coating thickness turns into 30 μm, with frame-like (profile：It is vertical 90mm × horizontal 50mm, width 5mm) screen painting ultraviolet curable ink (Teikoku Printing Inks Mfg.Co., Ltd. manufacture, name of product " POS-911 ink ").Then, irradiation ultraviolet radiation (80W/cm2, two metal halide lamps, lamp height 15cm, 10~15 ms/min of belt speed), solidify printed above-mentioned ultraviolet curable ink, so as to make with by printing The glass plate with segment difference of the segment difference of formation.
Adhesive sheet obtained by from embodiment and comparative example peels light exfoliated stripping film off, and the adhering agent layer exposed is pasted Together in the polyethylene terephthalate film with adhesive layer, (TOYOBO Co., Ltd.s manufacture, name of product " PET A4300 ", thickness：100 μm) adhesive layer.Then, peel re-release type stripping film off, expose adhering agent layer.Also, use Plastic packaging machine (FUJIPLA Inc. are manufactured, name of product " LPD3214 "), with the whole printing surface of adhering agent layer covering frame rack-like Mode is fitted the face exposed of adhering agent layer and the face with segment difference of the above-mentioned glass plate with segment difference, regard this as evaluation sample Product.
By resulting sample for evaluation under conditions of 50 DEG C, the 0.5MPa after autoclave process 30 minutes, normal pressure, 23 DEG C, place 24 hours under 50%RH.Then, 85 DEG C, 85%RH it is hot and humid under the conditions of take care of (durable examination in 72 hours Test), then, confirm adhering agent layer (especially near the segment difference that printing layer is produced) by visual observation, and utilize following benchmark Evaluate segment difference tracing ability.It the results are shown in table 1.
◎：Stripping is not floated near segment difference, sticker is followed in gapless mode.
○：Near segment difference observe somewhat float stripping.
×：Larger bubble is mixed near segment difference.
[table 1]
As shown in Table 1, adhesive sheet resulting in embodiment, its resistance to foaming is excellent, and wet-heat resisting albefaction and section Poor tracing ability is also excellent.
Industrial applicibility
No-solvent type adherence composition, sticker and the adhesive sheet of the present invention can for example be adapted to be used in laminating display Body component parts.

Claims (10)

1. a kind of no-solvent type adherence composition, it is characterised in that contain：
Selected from polymerizable vinyl monomer, polymerizable vinyl prepolymer, multifunctional (methyl) acrylate monomer and multifunctional At least one of (methyl) acrylate oligomer polymeric composition；And
Organoalkoxysilane, has alkoxysilyl with straight chain structure, and in its two end,
At least a portion in the polymeric composition contains active hydrogen-based.
2. no-solvent type adherence composition according to claim 1, it is characterised in that the active hydrogen-based is hydroxyl.
3. no-solvent type adherence composition according to claim 1, it is characterised in that the no-solvent type adherence group Compound at least contains the polymerizable vinyl monomer and multifunctional (methyl) the acrylate oligomer as the polymerization Composition.
4. no-solvent type adherence composition according to claim 1, it is characterised in that the no-solvent type adherence group Compound also contains Photoepolymerizationinitiater initiater.
5. no-solvent type adherence composition according to claim 1, it is characterised in that relative to the institute of 100 mass parts State the content of the organoalkoxysilane in polymeric composition, the no-solvent type adherence composition for 0.01 mass parts with Above and for below 20 mass parts.
6. a kind of sticker, it is by the way that the no-solvent type adherence composition solidification described in claim 1 is formed.
7. sticker according to claim 6, it is characterised in that the gel fraction of the sticker is more than 50% and is Less than 100%.
8. a kind of adhesive sheet, it has the adhering agent layer formed by the sticker described in claim 6.
9. adhesive sheet according to claim 8, it is characterised in that
The adhesive sheet possesses two panels stripping film,
The adhering agent layer is clamped in the way of the release surface with the two panels stripping film is contacted by the stripping film.
10. a kind of display body, it possesses：
One display body component parts, at least has segment difference in the face of side to be fit；
Another display body component parts；And
Adhering agent layer, the display body component parts bonded to each other and another display body component parts,
The display body is characterised by,
The adhering agent layer is the adhering agent layer of the adhesive sheet described in claim 8.
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